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
- Publication number
- CN102008965B CN102008965B CN201010539704A CN201010539704A CN102008965B CN 102008965 B CN102008965 B CN 102008965B CN 201010539704 A CN201010539704 A CN 201010539704A CN 201010539704 A CN201010539704 A CN 201010539704A CN 102008965 B CN102008965 B CN 102008965B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- amorphous alumina
- solution
- tin
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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.
Priority Applications (1)
| 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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102008965A CN102008965A (en) | 2011-04-13 |
| CN102008965B true CN102008965B (en) | 2012-10-17 |
Family
ID=43839407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010539704A Active CN102008965B (en) | 2010-11-09 | 2010-11-09 | Method for preparing ozone catalytic oxidation catalyst for treating cyanide waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102008965B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109794260A (en) * | 2019-02-22 | 2019-05-24 | 上海电气集团股份有限公司 | A kind of preparation method and ozone oxidation catalyst of ozone oxidation catalyst |
| 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 | Method for preparing multi-metal ozone catalyst by blending-impregnation combined method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999065828A1 (en) * | 1998-06-18 | 1999-12-23 | Degremont | Method for mineralization of organic pollutants in water by catalytic ozonization |
| CN1785507A (en) * | 2005-11-22 | 2006-06-14 | 天津化工研究设计院 | Ozone decomposition catalyst and its preparation method |
| CN101658789A (en) * | 2009-09-21 | 2010-03-03 | 国核电力规划设计研究院 | Metal-doped oxyhydroxide catalyst and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0616849B2 (en) * | 1989-03-29 | 1994-03-09 | 株式会社日本触媒 | Catalyst for treating gas containing harmful and odorous components |
-
2010
- 2010-11-09 CN CN201010539704A patent/CN102008965B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999065828A1 (en) * | 1998-06-18 | 1999-12-23 | Degremont | Method for mineralization of organic pollutants in water by catalytic ozonization |
| CN1785507A (en) * | 2005-11-22 | 2006-06-14 | 天津化工研究设计院 | Ozone decomposition catalyst and its preparation method |
| CN101658789A (en) * | 2009-09-21 | 2010-03-03 | 国核电力规划设计研究院 | Metal-doped oxyhydroxide catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP平2-253850A 1990.10.12 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102008965A (en) | 2011-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102008965B (en) | Method for preparing ozone catalytic oxidation catalyst for treating cyanide waste water | |
| Wang et al. | Microwave catalytic activities of supported perovskite catalysts MOx/LaCo0. 5Cu0. 5O3@ CM (M= Mg, Al) for salicylic acid degradation | |
| CN101982237B (en) | Preparation method of ozone catalytic oxidation catalyst used for treating oil refining waste water | |
| CN105457643B (en) | A kind of preparation method of activated carbon supported type catalyst for Electrocatalysis Degradation organic wastewater | |
| CN106957438B (en) | Preparation of modified MIL-53(Fe) metal organic framework and method for treating organic wastewater by activating persulfate | |
| CN102941084A (en) | Method for preparing double-component metallic oxide catalytic ozonation catalyst | |
| CN102029165A (en) | Method for preparing ozone catalytic oxidation catalyst for treating coking wastewater | |
| CN109647431B (en) | Catalyst for catalytic oxidation treatment of refractory wastewater by ozone, preparation method and application thereof | |
| CN101891297B (en) | Ozonization water treatment method using manganese dioxide one-dimensional nano material as catalyst | |
| CN111135823B (en) | Wet oxidation catalyst and preparation method and application thereof | |
| CN107824196B (en) | A kind of organic wastewater ozone oxidation catalyst and its preparation and application | |
| CN103990452B (en) | A kind of Sewage advanced treatment catalyst, catalyst carrier and this catalyst, the preparation method of catalyst carrier | |
| CN109364940A (en) | Charcoal loads ferrimanganic bimetallic oxide light Fenton composite material and preparation method | |
| CN109621941B (en) | Catalyst for catalytic oxidation of ozone prepared from waste argil and preparation and application thereof | |
| CN108993518A (en) | A kind of heterogeneous lightwave CATV catalyst of nanocomposite and its preparation and application | |
| CN106807362A (en) | One kind load manganese dioxide activated-carbon catalyst and preparation method and application | |
| CN105233838B (en) | A kind of O using activated bentonite as carrier3/H2O2Preparation method, catalyst and its application of catalyst | |
| CN109364924B (en) | Magnetic nano ozone catalyst CoFe2O4And preparation method and application thereof | |
| Liu et al. | Nitrogen doped Cu/Fe@ PC derived from metal organic frameworks for activating peroxymonosulfate to degrade Rhodamine B | |
| CN109482219A (en) | Activate the CoFe of persulfate advanced treatment on coking wastewater2O4/ N doping sludge-based activated carbon catalyst and preparation method | |
| CN107252685A (en) | A kind of hydroxyl aminated compounds functional magnetic graphene oxide catalysis material and its preparation method and application | |
| CN106552644B (en) | Ozone catalyst for difficult biochemical wastewater and preparation method thereof | |
| CN102049253A (en) | Preparation method of special catalyst for waste water treatment by ozone oxidation | |
| CN102218318A (en) | Method for preparing modified honeycomb ceramics used for removing organic pollutants from water through catalytic ozonation | |
| CN103949264B (en) | A kind of for high-temperature catalytic decomposing N 2the Catalysts and its preparation method of O |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |