CN103240115B - Supported catalytic ozonation catalyst and its preparation method - Google Patents

Supported catalytic ozonation catalyst and its preparation method Download PDF

Info

Publication number
CN103240115B
CN103240115B CN201210028551.XA CN201210028551A CN103240115B CN 103240115 B CN103240115 B CN 103240115B CN 201210028551 A CN201210028551 A CN 201210028551A CN 103240115 B CN103240115 B CN 103240115B
Authority
CN
China
Prior art keywords
catalyst
molecular sieve
weight ratio
nay molecular
manganese oxide
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
Application number
CN201210028551.XA
Other languages
Chinese (zh)
Other versions
CN103240115A (en
Inventor
李杨
马健维
王树勖
李晶蕊
周霞
赵雪芹
易春嵘
朱夔
曲大平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Natural Gas Co Ltd
Original Assignee
China Petroleum and Natural Gas Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Natural Gas Co Ltd filed Critical China Petroleum and Natural Gas Co Ltd
Priority to CN201210028551.XA priority Critical patent/CN103240115B/en
Publication of CN103240115A publication Critical patent/CN103240115A/en
Application granted granted Critical
Publication of CN103240115B publication Critical patent/CN103240115B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)

Abstract

The invention relates to a catalytic ozonation catalyst and its preparation method. The catalyst is mainly composed of a carrier NaY molecular sieve, active metal oxides manganese oxide and titanium dioxide, and catalyst molding auxiliary agents. The carrier NaY molecular sieve supported with manganese oxide is a main catalyst agent. The content of manganese oxide in the main agent is 10.5wt%-11.5wt%. The catalyst molding auxiliary agents contain kaolin, a binder, a lubricant and a pore forming agent, wherein the weight ratio of the main agent to kaolin is 1:0.3-0.6; the weight ratio of the main agent to the binder is 1:0.5-0.9; the weight ratio of the main agent to the lubricant is 1:0.5-0.85; the weight ratio of the main agent to the pore forming agent is 1:0.02-0.04; and the content of titanium dioxide in the catalyst is 1.5wt%-3.0wt%. By using the NaY molecular sieve as the carrier, by the adoption of ion exchange and dipping methods and with the combination of supporting heterogeneous metal, the comprehensive catalytic ozonation catalyst is prepared. The catalytic ozonation catalyst can be used to process organic wastewater and has advantages of high utilization rate, high dispersiveness, obvious processing effect and long service cycle.

Description

A kind of support type ozone catalytic oxidation catalyst and preparation method thereof
Technical field
The present invention relates to a kind of support type ozone catalytic oxidation catalyst processing organic wastewater and preparation method thereof.
Technical background
In organic waste water, aromatic hydrocarbons is because having the conjugated system of one or more closed hoop, and height delocalization and bond distance's equalization, although make this compounds be in highly undersaturated state, character is more stable, is difficult to addition and oxidation.Current process mainly comprises biology, physics and chemistry three kinds of methods containing the organic wastewater of aromatic hydrocarbons.Wherein, chemical method removes organic pollution by the oxidability of oxidant, have short, process running time thoroughly, the advantage of strong, the non-secondary pollution of resistance to impact.Ozone is as a kind of oxidant, convenient sources, processing cost are low, technical process is relatively simple, but to a lot of fragrant type organic matter and short chain oxidation operation scarce capacity, therefore increasing research trend is in the efficiency or the speed that how to improve ozone oxidation, and ozone catalytic oxidation catalyst also just arises at the historic moment.Catalytic ozonation mainly contains following mechanism: 1. produce the hydroxyl radical free radical more with high oxidation-reduction potential by catalyst strengthening, organic pollution is obtained degradable; 2. by catalyst and organic pollutants generation complex reaction, organic pollution is made to be easier to oxidized decomposition; 3. make ozone and organic matter enrichment by catalyst, thus accelerate oxidation Decomposition speed.
Conventional ozone catalytic oxidation catalyst has metal oxide (MgO, SnO 2, MnO 2deng), the metal oxide (Cu/Al of load on carrier 2o 3, Ce/AC, Pt/SiO 2deng), active carbon (AC) and natural minerals (zeolite, alumina, needle ironstone ore deposit and volcanic sand etc.).Research shows the aromatic hydrocarbons waste water processing difficult degradation, and the catalytic performance of mixed-metal oxides is better than single metal oxide; The activity of comprehensive catalyst (multiple catalysts is integrated) is better than single-activity charcoal, metal oxide and mineral matter.The metal oxide catalyst of load on carrier, i.e. heterogeneous catalyst, be by metal oxide supported on carrier, common carrier has aluminium oxide, silica, activated carbon, alumina silicate, diatomite, float stone, asbestos, potter's clay, magnesia, atlapulgite etc., it can be powdery, also can be shapingly make granular, metal oxide and carrier have the function of catalyst simultaneously, and the resultant effect thus processing organic wastewater is given prominence to.
Industrial molecular sieve, due to stable performance, has stronger activity, also has suction-operated as carrier simultaneously, has entered the visual field of people.Wherein Y zeolite belongs to silicone zeolite in one, has duct, specific area is 300 ~ 700m 2/ g, adsorptivity is strong, has stronger ion-exchange capacity simultaneously.Y-type zeolite is filled out in the system of ozone treatment waste water by patent CN101585577, and is used alone compared with ozone, effectively can improve the removal of Pyrogentisinic Acid.On this basis, in patent CN101259428 with molecular sieve (Y type and ZSM-5) for carrier by exchange mode, by MnO 2, CeO 2, Ag 2the catalyst that the load of O, CuO isoreactivity component is made over a molecular sieve, when ozone and illumination, to COD 5removal efficiency increase, simultaneously can maintain treatment effect for a long time.With loaded catalyst prepared by ion-exchange, there is high, the constitutionally stable advantage of decentralization, but also to there is catalyst duct size single simultaneously, the shortcoming that oxidation efficiency is limited.
And patent CN1695796A adopts infusion process by nanoscale TiO 2be carried on active carbon and make loaded catalyst, first butyl titanate is dissolved in absolute ethyl alcohol and makes colloidal sol, absorbent charcoal carrier (or active alundum (Al2O3), zeolite, molecular sieve) is dipped in this colloidal sol and vibrates, dry, agingly obtain solid catalyst, the degradation efficiency of this catalyst p-nitrophenyl is 55%.It is high that the catalyst that infusion process obtains has utilization rate, the obvious advantage for the treatment of effect.But because catalyst is in the liquid environment containing complicated organic matter and ozone all the time, metal oxide easily peels off from carrier, and carrier can be taken out of by this process, not only reduce the content of active metal, simultaneously because the scrambling of peeling off also can result in blockage to carrier pore, reduce catalytic effect.
Therefore, the carrying method constantly finding suitable carrier molecule sieve and metal oxide prepares new support type ozone catalytic oxidation catalyst, thus improves treatment of Organic Wastewater effect, is the problem that scientific research personnel is studying always.
Summary of the invention
The present invention take NaY molecular sieve as carrier, adopt ion-exchange and dipping two kinds of methods combining load heterogeneous metal to prepare comprehensive ozone catalytic oxidation catalyst, process organic wastewater has the advantage that utilization rate is high, decentralization is high, treatment effect is obvious, life cycle is long simultaneously.
Support type ozone catalytic oxidation catalyst of the present invention is primarily of carrier NaY molecular sieve, reactive metal oxides manganese oxide and titanium dioxide, shaping of catalyst auxiliary agent composition, be called catalyst host after carrier NaY molecular sieve load manganese oxide, in host, the content of manganese oxide is 10.5wt% ~ 11.5wt%; Shaping of catalyst auxiliary agent is kaolin, binding agent, lubricant and pore creating material, host and kaolinic weight ratio be 1: 0.3 ~ 0.6, be 1: 0.5 ~ 0.9 with the weight ratio of binding agent, be 1: 0.5 ~ 0.85 with the weight ratio of lubricant, be 1: 0.02 ~ 0.04 with the weight ratio of pore creating material, in catalyst, content of titanium dioxide is 1.5wt% ~ 3.0wt%.
The preparation method of support type ozone catalytic oxidation catalyst of the present invention comprises the following steps:
(1) synthesis of molecular sieve host.By the aqueous solution (300g/L) of NaY molecular sieve and the aqueous solution (2mol/L) of manganese sulfate, carry out ion-exchange, molecular sieve: manganese sulfate=1: 0.6 ~ 0.8 (volume ratio), in 400 ~ 600 DEG C of roasting 2 ~ 4h after exchange.If need to carry out second time to exchange.After ion-exchange completes, in molecular sieve host, the content of manganese oxide is 10.5wt% ~ 11.5wt%.
(2) molecular sieve molded.Molecular sieve host is mixed with kaolin, binding agent, lubricant, pore creating material and makes the bead that diameter is 3 ~ 5mm.Bead is roasting 1 ~ 2h at 400 ~ 600 DEG C.Molecular sieve host and kaolinic weight ratio are 1: 0.3 ~ 1: 0.6, are 1: 0.50 ~ 1: 0.85 with lubricant weight, are 1: 0.5 ~ 1: 0.9 with weight of binder ratio, are 1: 0.02 ~ 1: 0.04 with the weight ratio of pore creating material.
(3) flood.The bead made is immersed in 8 ~ 12h in TiO 2 sol maceration extract, in this TiO 2 sol maceration extract, content of titanium dioxide is 7wt% ~ 8wt%, drop dries 1.5 ~ 2h in 40 ~ 80 DEG C after going out to flood drop, 1 ~ 2h is dried at 400 DEG C ~ 600 DEG C, if needed, dipping process can carry out second time, finally obtained catalyst of the present invention.
Prepared by TiO 2 sol maceration extract either method of the prior art.As, butyl titanate and ethanol, diethanol amine are mixed by 1: 40: 025 (volume ratio), abundant stirring 5min, red fuming nitric acid (RFNA) (butyl titanate: red fuming nitric acid (RFNA)=1: 0125) (volume ratio) is dripped in whipping process, then mixed liquid is slowly added (butyl titanate: water=1: 10) (volume ratio) in deionized water, after stirring 30min, the at room temperature capping of this solution leaves standstill 2h and obtains translucent pale colloidal sol, namely obtains TiO 2 sol maceration extract.
NaY molecular sieve of the present invention is crystallization afterproduct in hydrothermal synthesis method production process, and kaolin is the crystalline aluminosilicate salt mineral of needle-like (tubulose) or sheet, has macroporous structure and has certain activity.Need to dry the particle (solid content is 84.95%) grinding to form particle diameter < 380 μm before NaY molecular sieve and kaolin test.Relative crystallinity>=82% of this molecular sieve, silica alumina ratio (SiO 2/ Al 2o 3)>=4.8, sodium oxide molybdena (Na 2o) content is 8.0 ~ 13.0wt%.Al2O3 >=36wt%, Fe2O3≤1.0wt%, Na2O+K2O≤wt0.76%, SiO2≤49wt% in kaolin.
Binding agent of the present invention is Alumina gel, and its effect is exactly that bi-material is passed through different interfaces, is bonded together by chemical force, physical force or two kinds of power had concurrently;
Lubricant of the present invention is glycerine and boehmite, and its effect reduces the frictional force between polymer and equipment, and the interior friction between polymer molecular chain;
Pore creating material of the present invention is powdered carbon and/or polyethylene glycol, and its effect is the mesoporous material synthesizing larger aperture (12nm).
Catalysts and its preparation method of the present invention, carries out catalytic ozonation test in the reactor by test water and evaluates.Establish absorbing column and oxide pillars two lucite posts as reactor in test, be provided with aeration head bottom absorbing column, through aeration head dispersion in the reactor, test water injects ozone gas bottom absorbing column, after having mixed ozone, enter oxide pillars bottom from top, absorption tower.Oxide pillars built with catalyst, the test water having mixed ozone in oxide pillars, by the assistance of ozone catalytic oxidation catalyst, by ozone oxidation.According to the COD (COD before and after the reaction of test water cr) and biochemical oxygen demand (BOD) BOD 5carry out characterization process effect.
The first test water A is the phenol solution (preparation water) of concentration 1000mg/L, its COD crfor 2047mg/L, BOD 5for 936mg/L; The second test water B is the nitrobenzene waste water that Lanzhou Petrochemical chemical fertilizer factory Aniline Unit is discharged, wherein containing many kinds of substances such as nitrobenzene, p-nitrophenyl, nitrophenols, and its COD crbe 532 ~ 598mg/L, BOD 5be 7.0 ~ 9.4mg/L.Test water amount is 1.5L, and the processing time is 30min ~ 40min, and ozone amount of filling is 7.8mg/L.The COD of test water A after process cr446 ~ 723mg/L can be down to, BOD 5reduce to 222 ~ 395mg/L; The COD of test water B cr201 ~ 261mg/L can be down to, BOD 5be upgraded to 99 ~ 115mg/L.
The invention has the advantages that: the catalyst that 1. based on NaY molecular sieve prepared by carrier, the activation of the activity of catalyst, adsorptivity, ion can be combined, the adsorption in co-treating wastewater.2. by exchanging and flooding two kinds of modes by active metal load in NaY molecular sieve.Exchange in the process of roasting and introduce manganese salt and be translated into manganese oxide, make molecular sieve have the activity of stable structure and catalytic oxidation; Dipping can make ozone catalytic oxidation catalyst surface and inside all be covered with titanium dioxide film, makes the organic matter in water can be alternately oxidized under the effect of two kinds of active matters, can the playing a role of high-efficient and lasting.3. the binding agent, lubricant and the pore creating material that add in shaping of catalyst process, at the passage that the capable one-tenth of catalytic inner is larger, and it is clear between the aperture duct of catalyst itself, molecular sieve and silicon, aluminium, catalyst is made to have the structure in different size duct, and larger specific area, the organic matter be conducive in waste water fully contacts with catalyst activity metal oxide, ozone, improves degree of oxidation and the oxidation scope of oxidation of organic compounds.
Detailed description of the invention
The NaY molecular sieve adopted in embodiment, kaolin, Alumina gel and boehmite all from Catalyst Factory of Lanzhou Petrochemical Company, wherein relative crystallinity>=82%, the silica alumina ratio (SiO of molecular sieve 2/ Al 2o 3)>=4.8, Na 2o8.0 ~ 13.0wt%; Kaolinic Al 2o 3>=36wt%, Fe 2o 3≤ 1.0wt%, Na 2o+K 2o≤0.76wt%, SiO 2≤ 49wt%; Alumina gel Al content 11.5 ~ 13.0wt%, Cl content 8.0 ~ 10.5wt%; The Fe of boehmite 2o 3≤ 0.03wt%, Na 2o≤0.3wt%, colloidal sol index≤95%.
Manganese sulfate, polyethylene glycol, carbon dust, glycerine, butyl titanate, ethanol, diethanol amine and red fuming nitric acid (RFNA) are AR level laboratory medicament.
Embodiment 1 ~ 5
1. get NaY molecular sieve 150g, make the aqueous solution of 300g/L, slowly drip manganese sulfate solution (2mol/L), molecular sieve: manganese sulfate=1: 0.6 ~ 0.8 (volume ratio), at 80 DEG C, stir 20 ~ 30min.Filter after exchanging, then roasting 4h at 400 DEG C, the molecular sieve after roasting carries out secondary exchange again, now molecular sieve: manganese sulfate=1: 0.6 ~ 0.8 (volume ratio), in 600 DEG C of roasting 4h after the product that secondary exchanges filters, obtains molecular sieve host.
Table 1: the molecular sieve of embodiment 1 ~ 5 correspondence and the aqueous solution ratio (volume ratio) of manganese sulfate
2. 40ml butyl titanate is got, 160ml ethanol, 10ml diethanol amine mixes, abundant stirring 5min, drip 0.5ml red fuming nitric acid (RFNA) in whipping process, then mixed liquid is slowly added in 400ml deionized water, after stirring 30min, the at room temperature capping of this solution leaves standstill 2h and obtains translucent pale colloidal sol, namely obtains TiO 2 sol maceration extract.
3. with the proportioning of table 2, molecular sieve host and each raw material are mixed and makes catalyst pellet.
Table 2: the component of embodiment 1 ~ 5 correspondence and proportioning (weight ratio) thereof
4. catalyst pellet is immersed in the maceration extract of titanium dioxide, mixing, soak 10hr, drain the liquid object on surface after taking-up, dry 1hr at 60 DEG C, dry 1hr at 400 DEG C, in maceration extract, soak 8hr again after being cooled to room temperature after taking-up, to drain after surperficial liquid object dry 1hr at 60 DEG C, at 400 DEG C of dry 2hr, cooling obtains ozone catalytic oxidation catalyst, and in catalyst, active metallic content is in table 3.
Table 3: active metallic content (wt%) in embodiment 1 ~ 5 catalyst
Evaluating catalyst result
Embodiment 1 ~ 5 catalyst preceding method carries out effect assessment test, and the result of the test obtained is in table 4.
Table 4: the evaluation test result (mg/L) that embodiment 1 ~ 5 catalyst is corresponding
Corresponding COD can be obtained as calculated crclearance and B/C, in table 5.
Wherein: COD crclearance=(COD former water-COD example 1 ~ 5)/COD former water, B/C value=BOD 5/ COD cr.
Table 5: the COD of implementation result crclearance and the change of B/C value

Claims (5)

1. an ozone catalytic oxidation catalyst, it is characterized in that primarily of carrier NaY molecular sieve, reactive metal oxides manganese oxide and titanium dioxide, shaping of catalyst auxiliary agent composition, be called catalyst host after carrier NaY molecular sieve load manganese oxide, in host, the content of manganese oxide is 10.5wt% ~ 11.5wt%; Shaping of catalyst auxiliary agent is kaolin, binding agent, lubricant and pore creating material, host and kaolinic weight ratio are 1: 0.3 ~ 0.6, be 1: 0.5 ~ 0.9 with the weight ratio of binding agent, be 1: 0.5 ~ 0.85 with the weight ratio of lubricant, be 1: 0.02 ~ 0.04 with the weight ratio of pore creating material, in catalyst, content of titanium dioxide is 1.5wt% ~ 3.0wt%, and wherein manganese oxide is carried on NaY molecular sieve by ion-exchange, and titanium dioxide is carried on NaY molecular sieve by impregnation method; Shaping of catalyst is the bead of 3 ~ 5mm; In ion-exchange, the aqueous solution of NaY molecular sieve is 1: 0.6 ~ 0.8 (volume ratio) with the amount of aqueous solution used ratio of manganese sulfate, 400 ~ 600 DEG C of roasting 2 ~ 4h after exchanging, in shaping of catalyst, catalyst host and shaping assistant are mixed into bead, and bead is roasting 1 ~ 2h at 400 ~ 600 DEG C; In dipping, bead is immersed in 8 ~ 12h in TiO 2 sol maceration extract, and drop dries 1.5 ~ 2h in 40 ~ 80 DEG C after going out to flood drop, at 400 DEG C ~ 600 DEG C, dry 1 ~ 2h.
2. ozone catalytic oxidation catalyst according to claim 1, is characterized in that described binding agent is Alumina gel.
3. ozone catalytic oxidation catalyst according to claim 1, is characterized in that described lubricant is glycerine and boehmite.
4. ozone catalytic oxidation catalyst according to claim 1, is characterized in that described pore creating material is powdered carbon, polyethylene glycol, and the two can be used alone also can be with the use of.
5. ozone catalytic oxidation catalyst according to claim 1, is characterized in that described NaY molecular sieve is crystallization afterproduct in hydrothermal synthesis method production process.
CN201210028551.XA 2012-02-09 2012-02-09 Supported catalytic ozonation catalyst and its preparation method Active CN103240115B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210028551.XA CN103240115B (en) 2012-02-09 2012-02-09 Supported catalytic ozonation catalyst and its preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210028551.XA CN103240115B (en) 2012-02-09 2012-02-09 Supported catalytic ozonation catalyst and its preparation method

Publications (2)

Publication Number Publication Date
CN103240115A CN103240115A (en) 2013-08-14
CN103240115B true CN103240115B (en) 2015-01-21

Family

ID=48920195

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210028551.XA Active CN103240115B (en) 2012-02-09 2012-02-09 Supported catalytic ozonation catalyst and its preparation method

Country Status (1)

Country Link
CN (1) CN103240115B (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103787488B (en) * 2014-02-10 2015-10-28 同济大学 A kind of method utilizing pyrite cinder O3 catalytic oxidation process waste water
CN103894202B (en) * 2014-04-11 2015-10-28 中国石油天然气集团公司 A kind of oil-polluted water ozone catalytic oxidation catalyst and manufacture method thereof
CN104014346B (en) * 2014-05-16 2015-12-09 程帆 A kind of heterogeneous metal catalyst and preparation method and application strengthening ozone oxidation
CN103990490B (en) * 2014-05-16 2016-05-25 上海纳米技术及应用国家工程研究中心有限公司 Be used for monoblock type ozone catalytic agent of dyeing waste water and preparation method thereof
CN104891713B (en) * 2015-06-23 2017-03-22 中节能大地（杭州）环境修复有限公司 Catalytic ozonation process for treatment of organic wastewater
CN105056948B (en) * 2015-08-07 2018-04-20 河北亚太环境科技发展股份有限公司 It is a kind of using porous substrate as ozone-eliminating catalyst of carrier and preparation method thereof
CN106540686B (en) * 2016-10-28 2019-04-16 上海纳米技术及应用国家工程研究中心有限公司 Activated carbon supported manganese dioxide-titanium dioxide ozone catalyst and preparation method for advanced treating
CN106622226B (en) * 2016-12-02 2019-03-05 东南大学 A kind of support type platinum based catalyst and preparation method thereof
CN107824196B (en) * 2017-11-08 2019-11-19 中国石油大学(北京) A kind of organic wastewater ozone oxidation catalyst and its preparation and application
CN108744964A (en) * 2018-07-12 2018-11-06 苏州佰德利环保科技有限公司 A kind of organic waste gas treatment device
CN109621975B (en) * 2019-01-17 2020-06-12 中国石油大学(北京) Supported ozone catalytic oxidation catalyst and preparation method and application thereof
CN111250145A (en) * 2019-12-16 2020-06-09 嘉兴市众盛环保科技有限公司 TiO 22OMS ozone oxidation catalyst, preparation method and application thereof
CN113101942A (en) * 2021-03-11 2021-07-13 江西省东茂环保材料有限公司 Molecular sieve composite catalytic material for catalytic oxidation of ozone and preparation method thereof
CN115041221B (en) * 2022-06-30 2023-03-24 扬州晨化新材料股份有限公司 NaY-containing molecular sieve composition of tertiary amine catalyst for continuously synthesizing polyurethane and preparation method thereof
CN115090319B (en) * 2022-08-09 2023-12-05 山东默同生态有限公司 Ozone catalyst and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1695796A (en) * 2005-03-11 2005-11-16 哈尔滨工业大学 Preparation for catalyst of Nano titanium dioxide, and method for treating ozonized water of catalysis
CN101259428A (en) * 2008-04-24 2008-09-10 福州大学 Preparation of catalyst for processing industrial wastewater and using method thereof
CN101837300A (en) * 2010-05-12 2010-09-22 上海交通大学 Photocatalysis coupled catalyst based on ozone and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6585863B2 (en) * 2000-08-08 2003-07-01 Procter & Gamble Company Photocatalytic degradation of organic compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1695796A (en) * 2005-03-11 2005-11-16 哈尔滨工业大学 Preparation for catalyst of Nano titanium dioxide, and method for treating ozonized water of catalysis
CN101259428A (en) * 2008-04-24 2008-09-10 福州大学 Preparation of catalyst for processing industrial wastewater and using method thereof
CN101837300A (en) * 2010-05-12 2010-09-22 上海交通大学 Photocatalysis coupled catalyst based on ozone and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱洪法等.催化剂成型.《催化剂制备及应用技术》.中国石化出版社,2011,(第1版), *

Also Published As

Publication number Publication date
CN103240115A (en) 2013-08-14

Similar Documents

Publication Publication Date Title
CN103240115B (en) Supported catalytic ozonation catalyst and its preparation method
CN101496994B (en) Method for preparing molecular self-assembly porous vermiculite air purification material
EP4032610A1 (en) Molecular sieve complex, composite material and application thereof
CN105413629A (en) Alga-calcium-mineral air purification medium and preparation method and application thereof
CN107398269A (en) High-efficiency multi-stage hole nanocatalyst applied to catalytic removal volatile organic matter and preparation method thereof
CN102233259A (en) Adsorbent for removing heavy metal from water and preparation method of adsorbent
CN101785988A (en) Polynary metal oxide arsenic adsorbent material and preparation method and application thereof
CN102600790A (en) Nanometer cerium oxide hydrate-based arsenic removing material, preparation method thereof and application in arsenic removing
CN102258990A (en) Method for preparing light sewage treatment material
CN102114403A (en) Compound arsenic-removing adsorbent and preparation method thereof
CN113248533B (en) Preparation method of porous ionic liquid extractant and extraction desulfurization application thereof
Wang et al. Synthesis of CMK/LDH and CMK/CLDH for sulfamethoxazole degradation by PS activation: a comparative study of characterization and operating parameter, mechanism pathway
CN101491757B (en) Synthetic method of TiO2 composite photocatalyst with high selective degradation
CN1714936A (en) Nano grade transition metal oxidation catalyst and its preparing method and use
CN105080529A (en) Normal temperature catalytic material for efficiently removing VOCs
CN101352677B (en) Sepiolite supported nano zinc oxide photocatalysis material and preparation method thereof
CN104478462A (en) Catalytic-materail-coated microcrystal bamboo-charcoal pottery bead and preparation method thereof
CN101327453B (en) Aluminum-silicon-titanium composite oxide carrier and load type catalytic hydro-dearomatization catalyst
CN101104141A (en) Technique method for preparing active carbon-oxide composite absorbing material and polysilicate-aluminium from coal gangue
CN103386312B (en) Method for preparing spherical shell type catalyst for catalytic combustion of VOCs (volatile organic compounds)
CN104941573A (en) Manganite-loaded adsorbent and preparation method thereof as well as application of manganite-loaded adsorbent in treating chemical nickel plating waste liquid
CN101830537A (en) Method for degrading organic components in ore-dressing wastewater of sulphide ores by catalysis under visible light
CN104689792B (en) Mercury ion adsorbent and preparation method thereof in a kind of mercury-containing waste water
CN109718726B (en) Production process of amphiphilic silica-chitosan composite aerogel
CN107473326B (en) Acidic TiO2Combined method for degrading dye wastewater by hydrosol regeneration aerobic granular sludge

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