CN103157517A - TiZrO2 carrier and precious metal/TIZrO2 catalyst and preparation and application thereof - Google Patents
TiZrO2 carrier and precious metal/TIZrO2 catalyst and preparation and application thereof Download PDFInfo
- Publication number
- CN103157517A CN103157517A CN2011104271598A CN201110427159A CN103157517A CN 103157517 A CN103157517 A CN 103157517A CN 2011104271598 A CN2011104271598 A CN 2011104271598A CN 201110427159 A CN201110427159 A CN 201110427159A CN 103157517 A CN103157517 A CN 103157517A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- tizro2
- reaction
- titanium zirconium
- 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.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a TiZrO2 carrier and a precious metal/TIZrO2 catalyst and preparation and application of the TiZrO2 carrier and the precious metal/TIZrO2 catalyst, and belongs to the field of water processing technology and environment function materials. The ZrO2 is stable in chemical property, and not only is not soluble in alkaline solution, but also can exist in acid solution stably. However, the specific surface area of the ZrO2 is small, and generally is only about 20m2/g to 50m2/g, and due to the fact that when the ZrO2 is calcined, the ZrO2 can generate martensite transformation, the fact that molded products have no intensity is caused. The precious metal/TIZrO2 catalyst is a catalytic wet air oxidation catalyst which is corrosion resisting, high-temperature resisting, high in strength, and big in specific surface area, and uses zirconium oxide stabilized by titanium oxide as a carrier to support precious metal Ru and Pt with high activity and difficult to run off, and prepares the excellent catalytic wet air oxidation catalyst. The prepared catalyst maintains good form after the prepared catalyst runs for 242 h under a high-temperature high-pressure acid environment with the temperature of 260 DEG C, the pressure of 5.7 MPa and the potential of hydrogen (PH) value of about 3, and the performance is beneficial to the popularization of a zirconium oxide supported catalyst in the industrialized application of catalytic wet air oxidation.
Description
Technical field
The present invention relates to take the titanium zirconium mixed oxide as carrier, loaded catalyst take noble metal Ru, Pd, Pt as active component and preparation method thereof, can be used for CWO and process high concentration, indegradable industrial effluent, belong to water technology and environment functional material field.
Background technology
Wet oxidation process (Wet Air Oxidation, be called for short WAO) is that a kind of important degraded that grows up from the 1950's is poisonous, harmful, the effective treating method of high concentrated organic wastewater.It is (under 0.5～20MPa) condition, take airborne oxygen as oxidant, in liquid phase, organic pollution to be oxidized to CO at high temperature (150～350 ℃) and high pressure
2And H
2The chemical process of the inorganic matters such as O or small organic molecule; There is no NO in this process
X, SO
2Discharge with the pernicious gas such as HCl.WAO technique is proposed in 1958 by the F.J.Zimmermann of the U.S. at first, and has obtained multinomial patent, therefore also claim the Annemarie Zimmermann method.This method has applied to process papermaking black liquor wastewater first since coming out, now worldwide be used widely, and existing more than 200 cover commercial plants move more than 160 countries and regions up to now.
Traditional Wet Oxidation Process needs higher temperature and pressure and the relatively long time of staying, especially is difficult to oxidized organic compound for some, and reaction condition requires more harsh.Therefore, since 20 century 70s, people are on traditional wet oxidation basis, development has played CWO technology (Catalytic Wet Air Oxidation is called for short CWAO), namely adds catalyst in system, to reduce the temperature and pressure of reaction, improve reaction efficiency.Catalytic wet air oxidation due to have the reaction condition gentleness, treatment effeciency is high, reaction speed is fast, little, applied widely, the recyclable resource of device and the advantage such as secondary pollution is low, is one of extremely promising technology of processing high concentration, organic wastewater with difficult degradation thereby.
The CWO reaction can be divided into Characteristic of Homogenous Catalytic Wet Air Oxidation reaction and heterogeneous catalysis wet oxidation reaction by reaction formation.The research work of CWO reaction concentrates in the Characteristic of Homogenous Catalytic Wet Air Oxidation reaction at first, this is mainly because the reaction mechanism of Characteristic of Homogenous Catalytic Wet Air Oxidation is clear, be suitable for research and grasp, such as can be by the selection of part, the modulation of reaction dissolvent and the selection of auxiliary agent etc., change catalyst system, improve treatment effect.Therefore relevant Characteristic of Homogenous Catalytic Wet Air Oxidation patent flow process just occurs at 20 century 70s, and obtained practical application in industry.But in the Characteristic of Homogenous Catalytic Wet Air Oxidation course of reaction, catalyst is miscible in handled waste water; The economic loss that causes and the secondary pollution angle that causes are considered from avoiding catalyst stream to become homeless, need to carry out the neutralisation treatment of postorder to reclaim catalyst, so just cause the problem that technological process is complicated, cost for wastewater treatment improves, also be difficult to avoid fully simultaneously secondary pollution.Therefore from 20 century 70 later stages, the research emphasis of CWO reaction has been transferred on the heterogeneous catalysis wet oxidation reaction, especially in recent years the article of delivering and the patent of applying for, be mainly for heterogeneous catalysis wet oxidation reaction system, and be seldom about the Characteristic of Homogenous Catalytic Wet Air Oxidation reaction system.This is mainly due in heterogeneous catalysis wet oxidation reaction process, and separating of catalyst and waste water is very easy, flow process is simple, and also to have catalytic activity high for the heterogeneous catalysis wet oxidizing catalyst in addition, the advantages such as good stability.
Have the ability of stronger absorption and activation oxygen due to transition metal oxide, mostly be greatly transition metal oxide so be applied to the catalyst of heterogeneous catalysis wet oxidation reaction.This type of catalyst can be divided into noble metal catalyst and the large class of non-precious metal catalyst two.Wherein the active component of noble metal catalyst has Ru, Pt, Pd, Rh and Ir etc., because it has the advantages such as catalytic activity is high, difficult loss, life-span length than non-precious metal catalyst, has actual application prospect, therefore in the CWO catalyst research, most of work concentrates on the noble metal catalyst system, is especially mainly about noble metal catalyst in the patent of twentieth century the 80s and 90s delivering and applying for.
In waste water, organic catalytic activity will be worse than other noble metals although noble metal Ru processes, but after the CWO reaction treatment, the biodegradability of waste water increases substantially, qualified discharge after waste water can further be processed by follow-up biochemical process fully.The price that further contemplates noble metal Ru wants cheap a lot of than other platinum group noble metals, and in its processing waste water, catalytic activity of ammonia nitrogen is also the highest in noble metal, and the research that therefore relevant Ru catalyst is used in the CWO reaction is more.Recognize just the prospect of catalyst aspect industrial applications take Ru as active component, so this some work is paid attention to the research that catalyst carrier is selected especially.This is mainly because the industrial condition of CWO reaction is harsh, catalyst wants long period of soaking in the waste water of high temperature, high pressure, and because the intermediate product of CWO reaction is little carboxylic acids, its stronger acidity is also that many common catalyst carriers can not be born.
Studies show that 6 kinds of ZrO commonly used
2Preparation method's (calcination, the precipitation method, azeotropic distillation method, Hydrolyze method, sol-gel process and reverse microemulsion method), under the identical condition of colloid processing mode, prepared ZrO
2Carrier specific area difference is little, is 60m
2The g left and right.The bigger serface zirconia of reporting in document is not all single zirconia, people (the Chuah such as Chuah G.K., G is investigation into the preparation of high surface areazirconia.Catalysis Today.49,131-139 K.1999.An) the high temperature ageing method be that Si is incorporated into ZrO in essence
2In carrier, thereby prepare the ZrO of bigger serface
2People (the LarsenG such as Larsen G.; Lotero E; Nabity is synthesis ofmesoporous zirconia powders with high surface areas.Journal ofcatalysis.164.246-248. M.1996.Surfactant-assisted) use the bigger serface ZrO of template agent method preparation
2Key is sulfate or phosphatic adding, thereby has adulterated S or P.Therefore, if only utilize single zirconia, no matter use what preparation method, the product specific area only has 60m
2/ g left and right wants to make high-specific surface area ZrO
2, some other elements that must adulterate are as cation Na, Mg, Ca, Y, La, Ti, Ce or anion sulfate acid root, phosphate radical etc.
ZrO
2Having three kinds of monoclinic phases, Tetragonal, Emission in Cubic is mutually; Monoclinic phase ZrO
2Anisotropic expansion can occur in temperature influence, easily causes the carrier cracking; And Tetragonal ZrO
2Linear expansion coefficient is not undergone mutation with the temperature relation that is in line that raises, and has toughening effect.Pure ZrO
2Can follow the change in volume of 3%-5% when occuring Tetragonal to the martensite phase transformation of monoclinic phase in the calcining cooling procedure, this bulk effect can cause that material ftractures, and makes ZrO
2Carrier is restricted on the CWAO commercial Application.Pure ZrO under normal temperature
2Can only be monoclinic phase, if want to generate stable Tetragonal ZrO
2, can be to ZrO
2Carry out doping vario-property, at ZrO
2Middle interpolation radius and Zr
4+Close cation can generate the Tetragonal ZrO of stable existence at normal temperatures
2Thereby, increase ZrO
2Fracture toughness and heat endurance.Therefore draw a conclusion: pure ZrO
2The carrier that is fit to industrial applications can not be prepared, stabilizing agent (Y must be added
2O
3, CaO, MgO, Al
2O
3, CeO
2, TiO
2) just can produce high-intensity ZrO
2Carrier.
In sum, no matter be in order to increase ZrO
2The carrier specific area still improves ZrO
2Support strength, doping vario-property are all reasonable methods.Consider catalyst carrier in CWO reaction must be under acidity and alkali condition stable existence, therefore select TiO
2Prepare TiO as stabilizing agent
2-ZrO
2The binary complex carrier.TiO
2-ZrO
2Complex carrier synthetic method commonly used has coprecipitation, sluggish precipitation and sol-gel process.Wherein the sluggish precipitation manufacturing cycle is long, and needs heating; The sol-gel process raw material is expensive, and preparation process is complicated, is difficult to realize large-scale production; And the coprecipitation raw material is cheap, and is simple to operate, and technology maturation, so coprecipitation is adopted in this research.Adopt the titanium zirconium complex carrier specific area of coprecipitation preparation can reach 200m
2/ g, the pure TiO that mentions in the patent
2(CN92109904) and ZrO
2(CN200880112916).
Generally speaking, be applied in the various noble metal catalysts of CWO reaction, noble metal catalyst take Ru as active component not only has larger cost advantage, and its catalytic activity during the ammonia nitrogen pollutant in processing waste water is the highest, so such catalyst is paid close attention to widely.In this type of loaded catalyst, with TiO
2-ZrO
2Being the catalyst of carrier, because it all has good stability under the acidity of heat and basic reaction conditions, is only catalyst with actual application prospect at present.
Summary of the invention
The objective of the invention is to propose a kind ofly to react for CWO, Catalysts and its preparation method with high activity and stability of processing persistent organic pollutants, to reduce the operating condition of wet oxidation reaction, and improve organic oxidation rate, thereby promote the extensive use of CWO technology.
The present invention also provides the preparation method of above-mentioned catalyst, comprises the following steps:
TiZrO
2The carrier preparation process is: (1) is with the ZrOCl of ax mol
28H
2Ti (the SO of O and a (1-x) mol
4)
2Be dissolved in the deionized water of 1～2.5L, a=0.2～0.8, x=0.1～0.9, the nitric acid precaution of hydrolysis that adds b mol, b/a=0.1～2, and add the hydrogen peroxide of c mol so that the titanium zirconium salt solution precipitates homogenization, and c/a=0.1～10, strong agitation 20～40min is mixed with titanium zirconium complex salt solution; (2) to being heated in the titanium zirconium complex salt solution of 60-80 ℃, dropwise add with the speed of 10～20ml/min in 12.5～25wt.% ammoniacal liquor of 1～2.5L (positive addition), perhaps titanium zirconium complex salt solution dropwise joins with the speed of 15ml/min in 12.5～25wt.% ammoniacal liquor of 1～2.5L (anti-addition), generates white jelly; (3) the aging 12～48h of colloid normal temperature, vacuum filtration and washing, gained filter cake and shaping assistant carry out extrusion after abundant kneading, shaping assistant is: one or two or more kinds in polyanion cellulose PAC, hydroxyethylcellulose HEC, xanthans or metatitanic acid, and in extrusion, the shaping assistant use amount is 0～2wt.%; (4) extrudate carries out a step or two dry 2～24h of step at 25～120 ℃, then carries out a step or two steps calcining, 2～8h makes titanium zirconium complex carrier at 500～800 ℃.
Noble metal/TiZrO
2The preparation method of catalyst is: titanium zirconium complex carrier normal pressure incipient impregnation or vacuum incipient impregnation RuCl
3, PdCl
2Or H
2PtCl
6Solution, activity component load quantity are 0.5-3wt.%, and 300～500 ℃ of calcining 2～8h prepare required catalyst.
Noble metal/TiZrO
2Catalyst is for the treatment of high concentration hard-degraded organic waste water (COD＞20000mg/L, BOD/COD＜0.3);
The intermittent reaction condition is: reaction temperature: 220-280 ℃, and oxygen partial pressure: 1.0-4.0MPa, mixing speed: 400-800r/min;
The successive reaction condition is: reaction temperature: 220-280 ℃, and reaction pressure: 4.0-8.0MPa, air speed: 0.5-4.0 h
-1
The present invention adopts ZrOCl
28H
2O and Ti (SO
4)
2Raw material, utilize the titanium oxide stabilizing zirconia to prepare the catalyst carrier of corrosion-resistant, high temperature resistant, high strength, bigger serface, use difficult noble metal Ru, the Pd that runs off of high activity, Pt as active component, prepare for degrading high concentration organic wastewater, have the wet oxidizing catalyst of high activity, high stability.
CWO catalyst of the present invention has the following advantages:
1. catalyst has very high activity for high concentration, organic wastewater with difficult degradation thereby;
2. catalyst has good stability in catalysis wet-type oxidation degradation organic matter process;
3. catalyst has larger specific area, and noble metal has good dispersiveness thereon;
4. the production cost of catalyst is lower.
Description of drawings
The Weibull distribution figure of Fig. 1 Ru/xTiZr catalyst crushing strength.
Fig. 2 Ru/0.5TiZr catalyst successive reaction life assessment figure.
The specific embodiment
Adopt CJF-0.5 type permanent magnetism rotating batch-type autoclave and the bubbling bed continuous reaction apparatus that Dalian sensible reactor factory produces to carry out the CWAO experiment.Adopt the concentration of the P1201 type high performance liquid chromatograph analytical model compound of Dalian Yilite Analytical Instrument Co., Ltd's production.Adopt the GB11914-89 potassium dichromate method to measure waste water COD.The TOC-VCPH/CPN analysis-e/or determining waste water TOC that employing Shimadzu company produces.Adopt thunder magnetic PHS-3C Accurate pH instrumentation to decide water sample pH.The BODTrakTM Instrumental Analysis water sample BOD that employing Hash company produces
5Adopt the ZQJ-II Intelligent testing machine for particle that large connection intelligent testing machine factory makes to measure catalyst strength.
The experimental technique scheme is:
TiZr carrier preparation → acetic acid corrosion experiment → dipping active component Ru → intermittent reaction → successive reaction.
Acetic acid corrosion experiment: add 200ml 1wt.% acetic acid solution in autoclave, put into the 2g carrier, close autoclave, be filled with 1.5MPa oxygen, at 260 ℃ of corrosion 3h.
Intermittent reaction: add 200ml waste water in autoclave, put into the 0.5g catalyst fines, close autoclave, be filled with the oxygen corresponding with waste water COD, react 1-3h under 250-280 ℃, mixing speed is 600r/min.
Successive reaction: add the 10ml catalyst in reaction tube, water sample air speed SV is 2h
-1, gas adopts pressure-air, and flow is 1.2 times of theoretical amount, and temperature adopts 250-270 ℃.
Select and then to carry out intermittent reaction and to estimate its activity by the carrier loaded active component Ru of corrosion experiment, select high activated catalyst to carry out successive reaction to estimate its life-span.
CWO Ru/TiZr catalyst of the present invention can be processed organic wastewater with difficult degradation thereby, has reduced the operating condition of wet oxidation reaction, and has improved organic oxidation rate, thereby promoted the extensive use of CWO technology.
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing.
Embodiment 1:
1. dissolve the zirconium oxychloride of titanium sulfate and 0.2 (1-x) mol of 0.2xmol in the 2.5L ultra-pure water, add the nitric acid precaution of hydrolysis of 5ml, strong agitation 20min is mixed with titanium zirconium complex salt solution.X=0.1-0.5 wherein.
2. titanium zirconium complex salt solution dropwise joins in 1L 12.5% ammoniacal liquor with the speed of 15ml/min, generates white jelly.
3. the aging 12h of colloid normal temperature, vacuum filtration and washing, the gained filter cake carries out extrusion after abundant kneading.
4. after the extrudate room temperature is dried, at 120 ℃ of dry 2h, a 500-900 ℃ of step or two goes on foot calcining 2-6h (seeing table 1 for details).
5. vacuum incipient impregnation RuCl
3Solution, 350 ℃ of calcining 6h.
As can be seen from Figure 1, Ru/xTiZr catalyst strength data statistic analysis shows that it all obeys Weibull distribution, and failure probability reduces along with the rising of titanium oxide content.Its moulding and acetic acid Corrosion results see Table 1.
Embodiment 2:
1. dissolve the zirconium oxychloride of the titanium sulfate of 0.1mol and 0.1mol in the 2.5L ultra-pure water, add the nitric acid precaution of hydrolysis of 5ml, add the 200ml hydrogen peroxide so that the homogenization of titanium zirconium salt solution precipitation, strong agitation 20min is mixed with titanium zirconium complex salt solution.
2. titanium zirconium complex salt solution dropwise joins in 1L 25% ammoniacal liquor with the speed of 15ml/min, generates white jelly.
3. the aging 12h of colloid normal temperature, vacuum filtration and washing, the gained filter cake carries out extrusion after abundant kneading.
4. after the extrudate room temperature is dried, at 120 ℃ of dry 2h, a 500-900 ℃ of step or two goes on foot calcining 2-6h.
5. vacuum incipient impregnation RuCl
3Solution, 350 ℃ of calcining 6h.Its moulding and acetic acid Corrosion results see Table 1.
Embodiment 3:
1. dissolve the zirconium oxychloride of the titanium sulfate of 0.1mol and 0.1mol in the 2.5L ultra-pure water, add the nitric acid precaution of hydrolysis of 5ml, strong agitation 20min is mixed with titanium zirconium complex salt solution.
2. titanium zirconium complex salt solution dropwise joins in 1L 25% ammoniacal liquor with the speed of 15ml/min, generates white jelly.
3. the aging 12h of colloid normal temperature, vacuum filtration and washing, gained filter cake and 2% metatitanic acid carry out extrusion after abundant kneading.
4. after the extrudate room temperature is dried, at 120 ℃ of dry 2h, a 500-900 ℃ of step or two goes on foot calcining 2-6h.
5. vacuum incipient impregnation RuCl
3Solution, 350 ℃ of calcining 6h.Its moulding and acetic acid Corrosion results see Table 1.As can be seen from Table 1, two step calcinings are better than one-step calcination, and carrier wants by acid corrosion, and its calcining heat must be greater than 600 ℃.
Form after the calcining of table 1 TiZr presoma and acid corrosion
Symbol description:
After the calcining of TiZr presoma: A: moulding is good, B: thread, and C: Powdered.After TiZr carrier acid corrosion experiment: the 0-efflorescence, the 1-shape does not change.MA: add metatitanic acid as shaping assistant.
Embodiment 4:
1. the zirconium oxychloride with 0.2mol is dissolved in the 2.5L ultra-pure water, and strong agitation 20min is mixed with salting liquid.
2. salting liquid dropwise joins in 1L 25% ammoniacal liquor with the speed of 15ml/min, generates white jelly.
3. the aging 12h of colloid normal temperature, vacuum filtration and washing after gained filter cake and shaping assistant kneading, are carried out extrusion with φ 4 moulds.
4. at 120 ℃ of dry 2h, carry out strength test after the extrudate room temperature is dried.Shaping assistant uses and the results are shown in Table 2.As can be seen from Table 2, when promoter addition was 1%, the HEC effect was best.Less than 0.25% the time, presoma does not have intensity substantially when auxiliary agent HEC consumption.
The impact of table 2 shaping assistant on TiZr presoma intensity
Embodiment 5:
1. dissolve the zirconium oxychloride of the titanium sulfate of 0.1mol and 0.1mol in the 2.5L ultra-pure water, add the nitric acid precaution of hydrolysis of 5ml, strong agitation 20min is mixed with titanium zirconium complex salt solution.
2. titanium zirconium complex salt solution dropwise joins in 1L 25% ammoniacal liquor with the speed of 15ml/min, generates white jelly.
3. the aging 12h of colloid normal temperature, vacuum filtration and washing, the gained filter cake carries out extrusion with φ 4 moulds.
4. at 120 ℃ of dry 2h, calcine respectively 2h for 500 ℃, 700 ℃ after the extrudate room temperature is dried.
5. vacuum incipient impregnation RuCl
3Solution, 400 ℃ of calcining 2h.
The gained catalyst is processed industrial wastewater in batch autoclave, result sees Table 3.
Table 3 catalytic wet air oxidation batch process high-concentration hardly-degradable industrial wastewater
Result shows that the prepared CWO catalyst of this patent has higher activity, and can process various industrial sewage.
Embodiment 6:
1. dissolve the zirconium oxychloride of the titanium sulfate of 0.06mol and 0.14mol in the 2.5L ultra-pure water, add the nitric acid precaution of hydrolysis of 5ml, add the 100ml hydrogen peroxide so that the homogenization of titanium zirconium salt solution precipitation, strong agitation 20min is mixed with titanium zirconium complex salt solution.
2. titanium zirconium complex salt solution dropwise joins in 1L 25% ammoniacal liquor with the speed of 15ml/min, generates white jelly.
3. the aging 12h of colloid normal temperature, vacuum filtration and washing, the gained filter cake carries out extrusion with φ 4 moulds.
4. at 120 ℃ of dry 2h, calcine respectively 2h for 500 ℃, 700 ℃ after the extrudate room temperature is dried.
5. vacuum incipient impregnation H
2PtCl
6Solution, load capacity are 0.5%, 500 ℃ of calcining 4h.
The gained catalyst is processed industrial wastewater in the bubbling bed continuous reaction apparatus, result sees Table 4.
Table 4 CWO bubbling bed continuous reaction apparatus is processed industrial wastewater
Result shows that the prepared CWO catalyst of this patent has higher activity, and can process various industrial sewage.
Embodiment 7:
1. dissolve the zirconium oxychloride of the titanium sulfate of 0.08mol and 0.12mol in the 2.5L ultra-pure water, add the nitric acid precaution of hydrolysis of 5ml, add the 50ml hydrogen peroxide so that the homogenization of titanium zirconium salt solution precipitation, strong agitation 20min is mixed with titanium zirconium complex salt solution.
2. titanium zirconium complex salt solution dropwise joins in 1L 25% ammoniacal liquor with the speed of 15ml/min, generates white jelly.
3. the aging 12h of colloid normal temperature, vacuum filtration and washing, gained filter cake and 0.5%HEC kneading are even, carry out extrusion with φ 4 moulds.
4. at 120 ℃ of dry 2h, calcine respectively 2h for 500 ℃, 700 ℃ after the extrudate room temperature is dried.
5. vacuum incipient impregnation RuCl
3Solution, load capacity are 1.0%, 350 ℃ of calcining 4h.
The gained catalyst is processed 5000mg/L isophorone model waste water in the bubbling bed continuous reaction apparatus, its evaluation result is seen Fig. 2.Result shows that the prepared CWO catalyst of this patent has higher Activity and stabill, its in 260 ℃, 5.7MPa, pH ≈ 3 HTHP sour environments after operation 242h form intact, and activity remains unchanged substantially, and this is conducive to promote the application of titanium zirconium composite catalyst in the CWO industrialization.
ZrO
2Stable chemical performance not only is insoluble to alkaline solution, and can be in acid solution stable existence; But its specific area is less, usually only has 20～50m
2About/g, and martensite transfor mation can occur during due to calcining, cause shaped article there is no intensity.The present invention is the CWO catalyst of a kind of corrosion-resistant, high temperature resistant, high strength, bigger serface, take the stable zirconia of titanium oxide as carrier, load high activity and difficult noble metal Ru, Pd, the Pt that runs off prepare good CWO catalyst; Institute's controlling catalyst in 260 ℃, 5.7MPa, pH ≈ 3 HTHP sour environments after operation 242h form intact, and activity remains unchanged substantially, this is conducive to the zirconia loaded catalyst and promotes in the CWO industrial applications.
Claims (4)
1.TiZrO
2Carrier is characterized in that:
Described carrier prepares as follows,
(1) with the ZrOCl of ax mol
28H
2Ti (the SO of O and a (1-x) mol
4)
2Be dissolved into 1～2.5
In the deionized water of L, a=0.2～0.8, x=0.1～0.9, the nitric acid precaution of hydrolysis that adds b mol, b/a=0.1～2, and add the hydrogen peroxide of c mol so that the homogenization of titanium zirconium salt solution precipitation, c/a=0.1～10, strong agitation 20～40min is mixed with titanium zirconium complex salt solution;
(2) to being heated in the titanium zirconium complex salt solution of 60～80 ℃, dropwise add with the speed of 10～20ml/min in 12.5～25wt.% ammoniacal liquor of 1～2.5L (positive addition), perhaps titanium zirconium complex salt solution dropwise joins with the speed of 15ml/min in 12.5～25wt.% ammoniacal liquor of 1～2.5L (anti-addition), generates white jelly;
(3) the aging 12～48h of colloid normal temperature, vacuum filtration and washing, gained filter cake and shaping assistant carry out extrusion after abundant kneading,
Shaping assistant is: one or two or more kinds in polyanion cellulose PAC, hydroxyethylcellulose HEC, xanthans or metatitanic acid, and in extrusion, the shaping assistant use amount is 0～2wt.%;
(4) extrudate carries out a step or two dry 2～24h of step at 25～120 ℃, then carries out a step or two steps calcining, 2～8h makes titanium zirconium complex carrier at 500～800 ℃.
2. noble metal/TiZrO
2Catalyst is characterized in that:
With the described TiZrO of claim 1
2Carrier is catalyst carrier, and in noble metal Ru, Pd, Pt, one or two or more kinds is as active component; Activity component load quantity is 0.5～3 wt.%.
3. described noble metal/TiZrO of claim 2
2The preparation method of catalyst is characterized in that: titanium zirconium complex carrier normal pressure incipient impregnation or vacuum incipient impregnation RuCl
3, PdCl
2Or H
2PtCl
6Solution, activity component load quantity are 0.5～3wt.%, and 300～500 ℃ of calcining 2～8h prepare required catalyst.
4. described noble metal/TiZrO of claim 2
2The application of catalyst is characterized in that:
Described catalyst is for the treatment of high concentration hard-degraded organic waste water, organic wastewater COD＞20000mg/L, BOD/COD＜0.3;
The intermittent reaction condition is: reaction temperature: 220～280 ℃, and oxygen partial pressure: 1.0～4.0MPa, mixing speed: 400-800r/min;
The successive reaction condition is: reaction temperature: 220～280 ℃, and reaction pressure: 4.0～8.0MPa, air speed: 0.5～4.0h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110427159.8A CN103157517B (en) | 2011-12-19 | 2011-12-19 | TiZrO2 carrier and precious metal/TIZrO2 catalyst and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110427159.8A CN103157517B (en) | 2011-12-19 | 2011-12-19 | TiZrO2 carrier and precious metal/TIZrO2 catalyst and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103157517A true CN103157517A (en) | 2013-06-19 |
| CN103157517B CN103157517B (en) | 2015-04-08 |
Family
ID=48581351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110427159.8A Active CN103157517B (en) | 2011-12-19 | 2011-12-19 | TiZrO2 carrier and precious metal/TIZrO2 catalyst and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103157517B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437478A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidation catalyst and preparation method and application thereof |
| CN107213918A (en) * | 2017-07-12 | 2017-09-29 | 中国矿业大学 | A kind of preparation method of balloon borne body of zirconium and its application in manganese base desulfurizer |
| CN107469818A (en) * | 2017-09-14 | 2017-12-15 | 利民化工股份有限公司 | CaZrO3The preparation method of carrier and by noble-metal-supported in supported catalyst and preparation method and application |
| CN113603493A (en) * | 2021-07-06 | 2021-11-05 | 宁波银瓷新材料有限公司 | Wear-resistant silicon nitride ceramic cutter material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498860A (en) * | 2002-11-06 | 2004-05-26 | 中国科学院大连化学物理研究所 | Catalyzer for catalyzing wet oxidation in treating wastewater of sensitization glue, and its application |
| CN1623664A (en) * | 2003-12-03 | 2005-06-08 | 浙江大学 | Titanium zirconium Sosoloid and preparation process thereof |
-
2011
- 2011-12-19 CN CN201110427159.8A patent/CN103157517B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498860A (en) * | 2002-11-06 | 2004-05-26 | 中国科学院大连化学物理研究所 | Catalyzer for catalyzing wet oxidation in treating wastewater of sensitization glue, and its application |
| CN1623664A (en) * | 2003-12-03 | 2005-06-08 | 浙江大学 | Titanium zirconium Sosoloid and preparation process thereof |
Non-Patent Citations (5)
| Title |
|---|
| R. MARISCAL ET AL.: "Support effects in Pt/TiO2–ZrO2 catalysts for NO reduction with CH4", 《CATALYSIS TODAY》 * |
| VALERIO CHOQUE ET AL.: "Ruthenium supported on new TiO2–ZrO2 systems as catalysts for the partial oxidation of methane", 《CATALYSIS TODAY》 * |
| 杨玮娇等: "H2O2 改性溶胶−凝胶法制备ZrO2基催化剂载体", 《过程工程学报》 * |
| 杨玮娇等: "H2O2 改性溶胶−凝胶法制备ZrO2基催化剂载体", 《过程工程学报》, vol. 9, no. 4, 31 August 2009 (2009-08-31), pages 819 - 823 * |
| 袁霞光等: "丙烯酸废水湿式氧化催化剂的研究", 《石油化工》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437478A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidation catalyst and preparation method and application thereof |
| CN104437478B (en) * | 2013-09-24 | 2016-05-18 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidizing catalyst and its production and use |
| CN107213918A (en) * | 2017-07-12 | 2017-09-29 | 中国矿业大学 | A kind of preparation method of balloon borne body of zirconium and its application in manganese base desulfurizer |
| CN107213918B (en) * | 2017-07-12 | 2020-06-09 | 中国矿业大学 | Preparation method of zirconium ball carrier and application of zirconium ball carrier in manganese-based desulfurizing agent |
| CN107469818A (en) * | 2017-09-14 | 2017-12-15 | 利民化工股份有限公司 | CaZrO3The preparation method of carrier and by noble-metal-supported in supported catalyst and preparation method and application |
| CN107469818B (en) * | 2017-09-14 | 2020-05-29 | 利民化学有限责任公司 | CaZrO3Preparation method of carrier, catalyst with noble metal loaded on carrier, preparation method and application thereof |
| CN113603493A (en) * | 2021-07-06 | 2021-11-05 | 宁波银瓷新材料有限公司 | Wear-resistant silicon nitride ceramic cutter material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103157517B (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Promotion of A-site Ag-doped perovskites for the catalytic oxidation of soot: synergistic catalytic effect of dual active sites | |
| CN105498755B (en) | A kind of SCR denitration and preparation method thereof | |
| CN101485987B (en) | Catalyst for normal temperature and pressure catalysis wet-type oxidation technology and preparation method | |
| CN103521222B (en) | Heterogeneous catalysis wet oxidizing catalyst and preparation method thereof | |
| CN103157517B (en) | TiZrO2 carrier and precious metal/TIZrO2 catalyst and preparation and application thereof | |
| CN111097422B (en) | Catalyst for removing formaldehyde and preparation method and application thereof | |
| CN101829556A (en) | Calcium titanate photocatalyst for removing arsenic by photocatalysis | |
| CN103877973B (en) | CWO process OIT waste water catalyst and Synthesis and applications thereof | |
| CN100537023C (en) | Photocatalyst having response to visible light and preparation thereof | |
| WO2012109846A1 (en) | Methods for preparation and use of catalyst for hydrazine degradation | |
| CN113070062A (en) | Cerium-based nano-sphere catalyst for catalyzing formic acid to produce hydrogen and preparation method thereof | |
| CN101380575B (en) | High stability nano gold catalyst for CO normal temperature oxidation and preparation method thereof | |
| CN100395021C (en) | Rare earth composite oxide catalyst in catalytic wet oxidation process and preparing method thereof | |
| CN104399460A (en) | Catalyst for industrial wastewater treatment and preparation method of catalyst | |
| CN104475089A (en) | General light source response modified titanium dioxide solid acid catalyst and preparation method | |
| CN102850304B (en) | Furfural preparation method by using complex perovskites for one-step hydrolysis of xylan | |
| CN101161649B (en) | Method for synthesizing lactone compound by catalytic oxidation of cyclone | |
| Zhou et al. | Preparation of ZrO2-based catalytic fibers via the assistance of microfluidic chips | |
| CN109894114B (en) | Monoatomic Au modified CeO for degrading formaldehyde at low temperature2Process for preparing catalyst | |
| CN104043449A (en) | Novel low-temperature SCR (selective catalytic reduction) catalyst based on cubic-phase zirconia carrier and preparation method of novel low-temperature SCR catalyst | |
| CN110975860B (en) | Chromium-doped titanium-oxygen cluster nano catalytic material, preparation method and application | |
| CN108993544B (en) | Catalyst for removing NOx and VOCs in low-temperature high-sulfur tail gas and preparation and application thereof | |
| CN102814196B (en) | Preparation method and application of dextrangel-supported nanogold catalyst | |
| CN112387276A (en) | Supported ruthenium cluster catalyst for ammonia synthesis and preparation method and application thereof | |
| CN112588295B (en) | Catalyst for organic wastewater treatment and preparation method thereof |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: HANGZHOU SUNRISE WATER AFFAIRS CO., LTD. Free format text: FORMER OWNER: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Effective date: 20150804 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Sun Chenglin Inventor after: Wei Huangzhao Inventor after: He Songbo Inventor after: Lai Yulong Inventor after: Ma Lei Inventor after: Ren Jian Inventor after: Liu Peijuan Inventor after: Yan Xiaomiao Inventor after: Wu Libo Inventor before: Sun Chenglin Inventor before: Wei Huangzhao Inventor before: He Songbo Inventor before: Lai Yulong Inventor before: Ma Lei Inventor before: Ren Jian Inventor before: Liu Peijuan Inventor before: Yan Xiaomiao |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: SUN CHENGLIN WEI HUANGZHAO HE SONGBO LAI YULONG MA LEI REN JIAN LIU PEIJUAN YAN XIAOMIAO TO: SUN CHENGLIN WEI HUANGZHAO HE SONGBO LAI YULONG MA LEI REN JIAN LIU PEIJUAN YAN XIAOMIAO WU LIBO |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20150804 Address after: 310000 Dongshan village, Renhe street, Yuhang District, Hangzhou, Zhejiang Patentee after: HANGZHOU SUNRISE WATER AFFAIRS CO., LTD. Address before: 116023 Zhongshan Road, Liaoning, No. 457, Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |