CN108940301A - A kind of preparation method of copper-based wet oxidizing catalyst - Google Patents
A kind of preparation method of copper-based wet oxidizing catalyst Download PDFInfo
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Abstract
The invention discloses a kind of wet oxidizing catalysts and preparation method thereof, and this method comprises the following steps: (1) being beaten activated alumina；(2) copper source presoma is dissolved to form solution, and (1) and (2) is mixed；(3) after mixing to step (2) acquired solution, it adjusts pH value and forms precipitating, filter, washing；(4) deionized water is added in the filter cake obtained by step (3), is tuned into pulpous state, cerium source precursor solution is added and is dried, roasts after evenly mixing, forms powder；(5) by the powder of step (4) and manganese source precursor solution mixing pulp, after stirring, add pore creating material, after secondary agitation, sealing and standing, drying, roasting form wet oxidizing catalyst.Wet oxidizing catalyst prepared by the present invention is used for high concentrated organic wastewater, has the characteristics that at low cost, performance is stablized.
Description
Technical field
It is specifically a kind of to be used for wet oxidation the present invention relates to catalyst of a kind of metal material field and preparation method thereof
The preparation method of catalyst.
Background technique
Wet type (air) aoxidizes (wet air oxidation, WAO) and handles high concentration hard-degraded organic waste water, usually needs
Want higher temperature and pressure (200~3l5 DEG C, 2~21MPa) and longer residence time, reaction condition very harsh.
Catalytic wet oxidation catalytic wetair oxidation, CWAO) under conditions of keeping treatment effect, reaction can be reduced
Temperature and pressure greatly pushes the development and application of wet oxidation.Therefore, developing has greater activity and stability and is applicable in
In the catalyst of CWAO, become the key points and difficulties studied at present.Except containing different dense in oil refining or ethylene waste lye (alkaline residue)
The free alkali (NaOH) of degree, also containing a large amount of highly concentrated Na2S, organic acidic substances (exist, such as creosote, cycloalkanes with sodium-salt form
Acid, mercaptan, thiophenol etc.), the organic sulfur compounds such as thioether and thiophene, in stench, toxic, COD content is up to 10000~
Catalyst poisoning, metal active ingredients from lossing and COD removal effect easily occur during catalytic wet oxidation for 150000mg/L
The problems such as rate is low becomes the difficult point of research.
CN1358567 discloses a kind of " copper-based catalysts and its preparation side for catalytic wet oxidation processing industrial wastewater
Method ", a kind of preparation and application of the copper-based catalysts for catalytic wet oxidation processing industrial wastewater.The main component of catalyst
For copper, zinc, nickel, magnesium, aluminium, chromium, iron and a part of rare earth metal oxide, wherein being to calculate: CuO with the content of oxide
20~55%；ZnO, NiO or MgO are 20~55%；Cr2O3、Al2O3Or Fe2O3It is 10~40%；Rare-earth oxide is 0
~10%.The catalyst is co-precipitated to obtain the catalyst precursor of hydrotalcite-like compound by the salt containing various metals, and is roasted
Gained.The catalyst can be effectively treated living containing phenol, sulfosalicylic acid, H- acid and surface by being once co-precipitated, roasting
Property toxic industrial organic waste water difficult to degrade, the copper number of dropouts such as agent it is lower, but be difficult to adapt to processing containing there are many toxic, nuisances
COD removal efficiency is low in the needs of matter waste water, especially oil refining or the processing of ethylene waste lye.
CN1669643 discloses a kind of rare-earth composite oxide catalyst, is solid powdery, and group is divided into ZrO2With
The molar ratio of the composite oxides of CeO, Zr and Ce are 1: 1~1: 11.The invention also discloses the preparation methods of the catalyst:
Zirconates and cerium solution are mixed, using a step precipitation method, primary drying, roasting obtain catalyst.It is urged prepared by the present invention
Agent only has good activity and higher stability for the small molecular organic acid waste water containing high-concentration hardly-degradable, it is difficult to adapt to
Processing is containing there are many needs of poisonous and harmful substances waste water, especially oil refining or the processing of ethylene waste lye.
CN104667934 discloses " a kind of preparation method of catalytic wet oxidation catalyst ", using excessive and rare earth metal
It for active metal component, is impregnated on carrier, after single-steeping and primary roasting, realizes the preparation of catalyst.
In conclusion the preparation of precipitation method wet oxidizing catalyst is all made of primary sedimentation, once roast, it is prepared
Catalyst there is certain removal to act on COD, the organic matter in waste water during catalytic wet oxidation, still, to salkali waste
During liquid treatment effect, catalyst is easily poisoned, COD removal efficiency is low, active ingredient copper is easy to be lost, and influences the property of catalyst
Energy.
Summary of the invention
The present invention provides a kind of improved wet oxidizing catalyst preparation method, resist the catalyst of preparation both can
Poisoning in system, inactivation, active constituent losing issue coexists in multiple pollutant, and improves stability and activity, waste soda residue
High treating effect.
A kind of wet oxidizing catalyst preparation method of the present invention, includes the following steps:
(1) activated alumina is beaten to form slurries；
(2) copper source presoma is dissolved, and it is mixed with the solution of step (1)；
(3) after evenly mixing to step (2) acquired solution, it adjusts pH value and forms precipitating, filter, washing；
(4) deionized water is added in the filter cake obtained by step (3), is tuned into pulpous state, cerium source presoma is added after evenly mixing,
It is directly dried, roasts, form powder；
(5) by the powder of step (4) and manganese source precursor solution mixing pulp, after stirring, add pore creating material, it is secondary mixed
After conjunction, sealing and standing, drying, roasting form wet oxidizing catalyst.
The preparation method of wet oxidizing catalyst of the present invention, it is internal that there is nanoscale abundant using activated alumina
Micropore is more advantageous to the dispersion and absorption of active material.After activated alumina is mixed with the copper of ionic state, it can promote unformed
Copper oxide better disperses, inside adsorption activity aluminium oxide, simultaneous oxidation copper and the even closer package of activated alumina, can be effective
Loss of the copper in catalytic process is reduced, catalyst strength is improved, improves specific surface area of catalyst and porosity, increase and urge
Active sites inside agent improve the efficiency of catalyst.
The preparation method of wet oxidizing catalyst of the present invention, wherein activated alumina is beaten by the step (1), formation contains
Al2O3For the slurries of 50~600g/L, content preferably 200~500g/L.
The preparation method of wet oxidizing catalyst of the present invention, wherein the step (2) copper source presoma is solubility
Mantoquita, preferably copper nitrate, the dissolution to copper source presoma forms solution in terms of CuO, and content is preferably 15~40g/L.
The preparation method of wet oxidizing catalyst of the present invention, wherein incorporation time is equal in the step (3) and step (4)
Preferably 0.5~3h, mixing time is both preferably 10~60min in the step (5), in the step (5) when sealing and standing
Between preferably 8~30h.
The acid-base modifiers such as ammonium hydroxide, sodium hydroxide, preferably ammonium hydroxide, pH can be used in the adjusting of step (3) pH value in the present invention
Range 4~13, preferably 8~11.
The preparation method of wet oxidizing catalyst of the present invention, wherein the step (4) the cerium source presoma be cerous nitrate,
Cerous acetate or cerium citrate, preferably cerous nitrate, the step (4) form material in terms of CeO, and content is preferably 15~40g/L.
The preparation method of wet oxidizing catalyst of the present invention, wherein the step (5) the manganese source presoma is solubility
Manganese salt, preferably manganese nitrate, the step (5) forms material in terms of MnO, and content is preferably 15~40g/L.
The preparation method of wet oxidizing catalyst of the present invention, wherein the step (5) described pore creating material can be citric acid,
Urea, three fluoroacetic acid, active carbon, sesbania powder are one or more, preferably sesbania powder, pore creating material and Al2O3Mass ratio is preferably in a proportion of
0.5~1.5:100.
The preparation method of wet oxidizing catalyst of the present invention, wherein maturing temperature is in the step (4) and step (5)
400~850 DEG C, preferably 500~650 DEG C, calcining time is no less than 1 hour, preferably 2~7h.Maturing temperature is too low, metal
Hydroxide cannot completely decomposition and inversion at the oxide for having catalytic activity, oxide crystal form cannot sufficiently be reset, and influence to be catalyzed
The catalytic performance of agent；Maturing temperature is excessively high, causes oxide crystal form to change, while catalyst excess agglomeration occur, can also reduce
The catalyst performance of catalyst.
The preparation method of wet oxidizing catalyst of the present invention, wherein the step is mixed described in rapid (3), (4) and (5)
Conjunction method includes various mechanical stirrings, fluid mixing and ultrasonic wave mixing, wherein it is preferred that supercritical ultrasonics technology.
The catalyst of wet oxidizing catalyst preparation method preparation of the present invention, by weight percentage, wherein containing active oxygen
Change aluminium 30~75%, contain copper oxide 10~30%, oxidation-containing cerium 5~20%, manganese oxide be 10~30%, specific surface be 60~
160m2/ g, hole hold 0.30~0.70cm3/ g, wherein it is preferred that contain activated alumina 40~75%, contain copper oxide 10~20%, it is oxygen-containing
Change cerium 5%~12%, manganese oxide is 10~20%, and specific surface is 70~120m2/ g, hole hold 0.40~0.60cm3/g。
The wet oxidizing catalyst of the method for the present invention preparation is added to simultaneously using the metal oxide of Cu as active constituent
The oxide of Ce, Mn make auxiliary agent.Wherein the effect of component C uO is to promote the oxidation reaction of organic matter, component Al2O3Main work
With being the structure for adjusting catalyst, but if too high, then active constituent content will be insufficient, the same performance for influencing catalyst；Examination
It tests and shows that CuO content more high catalyst conversion ratio is higher and it is serious to be lost, catalyst performance is unstable；Co-catalyst Mn, Ce's
Oxide is primarily served to organic matter (a large amount of highly concentrated Na2S, organic acidic substances such as creosote, aphthenic acids, mercaptan, thiophenol etc. with
And the organic sulfur compounds such as thioether, thiophene) deep oxidation and sulfur poisoning-resistant effect, find in test: auxiliary agent oxidation be used alone
Manganese, catalyst activity is obviously poor, the oxide of auxiliary agent cerium is used alone, catalyst activity is also undesirable, when copper, cerium, nickel, aluminium
Oxide when existing simultaneously, obtained catalyst comprehensive performance has compared with the catalyst containing only wherein certain several composition obviously to be mentioned
It is high.
The preparation method of wet oxidizing catalyst of the present invention, by copper, cerium powder material after once roasting, and in its table
Face covers one layer of manganese oxide, while joined pore creating material, adheres to catalyst particle surface with more manganese oxide, while also gathering around
There is the nanometer level microporous and higher crushing strength of spatial network shape abundant, can not only reduce the loss of copper ion, but also can protect
Demonstrate,prove high catalytic performance.
The spent lye generated in the catalyst treatment oil refining of the method for the present invention preparation or ethylene production, COD content model
Enclosing the waste water between 10000~150000 can directly be handled, pressure be 1.0~5.0MPa, react for temperature 190~
260 DEG C, 0.5~4.0h of reaction time are handled using excess air or rich feeding air as oxide isolation by catalytic wet oxidation
Afterwards, for the conversion ratio of sulfide up to 99.9% or more, phenols conversion ratio is reachable to the removal rate of COD up to 90% or more
85.0% or more, the ratio of BOD/COD is conducive to further reaching for waste water by 0.1 mentioned below 0.40 or more after wastewater treatment
Mark processing.
Specific embodiment
Following embodiment is illustrated to of the invention, and " % " described in embodiment and comparative example refers to that quality percentage contains
Amount.
Embodiment 1
70g activated alumina is beaten, is formed and contains Al2O3For 300g/L slurries, it is molten that the copper nitrate containing the 20g in terms of CuO is added
Liquid is gradually added ammonium hydroxide after supersonic oscillations 2h and adjusts pH value to 8.5, precipitating completely after, be filtered, washed；Object after washing again
Material spends the slurry that ion water making is 50% at moisture content, and the cerous nitrate solution of the 8g in terms of CeO is added, ultrasonic wave while stirring
1.5h is vibrated, after convection drying, roasts 2h at 620 DEG C；Powder is made with the manganese nitrate solution of the 10g in terms of MnO contains again after roasting
The slurry of water 30%, after stirring be added 1g citric acid-sesbania powder composite drug, stirring 40min, sealing and standing for 24 hours, drying, 650
DEG C roasting 7h after obtain wet oxidizing catalyst sample A.
Comparative example 1
Other conditions are constant, reduce CuO dosage.70g activated alumina bead is beaten, is formed and contains Al2O3For 300g/L
The copper nitrate solution for containing the 2g in terms of CuO is added in slurries, and ammonium hydroxide is gradually added after supersonic oscillations 2h and adjusts pH value to 8.5, is precipitated
After completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, the 8g in terms of CeO is added
Cerous nitrate solution, supersonic oscillations 1.5h while stirring after convection drying, roasts 2h at 620 DEG C；After roasting powder again with
Aqueous 30% slurry is made in the manganese nitrate solution of the 10g in terms of MnO, and 1g citric acid-sesbania powder composite drug is added after stirring, stirs
Mix 40min, sealing and standing for 24 hours, drying, obtain wet oxidizing catalyst sample F after 650 DEG C of roasting 7h.
Embodiment 2
50g activated alumina bead is beaten, is formed and contains Al2O3For 200g/L slurries, the nitric acid for containing the 10g in terms of CuO is added
Copper solution is gradually added ammonium hydroxide after supersonic oscillations 2h and adjusts pH value to 9.5, precipitating completely after, be filtered, washed；It again will washing
Material spends the slurry that ion water making is 50% at moisture content afterwards, the cerous nitrate solution of the 10g in terms of CeO is added, while stirring
Supersonic oscillations 1.5h after convection drying, roasts 2h at 520 DEG C；The powder manganese nitrate solution with the 10g in terms of MnO again after roasting
Aqueous 30% slurry is made, is added 1g urea after stirring, stirring 40min, sealing and standing for 24 hours, drying, after 600 DEG C of roasting 5h
Obtain wet oxidizing catalyst sample B.
Comparative example 2
Other conditions are constant, reduce CeO dosage.50g activated alumina bead is beaten, is formed and contains Al2O3For 200g/L slurry
The copper nitrate solution for containing the 10g in terms of CuO is added in liquid, and ammonium hydroxide is gradually added after supersonic oscillations 2h and adjusts pH value to 9.5, is precipitated
After completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, the 2g in terms of CeO is added
Cerous nitrate solution, supersonic oscillations 1.5h while stirring after convection drying, roasts 2h at 520 DEG C；After roasting powder again with
Aqueous 30% slurry is made in the manganese nitrate solution of the 10g in terms of MnO, and 1g urea is added after stirring, stirs 40min, sealing and standing
For 24 hours, wet oxidizing catalyst sample G is obtained after drying, 600 DEG C of roasting 5h.
Embodiment 3
50g activated alumina bead is beaten, is formed and contains Al2O3For 500g/L slurries, the nitric acid for containing the 16g in terms of CuO is added
Copper solution is gradually added ammonium hydroxide after supersonic oscillations 3h and adjusts pH value to 9.0, precipitating completely after, be filtered, washed；It again will washing
Material spends the slurry that ion water making is 50% at moisture content afterwards, the cerous nitrate solution of the 10g in terms of CeO is added, while stirring
Supersonic oscillations 1.0h after convection drying, roasts 2h at 550 DEG C；The powder manganese nitrate solution with the 10g in terms of MnO again after roasting
Aqueous 30% slurry is made, 1g urea is added after stirring, after stirring 30min, sealing and standing 20h, drying, 550 DEG C of roasting 2h
Obtain wet oxidizing catalyst sample C.
Comparative example 3
Other conditions are constant, reduce MnO dosage.50g activated alumina bead is beaten, is formed and contains Al2O3For 500g/L
The copper nitrate solution for containing the 16g in terms of CuO is added in slurries, and ammonium hydroxide is gradually added after supersonic oscillations 3h and adjusts pH value to 9.0, is sunk
After forming sediment completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added in terms of CeO
The cerous nitrate solution of 10g, supersonic oscillations 1.0h while stirring after convection drying, roast 2h at 550 DEG C；Powder after roasting
Aqueous 30% slurry is made with the manganese nitrate solution of the 5g in terms of MnO again, 1g urea is added after stirring, stirring 30min, sealing are quiet
Wet oxidizing catalyst sample H is obtained after setting 20h, drying, 550 DEG C of roasting 2h.
Embodiment 4
80g activated alumina bead is beaten, is formed and contains Al2O3For 400g/L slurries, the nitric acid for containing the 16g in terms of CuO is added
Copper solution is gradually added ammonium hydroxide after supersonic oscillations 3h and adjusts pH value to 9.0, precipitating completely after, be filtered, washed；It again will washing
Material spends the slurry that ion water making is 50% at moisture content afterwards, the cerous nitrate solution of the 10g in terms of CeO is added, while stirring
Supersonic oscillations 1.0h after convection drying, roasts 2h at 550 DEG C；The powder manganese nitrate solution with the 15g in terms of MnO again after roasting
Aqueous 30% slurry is made, 1g urea is added after stirring, after stirring 30min, sealing and standing 20h, drying, 550 DEG C of roasting 2h
Obtain wet oxidizing catalyst sample D.
Comparative example 4
Other conditions are constant, reduce maturing temperature.80g activated alumina bead is beaten, is formed and contains Al2O3For 400g/
The copper nitrate solution for containing the 16g in terms of CuO is added in L slurries, and ammonium hydroxide is gradually added after supersonic oscillations 3h and adjusts pH value to 9.0, is sunk
After forming sediment completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added in terms of CeO
The cerous nitrate solution of 10g, supersonic oscillations 1.0h while stirring after convection drying, roast 2h at 395 DEG C；Powder after roasting
Aqueous 30% slurry is made with the manganese nitrate solution of the 15g in terms of MnO again, 1g urea, stirring 30min, sealing are added after stirring
Wet oxidizing catalyst sample I is obtained after standing 20h, drying, 395 DEG C of roasting 2h.
Embodiment 5
80g activated alumina bead is beaten, is formed and contains Al2O3For 200g/L slurries, the nitric acid for containing the 12g in terms of CuO is added
Copper solution is gradually added ammonium hydroxide after supersonic oscillations 1h and adjusts pH value to 9.0, precipitating completely after, be filtered, washed；It again will washing
Material spends the slurry that ion water making is 50% at moisture content afterwards, and the cerous acetate solution of the 6g in terms of CeO is added, super while stirring
Sonication 1.0h after convection drying, roasts 2h at 650 DEG C；The powder manganese nitrate solution system with the 12g in terms of MnO again after roasting
At aqueous 30% slurry, 1g urea is added after stirring, after stirring 30min, sealing and standing 20h, drying, 650 DEG C of roasting 2h
To wet oxidizing catalyst sample E.
Comparative example 5
Other conditions are constant, improve maturing temperature.80g activated alumina bead is beaten, is formed and contains Al2O3For 200g/
The copper nitrate solution for containing the 12g in terms of CuO is added in L slurries, and ammonium hydroxide is gradually added after supersonic oscillations 1h and adjusts pH value to 9.0, is sunk
After forming sediment completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added in terms of CeO
The cerous acetate solution of 6g, supersonic oscillations 1.0h while stirring after convection drying, roast 2h at 910 DEG C；Powder is again after roasting
Aqueous 30% slurry is made with the manganese nitrate solution of the 12g in terms of MnO, 1g urea is added after stirring, stirring 30min, sealing are quiet
Wet oxidizing catalyst sample J is obtained after setting 20h, drying, 910 DEG C of roasting 2h.
Comparative example 6
Other conditions prepare wet oxidizing catalyst with embodiment 5, using primary co-precipitation, roasting method.I.e. by 80g activity
Aluminium oxide mashing, forms and contains Al2O3For 200g/L slurries, by the copper nitrate solution of the 12g in terms of CuO, by the acetic acid of the 6g in terms of CeO
Aqueous 30% slurry is made in the manganese nitrate solution of the 12g in terms of MnO by cerium solution, and 1g urea is transferred in a beaker,
It is gradually added ammonium hydroxide after supersonic oscillations 1h and adjusts pH value to 9.0, after precipitating is complete, stands 20h, is filtered, washed, convection drying
Afterwards, roasting 2h obtains wet oxidizing catalyst sample K at 650 DEG C.
Comparative example 7
Using CN1358567 method, prepare wet oxidizing catalyst i.e.: taking 550ml concentration is the Na of 1.0mol/L2CO3It is molten
Liquid is placed in the constant temperature water bath that bath temperature is 70 DEG C, heats 20min.Take the Cu (NO of 1.0mol/L3)2Solution 100ml,
Zn (the NO of 1.0mol/L3)2Solution 110ml takes the Al (NO of 0.5mol/L3)3Solution 75ml is transferred in a beaker, mixing
Na is slowly dropped to separatory funnel after uniformly2CO3In the beaker of solution, while quickly stirring.Guarantee mother liquor after titration
PH >=9, and allow precipitating and mother liquor aging is for 24 hours together.Mother liquor and precipitation and separation are made using vacuum filtration after aging, filter process
In adopt and be washed with deionized four times.Sediment is squeezed into 3 strip of Ф, is dried in air, is then done under the conditions of 110 DEG C
Dry 2h, Muffle kiln roasting 8h, maturing temperature are 700 DEG C, are ground into 70 mesh powder after cooling, obtain catalyst sample L.
The physical property of each catalyst sample is as shown in table 1:
1 catalyst sample physical data of table
Evaluation result:
By above-mentioned A~J catalyst breakage and sieve takes 10~40 mesh particle 5ml, and it is anti-to be seated in miniature continuous flow fixed bed
It answers in device, is passed through containing waste soda residue, composition COD is 60000mg/L, sulfide content 5000mg/L, phenols content are 85000mg/
Compressed air is added in L, and control reaction pressure is 3.2Mpa, 220 DEG C of temperature, carries out evaluation examination under conditions of reaction time 2.0h
It tests.
By evaluation test, the conversion data of each catalyst is shown in Table 2, table 3 respectively.
2 embodiment evaluating catalyst result of table
3 comparative example evaluating catalyst result of table
From table 2, table 3 it can be seen that using catalyst prepared by preparation method of the invention and condition, salkali waste is refined oil in processing
Slag or organic wastewater containing phenol, for sulfide removal rate up to 99.9%, COD removal rate up to 85% or more, phenols removal rate is reachable
90% or more.
Reaction time is 2 hours, other experiment conditions are constant, detects the concentration of copper ion in reaction solution, the results are shown in Table 4.
By experimental result it can be seen that, after catalyst treatment spent lye of the invention, catalyst D, E and former document report catalyst L
And compared with 6 catalyst K of comparative example, copper ion wastage is preferably controlled, and COD removal effect is more preferable.
4 spent lye COD removal rate of table and copper ion wastage
Reaction time is 2 hours, other experiment conditions are constant, and catalyst is reused 6 times, detects copper ion in reaction solution
Concentration, the results are shown in Table 5.By experimental result it can be seen that, after catalyst treatment spent lye of the invention, catalyst D, E with
Preceding document report catalyst L and compared with 6 catalyst K of comparative example, copper ion wastage is preferably controlled, and COD is gone
Except effect is higher, and catalyst activity keeps stablizing.
5 spent lye COD removal rate of table and copper ion wastage
Claims (8)
1. a kind of preparation method of copper-based wet oxidizing catalyst, which comprises the steps of:
(1) activated alumina is beaten；
(2) copper source presoma is dissolved, and it is mixed with the slurries of step (1)；
(3) it to pH value formation precipitating is adjusted after the mixing of step (2) resulting material, filters, washing；
(4) deionized water is added in the filter cake obtained by step (3), is added after cerium source presoma mixes and is dried, roasts, is formed
Powder；
(5) by the powder of step (4) and manganese source precursor solution mixing pulp, add pore creating material, after secondary mixing, seal quiet
It sets, dry, roast, form wet oxidizing catalyst, wherein by weight percentage, contain activated alumina 30~75%, it is oxygen-containing
Change copper 10~30%, oxidation-containing cerium 5~20%, manganese oxide is 10~30%.
2. the preparation method of copper-based wet oxidizing catalyst according to claim 1, which is characterized in that step (2) is described
Copper source presoma is soluble mantoquita.
3. the preparation method of copper-based wet oxidizing catalyst according to claim 1, which is characterized in that the pH value is 4
~13.
4. the preparation method of copper-based wet oxidizing catalyst according to claim 1, which is characterized in that the cerium source forerunner
Body is soluble cerium salt.
5. the preparation method of copper-based wet oxidizing catalyst according to claim 1, which is characterized in that institute in step (5)
Stating manganese source presoma is soluble manganese salt.
6. the preparation method of copper-based wet oxidizing catalyst according to claim 1, which is characterized in that the pore creating material is
Citric acid, urea, three fluoroacetic acid, active carbon, sesbania powder are one or more.
7. the preparation method of copper-based wet oxidizing catalyst according to claim 1, which is characterized in that step (4) and step
Suddenly the temperature of roasting described in (5) is 400~850 DEG C.
8. the preparation method of copper-based wet oxidizing catalyst according to claim 1, which is characterized in that the pH value is 8
~11.
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| CN110743549A (en) * | 2019-10-25 | 2020-02-04 | 北京工业大学 | Preparation method of copper-based heterogeneous catalyst taking activated carbon spheres as carrier for wet oxidation |
| CN110975854A (en) * | 2019-12-19 | 2020-04-10 | 万华化学集团股份有限公司 | Catalyst for treating sulfur-containing waste alkali and preparation method and application thereof |
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| CN110180494A (en) * | 2019-05-29 | 2019-08-30 | 河北科技大学 | A kind of dyeing waste water adsorbent and preparation method thereof |
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| CN110743549B (en) * | 2019-10-25 | 2022-09-09 | 北京工业大学 | Preparation method of copper-based heterogeneous catalyst taking activated carbon spheres as carrier for wet oxidation |
| CN110975854A (en) * | 2019-12-19 | 2020-04-10 | 万华化学集团股份有限公司 | Catalyst for treating sulfur-containing waste alkali and preparation method and application thereof |
| CN110975854B (en) * | 2019-12-19 | 2022-08-05 | 万华化学集团股份有限公司 | Catalyst for treating sulfur-containing waste alkali and preparation method and application thereof |
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