CN101318136B - Preparing method for catalyst Fe2O3-La2O3/ nano-carbon tube for microwave reinforced advanced oxidation technology - Google Patents
Preparing method for catalyst Fe2O3-La2O3/ nano-carbon tube for microwave reinforced advanced oxidation technology Download PDFInfo
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- CN101318136B CN101318136B CN2008100646297A CN200810064629A CN101318136B CN 101318136 B CN101318136 B CN 101318136B CN 2008100646297 A CN2008100646297 A CN 2008100646297A CN 200810064629 A CN200810064629 A CN 200810064629A CN 101318136 B CN101318136 B CN 101318136B
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Abstract
The invention relates to a preparation method for a catalyst Fe2O3-La2O3/carbon nanotube used in microwave-assisted advanced oxidation processes, which relates to the preparation method of a catalyst used in microwave-assisted advanced oxidation processes. The method solves the problems of low catalytic efficiency and short service life of the existing catalyst of MAOP and has the steps as follows: 1. carrying out purification treatment to the nanotube to obtain the purified nanotube; 2. adding the purified nanotube into absolute ethyl alcohol, stirring; 3. adding ferric nitrate solution, stirring, and dripping aqueous ammonia until the pH value of the solution is 7-14; 4. adding lanthanum nitrate solution, dripping aqueous ammonia until the pH value of the solution is 7-14 and stirring; 5. continuously irradiating by microwave, heating by water bath, washing and drying; 6. roasting and cooling to the room temperature. The catalyst prepared by the invention has the advantages of long life, little dosage and high catalytic efficiency.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method that is used for carbon tube for microwave reinforced advanced oxidation technology.
Background technology
Carbon tube for microwave reinforced advanced oxidation technology (MAOP) is a kind of novel water technology, persistent organic pollutants in water and the waste water is handled have good effect and wide application prospect.At present the catalyst that is used for MAOP of bibliographical information is mainly granular activated carbon and modification alundum (Al, its can be under microwave irradiation persistent organic pollutants in the oxidation processes water fast.Also has bibliographical information load Fe
2O
3With La
2O
3CNT as the catalyst that is used for MAOP, wait " the Fe that is used for water treatment such as history records outstanding person
2O
3/ La
2O
3The auxiliary preparation of the microwave of/CNTs catalyst with characterize " (material Leader, the 21st volume 11A phase of November in 2007 have reported to add in the absolute ethyl alcohol in the CNT of nitric acid pretreatment and disperse that substep adds Fe in P283-285)
3+, La
3+, use NH
3H
2The common deposition of O obtains presoma, obtains Fe behind microwave calcining
2O
3/ La
2O
3/ CNTs catalyst; But because major catalyst Fe
2O
3A little less than carbon nano tube surface skewness and matrix binding ability, caused that catalyst efficient is low, service life is short.
Summary of the invention
The objective of the invention is the problem that catalytic efficiency is low, service life is short for the catalyst that solves existing MAOP; And provide a kind of catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology
2O
3-La
2O
3The preparation method of/CNT.CNT is processed by carbon nano tube surface being carried out chemical modification as the MAOP catalyst carrier, strengthens its absorbability to microwave, reduces catalyst amount and extending catalyst life-span.Strong interaction takes place in the metal dots position of modified carbon nano-tube catalyst surface and microwave, can quickly and efficiently microwave energy be converted into heat energy, make some surface point position of catalyst be heated to very soon high temperature, near these some positions the microwave oxidation reaction taking place, processes persistent organic pollutants in the water thereby reach efficient Quick Oxidation.
The catalyst Fe that is used for carbon tube for microwave reinforced advanced oxidation technology among the present invention
2O
3-La
2O
3The preparation method of/CNT is realized by following step: one, CNT (CNTs) is carried out purification process, obtain purifying carbon nano-tube; Two, purifying carbon nano-tube is added stir 12～24h in the absolute ethyl alcohol, the weight of purifying carbon nano-tube and the volume ratio of absolute ethyl alcohol are 0.05～0.5g: 5～10mL; Three, after adding iron nitrate solution, the mixture that obtains to step 2 by the proportioning of purifying carbon nano-tube and ferric nitrate 0.05～0.5g: 0.5～5mmol stirs 10～24h, then with 0.2～1.0min/mL speed dropping ammonia solution to the pH value of solution=7～14, be about to iron hydroxide and be deposited on carbon nano tube surface; Four, have to surface deposition in the CNT of iron hydroxide by the proportioning of purifying carbon nano-tube and lanthanum nitrate 0.05～0.5g: 0.0005～0.01mmoL and add lanthanum nitrate hexahydrate, then with 0.2～1.0min/mL speed dropping ammonia solution to the pH=7 of solution～14, namely obtain lanthanum hydroxide in carbon nano tube surface, continue to stir 12～36h with 40～80r/min rotating speed again; Five, with the microwave continuous irradiation of the power 100～300W reactant 1～7min after step 4 is processed, in 65～95 ℃ of Water Unders are bathed, react 4～8h then, filter, will filter residue and clean three to five times, dry 3～12h under 100～110 ℃ of conditions namely gets catalyst precursor again; Six, catalyst precursor is put into Muffle furnace, be warming up to 300～400 ℃ with 1～5 ℃/min speed, roasting 60～180min is cooled to room temperature then; Namely obtain for carbon tube for microwave reinforced advanced oxidation technology Fe
2O
3-La
2O
3/ carbon nano-tube catalyst.
In the above-mentioned course of reaction in step 3 and step 4 the concentration of ammonia spirit be 0.05～0.5mol/L.Can also carry out ultrasonic processing to it after in the step 2 CNT being added absolute ethyl alcohol, the ultrasonic processing time is 10～60min.
The Fe that is used for MAOP that the present invention makes
2O
3-La
2O
3/ carbon nano-tube catalyst, the modification aluminum trioxide catalyst of at present extensive use, service life and catalytic activity are significantly improved; Fe
2O
3-La
2O
3The experiment of/carbon nano-tube catalyst is reused more than 10 times, and its clearance still can remain on more than 80%, and Fe
2O
3-La
2O
3/ Al
2O
3Catalyst is only reused 5 its catalytic activitys and just is reduced to about 50% under identical experiment condition.Effective Raise of the present invention the efficient of MAOP catalyst, prolonged service life of MAOP catalyst, reduced catalyst amount, the MAOP technology is further expanded.And yet there are no report in the catalyst of the present invention document at home and abroad.
Description of drawings
Fig. 1 is that the variety classes catalyst is to the treatment effect figure of high concentration phenol waste water, among the figure-catalyst Fe that ■-expression the present invention synthesizes
2O
3-La
2O
3/ CNT is to the treatment effect curve of high concentration phenol waste water ,-◆-expression catalyst Fe
2O
3/ CNT is to the treatment effect curve of high concentration phenol waste water ,-▲-the expression catalyst Fe
2O
3-La
2O
3/ Al
2O
3Treatment effect curve to high concentration phenol waste water.Fig. 2 is the SEM figure that the specific embodiment 12 makes product.Fig. 3 is the EDAX figure that the specific embodiment 12 makes product.
The specific embodiment:
The specific embodiment one: the catalyst Fe that is used for carbon tube for microwave reinforced advanced oxidation technology in the present embodiment
2O
3-La
2O
3The preparation method of/CNT is realized by following step: one, CNT (CNTs) is carried out purification process, obtain purifying carbon nano-tube; Two, purifying carbon nano-tube is added stir 12～24h in the absolute ethyl alcohol, the weight of purifying carbon nano-tube and the volume ratio of absolute ethyl alcohol are 0.05～0.5g: 5～10mL; Three, after adding iron nitrate solution, the mixture that obtains to step 2 by the proportioning of purifying carbon nano-tube and ferric nitrate 0.05～0.5g: 0.5～5mmol stirs 10～24h, then with 0.2～1.0min/mL speed dropping ammonia solution to the pH value of solution=7～14, be about to iron hydroxide and be deposited on carbon nano tube surface; Four, have to surface deposition in the CNT of iron hydroxide by the proportioning of purifying carbon nano-tube and lanthanum nitrate 0.05～0.5g: 0.0005～0.01mmoL and add lanthanum nitrate hexahydrate, then with 0.2～1.0min/mL speed dropping ammonia solution to the pH=7 of solution～14, namely obtain lanthanum hydroxide in carbon nano tube surface, continue to stir 12～36h with 40～80r/min rotating speed again; Five, with the microwave continuous irradiation of the power 100～300W reactant 1～7min after step 4 is processed, in 65～95 ℃ of Water Unders are bathed, react 4～8h then, filter, will filter residue and clean three to five times, dry 3～12h under 100～110 ℃ of conditions namely gets catalyst precursor again; Six, catalyst precursor is put into Muffle furnace, be warming up to 300～400 ℃ with 1～5 ℃/min speed, roasting 60～180min is cooled to room temperature then; Namely obtain for carbon tube for microwave reinforced advanced oxidation technology Fe
2O
3-La
2O
3/ carbon nano-tube catalyst.
In the present embodiment in step 3 and the step 4 concentration of ammonia spirit be 0.05～0.5mol/L.
The catalyst that present embodiment makes, the modification aluminum trioxide catalyst of extensive use at present, then obviously improve service life; The modified carbon nano-tube catalyst experiment is reused more than 10 times, its clearance still can remain on more than 80%, and the modification aluminum trioxide catalyst is only reused 5 its catalytic activitys and just is reduced to about 50% under identical experiment condition, the catalyst use amount obviously reduces, and its consumption only is 1/100 of an alundum (Al.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: adopting Chinese patent application in the step 1 number is that method in 200710071862.3 the invention is carried out purification process to CNT; Wherein the method for CNT purification process is as follows: CNT be impregnated in the acid solution, and in microwave field, carry out back flow reaction, after making the acid solution boiling and keeping 15～30min, regulate microwave power and keep acid solution to be slight boiling condition, be cooled to room temperature behind reaction 15～30min, use the distilled water diluting acid solution again, leave standstill, CNT is precipitated fully, remove upper strata liquid, remaining carbon nano tube suspension water circulating pump suction filtration, washing CNT to the filtrate of dripping is neutral, oven dry.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one were different is: can also carry out ultrasonic processing, ultrasonic processing 10～60min after in the step 2 CNT being added absolute ethyl alcohol.Other is identical with the specific embodiment one.
The specific embodiment four: what present embodiment and the specific embodiment one were different is: microwave power is 150～220W in the step 5.Other is identical with the specific embodiment one.
The specific embodiment five: what present embodiment and the specific embodiment one were different is: microwave power is 200W in the step 5.Other is identical with the specific embodiment one.
The specific embodiment six: what present embodiment and the specific embodiment one were different is: react in the reactant water-bath under 70～90 ℃ of conditions in the step 5.Other is identical with the specific embodiment one.
The specific embodiment seven: what present embodiment and the specific embodiment one were different is: reactant reacts in the reactant water-bath under 75 ℃ of conditions in the step 5.Other is identical with the specific embodiment one.
The specific embodiment eight: what present embodiment and the specific embodiment one were different is: heating rate is 2～4 ℃/min in the step 6.Other is identical with the specific embodiment one.
The specific embodiment nine: what present embodiment and the specific embodiment one were different is: heating rate is 3 ℃/min in the step 6.Other is identical with the specific embodiment one.
The specific embodiment ten: what present embodiment and the specific embodiment one were different is: sintering temperature is 300～400 ℃ in the step 6.Other is identical with the specific embodiment one.
The specific embodiment 11: what present embodiment and the specific embodiment one were different is: sintering temperature is 350 ℃ in the step 6.Other is identical with the specific embodiment one.
The specific embodiment 12: the catalyst Fe that is used for carbon tube for microwave reinforced advanced oxidation technology in the present embodiment
2O
3-La
2O
3The preparation method of/CNT is realized by following step: one, adopting Chinese patent application number is that method in 200710071862.3 the invention is carried out purification process to CNT, obtains purifying carbon nano-tube; Two, stir 12～24h with adding the 5mL absolute ethyl alcohol in the 0.2g purifying carbon nano-tube; Three, stir 12h after adding again the iron nitrate solution that 10ml concentration is 0.2mol/L in the mixture that obtains to step 2, the volume ratio of iron nitrate solution and the weight of purifying carbon nano-tube are 2.5～25mL: 0.05～0.5g, drip the pH value of concentration as the ammonia spirit of 0.3mol/L to solution=10 take 0.5min/mL speed then; Namely obtain iron hydroxide in carbon nano tube surface; Four, in the reactant after step 3 is processed step to add 0.5mL concentration be the lanthanum nitrate hexahydrate of 0.005mol/L, ammonia spirit take 0.5min/mL speed dropping concentration as 0.3mol/L namely obtains lanthanum hydroxide in carbon nano tube surface to the pH=10 that drops to solution then; Continue to stir 24h with the 60r/min rotating speed again; Five, with the reactant 3min of microwave continuous irradiation after step 4 is processed of power 200W, in bathing, 75 ℃ of Water Unders react 6h then; Filter, will filter residue and clean three to five times, dry 6h under 110 ℃ of conditions namely gets catalyst precursor again; Six, catalyst precursor is put into Muffle furnace, be warming up to 350 ℃ with 3 ℃/min speed, roasting 60min; Be cooled to then room temperature; Namely obtain the Fe for MAOP
2O
3-La
2O
3/ carbon nano-tube catalyst.
The carbon nanotube carrier, the Fe that are used for MAOP
2O
3/ carbon nano-tube catalyst, Fe
2O
3-La
2O
3/ Al
2O
3The Fe that catalyst and present embodiment make
2O
3-La
2O
3/ carbon nano-tube catalyst to the treatment effect of high concentration phenol waste water 6000mg/L shown in 1.The technology contrast of above variety classes catalyst treatment phenolic waste water is as shown in table 1.This shows that the catalytic effect of present embodiment catalyst significantly improves.
As shown in Figure 2, the present embodiment load Fe
2O
3And La
2O
3As shown in Figure 3, the Fe that is used for MAOP that present embodiment makes
2O
3-La
2O
3The percentage by weight of ferro element is 34% in the/carbon nano-tube catalyst, and the percentage by weight of lanthanum element is 1.32%, and the percentage by weight of oxygen element is 15.35%.
Table 1 is the variety classes catalyst treatment phenolic waste water technology table of comparisons.
| Catalyst type | Phenol clearance (%) |
| |
50 |
| Fe 2O 3/ CNT | 73 |
| Fe 2O 3-La 2O 3/ CNT | 82 |
| Fe 2O 3-La 2O 3/ Al 2O 3 | 64 |
Claims (10)
1. the catalyst Fe that is used for carbon tube for microwave reinforced advanced oxidation technology
2O
3-La
2O
3The preparation method of/CNT is characterized in that the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology
2O
3-La
2O
3The preparation method of/CNT is realized by following step: one, CNT is carried out purification process, obtain purifying carbon nano-tube; Two, purifying carbon nano-tube is added stir 12～24h in the absolute ethyl alcohol, the weight of purifying carbon nano-tube and the volume ratio of absolute ethyl alcohol are 0.05～0.5g: 5～10mL; Three, stir 10～24h after adding iron nitrate solution in the mixture that obtains to step 2 by the proportioning of purifying carbon nano-tube and ferric nitrate 0.05～0.5g: 0.5～5mmol, then with 0.2～1.0min/mL speed dropping ammonia solution to the pH value of solution=7～14, be about to iron hydroxide and be deposited on carbon nano tube surface; Four, have to surface deposition in the CNT of iron hydroxide by the proportioning of purifying carbon nano-tube and lanthanum nitrate 0.05～0.5g: 0.0005～0.01mmoL and add lanthanum nitrate hexahydrate, then with 0.2～1.0min/mL speed dropping ammonia solution to the pH=7 of solution～14, namely obtain lanthanum hydroxide in carbon nano tube surface, continue to stir 12～36h with 40～80r/min rotating speed again; Five, with the microwave continuous irradiation of the power 100～300W reactant 1～7min after step 4 is processed, in 65～95 ℃ of Water Unders are bathed, react 4～8h then, filter, will filter residue and clean three to five times, dry 3～12h under 100～110 ℃ of conditions namely gets catalyst precursor again; Six, catalyst precursor is put into Muffle furnace, be warming up to 300～400 ℃ with 1～5 ℃/min speed, roasting 60～180min is cooled to room temperature then; Namely obtain the Fe for carbon tube for microwave reinforced advanced oxidation technology
2O
3-La
2O
3/ carbon nano-tube catalyst.
2. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT, it is characterized in that in the step 1 adopting Chinese patent application number is that method in 200710071862.3 the invention is carried out purification process to CNT; Wherein the method for Purification of Carbon Nanotubes processing is as follows: CNT be impregnated in the acid solution, and in microwave field, carry out back flow reaction, after making the acid solution boiling and keeping 15～30min, regulate microwave power and keep acid solution to be slight boiling condition, be cooled to room temperature behind reaction 15～30min, use again the distilled water diluting acid solution, leave standstill, CNT is precipitated fully, remove upper strata liquid, remaining carbon nano tube suspension water circulating pump suction filtration, washing CNT to the filtrate of dripping is neutral, oven dry.
3. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT carries out ultrasonic processing 10～60min after it is characterized in that in the step 2 CNT added absolute ethyl alcohol.
4. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT is characterized in that the concentration of ammonia spirit in step 3 and the step 4 is 0.05～0.5mol/L.
5. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT is characterized in that microwave power is 150～220W in the step 5.
6. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT is characterized in that microwave power is 200W in the step 5.
7. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT is characterized in that heating rate is 2～4 ℃/min in the step 6.
8. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT is characterized in that heating rate is 3 ℃/min in the step 6.
9. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT is characterized in that in the step 6 300～400 ℃ of sintering temperatures.
10. the catalyst Fe for carbon tube for microwave reinforced advanced oxidation technology according to claim 1
2O
3-La
2O
3The preparation method of/CNT is characterized in that in the step 6 350 ℃ of sintering temperatures.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100646297A CN101318136B (en) | 2008-05-30 | 2008-05-30 | Preparing method for catalyst Fe2O3-La2O3/ nano-carbon tube for microwave reinforced advanced oxidation technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100646297A CN101318136B (en) | 2008-05-30 | 2008-05-30 | Preparing method for catalyst Fe2O3-La2O3/ nano-carbon tube for microwave reinforced advanced oxidation technology |
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| CN101318136B true CN101318136B (en) | 2011-06-22 |
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| CN102773092B (en) * | 2012-07-10 | 2014-09-10 | 燕山大学 | Nano perovskite/carbon nanotube compound photocatalyst and preparation method thereof |
| CN107910191A (en) * | 2017-11-21 | 2018-04-13 | 太原理工大学 | Iron oxide based on microwave irradiation/carbon nano-tube combination electrode material preparation method |
| CN113842883B (en) * | 2021-10-27 | 2022-08-12 | 北京师范大学珠海校区 | Lanthanum-loaded iron carbon nanotube film material for environmental remediation and preparation method and application thereof |
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