CN103861611A - Preparation method and application of Cu-Mn catalyst loaded on aluminum-pillared montmorillonite - Google Patents
Preparation method and application of Cu-Mn catalyst loaded on aluminum-pillared montmorillonite Download PDFInfo
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- CN103861611A CN103861611A CN201410099382.8A CN201410099382A CN103861611A CN 103861611 A CN103861611 A CN 103861611A CN 201410099382 A CN201410099382 A CN 201410099382A CN 103861611 A CN103861611 A CN 103861611A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910017566 Cu-Mn Inorganic materials 0.000 title claims abstract description 14
- 229910017871 Cu—Mn Inorganic materials 0.000 title claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 44
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 31
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 31
- 239000011734 sodium Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000004411 aluminium Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000002459 sustained effect Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims 1
- -1 wherein Substances 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
一种铝柱撑蒙脱土负载Cu-Mn催化剂的制备方法和应用属于催化氧化CO领域。将自然界广泛存在的蒙脱土为原料，通过钠化和铝柱撑对蒙脱土原矿进行改性，将Cu和Mn负载在铝柱撑蒙脱土上制备催化剂，其中Cu和Mn负载量分别都为4.8～9wt%。本发明催化剂适用于高空速（60,000h-1～100,000h-1）CO的催化氧化。对于负载型Cu-Mn催化剂，在温度为180℃时，可以完全（100%转化率）将CO转化成CO2，在此温度下，100小时内保持CO≈100%转化率。
A preparation method and application of an aluminum pillared montmorillonite supported Cu-Mn catalyst belong to the field of catalytic oxidation of CO. Using montmorillonite widely existing in nature as raw material, the montmorillonite raw ore was modified by sodium and aluminum pillars, and Cu and Mn were supported on the aluminum pillared montmorillonite to prepare the catalyst, in which the Cu and Mn loadings were respectively Both are 4.8-9wt%. The catalyst of the present invention is suitable for catalytic oxidation of CO at high space velocity (60,000h -1 to 100,000h -1 ). For the supported Cu-Mn catalyst, CO can be completely (100% conversion) converted to CO 2 at a temperature of 180 °C, and CO ≈ 100% conversion can be maintained within 100 hours at this temperature.
Description
Technical field
The present invention relates to a kind of aluminium pillared montmorillonite load type Catalysts and its preparation method and application for CO catalytic oxidation.
Background technology
CO is one of main air pollutants, is seriously endangering people's Health and Living.CO catalytic oxidation has practical application widely, as: in fuel cell, the hydrogen-rich gas that utilizes methanol recapitalization to produce, and the CO containing in common this mixture can cause Pt catalyst poisoning, effectively selectively removes H
2in a small amount of CO gas of mixing, for the normal work of fuel cell, be very important.The various aspects such as the CO elimination in CO sensor, breathing mask and closed system all relate to the catalytic oxidation problem of CO.Therefore, efficient, the low cost CO catalyst for catalytic oxidation of research and development has wide industrial prospect.
For realizing the catalytic oxidation of CO, the selection of catalyst and preparation are vital.Before the eighties in last century, it is mainly the noble metal catalyst taking Pt, Pd as active component that CO is oxidized catalyst used, but can only be applicable to the catalytic oxidation that CO concentration is lower.Manganese and Cu oxide, inexpensive because of its cost, the many merits such as high activity and durability, are widely used in various important reactions, and China has compared with the manganese of horn of plenty and copper resource.In view of the catalytic activity that manganese and copper catalyst possess, develop can continuous and effective CO catalytic oxidation effective catalyst have great importance.
This project implementation obtains project of national nature science fund project (21277008); Project of national nature science fund project (20777005); The subsidy of Education Commission of Beijing development in science and technology plan general project (KM2013100050010) is also the research contents of these projects.
Summary of the invention
The object of this invention is to provide a kind of preparation of aluminium pillared montmorillonite load Cu-Mn catalyst and for CO catalytic oxidation pollutant, the catalyst providing can be oxidized CO being less than under 300 DEG C of reaction temperatures, and obtain higher CO conversion ratio, catalyst stability is high, and preparation technology is simple, raw material extensively exist at nature.
The preparation of aluminium pillared montmorillonite provided by the invention is catalyst carrier, and Cu-Mn is carried on aluminium pillared montmorillonite carrier and makes catalyst.With imvite and aluminium chloride be raw material, use copolymerization method prepare aluminium pillared montmorillonite carrier, utilize improved infusion process loaded Cu-Mn catalyst.Concrete preparation is achieved through the following technical solutions:
The preparation method of above-mentioned catalyst provided by the present invention, comprises the steps:
According to a certain percentage the imvite of purification is joined and in distilled water, stir into thick shape solution, wherein water: imvite (mass ratio)=(5～10): 1, taking subsequently a certain proportion of NaCl is added in above-mentioned slurries, wherein slurries: NaCl(mass ratio)=(90～100): 1, under 60～80 DEG C of conditions, react 1～3 hour, centrifuge washing 8～12 times subsequently, until without Cl
-detect, product is placed in to 120～140 DEG C and is dried 24～48 hours, make sodium imvite.
Under 60～80 DEG C of conditions of temperature, the NaOH solution of 0.1～0.3mol/L is added to the AlCl of 0.1～0.3mol/L with the speed of 1～2ml/min
3in solution, wherein ([Al
3+]: [OH
-] (mol ratio)=(1～3): 1), continue to stir 1～3 hour, put 22～26 hours gentle and quiet solution chamber subsequently, obtain aluminium pillaring agent.
By a certain percentage above-mentioned sodium imvite is joined in distilled water, in distilled water: sodium imvite (mass ratio)=100:(1～3)) ratio makes sodium imvite suspension slurry, at ambient temperature, above aluminium post liquid is dropwise dropped in sodium imvite suspension slurry to wherein sodium imvite (mass number): [Al
3+] (molal quantity)=1g:(3～7) mmol, under 50～70 DEG C of temperature conditions, sustained response 1～3 hour, at room temperature leaves standstill 22～26 hours, and centrifuge washing 4～7 times detects until without Cl
-, 120～140 DEG C of dry 20～24h, take out dried product and grind and sieve, and put it into subsequently in muffle furnace, rise to 300～500 DEG C with 1～2 DEG C/min heating rate, keep this temperature to calcine 1～3 hour, and gained sample is aluminium pillared montmorillonite.
2, immerse stain legal system for aluminium pillared montmorillonite load Cu and Mn catalyst
By Mn (NO
3)
24H
2o and Cu (NO
3)
26H
2o is dissolved in distilled water, is made into molar concentration and is respectively 7～9mol/L solution, and wherein the mol ratio of Mn and Cu is 1:1.Above manganese nitrate and copper nitrate mixed solution are added to aluminium pillared montmorillonite, wherein the mass ratio of MnO and aluminium pillared montmorillonite is (0.05～0.1): 1, stir 1～2 hour, at room temperature leave standstill 24～48 hours subsequently, 120～140 DEG C are dried 24～48 hours, then in Muffle furnace, are warming up to 400 DEG C～500 DEG C with 1～3 DEG C/min, and keep this temperature calcining 4～6 hours, obtain MnO-CuO/ montmorillonite catalyst.
(3) catalyst of the present invention, (60,000h under high-speed
-1～100,000h
-1), 1%CO concentration is had to higher catalytic oxidation activity: 1) MnO-CuO/ montmorillonite catalyst is completely oxidized to CO by CO in the time of 180 DEG C～270 DEG C
2, in 100 hours, keep ≈ 100%CO oxygenation efficiency; 2) raw material that Kaolinite Preparation of Catalyst uses and preparation process is simple to operation, low price.The present invention does not need additional any fuel, directly utilizes O in air
2for oxidant, have that raw material are economical and practical, use procedure energy consumption is low, easy and simple to handle, reaction condition is gentle, can reduce secondary pollution and can continuous operation etc. advantage.
Imvite is a kind of natural silicate clay mineral, there is large specific area, the commutative performance of good absorption property and interlayer cation, it is a kind of good catalyst carrier, aluminium pillared montmorillonite is that hydroxy Al ion is inserted into a kind of duct composite between cheating engaging layer, utilize its table specific area large, heat resistance high, it is carried out to Cu-Mn Metal Supported, obtain Cu-Mn support type aluminium pillared montmorillonite, this catalyst has larger specific area and pore structure equally, the features such as higher heat resistance, aspect processing atmosphere pollution especially benzo pollutants, showing good application prospect as catalyst.
Brief description of the drawings
The XRD figure of M, Na-M, Al-PILC, Cu/PILC, Mn/PILC and the Cu-Mn/PILC of Fig. 1 embodiment 1,2 and 3 preparations
Fig. 2 is the CO catalytic combustion activity figure of the Cu-Mn/PILC for preparing of the embodiment of the present invention 3
Fig. 3 is the CO stability of the Cu-Mn/PILC for preparing of the embodiment of the present invention 3
Detailed description of the invention
Embodiment 1
(1) preparation of aluminium pillared montmorillonite carrier
According to a certain percentage the imvite of purification is joined and in distilled water, stir into thick shape solution, water: imvite (mass ratio)=5:1, taking subsequently a certain proportion of NaCl is added in above-mentioned slurries, wherein slurries: NaCl(mass ratio)=90:1,60 DEG C of reactions 1 hour, centrifuge washing 8 times subsequently, until without Cl
-detect, product is placed in to 120 DEG C and is dried 24 hours, make sodium imvite.
In the time of 60 DEG C, the NaOH solution of 0.1mol/L is added to the AlCl of 0.1mol/L with the speed of 1ml/min
3in solution, wherein [Al
3+]: [OH
-] (mol ratio)=1:1, continue to stir 1 hour, put 22 hours gentle and quiet solution chamber subsequently, obtain aluminium pillaring agent.
By a certain percentage above-mentioned sodium imvite is joined in distilled water, in distilled water: sodium imvite (mass ratio)=100:1) ratio makes sodium imvite suspension slurry, at ambient temperature, above aluminium post liquid is dropwise dropped in sodium imvite suspension slurry to wherein sodium imvite (mass number): [Al
3+] (molal quantity)=1g:3mmol, sustained response 1 hour at 50 DEG C, at room temperature leaves standstill 22 hours, and centrifuge washing 4 times detects until without Cl
-, 120 DEG C of dry 20h, take out dried product and grind and sieve, and put it into subsequently in muffle furnace, rise to 300 DEG C with 1 DEG C/min heating rate, keep this temperature calcining 1 hour, and gained sample is aluminium pillared montmorillonite.
(2) immerse stain legal system for aluminium pillared montmorillonite load Mn catalyst
By Mn (NO
3)
24H
2o is dissolved in distilled water, is made into 7mol/L solution.In the situation that stirring, above manganese nitrate solution is added to aluminium pillared montmorillonite, wherein the mass ratio of MnO and aluminium pillared montmorillonite is 0.05:1, stir 1 hour, at room temperature leave standstill 24 hours subsequently, 120 DEG C are dried 24 hours, again in Muffle furnace, be warming up to 400 DEG C with 1 DEG C/min, and keep this temperature calcining 4 hours, obtain MnO/ montmorillonite catalyst.
(3) catalyst activity evaluation.The concentration of CO is 1%, and air speed is 60,000h
-1.Gas-chromatography TCD detection reaction tail gas CO content.100% of the obtained catalyst of the embodiment of the present invention 1 oxidation CO(CO transforms) temperature be 240 DEG C, when temperature is in the scope of 100 DEG C～200 DEG C, CO conversion ratio straight line raises until reach 100%.
Embodiment 2
(1) preparation of aluminium pillared montmorillonite carrier
According to a certain percentage the imvite of purification is joined and in distilled water, stir into thick shape solution, wherein water: imvite (mass ratio)=8:1, taking subsequently a certain proportion of NaCl is added in above-mentioned slurries, wherein slurries: NaCl(mass ratio)=95:1,70 DEG C of reactions 2 hours, centrifuge washing 10 times subsequently, until without Cl
-detect, product is placed in to 130 DEG C and is dried 36 hours, make sodium imvite.
Under temperature 70 C condition, the NaOH solution of 0.2mol/L is added in the extreme to the AlCl of 0.2mol/L with the speed of 1.5ml/min
3in solution, wherein [Al
3+]/[OH
-] (mol ratio)=2:1, continue to stir 2 hours, put 24 hours gentle and quiet solution chamber subsequently, obtain aluminium pillaring agent.
By a certain percentage above-mentioned sodium imvite is joined in distilled water, in distilled water: sodium imvite (mass ratio)=100:2 ratio is made sodium imvite suspension slurry, at ambient temperature, above aluminium post liquid is dropwise dropped in sodium imvite suspension slurry to wherein sodium imvite (mass number): [Al
3+] (molal quantity)=1g:5mmol, under 60 DEG C of temperature conditions, sustained response 2 hours, at room temperature leaves standstill 24 hours, and centrifuge washing 5 times detects until without Cl
-, 130 DEG C of dry 22h, take out dried product and grind and sieve, and put it into subsequently in muffle furnace, rise to 400 DEG C with 1.5 DEG C/min heating rate, keep this temperature calcining 2 hours, and gained sample is aluminium pillared montmorillonite.
(2) immerse stain legal system for aluminium pillared montmorillonite load Cu-Mn catalyst
By Mn (NO
3)
24H
2o and Cu (NO
3)
26H
2o is dissolved in distilled water, is made into molar concentration and is respectively 8mol/L solution, and wherein the mol ratio of Mn and Cu is 1.5:1.5.In the situation that stirring, above manganese nitrate and copper nitrate mixed solution are added to aluminium pillared montmorillonite, wherein the mass ratio of MnO and aluminium pillared montmorillonite is 0.08:1, stir 1.5 hours, at room temperature leave standstill 36 hours subsequently, 130 DEG C are dried 36 hours, again in Muffle furnace, be warming up to 450 DEG C with 2 DEG C/min, and keep this temperature calcining 5 hours, obtain MnO-CuO/ montmorillonite catalyst.
(3) catalyst activity evaluation.The concentration of CO is 1%, and air speed is 80,000h
-1.Gas-chromatography TCD detection reaction tail gas CO content.100% of the obtained catalyst of the embodiment of the present invention 1 oxidation CO(CO transforms) temperature be 180 DEG C, when temperature is in the scope of 100 DEG C～160 DEG C, CO conversion ratio straight line raises until reach 100%.
Embodiment 3
(1) preparation of aluminium pillared montmorillonite carrier
According to a certain percentage the imvite of purification is joined and in distilled water, stir into thick shape solution, water: imvite (mass ratio)=10:1, taking subsequently a certain proportion of NaCl is added in above-mentioned slurries, wherein slurries: NaCl(mass ratio)=100:1, under 80 DEG C of conditions, react 3 hours, centrifuge washing 12 times subsequently, until without Cl
-detect, product is placed in to 140 DEG C and is dried 48 hours, make sodium imvite.
Under 80 DEG C of conditions of temperature, the NaOH solution of 0.3mol/L is added in the extreme to the AlCl of 0.1～0.3mol/L with the speed of 2ml/min
3in solution, wherein [Al
3+]/[OH
-] (mol ratio)=3, continue to stir 3 hours, put 26 hours gentle and quiet solution chamber subsequently, obtain aluminium pillaring agent.
By a certain percentage above-mentioned sodium imvite is joined in distilled water, in distilled water: sodium imvite (mass ratio)=100:3 ratio is made sodium imvite suspension slurry, at ambient temperature, above aluminium post liquid is dropwise dropped in sodium imvite suspension slurry to wherein sodium imvite (mass number): [Al
3+] (molal quantity)=1g:7mmol, under 70 DEG C of temperature conditions, sustained response 3 hours, at room temperature leaves standstill 26 hours, and centrifuge washing 7 times detects until without Cl
-, 140 DEG C of dry 24h, take out dried product and grind and sieve, and put it into subsequently in muffle furnace, rise to 500 DEG C with 2 DEG C/min heating rate, keep this temperature calcining 3 hours, and gained sample is aluminium pillared montmorillonite.
(2) immerse stain legal system for aluminium pillared montmorillonite load Cu catalyst
By Cu (NO
3)
26H
2o is dissolved in distilled water, is made into 9mol/L solution.In the situation that stirring, above copper nitrate mixed solution is added to aluminium pillared montmorillonite, wherein the mass ratio of CuO and aluminium pillared montmorillonite is 0.05:1, stir 2 hours, at room temperature leave standstill 48 hours subsequently, 140 DEG C are dried 48 hours, again in Muffle furnace, be warming up to 500 DEG C with 3 DEG C/min, and keep this temperature calcining 6 hours, obtain MnO-CuO/ montmorillonite catalyst.
(3) catalyst activity evaluation.The concentration of CO is 1%, and air speed is 100,000h
-1.Gas-chromatography TCD detection reaction tail gas CO content.100% of the obtained catalyst of the embodiment of the present invention 1 oxidation CO(CO transforms) temperature be 270 DEG C, when temperature is in the scope of 100 DEG C～260 DEG C, CO conversion ratio straight line raises until reach 100%.
Claims (2)
1. a preparation method for aluminium pillared montmorillonite load Cu-Mn catalyst, is characterized in that:
Imvite is joined and in distilled water, stirs into slurries, wherein water: mass ratio=(5～10) of imvite: 1, taking subsequently NaCl is added in above-mentioned slurries, wherein, mass ratio=(90～100) of slurries: NaCl: 1, under 60～80 DEG C of conditions, react 1～3 hour, centrifuge washing 8～12 times subsequently, until without Cl
-detect, product is placed in to 120～140 DEG C and is dried 24～48 hours, make sodium imvite;
Under 60～80 DEG C of conditions of temperature, the NaOH solution of 0.1～0.3mol/L is added to the AlCl of 0.1～0.3mol/L with the speed of 1～2ml/min
3in solution, wherein [Al
3+]: [OH
-] mol ratio=(1～3): 1, continue stir 1～3 hour, put 22～26 hours gentle and quiet solution chamber subsequently, obtain aluminium pillaring agent;
Above-mentioned sodium imvite is joined in distilled water, in distilled water: mass ratio=100:(1～3 of sodium imvite) ratio makes sodium imvite suspension slurry, the drop of above aluminium pillaring agent is added in sodium imvite suspension slurry, wherein, sodium imvite: [Al
3+] add ratio=1g:(3～7) mmol, under 50～70 DEG C of temperature conditions, sustained response 1～3 hour, leaves standstill 22～26 hours, centrifuge washing 4～7 times detects until without Cl
-, 120～140 DEG C of dry 20～24h, take out dried product and grind and sieve, and put it into subsequently in muffle furnace, rise to 300～500 DEG C with 1～2 DEG C/min heating rate, keep this temperature to calcine 1～3 hour, and gained sample is aluminium pillared montmorillonite;
By Mn (NO
3)
24H
2o and Cu (NO
3)
26H
2o is dissolved in distilled water, is made into molar concentration 7～9mol/L solution respectively, and wherein the mol ratio of Mn and Cu is 1:1; In the situation that stirring, above manganese nitrate and copper nitrate mixed solution are added to aluminium pillared montmorillonite, wherein the mass ratio of MnO and aluminium pillared montmorillonite is (0.05～0.1): 1, stir 1～2 hour, leave standstill 24～48 hours subsequently, 120～140 DEG C are dried 24～48 hours, again in Muffle furnace, be warming up to 400 DEG C～500 DEG C with 1～3 DEG C/min, and keep this temperature calcining 4～6 hours, obtain MnO-CuO/ montmorillonite catalyst.
2. the catalyst that according to claim 1 prepared by method, in the application of CO catalytic oxidation, is characterized in that: above-mentioned catalyst is placed on and in continuous-flow fixed bed device, passes into CO and react with air Mixture.Reaction pressure is normal pressure～2MPa, and reaction velocity is 60,000h
-1～100,000h
-1, in air and CO gaseous mixture, the concentration of CO is 1%, 25～300 DEG C of reaction temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410099382.8A CN103861611A (en) | 2014-03-17 | 2014-03-17 | Preparation method and application of Cu-Mn catalyst loaded on aluminum-pillared montmorillonite |
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| CN105540542A (en) * | 2015-12-07 | 2016-05-04 | 铜陵市明诚铸造有限责任公司 | Preparation process of Mn-Cu/Al-PILM deoxidizing agent |
| CN105709750A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Copper pillared montmorillonite catalyst, and preparation method and application thereof |
| CN106861607A (en) * | 2017-03-17 | 2017-06-20 | 武汉理工大学 | A kind of preparation method of the modified carbon/montmorillonite Composite sorbing material of organic-inorganic |
| CN108290142A (en) * | 2015-11-24 | 2018-07-17 | 株式会社世Fa | The complex composition for pernicious gas removal containing copper-manganese catalyst |
| CN109482141A (en) * | 2018-12-22 | 2019-03-19 | 北京工业大学 | The preparation method and application of aluminium pillared montmorillonite load C a-Nb compound adsorbent |
| CN110013826A (en) * | 2018-12-22 | 2019-07-16 | 北京工业大学 | Preparation method and application of aluminum pillared montmorillonite supported K-Nb or Mg-Nb composite adsorbent |
| CN115007125A (en) * | 2022-07-08 | 2022-09-06 | 湘潭大学 | Sepiolite supported manganese-cerium composite catalyst and preparation method and application thereof |
| CN115301243A (en) * | 2022-07-15 | 2022-11-08 | 西北大学 | A supported perovskite catalyst, preparation method and application thereof |
| CN116116387A (en) * | 2022-11-01 | 2023-05-16 | 邵阳学院 | A kind of soil heavy metal adsorbent and preparation method thereof |
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| CN105709750A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Copper pillared montmorillonite catalyst, and preparation method and application thereof |
| CN105709750B (en) * | 2014-12-04 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of copper pillared montmorillonite catalyst and its preparation method and application |
| CN108290142A (en) * | 2015-11-24 | 2018-07-17 | 株式会社世Fa | The complex composition for pernicious gas removal containing copper-manganese catalyst |
| CN108290142B (en) * | 2015-11-24 | 2021-04-27 | 株式会社世一Fa | Composite composition for harmful gas removal containing copper-manganese catalyst |
| CN105540542A (en) * | 2015-12-07 | 2016-05-04 | 铜陵市明诚铸造有限责任公司 | Preparation process of Mn-Cu/Al-PILM deoxidizing agent |
| CN106861607A (en) * | 2017-03-17 | 2017-06-20 | 武汉理工大学 | A kind of preparation method of the modified carbon/montmorillonite Composite sorbing material of organic-inorganic |
| CN110013826A (en) * | 2018-12-22 | 2019-07-16 | 北京工业大学 | Preparation method and application of aluminum pillared montmorillonite supported K-Nb or Mg-Nb composite adsorbent |
| CN109482141A (en) * | 2018-12-22 | 2019-03-19 | 北京工业大学 | The preparation method and application of aluminium pillared montmorillonite load C a-Nb compound adsorbent |
| CN109482141B (en) * | 2018-12-22 | 2021-10-15 | 北京工业大学 | Preparation method and application of aluminum-pillared montmorillonite-supported Ca-Nb composite adsorbent |
| CN110013826B (en) * | 2018-12-22 | 2022-05-24 | 北京工业大学 | Preparation method and application of aluminum-pillared montmorillonite supported K-Nb or Mg-Nb composite adsorbent |
| CN115007125A (en) * | 2022-07-08 | 2022-09-06 | 湘潭大学 | Sepiolite supported manganese-cerium composite catalyst and preparation method and application thereof |
| CN115301243A (en) * | 2022-07-15 | 2022-11-08 | 西北大学 | A supported perovskite catalyst, preparation method and application thereof |
| CN115301243B (en) * | 2022-07-15 | 2024-01-05 | 浙江聚泰新能源材料有限公司 | Supported perovskite catalyst, preparation method and application thereof |
| CN116116387A (en) * | 2022-11-01 | 2023-05-16 | 邵阳学院 | A kind of soil heavy metal adsorbent and preparation method thereof |
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