CN105457654B - Catalyst of room temperature catalytic oxidation removing formaldehyde and preparation method thereof - Google Patents

Catalyst of room temperature catalytic oxidation removing formaldehyde and preparation method thereof Download PDF

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CN105457654B
CN105457654B CN201510921942.8A CN201510921942A CN105457654B CN 105457654 B CN105457654 B CN 105457654B CN 201510921942 A CN201510921942 A CN 201510921942A CN 105457654 B CN105457654 B CN 105457654B
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ceo
catalyst
room temperature
carrier
noble metal
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CN105457654A (en
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杜世睿
王杰
余泽宇
杨泽奇
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Xiamen Yujing Environmental Protection Science And Technology Co Ltd
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Xiamen Yujing Environmental Protection Science And Technology Co Ltd
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Abstract

The invention discloses a kind of catalyst and preparation method thereof for being capable of efficient stable catalysis oxidation removal formaldehyde at room temperature, and the methanal removing catalyst is using noble metal non-noble metal nano alloy as active component, to make CeO by oneself2For carrier, general formula is expressed as M1M2/CeO2, M1 represents one kind in noble metal Ru, Rh, Pt, Pd in formula, and M2 represents one kind in base metal Fe, Co, Ni, Cu, by mass percentage, it is 0.05% ~ 5%, preferably 0.1% ~ 3% that the content of catalyst components, which is M1, M2 is 1% ~ 15%, preferably 2% ~ 12%, and surplus is support C eO2.Preparation method：With hydro-thermal legal system CeO2Carrier, with alcohothermal method by noble metal non-noble metal nano alloying pellet load C eO2Carrier.Prepared catalyst has excellent room temperature catalytic oxidation removing formaldehyde catalytic performance, and with good stability.

Description

Catalyst of room temperature catalytic oxidation removing formaldehyde and preparation method thereof
Technical field
The present invention relates to room temperature, often it is wet under the conditions of the formaldehyde pollutants in air are completely oxidized to harmless titanium dioxide Efficient stable catalyst of carbon and water and preparation method thereof, suitable for removal Wood-based Panel Production workshop, room, household building materials market Deng closing or the formaldehyde pollution of hemi-closure space, belong to chemical engineering industry catalysis, environmental protection, catalysis material technical field.
Background technology
The main harm of formaldehyde is shown as to mucocutaneous stimulation, when formaldehyde reaches a certain concentration indoors, people Just there is sense of discomfort.Concentration of formaldehyde more than 0.08m3 can cause furious, eye to be itched, throat discomfort or pain, hoarseness, sneeze, Uncomfortable in chest, asthma, dermatitis etc..Newly-decorated room content of formaldehyde is higher, is the main inducing of numerous diseases.Formaldehyde is to eye, nose, larynx Mucous membrane have a strong impulse effect, most common symptom is exactly that eyes are stimulated and headache, serious to cause anaphylaxis skin Scorching and asthma.The protein coagulating in cell is denaturalized since formaldehyde can generate nitrogen methylidyne compound with albumen qualitative response, Thus function capable of inhibiting cell.In addition, formaldehyde can also react generation dichlormetbylether with the ionic chloride in air, then Person is a kind of carcinogen.Formaldehyde can again be released by indoor high-ratio surface material adsorption and enrichment when indoor temperature increases It releases, aggravates polluting effect.China《Indoor Air Quality standards》The limit value for providing formaldehyde in indoor air is 0.10mg/ m3。
The major technique for being presently used for eliminating formaldehyde is as adsorbent using activated carbon, and such method is relatively simple, but Purification cycle is long, and activated carbon needs to regularly replace.Ideal elimination method of formaldehyde is catalytic oxidation technologies, the method be By formaldehyde through catalytic oxidation it is to the mankind harmless H completely using air under the catalytic action of catalyst2O and CO2.Catalysis oxidation disappears Except the key of formaldehyde technology is low cost and efficient cryogenic（Preferably room temperature）The research and development of stable catalyst.Can room temperature compared with Catalyst to effectively eliminate formaldehyde is mostly noble metal catalyst, such as nanocube CeO2The Pd of load（1wt%）Catalyst energy It is 10000 h in room temperature and air speed−1Under the conditions of effectively remove formaldehyde（Concentration：600ppm）（Environmental Science& Technology2015, 49, 8675−8682）.Compared with conventional impregnation method, deposition-precipitation prepare and it is pre- through formalin The Pt/TiO of reduction2Catalyst has good methanal removing performance, even if the load capacity of Pt is down to 0.4 % and in room temperature condition Under, in 100 h of METHOD FOR CONTINUOUS DETERMINATION, effective removing formaldehyde can be stablized, but the catalyst is only applicable to the formaldehyde of removing low concentration （50 ppb）（Chinese Journal of Catalysis 201536 188–196）.0.1%Pt/TiO2Catalyst is steamed in water Gas（Humidity 30%）Under existence condition, the formaldehyde that pollution concentration is 22 ppm can be removed completely, but in dry conditions in room temperature, Removing same amount formaldehyde, the load capacity of Pt will be up to 1% completely（Applied Catalysis B: Environmental 2015 163 436–443）.Low cost（Low noble metal dosage）, efficiently and persistently effective formaldehyde eliminates catalyst to room temperature is still research and development Hot and difficult issue.
Invention content
The object of the present invention is to provide room temperature activity height, stability are good and at low cost（Low noble metal dosage）A kind of catalysis Catalyst of oxidation removal formaldehyde and preparation method thereof.
To achieve the above object, solution of the invention is：
A kind of catalyst of room temperature catalytic oxidation removing formaldehyde, it is characterised in that with noble metal-non-noble metal nano alloy For active component, to make CeO by oneself2For carrier, general formula is expressed as M1M2/CeO2, M1 represents noble metal Ru, Rh, Pt, Pd in formula In one kind, M2 represents one kind in base metal Fe, Co, Ni, Cu, and by mass percentage, the content of catalyst components is M1 is that 0.05% ~ 5%, M2 is 1% ~ 15%, and surplus is support C eO2。
By mass percentage, M1 contents are that 0.1% ~ 3%, M2 contents are 2% ~ 12% to the catalyst components, remaining Loading gage body CeO2。
The CeO2The preparation method of carrier is synthesized with hydro-thermal method, is as follows：
1）By the desired amount of Ce (NO3)3·6H2O aqueous solutions are added in water heating kettle and are stirred；
2）NaOH solution to mixed liquor pH value is added dropwise and is more than 10, continues to stir after being added dropwise to complete；
3）It is placed in baking oven dry；
4）It filters, wash, is dry；
5）CeO is made in Muffle kiln roasting2Carrier.
The step 2）In be added dropwise to complete after continue stir 30min.
The step 3）Drying temperature for 80 ~ 120 o C, drying time is 12 ~ 24 h.
The step 5）Calcination temperature for 300 ~ 500 oC, roasting time is 2 ~ 5 h.
A kind of preparation method of the catalyst of room temperature catalytic oxidation removing formaldehyde, it is characterised in that with the hot method reduction system of alcohol It is standby, it is as follows：
1）The desired amount of glycerine and self-control CeO are added in round-bottomed flask2Carrier（100mL glycerine/1gCeO2）, surpass 60 min of sound；
2）Base metal precursor salt and precious metal solution are added in, 1 h is stirred under the protection of inert gas；
3）Mixed liquor pH value, which is adjusted, with NaOH- glycerin solutions is more than 10；
4）It is cooled to room temperature, adjusting solution ph with HCl solution is less than 3, continues 2 ~ 5 h of stirring；
5）It filters, wash, is dry；
6）N2It is roasted in atmosphere and M1M2/CeO is made2Catalyst.
The step 3）It is middle to adjust mixed liquor pH value more than 10,120 ~ 180 o C perseverances with NaOH- glycerin solutions 2 ~ 5 h of temperature.
The step 6）Calcination temperature for 300 ~ 500 o C, roasting time is 2 ~ 5 h.
The room temperature catalytic oxidation that room temperature catalytic oxidation removing formaldehyde catalyst of the present invention is suitable for formaldehyde pollutants takes off It removes, before use with being reacted after 1 h of hydrogen 350oC prereduction, formaldehyde pollutants concentration≤1000ppm, suitable for reaction pressure Power >=normal pressure, suitable for reaction temperature >=room temperature.
Catalyst provided by the invention is compared with conventional load type noble metal catalyst, since noble metal-your non-gold used Belong to Nanoalloy as active component so that required bullion content substantially reduces（0.1% can be less than）, saved cost.By There are electronics between noble metal and base metal（It transmits）Interaction, therefore the catalyst of the present invention has good room temperature first Aldehyde catalyzed conversion performance.In addition, the electron interaction between noble metal and base metal also causes catalyst of the present invention to have Good stability, in 200 h of follow-on test, excellent stable in catalytic performance remains unchanged.
Description of the drawings
Fig. 1 is Pt of the present invention0.1Co4.0/CeO2Catalyst formaldehyde catalytic eliminating stability test chart.
Specific embodiment
Present invention is disclosed a kind of catalyst of room temperature catalytic oxidation removing formaldehyde, with noble metal-non-noble metal nano Alloy is active component, to make CeO by oneself2For carrier, general formula is expressed as M1M2/CeO2, in formula M1 represent noble metal Ru, Rh, One kind in Pt, Pd, M2 represent one kind in base metal Fe, Co, Ni, Cu, and by mass percentage, catalyst components contain It is 0.05% ~ 5%, M2 is 1% ~ 15% that amount, which is M1, and surplus is support C eO2。
By mass percentage, M1 contents are that 0.1% ~ 3%, M2 contents are 2% ~ 12% to further catalyst components, Balance carriers CeO2。
The CeO2The preparation method of carrier is synthesized with hydro-thermal method, is as follows：
1）By the desired amount of Ce (NO3)3·6H2O aqueous solutions are added in water heating kettle and are stirred；
2）NaOH solution to mixed liquor pH value is added dropwise and is more than 10, continues to stir 30min after being added dropwise to complete；
3）Dry 12 ~ 24 h are placed in 80 ~ 120 o C baking ovens；
4）It filters, wash, is dry；
5）300 ~ 500 oC roast 2 ~ 5 h in Muffle furnace, and CeO is made2Carrier.
A kind of preparation method of the catalyst of room temperature catalytic oxidation removing formaldehyde, is prepared with the hot method reduction of alcohol, specific to walk It is rapid as follows：
1）The desired amount of glycerine and self-control CeO are added in round-bottomed flask2Carrier（100mL glycerine/1gCeO2）, surpass 60 min of sound；
2）Base metal precursor salt and precious metal solution are added in, 1 h is stirred under the protection of inert gas；
3）Mixed liquor pH value, which is adjusted, with NaOH- glycerin solutions is more than 10,120 ~ 180 o C constant temperature, 2 ~ 5 h；
4）It is cooled to room temperature, adjusting solution ph with HCl solution is less than 3, continues 2 ~ 5 h of stirring；
5）It filters, wash, is dry；
6）N2300 ~ 500 o C roast 2 ~ 5 h in atmosphere, and M1M2/CeO is made2Catalyst.
Here is the embodiment of the present invention, but the present invention is not limited only to these embodiments.
Embodiment 1
Catalyst preparation
By 6 g Ce (NO3)3·6H2O adds in hydrothermal reaction kettle and stirs after being dissolved in 40 mL deionized waters, be added dropwise PH value of solution is adjusted to 12 by 10%NaOH, after 30 min of ultrasound, by hydrothermal reaction kettle in 18 h of 100oC constant temperature, be down to room temperature filtering, Washing, 400 oC roast 4 h and CeO are made in Muffle furnace after drying2Carrier.
Weigh the CeO prepared by 1g2Carrier is placed in the round-bottomed flask of 250mL, adds in 100mL glycerine, ultrasonic 60min Afterwards, 0.1600 g FeSO are added in4·4H2O and 2.08mLRuCl3Solution（1mg Ru/mL）And it is passed through N2It is protected, after 1 h Mixed liquor pH value is adjusted to 13 with the NaOH of 1mol/L, then in 4 h of 150oC constant temperature, is cooled to room temperature, is adjusted and mixed with HCl Liquid pH value is to 1.5, and after 12 h are stirred at room temperature, washing filters, is dry, most after N2400 oC roast 4 h and are made in atmosphere Ru0.1Fe4.0/CeO2Catalyst.
Examination condition：Before reaction, catalyst uses 1 h of hydrogen prereduction under 350oC.It is carried out in continuous flow fixed bed Reaction, 15000 h of reaction velocity-1, 500 ppm of formaldehyde pollutants concentration, room temperature, normal pressure, gas chromatographic detection.Appraisal result It is shown in Table 1.
Embodiment 2
Catalyst preparation is with reference to embodiment 1, by RuCl3Solution is exchanged with 2.64mL 1mg/mL H2PtCl6·6H2O solution. Remaining condition is identical, and Pt is made0.1Fe4.0/CeO2Catalyst.For examination condition with embodiment 1, appraisal result is shown in Table 1.
Embodiment 3
Catalyst preparation is with reference to embodiment 1, by RuCl3Solution is exchanged with 2.56mL 1mg/mL RhCl3·3H2O solution.Its Remaining condition is identical, and Rh is made0.1Fe4.0/CeO2Catalyst.For examination condition with embodiment 1, appraisal result is shown in Table 1.
Embodiment 4
Catalyst preparation is with reference to embodiment 1, by RuCl3Solution is exchanged with 1.68mL 1mg/mLPdCl2Solution.Remaining condition phase Together, Pd is made0.1Fe4.0/CeO2Catalyst.For examination condition with embodiment 1, appraisal result is shown in Table 1.
The formaldehyde catalytic eliminating performance of the different noble metal-non-noble metal nano alloy catalysts of table 1a
Embodiment Catalyst Formaldehyde（ppm） Formaldehyde conversion（%） CO2 selectivity（%）
8 Pt0.1Cu2.0/CeO2 500 98.7 100
9 Pt2.0Cu6.0/CeO2 500 99.9 100
10 Pt3.0Cu12/CeO2 500 99.9 100
The test result of 10 h of a successive reactions
Embodiment 5
Catalyst preparation is with reference to embodiment 1, by FeSO4·4H2O is exchanged with 0.1624 g NiCl2·6H2O, by RuCl3Solution It is exchanged with 2.64 mL 1mg/mL H2PtCl6·6H2O solution.Remaining condition is identical, and Pt is made0.1Ni4.0/CeO2Catalyst.It examines Commenting condition, appraisal result is shown in Table 2. with embodiment 1
Embodiment 6
Catalyst preparation is with reference to embodiment 1, by FeSO4·4H2O is exchanged with 0.1624 g CoCl2·6H2O, by RuCl3Solution It is exchanged with 2.64 mL 1mg/mL H2PtCl6·6H2O solution.Remaining condition is identical, and Pt is made0.1Co4.0/CeO2Catalyst.It examines Commenting condition, appraisal result is shown in Table 2. with embodiment 1
Embodiment 7
Catalyst preparation is with reference to embodiment 1, by FeSO4·4H2O is exchanged with 0.1044 g CuCl2·2H2O, by RuCl3Solution It is exchanged with 2.64 mL 1mg/mL H2PtCl6·6H2O solution.Remaining condition is identical, and Pt is made0.1Cu4.0/CeO2Catalyst.It examines Commenting condition, appraisal result is shown in Table 2. with embodiment 1
The formaldehyde catalytic eliminating performance of the different noble metal-non-noble metal nano alloy catalysts of table 2a
Embodiment Catalyst Formaldehyde（ppm） Formaldehyde conversion（%） CO2Selectivity（%）
5 Pt0.1Ni4.0/CeO2 500 99.8 100
6 Pt0.1Co4.0/CeO2 500 99.6 100
7 Pt0.1Cu4.0/CeO2 500 99.9 100
The test result of 10 h of a successive reactions
Embodiment 8
Catalyst preparation is with reference to embodiment 7, by CuCl2·6H2O is exchanged with 0.0522g.Remaining condition is identical, is made Pt0.1Cu2.0/CeO2Catalyst.For examination condition with embodiment 1, appraisal result is shown in Table 3.
Embodiment 9
Catalyst preparation is with reference to embodiment 7, by CuCl2·6H2O is exchanged with 0.1566g, by H2PtCl6·6H2O solution is exchanged with 52.8mL.Remaining condition is identical, and Pt is made2.0Cu6.0/CeO2Catalyst.For examination condition with embodiment 1, appraisal result is shown in Table 3.
Embodiment 10
Catalyst preparation is with reference to embodiment 7, by CuCl2·6H2O is exchanged with 0.3132g, by H2PtCl6·6H2O solution is exchanged with 79.2mL.Remaining condition is identical, and Pt is made3.0Cu12/CeO2Catalyst.For examination condition with embodiment 1, appraisal result is shown in Table 3.
The formaldehyde catalytic eliminating performance of the different noble metal-non-noble metal nano alloy catalysts of table 3a
Embodiment Catalyst Formaldehyde（ppm） Formaldehyde conversion（%） CO2 selectivity（%）
8 Pt0.1Cu2.0/CeO2 500 98.7 100
9 Pt2.0Cu6.0/CeO2 500 99.9 100
10 Pt3.0Cu12/CeO2 500 99.9 100
The test result of 10 h of a successive reactions
Embodiment 11
Catalyst preparation is with embodiment 6, and for examination condition with reference to embodiment 1, appraisal result is shown in Fig. 1.

Claims (3)

1. a kind of catalyst of room temperature catalytic oxidation removing formaldehyde, it is characterised in that using noble metal-non-noble metal nano alloy as Active component, to make CeO by oneself2For carrier, general formula is expressed as M1M2/CeO2, M1 is represented in noble metal Ru, Rh, Pt, Pd in formula One kind, M2 represents one kind in base metal Fe, Co, Ni, Cu, and by mass percentage, the content of catalyst components is M1 It is 1% ~ 15% for 0.05% ~ 5%, M2, surplus is support C eO2；
The CeO2The preparation method of carrier is synthesized with hydro-thermal method, is as follows：
1）By the desired amount of Ce (NO3)3·6H2O aqueous solutions are added in water heating kettle and are stirred；
2）NaOH solution to mixed liquor pH value is added dropwise and is more than 10, continues to stir 30min after being added dropwise to complete；
3）It is placed in baking oven and reacts, reaction temperature is 80 ~ 120 o C, and the reaction time is 12 ~ 24 h；
4）It filters, wash, is dry；
5）CeO is made in Muffle kiln roasting2Carrier, the calcination temperature are 300 ~ 500 oC, and roasting time is 2 ~ 5 h；
The catalyst is prepared with the hot method reduction of alcohol, is as follows：
1）Add in the desired amount of glycerine and self-control CeO2Carrier, the CeO2Dispersion concentration of the carrier in glycerine be 0.01g/mL, ultrasonic 60min；
2）Base metal precursor salt and precious metal solution are added in, 1h is stirred under the protection of inert gas；
3）Mixed liquor pH value, which is adjusted, with NaOH- glycerin solutions is more than 10,120 ~ 180 DEG C of 2 ~ 5h of constant temperature；
4）It is cooled to room temperature, adjusting solution ph with HCl solution is less than 3, continues 2 ~ 5h of stirring；
5）It filters, wash, is dry；
6）N2It is roasted in atmosphere and M1M2/CeO is made2Catalyst, the calcination temperature are 300 ~ 500 DEG C, and roasting time is 2 ~ 5h.
2. the catalyst of room temperature catalytic oxidation removing formaldehyde as described in claim 1, it is characterised in that by mass percentage, catalysis Agent each component content M1 is that 0.1% ~ 3%, M2 is 2% ~ 12%, balance carriers CeO2。
3. the preparation method of the catalyst of the room temperature catalytic oxidation removing formaldehyde described in claims 1 or 2, it is characterised in that with alcohol Prepared by hot method reduction, be as follows：
1）The desired amount of glycerine and self-control CeO are added in round-bottomed flask2Carrier, the CeO2Point of the carrier in glycerine Dissipate a concentration of 0.01g/mL, 60 min of ultrasound；
2）Base metal precursor salt and precious metal solution are added in, 1 h is stirred under the protection of inert gas；
3）Mixed liquor pH value, which is adjusted, with NaOH- glycerin solutions is more than 10,120 ~ 180 o C constant temperature, 2 ~ 5 h；
4）It is cooled to room temperature, adjusting solution ph with HCl solution is less than 3, continues 2 ~ 5 h of stirring；
5）It filters, wash, is dry；
6）N2It is roasted in atmosphere and M1M2/CeO is made2Catalyst, the calcination temperature are 300 ~ 500 o C, roasting time for 2 ~ 5 h。
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CN107185550A (en) * 2017-05-09 2017-09-22 江西省科学院能源研究所 A kind of platinum catalyst of room temperature catalytic oxidation removing formaldehyde and preparation method thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102836172A (en) * 2012-09-20 2012-12-26 王伟 Powder combination containing glucose
CN103143717A (en) * 2011-12-06 2013-06-12 中国科学院大连化学物理研究所 Platinoid bimetallic nanometer material and preparation method and application thereof
CN104646029A (en) * 2015-02-24 2015-05-27 中山大学惠州研究院 Metal alloy catalyst for formaldehyde purification and preparation method thereof
CN104722299A (en) * 2013-12-20 2015-06-24 中国科学院大学 Formaldehyde room temperature elimination catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4062053B2 (en) * 2002-10-29 2008-03-19 株式会社豊田中央研究所 Formaldehyde decomposition catalyst and method for producing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103143717A (en) * 2011-12-06 2013-06-12 中国科学院大连化学物理研究所 Platinoid bimetallic nanometer material and preparation method and application thereof
CN102836172A (en) * 2012-09-20 2012-12-26 王伟 Powder combination containing glucose
CN104722299A (en) * 2013-12-20 2015-06-24 中国科学院大学 Formaldehyde room temperature elimination catalyst
CN104646029A (en) * 2015-02-24 2015-05-27 中山大学惠州研究院 Metal alloy catalyst for formaldehyde purification and preparation method thereof

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