CN109759075A - The preparation method and application of the sepiolite supported Cu-Er composite catalyst of sodium - Google Patents
The preparation method and application of the sepiolite supported Cu-Er composite catalyst of sodium Download PDFInfo
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- CN109759075A CN109759075A CN201910110305.0A CN201910110305A CN109759075A CN 109759075 A CN109759075 A CN 109759075A CN 201910110305 A CN201910110305 A CN 201910110305A CN 109759075 A CN109759075 A CN 109759075A
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Abstract
The present invention provides the preparation method and application of the sepiolite supported Cu-Er composite catalyst of sodium.Sepiolite progress sodium is prepared into sodium sepiolite, then Cu and Er are supported on sodium sepiolite, Cu-Er/NaSep catalyst is prepared by rotary evaporation, wherein Cu load capacity is≤5wt%, Er load capacity≤0.5wt%.The made catalyst of the present invention is in temperature (30~170 DEG C), air speed (10,000~200,000h‑1) in the case where, there is good catalytic removal effect (formaldehyde conversion 5~100%) and stability to high-concentration formaldehyde (1000~3000ppm) (42 hours activity of reaction are constant).Catalyst preparation materials of the present invention are cheap and preparation process is simple.
Description
Technical field
The present invention relates to a kind of preparations of the sepiolite supported Cu-Er composite catalyst of sodium for catalytic removal formaldehyde
Method and its selective catalysis eliminate the application of formaldehyde.
Background technique
Formaldehyde (HCHO) is that one kind is colourless, there is the gas of intense irritation smell, soluble easily in water, alcohol ether etc..Formaldehyde is normal
It is gaseous state under temperature, and the highly volatile in room temperature, as the rising evaporation rate of temperature is accelerated.Usually go out as an aqueous solution
Existing, 40% aqueous solution is known as formalin, and solution boiling point is 19 DEG C.
The source of formaldehyde is very extensive, construction material newly developed, and the formaldehyde that plastic cement and paint generate is indoor ring
The main source in border.In addition, formaldehyde may also come from cosmetics, detergent, insecticide, disinfectant, preservative, printing ink, paper
, a variety of chemical industry light industrial goods such as textile fabric.
Formaldehyde is in second on China's toxic chemical priority acccess control list as the higher substance of toxicity.
And it is determined as carcinogenic by the World Health Organization and causes deformed material, be generally acknowledged allergen, and is potential strong
One of mutagen.Research shows that: formaldehyde has strong carcinogenic and tumor promotion.Lot of documents is recorded, and formaldehyde is strong to human body
The influence of health is mainly manifested in the side such as allotriosmia, stimulation, allergy, abnormal pulmonary function, dysfunction of liver and immunologic dysfunction
Face.When air formaldehyde concentration is reaching every cubic metre of 0.06-0.07mg/m3When, children will occur slightly to pant；Formaldehyde contains
Amount reaches 0.1mg/m3When, just there are peculiar smell and sense of discomfort；Reach 0.5mg/m3When, eyes can be stimulated, cause to shed tears；Reach
0.6mg/m3, throat discomfort or pain can be caused.When concentration is higher, nausea and vomiting can be caused, coughed uncomfortable in chest, asthma even edema with the lung involved
It is swollen, reach 30mg/m3When, it will causing death immediately.In 2004, international cancer tissue (IARC) was qualitative for level-one formaldehyde
Carcinogenic substance.Provide that the limit value of the indoor formaldehyde concentration of inoperative occasion is not higher than 0.1mg/ in the standard of implementation of China in 2002
m3, and this standard value may be increasingly stringenter with the further assessment of chemicals priority and exposure.
Toxicity in view of formaldehyde and its harm to human body, commonly using processing method mainly includes physical absorption and catalysis
Method.Wherein, catalysis technique can make formaldehyde complete oxidation carbon dioxide and water at room temperature, be a kind of first truly
Aldehyde harmless treatment.For now, noble metal catalyst shows preferable performance to low-temperature catalytic oxidation, but due to it
It is expensive, at high temperature be easier to sintering etc. factors, limit its application in practice to a certain extent.Therefore, it seeks
New catalytic material is looked for partly or completely to substitute the development trend that noble metal catalyst has become catalytic field.
Column clay receives significant attention in recent years, and rapidly develops into a kind of novel molecular sieve catalysis material.After pillared
Clay have biggish specific surface area and aperture, extraneous ion entrance so that its catalytic activity enhance, thus have well
Absorption and catalytic effect.Sepiolite is a natural fiber the silicate clay mineral of form, standard crystal chemical formula are as follows: Mg8
(H2O)4[Si6O16]2(OH)4·8H2Its key structural feature of O be it is porous, this special construction makes it have good heat resistance
And moisture-proof.Sepiolite also has the transiens feature of stratiform and chain, and the stability of crystal structure is stronger.Its biggish inside
Channel design makes sepiolite have biggish specific surface area and higher ion-exchange capacity.This patent selection is cheap,
Specific surface area is larger, the preferable sepiolite of adsorptivity.From the point of view of the document just being had been reported that at present, your mostly sepiolite supported gold
Belong to, but the research of loaded Cu-Er catalysis formaldehyde is few.Therefore, this patent passes through rotation using Cu-Er is adulterated after sepiolite sodium
Turn evaporation and be prepared into Cu-Er/NaSep composite catalyst, the catalysis for capableing of formaldehyde at a lower temperature is shown preferably
Activity and stability.
The implementation of this project obtains: project of national nature science fund project (number: 21277008；20777005)；Country's weight
The subsidy of point research and development plan (No.2017YFC0209905) and the research contents of these projects.
Summary of the invention
The present invention relates to a kind of preparation method of Cu-Er/NaSep composite catalyst for catalytic removal formaldehyde and its
The application of selective catalysis elimination formaldehyde.Provided catalyst efficiently eliminates high concentration first at 30~170 DEG C of reaction temperature
Aldehyde (1000~3000ppm), and there is good catalytic removal effect (formaldehyde conversion 5~100%).This catalyst has simultaneously
There is higher stability, and has many advantages, such as that preparation process is simple, low in cost, stability is good.
The present invention provides a kind of system of sepiolite supported Cu and Er composite catalyst of the sodium for catalytic removal formaldehyde
Preparation Method:
(1) preparation process is as follows: Na is added in 2wt% sepiolite aqueous solution2CO3It is stirred, sodium/sepiolite matter
Amount is than being 4:100, in 60 DEG C of uniform stirring 2h.Then aging for 24 hours, is filtered with deionized water at room temperature, washing, and at 80 DEG C
For 24 hours, obtained sodium sepiolite is expressed as NaSep for lower drying.
Sodium sepiolite is added to containing 0.01mol/L~0.05mol/L copper nitrate and 0.001mol/L~
In the erbium nitrate mixed solution of 0.005mol/L, 1~2h is stirred at 60~70 DEG C, wherein sodium sepiolite and copper nitrate ratio
For 100g:4.9g~24.5g, sodium sepiolite and erbium nitrate ratio are 100g:0.44g~2.2g.Mixed solution is packed into eggplant
Shape bottle, in 60 DEG C of stirrings until solution is evaporated.Sample is taken out, drying for 24 hours, later in 450 DEG C of roasting 2h, is made at 120 DEG C
Cu-Er/NaSep composite catalyst.
(2) catalyst of the present invention is normal pressure 1atm, air speed 10,000h in reaction pressure-1~200,000h-1、
20vol.%O2, 1000~3000ppm of concentration of formaldehyde and Balance Air be N2Under the conditions of, in 30~170 DEG C of temperature range, to first
Aldehyde has high catalytic activity (conversion ratio 5%~100%).；It is normal pressure 1atm, air speed 10,000h in reaction pressure-1~200,
000h-1, 20vol.%O2, 1000~3000ppm of concentration of formaldehyde and Balance Air be N2Under the conditions of, investigate support type Cu/NaSep and
Cu-Er/NaSep catalyst keeps a temperature spot in 70~100 DEG C of temperature ranges, measures 42 hours activity of catalyst.
Under the temperature range studied, catalytic activity still maintains high stability.
Detailed description of the invention
Fig. 1 is Cu/NaSep, Cu-Er/NaSep-I, Cu-Er/NaSep-II prepared by the embodiment of the present invention 1,2,3 and 4
With the XRD diagram of Cu-Er/NaSep-III catalyst.
Fig. 2 is Cu/NaSep, Cu-Er/NaSep-I, Cu-Er/NaSep-II prepared by the embodiment of the present invention 1,2,3 and 4
With the N of Cu-Er/NaSep-III catalyst2Absorption/desorption figure.
Fig. 3 is Cu/NaSep, Cu-Er/NaSep-I, Cu-Er/NaSep-II prepared by the embodiment of the present invention 1,2,3 and 4
With Cu-Er/NaSep-III catalysis oxidation formaldehyde activity figure.
Fig. 4 is Cu/NaSep, Cu-Er/NaSep-I, Cu-Er/NaSep-II prepared by the embodiment of the present invention 1,2,3 and 4
42 hours stability is reacted with 100 DEG C of Cu-Er/NaSep-III catalyst.
Specific embodiment
Embodiment 1
(1) preparation process is as follows: Na is added in 2wt% sepiolite aqueous solution2CO3It is stirred, sodium/sepiolite matter
Amount is than being 4:100, in 60 DEG C of uniform stirring 2h.Then aging for 24 hours, is filtered with deionized water at room temperature, washing, and at 80 DEG C
For 24 hours, obtained sodium sepiolite is expressed as NaSep for lower drying.
Copper nitrate is add to deionized water, 0.02mol/L copper nitrate solution is configured to.Pass through rotary evaporation legal system
Standby Cu/NaSep sample.The nitric acid of gained concentrations above is calculated by Cu load sodium sepiolite mass ratio (Cu wt%=2wt%)
Copper solution volume is added in the above-mentioned sodium sepiolite of 3g, after 60 DEG C of stirring 1h, mixed solution is packed into eggplant-shape bottle, at 60 DEG C
Water temperature under carry out rotary evaporation until solution be evaporated.Take out sample, at 120 DEG C it is dry for 24 hours, later in 450 DEG C of roasting 2h,
Obtained product is expressed as Cu/NaSep.
(2) catalyst of the present invention is normal pressure 1atm, air speed 200,000h in reaction pressure-1, 20vol.%O2, formaldehyde it is dense
It spends 3000ppm and Balance Air is N2Under the conditions of, in 30~170 DEG C of temperature range, with high catalytic activity (formaldehyde=5~
100%)；It is normal pressure 1atm, air speed 200,000h in reaction pressure-1, 20vol.%O2, concentration of formaldehyde 3000ppm and Balance Air
For N2Under the conditions of, the conversion ratio of formaldehyde in Cu/NaSep 42 hours is investigated at 100 DEG C.Studied at a temperature of, catalytic activity
High stability is still maintained,.
Embodiment 2
(1) preparation process is as follows: Na is added in 2wt% sepiolite aqueous solution2CO3It is stirred, sodium/sepiolite matter
Amount is than being 4:100, in 60 DEG C of uniform stirring 2h.Then aging for 24 hours, is filtered with deionized water at room temperature, washing, and at 80 DEG C
For 24 hours, obtained sodium sepiolite is expressed as NaSep for lower drying.
Copper nitrate, erbium nitrate are added separately in deionized water, 0.03mol/L copper nitrate and 0.001mol/L are configured to
Nitrate Solution, after 65 DEG C of stirring 1h, by Cu, Er load sodium sepiolite mass ratio (Cu wt%=3wt%, Er
Wt%=0.1wt%) copper nitrate of gained concentrations above is calculated, Nitrate Solution volume is added to the above-mentioned sodium sepiolite of 3g
In, mixed solution is packed into eggplant-shape bottle, carries out rotary evaporation under 60 DEG C of water temperature until solution is evaporated.Sample is taken out, 120
It is dried for 24 hours at DEG C.Later in 450 DEG C of roasting 2h, compound Cu-Er/NaSep-I composite catalyst is made.
(2) catalyst of the present invention is normal pressure 1atm, air speed 100,000h in reaction pressure-1, 20vol.%O2, formaldehyde it is dense
It spends 2000ppm and Balance Air is N2Under the conditions of, in 30~145 DEG C of temperature range, with high catalytic activity (formaldehyde=5~
100%)；It is normal pressure 1atm, air speed 100,000h in reaction pressure-1, 20vol.%O2, concentration of formaldehyde 2000ppm and Balance Air
For N2Under the conditions of, the conversion ratio of formaldehyde in Cu-Er/NaSep-I 42 hours is investigated at 100 DEG C.Studied at a temperature of, urge
Change activity and still maintains high stability.
Embodiment 3
(1) preparation process is as follows: Na is added in 2wt% sepiolite aqueous solution2CO3It is stirred, sodium/sepiolite matter
Amount is than being 4:100, in 60 DEG C of uniform stirring 2h.Then aging for 24 hours, is filtered with deionized water at room temperature, washing, and at 80 DEG C
For 24 hours, obtained sodium sepiolite is expressed as NaSep for lower drying.
Copper nitrate, erbium nitrate are added separately in deionized water, 0.05mol/L copper nitrate and 0.003mol/L are configured to
Nitrate Solution, after 65 DEG C of stirring 2h, by Cu, Er load sodium sepiolite mass ratio (Cu wt%=5wt%, Er
Wt%=0.3wt%) copper nitrate of gained concentrations above is calculated, Nitrate Solution volume is added to the above-mentioned sodium sepiolite of 3g
In, mixed solution is packed into eggplant-shape bottle, carries out rotary evaporation under 60 DEG C of water temperature until solution is evaporated.Sample is taken out, 120
It is dried for 24 hours at DEG C.Later in 450 DEG C of roasting 2h, compound Cu-Er/NaSep-I composite catalyst is made.
(2) catalyst of the present invention is normal pressure 1atm, air speed 50,000h in reaction pressure-1, 20vol.%O2, concentration of formaldehyde
1500ppm and Balance Air are N2Under the conditions of, in 30~125 DEG C of temperature range, with high catalytic activity (formaldehyde=5~
100%)；It is normal pressure 1atm, air speed 50,000h in reaction pressure-1, 20vol.%O2, concentration of formaldehyde 1500ppm and Balance Air be
N2Under the conditions of, the conversion ratio of formaldehyde in Cu-Er/NaSep-II 42 hours is investigated at 100 DEG C.Studied at a temperature of, catalysis
Activity still maintains high stability.
Embodiment 4
(1) preparation process is as follows: Na is added in 2wt% sepiolite aqueous solution2CO3It is stirred, sodium/sepiolite matter
Amount is than being 4:100, in 60 DEG C of uniform stirring 2h.Then aging for 24 hours, is filtered with deionized water at room temperature, washing, and at 80 DEG C
For 24 hours, obtained sodium sepiolite is expressed as NaSep for lower drying.
Copper nitrate, erbium nitrate are added separately in deionized water, 0.05mol/L copper nitrate and 0.005mol/L are configured to
Nitrate Solution, after 70 DEG C of stirring 1h, by Cu, Er load sodium sepiolite mass ratio (Cu wt%=5wt%, Er
Wt%=0.5wt%) copper nitrate of gained concentrations above is calculated, Nitrate Solution volume is added to the above-mentioned sodium sepiolite of 3g
In, mixed solution is packed into eggplant-shape bottle, carries out rotary evaporation under 60 DEG C of water temperature until solution is evaporated.Sample is taken out, 120
It is dried for 24 hours at DEG C.Later in 450 DEG C of roasting 2h, compound Cu-Er/NaSep-I composite catalyst is made.
(2) catalyst of the present invention is normal pressure 1atm, air speed 10,000h in reaction pressure-1, 20vol.%O2, concentration of formaldehyde
1000ppm and Balance Air are N2Under the conditions of, in 30~110 DEG C of temperature range, with high catalytic activity (formaldehyde=5~
100%)；It is normal pressure 1atm, air speed 10,000h in reaction pressure-1, 20vol.%O2, concentration of formaldehyde 1000ppm and Balance Air be
N2Under the conditions of, the conversion ratio of formaldehyde in Cu-Er/NaSep-III 42 hours is investigated at 100 DEG C.Studied at a temperature of, urge
Change activity and still maintains high stability.
Claims (4)
1. a kind of sodium sepiolite catalyst for catalytic removal formaldehyde, which is characterized in that two kinds of elements of Cu and Er are carried on
On sodium sepiolite carrier, sodium sepiolite is exchanged sodium carbonate liquor to a kind of composite material of sepiolite interlayer.
2. a kind of sodium sepiolite catalyst for catalytic removal formaldehyde according to claim 1, which is characterized in that Cu-Er/
The BET specific surface area of NaSep is 40~65m2/g。
3. a kind of sodium sepiolite catalyst for catalytic removal formaldehyde according to claim 1, which is characterized in that including with
Lower step:
(1) prepared by sodium sepiolite carrier
Na is added in 2wt% sepiolite aqueous solution2CO3It is stirred, sodium/sepiolite mass ratio is 4:100, at 60 DEG C
Even stirring 2h；Then aging for 24 hours, is filtered with deionized water at room temperature, washing, and is dried for 24 hours at 80 DEG C, obtained sodium
Sepiolite is expressed as NaSep；
Sodium sepiolite is added to containing 0.01mol/L~0.05mol/L copper nitrate and 0.001mol/L~0.005mol/L
Erbium nitrate mixed solution in, after 60~70 DEG C of 1~2h of stirring, wherein sodium sepiolite and copper nitrate ratio are 100g:4.9g
~24.5g, sodium sepiolite and erbium nitrate ratio are 100g:0.44g~2.2g, mixed solution are packed into eggplant-shape bottle, at 60 DEG C
Water temperature under carry out rotary evaporation, until solution is evaporated；Sample is taken out, is dried for 24 hours at 120 DEG C；It is roasted later at 450 DEG C
Sodium sepiolite catalyst is made in 2h.
4. sodium sepiolite catalyst described in claim 1 is in the application for eliminating formaldehyde, it is characterised in that: put above-mentioned catalyst
The formaldehyde containing 1000~3000ppm, 20vol.%O are passed through in continuous flow fixed bed device2And N2As the mixed of Balance Air
It closes and is reacted in gas；Reaction pressure is normal pressure 1atm, and reaction velocity is air speed 10,000~200,000h-1, reaction temperature is
30~170 DEG C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910110305.0A CN109759075A (en) | 2019-02-11 | 2019-02-11 | The preparation method and application of the sepiolite supported Cu-Er composite catalyst of sodium |
| CN201910332201.4A CN110052275A (en) | 2019-02-11 | 2019-04-24 | The preparation method and application of the sepiolite supported Cu-Er or Cu-Nb composite catalyst of sodium |
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| CN201910110305.0A CN109759075A (en) | 2019-02-11 | 2019-02-11 | The preparation method and application of the sepiolite supported Cu-Er composite catalyst of sodium |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068666A (en) * | 2019-11-18 | 2020-04-28 | 天津博雅大地新材料科技有限公司 | Sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN117399020A (en) * | 2023-12-14 | 2024-01-16 | 上海鸣桦环境科技有限公司 | Magnetic catalyst containing erbium and copper, preparation method and method for catalyzing and synthesizing lactic acid by using magnetic catalyst |
-
2019
- 2019-02-11 CN CN201910110305.0A patent/CN109759075A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068666A (en) * | 2019-11-18 | 2020-04-28 | 天津博雅大地新材料科技有限公司 | Sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN117399020A (en) * | 2023-12-14 | 2024-01-16 | 上海鸣桦环境科技有限公司 | Magnetic catalyst containing erbium and copper, preparation method and method for catalyzing and synthesizing lactic acid by using magnetic catalyst |
| CN117399020B (en) * | 2023-12-14 | 2024-04-16 | 上海鸣桦环境科技有限公司 | Magnetic catalyst containing erbium and copper, preparation method and method for catalyzing and synthesizing lactic acid by using magnetic catalyst |
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Application publication date: 20190517 |