CN104353465B - A kind of catalyst used by formaldehyde through catalytic oxidation and preparation method thereof - Google Patents

A kind of catalyst used by formaldehyde through catalytic oxidation and preparation method thereof Download PDF

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CN104353465B
CN104353465B CN201410656129.8A CN201410656129A CN104353465B CN 104353465 B CN104353465 B CN 104353465B CN 201410656129 A CN201410656129 A CN 201410656129A CN 104353465 B CN104353465 B CN 104353465B
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formaldehyde
catalyst
catalytic oxidation
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CN104353465A (en
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吴贵升
张叶
毛东森
卢冠忠
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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Abstract

The present invention discloses the catalyst used by a kind of formaldehyde through catalytic oxidation and preparation method, and the catalyst used by described formaldehyde through catalytic oxidation is core, shell structure, and core is Co3O4, shell is CeO2, the ratio of nucleocapsid press Co, Ce metallic atom molar percentage calculate, wherein Co is 95.55 97.60%, and Ce is 2.40 4.45%.Its preparation method, i.e. prepares Co initially with co-precipitation method3O4Catalyst granules, then at Co3O4The area load CeO of catalyst granules2Shell.Catalyst used by this formaldehyde through catalytic oxidation just can make the conversion ratio of formaldehyde reach 100% room temperature 25 DEG C, and this catalyst has good stability and CO simultaneously2Selectivity.

Description

A kind of catalyst used by formaldehyde through catalytic oxidation and preparation method thereof
Technical field
The present invention relates to catalyst used by a kind of formaldehyde through catalytic oxidation and preparation method thereof, belong to environmental catalysis technology neck Territory.
Background technology
Eliminate carbaldehyde Method and have a variety of, such as absorption method, chemical reaction method etc..Wherein, catalytic oxidation under temperate condition It is considered as the effective ways of a kind of thorough elimination formaldehyde: indoor HCHO is fully oxidized as H under gentle reaction condition2O And CO2, become researcher's focus of attention at present.
Since last century end, carry out substantial amounts of about indoor formaldehyde through catalytic oxidation reaction and catalyst system and catalyzing both at home and abroad Work.Its catalytic active component is generally noble metal (Pt, Au and Pd).Expensive price limit due to these noble metals Its popularity.
Therefore, exploitation transition-metal catalyst has certain practical significance.Compare with precious metal catalyst system, Co3O4Urge Agent is due to cheap, and the advantages such as reaction temperature is low, high catalytic activity show powerful answering in terms of CO low-temperature oxidation By potentiality, but Co3O4Catalyst but rarely has report at formaldehyde low-temperature oxidation area research.
Summary of the invention
An object of the present invention is in order to by Co3O4The catalysis that catalyst is applied to formaldehyde low-temperature catalytic oxidation and provides Agent.
The two of the purpose of the present invention are to provide the preparation method of a kind of above-mentioned formaldehyde through catalytic oxidation used catalyst.
The know-why of the present invention
Can be found by literature survey, body phase Co3O4Belong to spinel structure, have the Co of eight-coordinate simultaneously3+Join with four The Co of position2+, just because of the crystalline form of its uniqueness and the attribute that appraises at the current rate, showing relatively Strong oxdiative ability, it is low-temperature catalyzed at CO in recent years Oxidation aspect shows the catalytic performance of uniqueness and enjoys concern both domestic and external.But its research in terms of formaldehyde low-temperature oxidation is but Rarely has report.
At Co3O4Middle introducing CeO2Auxiliary agent, not only plays effect that is stable and that optimize, and CeO to catalyst structure2With Co3O4Component has the strongest cooperative effect so that CeO2Strong oxygen stores ability and greatly enhances the oxidability of catalyst.
The present invention is with Co3O4Catalyst, as key component, wraps up CeO at catalyst surface2Shell, is possible not only to stable Co3O4Form, stops its particle to be reunited in activation process.And the core-shell structure copolymer Rotating fields of its uniqueness can reach following effect Really: 1) regulation Co3O4Interior Co2+/Co3+Ratio, thus improve Co3O4Oxidability;2) in course of reaction, CeO2Also may be used To improve the oxidation activity of catalyst further by storing oxygen;3) improve the anti-caking power of catalyst, keep active component Decentralization;4) effectively suppress the formation of surface carbonate, maintain the activity of catalyst;5) Co is made3O4The incomplete oxygen in activated centre The formaldehyde changed is through CeO2The outside diffusion process of film in occur secondary oxidation improve oxidation efficiency further.
Technical scheme
Catalyst used by a kind of formaldehyde through catalytic oxidation, for core, shell structure, described core is Co3O4, shell is CeO2, nucleocapsid Ratio press Co, Ce metallic atom molar percentage calculate, specific as follows:
Co 95.55–97.60%
Ce 2.40–4.45%。
The preparation method of the above-mentioned catalyst used by a kind of formaldehyde through catalytic oxidation, i.e. initially with co-precipitation method Prepare Co3O4Catalyst granules, then at Co3O4The area load CeO of catalyst granules2Shell, its preparation process is specifically wrapped Include following steps:
(1), by the Co (NO of 1mol/L3)2Solution I and the Na of 0.5mol/L2CO3Solution II by volume ratio is that 1:3.5 enters Row mixing, controlling every amount is that the mixed liquor of gained is dropwise added drop-wise to the Na equipped with 0.5mol/L by 0.05 0.07mL2CO3Solution In the beaker of III, controlling speed of agitator during dropping is 200 300r/min, and temperature 60 C, by pH meter on-line monitoring by pH Value controls completion of dropwise addition in the range of 9.4-9.8, treats completion of dropwise addition, suction filtration after ageing 1h, and the filter cake of gained distilled water washs 6 After secondary, then filter cake is dried 12h through 120 DEG C, then in 300 DEG C of roasting 4h, obtain powder cobaltosic oxide, then sieve, obtain Granularity is the cobaltosic oxide powder of 200 250 mesh;
Above-mentioned in beaker equipped with the Na of 0.5mol/L2CO3The amount of solution III is close according to the stirring-head of mechanical agitator But without impinging at the bottom of beaker and the Na of 0.5mol/L can be touched2CO3Solution III is as the criterion;
(2), add, in the cerous nitrate aqueous solution IV that concentration is 0.035-0.066mol/L, the particle prepared by step (1) Degree is the powder cobaltosic oxide of 200 250 mesh, and is stirred continuously formation suspension, then uses 0.5mol/L under the conditions of 60 DEG C Na2CO3Aqueous solution V regulation suspension pH value is 7.0, suction filtration after ageing 2h, and the filter cake of gained is washed with deionized 6 times, After successively at 120 DEG C of dry 12h, roasting 4h at 350 DEG C, obtain the catalyst used by formaldehyde through catalytic oxidation;
The above-mentioned used cerous nitrate the aqueous solution IV and 200-250 purpose four that concentration is 0.035-0.066mol/L aoxidizes three The amount of cobalt dust, by mole calculating, i.e. Co:Ce is 95.55 97.60%:2.40 4.45%.
Beneficial effects of the present invention
The catalyst used by a kind of formaldehyde through catalytic oxidation of the present invention, owing to using transition metal oxide Co3O4As urging The core of agent, CeO2For shell, therefore its cost drastically reduces compared to noble metal catalyst.
Further, the catalyst used by a kind of formaldehyde through catalytic oxidation of the present invention, due to CeO2For shell, make formaldehyde complete Complete convert needed for reaction temperature reduce 85 100 DEG C, i.e. room temperature 25 DEG C just can make the conversion ratio of formaldehyde reach 100%, and The catalyst used by a kind of formaldehyde through catalytic oxidation of the present invention can continue at least 48h and continuously run, and the conversion ratio of formaldehyde reaches 100%, CO simultaneously2The most stable 100%;When continuously running 60h, the conversion ratio of formaldehyde still can reach 99.2%, and CO2 Selectivity reduced by only 0.80%, it is indicated above that the catalyst tool used by a kind of formaldehyde through catalytic oxidation of the present invention is the most stable Property and CO2Selectivity.
Further, the preparation method of the catalyst used by a kind of formaldehyde through catalytic oxidation of the present invention, its preparation method is simple, Easily operated, and catalyst performance repeatability is relatively good, easily accomplishes scale production.
Detailed description of the invention
Below by specific embodiment, the present invention is described further, but is not limiting as the present invention.
Used by various embodiments of the present invention:
Miniature quartz reaction tube fixed bed reactors (LW4, Wuxi drawing instrument factory);
Polyformaldehyde glass bubbler;
Carbon molecular sieve chromatographic column, Ramiin, GC2060, the sensitive Instrument Ltd. in Shanghai;
Nickel reburner, the sensitive Instrument Ltd. in Shanghai.
Embodiment 1
Catalyst used by a kind of formaldehyde through catalytic oxidation, for core, shell structure, described core is Co3O4, shell is CeO2, nucleocapsid Ratio press Co, Ce metallic atom molar percentage calculate, specific as follows:
Co 97.60%
Ce 2.40%。
The preparation method of the above-mentioned catalyst used by a kind of formaldehyde through catalytic oxidation, i.e. initially with co-precipitation method Prepare Co3O4Catalyst granules, then at Co3O4The area load CeO of catalyst granules2Shell, its preparation process is specifically wrapped Include following steps:
(1), by Co (NO that 125mL concentration is 1mol/L3)2Solution I and 437.5mL concentration is the Na of 0.5mol/L2CO3 Solution II by volume ratio is that 1:3.5 mixes, and controlling every amount is that the mixed liquor of gained is dropwise dripped by 0.05 0.07mL To being the Na of 0.5mol/L equipped with 30mL concentration2CO3In the beaker of solution III, controlling speed of agitator during dropping is 200 300r/min, temperature 60 C, by pH meter on-line monitoring, pH value is controlled completion of dropwise addition in the range of 9.4-9.8, treat dropping knot Bundle, suction filtration after ageing 1h, after the filter cake of gained washs 6 times with distilled water, then dries 12h by filter cake through 120 DEG C, then in 300 DEG C Roasting 4h, obtains powder cobaltosic oxide, then sieves, and obtains the cobaltosic oxide powder that granularity is 200 250 mesh;
Above-mentioned in beaker equipped with the Na of 0.5mol/L2CO3The amount of solution III is close according to the stirring-head of mechanical agitator But without impinging at the bottom of beaker and the Na of 0.5mol/L can be touched2CO3Solution III is as the criterion;
(2), 0.760g six nitric hydrate cerium salt is dissolved in 50mL water the cerous nitrate that concentration is 0.035mol/L obtained The aqueous solution IV, adds the powder cobaltosic oxide that granularity is 200 250 mesh prepared by 5g step (1) wherein, and constantly stirs Mix formation suspension, then with the Na of 0.5mol/L under the conditions of 60 DEG C2CO3Aqueous solution V regulation suspension pH value is 7.0, ageing Suction filtration after 2h, the filter cake of gained is washed with deionized 6 times, the most successively at 120 DEG C of dry 12h, roasting 4h at 350 DEG C, i.e. Obtain the catalyst A used by formaldehyde through catalytic oxidation;
The cobaltosic oxide powder of the above-mentioned used cerous nitrate the aqueous solution IV and 200-250 mesh that concentration is 0.035mol/L Amount, by mole calculating, i.e. Co:Ce is 97.60%:2.40%.
Application Example 1
By the catalyst A compressing tablet used by the formaldehyde through catalytic oxidation of above-described embodiment 1 gained and to be crushed to 40-60 mesh standby.
Catalyst A(40-60 mesh with used by the formaldehyde through catalytic oxidation of 0.5g embodiment 1 gained) and isopyknic quartz sand Being fixed to internal diameter in miniature quartz pipe fixed bed reactors after mixing is the interlude of the reaction tube of 6mm, is 30mL/ at flow velocity The N of min2Under atmosphere after 200 DEG C of pretreatment 30min, then dropping to room temperature, then switching overall flow rate is the reaction of 50mL/min Gas carries out catalytic reaction, in described reaction gas, is 600ppm containing formaldehyde gas, and surplus is air, and formaldehyde gas is by Balance Air N2Flowing through paraformaldehyde glass bubbler (heating water bath 36 DEG C) to bring into, in course of reaction, control reaction temperature is from 25 DEG C, 50 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C to 230 DEG C, after taking each temperature spot reaction 30min, by reaction end gas By nickel reburner after carbon molecular sieve chromatographic column separates, carried out the first in the tail gas of on-line determination outflow by fid detector Aldehyde, CO and CO2Content, record detects corresponding different temperatures 25 DEG C respectively, 50 DEG C, 80 DEG C, 120 DEG C, institute under the conditions of 150 DEG C Corresponding formaldehyde conversion and CO2Selectivity, the result of gained see table:
As can be seen from the above table the catalyst A used by formaldehyde through catalytic oxidation when 50 DEG C can by formaldehyde complete oxidation, And the CO when 120 DEG C2Selectivity reaches 99.32%.
Application comparative examples 1
With the cobaltosic oxide powder that granularity is 200 250 mesh of embodiment 1 step (1) gained for comparison;
By the cobaltosic oxide powder that granularity is 200 250 mesh of 0.5g embodiment 1 gained and isopyknic quartz sand Being fixed to internal diameter in miniature quartz pipe fixed bed reactors after mixing is the interlude of the reaction tube of 6mm, is 30mL/ at flow velocity The N of min2Under atmosphere after 200 DEG C of pretreatment 30min, then dropping to room temperature, then switching overall flow rate is the reaction of 50mL/min Gas carries out catalytic reaction, in described reaction gas, is 600ppm containing formaldehyde gas, and surplus is air, and formaldehyde gas is by Balance Air N2Flow through paraformaldehyde bubbler (heating water bath 36 DEG C) to bring into.In course of reaction, control reaction temperature is from 25 DEG C, 50 DEG C, and 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C to 230 DEG C, after taking each temperature spot reaction 30min, by reaction end gas warp Carbon molecular sieve chromatographic column separate after by nickel reburner, carried out by fid detector the formaldehyde in the tail gas of on-line determination outflow, CO and CO2Content, record detects corresponding different temperatures 25 DEG C respectively, and 50 DEG C, 80 DEG C, 120 DEG C, under the conditions of 150 DEG C, institute is right The formaldehyde conversion answered and CO2Selectivity, the result of gained see table:
As can be seen from the above table, compareGranularity is the cobaltosic oxide powder of 200 250 mesh ability when 150 DEG C Can be by formaldehyde complete oxidation, and the CO when 150 DEG C2Selectively it is only 60.00%.
Embodiment 2
Catalyst used by a kind of formaldehyde through catalytic oxidation, for core, shell structure, described core is Co3O4, shell is CeO2, nucleocapsid Ratio press Co, Ce metallic atom molar percentage calculate, specific as follows:
Co 95.55%
Ce 4.45%。
The preparation method of the above-mentioned catalyst used by a kind of formaldehyde through catalytic oxidation, i.e. initially with co-precipitation method Prepare Co3O4Catalyst granules, then at Co3O4The area load CeO of catalyst granules2Shell, its preparation process is specifically wrapped Include following steps:
(1), granularity be the cobaltosic oxide powder of 200 250 mesh, detailed process is with embodiment 1;
(2), 1.439g six nitric hydrate cerium salt is dissolved in 50mL water obtains the cerous nitrate water that concentration is 0.066mol/L Solution IV, adds the powder cobaltosic oxide that granularity is 200 250 mesh prepared by 5g step (1) wherein, and is stirred continuously Form suspension, then with the Na of 0.5mol/L under the conditions of 60 DEG C2CO3Aqueous solution V regulation suspension pH value is 7.0, is aged 2h Rear suction filtration, the filter cake of gained is washed with deionized 6 times, and the most successively at 120 DEG C of dry 12h, at 350 DEG C, roasting 4h, to obtain final product Catalyst B used by formaldehyde through catalytic oxidation;
The cobaltosic oxide powder of the above-mentioned used cerous nitrate the aqueous solution IV and 200-250 mesh that concentration is 0.066mol/L Amount, by mole calculating, i.e. Co:Ce is 95.55%:4.45%.
Application Example 2
By the catalyst B compressing tablet used by the formaldehyde through catalytic oxidation of above-described embodiment 2 gained and to be crushed to 40-60 mesh standby.
Catalyst B(40-60 mesh with used by the formaldehyde through catalytic oxidation of 0.5g embodiment 2 gained) and isopyknic quartz sand Being fixed to internal diameter in miniature quartz pipe fixed bed reactors after mixing is the interlude of the reaction tube of 6mm, is 30mL/ at flow velocity The N of min2Under atmosphere after 200 DEG C of pretreatment 30min, then dropping to room temperature, then switching overall flow rate is the reaction of 50mL/min Gas carries out catalytic reaction, in described reaction gas, is 600ppm containing formaldehyde gas, and surplus is air, and formaldehyde gas is by Balance Air N2Flow through paraformaldehyde bubbler (heating water bath 36 DEG C) to bring into.In course of reaction, control reaction temperature is from 25 DEG C, 50 DEG C, and 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C to 230 DEG C, take after each temperature spot reacts 30 min, by reaction end gas warp Carbon molecular sieve chromatographic column separate after by nickel reburner, carried out by fid detector the formaldehyde in the tail gas of on-line determination outflow, CO and CO2Content, record detects corresponding different temperatures 25 DEG C respectively, and 50 DEG C, 80 DEG C, 120 DEG C, under the conditions of 150 DEG C, institute is right The formaldehyde conversion answered and CO2Selectivity, the result of gained see table:
As can be seen from the above table the catalyst B used by formaldehyde through catalytic oxidation when 80 DEG C can by formaldehyde complete oxidation, And the CO when 180 DEG C2Selectivity reaches 100.00%.
Embodiment 3
Catalyst used by a kind of formaldehyde through catalytic oxidation, for core, shell structure, described core is Co3O4, shell is CeO2, nucleocapsid Ratio press Co, Ce metallic atom molar percentage calculate, specific as follows:
Co 96.98%
Ce 3.02%。
The preparation method of the above-mentioned catalyst used by a kind of formaldehyde through catalytic oxidation, i.e. initially with co-precipitation method Prepare Co3O4Catalyst granules, then at Co3O4The area load CeO of catalyst granules2Shell, its preparation process is specifically wrapped Include following steps:
(1), granularity be the cobaltosic oxide powder of 200 250 mesh, detailed process is with embodiment 1;
(2), 0.962g six nitric hydrate cerium salt is dissolved in 50mL water obtains the cerous nitrate water that concentration is 0.044mol/L Solution IV, adds the powder cobaltosic oxide that granularity is 200 250 mesh prepared by 5g step (1) wherein, and is stirred continuously Form suspension, then with the Na of 0.5mol/L under the conditions of 60 DEG C2CO3Aqueous solution V regulation suspension pH value is 7.0, is aged 2h Rear suction filtration, the filter cake of gained is washed with deionized 6 times, and the most successively at 120 DEG C of dry 12h, at 350 DEG C, roasting 4h, to obtain final product Catalyst C used by formaldehyde through catalytic oxidation;
The cobaltosic oxide powder of the above-mentioned used cerous nitrate the aqueous solution IV and 200-250 mesh that concentration is 0.044mol/L Amount, by mole calculating, i.e. Co:Ce is 96.98%:3.02%.
Application Example 3
By the catalyst C compressing tablet used by the formaldehyde through catalytic oxidation of above-described embodiment 3 gained and to be crushed to 40-60 mesh standby.
Catalyst C(40-60 mesh with used by the formaldehyde through catalytic oxidation of 0.5g embodiment 3 gained) and isopyknic quartz sand Being fixed to internal diameter in miniature quartz pipe fixed bed reactors after mixing is the interlude of the reaction tube of 6mm, is 30mL/ at flow velocity The N of min2Under atmosphere after 200 DEG C of pretreatment 30min, then dropping to room temperature, then switching overall flow rate is the reaction of 50mL/min Gas carries out catalytic reaction, in described reaction gas, is 600ppm containing formaldehyde gas, and surplus is air, and formaldehyde gas is by Balance Air N2Flowing through paraformaldehyde bubbler (heating water bath 36 DEG C) to bring into, in course of reaction, control reaction temperature is from 25 DEG C, 50 DEG C, and 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C to 230 DEG C, after taking each temperature spot reaction 30min, by reaction end gas warp Carbon molecular sieve chromatographic column separate after by nickel reburner, carried out by fid detector the formaldehyde in the tail gas of on-line determination outflow, CO and CO2Content, record detects corresponding different temperatures 25 DEG C respectively, and 50 DEG C, 80 DEG C, 120 DEG C, under the conditions of 150 DEG C, institute is right The formaldehyde conversion answered and CO2Selectivity, the result of gained see table:
As can be seen from the above table the catalyst C used by formaldehyde through catalytic oxidation when 25 DEG C can by formaldehyde complete oxidation, And the CO when 120 DEG C2Selectivity reaches 100.00%.
Contrasted by the result of Application Example 1-3 and application comparative examples 1 gained, it can be seen that the present invention The catalyst used by a kind of formaldehyde through catalytic oxidation catalysis oxidation of formaldehyde during, particularly urging used by formaldehyde through catalytic oxidation Agent C just can make the conversion ratio of formaldehyde reach 100% at 25 DEG C, and pure Co3O4Catalyst during formaldehyde through catalytic oxidation, formaldehyde Reaction temperature needed for conversion ratio reaches 100% oxidation wants more than 150 DEG C.
Application Example 4
By the catalyst C compressing tablet used by the formaldehyde through catalytic oxidation of above-described embodiment 3 gained and to be crushed to 40-60 mesh standby.
Catalyst C(40-60 mesh with used by the formaldehyde through catalytic oxidation of 0.5g embodiment 3 gained) and isopyknic quartz sand Being fixed to internal diameter in miniature quartz pipe fixed bed reactors after mixing is the interlude of the reaction tube of 6mm, is 30mL/ at flow velocity The N of min2Under atmosphere after 200 DEG C of pretreatment 30min, then dropping to room temperature, then switching overall flow rate is the reaction of 50mL/min Gas carries out catalytic reaction, in described reaction gas, is 600ppm containing formaldehyde gas, and surplus is air, and formaldehyde gas is by Balance Air N2Flow through paraformaldehyde bubbler (heating water bath 36 DEG C) to bring into.Course of reaction controls reaction temperature 120 DEG C, by reaction end gas By nickel reburner after carbon molecular sieve chromatographic column separates, by fid detector carry out the on-line determination reaction time be respectively 4h, Formaldehyde in the tail gas flowed out when 24h, 48h, 60h, CO and CO2Content, thus calculating reacting time be respectively 4h, 24h, Formaldehyde conversion and CO when 48h, 60h2Selectivity, the result of gained see table:
Catalyst C stability used by formaldehyde through catalytic oxidation is fine as can be seen from the above table, and formaldehyde conversion reaches 100% 48h, now CO can be stablized2Selectivity is also stabilized in 100%;And when the reaction time reaches 60h, under the conversion ratio of formaldehyde just starts It is down to 99.20%, CO2Selectivity is down to 99.82%, i.e. formaldehyde conversion only reduces by 0.8%, CO2Selectivity only reduces by 0.18%, by This shows, the catalyst used by a kind of formaldehyde through catalytic oxidation of the present invention has good stability and CO2Selectivity.
Application comparative examples 2
In embodiment 3, the cobaltosic oxide powder that granularity is 200 250 mesh of step (1) gained is comparison, with 0.5g is with the cobaltosic oxide powder that granularity is 200 250 mesh of step (1) gained in embodiment 3 for comparison, with equal-volume Quartz sand mixing after to be fixed to internal diameter in miniature quartz pipe fixed bed reactors be the interlude of the reaction tube of 6mm, at flow velocity N for 30mL/min2Under atmosphere after 200 DEG C of pretreatment 30min, then dropping to room temperature, then switching overall flow rate is 50mL/ The reaction gas of min carries out catalytic reaction, in described reaction gas, is 600ppm containing formaldehyde gas, and surplus is air, formaldehyde gas By Balance Air N2Flow through paraformaldehyde bubbler (heating water bath 36 DEG C) to bring into.Course of reaction controls reaction temperature 120 DEG C, will Reaction end gas by nickel reburner, carries out the on-line determination reaction time by fid detector after carbon molecular sieve chromatographic column separates Formaldehyde in the tail gas flowed out when being respectively 4h, 24h, 48h, 60h, CO and CO2Content, thus calculating reacting time be respectively Formaldehyde conversion and CO when 4h, 24h, 48h, 60h2Selectivity, the result of gained see table:
The purest Co3O4Catalyst stability is poor, and formaldehyde conversion is up to 84% and stablizes 4h, this Time CO2Selectivity is 78.52%;Then as the increase in reaction time, the conversion ratio of formaldehyde begins to decline to 71%, and CO2Select Property is increased to 82.44%;After 15h, formaldehyde conversion is down to 43%, CO2The most stable 82%;During 20h, catalyst all loses Living, formaldehyde conversion is reduced to 0, CO2Selectivity also drops to 0.
In sum, the catalyst used by a kind of formaldehyde through catalytic oxidation of the present invention just can make formaldehyde room temperature 25 DEG C Conversion ratio reaches 100%, and this catalyst has good stability and CO simultaneously2Selectivity.
Above said content is only the basic explanation under present inventive concept, and according to appointing that technical scheme is made What equivalent transformation, all should belong to protection scope of the present invention.

Claims (1)

1. a preparation method for the catalyst used by formaldehyde through catalytic oxidation, the described catalyst used by formaldehyde through catalytic oxidation is Core, shell structure, described core is Co3O4, shell is CeO2, the ratio of nucleocapsid press Co, Ce metallic atom molar percentage calculate, Specific as follows:
Co 95.55–97.60%
Ce 2.40–4.45%;
The preparation method of the described catalyst used by formaldehyde through catalytic oxidation, it is characterised in that i.e. initially with co-precipitation Method prepares Co3O4Catalyst granules, then at Co3O4The area load CeO of catalyst granules2Shell, its preparation process has Body comprises the steps:
(1) by the Co (NO of 1mol/L3)2Solution I and the Na of 0.5mol/L2CO3Solution II by volume ratio is that 1:3.5 mixes Closing, controlling every amount is that the mixed liquor of gained is dropwise added drop-wise to the Na equipped with 0.5mol/L by 0.05 0.07mL2CO3Solution III In beaker, controlling speed of agitator during dropping is 200 300r/min, and temperature 60 C, by pH meter on-line monitoring by pH value control System completion of dropwise addition in the range of 9.4-9.8, treats completion of dropwise addition, suction filtration after ageing 1h, and the filter cake of gained distilled water washs 6 times After, then filter cake is dried 12h through 120 DEG C, then in 300 DEG C of roasting 4h, obtain powder cobaltosic oxide, then sieve, obtain particle Degree is the cobaltosic oxide powder of 200 250 mesh;
Above-mentioned in beaker equipped with the Na of 0.5mol/L2CO3The amount of solution III according to the stirring-head of mechanical agitator near but not Encounter at the bottom of beaker and the Na of 0.5mol/L can be touched2CO3Solution III is as the criterion;
(2) adding, in the cerous nitrate aqueous solution IV that concentration is 0.035-0.066mol/L, the granularity prepared by step (1) is The powder cobaltosic oxide of 200 250 mesh, and it is stirred continuously formation suspension, then with 0.5mol/L's under the conditions of 60 DEG C Na2CO3Aqueous solution V regulation suspension pH value is 7.0, and suction filtration after ageing 2h, the filter cake of gained is washed with deionized 6 times, finally Successively at 120 DEG C of dry 12h, roasting 4h at 350 DEG C, obtain the catalyst used by formaldehyde through catalytic oxidation;
The cobaltosic oxide powder of the cerous nitrate the aqueous solution IV and 200-250 mesh of above-mentioned 0.035-0.066mol/L used Amount, by mole calculating, i.e. Co:Ce is 95.55 97.60%:2.40 4.45%.
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