CN104492433A - Adsorption catalyst based on activated carbon felt base as well as preparation method and application of adsorption catalyst - Google Patents
Adsorption catalyst based on activated carbon felt base as well as preparation method and application of adsorption catalyst Download PDFInfo
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- CN104492433A CN104492433A CN201410782254.3A CN201410782254A CN104492433A CN 104492433 A CN104492433 A CN 104492433A CN 201410782254 A CN201410782254 A CN 201410782254A CN 104492433 A CN104492433 A CN 104492433A
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Abstract
The invention discloses an adsorption catalyst based on an activated carbon felt base. The adsorption catalyst takes an activated carbon felt as a carrier, adopts one of noble metals Pd, Au, Ag or transitional metals Cu, Fe, Cr and Mn is taken as an active component and uses one of K, Zn, Ni or Ce as an auxiliary component. The adsorption catalyst comprises 1-10% by weight of the active component, 0.1-3% by weight of the auxiliary component and the balance of the activated carbon felt. The adsorption catalyst disclosed by the invention is applied to low-temperature treatment of waste water and waste gas which contain phenol, and has the advantages of good phenol adsorption performance, mild catalytic oxidation condition, and can be recycled.
Description
Technical field
The present invention relates to a kind of catalyst for the treatment of phenol wastewater, waste gas, particularly relate to a kind of catalyst simultaneously with adsorption function, the invention still further relates to the preparation method and application of this catalyst.
Background technology
In many industrial production or use aldehydes matter to be raw materials for production, or produce aldehydes matter accessory substance, these aldehydes matters enter in waste water and/or waste gas, form phenol wastewater or containing phenol waste gas.Toxicity of phenols in waste water is high, be difficult to biodegradation, and the phenol in waste gas easily causes dermal tokicity.Therefore, there is strict restriction in China to the concentration of emission of aldehydes matter in phenol wastewater and waste gas, the maximum permissible concentration of regulation volatile phenol in water is respectively: drinking water 0.002mg/ L, agricultural water 1.0mg/L, industrial wastewater discharge standard 0.5mg/L, in the flue gas of industrial waste gas, aldehydes matter 1 class district prohibits row, 2 class district limit row maximum permissible concentration 115mg/m
3.
Active carbon has more flourishing pore structure, has higher absorption property to the waste water of variable concentrations and waste gas, is therefore the improvement that the adsorption technology of adsorbent is widely used in organic wastewater and waste gas with active carbon.But, after charcoal absorption is saturated, need to carry out regeneration to recover its absorption property to it.Normally carry out the absorption property of activity recovery charcoal in industry with hot in-place recycling, hot recycling technique is specially the active carbon that process absorption is saturated under the hot conditions of 800 ~ 850 DEG C, and it belongs in fact organic thermal desorption (fraction oxidation Decomposition) process.Also need during active carbon hot recycling to carry out subsequent treatment to desorbs contaminants, technique is more complicated.Therefore, the hot recycling of active carbon has following comparatively significantly shortcoming: 1) because hot recycling needs high temperature, so regenerating active carbon energy consumption is larger; 2) hot conditions regeneration easily causes the polymerisation of adsorb organic compound, adds organic desorption difficulty, causes regenerating active carbon thorough, after active carbon hot recycling adsorbance loss be about 5 ~ 15%/time, adsorbance loss late is larger; 3) hot conditions of hot recycling needs specific regeneration reactor, adds permanent plant investment; 4) strange land regeneration is also corresponding adds cost of transportation.
Summary of the invention
The object of this invention is to provide a kind of adsorption catalyst based on activated carbon felt base, and the preparation method and application of this adsorption catalyst.
Adsorption catalyst based on activated carbon felt base of the present invention is a kind of is carrier with activated carbon felt, noble metal or transition metal are the multicomponent catalyst of main active component, particularly, described catalyst is with precious metals pd, Au, Ag or transition metal Cu, Fe, Cr, one in Mn is active component, with K, Zn, one in Ni or Ce is helper component, take activated carbon felt as carrier, in described catalyst, the percentage by weight of active component is 1% ~ 10%, the percentage by weight of helper component is 0.1% ~ 3%, all the other are activated carbon felt, and the surface area of activated carbon felt is 900 ~ 2000m
2/ g.
Wherein, the carrier active carbon felt that catalyst of the present invention uses is raw material by organic fiber felts such as polyacrylonitrile fibre felt, viscose rayon felt, pitch-based fiber felts, carbonizes, activates the activated carbon felt of the high-specific surface area made under certain temperature, pressure.
The present invention is by carried metal active component on described activated carbon felt, and Pyrogentisinic Acid has catalyzing oxidizing degrading activity.
Adsorption catalyst based on activated carbon felt base of the present invention adopts equal-volume or excess volume infusion process, to meet the hydrochloride of the described active component of load capacity or nitrate and to meet the mixed solution total immersion stain activated carbon felt carrier of nitrate of described helper component of load capacity, room temperature is placed 0.5 ~ 6 hour, 50 ~ 100 DEG C of dryings 6 ~ 18 hours, calcine 6 ~ 18 hours under 160 ~ 500 DEG C of inert atmospheres again, obtain the described adsorption catalyst based on activated carbon felt base.
Adsorption catalyst based on activated carbon felt base of the present invention can be used for waste water, the waste gas of K cryogenic treatment containing phenol.
The using method of the adsorption catalyst based on activated carbon felt base of the present invention is: under normal pressure and temperature, adsorb phenol in waste water or waste gas 0.5 ~ 18 hour with adsorption catalyst of the present invention, adsorption catalyst air drying after absorption, load fixed bed reactors, under normal pressure, 170 ~ 400 DEG C of conditions, with 500 ~ 2000h
-1air speed pass into oxidizing gas, reacting 0.5 ~ 6 hour, is carbon dioxide and water by oxidation of phenol, and adsorption catalyst after regeneration cooling Posterior circle utilizes.
Wherein, the air that described oxidizing gas can be air, oxygen volume content is 3 ~ 10%, oxygen volume content be 3 ~ 10% helium, oxygen volume content be the argon gas etc. of 3 ~ 10%.
Adsorption catalyst based on activated carbon felt base of the present invention compares with general carrier active carbon, the micropore of activated carbon felt is more flourishing, specific area is larger, adsorption catalyst has higher Adsorption of Phenol performance, the phenol in waste water, waste gas can be adsorbed efficiently, wastewater treatment capacity is larger, waste water after process can reuse, has saved water resource.
Adsorption catalyst of the present invention compares with the catalyst of existing a kind of active metal of load, bimetallic active is higher, and meanwhile, carried noble metal can significantly improve the catalytic activity of adsorption catalyst, oxidized by the phenol adsorbed to a greater extent, do not produce secondary pollution.
Adsorption catalyst of the present invention still has higher adsorption capacity after catalytic oxidation, significantly reduces the adsorbance loss late of catalyst, and can continuous several times use, easily promote, cost is low.
The catalytic oxidation mild condition of adsorption catalyst of the present invention, can carry out under low-temperature atmosphere-pressure, and the residual waste water in catalyst of draining before heating, do not heat a large amount of waste water, significantly can reduce energy consumption.
The present invention not only can process the phenol in waste water, can also process the phenol in waste gas, has widened the process range of adsorption catalyst, adopts two kinds of dipping methods to prepare adsorption catalyst, has widened the preparation method of catalyst, be conducive to large-scale production.
Detailed description of the invention
Embodiment 1
8.33g palladium bichloride is added in the zinc nitrate solution of 100mL 0.15mol/L and be mixed with dipping solution.Be 900m by 100g specific area
2the activated carbon felt of/g is poured in maceration extract and is stirred; room temperature places 0.5 hour; dry 6 hours at 110 DEG C; calcine 12 hours under 300 DEG C of argon shields again; naturally cool to room temperature, make adsorption catalyst Pd5Zn1/ACF, in adsorption catalyst, metal component content is Pd5%; Zn1%, all the other are activated carbon felt.
Will containing the waste water 50mL of 500ppm phenol by being equipped with the adsorption column of 0.5gPd5Zn1/ACF adsorption catalyst, after absorption terminates, in Catalyst Adsorption waste water 98% phenol.After emptying waste water, with 500h under normal pressure
-1air speed in catalyst, pass into air, and being warming up to 400 DEG C, constant temperature catalytic oxidation 1.5 hours, is carbon dioxide and water by the oxidation of phenol of absorption.After catalytic oxidation terminates, in oxidizing atmosphere, catalyst is dropped to room temperature, enter next absorption/oxidation cycle.
Embodiment 2
14.63g chlorauride is added in the potassium nitrate solution of 100mL 0.77mol/L and be mixed with dipping solution.Be 900m by 95g specific area
2the activated carbon felt of/g is poured in maceration extract and is stirred; room temperature places 1.5 hours; dry 6 hours at 110 DEG C; calcine 8 hours under 250 DEG C of argon shields again; naturally cool to room temperature, make adsorption catalyst Au7K3/ACF, in adsorption catalyst, metal component content is Au7%; K3%, all the other are activated carbon felt.
Will containing the waste water 50mL of 700ppm phenol by being equipped with the adsorption column of 0.5gAu7K3/ACF adsorption catalyst, after absorption terminates, in Catalyst Adsorption waste water 96% phenol.After emptying waste water, with 700h under normal pressure
-1air speed in catalyst, pass into air, and being warming up to 200 DEG C, constant temperature catalytic oxidation 0.5 hour, is carbon dioxide and water by the oxidation of phenol of absorption.After catalytic oxidation terminates, in oxidizing atmosphere, catalyst is dropped to room temperature, enter next absorption/oxidation cycle.
Embodiment 3
4.72g silver nitrate is added in the nickel nitrate solution of 100mL 0.085mol/L and be mixed with dipping solution.Be 1300m by 95g specific area
2the activated carbon felt of/g is poured in maceration extract and is stirred; room temperature places 1.5 hours; dry 4 hours at 110 DEG C; calcine 8 hours under 250 DEG C of argon shields again; naturally cool to room temperature, make adsorption catalyst Ag3Ni0.5/ACF, in adsorption catalyst, metal component content is Ag3%; Ni0.5%, all the other are activated carbon felt.
Will containing the waste gas of 300ppm phenol by being equipped with the adsorption column of 0.5g Ag3Ni0.5/ACF adsorption catalyst, upon adsorption penetrate into 0.1ppm after, with 900h under normal pressure
-1air speed in catalyst, pass into the air that oxygen content is 10%, and being warming up to 200 DEG C, constant temperature catalytic oxidation 0.5 hour, is carbon dioxide and water by the oxidation of phenol of absorption.After catalytic oxidation terminates, in oxidizing atmosphere, catalyst is dropped to room temperature, enter next absorption/oxidation cycle.
Embodiment 4
Mixed solution pH value 100mL being contained 176.5mg/L copper nitrate and 12mg/L cerous nitrate is adjusted to 5.5, adds 3g 1500m
2/ g activated carbon felt, vibrate under room temperature 3h, carries out Static Adsorption.The solid phase obtained is filtered in absorption afterwards dries 8 hours at 80 DEG C, then calcines 10 hours under 400 DEG C of argon shields, naturally cools to room temperature; make adsorption catalyst Cu1Ce0.1/ACF; in adsorption catalyst, metal component content is Cu1%, Ce0.1%, and all the other are activated carbon felt.
Will containing the waste water 50mL of 900ppm phenol by being equipped with the adsorption column of 0.5gCu1Ce0.1/ACF adsorption catalyst, after absorption terminates, in Catalyst Adsorption waste water 95% phenol.After emptying waste water, with 1100h under normal pressure
-1air speed in catalyst, pass into air, and being warming up to 250 DEG C, constant temperature catalytic oxidation 1.5 hours, is carbon dioxide and water by the oxidation of phenol of absorption.After catalytic oxidation terminates, in oxidizing atmosphere, catalyst is dropped to room temperature, enter next absorption/oxidation cycle.
Embodiment 5
64.93g ferric nitrate is added in the potassium nitrate solution of 100mL 0.77mol/L and be mixed with dipping solution.Be 1600m by 95g specific area
2the activated carbon felt of/g is poured in maceration extract and is stirred; room temperature places 3 hours; dry 7 hours at 90 DEG C; calcine 12 hours under 350 DEG C of argon shields again; naturally cool to room temperature, make adsorption catalyst Fe9K3/ACF, in adsorption catalyst, metal component content is Fe9%; K3%, all the other are activated carbon felt.
Will containing the waste water 50mL of 1200ppm phenol by being equipped with the adsorption column of 0.5gFe9K3/ACF adsorption catalyst, after absorption terminates, in Catalyst Adsorption waste water 90% phenol.After emptying waste water, with 1300h under normal pressure
-1air speed in catalyst, pass into air, and being warming up to 300 DEG C, constant temperature catalytic oxidation 2 hours, is carbon dioxide and water by the oxidation of phenol of absorption.After catalytic oxidation terminates, in oxidizing atmosphere, catalyst is dropped to room temperature, enter next absorption/oxidation cycle.
Embodiment 6
92.31g chromic nitrate is added in the zinc nitrate solution of 100mL 0.62mol/L and be mixed with dipping solution.Be 1700m by 95g specific area
2the activated carbon felt of/g is poured in maceration extract and is stirred; room temperature places 4 hours; dry 8 hours at 70 DEG C; calcine 13 hours under 300 DEG C of argon shields again; naturally cool to room temperature, make adsorption catalyst Cr6Zn2/ACF, in adsorption catalyst, metal component content is Cr 6%; Zn2%, all the other are activated carbon felt.
Will containing the waste water 50mL of 1000ppm phenol by being equipped with the adsorption column of 0.5gCr6Zn2/ACF adsorption catalyst, after absorption terminates, in Catalyst Adsorption waste water 93% phenol.After emptying waste water, with 1500h under normal pressure
-1air speed in catalyst, pass into air, and being warming up to 260 DEG C, constant temperature catalytic oxidation 3 hours, is carbon dioxide and water by the oxidation of phenol of absorption.After catalytic oxidation terminates, in oxidizing atmosphere, catalyst is dropped to room temperature, enter next absorption/oxidation cycle.
Embodiment 7
9.14g manganese nitrate is added in the nickel nitrate solution of 100mL 0.17mol/L and be mixed with dipping solution.Be 1900m by 95g specific area
2the activated carbon felt of/g is poured in maceration extract and is stirred; room temperature places 5 hours; dry 8 hours at 70 DEG C; calcine 14 hours under 350 DEG C of argon shields again; naturally cool to room temperature, make adsorption catalyst Mn2Ni1/ACF, in adsorption catalyst, metal component content is Mn2%; Ni1%, all the other are activated carbon felt.
Will containing the waste water 50mL of 700ppm phenol by being equipped with the adsorption column of 0.5gMn2Ni1/ACF adsorption catalyst, after absorption terminates, in Catalyst Adsorption waste water 98% phenol.After emptying waste water, with 1700h under normal pressure
-1air speed in catalyst, pass into air, and being warming up to 280 DEG C, constant temperature catalytic oxidation 5 hours, is carbon dioxide and water by the oxidation of phenol of absorption.After catalytic oxidation terminates, in oxidizing atmosphere, catalyst is dropped to room temperature, enter next absorption/oxidation cycle.
Claims (6)
1. the adsorption catalyst based on activated carbon felt base, it is characterized in that taking activated carbon felt as carrier, with the one in precious metals pd, Au, Ag or transition metal Cu, Fe, Cr, Mn for active component, one in K, Zn, Ni or Ce is helper component, in described catalyst, the percentage by weight of active component is 1% ~ 10%, and the percentage by weight of helper component is 0.1% ~ 3%, and all the other are activated carbon felt.
2. adsorption catalyst according to claim 1, is characterized in that the surface area of described activated carbon felt is 900 ~ 2000m
2/ g.
3. the preparation method of adsorption catalyst described in claim 1, it is characterized in that adopting equal-volume or excess volume infusion process, to meet the hydrochloride of the described active component of load capacity or nitrate and to meet the mixed solution total immersion stain activated carbon felt carrier of nitrate of described helper component of load capacity, room temperature is placed 0.5 ~ 6 hour, 50 ~ 100 DEG C of dryings 6 ~ 18 hours, calcine 6 ~ 18 hours under 160 ~ 500 DEG C of inert atmospheres again, obtain the described adsorption catalyst based on activated carbon felt base.
4. adsorption catalyst described in claim 1 is at K cryogenic treatment phenol wastewater or containing the application in phenol waste gas.
5. the using method of adsorption catalyst described in claim 1, it is characterized in that under normal pressure and temperature, adsorbing phenol in waste water or waste gas 0.5 ~ 18 hour with described adsorption catalyst, fixed bed reactors are loaded, under normal pressure, 170 ~ 400 DEG C of conditions, with 500 ~ 2000h after air drying
-1air speed pass into oxidizing gas reaction 0.5 ~ 6 hour.
6. using method according to claim 5, it is characterized in that described oxidizing gas is air, oxygen volume content is 3 ~ 10% air, oxygen volume content be 3 ~ 10% helium or oxygen volume content be the argon gas of 3 ~ 10%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007125A (en) * | 2016-07-08 | 2016-10-12 | 重庆交通大学 | Dye wastewater treatment technology |
| CN107051388A (en) * | 2017-06-07 | 2017-08-18 | 吉林大学 | A kind of preparation method for the modified active carbon fiber cotton for removing tetracycline compound |
| CN109569273A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The administering method of petrifaction sewage treatment plant exhaust gas |
| CN109046327A (en) * | 2018-09-14 | 2018-12-21 | 宁波中傲环保科技有限公司 | A kind of adsorption catalyst |
| CN109173565A (en) * | 2018-09-14 | 2019-01-11 | 宁波中傲环保科技有限公司 | A method of processing exhaust gas |
| CN109701548A (en) * | 2018-12-31 | 2019-05-03 | 柏美迪康环境科技（上海）股份有限公司 | A kind of monoblock type VOCs catalyst for catalytic combustion and preparation method thereof |
| CN112892475A (en) * | 2021-01-15 | 2021-06-04 | 仲恺农业工程学院 | Iron modified biochar and preparation method and application thereof |
| CN112892475B (en) * | 2021-01-15 | 2023-02-28 | 仲恺农业工程学院 | Iron modified biochar and preparation method and application thereof |
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Application publication date: 20150408 |