CN103071455A - Preparation method of composite adsorption purifying agent - Google Patents
Preparation method of composite adsorption purifying agent Download PDFInfo
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Abstract
The invention provides a preparation method of a composite adsorption purifying agent. The method comprises the following steps of: washing a dead catalyst with water to remove impurities, and drying at the temperature of 100-120 DEG C for three hours; introducing a protective gas, and raising the temperature to 700-900 DEG C by microwave heating; and stopping introducing the protective gas, simultaneously introducing activating gas for activating for 20-40 minutes, cooling to the room temperature, and drying to obtain the composite adsorption purifying agent. The composite adsorption purifying agent has the advantages of rich source, low price, great reduction in the production cost, protection of the environment, saving of resources and realization of recycling. A production method is simpler, is easy to operate, has low energy consumption, contributes to reducing the emission of pollutants in a production process and no secondary pollution. The reaction rate is increased, the reaction time is shortened, and the reaction cost is reduced. A produced ZnO/active carbon composite adsorption purifying agent has ideal effects on the degradation of organic dyes, treatment of heavy metal ions in waste water and photocatalysis sterilization, and plays an important role in comprehensively treating environmental pollution.
Description
Technical field
The present invention relates to
OneThe preparation method of kind of composite adsorption cleanser especially relates to a kind of preparation method of the composite adsorption cleanser for degraded dyeing waste-water direct dyes, belongs to smelting absorption purifier preparing technical field.
Background technology
The waste water from dyestuff that printing and dyeing and dye industry produce is one of industrial wastewater, and this is normally manually synthetic because of dyestuff, has complicated aromatic molecules structure, so dye molecule is stable, is difficult to by biological decomposition.If deal with improperly, enter in the water body, can cause serious water pollution.
In recent years, the dye industry of China has been obtained huge development.Also brought serious problem of environmental pollution in the time of the dye industry development.Waste water from dyestuff enters water body, not only can cause uncomfortable on the sense organ, and can cause the water body light transmittance to reduce the destruction that causes water ecosystem.Contain the multiple organic matter that bio-toxicity or three causes performance that has in the waste water from dyestuff, may cause the breaking-up of community of aquatic organism.China is one of more serious country of shortage of water resources and water damage ratio; aggravation along with water resources crisis; how to carry out cleaner production in each operation of printing and dyeing; reduce water consumption and wastewater discharge; and the production technology of in waste water treatment, using cleaning; the transfer of control secondary pollution and pollutant, and realize reuse after the wastewater treatment, this has great realization meaning and economic implications to the sustainable development of alleviating water resources crisis, keeping dyeing.Simultaneously effective improvement of waste water from dyestuff also has important positive effect to human health and environmental protection.
It is to utilize the porosu solid adsorbent that one or more materials in the sewage are adsorbed on the surface of solids and remove that absorption method is disposed of sewage, and is one of current most important method for treating water, is widely used in the various wastewater treatments by people.Utilize absorption method to remove water pollutant to have that efficient height, speed are fast, strong adaptability and the advantage such as easy to operate.In addition, because adsorbent is all water insoluble, absorption only occurs in the surface of solids, and chemical reaction does not further occur, and therefore generally can not introduce new chemical substance in handled water.Sorbing material commonly used has following several at present: acticarbon, mineral adsorbent, coal and coal slag adsorbent, ion exchange resin adsorbent etc.
Porous adsorbent commonly used is combined with the semi-conducting material catalysis material, just day by day comes into one's own by the Treatment by Photocatalysis Oxidation toxic pollutant.Zinc oxide (ZnO) is that (energy gap is 3.37meV to a kind of novel II-VI family semiconductor material with wide forbidden band; The free exciton binding energy is 60meV, its binding energy can surpass 100 meV in superlattices), the exciton of larger binding energy is easier at room temperature realizes high efficiency Laser emission owing to have, so ZnO is a kind of short-wave long light-emitting material very promising aspect ultraviolet and blue emission.ZnO is except can being widely used in various optics and electronics devices at present, and the aspects such as the heavy metal ion in photocatalysis treatment of waste water and degradating organic dye also have broad application prospects.Especially photochemical catalytic oxidation phenol and the degraded azo dyes aspect ZnO photocatalysis effect in addition be better than titanium dioxide (TiO
2), be considered to alternative TiO
2One of high-activity photocatalyst.But single zinc oxide material surface adsorption property is relatively poor, the material specific area is little, exists serious photoetch problem, thereby greatly reduces its photocatalysis performance.
Active carbon is as porous inertia adsorbent, because of its price relatively cheap, and have larger specific area and good absorption property, special vestibule space multistory is selective, specificity catalysis and photocatalysis property with metallic catalyst produces by stronger interaction are used as various catalyst carriers more and more.Carbon based material and zinc oxide not only can be overcome the defectives such as zinc oxide photocatalysis efficient is low in conjunction with preparing charcoal base zinc oxide composite, have good chemical stability, the high mechanical properties that the carbon based material of high-specific surface area and absorption property has, the loose structure feature that is conducive to the reactant diffusion, and the specificity photocatalysis property that obtains by stronger interaction with zinc oxide, quick adsorption purification and the rich surface that can realize organic pollution are poly-, accelerating the photocatalytic degradation reaction rate, is one of effective way that improves the zinc oxide utilization rate.
The method for preparing at present charcoal base zinc oxide composite photocatalyst both at home and abroad mainly contains and is divided into liquid phase method (sluggish precipitation, infusion process, sol-gel process, microemulsion method, hydro-thermal method etc.) and solid phase method, also has in addition the methods such as injection method and catalyzed carbon thermal reduction.K. Byrappa etc. in " Journal of Material Science " 41 volumes the 5th interim proposition in 2006 at 150 ℃, 20 ~ 30 normal atmospheres are depressed photocatalyst of zinc oxide loaded to infusion process and be can be made into the ZnO/AC composite photo-catalyst on the active carbon, this composite photo-catalyst acid violet dyestuff of can effectively degrading, its photocatalytic degradation successful is better than commercial ZnO and undressed active carbon.K. Zhang etc. at " Journal of the Korean Ceramic Society " 47 volumes the 2nd interim report in 2010 by sol-gal process, with NACF (ACF) and Zn (NO
3)
2For presoma has prepared the ACF/ZnO composite, research finds that this material has higher absorption and photocatalytic activity to methylene blue solution under UV-irradiation and ul-trasonic irradiation, particularly when reaction temperature is 500 ℃ its photocatalytic activity apparently higher than other samples.Ma Chuanguo etc. reported in the 37 volume o. 11ths " New Chemical Materials " in 2009 and adopt sluggish precipitation to prepare carbon nanotube loaded ZnO particle composite material.Studies show that in the situation of carbon zinc constant rate zinc ion concentration is in 0.4 ~ 1.0mol/L scope, the zinc oxide major part in the composite loads on the CNT, and take the graininess form as main, particle size is about 40nm, and is better dispersed.Song Younan etc. adopt sol method to synthesize ZnO/ CNT (CNTs) composite photocatalyst material at " application chemical industry " 41 volumes in 2012 the 7th interim report.Experiment shows that this composite photo-catalyst has good absorption and photocatalysis performance, and the purer ZnO of its photocatalytic activity is significantly increased, and reaction is 2 hours under the 300W xenon source, can reach 82.38% to the degradation rate of quadracycline.The photoetch of the electronics character energy establishment ZnO of CNT excellence promote ZnO stability and photocatalytic oxidation properties in the aqueous solution, so this composite photo-catalyst is having potential using value aspect the processing of antibiotic waste water.
Although the method for making ZnO/absorbent charcoal composite material is numerous, but existing method is confined to presoma be mixed with various forms with active carbon, carbon fiber and CNT etc. or flood, take subsequently mode dry and that solidify to obtain charcoal base ZnO composite, these method costs are high, complex process, be difficult to suitability for industrialized production, even also pollute the environment.For example the used solvent of sol-gel process reaction mostly is organic solvent, does not utilize then can cause certain harm to environment if do not add to reclaim, if the reaction time is longer, also can cause certain harm to human body; The employed HTHP synthesis device of hydro-thermal method is expensive, and investment is large, and operation requirements is high.This shows, if can utilize existing recyclable regenerative waste resource, prepare high performance charcoal base ZnO compound adsorbent by simple technological process, to reducing the photocatalysis performance of cost, raising ZnO, promote its industrialization promotion to have important practical significance.
As everyone knows, vinyl acetate is one of Organic Chemicals of in the world output maximum, the active carbon that needs in the production process of vinyl acetate to be loaded with zinc acetate is as catalyst, and these catalyst just can lose activity in use for some time, causes a large amount of discarded of catalyst.Contain the zinc acetate about 25% in the dead catalyst, it is the important source material of producing zinc oxide, the active carbon of inactivation also can obtain regeneration through Overheating Treatment, but owing to lack suitable processing method and means, these dead catalyst are not effectively utilized, not only caused the waste of resource, simultaneously also to environment structure threat.And microwave heating technique develops into a kind of new heating technique gradually in recent years, compare with traditional heating means, heating using microwave has heating high efficiency, selective, untouchable, globality, uniformity, cleanliness without any pollution, startup and stopped heating is very fast and can improve the advantageous characteristic feature such as material property, is widely used in the fields such as synthetic material science.Characteristics in conjunction with microwave heating technique, the dead catalyst that produces in the vinyl acetate production is prepared ZnO/ active carbon composite adsorption cleanser by the heating using microwave one-step method, can make the product pattern more excellent, the ZnO particle size is less, the active carbon pore distribution is more even, has greatly shortened the time of ZnO crystallization process and regenerating active carbon process simultaneously, has improved production efficiency, and preparation process cleanliness without any pollution, process are easy to control, also can realize the serialization production run.Therefore the method has found new direction for the comprehensive utilization waste catalyst for vinyl acetate synthesis.
In sum, seek the method for effectively utilizing a large amount of dead catalyst that produce in the vinyl acetate production process, can alleviate environmental pressure, can utilize greatly resource again.Therefore the present invention's method of proposing a kind of heating using microwave one-step method making ZnO/active carbon composite adsorption cleanser has important science and practical value, meets national medium-term and long-term science and development planning outline.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of composite adsorption cleanser for degraded dyeing waste-water direct dyes, adopt the adjustable tubular type microwave heating equipment of power, in the stages such as removal of impurities, calcinings, the flow of control reaction temperature, soak time and activated gas, dead catalyst is utilized effectively, when namely regenerating active carbon, load on activated carbon surface so that the zinc acetate decomposes is zinc oxide, obtain ZnO/ active carbon composite adsorption cleanser.
The present invention is achieved through the following technical solutions:
OnePlant the preparation method of composite adsorption cleanser, following each step of process:
(1) dead catalyst is lower dry 3 hours at 100～120 ℃ after impurity is removed in washing;
(2) material with step (1) passes into protective gas, and heating using microwave is warming up to 700～900 ℃; Then stop to pass into protective gas, pass into simultaneously activated gas and activate 20～40min, be cooled to room temperature again after, drying namely obtains the composite adsorption cleanser.
The dead catalyst of described step (1) is to produce the dead catalyst that produces in the vinyl acetate process, and the mass percent that contains zinc acetate is 20～30%.
The protective gas of described step (2) is nitrogen.
The speed of described step (2) heat temperature raising is 15～20 ℃/min.
The activated gas of described step (2) is the carbon dioxide of 500～600ml/min, perhaps the mist of 500～600ml/mim carbon dioxide and 0.5～1.0ml/min steam.
This charcoal base zinc oxide composite adsorption cleanser is to contain the waste active carbon of zinc acetate amount as 20～30% as raw material, by one step of heating using microwave modification, the Zinc oxide particles that is become by the zinc acetate decomposes in the load when making Regenevating Waste Activated Carbon.The present invention has not only realized the secondary utilization of discarded object, and overcome the defectives such as single zinc oxide material surface adsorption property is relatively poor, the material specific area is little, photocatalysis efficiency is low, obtain the specificity photocatalysis property so that have charcoal base and the zinc oxide of high-specific surface area and absorption property by stronger interaction.This composite purifying agent can adapt to direct dyes difficult degradation in the waste water, colourity high, and the clearance of direct dyes is reached more than 90%.
The present invention has the following advantages:
(1) waste resource of the existing recycling capable of circulation of prepared using, the source is sufficient, and price is low, has greatly reduced production cost, has also protected environment simultaneously, has saved resource, has realized resource reutilization.
(2) production method is simpler, processing ease, and energy consumption is low, and the production process pollutant emission is low, non-secondary pollution.
(3) adopt the heating using microwave new technology, improved reaction rate, shortened the reaction time, reduced reaction cost.
(4) the ZnO/ active carbon composite adsorption cleanser of producing to degradating organic dye, process the ideal effect that heavy metal ion in the waste water and photo-catalyst all have, significant aspect comprehensive regulation environmental pollution.
The specific embodiment
The present invention will be further described below by embodiment.
Embodiment 1
(1) 25g being produced the dead catalyst (mass percent that contains zinc acetate is 20～25%) that produces in the vinyl acetate process removes impurity through washing and is placed in the baking oven lower dry 3 hours at 100 ℃;
(2) material with step (1) places in the microwave tube type heating furnace, passes into protective gas nitrogen, and is warming up to 750 ℃ take speed as 15 ℃/min heating using microwave; Then stop to pass into protective gas, the carbon dioxide that passes into simultaneously 500ml/min activates 35min, be cooled to room temperature again after, drying namely obtains the composite adsorption cleanser, its specific area is 1156m
2/ g, yield is 65.3%.
The composite adsorption cleanser that 0.7g is made joins in the congo red solution that 200mL concentration is 40mg/L, reaches balance 25 ℃ of lower stirrings of constant temperature, and the percent of decolourization of congo red reaches 91% behind the 295min.
Embodiment 2
(1) 25g being produced the dead catalyst (mass percent that contains zinc acetate is 20～25%) that produces in the vinyl acetate process removes impurity through washing and is placed in the baking oven lower dry 3 hours at 110 ℃;
(2) material with step (1) places in the microwave tube type heating furnace, passes into protective gas nitrogen, and is warming up to 800 ℃ take speed as 18 ℃/min heating using microwave; Then stop to pass into protective gas, the carbon dioxide that passes into simultaneously 600ml/min activates 30min, be cooled to room temperature again after, drying namely obtains the composite adsorption cleanser, its specific area is 1156m
2/ g, yield is 65.3%.
The composite adsorption cleanser that 0.7g is made joins in the direct dark blue solution that 200mL concentration is 40mg/L, reaches balance 25 ℃ of lower stirrings of constant temperature, and direct dark blue percent of decolourization reaches 93% behind the 280min.
Embodiment 3
(1) 25g being produced the dead catalyst (mass percent that contains zinc acetate is 20～25%) that produces in the vinyl acetate process removes impurity through washing and is placed in the baking oven lower dry 3 hours at 120 ℃;
(2) material with step (1) places in the microwave tube type heating furnace, passes into protective gas nitrogen, and is warming up to 800 ℃ take speed as 20 ℃/min heating using microwave; Then stop to pass into protective gas, the mist that passes into simultaneously 550ml/mim carbon dioxide and 0.5～1.0ml/min steam activates 40min, be cooled to room temperature again after, drying namely obtains the composite adsorption cleanser, its specific area is 1109m
2/ g, yield is 54.6%.
The composite adsorption cleanser that 0.7g is made joins in the congo red solution that 200mL concentration is 40mg/L, reaches balance 25 ℃ of lower stirrings of constant temperature, and the percent of decolourization of congo red reaches 90% behind 300 min.
Embodiment 4
(1) 25g being produced the dead catalyst (mass percent that contains zinc acetate is 26～30%) that produces in the vinyl acetate process removes impurity through washing and is placed in the baking oven lower dry 3 hours at 105 ℃;
(2) material with step (1) places in the microwave tube type heating furnace, passes into protective gas nitrogen, and is warming up to 850 ℃ take speed as 20 ℃/min heating using microwave; Then stop to pass into protective gas, pass into simultaneously the 550ml/mim carbon dioxide and activate 25min, be cooled to room temperature again after, drying namely obtains the composite adsorption cleanser, its specific area is 1112m
2/ g, yield is 63.5%.
Is it 40mg/L's that the composite adsorption cleanser that 0.7g is made joins 150mL concentration? in the solution, reach balance 25 ℃ of lower stirrings of constant temperature, direct dark blue percent of decolourization reaches 92% behind the 290min.
Embodiment 5
(1) will produce the dead catalyst (mass percent that contains zinc acetate is 26～30%) that produces in the vinyl acetate process removes impurity through washing and is placed in the baking oven lower dry 3 hours at 112 ℃;
(2) material with step (1) places in the microwave tube type heating furnace, passes into protective gas nitrogen, and is warming up to 700 ℃ take speed as 20 ℃/min heating using microwave; Then stop to pass into protective gas, the mist that passes into simultaneously 600ml/mim carbon dioxide and 0.5～1.0ml/min steam activates 35min, be cooled to room temperature again after, drying namely obtains the composite adsorption cleanser, its specific area is 1008m
2/ g, yield is 64.5%.
Is it 50mg/L's that the composite adsorption cleanser that 0.5g is made joins 150mL concentration? in the solution, reach balance 25 ℃ of lower stirrings of constant temperature, direct dark blue percent of decolourization reaches 94% behind the 340min.
Embodiment 6
(1) 25g being produced the dead catalyst (mass percent that contains zinc acetate is 25～30%) that produces in the vinyl acetate process removes impurity through washing and is placed in the baking oven 115 ℃ of dryings 3 hours;
(2) material with step (1) places in the microwave tube type heating furnace, passes into protective gas nitrogen, and is warming up to 900 ℃ take speed as 20 ℃/min heating using microwave; Then stop to pass into protective gas, the mist that passes into simultaneously 500ml/mim carbon dioxide and 0.5～1.0ml/min steam activates 20min, be cooled to room temperature again after, drying namely obtains the composite adsorption cleanser, its specific area is 1100m
2/ g, yield is 58.9%.
The composite adsorption cleanser that 0.5g is made joins in the direct dark blue solution that 150mL concentration is 50mg/L, reaches balance 25 ℃ of lower stirrings of constant temperature, and direct dark blue percent of decolourization reaches 96% behind the 320min.
Claims (5)
1.
OnePlant the preparation method of composite adsorption cleanser, it is characterized in that through following each step:
(1) dead catalyst is lower dry 3 hours at 100～120 ℃ after impurity is removed in washing;
(2) material with step (1) passes into protective gas, and heating using microwave is warming up to 700～900 ℃; Then stop to pass into protective gas, pass into simultaneously activated gas and activate 20～40min, be cooled to room temperature again after, drying namely obtains the composite adsorption cleanser.
2. the preparation method of composite adsorption cleanser according to claim 1 is characterized in that: the dead catalyst of described step (1) is to produce the dead catalyst that produces in the vinyl acetate process, and the mass percent that contains zinc acetate is 20～30%.
3. the preparation method of composite adsorption cleanser according to claim 1 and 2, it is characterized in that: the protective gas of described step (2) is nitrogen.
4. the preparation method of composite adsorption cleanser according to claim 1 and 2, it is characterized in that: the speed of described step (2) heat temperature raising is 15～20 ℃/min.
5. the preparation method of composite adsorption cleanser according to claim 1 and 2, it is characterized in that: the activated gas of described step (2) is the carbon dioxide of 500～600ml/min, perhaps the mist of 500～600ml/mim carbon dioxide and 0.5～1.0ml/min steam.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103754977A (en) * | 2014-01-17 | 2014-04-30 | 哈尔滨工业大学 | Active carbon modification method for emergently treating sudden organic pollution of drinking water |
| CN103752287A (en) * | 2014-01-26 | 2014-04-30 | 河北工程大学 | Building finishing pollutant treating agent and preparation method thereof |
| CN104940034A (en) * | 2015-07-10 | 2015-09-30 | 崇明本 | Diisostearyl malate decolorizing agent and deep decolorizing method |
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| CN109499563A (en) * | 2017-09-15 | 2019-03-22 | 张家港市沐和新材料技术开发有限公司 | A kind of preparation method of zinc oxide-active carbon composite catalyst |
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| CN111068777A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Regeneration method of waste catalyst for acetylene method vinyl acetate |
| CN112439463A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Regeneration method of waste catalyst for acetylene method vinyl acetate |
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| CN114763348A (en) * | 2021-05-18 | 2022-07-19 | 上海素馨化工科技有限公司 | Preparation method of 2, 5-thiophenedicarboxylic acid and 2, 5-thiophenedicarboxylic acid |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710116A (en) * | 2005-06-09 | 2005-12-21 | 昆明理工大学 | Method for extracing zinc from waste zinc acetate |
| CN1724165A (en) * | 2005-06-07 | 2006-01-25 | 昆明理工大学 | Process of treating catalyst carrier waste active carbon for synthesizing vinyl acetate |
| CN101224377A (en) * | 2007-10-16 | 2008-07-23 | 昆明理工大学 | Compound depurative preparing method for removing organic volatiles from air |
| CN102133523A (en) * | 2011-01-11 | 2011-07-27 | 湘潭大学 | Method for re-activating inactivated catalyst through catalytic chlorination of pyridine nitrile |
| US20110312485A1 (en) * | 2010-06-18 | 2011-12-22 | The Governors Of The University Of Alberta | Method for preparation of activated carbon |
-
2013
- 2013-02-26 CN CN2013100597910A patent/CN103071455A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724165A (en) * | 2005-06-07 | 2006-01-25 | 昆明理工大学 | Process of treating catalyst carrier waste active carbon for synthesizing vinyl acetate |
| CN1710116A (en) * | 2005-06-09 | 2005-12-21 | 昆明理工大学 | Method for extracing zinc from waste zinc acetate |
| CN101224377A (en) * | 2007-10-16 | 2008-07-23 | 昆明理工大学 | Compound depurative preparing method for removing organic volatiles from air |
| US20110312485A1 (en) * | 2010-06-18 | 2011-12-22 | The Governors Of The University Of Alberta | Method for preparation of activated carbon |
| CN102133523A (en) * | 2011-01-11 | 2011-07-27 | 湘潭大学 | Method for re-activating inactivated catalyst through catalytic chlorination of pyridine nitrile |
Non-Patent Citations (2)
| Title |
|---|
| 曲雯雯等: ""废触媒再生制备ZnO/活性炭复合材料及表征"", 《化工新型材料》 * |
| 解瑞等: ""废催化剂再生后吸附甲基橙的热力学研究"", 《中国稀土学报》 * |
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