CN103071455A - Preparation method of composite adsorption purifying agent - Google Patents
Preparation method of composite adsorption purifying agent Download PDFInfo
- Publication number
- CN103071455A CN103071455A CN2013100597910A CN201310059791A CN103071455A CN 103071455 A CN103071455 A CN 103071455A CN 2013100597910 A CN2013100597910 A CN 2013100597910A CN 201310059791 A CN201310059791 A CN 201310059791A CN 103071455 A CN103071455 A CN 103071455A
- Authority
- CN
- China
- Prior art keywords
- composite adsorption
- preparation
- purifying agent
- protective gas
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012629 purifying agent Substances 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 230000001681 protective effect Effects 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 13
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004246 zinc acetate Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000003595 mist Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052799 carbon Inorganic materials 0.000 abstract description 16
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000000975 dye Substances 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 12
- 239000002351 wastewater Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011282 treatment Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 230000001954 sterilising effect Effects 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 72
- 239000011787 zinc oxide Substances 0.000 description 36
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 6
- 238000004042 decolorization Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000000982 direct dye Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- -1 ZnO compound Chemical class 0.000 description 1
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100597910A CN103071455A (en) | 2013-02-26 | 2013-02-26 | Preparation method of composite adsorption purifying agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100597910A CN103071455A (en) | 2013-02-26 | 2013-02-26 | Preparation method of composite adsorption purifying agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103071455A true CN103071455A (en) | 2013-05-01 |
Family
ID=48148272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100597910A Pending CN103071455A (en) | 2013-02-26 | 2013-02-26 | Preparation method of composite adsorption purifying agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103071455A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752287A (en) * | 2014-01-26 | 2014-04-30 | 河北工程大学 | Building finishing pollutant treating agent and preparation method thereof |
| 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 |
| CN104940034A (en) * | 2015-07-10 | 2015-09-30 | 崇明本 | Diisostearyl malate decolorizing agent and deep decolorizing method |
| CN104974040A (en) * | 2015-07-10 | 2015-10-14 | 宜兴市恒兴精细化工有限公司 | Decolorizing agent and decolorizing method of geranyl butyrate |
| CN105130817A (en) * | 2015-07-10 | 2015-12-09 | 崇明本 | Decolorizing agent of tridecyl trimellitate and deep decolorizing method |
| 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 |
| 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 |
| CN111068792A (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 synthesizing vinyl acetate by acetylene method |
| 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 |
| CN113387469A (en) * | 2021-05-31 | 2021-09-14 | 浙江中金格派锂电产业股份有限公司 | Method for treating cobalt-nickel raffinate |
| CN113731364A (en) * | 2021-09-17 | 2021-12-03 | 苏州中材非金属矿工业设计研究院有限公司 | Black talc adsorbent and preparation method and application thereof |
| 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 |
| CN114917922A (en) * | 2022-06-21 | 2022-08-19 | 杭州星宇炭素环保科技有限公司 | Magnetically separable photocatalytic regenerated active carbon and preparation method thereof |
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》 * |
Cited By (18)
| 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 |
| CN103754977B (en) * | 2014-01-17 | 2015-04-01 | 哈尔滨工业大学 | Active carbon modification method for emergently treating sudden organic pollution of drinking water |
| CN103752287B (en) * | 2014-01-26 | 2015-12-02 | 河北工程大学 | A kind of construction and decoration pollutant inorganic agent and preparation method thereof |
| CN103752287A (en) * | 2014-01-26 | 2014-04-30 | 河北工程大学 | Building finishing pollutant treating agent and preparation method thereof |
| CN104940034B (en) * | 2015-07-10 | 2018-12-14 | 义乌市欧雅化妆品有限公司 | A kind of diisooctadecanol malate decolorising agent and depth discoloration method |
| CN104974040A (en) * | 2015-07-10 | 2015-10-14 | 宜兴市恒兴精细化工有限公司 | Decolorizing agent and decolorizing method of geranyl butyrate |
| CN105130817A (en) * | 2015-07-10 | 2015-12-09 | 崇明本 | Decolorizing agent of tridecyl trimellitate and deep decolorizing method |
| CN104974040B (en) * | 2015-07-10 | 2017-06-23 | 宜兴市恒兴精细化工有限公司 | The decolorising agent and its discoloration method of a kind of geranyl butyrate |
| CN104940034A (en) * | 2015-07-10 | 2015-09-30 | 崇明本 | Diisostearyl malate decolorizing agent and deep decolorizing method |
| 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 |
| CN111068792A (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 synthesizing vinyl acetate by acetylene method |
| 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 |
| 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 |
| CN114763348B (en) * | 2021-05-18 | 2024-02-06 | 上海素馨化工科技有限公司 | Preparation method of 2, 5-thiophene dicarboxylic acid and 2, 5-thiophene dicarboxylic acid |
| CN113387469A (en) * | 2021-05-31 | 2021-09-14 | 浙江中金格派锂电产业股份有限公司 | Method for treating cobalt-nickel raffinate |
| CN113731364A (en) * | 2021-09-17 | 2021-12-03 | 苏州中材非金属矿工业设计研究院有限公司 | Black talc adsorbent and preparation method and application thereof |
| CN114917922A (en) * | 2022-06-21 | 2022-08-19 | 杭州星宇炭素环保科技有限公司 | Magnetically separable photocatalytic regenerated active carbon and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103071455A (en) | Preparation method of composite adsorption purifying agent | |
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN105749893B (en) | A kind of preparation method of the modified active carbon fiber silk of area load nano titanium oxide | |
| CN107285452B (en) | Method for rapidly degrading antibiotics | |
| CN101862662B (en) | Multi-doped half-load type Fenton-assisting titanium dioxide photochemical catalyst as well as preparation method and application method | |
| CN106865685B (en) | Treatment method for photocatalytic degradation of rhodamine B dye wastewater | |
| CN103464122B (en) | A kind of preparation method of graphene/chitosan adsorbent resin | |
| CN106881111A (en) | Composite bismuth vanadium photocatalyst of cuprous oxide and silver-colored mutual load and its preparation method and application | |
| CN104277219A (en) | Photocatalytic material polyimide, as well as preparation method and applications thereof | |
| CN103159260B (en) | Preparation method and application of molecular-level-thickness HNb3O8 nanosheet | |
| Tang et al. | A novel S-scheme heterojunction in spent battery-derived ZnFe2O4/g-C3N4 photocatalyst for enhancing peroxymonosulfate activation and visible light degradation of organic pollutant | |
| CN110624566A (en) | CuInS2Preparation method and application of quantum dot/NiAl-LDH composite photocatalyst | |
| CN114105280A (en) | Method for treating organic wastewater based on activation of peroxydisulfate by nonmetal composite catalytic material | |
| CN102583636A (en) | Nanometer cobalt-doped titanium dioxide/chitosan composite microspheres for photolyzing organophosphorus pesticide wastewater | |
| CN104801308A (en) | NiFe2O4/TiO2/sepiolite composite photocatalyst and preparation method thereof | |
| CN105664988A (en) | Composite (BiO)2CO3/C photocatalyst and application thereof | |
| CN102580727B (en) | Preparation method of active carbon loaded titanium dioxide silver-doped photochemical catalyst | |
| CN104096555A (en) | Preparation method for rare earth doped silicon dioxide-titanium dioxide photocatalytic material | |
| CN104399511B (en) | A kind of g-C3N4/S-TiO2/ AC photochemical catalyst and its preparation method and application | |
| CN104399506B (en) | A kind of g-C3N4/TiO2/ AC composite photo-catalyst and its preparation method and application | |
| CN103752273A (en) | Water environmental remediation material as well as preparation method and application thereof | |
| CN107117683B (en) | Method for catalytically degrading low-concentration antibiotics In water body by using MOFs containing In-Co under visible light | |
| CN102380416B (en) | Method for preparing metal-free high molecular polymer photocatalysis material | |
| CN109896574B (en) | Carbon ferrite-titanium oxide multifunctional water purification material and preparation method thereof | |
| CN106362800A (en) | Graphene-doped zinc oxide photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130501 |