CN108745361A - A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application - Google Patents
A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application Download PDFInfo
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- CN108745361A CN108745361A CN201810520586.2A CN201810520586A CN108745361A CN 108745361 A CN108745361 A CN 108745361A CN 201810520586 A CN201810520586 A CN 201810520586A CN 108745361 A CN108745361 A CN 108745361A
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 61
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 54
- 230000003647 oxidation Effects 0.000 title claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 121
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 34
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 15
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000746 purification Methods 0.000 claims abstract description 11
- 239000003610 charcoal Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000002250 absorbent Substances 0.000 claims abstract description 5
- 230000002745 absorbent Effects 0.000 claims abstract description 5
- 239000011149 active material Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000013543 active substance Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 3
- 229910052760 oxygen Inorganic materials 0.000 claims 3
- 239000001301 oxygen Substances 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000003245 coal Substances 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The present invention provides a kind of VOCs room-temperature catalytic oxidations materials and its preparation method and application, using modified activated carbon as matrix, using Al2O3 as catalytic active substance carrier, active material is composite oxide supported on Al2O3 carriers, catalysis material is uniformly distributed on modified active carbon matrix inner hole structure, in high dispersion state, the mass fraction that wherein modified activated carbon accounts for VOCs room-temperature catalytic oxidation materials is 80%-90%, the mass fraction that Al2O3 carriers account for VOCs room-temperature catalytic oxidation materials is 5%-15%, the absorbent charcoal material that composite oxides account for room temperature VOCs catalysis oxidation functions is 1%-5%.The material has both the adsorptivity and catalytic oxidative to VOCs, have the characteristics that adsorption capacity is big and constant temperature catalyzing purification efficiency is high, it is particularly suitable for collocation photocatalysis technology to use, purification efficiency can effectively be promoted by being applied in photocatalysis+activated carbon adsorption group technology, significantly reduce activated carbon replacement frequency, ozone utilization rate is greatly improved, is fully solved the ozone secondary pollution problem that single photocatalysis technology is brought.
Description
Technical field
The present invention relates to VOCs room-temperature catalytic oxidation technical field of material, more particularly, to a kind of VOCs room temperature
Catalysis oxidation material and its preparation method and application and its preparation method and application.
Background technology
Photocatalysis oxidation technique be a kind of low input, low energy consumption exhaust gas treatment technology, have that oxidation is strong, it is useless to be applicable in
The advantages that gas ingredient is wide, reaction condition is mild, therefore be widely used in the processing of gaseous pollutant.However it is single
Photocatalysis oxidation technique that there is purification efficiencies is low, is aoxidized to VOCs and not exclusively generates toxicity bigger by-product, to difficult to degrade
Material effect unobvious, residual ozone secondary pollution problems.
Therefore, photocatalysis oxidation technique combines active carbon adsorption technology formation group technology collocation to make more in practical applications
With, although the combination technique effectively promotes the purification efficiency of entire technique, it is replaced frequently after being saturated there are activated carbon adsorption,
The defects of ozone discharge is exceeded, always for This is what people generally disapprove of.
Invention content
The technical problem to be solved by the present invention is to overcome deficiencies of the prior art, a kind of VOCs is provided first
Room-temperature catalytic oxidation material and its preparation method and application, which, which has, urges the high-adsorption-capacity and room temperature height of VOCs exhaust gas
Change degrading activity.
Second object of the present invention is to provide the preparation method of the VOCs room-temperature catalytic oxidations material.
Third object of the present invention is to provide the applications of the VOCs room-temperature catalytic oxidations material.
The purpose of the present invention is what is be achieved by the following technical programs：
A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application, using modified activated carbon as matrix, with Al2O3To urge
Change active ingredient carriers, active material is composite oxide supported in Al2O3On carrier, catalysis material is uniformly distributed in modified active
It is in high dispersion state on carbon matrix inner hole structure, wherein modified activated carbon accounts for the mass fraction of VOCs room-temperature catalytic oxidation materials
For 80%-90%, Al2O3The mass fraction that carrier accounts for VOCs room-temperature catalytic oxidation materials is 5%-15%, and composite oxides account for room temperature
The absorbent charcoal material of VOCs catalysis oxidation functions is 1%-5%.
Activated carbon matrix has high-specific surface area, and of low cost, but it is only simple when using to arrange in pairs or groups with photocatalysis technology
As sorbing material, exists in practical application and replace frequent, easily to be generated in photocatalysis ozone, hydroxyl radical free radical and high energy activity
It is aoxidized in group, the problem of severe attrition.
Material of the present invention is using modified activated carbon as matrix, with Al2O3For catalytic active substance carrier, active material composite oxygen
Compound is supported on Al2O3On carrier, catalysis material is uniformly distributed on modified active carbon matrix inner hole structure, is in high dispersion state,
As catalytic active component, which keeps the high-adsorption-capacity of Activated carbon matrix, and with excellent to small molecule VOCs under room temperature
Different catalytic degradation performance and ozone degradation ability can significantly improve the purification efficiency of photocatalysis+activated carbon process, reduce activity
Charcoal replacement frequency avoids ozone secondary pollution from generating.
Preferably, the composite oxides cobalt oxide, chromium oxide, manganese dioxide, copper oxide, one kind in cerium oxide or two
Kind is two or more.
Preferably, the one kind or two of the Activated carbon matrix in coaly activated carbon, cocoanut active charcoal, activated carbon fibre
Kind is two or more.
The present invention also provides the preparation methods of the VOCs room-temperature catalytic oxidation materials, include the following steps：（1）Activity
Charcoal is modified：Oxidant is added in activated carbon, stirred in water bath with thermostatic control, flow back and then filter mixture, wash most PH
Value is neutrality, and then drying can obtain modified activated carbon；（2）Al2O3Support precursor is adhered to：By modified activated carbon, intend thin water aluminium
Stone and deionized water mixing stir evenly, the heated at constant temperature in water-bath, and after stirring a period of time, dilute hydrochloric acid adjusting pH value is added dropwise dropwise is
Acidity, then attachment Al is obtained after filtering, drying2O3The activated carbon of support precursor；（3）Load composite oxides：It will attachment
Al2O3The activated carbon of support precursor is soaked in the corresponding salting liquid of composite oxides, and it is alkali to instill EDTA dropwise and adjust pH value
Property, VOCs room-temperature catalytic oxidation materials are made through filtering, drying, roasting and activation.
Preferably, step（1）The oxidant is in concentrated nitric acid solution, hydrogenperoxide steam generator, peracetic acid soln
One or two or two or more, the dosage of the oxidant is that every gram of activated carbon adds 0.2ml~1ml.
Preferably, step（2）The mass ratio of the addition of boehmite and the deionized water is 1~20:1000；
Bath temperature is 40 DEG C~80 DEG C；Soaking time is 1h~5h；The control of hydrochloric acid pH value is added dropwise 2~6.
Preferably, step（3）The time of the immersion is 1h~3h；With EDTA control pH value controls 8~12；It is described
Drying temperature is 40 DEG C~80 DEG C, and the program of the roasting is 350 DEG C~600 DEG C of temperature, and heating rate is 5~15 DEG C/min,
Keep the temperature 1h~3h.
Preferably, step（3）The roasting carries out in the tube furnace of inert gas shielding, and material is activated in atmosphere of hydrogen
Middle progress.
The present invention also provides application of the VOCs room-temperature catalytic oxidation materials in terms of gas purification, the gas packets
Include VOCs and ozone；Specifically refer to have the function of that high-adsorption-capacity, VOCs catalysis oxidations are decomposed and ozone degradation.
The present invention also provides the VOCs room-temperature catalytic oxidations materials to be used in terms of gas purification.
Compared with prior art, the present invention has the advantage that：
The present invention provides a kind of VOCs room-temperature catalytic oxidations materials and its preparation method and application, using modified activated carbon as base
Body, with Al2O3For catalytic active substance carrier, active material is composite oxide supported in Al2O3On carrier, catalysis material is uniform
It is distributed on modified active carbon matrix inner hole structure, is in high dispersion state, wherein modified activated carbon accounts for VOCs room-temperature catalytic oxidations
The mass fraction of material is 80%-90%, Al2O3The mass fraction that carrier accounts for VOCs room-temperature catalytic oxidation materials is 5%-15%, compound
The absorbent charcoal material that oxide accounts for room temperature VOCs catalysis oxidation functions is 1%-5%.The material has both the adsorptivity to VOCs and urges
The property changed has adsorption capacity big（The material specific surface is 1200 ㎡/g~2200 ㎡/g, does not make to compare table because of modification, modification
Face significantly reduces）The efficient feature with constant temperature catalyzing（Wherein, at 20 DEG C of room temperature, the small molecules such as PARA FORMALDEHYDE PRILLS(91,95), formic acid, acetaldehyde
Organic matter purifying rate > 98%）.
The material keeps the high-adsorption-capacity of Activated carbon matrix, and with catalysis drop excellent to small molecule VOCs under room temperature
Performance and ozone degradation ability are solved, the purification efficiency of photocatalysis+activated carbon process can be significantly improved, activated carbon is reduced and replaces frequency
Rate avoids ozone secondary pollution from generating.
Specific implementation mode
The content further illustrated the present invention with reference to specific embodiment, but should not be construed as limiting the invention.
Without departing from the spirit and substance of the case in the present invention, to simple modifications or substitutions made by the method for the present invention, step or condition,
It all belongs to the scope of the present invention unless otherwise specified, technological means used in embodiment is well known to those skilled in the art often
Rule means.
1 2%Co-8%Al of embodiment2O3/ 90%AC, 450 DEG C, HNO3
A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application, using modified activated carbon as matrix, raw material presses quality
Percentages contain modified activated carbon 90%, Al2O38%, cobalt/cobalt oxide 2%.Specific preparation process is as follows：
（1）It is activated carbon modified：Dense HNO is added in cocoanut active charcoal3Solution 0.2ml/g is stirred in 60 DEG C of waters bath with thermostatic control, is returned
1h is flowed, then filters mixture, deionized water washing most pH value is neutrality, then 80 DEG C of drying；
（2）Al2O3Support precursor is adhered to：Boehmite, deionized water and modified activated carbon are mixed and stirred evenly, thin water aluminium is intended
The mass ratio of the addition of stone and deionized water is 8:1000, gained mixed solution is 2 with modified activated carbon volume ratio:1；By its
The heated at constant temperature in 80 DEG C of water-baths, after stirring 2h, it is 2~6 that dilute hydrochloric acid is added dropwise dropwise and adjusts pH value, then through filtering, 60 DEG C of dryings
After obtain attachment Al2O3The activated carbon of support precursor；
（3）Load composite oxides：Prepare the Co (NO with modified activated carbon same volume3)2Solution, Co (NO3)2Mass fraction is
The 2% of modified activated carbon, the Co (NO that will have been configured3)2Solution and attachment Al2O3Dipping is mixed in the activated carbon of support precursor
3h, dropwises that instill EDTA solution to adjust pH value be 8~12 while stirring, after filtering, in 80 DEG C of dryings of baking oven, it is dry after
450 DEG C are warming up to 5 DEG C/min in tube furnace, keeps the temperature 1h, and activated in atmosphere of hydrogen and VOCs room-temperature catalytic oxidation materials are made
Material.
2 5%Cr-10%Al of embodiment2O3/ 85%AC, 500 DEG C, H2O2
A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application, using modified activated carbon as matrix, raw material presses quality
Percentages contain modified activated carbon 85%, Al2O310%, chromated oxide 5%.Specific preparation process is as follows：
（1）It is activated carbon modified：H is added in coaly activated carbon2O2Solution 0.6ml/g stirs in 60 DEG C of waters bath with thermostatic control, flows back
Then 1h filters mixture, deionized water washing most pH value is neutrality, then 80 DEG C of drying；
（2）Al2O3Support precursor is adhered to：Boehmite, deionized water and modified activated carbon are mixed and stirred evenly, thin water aluminium is intended
The mass ratio of the addition of stone and deionized water is 13:1000, gained mixed solution is 1.5 with modified activated carbon volume ratio:1；
By it in 80 DEG C of water-baths heated at constant temperature, stir 2h after, dropwise be added dropwise dilute hydrochloric acid adjust pH value be 3~6, then through filter, 80 DEG C
Attachment Al is obtained after drying2O3The activated carbon of support precursor；
（3）Load composite oxides：Prepare the Cr (NO with modified activated carbon same volume3)3Solution, Cr (NO3)3Mass fraction is
The 5% of modified activated carbon, the Cr (NO that will have been configured3)3Solution and attachment Al2O3Dipping is mixed in the activated carbon of support precursor
2h, dropwises that instill EDTA solution to adjust pH value be 9~10 while stirring, after filtering, in 80 DEG C of dryings of baking oven, it is dry after
500 DEG C are warming up to 8 DEG C/min in tube furnace, keeps the temperature 2h, and activated in atmosphere of hydrogen and VOCs room-temperature catalytic oxidation materials are made
Material.
3 5%Mn-15Al of embodiment2O3/ 80AC, 550 DEG C, Peracetic acid
A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application, using modified activated carbon as matrix, raw material presses quality
Percentages contain modified activated carbon 80%, Al2O315%, Mn oxide 5%.Specific preparation process is as follows：
（1）It is activated carbon modified：Peracetic acid soln 1ml/g is added in activated carbon fibre, stirs, return in 80 DEG C of waters bath with thermostatic control
1h is flowed, then filters mixture, deionized water washing most pH value is neutrality, then 60 DEG C of drying；
（2）Al2O3Support precursor is adhered to：Boehmite, deionized water and modified activated carbon are mixed and stirred evenly, thin water aluminium is intended
The mass ratio of the addition of stone and deionized water is 20:1000, gained mixed solution is 1.2 with modified activated carbon volume ratio:1；
By it in 60 DEG C of water-baths heated at constant temperature, stir 2h after, dropwise be added dropwise dilute hydrochloric acid adjust pH value be 2~5, then through filter, 70 DEG C
Attachment Al is obtained after drying2O3The activated carbon of support precursor；
（3）Load composite oxides：Prepare the Mn (NO with modified activated carbon same volume3)2Solution, Mn (NO3)2Mass fraction is
The 5% of modified activated carbon, the Mn (NO that will have been configured3)2Solution and attachment Al2O3Dipping is mixed in the activated carbon of support precursor
3h, dropwises that instill EDTA solution to adjust pH value be 9~12 while stirring, after filtering, in 80 DEG C of dryings of baking oven, it is dry after
550 DEG C are warming up to 10 DEG C/min in tube furnace, keeps the temperature 1.5h, and activated in atmosphere of hydrogen and VOCs room-temperature catalytic oxidations are made
Material.
4 3%Cu-12Al of embodiment2O3/ 85AC, 500 DEG C, HNO3
A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application, using modified activated carbon as matrix, raw material presses quality
Percentages contain modified activated carbon 85%, Al2O312%, Cu oxide 3%.Specific preparation process is as follows：
（1）It is activated carbon modified：Dense HNO is added in activated carbon fibre3Solution 0.5ml/g is stirred in 60 DEG C of waters bath with thermostatic control, is returned
2h is flowed, then filters mixture, deionized water washing most pH value is neutrality, then 80 DEG C of drying；
（2）Al2O3Support precursor is adhered to：Boehmite, deionized water and modified activated carbon are mixed and stirred evenly, thin water aluminium is intended
The mass ratio of the addition of stone and deionized water is 9:1000, gained mixed solution is 1.5 with modified activated carbon volume ratio:1；It will
Its heated at constant temperature in 60 DEG C of water-baths, after stirring 3h, it is 2~6 that dilute hydrochloric acid is added dropwise dropwise and adjusts pH value, then through filtering, 80 DEG C dry
Attachment Al is obtained after dry2O3The activated carbon of support precursor；
（3）Load composite oxides：Prepare the Cu (NO with modified activated carbon same volume3)2Solution, Cu (NO3)2Mass fraction is
The 3% of modified activated carbon, the Cu (NO that will have been configured3)2Solution and attachment Al2O3Dipping is mixed in the activated carbon of support precursor
2h, dropwises that instill EDTA solution to adjust pH value be 8~12 while stirring, after filtering, in 80 DEG C of dryings of baking oven, it is dry after
500 DEG C are warming up to 15 DEG C/min in tube furnace, keeps the temperature 1h, and activated in atmosphere of hydrogen and VOCs room-temperature catalytic oxidation materials are made
Material.
Comparative example 1
The same embodiment of experimental method, uniquely the difference is that, step is preparing Al2O3When support precursor is adhered to, boehmite
Mass ratio with the addition of deionized water is 120:When 1000, thick gel will be obtained, made in next step to composite oxides
Load cannot carry out.
Comparative example 2
The same embodiment of experimental method, uniquely the difference is that, step is preparing Al2O3When support precursor is adhered to, boehmite
Mass ratio with the addition of deionized water is 1:When 15000, Al is obtained2O3The modified activated carbon of support precursor attachment, makes
The composite oxide supported amount of VOCs room-temperature catalytic oxidation materials is extremely low, seriously affects catalytic oxidative of the material to VOCs
Can, so that it is no different with normal activated carbon material property.
Comparative example 3
The same embodiment of experimental method, uniquely the difference is that, step is warming up to 200 DEG C in tubular type kiln roasting, with 10 DEG C/min,
1h is kept the temperature, the VOCs room-temperature catalytic oxidation materials of acquisition are tested according to the method described above, as a result show the VOCs room temperature of gained
The ability of catalysis oxidation material, purification degradation VOCs and ozone drastically declines, the study found that the catalysis in the low-temperature bake material
The presoma of active constituent decomposes not exclusively, and material catalytic degradation efficiency is caused to drastically reduce.
Comparative example 4
The same embodiment of experimental method, uniquely the difference is that, step is warming up to 700 DEG C in tubular type kiln roasting, with 5 DEG C/min,
3h is kept the temperature, the VOCs room-temperature catalytic oxidation materials of acquisition are tested according to the method described above, as a result show the VOCs room temperature of gained
The ability of catalysis oxidation material, purification degradation VOCs and ozone is remarkably decreased, the study found that roasting leads to material to high temperature for a long time
In catalytic active component reunite it is serious, this is because high-temperature roasting leads to Al2O3Carrier crystal grain is reunited, is collapsed seriously, and material is made
Catalytic oxidation activity significantly reduces.
Claims (9)
1. a kind of VOCs room-temperature catalytic oxidations material and its preparation method and application, using modified activated carbon as matrix, with Al2O3For
Catalytic active substance carrier, active material are composite oxide supported in Al2O3On carrier, catalysis material is uniformly distributed in modified work
Property carbon matrix inner hole structure on, be in high dispersion state, wherein modified activated carbon accounts for the quality point of VOCs room-temperature catalytic oxidation materials
Number is 80%-90%, Al2O3The mass fraction that carrier accounts for VOCs room-temperature catalytic oxidation materials is 5%-15%, and composite oxides account for room temperature
The absorbent charcoal material of VOCs catalysis oxidation functions is 1%-5%.
2. requiring the VOCs room-temperature catalytic oxidation materials according to right 1, it is characterised in that, the composite oxides are selected from oxygen
Change two kinds in cobalt, chromium oxide, manganese dioxide, copper oxide, cerium oxide, or two or more.
3. requiring the VOCs room-temperature catalytic oxidation materials according to right 1, it is characterised in that, the Activated carbon matrix is selected from coal
One or both of activated carbon, cocoanut active charcoal, activated carbon fibre, or it is two or more.
4. the preparation method of claim 1-3 any one of them VOCs room-temperature catalytic oxidation materials, it is characterised in that, including with
Lower step：
（1）It is activated carbon modified：Oxidant is added in activated carbon, stirred in water bath with thermostatic control, flow back and then filter mixture,
Washing most pH value is neutrality, and then drying can obtain modified activated carbon；
（2）Al2O3Support precursor is adhered to：Modified activated carbon, boehmite and deionized water are mixed and stirred evenly, in water-bath
Heated at constant temperature, after stirring a period of time, it is acidity that dilute hydrochloric acid is added dropwise dropwise and adjusts pH value, then is adhered to after filtering, drying
Al2O3The activated carbon of support precursor；
（3）Load composite oxides：Al will be adhered to2O3It is molten that the absorbent charcoal material of presoma is soaked in the corresponding salt of composite oxides
In liquid, it is alkalinity to instill EDTA dropwise and adjust pH value, and VOCs room-temperature catalytic oxidation materials are made through filtering, drying, roasting and activation
Material.
5. VOCs room-temperature catalytic oxidations material preparation method according to claim 4, it is characterised in that step（1）Oxygen used
Agent is selected from one or both of concentrated nitric acid solution, hydrogenperoxide steam generator, peracetic acid soln or two or more, the oxygen
The dosage of agent is that every gram of activated carbon adds 0.2ml~1ml.
6. VOCs room-temperature catalytic oxidations material preparation method according to claim 4, it is characterised in that step（2）Intend thin water
The mass ratio of the addition of aluminium stone and deionized water is 1~20:1000；Bath temperature is 40 DEG C~80 DEG C；Soaking time is 1h
~5h；The control of hydrochloric acid pH value is added dropwise 2~6.
7. VOCs room-temperature catalytic oxidations material preparation method according to claim 4, it is characterised in that step（3）The leaching
The time of bubble is 1h~3h；With EDTA control pH value controls 8~12；The drying temperature is 40 DEG C~80 DEG C, the roasting
Program be 350 DEG C~600 DEG C of temperature, heating rate be 5~15 DEG C/min, keep the temperature 1h~3h.
8. claims 1 to 3 any one of them VOCs room-temperature catalytic oxidation materials, it is characterised in that have both high-adsorption-capacity and
Room temperature high catalytic activity.
9. application of the claims 1 to 3 any one of them VOCs room-temperature catalytic oxidation materials in terms of gas purification, feature
It is, the gas includes VOCs and ozone.
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