CN116173896A - Adsorbent for purifying alcohol VOCs and preparation method thereof - Google Patents
Adsorbent for purifying alcohol VOCs and preparation method thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 75
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 112
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 111
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 111
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 45
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 45
- 238000011068 loading method Methods 0.000 claims abstract description 20
- 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 14
- 239000000203 mixture Substances 0.000 claims description 73
- 238000001035 drying Methods 0.000 claims description 36
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000012530 fluid Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 17
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims 3
- 238000001179 sorption measurement Methods 0.000 abstract description 83
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 3
- 239000002808 molecular sieve Substances 0.000 description 63
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 63
- 230000000694 effects Effects 0.000 description 26
- 239000011521 glass Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 13
- 229940071125 manganese acetate Drugs 0.000 description 13
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 230000035515 penetration Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002156 adsorbate Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000000329 molecular dynamics simulation Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides an adsorbent for purifying alcohol VOCs, which comprises the following components: a zeolite having a silica-alumina ratio of not less than 3, and a metal oxide supported on the zeolite; the loading of the metal oxide is 1-15 wt% of the zeolite. The adsorbent has the advantages of good hydrophobicity, good adsorption performance, high purification efficiency, good stability, low cost and the like.
Description
Technical Field
The invention relates to the technical field of alcohol VOCs purification, in particular to an adsorbent for purifying alcohol VOCs and a preparation method thereof.
Background
VOCs (Volatile Organic Compounds) generally refers to various organic compounds having boiling points of 50℃to 260℃under normal pressure. Alcohol VOCs are organic compounds with hydroxyl (-OH) as functional groups, and are produced by substituting one or more hydrogens in hydrocarbon molecules with hydroxyl groups. In the production process of the chemical industry such as printing, pulping, pharmacy and the like, a large amount of alcohol VOCs such as methanol, ethanol, isopropanol, butanol and the like can be volatilized and discharged due to unstructured discharge and leakage. Most of alcohol VOCs are inflammable and explosive, have certain toxicity, and can harm the environment and human health, but have certain recovery value as important chemical materials, so the alcohol VOCs need to be purified.
In the VOCs purifying treatment technology, the adsorption method has the advantages of simple process, strong operability, low energy consumption, safety, environmental protection and the like, and is the most widely used VOCs purifying method at present. The key of the adsorption technology is the selection of adsorption materials, and the currently commonly used adsorbents include activated carbon, activated alumina, silica gel and the like. Although the adsorbents have universality of adsorption and better adsorptivity to most VOCs, the adsorptivity to common alcohol VOCs is relatively poor. In order to further increase the adsorption capacity and adsorption efficiency of adsorbents for alcohol VOCs for industrial discharge, new adsorbents have to be developed.
Regarding the adsorption material of alcohol VOCs, a new organic waste gas adsorption material and a preparation method thereof (patent number 201310501262.1) have been reported in the literature, and the new organic waste gas adsorption material prepared by using olive pits as raw materials is more sensitive to adsorption of alcohol organic waste gas. The patent adopts pretreatment such as olive pit acid washing, impurity removal and the like, and after activation, water washing and steam activation, a modifier is added to modify the functional groups of the adsorption material, and finally, the special material for adsorbing organic waste gas is obtained through drying, so that the preparation process is complex and complicated. In addition, in the actual industrial exhaust gas, water vapor and VOCs coexist, the hydrophobicity of activated carbon is poor, and the adsorption capacity of the adsorbent to alcohol VOCs is inhibited by humidity, and the adsorption capacity to alcohol VOCs under the condition of humidity is not considered in the patent.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide an adsorbent for purifying alcohol VOCs, which has improved adsorption performance by loading metal oxides on zeolite molecular sieves, so that the prepared adsorbent has more active adsorption sites; when the adsorbent is used for purifying industrial alcohol VOCs, the adsorbent has the advantages of good hydrophobicity, good adsorption performance, high purification efficiency, good stability, low cost and the like.
The second object of the present invention is to provide a method for preparing the above adsorbent, in which the metal oxide is supported on zeolite through specific steps, the supported amount of the metal oxide can be controlled to be 1-15 wt%, and the metal oxide is distributed more uniformly on the zeolite by means of fully grinding and programmed heating and roasting after drying, so as to generate more active adsorption points, and the adsorption force on alcohol VOCs is enhanced by the presence of the metal oxide, so that the selective adsorption effect on alcohol VOCs is improved.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides an adsorbent for purifying alcohol VOCs, which comprises the following components: a zeolite having a silica-alumina ratio of not less than 3, and a metal oxide supported on the zeolite;
the loading of the metal oxide is 1-15 wt% of the zeolite.
The zeolite molecular sieve is artificially synthesized silicate in a crystalline state, has microporous channels with highly ordered molecular size and adjustable aperture, has a rich framework structure, and is considered to have good application prospect in the adsorption field due to good regeneration performance, excellent thermal stability and incombustibility. In the prior art, the following problems exist in VOCs adsorption:
1. conventional VOCs adsorbents achieve reduced moisture adsorption by hydrophobic modification, typically by increasing the silica to alumina ratio, but at the cost of reduced specific surface area of the zeolite molecular sieve. The adsorption capacity of the zeolite molecular sieve is closely related to the specific surface area, which severely restricts the application of the zeolite adsorbent in the field of VOCs adsorption.
2. Metals and metal oxides have been widely used for catalysis and adsorption. However, aggregation of metal and metal oxide particles occurs at high temperatures, which reduces specific surface area, and hinders the application prospect as an adsorbent.
In order to solve the technical problems, the invention provides the adsorbent for purifying the alcohol VOCs, which is characterized in that metal oxide is loaded on a zeolite molecular sieve, nano particles can be dispersed and agglomerated by utilizing the porous structure of zeolite, and the adsorbent can be used as an active adsorption point to generate weak chemical adsorption effect with oxygen-containing functional groups of the alcohol VOCs, so that the selective adsorption capability of specific gas is effectively improved, and the adsorption effect of the adsorbent on the alcohol VOCs is ensured.
The metal oxide is supported instead of the metal ion because the metal oxide can be used as an active adsorption point, thereby improving the adsorption effect.
Preferably, the zeolite is one or more of FAU type, MFI type, MOR type, BEA type, CHA type and STT type.
Preferably, the zeolite is a mixture of FAU-type zeolite and MFI-type zeolite.
Preferably, the mass ratio of the FAU-type zeolite to the MFI-type zeolite is (0.5-2): 1;
preferably, the mass ratio of the FAU-type zeolite to the MFI-type zeolite is 1:1.
The two zeolite are mixed for adsorption, so that the synergistic effect of the two zeolite molecular sieves with different pore sizes is utilized for carrying out double active site loading, and a better adsorption effect is achieved.
Preferably, when the zeolite is of the FAU type, the silica-alumina ratio is 3 to 15; when the zeolite is of MFI type, the silicon-aluminum ratio is 5-600; when the zeolite is of CHA type, the silicon-aluminum ratio is 5-20; when the zeolite is MOR type, the silicon-aluminum ratio is 5-40, when the zeolite is BEA type, the silicon-aluminum ratio is not less than 25, and when the zeolite is STT type, the silicon-aluminum ratio is not less than 10.
Preferably, the silicon-aluminum ratio of the zeolite is 4-15; preferably, the zeolite has a silica to alumina ratio of 5.3.
Preferably, the metal oxide is an oxide of one or more of Cu, fe, zn, co, ni, mn, na, K, ca, ba, ce and La, the metal oxide being supported on the zeolite as a metal soluble salt.
Preferably, the metal oxides are two.
Preferably, the metal oxide is cobalt oxide and manganese oxide; wherein the mole ratio of CoO to MnO is (1-5): 1.
Preferably, the molar ratio of CoO to MnO is 2:1.
Preferably, the zeolite is FAU type and MFI type, the silicon-aluminum ratio of the zeolite is 5.3, the loading of the metal oxide is 15wt%, and the metal oxide is cobalt oxide and manganese oxide; wherein the molar ratio of CoO to MnO is 2:1.
Preferably, the metal soluble salt is at least one of nitrate, acetate or chloride.
The adsorbent for purifying alcohol VOCs achieves good adsorption effect by loading metal oxide on zeolite and optimizing parameters such as zeolite type, silicon-aluminum ratio, loaded metal oxide type, loading capacity and proportion.
On the one hand, the trapping of the specific adsorbate can be improved by limiting the zeolite type and the silicon-aluminum ratio, and the influence of molecular diffusion and Knudsen diffusion effect can be weakened by selecting the zeolite with the pore diameter matched with the kinetic diameter, so that the adsorption rate in the pores is improved, the effective adsorption of adsorbate molecules in the pores is enhanced, and the adsorption capacity of the adsorbent is improved. The molecular dynamics diameter of the alcohol VOCs is in the range of 0.36-0.5 nm, the pore sizes of different types of zeolite are different, and the zeolite molecular sieve is subjected to metal modification to adjust the pore size, so that the pore size is matched with the molecular dynamics diameter of the alcohol VOCs, and the adsorption capacity is effectively improved;
on the other hand, alcohol VOCs are polar molecules, and the polarity of the alcohol VOCs is stronger than that of other VOCs, so that the alcohol VOCs adopt an adsorbent with strong polarity, namely a zeolite molecular sieve. The adsorption of zeolite molecular sieve and alcohol VOCs belongs to physical adsorption, and under certain humidity condition, water molecules with stronger polarity can replace adsorbed organic matters. Alcohol VOCs contain oxygen-containing functional group hydroxyl, and can be combined with metal oxide loaded on zeolite to generate certain weak chemical adsorption, so that the metal oxide has positive effect on improving the capability of the zeolite molecular sieve for adsorbing alcohol VOCs.
The invention also provides a preparation method of the adsorbent, which comprises the following steps:
obtaining zeolite raw powder with preset quality, and dissolving at least one metal salt in deionized water according to theoretical loading capacity to form a metal salt solution;
dripping the metal salt solution into zeolite raw powder, and stirring the mixture until the mixture reaches a gelatinous non-Newtonian fluid, wherein the dripping amount of the metal salt solution is determined according to the saturation amount of the zeolite raw powder;
drying the mixture, grinding after drying so that the metal oxide can be uniformly loaded on the zeolite;
and (3) heating and roasting the ground zeolite to obtain the zeolite adsorbent loaded with the metal oxide.
Preferably, the method for determining the saturation amount of the zeolite raw powder comprises the following steps:
taking quantitative zeolite raw powder, dropwise adding a metal salt solution, stirring until the mixture becomes a non-Newtonian fluid state, and calculating the saturation quantity of the zeolite raw powder according to the quantity of the dropwise added metal salt solution. Specifically, the saturation amount (mL/g) =the amount of solution/the mass of the zeolite raw powder
The saturation amount of the zeolite raw powder is required to be obtained in order to ensure quantitative dropwise addition of the metal salt solution, and if the dropwise addition amount is excessive, the mixture is too dilute to form a non-Newtonian fluid, so that the zeolite raw powder is not easy to dry in the subsequent process, and the loading amount of the metal oxide is influenced, thereby being unfavorable for the adsorption effect of the adsorbent prepared in the subsequent process.
Preferably, the mixture is twisted into a uniform cake shape before the mixture is dried, so that a water film is formed on the surface of the mixture to facilitate rapid drying.
Preferably, the drying mode is any one of flash drying and microwave drying.
Preferably, the drying mode is microwave drying, the microwave power is 600-900W, and the time is 30-240 s.
Preferably, the grinding time is 5 to 20 minutes.
Preferably, the temperature-rising roasting process is as follows: heating to 100-200 ℃ at a heating rate of 5-20 ℃/min, maintaining for 0.5-2 h, heating to 300-550 ℃ and maintaining for 3-5 h.
According to the preparation method disclosed by the invention, the metal oxide is loaded on the zeolite through specific steps, the loading capacity of the metal oxide can be controlled to be 1-15 wt%, and the metal oxide is more uniformly distributed on the zeolite by utilizing a mode of fully grinding after drying and carrying out programmed heating roasting, so that more active adsorption points are generated, and the adsorption effect on alcohol VOCs is improved.
Compared with the prior art, the invention has the beneficial effects that:
according to the adsorbent for purifying alcohol VOCs, the metal oxide is loaded on the zeolite molecular sieve, the porous structure of zeolite can be used for dispersing metal oxide nano particles and reducing agglomeration of the metal oxide nano particles, and meanwhile, the adsorbent can be used as an active adsorption point, so that the selective adsorption capacity of specific gas is effectively improved, and the adsorption effect of the adsorbent on alcohol VOCs is ensured.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to designate like parts throughout the figures. In the drawings:
FIG. 1 is a graph showing the adsorption penetration curve of the alcohol adsorbent according to example 1 of the present invention;
FIG. 2 is a graph showing the adsorption penetration curve of the alcohol adsorbent according to example 7 of the present invention;
fig. 3 is an adsorption penetration curve of the alcohol adsorbent provided in example 9 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
10g of H-FAU molecular sieve with the silicon-aluminum ratio of 5.3 is weighed and put into a beaker, 1.6g of copper nitrate is weighed according to the theoretical load amount of 5wt%, and 8.9mL of deionized water is added for dissolution. The prepared Cu (NO) 3 ) 2 ·3H 2 O metal salt solution. The prepared solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the gelatinous mixture is placed in a culture dish, twisted into a uniform cake shape by a spoon, placed in a microwave heater, and flashed for 90s at a constant power of 900W until all are dried. The mixture was taken out and ground for 10min, then heated to 200℃at 10℃per min in a muffle furnace for 0.5h, and then heated to 550℃at 10℃per min for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with copper oxide CuO.
Example 2
10g of H-MFI molecular sieve with a silicon to aluminum ratio of 55 is weighed into a beaker, and 1.135g of copper chloride is weighed according to the theoretical load amount of 5wt% and dissolved in 8.2ml of deionized water. The prepared CuCl is removed by a pipette 2 ·2H 2 The O solution is added into the raw powder successively, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed for 240s at a constant power of 600W until all dried. The mixture was taken out and ground for 5min, then heated to 160℃in a muffle furnace at 5℃per min for 1h, heated to 400℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with copper oxide CuO.
Example 3
Weighing silicon10g of CHA molecular sieve having an Al ratio of 10 was placed in a beaker while 2.39g of lanthanum nitrate was weighed out to dissolve in 9ml of deionized water according to a theoretical loading of 5wt%. The prepared La (NO) 3 ) 3 ·6H 2 The O metal solution is added into the raw powder successively, and is continuously stirred by a glass rod until the mixture is completely in a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flash-evaporated at a constant power of 700W for 150s until all drying. The mixture was taken out and ground for 10min, then heated to 200℃at 20℃per min in a muffle furnace for 2h, and then heated to 300℃at 20℃per min for 5h. Thus obtaining the loaded lanthanum oxide La 2 O 3 Is a zeolite molecular sieve adsorbent.
Example 4
10g of MOR molecular sieve with a silicon-aluminum ratio of 15 is weighed into a beaker, and 1.43g of zinc acetate is weighed according to the theoretical load amount of 5wt% and dissolved in 8.9ml of deionized water. The prepared Zn (CH) was removed by pipetting 3 COO) 2 ·2H 2 The O metal solution is added into the raw powder successively, and is continuously stirred by a glass rod until the mixture is completely in a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flash-evaporated at a constant power of 800W for 200s until all drying. The mixture was taken out and ground for 10min, then heated to 160℃in a muffle furnace at 5℃per min for 1h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with zinc oxide ZnO.
Example 5
10g of BEA molecular sieve with a silicon-aluminum ratio of 30 is weighed into a beaker, and 2.06g of cobalt nitrate is weighed according to the theoretical load amount of 5wt% and dissolved in 10ml of deionized water. The prepared Co (NO) 3 ) 2 ·6H 2 The O metal salt solution is added into the raw powder successively, and is continuously stirred by a glass rod until the mixture is completely in a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. Taking out, grinding the mixture for 10min, and then rising to a temperature of 10deg.C/min in a muffle furnace200 ℃, maintaining for 0.5h, raising to 550 ℃ and maintaining for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide CoO.
Example 6
10g of STT molecular sieve with a silicon-aluminum ratio of 15 is weighed into a beaker, and 1.8g of manganese acetate is weighed according to the theoretical load amount of 5wt% and dissolved in 7ml of deionized water. The prepared (CH) was transferred by a pipette 3 COO) 2 Mn·4H 2 The O metal salt solution is added into the raw powder successively, and is continuously stirred by a glass rod until the mixture is completely in a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with manganese oxide.
Example 7
5g of H-FAU type molecular sieve and 5g of MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed, put into a beaker, and simultaneously, 4.12g of cobalt nitrate is weighed according to the theoretical load amount of 10wt%, and 1.8g of manganese acetate is weighed according to the theoretical load amount of 5wt% and dissolved in 10.2ml of deionized water. The prepared metal mixed salt solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Example 8
The specific operating conditions were the same as in example 7, except that the zeolite silica-alumina ratio in this example was 4.
Example 9
The specific operating conditions were the same as in example 7, except that the zeolite silica-alumina ratio in this example was 15.
Example 10
5g of CHA molecular sieve and 5g of MOR molecular sieve with the silicon-aluminum ratio of 5.3 are weighed and put into a beaker, meanwhile, 4.12g of cobalt nitrate is weighed according to the theoretical load amount of 10wt%, and 1.8g of manganese acetate is weighed according to the theoretical load amount of 5wt% and dissolved in 10.6ml of deionized water. The prepared solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Example 11
5g of H-FAU type molecular sieve and 5g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed and put into a beaker, and simultaneously 6.18g of cobalt nitrate is weighed according to 15wt% of theoretical load and dissolved in 7.4ml of deionized water. The prepared metal salt solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide.
Example 12
5g of H-FAU type molecular sieve and 5g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed and put into a beaker, and 5.4g of manganese acetate is weighed and dissolved in 7.4ml of deionized water according to the theoretical load amount of 15wt%. The prepared solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with manganese oxide.
Example 13
10g of H-FAU type molecular sieve with the silicon-aluminum ratio of 5.3 is weighed and put into a beaker, meanwhile, 4.12g of cobalt nitrate is weighed according to the theoretical load amount of 10wt%, and 1.8g of manganese acetate is weighed according to the theoretical load amount of 5wt% and dissolved in 9.1ml of deionized water. The prepared metal mixed solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Example 14
10g of MFI type molecular sieve with the silicon-aluminum ratio of 5.3 is weighed and put into a beaker, meanwhile, 4.12g of cobalt nitrate is weighed according to the theoretical load amount of 10wt%, and 1.8g of manganese acetate is weighed according to the theoretical load amount of 5wt% and dissolved in 9ml of deionized water. The prepared metal mixed solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Example 15
5g of H-FAU type molecular sieve and 5g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed, put into a beaker, and simultaneously 2.06g of cobalt nitrate is weighed according to 5wt% of theoretical load, 1.8g of manganese acetate is weighed according to 5wt% of theoretical load, and 2.7g of ferric nitrate is weighed according to 5wt% of theoretical load and dissolved in 9.1ml of deionized water. The prepared metal mixed solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide, manganese oxide and ferric oxide.
Example 16
5g of H-FAU type molecular sieve and 5g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed, put into a beaker, 2.47g of cobalt nitrate is weighed according to the theoretical load amount of 6wt%, and 1.08g of manganese acetate is weighed according to the theoretical load amount of 3wt% and dissolved in 7.4ml of deionized water. The prepared mixed solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Example 17
5g of H-FAU type molecular sieve and 5g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed, put into a beaker, and simultaneously, 4.12g of cobalt nitrate is weighed according to the theoretical load amount of 10wt%, and 1.8g of manganese acetate is weighed according to the theoretical load amount of 5wt% and dissolved in 7.5ml of deionized water. The prepared solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. After removal the mixture was milled for 10min and then rapidly warmed to 200 ℃ in a muffle furnace for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Example 18
5g of H-FAU type molecular sieve and 5g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed, put into a beaker, 2.06g of cobalt nitrate is weighed according to 5wt% of theoretical load, and 1.8g of manganese acetate is weighed according to 5wt% of theoretical load and dissolved in 7.4ml of deionized water. The prepared solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Example 19
5g of H-FAU type molecular sieve and 5g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed, put into a beaker, and simultaneously, 4.12g of cobalt nitrate is weighed according to 10wt% of theoretical load capacity, and 0.72g of manganese acetate is weighed according to 2wt% of theoretical load capacity and dissolved in 7.4ml of deionized water. . The prepared solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Example 20
8g of H-FAU type molecular sieve and 2g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed, put into a beaker, 4.12g of cobalt nitrate is weighed according to the theoretical load amount of 10wt%, and 1.8g of manganese acetate is weighed according to the theoretical load amount of 5wt% and dissolved in 8.1ml of deionized water. The prepared mixed solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Comparative example 1
5g of H-FAU type molecular sieve and 5g of H-MFI type molecular sieve with the silicon-aluminum ratio of 5.3 are weighed, put into a beaker, and simultaneously 4.12g of cobalt nitrate is weighed according to 10wt% of theoretical load capacity, and 5.4g of manganese acetate is weighed according to 15wt% of theoretical load capacity and dissolved in 7.4ml of deionized water. The prepared solution is added into the raw powder successively by a liquid transfer device, and is stirred continuously by a glass rod until the mixture is completely a gelatinous non-Newtonian fluid. Then, the mixture was placed in a petri dish, twisted into a uniform cake shape with a spoon, placed in a microwave heater, and flashed at a constant power of 900W for 90s to complete drying. The mixture was taken out and ground for 10min, then heated to 200℃in a muffle furnace at 10℃per min for 0.5h, heated to 550℃and held for 4h. Thus obtaining the zeolite molecular sieve adsorbent loaded with cobalt oxide and manganese oxide.
Experimental example 1
Adsorption breakthrough experiments on isopropyl alcohol VOCs were performed using the adsorbents of examples 1 to 20 and comparative example 1, and adsorption performance of the adsorbents was evaluated by breakthrough time and breakthrough adsorption amount. Wherein the adsorption penetration curves of examples 1-3 are shown in FIGS. 1-3.
Experimental conditions: the particle size of the adsorbent is 60-40 meshes, the adsorption column is a quartz tube with the outer diameter of 6mm and the inner diameter of 4mm, 25mg of adsorbent is filled, the total gas flow is 50mL/min, the initial concentration of organic matters is 80ppm, and the adsorption temperature is 30 ℃.
The inlet concentration was constant throughout the adsorption process, and when the outlet concentration reached 10% of the inlet concentration, it was determined that the adsorbent had penetrated. The breakthrough adsorption amount was calculated from the breakthrough curve as follows:
m is the molar mass of the adsorbate, and the unit is g/mol; f is the flow rate of raw material gas, and the unit is mL/min;
C 0 is the initial concentration of adsorbate in mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the C is the concentration of adsorbate in the tail gas at time t, and the unit is mg/m 3
m is the loading of the adsorbent, and the unit is g; t is t 0 The unit is min for the adsorption starting time;
t s to start the penetration time, min; q is the penetrating adsorption quantity of the adsorbent, and the unit is mg/g;
Table 1 experimental results
As can be seen from Table 1, the adsorbent of the present invention has a good adsorption effect on VOCs of isopropyl alcohol, and the adsorption effect of example 7 is the best.
Comparing example 7 with examples 8 and 9, it can be seen that the adsorption performance of the adsorbent is adversely affected when the silica to alumina ratio is increased or decreased, because the increase or decrease in silica to alumina ratio affects the polarity of the zeolite molecular sieve, and the best polarity matching effect with alcohol VOCs is achieved only when the silica to alumina ratio is 5.3.
Comparing example 7 with example 10, example 13 and example 14, it can be seen that example 10 does not have as much adsorption effect as example 7, indicating that the mixed adsorption effect of H-FAU and MFI is stronger than the combination of other zeolites; the adsorption effect of example 7 is better than that of examples 13 and 14, because the two zeolite molecular sieves can provide reasonably matched pore channel structures and gradient distributed acidity, and the synergistic effect between the two zeolite molecular sieves can be realized, so that a better adsorption effect is achieved.
Comparing example 7 with example 11, example 12 and example 15, it can be seen that the adsorption effect of example 7 is better than that of example 11, example 12 and example 15, because the loading of two oxides can act synergistically, the effect is better than the case of loading only one metal oxide, and the loading of three metal oxides can affect the strength of the adsorbent due to competing loads therebetween, which adversely affects the adsorption effect.
Comparing example 7 with example 16 and comparative example 1, it can be found that the adsorption effect of example 7 is superior to that of example 16 and comparative example 1, which shows that too high a loading can adversely affect the adsorption effect of the adsorbent, and that the optimum adsorption effect can be achieved only at a total loading of 15wt%.
Comparing example 7 with example 17, it can be seen that the adsorption effect of example 17 is much lower than that of example 7, because example 7 uses a programmed temperature-rising roasting mode, this specific temperature-rising mode can make the metal oxide distributed on zeolite more uniformly, and generate more active adsorption points, so that the adsorption effect on alcohol VOCs is improved.
Experimental example 2
The adsorption penetration experiment of isopropyl alcohol VOCs under the condition of water vapor was carried out by adopting the example with higher adsorption amount in the experimental example 1, and the adsorption performance of the adsorbent was evaluated by the penetration time and the penetration adsorption amount. Experimental conditions: the particle size of the adsorbent is 60-40 meshes, the adsorption column is a quartz tube with the outer diameter of 6mm and the inner diameter of 4mm, 25mg of adsorbent is filled, the total gas flow is 50mL/min, the relative humidity of gas flow is RH=50%, the initial concentration of organic matters is 80ppm, and the adsorption temperature is 30 ℃.
Table 2 experimental results
As can be seen from table 2, the adsorbent of the present invention can still ensure good adsorption effect on VOCs under the condition of water vapor.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. An adsorbent for purifying alcohol VOCs, comprising: a zeolite having a silica-alumina ratio of not less than 3, and a metal oxide supported on the zeolite;
the loading of the metal oxide is 1-15 wt% of the zeolite.
2. The adsorbent of claim 1, wherein the zeolite is one or more of FAU type, MFI type, MOR type, BEA type, CHA type and STT type.
3. The adsorbent of claim 1 wherein the zeolite is a mixture of FAU-type zeolite and MFI-type zeolite.
4. The adsorbent according to claim 3, wherein the mass ratio of the FAU-type zeolite to the MFI-type zeolite is (0.5-2): 1;
preferably, the mass ratio of the FAU-type zeolite to the MFI-type zeolite is 1:1.
5. The adsorbent of claim 1 wherein the zeolite has a silica to alumina ratio of 4 to 15;
preferably, the zeolite has a silica to alumina ratio of 5.3.
6. The sorbent of claim 1, wherein the metal oxide is an oxide of one or more of Cu, fe, zn, co, ni, mn, na, K, ca, ba, ce and La.
7. The sorbent of claim 6, wherein the metal oxides are two;
preferably, the metal oxide is cobalt oxide and manganese oxide; wherein the mass ratio of CoO to MnO is (1-5): 1.
8. the sorbent of claim 7, wherein a molar ratio of CoO to MnO is 2:1;
preferably, the zeolite is FAU type and MFI type, the silicon-aluminum ratio of the zeolite is 5.3, the loading of the metal oxide is 15wt%, and the metal oxide is cobalt oxide and manganese oxide; wherein the molar ratio of CoO to MnO is 2:1.
9. A method for preparing the adsorbent according to any one of claims 1 to 8, comprising the steps of:
obtaining zeolite raw powder with preset quality, and dissolving at least one metal salt in deionized water according to theoretical loading capacity to form a metal salt solution;
dripping the metal salt solution into zeolite raw powder, and stirring the mixture until the mixture reaches a gelatinous non-Newtonian fluid, wherein the dripping amount of the metal salt solution is determined according to the saturation amount of the zeolite raw powder;
drying the mixture, grinding after drying so that the metal oxide can be uniformly loaded on the zeolite;
heating and roasting the ground zeolite to obtain a zeolite adsorbent loaded with metal oxide;
preferably, the method for determining the saturation amount of the zeolite raw powder comprises the following steps:
taking quantitative zeolite raw powder, dropwise adding a metal salt solution, stirring until the mixture becomes a non-Newtonian fluid state, and calculating the saturation quantity of the zeolite raw powder according to the quantity of the dropwise added metal salt solution;
preferably, the mixture is twisted into a uniform cake shape before being dried, so that a water film is formed on the surface of the mixture to facilitate quick drying;
preferably, the drying mode is any one of rapid flash drying and microwave drying;
preferably, the drying mode is microwave drying, the microwave power is 600-900W, and the time is 30-240 s;
preferably, the grinding time is 5 to 20 minutes.
10. The method according to claim 9, wherein the temperature-raising roasting process is: heating to 100-200 ℃ at a heating rate of 5-20 ℃/min, maintaining for 0.5-2 h, heating to 300-550 ℃ and maintaining for 3-5 h.
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