CN109364912A - Alkaline-earth metal ions replace OMS-2 catalyst and its preparation method and application - Google Patents
Alkaline-earth metal ions replace OMS-2 catalyst and its preparation method and application Download PDFInfo
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- CN109364912A CN109364912A CN201811148151.6A CN201811148151A CN109364912A CN 109364912 A CN109364912 A CN 109364912A CN 201811148151 A CN201811148151 A CN 201811148151A CN 109364912 A CN109364912 A CN 109364912A
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- earth metal
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- oms
- metal ions
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 93
- 230000000694 effects Effects 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 15
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract 2
- 229910001427 strontium ion Inorganic materials 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001447 alkali salts Chemical class 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 150000007516 brønsted-lowry acids Chemical class 0.000 claims description 2
- 150000007528 brønsted-lowry bases Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 2
- QDMGKUOANLJICG-UHFFFAOYSA-N [Mg].[N+](=O)(O)[O-] Chemical group [Mg].[N+](=O)(O)[O-] QDMGKUOANLJICG-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 238000009938 salting Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000012855 volatile organic compound Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- ANBJNNOVODZPET-UHFFFAOYSA-N oxalic acid;strontium Chemical compound [Sr].OC(=O)C(O)=O ANBJNNOVODZPET-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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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
- 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
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a kind of alkaline-earth metal ions to replace OMS-2 catalyst, including OMS-2 carrier and active alkaline-earth metal, active alkaline-earth metal are Mg, Ca or Sr ion, and active alkaline-earth metal ions are supported in the duct of the OMS-2 carrier；The molar ratio of Mn is 0.01~0.08:1 in the activity alkaline-earth metal ions and the OMS-2 carrier.For preparation method of the present invention using potassium permanganate as oxidant, manganese nitrate is reducing agent, and a certain concentration alkaline including earth metal salting liquid is introduced in system, using a mild step hydrothermal synthesis method, has synthesized alkaline-earth metal ions and has replaced OMS-2 catalyst.The catalyst activity is high, cheap, and at a temperature of 180~260 DEG C, benzene catalytic purification efficiency is more than 90%, and success is instead of noble metal catalyst.
Description
Technical field
The present invention relates to catalyst technologies, replace OMS-2 catalyst and its preparation in particular to a kind of alkaline-earth metal ions
Methods and applications.
Background technique
Important pollution of the volatile organic matter (volatile organic compounds, VOCs) as atmosphere pollution
The factor is not only to cause the arch-criminal of multiple environment effect (such as photochemical fog, secondary organic aerosol), while
It is the stealthy killer (such as teratogenesis carcinogenic, mutagenesis) for leading to human health risk.With the rapid development of economy, China
The discharge amount of VOCs has been in increase trend year by year, and the new technology and method for developing high-efficient purification VOCs has become in recent years
Come the important problem for hot spot and control air pollution in China object the discharge urgent need to resolve studied.
Heat catalytic oxidation technology due to have processing VOCs exhaust gas it is high-efficient, do not have secondary pollution, and there is no absorption
The advantages that saturation, it is considered to be one of most promising VOCs processing technique.Carried noble metal (such as: Pt, Pd) catalyst is to work as
It is preceding using more mature effective catalyst, maximum technical bottleneck is content of the noble metals such as Pt and Pd in the earth's crust
It is very low, resource scarcity, therefore it is higher using the economic cost of noble metal catalyst, to limit its popularization and application.It is based on
This, development environment is friendly, cheap and easy to get, high activity, stability are good and the catalyst that noble metal can be replaced to use, can not only
It enough brings huge economic benefit, while may be that positive impetus is played in the development of China VOCs control technology.
Cryptomelane (KMn8O16, OMS-2) and due to cheap, environmental-friendly and unique physical chemistry
It can be such as: 2 × 2 molecular sieve pore passage structures, mixed valence (3+, 4+), be easy release Lattice Oxygen etc., be widely used in being catalyzed in recent years
Aoxidize VOCs, it is considered to be most it is hopeful one of the material of catalytic purification for replacing noble metal to be used for VOCs, it is extensive by people
Concern.However the low temperature VOCs catalytic activity of unmodified OMS-2 is generally all very low, therefore, it is necessary to by physics and change
Means regulate and control the micro-structure of OMS-2, make it have higher catalysis oxidation VOCs performance.Replaced by metal ion
Mn ion in the duct OMS-2 on K+ and/or skeleton is come to change OMS-2 physical and chemical performance strategy be improve OMS-2 low
Warm catalytic activity uses relatively broad one of method.However, existing report substitution OMS-2 catalyst mainly collects
In in alkali metal, transition metal and rare earth ion, these metal ions replace OMS-2 catalyst to have the following problems:
1) catalytic purification VOCs efficiency is not high enough；2) concentration of accurate control metal ion is needed (such as: Rb+Replace OMS-2 catalyst,
Only as the Rb of substitution+In the low-down situation of concentration, OMS-2 catalytic performance can be improved, and excessive Rb+Then reduce
OMS-2 catalytic performance), this limits the mass production that metal ion replaces OMS-2 catalyst to a certain extent.
Summary of the invention
Present invention aim to provide a kind of alkaline-earth metal ions replace OMS-2 catalyst and preparation method thereof and
Using catalyst purifying VOCs of the present invention are high-efficient, preparation process is simple, cheap.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of alkaline-earth metal ions replace OMS-2 catalysis
Agent, including OMS-2 carrier, it is characterised in that: further include active alkaline-earth metal, it is described activity alkaline-earth metal be Mg, Ca or Sr from
Son, the activity alkaline-earth metal ions are supported in the duct of the OMS-2 carrier；The activity alkaline-earth metal ions and institute
The molar ratio for stating Mn in OMS-2 carrier is 0.01~0.08:1.
Further, the active alkaline-earth metal ions are loaded in the duct of the OMS-2 carrier and not by alkaline-earth metal
The molar ratio of Mn is 0.06~0.11:1 in substituted K ion, the K ion and the OMS-2 carrier.
Further, the active alkaline-earth metal ions are loaded in the duct of the OMS-2 carrier and not by alkaline-earth metal
Substituted K ion, 0.09~1.33:1 of molar ratio of the activity alkaline-earth metal ions and the K ion.
Further, the alkaline-earth metal ions are supported in 2 × 2 molecular sieve pore passages of the OMS-2 carrier.
Above-mentioned alkaline-earth metal ions replace the preparation method of OMS-2 catalyst, comprising the following steps:
1) it weighs potassium permanganate to be dissolved in distilled water, compound concentration is the potassium permanganate of 0.0001~0.002mmol/mL
Solution；
2) bronsted lowry acids and bases bronsted lowry earth metal salt is sequentially added into liquor potassic permanganate described in step 1), acid is pressed and the permanganic acid
The ratio that potassium solution volume ratio is 0.1~3.0:100 is added, and alkali salt is by alkaline-earth metal ions and potassium permanganate 0.02
The molar ratio of~0.6:1 is added, and stirs evenly；
3) manganese nitrate is added into step 2) acquired solution, manganese nitrate is by the molar ratio with 0.5~4:1 of potassium permanganate
Be added, stir evenly, then in 50~90 DEG C of temperature and under confined conditions reaction 6~for 24 hours；
4) precipitated product obtained by step 3) is filtered, the alkaline-earth metal ions can be obtained after washing and drying and replace OMS-2
Catalyst.
Further, in the step 2), acid is one or more of nitric acid, hydrochloric acid, citric acid, acetic acid, oxalic acid
Mixing；Alkali salt is magnesium nitrate, magnesium chloride, magnesium acetate, calcium nitrate, calcium chloride, calcium acetate, strontium nitrate, strontium chloride, second
The mixing of one or more of sour strontium.
Further, in the step 3), the molar ratio of Mn is 0.04 in alkaline-earth metal ions and the manganese nitrate solution
~1.2:1.
Further, in the step 4), drying temperature is 50~80 DEG C.
Above-mentioned alkaline-earth metal ions replace the application of OMS-2 catalyst, replace OMS-2 using the alkaline-earth metal ions
Catalyst low-temperature catalytic oxidation volatile organic matter, to reduce pollutant.
Further, replace OMS-2 catalyst catalysis oxidation at 180~260 DEG C using the alkaline-earth metal ions
Benzene.
Compared with prior art, the invention has the following advantages that
One, in the prior art metal ion replace catalyst to be concentrated mainly on alkali metal, transition metal and rare earth gold
Belong to, the present invention uses alkaline-earth metal ions as substitution ion for the first time, and catalyst of the present invention is replaced by alkaline-earth metal ions
K in OMS-2 molecular sieve pore passage+, so that lattice oxygen activity is effectively promoted in OMS-2 catalyst, improve OMS-2's
Low-temperature catalytic activity, to significantly improve the activity of catalyst cleaning VOCs.Catalyst of the present invention is at 220~250 DEG C
Under, the efficiency of catalytic purification benzene is more than 90%, under equal conditions, the temperature (T of benzene transformation efficiency 90%90) can be sold better than market
Pt supported catalyst.
Second, cheap alkaline-earth metal ions are successfully introduced into the duct of OMS-2 by the present invention, so that originally urging
Agent is cheap and easy to get, high activity and becomes the catalyst that noble metal can be replaced to use, and solves existing noble metal catalyst
Using economic cost height, it is difficult to which the problems such as popularization and application produce huge economic and social benefits, are also Environmental Protection in China strategy
Make tremendous contribution.
Third, the present invention using potassium permanganate as oxidant, using manganese nitrate as reducing agent, introduces a certain concentration in system
Alkaline-earth metal salt solution synthesized alkaline-earth metal ions and replaced OMS-2 catalyst (M-OMS- using a step hydrothermal synthesis method
2, M=Mg, Ca, Sr), process flow is simply smooth, operation is convenient, further reduced production cost.
Fourth, the present invention does not need the concentration for accurately controlling metal ion, can produce in enormous quantities, so as to substantially
Degree promotes and applies (such as: Rb+Replace OMS-2 catalyst, only as the Rb of substitution+In the low-down situation of concentration, it can improve
OMS-2 catalytic performance, and excessive Rb+Then reduce OMS-2 catalytic performance, it is therefore desirable to accurately control Rb+Concentration, this
Certain difficulty is brought to Rb-OMS-2 catalyst is produced in enormous quantities).
Detailed description of the invention
Fig. 1 is the distinctive X-ray diffraction figure (XRD) that alkaline-earth metal ions replace OMS-2 catalyst.
Fig. 2 is the activity figure that alkaline-earth metal ions replace OMS-2 catalyst Oxybenzene.
Fig. 3 is Sr-OMS-2-D catalyst stability diagram.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawing, convenient for more clearly understanding the present invention, but they
Limiting the invention.
Alkaline-earth metal ions made from following Examples 1 to 6 replace OMS-2 catalyst in, active alkaline-earth metal ions with
The molar ratio of Mn is 0.01~0.08:1 in OMS-2 carrier；The K ion not replaced by alkaline-earth metal in the duct of OMS-2 carrier
Molar ratio with Mn in OMS-2 carrier is 0.06~0.11:1；In the duct of active alkaline-earth metal ions and OMS-2 carrier not
0.09~1.33:1 of molar ratio of the K ion replaced by alkaline-earth metal.In preparation process, nitric acid, hydrochloric acid, lemon is can be used in acid
The mixing of one or more of acid, acetic acid, oxalic acid；Strontium nitrate, magnesium nitrate, magnesium chloride, acetic acid can be used in alkali salt
Magnesium, the mixing of one or more of calcium nitrate, calcium chloride, calcium acetate, strontium chloride, strontium acetate.
Embodiment 1
(1) potassium permanganate for weighing 0.02mol is dissolved in the distilled water of 100mL, makes it sufficiently molten under magnetic stirring
Solution；
(2) strontium nitrate of the nitric acid of 0.5mL and 0.001mol is added to solution in step (1), stirred evenly；
(3) manganese nitrate of 0.01mol is added in step (2) solution, stirs evenly, then seals burning with preservative film
Rim of a cup reacts for 24 hours at 80 DEG C.
(4) to the end of reacting, it is 100 μ s/cm that the substrate that above-mentioned reaction obtains, which is washed with distilled water to conductivity,；It will
Sample after washing is placed dries at 60 DEG C, it can obtains Sr ionic compartmentation OMS-2 catalyst, which is labeled as
Sr-OMS-2-A。
Catalyst Discriminating materials: the XRD spectrum for the catalyst that embodiment 1 obtains is as shown in Figure 1, be cryptomelane structure.
Catalyst activity evaluation: the concentration of benzene is 2000mg/m3, air speed 48000h-1, the conversion of gas chromatographic detection benzene
The production rate of rate and CO2.The sample prepared using embodiment 1 is catalyst, the T of catalyzing, oxidizing and purifying benzene50And T90(the catalysis of benzene
Oxidation, purification rate is respectively temperature corresponding to 50% and 90%) it is respectively 218 DEG C and 240 DEG C (Fig. 2), as shown in Fig. 2, real
Apply the T of the low-temperature catalytic oxidation benzene of the resulting catalyst of example 190It is better than certain commodity Pt supported catalyst sold market under equal conditions
Agent (T90=260 DEG C).
Embodiment 2
(1) potassium permanganate for weighing 0.02mol is dissolved in the distilled water of 100mL, makes it sufficiently molten under magnetic stirring apparatus
Solution；
(2) strontium nitrate of the nitric acid of 0.5mL and 0.003mol are successively added to solution in step (1), stirred evenly；
(3) manganese nitrate of 0.01mol is added in step (2) solution, stirs evenly, then seals burning with preservative film
Rim of a cup reacts for 24 hours at 80 DEG C.
(4) to the end of reacting, it is 100 μ s/cm that the substrate that above-mentioned reaction obtains, which is washed with distilled water to conductivity,；It will
Sample after washing is placed dries at 60 DEG C, it can obtains Sr ionic compartmentation OMS-2 catalyst, which is labeled as
Sr-OMS-2-B。
Catalyst Discriminating materials: the XRD spectrum for the catalyst that embodiment 2 obtains is as shown in Figure 1, be cryptomelane structure.
Catalyst activity evaluation: the concentration of benzene is 2000mg/m3, air speed 48000h-1, the conversion of gas chromatographic detection benzene
The production rate of rate and CO2.The sample prepared using embodiment 2 is catalyst, the T of catalyzing, oxidizing and purifying benzene50And T90(the catalysis of benzene
Oxidation, purification rate is respectively temperature corresponding to 50% and 90%) it is respectively 211 DEG C and 234 DEG C (Fig. 2), as shown in Fig. 2, real
Apply the T of the low-temperature catalytic oxidation benzene of the resulting catalyst of example 290Purification efficiency is better than certain commodity Pt sold market under equal conditions
Supported catalyst (T90=260 DEG C).
Embodiment 3
(1) potassium permanganate for weighing 0.02mol is dissolved in the distilled water of 100mL, is dissolved under magnetic stirring apparatus；
(2) strontium nitrate of the nitric acid of 0.5mL and 0.006mol are successively added to solution in step (1), stirred evenly；
(3) manganese nitrate of 0.01mol is added in step (2) solution, stirs evenly, then seals burning with preservative film
Rim of a cup reacts for 24 hours at 80 DEG C.
(4) to the end of reacting, it is 100 μ s/cm that the substrate that above-mentioned reaction obtains, which is washed with distilled water to conductivity,；It will
Sample after washing is placed dries at 60 DEG C, it can obtains Sr ionic compartmentation OMS-2 catalyst, which is labeled as
Sr-OMS-2-C。
Catalyst Discriminating materials: the XRD spectrum for the catalyst that embodiment 3 obtains is as shown in Figure 1, be cryptomelane structure.
Catalyst activity evaluation: the concentration of benzene is 2000mg/m3, air speed 48000h-1, the conversion of gas chromatographic detection benzene
Rate and CO2Production rate.The sample prepared using embodiment 3 is catalyst, the T of catalyzing, oxidizing and purifying benzene50And T90(the catalysis of benzene
Oxidation, purification rate is respectively temperature corresponding to 50% and 90%) it is respectively 201 DEG C and 224 DEG C (Fig. 2), as shown in Fig. 2, real
Apply the T of the resulting catalyst of example 390Purification efficiency is better than certain commodity Pt supported catalyst (T sold market under equal conditions90=
260℃)。
Catalyst stability evaluation: as shown in figure 3, Sr ionic compartmentation OMS-2 catalyst is in benzene prepared by embodiment 3
Concentration is 2000mg/m3, air speed 48000h-1When, the catalytic conversion of continuous work 48h, benzene still remain in 97% or more,
With good stability.
Embodiment 4
(1) potassium permanganate for weighing 0.02mol is dissolved in the distilled water of 100mL, is dissolved under magnetic stirring apparatus；
(2) strontium nitrate of the nitric acid of 0.5mL and 0.009mol are successively added to solution in step (1), stirred evenly；
(3) manganese nitrate of 0.01mol is added in step (2) solution, stirs evenly, then seals burning with preservative film
Rim of a cup reacts for 24 hours at 80 DEG C.
(4) to the end of reacting, it is 100 μ s/cm that the substrate that above-mentioned reaction obtains, which is washed with distilled water to conductivity,；It will
Sample after washing is placed dries at 60 DEG C, it can obtains Sr ionic compartmentation OMS-2 catalyst, which is labeled as
Sr-OMS-2-D。
Catalyst Discriminating materials: the XRD spectrum for the catalyst that embodiment 3 obtains is as shown in Figure 1, be cryptomelane structure.
Catalyst activity evaluation: the concentration of benzene is 2000mg/m3, air speed 48000h-1, the conversion of gas chromatographic detection benzene
Rate and CO2Production rate.The sample prepared using embodiment 4 is catalyst, the T of catalyzing, oxidizing and purifying benzene50And T90(the catalysis of benzene
Oxidation, purification rate is respectively temperature corresponding to 50% and 90%) it is respectively 197 DEG C and 220 DEG C (Fig. 2), as shown in Fig. 2, real
Apply the T of the resulting catalyst of example 490Purification efficiency is better than certain commodity Pt supported catalyst (T sold market under equal conditions90=
260℃)
Embodiment 5
(1) potassium permanganate for weighing 0.02mol is dissolved in the distilled water of 100mL, is dissolved under magnetic stirring apparatus；
(2) magnesium nitrate of the nitric acid of 0.5mL and 0.006mol are successively added to solution in step (1), stirred evenly；
(3) manganese nitrate of 0.01mol is added in step (2) solution, stirs evenly, then seals burning with preservative film
Rim of a cup reacts for 24 hours at 80 DEG C.
(4) to the end of reacting, it is 100 μ s/cm that the substrate that above-mentioned reaction obtains, which is washed with distilled water to conductivity,；It will
Sample after washing is placed dries at 60 DEG C, it can obtains Ca-OMS-2 catalyst, which is labeled as Ca-OMS-
2-A。
Catalyst Discriminating materials: the XRD spectrum for the catalyst that embodiment 5 obtains is as shown in Figure 1, be cryptomelane structure.
Catalyst activity evaluation: the concentration of benzene is 2000mg/m3, air speed 48000h-1, the conversion of gas chromatographic detection benzene
The production rate of rate and CO2.The sample prepared using embodiment 5 is catalyst, the T of catalyzing, oxidizing and purifying benzene50And T90(the catalysis of benzene
Oxidation, purification rate is respectively temperature corresponding to 50% and 90%) it is respectively 216 DEG C and 245 DEG C (Fig. 2), as shown in Fig. 2, real
Apply the T of the resulting catalyst of example 590Purification efficiency is better than certain commodity Pt supported catalyst (T sold market under equal conditions90=
260℃)。
Embodiment 6
(1) potassium permanganate for weighing 0.02mol is dissolved in the distilled water of 100mL, is dissolved under magnetic stirring apparatus；
(2) magnesium nitrate of the nitric acid of 0.5mL and 0.001mol are successively added to solution in step (1), stirred evenly；
(3) manganese nitrate of 0.01mol is added in step (2) solution, stirs evenly, then seals burning with preservative film
Rim of a cup reacts for 24 hours at 80 DEG C.
(4) to the end of reacting, it is 100 μ s/cm that the substrate that above-mentioned reaction obtains, which is washed with distilled water to conductivity,；It will
Sample after washing is placed dries at 60 DEG C, it can obtains Mg ionic compartmentation OMS-2 catalyst, which is labeled as
Mg-OMS-2。
Catalyst Discriminating materials: the XRD spectrum for the catalyst that embodiment 5 obtains is as shown in Figure 1, be cryptomelane structure.
Catalyst activity evaluation: the concentration of benzene is 2000mg/m3, air speed 48000h-1, the conversion of gas chromatographic detection benzene
The production rate of rate and CO2.The sample prepared using embodiment 5 is catalyst, the T of catalyzing, oxidizing and purifying benzene50And T90(the catalysis of benzene
Oxidation, purification rate is respectively temperature corresponding to 50% and 90%) it is respectively 207 DEG C and 235 DEG C (Fig. 2), as shown in Fig. 2, real
Apply the T of the resulting catalyst of example 690Purification efficiency is better than certain commodity Pt supported catalyst (T sold market under equal conditions90=
260℃)。
Claims (10)
1. a kind of alkaline-earth metal ions replace OMS-2 catalyst, including OMS-2 carrier, it is characterised in that: further include active alkaline earth
Metal, the activity alkaline-earth metal is Mg, Ca or Sr ion, and the activity alkaline-earth metal ions are supported on the OMS-2 carrier
Duct in；The molar ratio of Mn is 0.01~0.08:1 in the activity alkaline-earth metal ions and the OMS-2 carrier.
2. alkaline-earth metal ions replace OMS-2 catalyst according to claim 1, it is characterised in that: the OMS-2 carrier
The K ion for loading the active alkaline-earth metal ions in duct and not replaced by alkaline-earth metal, the K ion and the OMS-2
The molar ratio of Mn is 0.06~0.11:1 in carrier.
3. alkaline-earth metal ions replace OMS-2 catalyst according to claim 1, it is characterised in that: the OMS-2 carrier
The K ion for loading the active alkaline-earth metal ions in duct and not replaced by alkaline-earth metal, the activity alkaline-earth metal ions
With 0.09~1.33:1 of molar ratio of the K ion.
4. according to claim 1 or 2 or 3 alkaline-earth metal ions replace OMS-2 catalyst, it is characterised in that: the alkaline earth
Metal ion is supported in 2 × 2 molecular sieve pore passages of the OMS-2 carrier.
5. the preparation method of the substitution OMS-2 catalyst of alkaline-earth metal ions described in claim 1, comprising the following steps:
1) it weighs potassium permanganate to be dissolved in distilled water, compound concentration is the liquor potassic permanganate of 0.0001~0.002mmol/mL；
2) bronsted lowry acids and bases bronsted lowry earth metal salt is sequentially added into liquor potassic permanganate described in step 1), acid is pressed and the liquor potassic permanganate
The ratio that volume ratio is 0.1~3.0:100 is added, and alkali salt is by alkaline-earth metal ions and 0.02~0.6:1 of potassium permanganate
Molar ratio be added, stir evenly；
3) manganese nitrate is added into step 2) acquired solution, manganese nitrate is pressed to be added with the molar ratio of 0.5~4:1 of potassium permanganate,
Stir evenly, then in 50~90 DEG C of temperature and under confined conditions reaction 6~for 24 hours；
4) precipitated product obtained by step 3) is filtered, the alkaline-earth metal ions can be obtained after washing and drying and replace OMS-2 catalysis
Agent.
6. alkaline-earth metal ions replace the preparation method of OMS-2 catalyst according to claim 5, it is characterised in that: described
In step 2), acid is the mixing of one or more of nitric acid, hydrochloric acid, citric acid, acetic acid, oxalic acid；Alkali salt is nitric acid
Magnesium, magnesium chloride, magnesium acetate, one or more of calcium nitrate, calcium chloride, calcium acetate, strontium nitrate, strontium chloride, strontium acetate mix
It closes.
7. alkaline-earth metal ions replace the preparation method of OMS-2 catalyst according to claim 5, it is characterised in that: described
In step 3), the molar ratio of Mn is 0.04~1.2:1 in alkaline-earth metal ions and the manganese nitrate solution.
8. alkaline-earth metal ions replace the preparation method of OMS-2 catalyst according to claim 5, it is characterised in that: described
In step 4), drying temperature is 50~80 DEG C.
9. alkaline-earth metal ions replace the application of OMS-2 catalyst according to claim 1, it is characterised in that: described in utilization
Alkaline-earth metal ions replace OMS-2 catalyst low-temperature catalytic oxidation volatile organic matter, to reduce pollutant.
10. alkaline-earth metal ions replace the application of OMS-2 catalyst according to claim 8, it is characterised in that: described in utilization
Alkaline-earth metal ions replace OMS-2 catalyst catalysis oxidation benzene at 180~260 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644181A (en) * | 2020-06-30 | 2020-09-11 | 华中农业大学 | Water poisoning resistant cobalt ion doped potassium manganese ore catalyst and preparation method and application thereof |
| CN113042065A (en) * | 2021-04-01 | 2021-06-29 | 烟台通盛环境科技有限公司 | CoCa-OMS-2 nanowire catalyst for removing formaldehyde and preparation method thereof |
| CN114653172A (en) * | 2022-03-15 | 2022-06-24 | 江苏理工学院 | Remove VOCs and Hg in coordination0Method (2) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108499558A (en) * | 2018-03-26 | 2018-09-07 | 华中农业大学 | Rb ionic compartmentation OMS-2 catalyst and its preparation method and application |
-
2018
- 2018-09-29 CN CN201811148151.6A patent/CN109364912A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108499558A (en) * | 2018-03-26 | 2018-09-07 | 华中农业大学 | Rb ionic compartmentation OMS-2 catalyst and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| PENG LIU ET AL.: "Promoting effect of unreducible metal doping on OMS-2 catalysts for gas-phase selective oxidation of ethanol", 《JOURNAL OF CATALYSIS》 * |
| SHIMING FANG ET AL.: "Mg-doped OMS-2 nanorods: a highly efficient catalyst for purification of volatile organic compounds with full solar spectrum irradiation", 《ENVIRONMENTAL SCIENCE: NANO》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644181A (en) * | 2020-06-30 | 2020-09-11 | 华中农业大学 | Water poisoning resistant cobalt ion doped potassium manganese ore catalyst and preparation method and application thereof |
| CN111644181B (en) * | 2020-06-30 | 2022-01-11 | 华中农业大学 | Water poisoning resistant cobalt ion doped potassium manganese ore catalyst and preparation method and application thereof |
| CN113042065A (en) * | 2021-04-01 | 2021-06-29 | 烟台通盛环境科技有限公司 | CoCa-OMS-2 nanowire catalyst for removing formaldehyde and preparation method thereof |
| CN114653172A (en) * | 2022-03-15 | 2022-06-24 | 江苏理工学院 | Remove VOCs and Hg in coordination0Method (2) |
| CN114653172B (en) * | 2022-03-15 | 2023-11-14 | 江苏理工学院 | Synergistic removal of VOCs and Hg 0 Is a method of (2) |
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