CN114682295B - Preparation method and application of catalytic ethylene removal agent - Google Patents
Preparation method and application of catalytic ethylene removal agent Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000005977 Ethylene Substances 0.000 title claims abstract description 87
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 33
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 235000013399 edible fruits Nutrition 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- KEEBYTMTZVIEKL-UHFFFAOYSA-M azanium;silver;sulfate Chemical compound [NH4+].[Ag+].[O-]S([O-])(=O)=O KEEBYTMTZVIEKL-UHFFFAOYSA-M 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001569 carbon dioxide Substances 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 229940093470 ethylene Drugs 0.000 description 6
- 229940062056 nitrogen 79 % Drugs 0.000 description 6
- 229940063821 oxygen 21 % Drugs 0.000 description 6
- -1 silver ions Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 244000282866 Euchlaena mexicana Species 0.000 description 1
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JNKQKOKSOYJQIZ-UHFFFAOYSA-O azanium;silver;dinitrate Chemical compound [NH4+].[Ag+].[O-][N+]([O-])=O.[O-][N+]([O-])=O JNKQKOKSOYJQIZ-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23B7/152—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The application discloses a preparation method and application of a catalytic ethylene removal agent, comprising the following steps: preparing ZSM-5 molecular sieve by a solid phase method; adding ZSM-5 molecular sieve into silver ion-containing solution, and aging; evaporating the water to dryness to obtain the Ag-loaded ZSM-5 molecular sieve; and roasting the obtained ZSM-5 molecular sieve loaded with Ag to obtain the catalytic ethylene remover. In the application, the content of surface hydroxyl and the proportion of surface active oxygen are increased by utilizing the highly dispersed Ag nano particles, and the migration capability of active oxygen is enhanced, so that ethylene adsorbed on the surface of the catalyst rapidly reacts with the active oxygen in the catalyst to generate nontoxic and harmless carbon dioxide and water.
Description
Technical Field
The invention relates to the technical field of ethylene room temperature catalytic oxidation, in particular to a preparation method and application of a catalytic ethylene removal agent.
Background
Along with the continuous improvement of the living standard of people, the fruit industry in China gradually becomes a trillion-level industry. The fruit market size is estimated to reach about 27460.1 billions of yuan by 2025. However, due to the fact that fruit fresh-keeping technology is behind in the transportation and storage processes, loss of fruits is serious from the time of picking to the time of entering a circulation stage, the loss rate of fruits in China in the present stage is about 30 percent, the loss rate of fruits is far higher than the average 7 percent level in developed countries, about 800 ten thousand tons of fruits are spoiled each year, and economic loss is more than 800 hundred million yuan, so that the importance of fruit fresh-keeping is seen. Among them, ethylene is the greatest cause of fruit spoilage. Ethylene removal is particularly important in order to extend the fresh-keeping period of the fruit. The current control of ethylene content is generally divided into two directions: firstly, inhibiting the synthesis of ethylene in fruits; another class is the control of exogenous ethylene content by the use of ethylene scavengers. Among them, the first type of method is not widely used because the use condition is limited and the effect is not obvious. Methods for eliminating exogenous ethylene can be roughly divided into five types: ventilation, storage under reduced pressure, chemical or physical adsorption, catalytic oxidation or direct oxidation, biological methods. In recent years, attention has been focused on the development of the latter three types of ethylene removal processes. The physical adsorbent mainly refers to substances such as active carbon, mineral substances, molecular sieves, synthetic resins and the like with porous structures. It is usually made into small packages and placed in a packing box or a storage warehouse, or mixed with paper pulp to make into preservative paper. Physical adsorbents have high adsorption speed and are less affected by temperature, but the adsorbents have no selectivity to adsorbates, have limited adsorption capacity and need to be replaced frequently. When the activated carbon is placed in a fruit and vegetable storage warehouse, the activated carbon is easy to be wetted, so that the adsorption performance is reduced, and therefore, the activated carbon needs to be replaced frequently, and is inconvenient in long-distance transportation. Chemisorption is the removal of ethylene from the environment by the formation of chemical bonds between the adsorbent and ethylene molecules, which are generally stronger than van der waals forces due to the electron transfer involved. Such adsorbents are often prepared by introducing a metal or metal oxide onto a porous support, the metal or metal oxide having a coordination complex with ethylene molecules to adsorb ethylene. At present, pd, pt, cu, fe, ag and other metals are supported on molecular sieves or other carriers, and have a certain adsorption effect on ethylene. In general, chemisorption is superior to physisorption, but either the physisorbent or the chemisorber is extremely susceptible to damage after heat treatment to desorb ethylene molecules adsorbed on the adsorbent, resulting in secondary pollution. The direct oxidation technology is used for removing ethylene by utilizing the oxidability of a strong oxidant to oxidize double bonds between two carbon atoms in ethylene into substances such as acetic acid, ethylene glycol or carbon dioxide, and the like, so that the purpose of removing ethylene is achieved. The main agents of the direct oxidation ethylene removing agent comprise strong oxidants such as KMnO 4 (potassium permanganate), O 3 (ozone), clO 2 (chlorine dioxide), H 2O2 (hydrogen dioxide) and the like. However, these materials are harmful to human bodies, so that certain food safety problems exist in practical applications.
Catalytic oxidation means that the purpose of degrading ethylene is achieved under the action of a catalyst, and the catalyst is not influenced. Generally, ethylene is oxidized into carbon dioxide and water by using oxygen in air under the catalysis of a catalyst, so that the catalyst has no secondary pollution and is easy to put into practical application, and the catalyst becomes a hot spot for research in recent years. According to the preparation mode, the catalyst can be divided into a supported catalyst, a pure metal catalyst and the like; according to the nature of the active components, the catalyst can be divided into noble metal, non-noble metal catalyst and the like; according to the mode of action, it can be classified into photocatalyst, thermal catalyst, room temperature catalyst, etc. The porous carrier material is prepared by loading single or multiple noble metals or non-noble metals as active components on a porous carrier material, wherein common active metals include Pt, pd, au, ag, cu, ag, mn, oxides thereof and the like, and the porous carrier material comprises a carbon-based material, a zeolite molecular sieve, alumina and the like. The Pt, pd, au and other noble metals have relatively good effect on the catalytic oxidation of ethylene, and can finish the catalytic oxidation of ethylene at a lower temperature. At present, catalytic ethylene removal agents have been applied to apple preservation in the united states, italy and other countries. However, the catalysts capable of thoroughly degrading ethylene at room temperature are few at present, the content of supported noble metals is extremely high, and the noble metals are expensive, so that the catalyst brings great challenges to large-scale popularization. Thus, developing a relatively inexpensive catalyst that completely degrades ethylene at room temperature presents a significant challenge.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a solid phase ZSM-5 for purifying ethylene at room temperature and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following solutions:
A preparation method of a catalytic ethylene removal agent comprises the following steps:
step 1) preparing ZSM-5 molecular sieve by a solid phase method;
Step 2) adding the ZSM-5 molecular sieve obtained in the step 1) into a silver ion-containing solution, and aging; evaporating the water to dryness to obtain the Ag-loaded ZSM-5 molecular sieve;
And 3) roasting the ZSM-5 molecular sieve loaded with Ag obtained in the step 2) to obtain the catalytic ethylene remover.
Optionally, in step 2), the moisture is evaporated to dryness at 80 ℃.
Optionally, the ratio of the mass of the ZSM-5 molecular sieve to the silver active component aqueous solution is 1g to 0.1-20 ml; the concentration of Ag ions is 1-1000 g/L;
optionally, the silver ion-containing solution is at least one of a silver nitrate aqueous solution, a silver acetate aqueous solution, a silver sulfate aqueous solution and a silver ammonium sulfate aqueous solution.
Optionally, the mass fraction of Ag in the catalytic ethylene removal agent is 0.1-20%.
Optionally, the mass fraction of Ag in the catalytic ethylene removal agent is 5-12%.
Optionally, the method for preparing the ZSM-5 molecular sieve in the step 1) by a solid phase method comprises the following steps: and (3) reacting a solid mixture containing a silicon source, an aluminum source, an alkali source and a template agent, transferring the product into a reaction kettle, crystallizing for 3 days at 180 ℃, centrifuging the crystallized sample, washing, and drying to obtain the ZSM-5 molecular sieve.
Optionally, the reaction of the solid mixture containing the silicon source, the aluminum source, the alkali source and the template agent is specifically: 9 to 11 parts by weight of white carbon black, 9 to 11 parts by weight of tetrapropylammonium hydroxide with 40% weight and 0.032 to 0.034 part by weight of pseudo-boehmite are mixed and added into a mortar, and stirred for 0.5 hour.
Optionally, in the step 2), adding ZSM-5 molecular sieve into the silver ion-containing solution, performing ultrasonic treatment for 5-30 minutes, stirring for 1-4 hours, and aging;
Optionally, the aging time is 3-12 h.
Optionally, in the step 3), the Ag-loaded ZSM-5 molecular sieve is dried at 100 ℃ for 3 to 5 hours after the moisture is evaporated to dryness.
Optionally, the ZSM-5 molecular sieve loaded with Ag is moved into a muffle furnace and baked for 1-8 hours at 400-550 ℃ in the air.
The application also provides application of the catalytic ethylene removal agent in fruit fresh-keeping.
The preparation method of the solid phase synthesis ZSM-5 catalyst in the application specifically comprises the following steps:
The ZSM-5 molecular sieve is synthesized by a solid phase synthesis method, and the specific process is as follows: 10g of white carbon black, 10g of TPAOH (tetrapropylammonium hydroxide) and 0.333g of pseudo-boehmite were mixed and added to a mortar, stirred at room temperature for 0.5 hours, then transferred to a polytetrafluoroethylene-lined hydrothermal kettle, and crystallized at 180℃for 3 days. And centrifuging, washing and drying the crystallized sample to obtain the solid phase ZSM-5 carrier.
Immersing solid-phase ZSM-5 serving as a carrier in an aqueous solution of a silver active component, carrying out ultrasonic treatment for 5-30 minutes, stirring for 1-4 hours, and aging overnight; evaporating the water at 80 ℃ under stirring, and continuing to dry for 3-5 hours at 100 ℃; then moving into a muffle furnace, and roasting for 1-8 hours at 400 ℃ under the air condition; obtaining a silver-loaded solid-phase OMS-2 molecular sieve catalyst;
the aqueous solution of the silver active component refers to silver inorganic salt solution or silver complex solution; the ratio of the mass of the solid phase ZSM-5 to the silver active component aqueous solution is 1 g:0.1-20 mL.
In the invention, the solid phase ZSM-5 molecular sieve is synthesized by a solvent-free method.
In the invention, the catalyst can completely purify and eliminate ethylene generated in the fruit fresh-keeping process under the conditions of the temperature of 20 ℃ and above and the airspeed of 60000h -1 and below.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation process of the invention adopts nontoxic and harmless components, which can not cause harm to human health and ecological environment, and the preparation method is simple and easy to implement.
(2) The catalyst can maintain the ethylene removal rate of 100% in a wide temperature operating range (20 ℃ and above) and a wide space velocity operating range (60000 h -1 and below), so that the catalyst is especially suitable for completely eliminating ethylene generated in the fruit fresh-keeping process and has excellent carbon dioxide generation selectivity.
(3) Compared with the existing catalyst for catalyzing and oxidizing ethylene at room temperature by noble metal, the solid phase ZSM-5 catalyst loaded with Ag has relatively low price and is more suitable for large-scale popularization and application.
(4) Compared with ZSM-5 synthesized by common hydrothermal method, the solid phase synthesis method has higher yield, does not generate any waste water, and greatly improves the synthesis efficiency.
In the invention, the content of surface hydroxyl and the proportion of surface active oxygen are increased by utilizing the highly dispersed Ag nano particles, and the migration capability of active oxygen is enhanced, so that ethylene adsorbed on the surface of the catalyst rapidly reacts with the active oxygen in the catalyst to generate nontoxic and harmless carbon dioxide and water. The silver is innovatively loaded on the solid phase ZSM-5, so that the room temperature degradation activity of the ethylene on the catalyst is greatly improved, and the ethylene generated in the fruit fresh-keeping process is completely purified and eliminated by the catalyst under the conditions of the temperature of 20 ℃ and above and the space velocity of 60000h -1 and below.
Drawings
FIG. 1 is a graph showing ethylene conversion at various space velocities for a 5% Ag/ZSM-5 catalyst;
FIG. 2 shows ethylene conversion for a 5% Ag/ZSM-5 catalyst under various humidity conditions;
FIG. 3 shows ethylene conversion at 20℃for a 5% Ag/ZSM-5 catalyst.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
Example 1
Firstly, synthesizing a ZSM-5 molecular sieve by a solid phase synthesis method, wherein the specific process is as follows: 10g of white carbon black, 10g of TPAOH (tetrapropylammonium hydroxide) and 0.333g of pseudo-boehmite were mixed and added to a mortar, stirred at room temperature for 0.5 hours, then transferred to a polytetrafluoroethylene-lined hydrothermal kettle, and crystallized at 180℃for 3 days. Centrifuging, washing and drying the crystallized sample to obtain the MFI type zeolite molecular sieve solid phase ZSM-5 carrier.
Immersing solid-phase ZSM-5 serving as a carrier in an aqueous solution containing silver nitrate, carrying out ultrasonic treatment for 30 minutes, stirring for 4 hours, and aging overnight; stirring the mixed solution with a glass rod at 80 ℃, evaporating water in the mixed solution to dryness to uniformly load active components on the solid phase ZSM-5, and continuously drying at 100 ℃ for 5 hours; then moving the mixture into a muffle furnace under the air condition, and roasting the mixture for 5 hours at 450 ℃; the ZSM-5 containing the silver active component is roasted to obtain the catalyst taking silver ions as the active component. The mass content of the active component is 0.1%. Sieving the catalyst into particles with the size of 40-60 meshes for standby.
Example 2
The preparation method is the same as in example 1, the percentage of silver ion is 0.5%, ultrasonic treatment is carried out for 5 minutes, stirring is carried out for 1 hour, drying is carried out at 100 ℃ for 3 hours, and roasting is carried out at 450 ℃ for 1 hour under the air condition.
Example 3
The preparation method is the same as in example 1, the percentage of silver ion is 1%, ultrasonic treatment is carried out for 10 minutes, stirring is carried out for 2 hours, drying is carried out at 100 ℃ for 4 hours, and roasting is carried out at 450 ℃ for 8 hours under the air condition.
Example 4
The preparation method is the same as in example 1, the percentage of silver ion is 2%, ultrasonic treatment is carried out for 15 minutes, stirring is carried out for 3 hours, and roasting is carried out for 3 hours at 450 ℃ under the air condition.
Example 5
The preparation method is the same as in example 1, the percentage of silver ion removal is 5%, and the ultrasonic treatment is carried out for 20 minutes.
Example 6
The preparation method is the same as in example 1, the percentage of silver ion removal is 10%, and roasting is carried out for 4 hours at 450 ℃ under the air condition.
Example 7
The preparation method is the same as in example 1, the percentage of silver ion removal is 12%, and the silver ion removal is carried out for 2 hours at 100 ℃.
Example 8
The preparation was carried out in the same manner as in example 1 except that the percentage of silver ions was 15%, and the mixture was dried at 100℃for 4 hours.
Example 9
The preparation method is the same as in example 1, the percentage of silver ion removal is 20%, and roasting is carried out for 3 hours at 450 ℃ under the air condition.
Example 10
The preparation method is the same as in example 5, except that an aqueous solution containing silver ammonium nitrate is used in the impregnation to obtain a catalyst containing silver ions as an active component.
Example 11
The preparation method was the same as in example 5 except that an aqueous solution containing silver acetate was used for impregnation to obtain a catalyst containing silver ions as an active component.
Example 12
The preparation method was the same as in example 5 except that an aqueous solution containing silver sulfate was used during impregnation to obtain a catalyst containing silver ions as an active component.
Example 13
The preparation method is the same as in example 5, except that an aqueous solution containing silver ammonium sulfate is used for impregnation to obtain a catalyst with silver ions as an active component.
Example 14
The preparation method was the same as in example 5 except that the hydrothermal synthesized ZSM-5 was used as a carrier. The specific method for synthesizing ZSM-5 by hydrothermal method comprises the following steps: firstly, 0.17g of NaAlO 2 is dissolved in 40.05m deionized water, and 16.62mL of TPAOH solution is added after stirring for a period of time; stirring at room temperature for 15min, and adding 15.20mL of TEOS into the mixture; stirring at room temperature for 5-6 h, and then filling into a reaction kettle for crystallization for 4 days at 180 ℃. After crystallization is completed, obtaining a ZSM-5 zeolite molecular sieve product by centrifuging, washing with deionized water, drying and roasting at 550 ℃ for 5 hours to eliminate the organic template agent.
Example 15
The preparation was the same as in example 5 except that commercial beta-MnO 2 was used as the carrier. (Ala Ding Shiji Co., ltd., 1313-13-9)
Effect verification of the invention
The catalyst obtained in example 5 was used for the catalytic oxidation of ethylene:
The catalyst of example 5 was used in amounts of 200mg, 100mg, 50mg and 25mg, and the respective space velocities were 30,000 mL/(g.h), 60,000 mL/(g.h), 120,000 mL/(g.h) and 240,000 mL/(g.h), respectively, and the respective condition numbers were A, B, C, D. The experimental conditions were as follows: oxygen 21%, nitrogen 79%, ethylene concentration was controlled at 80ppm, relative humidity at 50%, and reaction temperature at room temperature. CO 2 was measured using an infrared gas cell. Ethylene was measured by a hand-held portable VOC detector (PV 6001-VOC-EX).
The catalytic activity of the obtained catalyst was carried out on a fixed reaction bed until the reaction was carried out until the composition of the reaction gas was measured at steady state, and the catalytic activity of the catalyst was shown in fig. 1 under the four test conditions A, B, C, D.
As can be seen from fig. 1, the catalyst has excellent room temperature ethylene catalytic activity. Under conditions A, B, C, the conversion of ethylene at 20℃of the catalyst was 100%. While at the extreme space velocity of condition D, the ethylene conversion remained above 50%, indicating that the catalyst had very excellent ethylene catalytic oxidation properties.
The catalyst prepared in example 5 was used in the catalytic oxidation of ethylene
100Mg of the catalyst of example 5 was taken and the corresponding space velocities were 60,000 mL/(g.h), respectively. The experimental conditions were as follows: oxygen 21%, nitrogen 79%, ethylene concentration was controlled to 80ppm, and the reaction temperature was room temperature. In addition, water with relative humidity of 0,50% and 90% was introduced into the reaction system, respectively. The corresponding condition numbers are A, B, C respectively. CO 2 was measured using an infrared gas cell. Ethylene was measured by a hand-held portable VOC detector (PV 6001-VOC-EX).
The catalytic activity of the obtained catalyst was carried out on a fixed reaction bed until the reaction was carried out until the composition of the reaction gas was measured at a steady state, and the catalytic activity of the catalyst was as shown in fig. 2.
As can be seen from fig. 2, the catalyst has excellent room temperature ethylene catalytic activity. At a relative humidity of 0 to 90%, the catalyst maintains the conversion of ethylene at 100%. This indicates that the catalyst has very excellent catalytic oxidation properties for ethylene.
The catalyst obtained in example 5 was used for the catalytic oxidation of ethylene:
100mg of the catalyst of example 5 was taken and the corresponding space velocities were 60,000 mL/(g.h), respectively. The experimental conditions were as follows: oxygen 21%, nitrogen 79%, ethylene concentration 80ppm, relative humidity 50% and reaction temperature 20 ℃. CO 2 was measured using an infrared gas cell. Ethylene was measured by a hand-held portable VOC detector (PV 6001-VOC-EX).
The catalytic activity of the obtained catalyst was carried out on a fixed reaction bed until the reaction was carried out until the composition of the reaction gas was measured at a steady state, and the catalytic activity of the catalyst was as shown in fig. 3.
As can be seen from fig. 3, the catalyst has excellent room temperature ethylene catalytic activity. At a reaction temperature of 20 ℃, the catalyst maintains the conversion of ethylene at 100% over a longer period of time. This indicates that the catalyst has very excellent catalytic oxidation properties for ethylene.
The catalysts prepared in examples 1-9 were used for the catalytic oxidation of ethylene:
0.1g of each of the catalysts of examples 1 to 9 was placed in a tubular fixed bed reactor to conduct experiments under the following conditions: oxygen 21%, nitrogen 79%, ethylene concentration was controlled to 80ppm, relative humidity to 50%, reaction space velocity (GHSV) to 60000 mL/(g.h), reaction temperature to room temperature, and CO 2 was measured using an infrared gas cell. Ethylene was measured by a hand-held portable VOC detector (PV 6001-VOC-EX). The results of the activity evaluation are shown in Table 1.
As can be seen from Table 1, the catalysts of examples 1-9 have very excellent room temperature ethylene catalytic activity.
Table 1: ethylene conversion and carbon dioxide selectivity of Ag/ZSM-5 catalysts under different Ag loadings at room temperature;
The catalysts prepared in examples 10-13 were used for catalytic oxidation of ethylene:
0.1g of each of the catalysts of examples 10 to 13 was placed in a tubular fixed bed reactor to conduct experiments under the following conditions: oxygen 21%, nitrogen 79%, ethylene concentration was controlled to 80ppm, relative humidity was controlled to 50%, reaction space velocity (GHSV) was 60000 mL/(g.h), reaction temperature was room temperature, and activity evaluation results are shown in Table 2.
As can be seen from table 2, the precursors with different Ag still have very excellent room temperature catalytic ethylene activity.
Table 2: ethylene conversion and carbon dioxide selectivity of Ag/ZSM-5 catalysts under different Ag precursor conditions at room temperature;
| Ethylene selectivity/% | Carbon dioxide selectivity/% | |
| Example 10 | 100 | 100 |
| Example 11 | 100 | 100 |
| Example 12 | 99 | 100 |
| Example 13 | 100 | 100 |
Comparative examples:
the catalysts prepared in comparative examples 14 to 15 were used for catalytic oxidation of ethylene:
0.1g of each of the catalysts of examples 14 to 15 was placed in a tubular fixed bed reactor to conduct experiments under the following conditions: oxygen 21%, nitrogen 79%, ethylene concentration was controlled to 80ppm, relative humidity was controlled to 50%, reaction space velocity (GHSV) was 60000 mL/(g.h), reaction temperature was room temperature, and activity evaluation results are shown in Table 3.
As can be seen from Table 3, the room temperature catalytic ethylene activity of the catalyst was greatly reduced by using the hydrothermally synthesized ZSM-5 or commercial beta-MnO 2 as a carrier.
Table 7: ethylene conversion rate and carbon dioxide selectivity of Ag-containing catalysts under different carrier conditions at room temperature;
| Ethylene selectivity/% | Carbon dioxide selectivity/% | |
| Example 14 | 13 | 100 |
| Example 15 | 5 | 43 |
The present invention will be described in detail by way of the above examples, but the present invention is not limited to the above detailed application methods, i.e., it does not mean that the present invention must be practiced in dependence upon the above detailed methods. It should be apparent to those skilled in the art that modifications to the invention as applied to any ethylene abatement reaction, changes to the conditions of the invention, equivalent changes to the apparatus, and the selection of auxiliary conditions, modes, etc., are within the scope of the invention and the disclosure.
Claims (8)
1. The application of the catalytic ethylene remover in fruit preservation in a high humidity environment is characterized in that the preparation method of the catalytic ethylene remover comprises the following steps:
step 1) preparing ZSM-5 molecular sieve by a solid phase method;
Step 2) adding the ZSM-5 molecular sieve obtained in the step 1) into a silver ion-containing solution, and aging; evaporating the water to dryness to obtain the Ag-loaded ZSM-5 molecular sieve;
Step 3) roasting the ZSM-5 molecular sieve loaded with Ag obtained in the step 2) to obtain a catalytic ethylene remover;
The mass fraction of Ag in the catalytic ethylene removing agent is 5-12%;
The method for preparing the ZSM-5 molecular sieve by the solid phase method in the step 1) comprises the following steps: reacting a solid mixture containing a silicon source, an aluminum source, an alkali source and a template agent, crystallizing for 2-4 days at 160-200 ℃, centrifuging after crystallization, washing, and drying to obtain a ZSM-5 molecular sieve;
The reaction of the solid mixture containing the silicon source, the aluminum source, the alkali source and the template agent is specifically as follows: 9 to 11 parts by weight of white carbon black, 9 to 11 parts by weight of tetrapropylammonium hydroxide with 40% weight and 0.032 to 0.034 part by weight of pseudo-boehmite are mixed and added into a mortar, and stirred for 0.5 hour.
2. The use according to claim 1, wherein in step 2) the moisture is evaporated to dryness at 60-90 ℃.
3. Use according to claim 1, wherein the ratio of the mass of the ZSM-5 molecular sieve to the aqueous silver active component solution is 1 g:0.1-20 ml; the concentration of Ag ions is 1-1000 g/L.
4. The use according to claim 1, wherein the silver ion-containing solution is at least one of an aqueous silver nitrate solution, an aqueous silver acetate solution, an aqueous silver sulfate solution, and an aqueous silver ammonium sulfate solution.
5. The use according to claim 1, wherein in step 2), the ZSM-5 molecular sieve is added to the silver ion containing solution, sonicated for 5 to 30 minutes, then stirred for 1 to 4 hours, and then aged.
6. The method according to claim 5, wherein the aging time is 3 to 12 hours.
7. The use according to claim 1, wherein in step 3), the Ag-loaded ZSM-5 molecular sieve is dried at 80-120 ℃ for 3-5 hours after the moisture is evaporated to dryness.
8. Use according to claim 1, characterized in that the Ag-loaded ZSM-5 molecular sieve is moved into a muffle furnace and calcined in air at 400-550 ℃ for 1-8 hours.
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| CN101623618A (en) * | 2009-08-06 | 2010-01-13 | 浙江大学 | Modified silver nitrate ethylene absorbent, preparation method and application thereof |
| CN105344213A (en) * | 2015-11-23 | 2016-02-24 | 中国科学院生态环境研究中心 | Method for long-time stable low-temperature catalysis complete oxidation removal of ethylene |
| CN108264057A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Method for solid-phase synthesis of wettability-controllable ZSM-5 zeolite |
| CN112642468A (en) * | 2020-12-04 | 2021-04-13 | 广东省科学院化工研究所 | Catalyst for catalyzing and oxidizing ethylene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101623618A (en) * | 2009-08-06 | 2010-01-13 | 浙江大学 | Modified silver nitrate ethylene absorbent, preparation method and application thereof |
| CN105344213A (en) * | 2015-11-23 | 2016-02-24 | 中国科学院生态环境研究中心 | Method for long-time stable low-temperature catalysis complete oxidation removal of ethylene |
| CN108264057A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Method for solid-phase synthesis of wettability-controllable ZSM-5 zeolite |
| CN112642468A (en) * | 2020-12-04 | 2021-04-13 | 广东省科学院化工研究所 | Catalyst for catalyzing and oxidizing ethylene and preparation method thereof |
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