WO2022248845A1 - Adsorbent materials - Google Patents
Adsorbent materials Download PDFInfo
- Publication number
- WO2022248845A1 WO2022248845A1 PCT/GB2022/051300 GB2022051300W WO2022248845A1 WO 2022248845 A1 WO2022248845 A1 WO 2022248845A1 GB 2022051300 W GB2022051300 W GB 2022051300W WO 2022248845 A1 WO2022248845 A1 WO 2022248845A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- doped
- ethylene
- doped zeolite
- bismuth
- Prior art date
Links
- 239000000463 material Substances 0.000 title description 13
- 239000003463 adsorbent Substances 0.000 title description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 97
- 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 85
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 83
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 74
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000005977 Ethylene Substances 0.000 claims abstract description 61
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 47
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 42
- 238000004806 packaging method and process Methods 0.000 claims abstract description 37
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 239000004411 aluminium Substances 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 239000005416 organic matter Substances 0.000 claims description 14
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 description 12
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- -1 £ 0.2 wt% Chemical compound 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 235000013311 vegetables Nutrition 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 241000220324 Pyrus Species 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 235000021017 pears Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PQVHMOLNSYFXIJ-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]pyrazole-3-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(N1CC2=C(CC1)NN=N2)=O)C(=O)O PQVHMOLNSYFXIJ-UHFFFAOYSA-N 0.000 description 1
- 244000298697 Actinidia deliciosa Species 0.000 description 1
- 235000009436 Actinidia deliciosa Nutrition 0.000 description 1
- 244000291564 Allium cepa Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000017647 Brassica oleracea var italica Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 244000025272 Persea americana Species 0.000 description 1
- 235000008673 Persea americana Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000006029 Prunus persica var nucipersica Nutrition 0.000 description 1
- 244000017714 Prunus persica var. nucipersica Species 0.000 description 1
- 244000235659 Rubus idaeus Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000004775 Tyvek Substances 0.000 description 1
- 229920000690 Tyvek Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000021015 bananas Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004345 fruit ripening Effects 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000009448 modified atmosphere packaging Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 235000021013 raspberries Nutrition 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000010555 transalkylation reaction Methods 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
- 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
- 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
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
- A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
- B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
- B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
- B65D81/268—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants the absorber being enclosed in a small pack, e.g. bag, included in the package
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/30—Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure
- B65D85/34—Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure for fruit, e.g. apples, oranges or tomatoes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- 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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
Definitions
- the present invention relates to metal-doped zeolites and their use for adsorbing ethylene from perishable organic matter such as fruit, vegetables and cut flowers.
- VOCs volatile organic compounds
- Other strategies involve the removal of volatile organic compounds (VOCs) from within, or surrounding, the produce packaging.
- VOCs are typically emitted by the produce itself, or may be present in the environment in which the produce is stored or transported. The presence of such VOCs can, for example, accelerate the spoiling of produce, lead to unwanted odours or tastes, or produce colour changes or other changes in appearance.
- VOC is ethylene.
- Ethylene is a plant hormone and has a key role in many physiological processes in plants. For example, exogenous ethylene can initiate fruit ripening which in turn can lead to release of ethylene as the fruit ripens leading to high local concentrations. Other fresh produce types are also sensitive to ethylene even if their own ethylene production is low. The rate of ethylene generation can be a key factor in determining local ethylene concentrations, and this rate varies significantly between produce types. Excessive ethylene levels can lead to, for example, the premature ripening of fruit and vegetables, the wilting of fresh flowers, and the loss of green colour and an increase in bitterness of vegetables.
- the control of ambient ethylene levels has been found to be effective in prolonging the shelf-life of many horticultural products, and various methods of ethylene control are utilised commercially. Methods include those based on ethylene adsorption and oxidation, for example the use of potassium permanganate.
- Palladium-doped zeolites have been found to act as ethylene adsorbents. For example, it is described in W02007/052074 (Johnson Matthey Public Limited Company) that palladium-doped ZSM-5 may be used to adsorb VOCs, such as ethylene, which are derived from organic matter. The rate of generation of ethylene by different types of organic matter can vary significantly, which can lead to high local ethylene concentrations. There remains a need to develop additional adsorbent materials with increased capacity and / or with different rates of adsorption, and therefore with the potential to enhance produce shelf-life.
- the invention in a first aspect relates to a doped zeolite having the BEA framework type and a silica to alumina ratio (SAR) between 100 : 1 and 5 : 1 , wherein the zeolite is doped with palladium and bismuth and wherein the content of any individual metal other than aluminium, bismuth and palladium is £ 0.5 wt% based on the total weight of doped zeolite.
- SAR silica to alumina ratio
- the invention in a second aspect relates to the use of a doped zeolite according to the first aspect for the adsorption of ethylene.
- the materials described herein have particular utility for the adsorption of ethylene derived from perishable organic matter, such as fruit, vegetables or cut flowers.
- the invention in a third aspect relates to a packaging insert for the adsorption of ethylene, wherein the packaging insert comprises a doped zeolite according to the first aspect.
- a packaging insert is a material which is intended to be used in conjunction with packaging in order to adsorb ethylene from perishable organic matter held within the packaging.
- a particularly preferred form of packaging insert is a sachet.
- perishable organic matter is stored and /or transported in a packaging structure, such as a crate, bag, box, tray, or punnet. Therefore, in a fourth aspect the invention relates to a packaging structure comprising a container, perishable organic matter and a packaging insert according to the third aspect. Particularly preferred contains are a crate, a bag, a bottle, a box, a tray or a punnet.
- Figure 3 shows the ethylene removal by 1 wt% Pd or 1 wt% Pd 0.2 wt% Bi samples with framework types BEA, MFI and CHA.
- the invention relates to zeolites which are doped with bismuth and palladium and their utility for adsorption of ethylene.
- Zeolites are classified according to framework type, such framework types describing the connectivity of the tetrahedrally coordinated atoms of the framework in the highest possible symmetry.
- framework type such framework types describing the connectivity of the tetrahedrally coordinated atoms of the framework in the highest possible symmetry.
- Three letter codes are assigned to each framework type in accordance with the “HJPAC Commission on Zeolite Nomenclature” and/or the “Structure Commission of the International Zeolite Association”.
- the zeolite has the beta (BEA) framework type and a silica to alumina ratio (SAR) between 100 : 1 and 5 : 1. It is preferred that the zeolite has a SAR of 10 : 1 to 50 : 1 , such as 20 : 1 to 40 : 1.
- US2009/0112006 (LyondellBasell Industries) describes a catalyst comprising palladium, lead, bismuth and a titanium or vanadium zeolite and their use as epoxidation catalysts.
- the zeolites described in these references are the titanium or vanadium counterparts of the aluminosilicate structure in which Ti or V units have replaced Al.
- the zeolites in this reference have a SAR » 100 : 1.
- CN101121132A (China Petroleum & Chemical Corporation) describes a catalyst for the transalkylation and dealkylation of aromatic hydrocarbons.
- the catalyst comprises a hydrogen type zeolite having a SAR of 12 to 70, 0.002-8 parts molybdenum oxide, 0.005- 8 parts of palladium or nickel oxide, 0.02-8 parts of an oxide selected from at least one of iron, bismuth, tin, platinum, rhodium, magnesium or titanium, and 10-60 parts of binder.
- Examples 2, 4 and 7 include 0.1 -0.3 wt% palladium and 1.9-2.4 wt% bismuth, and in addition contain various other dopant metals, which are impregnated on a mixture of zeolite frameworks (b/MOR or /MOR/ZSM-5)
- the content of any individual metal other than aluminium, bismuth and palladium is £ 0.5 wt% based on the total weight of the doped zeolite, such as £ 0.2 wt%, such as £ 0.1 wt%. It is preferred that the combined content of metals (other than aluminium, bismuth and palladium) is £ 0.5 wt%, such as £ 0.2 wt%, such as £ 0.1 wt%.
- the content of metals within the doped zeolite can be measured by any suitable technique known to those skilled in the art, such as by Inductively Coupled Plasma (ICP) spectroscopy.
- ICP Inductively Coupled Plasma
- the content of each of bismuth and palladium may be 3 0.5 wt% or £ 0.5 wt%.
- the zeolite framework may be counterbalanced by cations, such as by cations of alkali and/or alkaline earth elements (e.g., Na, K, Mg, Ca, Sr, and Ba), ammonium cations and/or protons. Where these are present, the content of each metal is £ 0.5 wt% based on the total weight of the doped zeolite.
- the zeolite is in the hydrogen form.
- the zeolite is doped with palladium, and typically comprises 0.1 to 5 wt% palladium based on the total weight of doped zeolite, preferably 0.2 to 2 wt%, 0.3 to 1.6 wt%, 0.3 to 1.4 wt%, more preferably 0.3 to 1.2 wt%.
- adsorbent and “adsorption” as used herein should not be construed as being limited to the uptake of ethylene to a particular route and includes the chemical conversion of ethylene into secondary compounds.
- adsorbent is synonymous with “absorbent”.
- the zeolite typically comprises 0.05 to 2 wt% bismuth based on the total weight of doped zeolite, preferably 0.05 to 1 %.
- a level of about 0.2 wt% bismuth has been shown to provide a particularly high ethylene scavenging rate, and it is therefore preferred that the zeolite comprises 0.1 to 0.3 wt% bismuth.
- the zeolite comprises 0.2 to 2 wt% palladium and 0.05 to 1 wt% bismuth, preferably 0.05 to 0.5 wt% bismuth, more preferably 0.15 to 0.35 wt%. More preferably, the zeolite comprises 0.2 to 1.2 wt% palladium and 0.05 to 1 wt% bismuth, preferably 0.05 to 0.5 wt% bismuth, more preferably 0.15 to 0.35 wt% bismuth.
- the content of molybdenum oxide in the doped zeolite is less than 0.002 wt% based on the total weight of doped zeolite.
- the content of molybdenum oxide is less than 0.001 wt%. It is preferred that the zeolite is free of molybdenum oxide.
- the zeolite is free from phases other than BEA.
- the presence of other zeolite phases can be determined by X-ray diffraction.
- the zeolites as described herein may be advantageously used for the adsorption of ethylene, in particular ethylene originating from perishable organic matter, such as fruit, vegetables, cut flowers or other foodstuffs.
- perishable organic matter such as fruit, vegetables, cut flowers or other foodstuffs.
- the perishable organic matter is selected from avocados, bananas, broccoli, cabbage, cut flowers, kiwi fruits, nectarines, melons, onions, pears, potatoes, raspberries and strawberries.
- a packaging insert is a material which is intended to be used in conjunction with packaging in order to adsorb ethylene from perishable organic matter held within the packaging.
- a preferred packaging insert is a sachet.
- a “sachet” means an article comprising: a first ethylene-permeable layer and a second ethylene-permeable layer sealed together at the edges of each layer; wherein the doped zeolite is present between the layers.
- a preferred material for the ethylene-permeable layer is a fibrous material, preferably a fibrous non-woven material.
- Exemplary and preferred material for the ethylene-permeable layer is TyvekTM which is a non-woven LDPE.
- An alternative exemplary and preferred material is glassine.
- the sachet may be formed by folding a single ethylene-permeable material to provide a first ethylene-permeable layer and a second ethylene-permeable layer, providing doped zeolite between the layers, and sealing the remaining edges together to produce a sachet.
- packaging structure means an article comprising a container, perishable organic matter and a packaging insert.
- suitable containers are a crate, a bag, a bottle, a box, a tray or a punnet.
- one or more packaging inserts will be included within the container, either loose or adhered to a surface of the container.
- the presence of a palladium and bismuth-doped zeolite with the BEA structure may be used to control ethylene levels within such packaging structures.
- the packaging structure may comprise a polymer film, such as a polyamide, polyethylene, polyethylene terephthalate, or polypropylene film, or blends or co-polymers thereof.
- the film may be used to seal the packaging structure, for example to seal a punnet or tray, or may, for example, form the majority of the packaging structure, such as in the case of a bag.
- the polymer film may be a single polymer layer, or may comprise a laminate structure of two or more layers which may be different materials.
- the packaging structure may comprise a polymer film that is perforated, for example with holes or slits which are typically 50-500 pm in diameter or length as appropriate. Such perforations may be formed by laser perforation. In use, the degree of perforation may be used to control the gaseous composition within the packaging structure once produce has been placed inside, leading to a lower oxygen content.
- a packaging structure may be known as modified atmosphere packaging.
- the atmosphere within the packaging structure comprises less than around 20% oxygen by volume, such as less than 18% oxygen by volume, for example 10-15% oxygen by volume.
- the zeolites are typically used in the form of a powder or may be formulated, for example as granules.
- Palladium and bismuth doped BEA zeolite Samples were prepared by incipient wetness impregnation. Solid Bi nitrate and Pd nitrate ( ⁇ 8%) solution were weighed out to give the desired weight % of metal on the zeolite. The Bi nitrate was fully dissolved, by manual stirring, into the Pd nitrate solution. This solution was then diluted with water up to around 90-95% pore fill of the zeolite. The solution was added to the H-BEA zeolite (SAR 28) powder with stirring. The sample was then dried at 105°C (2-16 h) and then calcined at 500°C for 2 h with a 10°C/min ramp rate.
- the plug flow test gives an ultimate capacity for a sample by passing a known concentration of ethylene over it and measuring when ethylene is no longer adsorbed.
- a fixed bed of 0.2 g of sample pelletized to 250-355 pm was loaded into a quartz tube with an I.D. of 4 mm.
- the tube was fitted onto a plug flow reactor and a gas mixture of Ethylene/N2/C>2 was passed through a water bubbler to humidify it and over the sample.
- Data was collected using a mass spectrometer and ethylene mass peaks 26 and 27 were recorded to give an ethylene breakthrough curve.
- the examples used either 1 g of 0.4%Pd/BEA, 2 g of 0.4%Pd/BEA, or 1 g of 1%Pd/0.2%Bi/BEA. In each case, the materials were provided in a tray within the bag.
- the control was an XtendTM modified atmosphere bag with no ethylene absorber added. Ethylene levels were recorded and averaged over four bags running concurrently for every sample ( Figure 4).
- the bag without an ethylene absorber was above desired ethylene levels within 1 day and quickly rose to levels above that displayed on Figure 1, reaching 7000 ppb in 15 days. As can be seen 1 g of the Bi-doped sample shows prolonged ethylene adsorption and remains effective after 47 days.
- Trial 2 The 0.4%Pd/0.2%Bi/BEA zeolite (SAR 28) sample was tested in a fruit trial alongside undoped 0.4%Pd/BEA zeolite (SAR 28). The samples were provided either in a tray within the bag or in Tyvek sachets (TyvekTM grade 1059B available from DuPont). 2 g of zeolite material was used in each case. Ethylene levels were recorded every few days (Figure 5).
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Abstract
The specification describes a doped zeolite having the BEA framework type and a silica to alumina ratio (SAR) between 100 : 1 and 5 : 1, wherein: the zeolite is doped with palladium and bismuth, and the content of any individual metal other than aluminium, bismuth and palladium is ≤ 0.5 wt% based on the total weight of doped zeolite. Also described is the use of such doped zeolites for the adsorption of ethylene, and packaging inserts containing the doped zeolite.
Description
Adsorbent Materials
Field of the Invention
The present invention relates to metal-doped zeolites and their use for adsorbing ethylene from perishable organic matter such as fruit, vegetables and cut flowers.
Background
The over-ripening or spoiling of fruit, vegetables and other organic matter during transit or storage can lead to significant produce loss and wastage. This is an increasing issue for those involved in fresh produce supply chains which may involve long transit times and variable climatic conditions. Modification of the atmosphere in which the organic matter is stored has been shown to be an effective strategy to prolong produce life. For example, alterations in oxygen and carbon dioxide levels within produce packaging can reduce produce respiration rates and therefore slow down the spoiling of fresh produce.
Other strategies involve the removal of volatile organic compounds (VOCs) from within, or surrounding, the produce packaging. VOCs are typically emitted by the produce itself, or may be present in the environment in which the produce is stored or transported. The presence of such VOCs can, for example, accelerate the spoiling of produce, lead to unwanted odours or tastes, or produce colour changes or other changes in appearance.
One such VOC is ethylene. Ethylene is a plant hormone and has a key role in many physiological processes in plants. For example, exogenous ethylene can initiate fruit ripening which in turn can lead to release of ethylene as the fruit ripens leading to high local concentrations. Other fresh produce types are also sensitive to ethylene even if their own ethylene production is low. The rate of ethylene generation can be a key factor in determining local ethylene concentrations, and this rate varies significantly between produce types. Excessive ethylene levels can lead to, for example, the premature ripening of fruit and vegetables, the wilting of fresh flowers, and the loss of green colour and an increase in bitterness of vegetables.
The control of ambient ethylene levels has been found to be effective in prolonging the shelf-life of many horticultural products, and various methods of ethylene control are utilised commercially. Methods include those based on ethylene adsorption and oxidation, for example the use of potassium permanganate.
Palladium-doped zeolites have been found to act as ethylene adsorbents. For example, it is described in W02007/052074 (Johnson Matthey Public Limited Company) that palladium-doped ZSM-5 may be used to adsorb VOCs, such as ethylene, which are derived from organic matter.
The rate of generation of ethylene by different types of organic matter can vary significantly, which can lead to high local ethylene concentrations. There remains a need to develop additional adsorbent materials with increased capacity and / or with different rates of adsorption, and therefore with the potential to enhance produce shelf-life.
Summary of the Invention
It has been surprisingly found that the addition of bismuth to palladium-doped zeolite materials with a BEA framework type can yield compositions with an enhanced ethylene adsorption profile, in particular for the adsorption of ethylene within fresh produce packages. Surprisingly, the addition of bismuth to palladium-doped zeolites with framework types other than BEA leads to only a minor improvement or a decrease in ethylene absorbing activity. The framework type BEA is also referred to as b in the literature.
In a first aspect the invention relates to a doped zeolite having the BEA framework type and a silica to alumina ratio (SAR) between 100 : 1 and 5 : 1 , wherein the zeolite is doped with palladium and bismuth and wherein the content of any individual metal other than aluminium, bismuth and palladium is £ 0.5 wt% based on the total weight of doped zeolite.
In a second aspect the invention relates to the use of a doped zeolite according to the first aspect for the adsorption of ethylene. The materials described herein have particular utility for the adsorption of ethylene derived from perishable organic matter, such as fruit, vegetables or cut flowers.
In a third aspect the invention relates to a packaging insert for the adsorption of ethylene, wherein the packaging insert comprises a doped zeolite according to the first aspect.
A packaging insert is a material which is intended to be used in conjunction with packaging in order to adsorb ethylene from perishable organic matter held within the packaging. A particularly preferred form of packaging insert is a sachet.
Typically, perishable organic matter is stored and /or transported in a packaging structure, such as a crate, bag, box, tray, or punnet. Therefore, in a fourth aspect the invention relates to a packaging structure comprising a container, perishable organic matter and a packaging insert according to the third aspect. Particularly preferred contains are a crate, a bag, a bottle, a box, a tray or a punnet.
Description of the Figures
Figure 1 shows the ethylene removal by 1 wt% Pd BEA zeolite (SAR=28) samples doped with different amounts of bismuth.
Figure 2 shows the ethylene removal by 0.4 wt% Pd BEA zeolite (SAR=28) samples doped with different amounts of bismuth.
Figure 3 shows the ethylene removal by 1 wt% Pd or 1 wt% Pd 0.2 wt% Bi samples with framework types BEA, MFI and CHA.
Figure 4 shows the results of a fruit trial of 1 wt% Pd / 0.2 wt% Bi / BEA zeolite (SAR=28) Figure 5 shows the results of a fruit trial of 0.4 wt% Pd / 0.2 wt% Bi / BEA zeolite (SAR=28) Detailed Description
Preferred and/or optional features of the invention will now be set out. Any aspect of the invention may be combined with any other aspect of the invention unless the context demands otherwise. Any of the preferred and/or optional features of any aspect may be combined, either singly or in combination, with any aspect of the invention unless the context demands otherwise.
Any sub-headings are included for convenience only, and are not to be construed as limiting the disclosure in any way
Zeolite
The invention relates to zeolites which are doped with bismuth and palladium and their utility for adsorption of ethylene.
Zeolites are classified according to framework type, such framework types describing the connectivity of the tetrahedrally coordinated atoms of the framework in the highest possible symmetry. Three letter codes are assigned to each framework type in accordance with the “HJPAC Commission on Zeolite Nomenclature” and/or the “Structure Commission of the International Zeolite Association”.
In all aspects of the present invention the zeolite has the beta (BEA) framework type and a silica to alumina ratio (SAR) between 100 : 1 and 5 : 1. It is preferred that the zeolite has a SAR of 10 : 1 to 50 : 1 , such as 20 : 1 to 40 : 1.
US2009/0112006 (LyondellBasell Industries) describes a catalyst comprising palladium, lead, bismuth and a titanium or vanadium zeolite and their use as epoxidation catalysts. Unlike the doped zeolites of the present invention, the zeolites described in these references are the titanium or vanadium counterparts of the aluminosilicate structure in which Ti or V units have replaced Al. The zeolites in this reference have a SAR » 100 : 1.
CN101121132A (China Petroleum & Chemical Corporation) describes a catalyst for the transalkylation and dealkylation of aromatic hydrocarbons. The catalyst comprises a hydrogen type zeolite having a SAR of 12 to 70, 0.002-8 parts molybdenum oxide, 0.005- 8 parts of palladium or nickel oxide, 0.02-8 parts of an oxide selected from at least one of iron, bismuth, tin, platinum, rhodium, magnesium or titanium, and 10-60 parts of binder. Examples 2, 4 and 7 include 0.1 -0.3 wt% palladium and 1.9-2.4 wt% bismuth, and in addition contain various other dopant metals, which are impregnated on a mixture of zeolite frameworks (b/MOR or /MOR/ZSM-5)
In the present invention the content of any individual metal other than aluminium, bismuth and palladium is £ 0.5 wt% based on the total weight of the doped zeolite, such as £ 0.2 wt%, such as £ 0.1 wt%. It is preferred that the combined content of metals (other than aluminium, bismuth and palladium) is £ 0.5 wt%, such as £ 0.2 wt%, such as £ 0.1 wt%. The content of metals within the doped zeolite can be measured by any suitable technique known to those skilled in the art, such as by Inductively Coupled Plasma (ICP) spectroscopy. For the avoidance of doubt, the content of each of bismuth and palladium may be ³ 0.5 wt% or £ 0.5 wt%.
The zeolite framework may be counterbalanced by cations, such as by cations of alkali and/or alkaline earth elements (e.g., Na, K, Mg, Ca, Sr, and Ba), ammonium cations and/or protons. Where these are present, the content of each metal is £ 0.5 wt% based on the total weight of the doped zeolite. Preferably, the zeolite is in the hydrogen form.
The zeolite is doped with palladium, and typically comprises 0.1 to 5 wt% palladium based on the total weight of doped zeolite, preferably 0.2 to 2 wt%, 0.3 to 1.6 wt%, 0.3 to 1.4 wt%, more preferably 0.3 to 1.2 wt%.
It has been unexpectedly found that the addition of bismuth can lead to an enhanced ethylene adsorption profile. It should be noted that the term “adsorbent” and “adsorption” as used herein should not be construed as being limited to the uptake of ethylene to a particular route and includes the chemical conversion of ethylene into secondary compounds. As used herein, the term “adsorbent” is synonymous with “absorbent”.
The zeolite typically comprises 0.05 to 2 wt% bismuth based on the total weight of doped zeolite, preferably 0.05 to 1 %. A level of about 0.2 wt% bismuth has been shown to provide a particularly high ethylene scavenging rate, and it is therefore preferred that the zeolite comprises 0.1 to 0.3 wt% bismuth.
Typically, the zeolite comprises 0.2 to 2 wt% palladium and 0.05 to 1 wt% bismuth, preferably 0.05 to 0.5 wt% bismuth, more preferably 0.15 to 0.35 wt%. More preferably,
the zeolite comprises 0.2 to 1.2 wt% palladium and 0.05 to 1 wt% bismuth, preferably 0.05 to 0.5 wt% bismuth, more preferably 0.15 to 0.35 wt% bismuth.
It is preferred that, if present, the content of molybdenum oxide in the doped zeolite is less than 0.002 wt% based on the total weight of doped zeolite. Preferably the content of molybdenum oxide is less than 0.001 wt%. It is preferred that the zeolite is free of molybdenum oxide.
It is preferred that the zeolite is free from phases other than BEA. The presence of other zeolite phases can be determined by X-ray diffraction.
The zeolites as described herein may be advantageously used for the adsorption of ethylene, in particular ethylene originating from perishable organic matter, such as fruit, vegetables, cut flowers or other foodstuffs. In preferred embodiments the perishable organic matter is selected from avocados, bananas, broccoli, cabbage, cut flowers, kiwi fruits, nectarines, melons, onions, pears, potatoes, raspberries and strawberries.
Packaging insert
A packaging insert is a material which is intended to be used in conjunction with packaging in order to adsorb ethylene from perishable organic matter held within the packaging.
A preferred packaging insert is a sachet. As used herein, a “sachet” means an article comprising: a first ethylene-permeable layer and a second ethylene-permeable layer sealed together at the edges of each layer; wherein the doped zeolite is present between the layers.
A preferred material for the ethylene-permeable layer is a fibrous material, preferably a fibrous non-woven material. Exemplary and preferred material for the ethylene-permeable layer is Tyvek™ which is a non-woven LDPE. An alternative exemplary and preferred material is glassine.
In some embodiments the sachet may be formed by folding a single ethylene-permeable material to provide a first ethylene-permeable layer and a second ethylene-permeable layer, providing doped zeolite between the layers, and sealing the remaining edges together to produce a sachet.
Packaging structure
As used herein, the term “packaging structure” means an article comprising a container, perishable organic matter and a packaging insert.
Examples of suitable containers are a crate, a bag, a bottle, a box, a tray or a punnet. Typically, one or more packaging inserts will be included within the container, either loose or adhered to a surface of the container.
The presence of a palladium and bismuth-doped zeolite with the BEA structure may be used to control ethylene levels within such packaging structures.
The packaging structure may comprise a polymer film, such as a polyamide, polyethylene, polyethylene terephthalate, or polypropylene film, or blends or co-polymers thereof. The film may be used to seal the packaging structure, for example to seal a punnet or tray, or may, for example, form the majority of the packaging structure, such as in the case of a bag. The polymer film may be a single polymer layer, or may comprise a laminate structure of two or more layers which may be different materials.
The packaging structure may comprise a polymer film that is perforated, for example with holes or slits which are typically 50-500 pm in diameter or length as appropriate. Such perforations may be formed by laser perforation. In use, the degree of perforation may be used to control the gaseous composition within the packaging structure once produce has been placed inside, leading to a lower oxygen content. Such a packaging structure may be known as modified atmosphere packaging. In a preferred embodiment the atmosphere within the packaging structure comprises less than around 20% oxygen by volume, such as less than 18% oxygen by volume, for example 10-15% oxygen by volume.
The zeolites are typically used in the form of a powder or may be formulated, for example as granules.
The invention is now illustrated with the following non-limiting examples:
Examples
Sample Preparation
Palladium and bismuth doped BEA zeolite: Samples were prepared by incipient wetness impregnation. Solid Bi nitrate and Pd nitrate (~8%) solution were weighed out to give the desired weight % of metal on the zeolite. The Bi nitrate was fully dissolved, by manual stirring, into the Pd nitrate solution. This solution was then diluted with water up to around 90-95% pore fill of the zeolite. The solution was added to the H-BEA zeolite (SAR 28) powder with stirring. The sample was then dried at 105°C (2-16 h) and then calcined at 500°C for 2 h with a 10°C/min ramp rate.
Samples of 1% Pd MFI, 1% Pd 0.2% Bi MFI, 1% Pd CHA and 1% Pd 0.2% Bi CHA were prepared according to the above method using MFI (SAR 23) and chabazite CHA (SAR 22) in place of H-BEA zeolite (BEA).
Sample Testing - Plug flow test
The plug flow test gives an ultimate capacity for a sample by passing a known concentration of ethylene over it and measuring when ethylene is no longer adsorbed. A fixed bed of 0.2 g of sample pelletized to 250-355 pm was loaded into a quartz tube with an I.D. of 4 mm. The tube was fitted onto a plug flow reactor and a gas mixture of Ethylene/N2/C>2 was passed through a water bubbler to humidify it and over the sample. Data was collected using a mass spectrometer and ethylene mass peaks 26 and 27 were recorded to give an ethylene breakthrough curve.
Effect of bismuth content on ethylene uptake at 1% Pd BEA
A series of doped 1 %Pd/#%Bi BEA zeolite samples were prepared and tested for ethylene uptake using the plug flow test (Figure 1). The results show ethylene uptake across the range of samples tested with the highest uptake at 0.2 and 0.3 wt% Bi.
Effect of bismuth content on ethylene uptake at 0.4% Pd BEA
A series of doped 0.4%Pd/#%Bi BEA zeolite samples were prepared and tested for ethylene uptake using the plug flow test (Figure 2). The results show ethylene uptake across the range of samples tested with the highest uptake at 0.2 wt% Bi.
Effect of zeolite structure
A series of doped zeolites having 1% Pd or 1% Pd / 0.2% Bi with the framework BEA, MFI or CHA were prepared and tested for ethylene uptake using the plug flow test (Figure 3). The results show that there was a notable improvement in ethylene uptake in the case of BEA zeolite. Bi-doping only moderately improved the activity of 1% Pd MFI, and Bi-doping decreased the ethylene uptake of 1% Pd CHA.
Fruit trials
A series of fruit trials were carried out using Pd / Bi doped BEA. Each zeolite sample was sealed with 1 kg of pears in a polyethylene bag containing mechanical perforations made using 700 micron diameter needles (Xtend™ Bag). The bag was stored at 0°C. Ethylene levels in the fruit bag were measured every few days by taking a sample of the head space gas and measuring by gas chromatography. The steady state gas compositions achieved during the storage at 0°C are typically 18-20 vol% C>2and 0.5-1.0 vol% CO2.
T rial 1 - The 1 %Pd/0.2%Bi/BEA zeolite (SAR 28) sample was tested in a fruit trial alongside undoped 0.4%Pd/BEA zeolite (SAR 28). The examples used either 1 g of 0.4%Pd/BEA, 2 g of 0.4%Pd/BEA, or 1 g of 1%Pd/0.2%Bi/BEA. In each case, the materials were provided in a tray within the bag. The control was an Xtend™ modified atmosphere bag with no ethylene absorber added. Ethylene levels were recorded and averaged over four bags
running concurrently for every sample (Figure 4). The bag without an ethylene absorber was above desired ethylene levels within 1 day and quickly rose to levels above that displayed on Figure 1, reaching 7000 ppb in 15 days. As can be seen 1 g of the Bi-doped sample shows prolonged ethylene adsorption and remains effective after 47 days. Trial 2 - The 0.4%Pd/0.2%Bi/BEA zeolite (SAR 28) sample was tested in a fruit trial alongside undoped 0.4%Pd/BEA zeolite (SAR 28). The samples were provided either in a tray within the bag or in Tyvek sachets (Tyvek™ grade 1059B available from DuPont). 2 g of zeolite material was used in each case. Ethylene levels were recorded every few days (Figure 5). As can be seen 2 g of the Bi-doped samples showed significantly improved performance in comparison with the un-doped sample as a powder and in sachets. Sachets containing the Bi-doped sample showed prolonged ethylene adsorption until the end of the study (~80 days).
Claims
1. A doped zeolite having the BEA framework type and a silica to alumina ratio (SAR) between 100 : 1 and 5 : 1, wherein: the zeolite is doped with palladium and bismuth, and the content of any individual metal other than aluminium, bismuth and palladium is £ 0.5 wt% based on the total weight of doped zeolite.
2. A doped zeolite according to claim 1 , wherein the doped zeolite comprises 0.1 to 5 wt% palladium based on the total weight of doped zeolite.
3. A doped zeolite according to claim 1 or claim 2, wherein the doped zeolite comprises 0.2 to 2 wt% palladium based on the total weight of doped zeolite.
4. A doped zeolite according to any of claims 1 to 3, wherein the doped zeolite comprises 0.05 to 2 wt% bismuth based on the total weight of doped zeolite.
5. A doped zeolite according to any of claims 1 to 4, wherein the zeolite comprises 0.1 to 0.3 wt% bismuth based on the total weight of doped zeolite.
6. A doped zeolite according to any of claims 1 to 5, wherein, if present, the content of molybdenum oxide is less than 0.002 wt% based on the total weight of doped zeolite.
7. A doped zeolite according to any of claims 1 to 6, where the zeolite has a SAR of 10:1 to 50:1.
8. A doped zeolite according to any of claims 1 to 7, where the content of any individual metal other than aluminium, bismuth and palladium is £ 0.2 wt% based on the total weight of doped zeolite.
9. A doped zeolite according to any of claims 1 to 7, where the content of any individual metal other than aluminium, bismuth and palladium is £ 0.1 wt% based on the total weight of doped zeolite.
10. A doped zeolite according to any of claims 1 to 9, where zeolite is free from phases other than BEA.
11. A doped zeolite according to any of claims 1 to 10, in the form of a powder.
12. Use of a doped zeolite according to any of claims 1 to 11 for the adsorption of ethylene.
13. A packaging insert for the adsorption of ethylene, wherein the packaging insert comprises a doped zeolite according to any of claims 1 to 11.
14. A packaging insert according to claim 13, wherein the insert is in the form of a sachet comprising: a first ethylene-permeable layer and a second ethylene-permeable layer sealed together at the edges of each layer; wherein the doped zeolite is present between the layers.
15. A packaging insert according to claim 14, wherein the first and second ethylene- permeable layers are made from a fibrous LDPE.
16. A packaging structure comprising a container, perishable organic matter and a packaging insert according to any of claims 13 to 15.
17. A packaging structure according to claim 16, wherein the container structure is a crate, bag, bottle, box, tray or punnet.
18. A packaging structure according to claim 16 or claim 17, wherein the container is sealed with a polymer film.
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Citations (6)
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WO2007052074A2 (en) | 2005-11-01 | 2007-05-10 | Johnson Matthey Public Limited Company | Adsorption of volatile organic compounds derived from organic matter |
CN101121132A (en) | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Low ethylbenzene by product aromatics alkyl transferring and dealkylation catalyst |
US20090112006A1 (en) | 2007-10-24 | 2009-04-30 | Grey Roger A | Direct epoxidation process using improved catalyst composition |
WO2018189518A1 (en) * | 2017-04-11 | 2018-10-18 | Johnson Matthey Public Limited Company | Packaging materials |
WO2019155491A1 (en) * | 2018-02-06 | 2019-08-15 | Nichem Solutions | Shelf-life enhancer composition for ethylene susceptible and perishable articles |
CN111604085A (en) * | 2020-05-28 | 2020-09-01 | 万华化学集团股份有限公司 | Metal catalyst containing palladium-bismuth element, preparation method and application |
Family Cites Families (2)
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EP4126356B1 (en) * | 2020-03-30 | 2023-06-07 | Johnson Matthey Public Limited Company | Layered zone-coated diesel oxidation catalysts for improved co/hc conversion and no oxidation |
WO2022069465A1 (en) * | 2020-09-30 | 2022-04-07 | Umicore Ag & Co. Kg | Bismut containing dieseloxidation catalyst |
-
2021
- 2021-05-27 GB GBGB2107524.7A patent/GB202107524D0/en not_active Ceased
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2022
- 2022-05-24 WO PCT/GB2022/051300 patent/WO2022248845A1/en active Application Filing
- 2022-05-24 GB GB2207571.7A patent/GB2607193A/en active Pending
Patent Citations (6)
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WO2007052074A2 (en) | 2005-11-01 | 2007-05-10 | Johnson Matthey Public Limited Company | Adsorption of volatile organic compounds derived from organic matter |
CN101121132A (en) | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Low ethylbenzene by product aromatics alkyl transferring and dealkylation catalyst |
US20090112006A1 (en) | 2007-10-24 | 2009-04-30 | Grey Roger A | Direct epoxidation process using improved catalyst composition |
WO2018189518A1 (en) * | 2017-04-11 | 2018-10-18 | Johnson Matthey Public Limited Company | Packaging materials |
WO2019155491A1 (en) * | 2018-02-06 | 2019-08-15 | Nichem Solutions | Shelf-life enhancer composition for ethylene susceptible and perishable articles |
CN111604085A (en) * | 2020-05-28 | 2020-09-01 | 万华化学集团股份有限公司 | Metal catalyst containing palladium-bismuth element, preparation method and application |
Non-Patent Citations (1)
Title |
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DATABASE WPI Week 200872, Derwent World Patents Index; AN 2008-M13763, XP002807470 * |
Also Published As
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GB202207571D0 (en) | 2022-07-06 |
GB202107524D0 (en) | 2021-07-14 |
GB2607193A (en) | 2022-11-30 |
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