EP2155848B1 - Procede de nettoyage de surfaces de materiaux a base de polyolefine(s) souilles par des denrees alimentaires notamment des produits laitiers - Google Patents
Procede de nettoyage de surfaces de materiaux a base de polyolefine(s) souilles par des denrees alimentaires notamment des produits laitiers Download PDFInfo
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- EP2155848B1 EP2155848B1 EP08805802.9A EP08805802A EP2155848B1 EP 2155848 B1 EP2155848 B1 EP 2155848B1 EP 08805802 A EP08805802 A EP 08805802A EP 2155848 B1 EP2155848 B1 EP 2155848B1
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- EP
- European Patent Office
- Prior art keywords
- polyolefin
- cleaning
- acid
- optionally
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004140 cleaning Methods 0.000 title claims description 29
- 229920000098 polyolefin Polymers 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 10
- 235000013365 dairy product Nutrition 0.000 title claims description 5
- 235000013305 food Nutrition 0.000 title claims description 4
- 239000000463 material Substances 0.000 title description 9
- 239000000203 mixture Substances 0.000 claims description 23
- -1 polypropylene Polymers 0.000 claims description 21
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 239000004872 foam stabilizing agent Substances 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 235000013351 cheese Nutrition 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000004439 roughness measurement Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- WMZHDICSCDKPFS-UHFFFAOYSA-N triacont-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCC=C WMZHDICSCDKPFS-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2MP Natural products CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001080024 Telles Species 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N hex-2-ene Chemical compound CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Natural products NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/18—Glass; Plastics
Definitions
- the present invention relates to the field of cleaning equipment in contact with foodstuffs.
- Cleaning means the removal of soiling from these foodstuffs, such as carbohydrates, fats, proteins, inorganic mineral constituents such as calcium carbonate, calcium phosphate or other types of scale, for example oxalates, sulphates, hydroxides and / or sulphides combined with metals, metalloids, or alkaline earth metals, and other residues encountered in the food processing industry.
- the patent application US 2006/0035808 discloses non-chlorinated detergent acid compositions comprising a fatty alkyl 1,3-diaminopropane and optionally an alkane sulfonic acid.
- compositions based on acid for cleaning equipment (containers, filters, molds, ).
- the cheese industry uses cleaning compositions based on inorganic acids such as phosphoric acid, sulfuric acid, sulphamic acid and or organic acids such as citric acid, acetic acid.
- inorganic acids such as phosphoric acid, sulfuric acid, sulphamic acid and or organic acids such as citric acid, acetic acid.
- polyolefins such as PP or PE, polyvinyl chloride (PVC) polytetrafluoroethylene vis-à-vis acids such as sulfuric acid, phosphoric acid, nitric acid, acetic acid or citric acid at different concentrations and temperatures has been studied.
- PVC polyvinyl chloride
- Organic acids such as acetic acid and citric acid can however be used in a generalized manner because of their lower acidity and therefore their lower cleaning power.
- the present invention provides a process for cleaning polyolefin-based materials contaminated by foodstuffs and more particularly by dairy products, characterized by the use of aqueous cleaning compositions which do not degrade the surface of the materials based on polyolefin and are free of nitrogen and phosphorus.
- the cleaning compositions used in the process according to the invention contain in particular one or more short-chain alkanesulphonic acids having from 1 to 4 carbon atoms, and preferably contain methanesulfonic acid (AMS).
- AMS methanesulfonic acid
- compositions of the invention contain from 0.5 to 100% by weight of alkane sulphonic acid (s), in particular from 0.5 to 20%, and more particularly from 0.5 to 5% by weight. .
- the cleaning compositions optionally contain one or more co-solvents, one or more co-acids (such as sulfuric, sulfamic, citric acid) which are miscible with water, optionally one or more thickeners. optionally one or more surfactants and optionally various other additives such as foaming agents, foam stabilizers.
- the contacting of the polyolefin material (s) and the cleaning composition is generally carried out between 10 and 90 ° C for a period generally of about one minute a few tens of minutes. Then it is rinsed in general with water to remove the cleaning composition remaining on the material that has just been cleaned and dried, for example in the open air.
- Such cleaning compositions based on alkane sulphonic acid (s) are for example described in EP 271 791 B1 , in CA 2.499.592 A1 where they are only used for the cleaning of metal objects (copper, aluminum, steel) and glass vials.
- polyolefin (s) is understood to mean homo- or copolymers of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene, alone or in mixed.
- alpha-olefins having 3 to 30 carbon atoms as optional comonomers include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 1-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene , and 1-triacontene.
- These alpha-olefins can be used alone or in a mixture of two or more than two.
- polyolefins is also intended to mean halogenated polyolefins such as plasticized or non-chlorinated polyvinyl chloride (PVC), whether superchlorinated or not, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), alone in admixture with one or more other halogenated polyolefins or not.
- PVC plasticized or non-chlorinated polyvinyl chloride
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- a 1 L flask filled with a solution of phosphoric acid or methanesulfonic acid at 1% by weight is immersed and a polypropylene mold plate is introduced into this flask.
- the plate is then removed, rinsed with distilled water at room temperature and then dried in the open air for 4 hours, and AFM (atomic force microscopy) is then measured in intermittent contact mode. allows to obtain a microscopic image of the surface of the sample probed and to give quantitative measurements of surface quadratic roughness. The lower the roughness, the greater the wear and degradation.
- the roughness of each sample is calculated automatically by computer software. There are two roughness values: the quadratic roughness (Rq) and the average roughness (Ra). We arbitrarily chose to compare our samples from quadratic roughness.
- Rq therefore informs us about the micro-relief of the surface: the lower it is, the smoother the surface and the more the surface is worn.
- the roughness measurements Rq (average of 3 measurements) and thus of immersion wear are expressed by the ratio of the roughness at time t to the initial roughness in Table 1: Table 1 aging time roughness time t / initial roughness with aqueous solution of AMS at 1% roughness time t / initial roughness with aqueous solution of H 3 PO 4 at 1% 0 100% 100% 15 days 78% 57%
- the cleaning solution is sprayed under pressure.
- a double-jacketed reactor coupled to a thermostatically controlled oil bath is used.
- the molds studied are cut into plates of 3 cm x 3 cm x 0.5 cm side and these plates are placed on a 316 L stainless steel grid about 5 cm from the bottom of the reactor.
- the studied solution is then circulated using a centrifugal pump.
- the plates are thus watered by the solution according to the diagram of the Figure 1 .
- the cleaning compositions studied contain respectively 1% of methanesulphonic acid or 1% of phosphoric acid (the rest being water) and are brought into contact with the PP at 70 ° C. for a period of 4 and 6 days. . After this spraying time, the plate is then removed, rinsed with distilled water at room temperature, and then dried in the open air for 4 hours and then measured by AFM.
- Table 2 shows the roughness measurements made on the polypropylene mold samples contacted with the spray cleaning solutions. These measurements are expressed by the ratio of the roughness at time t on the initial roughness: Table 2 Aging time in days roughness time t / initial roughness with 1% AMS solution roughness time t / initial roughness with solution 1% H 3 PO 4 0 100% 100% 4 days 72% 68% 6 days 71% 62%
- the AMS-based compositions use the polypropylene molds less than the phosphoric acid-based compositions.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Dairy Products (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
- La présente invention concerne le domaine du nettoyage du matériel en contact avec les denrées alimentaires.
- Par nettoyage, on entend l'élimination des salissures provenant de ces denrées alimentaires, telles qu'hydrates de carbone, graisses, protéines, constituants minéraux inorganiques tel que carbonate de calcium, phosphate de calcium ou d'autres types de tartres constitués par exemple d'oxalates, sulfates, hydroxydes et/ou sulfures combinés à des métaux, métalloïdes, ou alcalino-terreux, et autres résidus rencontrés dans l'industrie du traitement des denrées alimentaires. La demande de brevet
US 2006/0035808 propose des compositions acides détergentes non chlorées comprenant un 1,3-diaminopropane d'alkyle gras et éventuellement un acide alcane sulfonique. - Pour le nettoyage du matériel à base de polyoléfine souillé par les denrées alimentaires, telles que les produits laitiers, l'industrie du traitement des denrées alimentaires et notamment l'industrie laitière, (fromageries, ....) utilise des compositions à base d'acide pour le nettoyage du matériel (récipients, filtres, moules,...).
- Par exemple, pour le nettoyage des moules à fromage en polypropylène (PP) qui sont ré-utilisés de nombreuses fois, l'industrie fromagère utilise des compositions de nettoyage à base d'acides inorganiques comme l'acide phosphorique, sulfurique, sulfamique et/ou d'acides organiques comme l'acide, citrique, acétique.
- La résistance des polyoléfines tels que le PP ou le PE, du polychlorure de vinyle (PVC) du polytétrafluoroéthylène vis-à -vis d'acides tels que l'acide sulfurique, l'acide phosphorique, l'acide nitrique, l'acide acétique ou l'acide citrique à différentes concentrations et différentes températures a été étudiée. On trouve par exemple sur le site www.engineeringtoolbox.com des données sur la résistance chimique du PP vis à vis de l'acide phosphorique, de l'acide nitrique, de l'acide sulfurique, de l'acide acétique et de l'acide citrique :
Composition (qsp 100 % : eau) classement1) 20°C 60°C H3PO4 25 % 1 1 H3PO4 85 % 1 1 HNO3 5 % 2 3 HNO3 65 % 4 4 H2SO4 10 % 1 1 H2SO4 78 % 2 4 H2SO4 93 % 3 4 Acide acétique 10 % 1 1 Acide citrique 1 1 1) classement : 1. Excellent (pas d'attaque) /2. Bon (attaque non significative)/3. Acceptable (faible attaque, utilisation modérée) /4. Inacceptable (attaque significative) /5. Inférieur (déchirure ou dissolution possible) Composition (qsp 100 % : eau) classement2) H3PO4 > 45 % à 27°C A H3PO4 < 45 % à 27°C A H3PO4 100 % à 80 °C B HNO3 concentré à 80 °C F HNO3 dilué à 80°C B H2SO4 entre 10 et 75 % à 80 °C C H2SO4 > 10 % à 80 °C C Acide acétique 50 % à 80 °C A 2)classement : A : très bon / B : modéré/ C : limité F : insatisfaisant / - Les acides organiques comme l'acide acétique et l'acide citrique ne peuvent toutefois être mis en oeuvre de manière généralisée du fait de leur acidité plus faible et donc de leur plus faible pouvoir nettoyant.
- Concernant les acides inorganiques, il a été constaté que les compositions de nettoyage commerciales à base d'acide sulfurique et/ou nitrique ont tendance à attaquer les surfaces des matériaux à base de polyoléfine au cours des nettoyages successifs, ce qui oblige à les remplacer par du matériel neuf.
- Pour l'acide phosphorique et/ou sulfamique, bien qu'ayant un bon pouvoir nettoyant, compte tenu du fait qu'ils contiennent respectivement du phosphore et de l'azote, ils sont générateurs respectivement de phosphates et de nitrates dans les rejets et ont tendance à être remplacé pour des raisons de technique écologique car les directives européennes sur les taux de rejets de phosphore et d'azote dans les cours d'eau deviennent de plus en plus strictes.
- Il existe donc un besoin de remplacer ces compositions de nettoyage à base d'acide phosphorique et/ou sulfamique et/ou nitrique et/ou sulfurique, généralement mises en oeuvre dans des gammes de température allant en général de 10 à 90 °C, par d'autres solutions techniques à la fois plus respectueuses pour l'environnement mais aussi pour le matériel souillé à base de polyoléfine que l'on souhaite nettoyer dans des plages de température similaires.
- La présente invention propose un procédé de nettoyage de matériaux à base de polyoléfine(s) souillés par des denrées alimentaires et plus particulièrement par des produits laitiers, caractérisé par l'utilisation de compositions aqueuses de nettoyage qui ne dégradent pas la surface des matériaux à base de polyoléfine et sont exemptes d'azote et de phosphore.
- Les compositions de nettoyage mises en oeuvre dans le procédé selon l'invention contiennent notamment un ou plusieurs acides alcane sulfoniques à chaîne courte ayant de 1 à 4 atomes de carbone, et de préférence contiennent de l'acide méthane sulfonique (AMS).
- En général, les compositions de l'invention contiennent de 0,5 à 100 % en poids d'acide(s) alcane sulfonique(s), en particulier de 0,5 à 20 %, et plus particulièrement 0,5 à 5 %.
- Elles sont souvent préparées sous forme de mélange concentré qui est dilué par l'utilisateur final.
- Outre le ou les acides alcane sulfoniques, les compositions de nettoyage contiennent éventuellement un ou plusieurs co-solvants, un ou plusieurs co-acides (comme l'acide sulfurique, sulfamique, citrique) miscibles à l'eau, éventuellement un ou plusieurs agents épaississants, éventuellement un ou plusieurs tensioactifs et éventuellement divers autres additifs tels qu'agents moussants, agents stabilisateurs de mousse.
- Dans le procédé de nettoyage selon l'invention, la mise en contact du matériau à base de polyoléfine(s) et de la composition de nettoyage est en général effectuée entre 10 et 90 °C pendant une durée allant en général d'environ une minute à quelques dizaines de minutes. Puis on rince en général à l'eau pour éliminer la composition de nettoyage restant sur le matériau qui vient d'être nettoyé et on sèche, par exemple à l'air libre.
- De telles compositions de nettoyage à base d'acide(s) alcane sulfonique(s) sont par exemple décrites dans
EP 271.791 B1 CA 2.499.592 A1 où elles ne sont utilisées que pour le nettoyage d'objets métalliques (cuivre, aluminium, acier) et de flacons en verre. - Au sens de la présente invention, par polyoléfine(s), on entend les homo- ou copolymères d'alpha oléfines ou de dioléfines, telles que par exemple, éthylène, propylène, butène-1, octène-1, butadiène, seuls ou en mélange.
- Des exemples d'alpha-oléfines ayant 3 à 30 atomes de carbone comme comonomères éventuels comprennent le propylène, 1-butène, 1-pentène, 3-méthyl-1-butène, 1-hexène, 4-méthyl-1-pentène, 3-méthyl-1-pentène, 1-octène, 1-décène, 1-dodécène, 1-tétradécène, 1-hexadécène, 1-octadécène, 1-eicocène, 1-dococène, 1-tétracocène, 1-hexacocène, 1-octacocène, et 1-triacontène. Ces alpha-oléfines peuvent être utilisées seules ou en mélange de deux ou de plus de deux.
- A titre d'exemple de polyoléfines, on peut citer :
- les homo polymères et copolymères de l'éthylène, en particulier à titre d'exemple de polyéthylènes on peut citer :
- le polyéthylène basse densité (LDPE)
- le polyéthylène haute densité (HDPE)
- le polyéthylène linéaire basse densité (LLDPE)
- le polyéthylène très basse densité (VLDPE)
- le polyéthylène obtenu par catalyse métallocène, c'est-à-dire les polymères obtenus par copolymérisation d'éthylène et d'alpha-oléfine telle que propylène, butène, hexène ou octène en présence d'un catalyseur mono-site constitué généralement d'un atome de zirconium ou de titane et de deux molécules cycliques alkyles liées au métal. Plus spécifiquement, les catalyseurs métallocènes sont habituellement composés de deux cycles cyclopentadiéniques liés au métal. Ces catalyseurs sont fréquemment utilisés avec des aluminoxanes comme cocatalyseurs ou activateurs, de préférence le méthylaluminoxane (MAO). Le hafnium peut aussi être utilisé comme métal auquel le cyclopentadiène est fixé. D'autres métallocènes peuvent inclure des métaux de transition des groupes IV A, V A, et VI A. Des métaux de la série des lanthanides peuvent aussi être utilisés.
- les homopolymères ou copolymères du propylène.
- les copolymères éthylène/alpha-oléfine tels qu'éthylène/propylène, les EPR (abréviation d'éthylène-propylene-rubber) et éthylène/propylène/diène (EPDM).
- les copolymères blocs styrène/éthylène-butène/styrène (SEBS), styrène/butadiène/styrène (SBS), styrène/isoprène/ styrène (SIS), styrène/éthylène-propylène/styrène (SEPS).
- les copolymères de l'éthylène avec au moins un produit choisi parmi les sels ou les esters d'acides carboxyliques insaturés tels que par exemple les (méth)acrylates d'alkyle, les alkyles pouvant avoir jusqu'à 24 atomes de carbone.
- Au sens de la présente invention on entend également par polyoléfines, les polyoléfines halogénées tels que le polychlorure de vinyle (PVC) plastifié ou non, surchloré ou non, le poytétrafluoroéthylène (PTFE), le polyfluorure de vinylidène (PVDF), seuls en mélange avec une ou plusieurs autres polyoléfines halogénées ou non.
- Dans un bain agité à 70 °C, on immerge un flacon d'1 L rempli d'une solution d'acide phosphorique ou d'acide méthane sulfonique à 1 % en poids, et on introduit dans ce flacon une plaque de moule en polypropylène PP de dimension 3 cm x 3 cm x 0,5 cm que l'on laisse pendant 15 jours. On retire ensuite la plaque, on la rince à l'eau distillée à température ambiante, puis on la sèche à l'air libre pendant 4 h et on effectue alors des mesures par AFM (microscopie à force atomique) en mode contact intermittent, qui permet d'obtenir une image microscopique de la surface de l'échantillon sondé et de donner des mesures quantitatives de rugosité quadratique de surface. Plus la rugosité est faible, plus l'usure et la dégradation sont importantes.
- La rugosité de chaque échantillon est calculée automatiquement par un logiciel informatique. Il y a deux valeurs de rugosités : la rugosité quadratique (Rq) et la rugosité moyenne (Ra). Nous avons choisi arbitrairement de comparer nos échantillons à partir de la rugosité quadratique.
-
- ■ Zi est la valeur de Z au point i de la surface (en nm),
- ■ ZM est la valeur moyenne de Z sur une surface donnée (en nm),
- ■ N le nombre de points analysés dans cette surface
- Rq nous renseigne donc sur le micro relief de la surface : plus il est faible, plus la surface est lisse et plus la surface est usée.
- Les mesures de rugosité Rq (moyenne de 3 mesures) et donc d'usure par immersion sont exprimées par le rapport de la rugosité au temps t sur la rugosité initiale dans le tableau 1 :
Tableau 1 temps de vieillissement rugosité temps t /rugosité initiale avec solution aqueuse d'AMS à 1 % rugosité temps t /rugosité initiale avec solution aqueuse d'H3PO4 à 1 % 0 100 % 100 % 15 jours 78 % 57 % - On observe une baisse moindre de rugosité et donc une usure moindre de la plaque de PP avec la solution aqueuse d'AMS par rapport à la solution aqueuse d'H3PO4.
- Dans les fromageries, la solution nettoyante est projetée sous pression. Pour simuler au mieux ces conditions de nettoyage, on met en place un système de vieillissement par aspersion plus sévère que les conditions expérimentales par immersion précédentes.
- Pour cela, on utilise un réacteur double enveloppe couplé à un bain d'huile thermostaté. Les moules étudiés sont découpés en plaques de 3 cm x 3 cm x 0,5 cm de côté puis ces plaques sont placées sur une grille en inox 316 L à environ 5 cm du fond du réacteur. On fait ensuite circuler la solution étudiée à l'aide d'une pompe centrifuge. Les plaques sont ainsi arrosées par la solution suivant le schéma de la
Figure 1 . - Les compositions de nettoyage étudiées contiennent respectivement 1 % d'acide méthane sulfonique ou 1 % d'acide phosphorique (le reste étant de l'eau) et sont mises en contact avec le PP à 70 °C pendant une durée de 4 et 6 jours. Après ce temps d'aspersion, on retire ensuite la plaque, on la rince à l'eau distillée à température ambiante, puis on la sèche à l'air libre pendant 4 h et on effectue alors les mesures par AFM.
- Le tableau 2 ci-dessous réunit les mesures de rugosité effectuées sur les échantillons de moule en polypropylène mis en contact avec les solutions de nettoyage par aspersion. Ces mesures sont exprimées par le rapport de la rugosité au temps t sur la rugosité initiale :
Tableau 2 Temps de vieillissement en jours rugosité temps t /rugosité initiale avec solution 1 % AMS rugosité temps t /rugosité initiale avec solution 1 % H3PO4 0 100 % 100 % 4 jours 72 % 68 % 6 jours 71 % 62 % - Que ce soit par immersion ou par aspersion, on constate que les compositions à base d'AMS usent moins les moules en polypropylène que les compositions à base d'acide phosphorique.
Claims (5)
- Procédé de nettoyage de matériaux à base de polyoléfine(s) souillés par des denrées alimentaires et plus particulièrement par des produits laitiers, caractérisé par l'utilisation de compositions aqueuses de nettoyage contenant un ou plusieurs acides alcane sulfoniques à chaîne courte ayant de 1 à 4 atomes de carbone, et de préférence contiennent de l'acide méthane sulfonique (AMS).
- Procédé selon la revendication 1, caractérisé en ce que les compositions de nettoyage contiennent de 0,5 à 100 % en poids d'acide(s) alcane sulfonique(s), de préférence de 0,5 à 20 %, et avantageusement de 0,5 à 5 %.
- Procédé selon la revendication 1 ou 2, caractérisé en ce que les compositions contiennent éventuellement un ou plusieurs co-solvants, un ou plusieurs co-acides miscibles à l'eau, éventuellement un ou plusieurs agents épaississants, éventuellement un ou plusieurs tensioactifs et éventuellement divers autres additifs tels qu'agents moussants, agents stabilisateurs de mousse, ....
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le matériau à base de polyoléfine(s) contient du prolypropylène (PP) et de préférence consiste essentiellement en PP.
- Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la mise en contact du matériau à base de polyoléfine(s) souillé et de la composition de nettoyage est effectuée entre 10 et 90 °C, de préférence pendant une durée allant d'environ une minute à quelques dizaines de minutes, suivie d'un ou plusieurs rinçages, de préférence à l'eau, et d'un séchage.
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PL08805802T PL2155848T3 (pl) | 2007-05-24 | 2008-05-19 | Sposób oczyszczania powierzchni z tworzyw na bazie poliolefiny(in), zabrudzonych przez produkty żywnościowe, zwłaszcza przez produkty mleczne |
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FR0755251A FR2916322B1 (fr) | 2007-05-24 | 2007-05-24 | Procede de nettoyage de surfaces de materiaux a base de polyolefine(s) souilles par des denrees alimentaires notamment des produits laitiers |
PCT/FR2008/050856 WO2008142354A2 (fr) | 2007-05-24 | 2008-05-19 | Procede de nettoyage de surfaces de materiaux a base de polyolefine(s) souilles par des denrees alimentaires notamment des produits laitiers |
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DE10127919A1 (de) * | 2001-06-08 | 2002-12-19 | Ecolab Gmbh & Co Ohg | Reinigungsverfahren zur Stärkeentfernung |
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JP2013014769A (ja) | 2013-01-24 |
DK2155848T3 (da) | 2013-09-02 |
JP6224740B2 (ja) | 2017-11-01 |
FR2916322B1 (fr) | 2009-08-21 |
PL2155848T3 (pl) | 2013-10-31 |
CA2688162A1 (fr) | 2008-11-27 |
EP2155848A2 (fr) | 2010-02-24 |
PT2155848E (pt) | 2013-08-23 |
WO2008142354A2 (fr) | 2008-11-27 |
AU2008252702A1 (en) | 2008-11-27 |
NZ581455A (en) | 2011-04-29 |
FR2916322A1 (fr) | 2008-11-28 |
ES2425071T3 (es) | 2013-10-11 |
MX2009012657A (es) | 2009-12-14 |
US20100229898A1 (en) | 2010-09-16 |
HRP20130870T1 (hr) | 2013-10-25 |
JP2010530292A (ja) | 2010-09-09 |
CA2688162C (fr) | 2013-07-16 |
JP2016135853A (ja) | 2016-07-28 |
WO2008142354A3 (fr) | 2009-04-09 |
JP6223666B2 (ja) | 2017-11-01 |
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