AU672011B2 - A method and system for sampling and determining the presence of contaminants in containers - Google Patents
A method and system for sampling and determining the presence of contaminants in containers Download PDFInfo
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- AU672011B2 AU672011B2 AU43829/93A AU4382993A AU672011B2 AU 672011 B2 AU672011 B2 AU 672011B2 AU 43829/93 A AU43829/93 A AU 43829/93A AU 4382993 A AU4382993 A AU 4382993A AU 672011 B2 AU672011 B2 AU 672011B2
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- container
- sample
- volatiles
- beverage
- contaminants
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- 239000000356 contaminant Substances 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 28
- 238000005070 sampling Methods 0.000 title claims description 22
- 235000013361 beverage Nutrition 0.000 claims description 48
- 239000003039 volatile agent Substances 0.000 claims description 46
- 230000005855 radiation Effects 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 235000021443 coca cola Nutrition 0.000 claims 1
- 239000000523 sample Substances 0.000 description 65
- 238000012360 testing method Methods 0.000 description 33
- 239000003570 air Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 21
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 16
- 230000037213 diet Effects 0.000 description 9
- 235000005911 diet Nutrition 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000005979 Citrus limon Nutrition 0.000 description 5
- 244000131522 Citrus pyriformis Species 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- -1 nitrogen containing compound Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 102100032533 ADP/ATP translocase 1 Human genes 0.000 description 1
- 101710180366 CDP-L-myo-inositol myo-inositolphosphotransferase Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 108010038447 Chromogranin A Proteins 0.000 description 1
- 102100031186 Chromogranin-A Human genes 0.000 description 1
- 101000768061 Escherichia phage P1 Antirepressor protein 1 Proteins 0.000 description 1
- 101000796932 Homo sapiens ADP/ATP translocase 1 Proteins 0.000 description 1
- 101150081099 OGA gene Proteins 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPTIBDHUFVHUJK-NZYDNVMFSA-N mitopodozide Chemical compound C1([C@@H]2C3=CC=4OCOC=4C=C3[C@H](O)[C@@H](CO)[C@@H]2C(=O)NNCC)=CC(OC)=C(OC)C(OC)=C1 CPTIBDHUFVHUJK-NZYDNVMFSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0011—Sample conditioning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07C—POSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
- B07C5/00—Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
- B07C5/34—Sorting according to other particular properties
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/90—Investigating the presence of flaws or contamination in a container or its contents
- G01N21/9018—Dirt detection in containers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0078—Testing material properties on manufactured objects
- G01N33/0081—Containers; Packages; Bottles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
- G01N35/02—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a plurality of sample containers moved by a conveyor system past one or more treatment or analysis stations
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/24—Suction devices
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
- G01N2001/222—Other features
- G01N2001/2223—Other features aerosol sampling devices
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2226—Sampling from a closed space, e.g. food package, head space
- G01N2001/2229—Headspace sampling, i.e. vapour over liquid
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Sampling And Sample Adjustment (AREA)
- Automatic Analysis And Handling Materials Therefor (AREA)
- Measurement Of Radiation (AREA)
Description
I I OPI DATE 30/12/93 APPIN. ID 43829/93 IIIIiI~II~II~IIII AOJP DATE 10/03/94 PCT NUM~BER PCT/US93/04766 ItIlII111 I I W k itI 1 'A1 I$ 141 k A wi l 9 otA t I .It 1 %i 1, (MI) International Patent Chi ification S G~OIN 21/76, 35/02, 110C5134 (21) International Application Nsumber: (22) International filing Date: Priorlt) data: W9I'U64 I June 92 1 AlI P( I t SOJ' 14 011) International Publication Nunulier: NN 0) 93/24825 (43) International Publication D~ate: 9~ l)2,:mil 111 OP 9~ 1) (u66 C(4) kg~ts- IIR( IL.\t I t al! 1Itrb. W~it Ko.
L1,01 HIWO. PII) Box~ 1 1ll, k hun,.l. N 2:($4 (81) 1)esignatced States: %I lil. A. III IP. Kit. NO W/.
D.I SP I R. 611 It I jIte I \1 11. St j 111116b92) (71) Applicant: THUl 0( (1 A ()\ItPX*N It S I "I1) North \\couc. Ilo\ 1"14. Atlatnta. 0~ 11111" It'Su (72) Insentors: M(I) l).Stephen. J3 I" od Road. Salem. Nsl 10 tt09 L'S) 01 N NIS(Ps. Daniel. H1 201" 1)131) 1r ye Uke Road. enne~a\%. 0i 1tI144 WLS). lINt-. Dmisd. 11. 4 \\lhnspering Pine, Sudbur %IA 017"6 WS), ROUNI'IiLi It. IDa~id. R, .14 Great Road. Bedford. MA, 01I30 S) \4 N11:L Ore.
gor). 435 ashingti i Street. Sornerv ille. M A 1 11 Published 6720mrannl ,m twii 54) 1TileT AEH \tl-D)ANT1) FYST 0 It"S.A\PLINO AND) l)I.TIRIINO lIFIi PIM SMN L~ OF' NANTS IN CONTAINEiRS (57) Abstract (ONT \MI- A method or sampling and determining the presence of certain residues of contaminants in containers comprising the steps of: injecting compressed air into said containers in order to displace 'at least a portion of the contents thereof: evacuating a sample or the container contents so displaced by applying suction thereto-, and analyzing the sample esacuated to determine the prescnce or absence of the certain residues therein. The compressed air is injected through a nozzle into in opening in the containers to displace a portion of the container contents and form a sample cloud outside of the container. The sample cloud is then at least partially evacuated by suction and the sample is analyzed for the presence of contaminant% such as nitrogen containing Comnpounds or hydrocarbons. In one embodiment about go 3% of the sample evacuated is diverted from the analyzer and recirculated into the air injector. A wide range of potential contaminants are detectable if beserage bettles are stored uncapped. prior to testing to give beverage product volatiles sufficient time to dissipate.
WO 93/24825 PCT/US93/04766 -1- A METHOD AND SYSTEM FOR SAMPLING AND DETERMINING THE PRESENCE OF CONTAMINANTS IN CONTAINERS BACKGROUND OF THE INVENTION The present invention relates to a container inspection system for sampling and determining the presence or certain substances, such as residues of contaminants within containers such as glass or plastic bottles. More specifically, the present invention relates to an improved sampling and analyzing system and method for determining the presence of residues of these contaminants in containers such as beverage bottles rapidly moving along a conveyor past a test station in a container sorting system.
In many industries, including the beverage industry, products are packaged in containers which are returned after use, washed and refilled. Typically refillable containers, such as beverage bottles, are made of glass which can be easily cleaned. These containers are washed and then inspected for the presence of foreign matter.
Glass containers have the disadvantage of being fragile and, in larger volumes, of being relatively heavy.
Accordingly, it is highly desirable to use plastic containers because they are less fragile and lighter than glass containers of the same volume. However, plastic materials tend to absorb a variety of organic compounds which may later be desorbed into the product thereby potentially adversely r -2affecting the quality of the product packed in the container. Examples of such organic compounds are nitrogen containing compounds such as ammonia, organic nitrogen compounds, and hydrocarbons including gasoline and various cleaning fluids.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for detecting the presence of substances, in containers.
According to one aspect of the invention there is provided a method of sampling and determining the presence of volatiles of certain contaminants in a container which was previously filled with a beverage said container including an opening which is closeable by a cap, including the steps of: storing said container with the cap removed for a sufficient period of time to permit detectable quantities of volatiles of residues of the beverage to evaporate and egress from said container; evacuating a sample of volatiles remaining in the container after expiration of said sufficient period of time; mixing the sample with a chemical reactant to cause a chemical reaction therewith in order to generate chemiluminescence of the reactants; t analyzing radiation emitted by chemiluminescence of the sample and reactant 20 to determine the presence or absence of said volatiles of certain contaminants S without interference from chemiluminescence of volatiles of the beverage by filtering radiation emitted by chemiluminescence of the sample to detect the presence of radiation having wavelengths above about 0.19 micron; and identifying the presence or absence of said certain contaminants from the radiation detected at characteristic wavelengths above about 0.19 micron.
According to another aspect of the invention there is provided a method of sampling and determining the presence of volatiles of certain contaminants in a container which was previously filled with a beverage, said container including an opening which is closeable by a cap, including the steps of: storing said container with the cap removed for a sufficient period of time to permit detectable quantities of volatiles of residues of the beverage to evaporate and egress from said container; JPD C lWINWORDUACQUELr.BFNODELE43829 DOC -2ainjecting fluid into the opening in said container after expiration of said sufficient period of time in order to displace at least a portion of the volatiles therefrom to create a sample cloud in a region outside of said container; evacuating a sample of the volatiles so displaced from said region outside of said container by applying suction thereto; and analyzing the sample evacuated to determine the presence or absence of said volatiles of certain contaminants.
According to another aspect of the invention there it provided a method of sampling and determining the presence of certain substances in a container which io was previously filled with a beverage, said container including an opening which is closeable by a cap, including the steps of: storing said container with the cap removed for a sufficient period of time to permit detectable quantities of volatiles of residues of the beverage to evaporate and egress from said container; Is displacing a portion of the container contents to form a sample cloud at regions outside of the container adjacent the opening thereof; and analyzing the sample cloud to determine the presence or absence of the certain substances therein.
.i According to another aspect of the invention there is provided a method of o sampling and determining the presence of volatiles of certain contaminants in a container which was previously filled with a beverage, said container including an opening which is closeable by a cop, including the steps of: storing said container with the cap removed for a sufficient period of time to permit detectable quantities of volatiles of residues of the beverage to evaporate and egress from said container; after expiration of said sufficient period of time and without further pretreatment to remove volatiles of the residues of the beverages for the purpose of avoiding interference between the residues and the contaminants to be detected, evacuating for analysis a sample of volatiles remaining in the container; and analyzing the sample evacuated to determine the presence or absence of the certain contaminants therein.
JPD C ,W1MNWORDUACQUEL'BFNDDELEA3829 DOC
SI
WO 93/24825 PCr/S93/04766 -3from vylntile ef- bevragc ingdAAn.t Aooidu the bottles.
The objects of the present invention arfulfilled by providing a method of sampling and dete ning the presence of certain substances such as vola -e residues in containers comprising the steps of: injecting fluid into said containers in order displace at least a portion of the contents there evacuating a sample of the container contents displaced by applying suction thereto; and an zing the sample evacuated to determine the presence or In a preferred embodiment the fluid injected into the containers is compressed air which is injected through a nozzle to provide an air blast within the interior of the container. This air blast creates a cloud of the vaporous contents of the container which emerges from its opening whereby it may be evacuated by suction from outside of the container to sample a portion of the container contents.
Injection of fluid and evacuation of sample may be continuous operations or may be performed in steps. If steps are utilized, the step of initiating the injection of fluid into the container preferably precedes in time the initiation of the step of evacuating a sample in order to provide time for the formation of the sample cloud. However, the performance of the steps of injecting and evacuating may slightly overlap in time. Alternatively, the steps of injecting and evacuation may be spaced in time but this is dependent on the rate of sampling desired. A still further alternative is to synchronize the steps of injecting and evacuating to occur simultaneously for the same duration.
In a preferred embodiment the injection of fluid from the nozzle and the suction applied by the evacuation means are continuously on at the test station. In this embodiment -I s F
C
I I WO 93/24825 I'PC/US93/04766 -4the containers or bottles are rapidly and continuously moved through the test station on a rapidly moving conveyor. The bottles are moved through the test station at a rate of 200 to 1000 bottles per minute. A rate of 400 bottles per minute is preferable and is compatible with current beverage bottle filling speeds. The desired test rate may vary with the size of the bottles being inspected and filled. The injector nozzle is disposed upstream of the direction of conveyor movement from the suction tube of the evacuator so the injection of fluid into each container slightly precedes in time the evacuation of the resulting sample cloud.
In anoteembodiment of the present invention a portion of the sample evacuated (about 90%) is diverted and the remaining portion of the sample passes to an analyzer for determination of the presence or absence of the certain residues. The purpose of diverting the first portion of the sample is to limit the amount of sample that passes to the analyzer to manageable quantities in order to achieve high speed analysis. In addition if the volume of the sample is too large it may foul or clog the detector. However, it is initially desirable to evacuate essentially the entire sample cloud to clear the area of the test station from the contents of that sample cloud to provide clean surroundings for the successive containers. This eliminates spurious carry over signals of residue (crosstalk of container contaminants) unrelated to the container being tested at a given point in time.
If desired the diverted portion of the first sample may be channeled through an optional air filter and recirculated into the compressed air being injected into subsequent containers to arrive at the test station. This provides for an efficient use of the diverted first portion of the sample and of a pump utilized for diversion and compression, and Y'll 0 I WO 93/24825 PCT/US93/04766 5 avoids the need to exhaust that first portion of the sample to the atmosphere surrounding the test site.
In fu'rther 2mbaimont a range of r-nn-a-ta detectable without interference from product volatiles y providing a method of sampling and determining the pr ence of volatiles of certain contaminants in a container ich was previously filled with a beverage, said contain including an opening which is closeable by a cap, compring the steps of: storing said container with the cap removed for a sufficient period of time to permit ectable quantities of volatiles of ingredients in res' ues of the beverages to evaporate and egress from sai container; evacuating a sample f volatiles remaining in the container after expirati of said sufficient period of time; mixing the sampe with a chemical reactant to cause a chemical reactio therewith in order to generate chemiluminesce e of the reactants; and optica y analyzing radiation emitted by chemilum escence of the sample and reactant to determine the prese e or absence of said volatiles of certain contaminants wit ut interference from detectable levels of 3 emiluminescence of volatiles of ingredients of beverage Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
WOo 93/24825 PCT/US93/04766 6 BRIEF DESCRIPTION OF THE DRAWINGS The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus, are not limitative of the present invention and wherein: Fig. 1 is a schematic block diagram of the sampling and residue analyzing system of the present invention illustrating a plurality of containers moving seriatim along a conveyor system through a test station, reject mechanism and washer station; Fig. 2 is a block diagram illustrating a possible implementation of the system of Fig. 1 in a detector system in which the contaminant being detected may be a nitrogen containing compound; and Fig. 3 is a graph of signal intensity vs. wavelength of defected radiation emitted by chemiluminescence in the analyzer of the system of Fig. 2.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Referring to Fig. 1 there is illustrated a conveyor moving in the direction of arrow A having a plurality of uncapped, open-topped spaced containers C plastic beverage bottles of about 1500 c.c. volume) disposed thereon for movement seriatim through a test station 12, reject mechanism 28 and conveyor 32 to a washer system. The contents of containers C would typically include air, volatiles of residues of contaminants, if any, and volatiles of any products such as beverages which had been in the containers. An air injector 14 which is a source of compressed air is provided with a nozzle 16 spaced from but aligned with a container C at test station 12. That is nozzle 16 is disposed outside of the containers and makes no WO 93/24825 PCT/US93/04766 7 contact therewith. Nozzle 16 directs compressed air into containers C to displace at least a portion of the contents of the container to thereby emit a sample cloud 18 to a region outside of the container being tested.
The column of injected air through nozzle 16 into a container C would be typically of the order of about 10 c.c.
for bottle speeds of about 200 to 1000 bottles per minute.
A rate of 400 bottles per minute is preferable and is compatible with current beverage bottle filling speeds. The desired test rate may vary with the size of the bottles being inspected and filled. Only about 10 c.c. of the container contents would be displaced to regions outside of the bottle to form sample cloud 18.
Also provided is an evacuator sampler 22 which may comprise a vacuum pump or the like coupled to a sampling tube or conduit 20. The tube is mounted near, and preferably downstream about 1.APAM) of the air injector 14 so as to be in fluid communication with sample cloud 18 adjacent to the opening at the top of containers C.
Neither nozzle 16 nor tube 20 contacts the containers C at test station 12; rather both are spaced at positions outside of the containers in close proximity to the openings thereof. This is advantageous in that no physical coupling is required to the containers C, or insertion of probes into the containers, which would impede their rapid movement along conveyor 10 and thus slow down the sampling rate. High speed sampling rates of from about 200 to 1000 bottles per minute are possible with the system and method of the present invention. The conveyor 10 is preferably driven continuously to achieve these rates without stopping or slowing the bottles down at the test station.
A bypass line 24 is provided in communication with the evacuator sampler 22 so that a predetermined portion V. 93/24825 PCT/US3/04766 -8- (preferably about 90%) of the sample from cloud 18 entering tube 20 can be diverted through bypass line 24. The remaining sample portion passes to a residue analyzer 26, which determines whether specific substances are present, and then is exhausted. One purpose of diverting a large portion of the sample from cloud 18 is to reduce the amount of sample passing from evacuator sampler 22 to residue analyzer 26 in order to achieve high speed analysis. This is done in order to provide manageable levels of samples to ue tested by the residue analyzer 26. Another purpose for diverting a portion of the sample is to be able to substantially remove all of sample cloud 18 by evacuator 22 from the test station area and divert the excess through bypass line 24. In a preferred embodiment the excess portion of the sample passing through bypass line 24 returned to air injector 14 for introduction into the subsequent containers moving along conveyor through nozzle 16. However, it would also be possible to simply vent bypass line 24 to the atmosphere.
A microprocessor controller 34 is provided for controlling the operation of air injector 14, evacuator sampler 22, residue analyzer 26, a reject mechanism 28 and an optional fan 15. Container sensor 17 including juxtaposed radiation source and photodetector is disposed opposite a reflector (not shown) across conveyor 10. Sensor 17 tells controller 34 when a container arrives at the test station and briefly interrupts the beam of radiation reflected to the photodetector. Optional fan 15 is provided to generate an air blast towards sample cloud 18 and preferably in the direction of movement of containers C to assist in the removal of sample cloud 18 from the vicinity of test station 12 after each container C is sampled. This clears out the air from the region of the test station so that no lingering residues from an existing sample cloud 18 can contaminate the
I
WO 93/24825 IPCT/US93/04766 -9test station area when successive containers C reach the test station for sampling. Thus, sample carryover between containers is precluded. The duty cycle for operation of fan is controlled by microprocessor 34 as indicated diagrammatically in Fig. i. Preferably fan 15 is continuously operating for the entire time the rest of the system is operating.
A reject mechanism 28 receives a reject signal from microprocessor controller 34 when residue analyzer 26 determines that a particular containur C is contaminated with a residue of various undesirable types. Reject mechanism 28 diverts contaminated rejected bottles to a conveyor 30 and allows passage of uncontaminated, acceptable bottles to a washer (not shown) on a conveyor 32.
An alternative option is to place the bottle test station downstream of the bottle washer in the direction of conveyor travel, or to place an additional test station and sample and resiAue analyzing system after the washer. In fact it may be preferable to position the test station and system after the washer when inspecting bottles for some contaminants. For example, if the contaminant is a hydrocarbon, such as gasoline which is insoluble in water, it is easier to detect residues of hydrocarbons after the bottles have been washed. This is because during the washing process in which the bottles are heated and washed with water, water soluble chemical volatiles are desorbed from the bottles by the heating thereof and then dissolved in the washing water. Certain hydrocarbons, on the other hand, not being water soluble, may then be sampled by a sampler 22 downstream of the washer, to the exclusion of the dissolved, water-soluble chemicals. Therefore, the detection of such hydrocarbons can be performed without potential interference WO 93/24825 ICT/US93/04766 10 from other water soluble chemicals if the bottles pass through a washer before testing.
Referring to Fig. 2 there is illustrated a specific embodiment of a detector system for use with the sampling and analyzing system of Fig. 1 wherein like reference numerals refer to like parts. As illustrated, a nozzle 16 is provided for generating an air blast which passes into a container (not shown) being inspected. The air passing through nozzle 16 may be heated or unheated it being advantageous to heat the air for some applications. Juxtaposed to the nozzle 16 is sample inlet tube 20 including a filter 40 at the output thereof for filtering out particles from the sample. Suction is provided to tube 20 from the suction side of pump 82 connected through the residue analyzer 26 A portion of the sample (for example, 90-95% of a total sample flow of about 6000 c.c. per minute), as described in connection with Fig. 1, is diverted through a bypass lin& 24 by means of connection to the suction side of a pump 46.
Pump 46 recirculates the air through an accumulator 48, a normally open blast control valve 50, and back to the air blast output nozzle 16. A backpressure regulator 54 helps control pressure of the air blast through nozzle 16 and ,nts excess air to exhaust 57. Blast control valve 50 receives control signals through line 50A from microprocessor controller 34 to normally maintain the valve open to permit the flow of air to the nozzle.
Electrical power is provided to pump 46 via line 46A coupled to the output of circuit breaker 76 which is in turn coupled to the output of AC filter 74 and AC power supply PS.
The ,tector assembly 27 in the embodiment of Fig. 2 is an analyz which detects the residue of selected compounds such as nitrogen containing compounds in the containers being inspected by means of a method of chemiluminescence. This WO 93/24825 CNt/S93/04766 11 type of detector is generally known and includes a chamber for mixing ozone with nitric oxide, or with other compounds which react with ozone, in order to allow them to react, a radiation-transmissive element (with appropriate filter), and a radiation detector to detect chemiluminescence from the products of reaction. For example, when NO, produced from heating nitrogen compounds (such as ammonia) in the presence of an oxidant oxygen in air), chemically reacts with the ozone, characteristic light emission is given off at predetermined wavelengths such as wavelengths in the range of about 0.6 to 2.8 microns. Selected portions of the emitted radiation of chemiluminescence, and its intensity, can be detected by a photomultiplier tube.
Accordingly, in the system of Fig. 2 ambient air is drawn in through intake 60 and air filter 62 to an ozone generator 64. Ozone is generated therein, as by electrical discharge into air, and is output through ozone filter 66 and flow control valve 68 to the detector assembly 27 wherein it is mixed with samples from containers input through intake tube 20, filter 40, flow restrictor 42, and converter 44.
The sample from intake tube 20 is passed through a converter 44, such as an electrically-heated nickel tube, in which the temperature is raised to approximately 800*C to 900'C before being input to detector assembly 27. Temperatures in the range of 400'C to 1400'C may also be acceptable. When nitrogen-containing compounds such as ammonia are so heated, NO (nitric oxide) is produced, and the nitric oxide is supplied to the chamber of the detector assembly 27.
Compounds other than NO which may react with 03 and chemiluminescence may also be produced in converter 44 e.g., organic compounds derived from heating of gasoline or cleaning residue.
WO 93/24825 CI'r/iS93/04766 12 A temperature controller 70 supplied With electrical power through a transformer 72 is used to control the temperature of converter 44.
The samples in the detector assembly 27 after passage thrrugh its chamber are output through an accumulator 85 and pump 82 to an ozone scrubber 56, and to an exhaust output 57 in order to clear the residue detector for the next sample from the next container moving along the conveyor 10 of Fig.
i. (As indicated above, an (optinal) fan, not shown in Fig.
2, may be employed to help clear any remaining sample cloud from near the sample inlet tube 20). Outputs from detector assembly 27 relating to the results of the tests are output through a preamp 84 to microprocessor 34 which feeds this information in an appropriate manner to a recorder 83. The recorder 83 is preferably a conventional strip recorder, or the like, which displays signal amplitude vs. time of the sample being analyzed.
The microprocessor 34 may be programmed to recognize, as a "hit" or the detection of a specific residue, a signal peak from a photodetector of the detector assembly 27 which is present in a predetermined time interval (based on the sensed arrival of a container at the test station) and whose slope and amplitude reach predetermined magnitudes and thereafter maintain such levels for a prescribed duration.
The microprocessor controller 34 also has an output to a bottle ejector 28 to reject contaminated bottles and separate them from bottles en route to a washer.
A calibration terminal 86 is provided for residue analyzer 26 for adjusting the high voltage supply 26A associated with the detector assembly. Also provided is a recorder attenuator input terminal 88 connected to the microprocessor controller 34 for adjusting the operation of f WO 93/24825 PI'CT/JS93/04766 13 the recorder. Detector assembly 27 receives electrical power from the high voltage supply 26A.
Additional controls include operator panel 90 including a key pad and display section permitting an operator to control the operation of the detector assembly 27 in an appropriate fashion.
DC power is supplied to all appropriate components through DC power supply 78 coupled to the output of power supply PS.
An optional alarm enunciator 80A is provided for signaling an operator of the presence of a contaminated container. Alarm enunciator 80A is coupled to the output of microprocessor controller 34 via output control line 80C. A malfunction alarm 80B is also coupled to microprocessor controller 34 for receiving fault or malfunction signals such as from pressure switch 58 or vacuum switch 87 when pressures are outside of certain predetermined limits.
Other safety, devices may be provided such as vacuum gauge 89, and back pressure control valve 54 for ensuring proper operation of the system.
Most components of the entire system of Fig. 2 are preferably enclosed in a rust-proof, stainless steel cabinet 92. The cabinet is cooled by a counter-flow heat exchanger 91 having hermetically separated sections 91A and 91B in which counter air flow is provided by appropriate fans.
As described hereinbefore the system of Fig. 2 in a preferred embodiment is utilized to detect the presence of nitrogen containing compounds in a sample, such as a refillable beverage bottle. However, it would be desirable to utilize the system of Fig. 2 to detect as wide a range of contaminants as possible including potential contaminants that would chemiluminesce in regions of the radiation spectrum, which might overlap with chemiluminescence of WO 93/24825 PCr/ US93/04766 14 ingredients of a beverage (hereinafter "product") that was packaged in the beverage bottle.
This is accomplished in accordance with the present invention by a method partially illustrated in Fig. 3, and described hereinafter.
Referring to Fig. 3, which is a graph of signal intensity of radiation (in millivolts) vs. wavelength emitted by chemiluminescence, it can be observed that radiation emitted by chemiluminescence of nitrogen containing compounds (the reaction of NO 03) is in the range of about 0.6 to 2.8 microns (near infrared to infrared radiation). Consequently, when using the system of Fig. 2 and detector assembly 27 thereof, to look only for nitrogen containing compounds a cut-off filter 100 is utilized to block all chemiluminescent radiation of a sample of wavelengths below about 1 micron from reaching the photomultiplier detector of detector assembly 27. This is desirable if the detection of nitrogen compounds is of primary interest because chemiluminescent radiation emitted below 1 micron (visible light to near infrared) is potentially emitted by "product" residue in samples evacuated from refillable beverage bottles.
Therefore, the 1 micron cut-off filter 100 eliminates false reject signals which might be caused by high levels of "product" residue in a bottle under test. It is of course very important to eliminate, or minimize false reject signals to minimize, waste of refillable bottles.
However, it is a discovery of the present invention that if a beverage bottle is stored in an uncapped state, i.e. the top opening thereof uncovered, for a sufficient time prior to testing with the system of Fig. 2, that volatiles of "product" residue are sufficiently dissipated from the bottle that such are not detectable at sufficient levels to cause false reject signals. That is, if the 1 micron filter 100 is
I
WO 93/24825 PCT/US93/04766 15 removed, and replaced by a quartz cut-off filter having a cut-off characteristic at .19 micron, "product" volatiles will not exist in large enough quantities to generate reject signals if the bottles were stored uncapped for a sufficient period of time. This period of time will vary for various "products". However, a storage period of about fifteen hours for an uncapped bottle has yielded good results in tests conducted. These results are tabulated in the following Table I for samples evacuated from beverage bottles containing a wide range of contaminants, and "product" residues.
WO 93/24825 P'/US93/04766 16 TABLE I SAMPLE Fitter 102 Fitter 106 Fitter 100 (0.19 micron) (0.4 micron) (1 micron) Acetatdehye 40 3 Acetone 1100 Acetone, 1511r, Uncapped 40 0 Brazil Gas Os Brazil Gas #4 1 Cyclohexanone 2500 CycLohexanone, l5Hir, Uncapped Os 0 Diesel Downy, 15Hr, Uncapped 3 0 Exxon 100 70 Exxon 150 25 Exxon 200 6 2 Fresh Downy 2 Gas #1 325 Gas #3 100 Hexane 50 Hexc~ne, lSHr, Uncapped 80 0 Isopropanot 40 7 IsopropanoL, 15Hr, Uncapped 200 2 Kerosine 6 Methanol 60 0 Methylene Chloride 12 3 Methylene Chloride, 15Hr, Uncapped 20 0 Wine Cola, Classic, ISlir, Cappcd 5 0 0 Cola, Classic, l5Hr, Uncapped 0 0 Cola, Classic Fresh 2 3 0 Cola, Diet, 15Hr, Capped 2 0 0 Cola, Diet, l5Hr, Uncapped 0 0 Cols, Diet, Fresh 3 2 0 Orange, l5Hr, Capped 15 3 0 Orange, 155Hr, Uncapped 0 0 Orange, Diet, l5Hr, Capped 25 3 1 Orange, Diet, l5Hr, Uncapped 0 0 Orange, Diet, Fresh 25 25 1 Fanta Fresh 20 25 0 Lemon/Lime, 1511r, Capped 2 0 0 LemoILirm!, 1511r, Uncapped 0 0 Lemon/Lirrie, Diet, l5Hr, Capped 20 0 0 Lemon/Llme, Diet, I5Hr, Uncapped 0 0 Lemon/Lim, Diet Fresh 2 3 0 Lemon/Lime, Fresh 3 2 0 N urbers In columns 2 to 4 In millivolts SOS Off Scale Reading WO 93/24825 PCT/US93, 17 Column 1 of Table I in the upper portion lists "samples" including potential contaminants in beverage bottles which are detectable by the method and system of the present invention. These contaminants are detectable in addition to nitrogen containing compounds. The designation "Uncapped" means that the residue-containing bottle was stored for the indicated time with its top opening uncovered; undesignated entries indicate that the contaminant was present, and top opening uncovered, for only a brief time prior to testing.
The "samples" in the lower part of column 1 include examples of beverage product tested ,and an indication of whether the bottles were capped, uncapped, and if uncapped the storage period of the residue-containing bottle with its top opening uncovered for example 15 hrs. The designation "Capped) means that the bottle was tested with a residue of the beverage procut present, and the top opening uncovered for only a brief period prior to testing. The designation "Fresh" means that the bottle was tested soon after opening it, and contained fresh product in liquid form, i.e. a substantially full bottle of beverage, rather than old fermented product.
Column 2 of Table I shows the intensity in millivolts of signals measured by a photomultiplier tube 104 in detector assembly 27 with a 0.19 micron quartz cut-off filter 102 at the input window of the photomultiplier tube 104. It can be seen that signals of significant detectable levels exist for these contaminants for capped or uncapped beverage bottles.
The data in column 2 also indicates that for "uncapped" beverage bottles stored for 15 hrs. that "product" volatiles are undetectable (0 millivolts) by photomultiplier tube 104.
Column 4 of Table I shows test results of a system including the 1 micron filter 100, and the levels in millivolts of detectable signals for the various contaminants
I
I
WO 93/24825 PCVUS93/04766 18 or products of column 1. It can be seen that essentially all useful signal data relating to contaminants in Table I is lost with the 1 micron filter 100 in place.
Column 3 of Table I shows results with a 0.4 micron cutoff filter 106 installed at the input of photomultiplier tube 104 in place of either filters 100 or 102. It can be seen that some useful contaminant data is detectable when using a 0.4 micron cut-off filter 102.
Therefore, the discovery of the present invention that storage of beverage bottles in an uncapped state removes the possibility of developing false reject signals from "product' volatiles, is a most significant and beneficial discovery.
That is, the process of the present invention which embodies the concept of storing uncapped beverage bottles for a sufficient time to permit "product" volatiles to dissipate, enables the detection of a wide range of other contaminants such as those listed in Table I in addition to contaminants including nitrogen containing compounds.
The invention being thus described, it will be obvious that the same may be varied in many ways. For example, other forms of high speed analyzers, such as electron capture detectors or photoionization detectors, may be suitable in place of the chemiluminescence analyzer described with reference to Fig. 2.
Also the sample sucked into the tube 20 may be separated into two or more streams and input to a plurality of analyzers 26. Consequently, each analyzer 26 could be used to detect different types of contaminants.
In addition the materials to be inspected are not limited to substances in containers. For example, the method and system of the present invention could be used to detect volatiles adsorbed in shredded strips or flakes of resins, or plastic stock to be recycled for manufacturing new plastic WO 93/24825 I'CT/US93/04766 19 beverage bottles. This shredded or flaked plastic stock could be placed directly on a conveyor belt 10 and passed through test station 12 of Fig. 1; or the plastic stock could be placed in baskets, buckets or other types of containers disposed thereon and inspected in batches.
Still further the bottles being tested may be new bottles that have never been filled with a beverage. Thus, new bottles could be tested for excessive acid aldehyde content, which may be a byproduct of the manufacturing process.
Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
Claims (12)
1. A method of sampling and determining the presence of volatiles of certain contaminants in a container which was previously filled with a beverage, said container including an opening which is closeable by a cap, including the steps of: storing said container with the cap removed for a sufficient period of time to permix volatiles of residues of the beverage to evaporate and egress from said container; evacuating a sample of volatiles remaining in the container after expiration of said sufficient period of time; mixing the sample with a chemical reactant to cause a chemical reaction therewith in order to generate chemiluminescence of the reactants; analyzing radiation emitted by chemiluminescence of the sample and reactant to determine the presence or absence of said volatiles of certain contaminants without interference from chemiluminescence of volatiles of the beverage by filtering radiation emitted by chemiluminescence of the sample to detect the presence of radiation having wavelengths above about 0.19 micron; and identifying the presence or absence of said certain 25 contaminants from the radiation detected at characteristic S wavelengths above about 0.19 micron.
2. The method of claim 1 including the further step of heating the sample to about 400 0 C to 1400 0 C prior S to said mixing step, and wherein the chemical reactant is ozone.
3. The method of claim 1 or claim 2 wherein said sufficient period of time is about 15 hours.
4. A method of sampling and determining the presence of volatiles of certain contaminants in a container which was previously filled with a beverage, said container including an opening which is closeable by a cap, including the steps of: storing said container with the cap removed for a 39 sufficient period of time to permit voltiled of residues 5VF 20 Zb/ of the beverage to evaporate and egress from said container; injecting fluid into the opening in said container after expiration of said sufficient period of time in order to displace at least a portion of the volatiles therefrom to create a sample cloud in a region outside of said container; evacuating a sample of the volatiles so displaced from said region outside of said container by applying suction thereto; and analyzing the sample evacuated to determine the presence or absence of said volatiles of certain S* contaminants.
5. The method of claim 1 wherein said analyzing step includes the steps of: mixing the sample with a chemical reactant to cause a chemical reaction therewith in order to generate chemiluminescence of the reactants; and analyzing radiation emitted by chemiluminescence of the sample and reactant to determine the presence or absence of said volatiles of certain contaminants without S.*0 interference from chemiluminescence of volatiles of residues of the beverage.
6. The method of claim wherein the step of S2 analyzing includes the steps of: e filtering radiation emitted by chemiluminescence of the sample to detect the presence of radiation having wavelengths above about 0.19 micron; and identifying the presence or absence of said certain contaminants from the radiation aetected at characteristic wavelengths above about 0.19 micron.
7. The method of any one cf claims 4 to 6 including the further step of heating the sample to about 4000 to 1400 0 C prior to said mixing step, and wherein the chemical reactant is ozone.
8. The method according to any one of claims 4 to 7 wherein said sufficient period of time is about 15 hours.
9. A method of sampling and determining the 39 presence of certain substances in a container which was VF 21 previously filled with a beverage, said container including an opening which is closeable by a cap, including the steps of: storing said container with the cap removed ,for a ce ecio.-b\e cqI-Cvkth he& sufficient period of time to permit volatiles of residues of the beverage to evaporate and egress from said container; displacing a portion of the container contents to form a sample cloud at regions outside of the container adjacent the opening thereof; and analyzing the sample cloud to determine the presence or absence of the certain substances therein.
10. A method of sampling and determining the g. presence of volatiles of certain contaminants in a container which was previously filled with a beverage, said container including an opening which is closeable by a cap, including the steps of: storing said container with the cap removed for a sufficient period of time to permit volatiles o residues of the beverage to evaporate and egress from said container; after expiration of said sufficient period of time and without further pretreatment to remove latiles of the residues of the beverages for the purpose of avoiding S2 interference between the residues and the contaminants to S be detected, evacuating for analysis a sample of volatiles remaining in the container; and S* analyzing the sample evacuated to det:.rmine the presence or absence of the certain contaminants therein.
11. A method substantially as hereinbefore described with respect to any one of the embodiments illustrated in the accompanying drawings. DATED: 24 November 1994 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE COCA-COLA COMPANY
39-. 6469b VF -22- Q i F
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JP (1) | JPH07507393A (en) |
KR (1) | KR0184531B1 (en) |
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DE4427314C2 (en) * | 1994-08-02 | 1997-02-20 | Graessle Walter Gmbh | Device for examining containers for foreign gases |
EP0752283A1 (en) * | 1995-07-05 | 1997-01-08 | Elpatronic Ag | Method and device for inspecting containers |
CN103675210A (en) * | 2013-12-12 | 2014-03-26 | 中国航空工业集团公司第六三一研究所 | Quick detection method for pollution degree of small type liquid cooling quick connector |
RU170386U1 (en) * | 2016-04-22 | 2017-04-24 | Федеральное государственное казенное военное образовательное учреждение высшего образования "Военная академия материально-технического обеспечения имени генерала армии А.В. Хрулёва" Министерства обороны Российской Федерации | DEVICE FOR DETERMINING THE CONTENT OF VOLATILE MATERIALS IN FOOD |
CN107991247A (en) * | 2017-12-08 | 2018-05-04 | 尹大路 | A kind of food inspection device and its detection method |
DE102018120693B4 (en) * | 2018-08-24 | 2024-05-23 | Joma-Polytec Gmbh | Process for cleaning media-carrying plastic components |
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US4880120A (en) * | 1987-09-02 | 1989-11-14 | The Coca-Cola Company | Plastic container inspection process |
EP0578146A1 (en) * | 1992-07-09 | 1994-01-12 | Elpatronic Ag | Method and device for testing of bottles for contamination |
AU5557894A (en) * | 1992-12-03 | 1994-06-22 | Photovac Incorporated | System for the detection of noxious contaminants in beverage and potable water containers |
Family Cites Families (4)
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US4193963A (en) * | 1974-09-20 | 1980-03-18 | Petroleo Brasileiro S.A.-Petrobras | Apparatus for the determination of chemical compounds by chemiluminescence with ozone |
US4843016A (en) * | 1974-10-07 | 1989-06-27 | Thermedics Inc. | Detection system and method |
US4775633A (en) * | 1984-04-26 | 1988-10-04 | Thermedics Inc. | Detection of hydrazine compounds in gaseous samples by their conversion to nitric oxide-yielding derivatives |
US5152963A (en) * | 1986-08-04 | 1992-10-06 | Wreyford Donald M | Total sulfur analyzer system operative on sulfur/nitrogen mixtures |
-
1993
- 1993-05-19 NZ NZ253476A patent/NZ253476A/en unknown
- 1993-05-19 KR KR1019940704382A patent/KR0184531B1/en not_active IP Right Cessation
- 1993-05-19 WO PCT/US1993/004766 patent/WO1993024825A1/en not_active Application Discontinuation
- 1993-05-19 CA CA002135878A patent/CA2135878A1/en not_active Abandoned
- 1993-05-19 HU HU9403443A patent/HUT75420A/en unknown
- 1993-05-19 RU RU94046340A patent/RU2125721C1/en active
- 1993-05-19 JP JP6500619A patent/JPH07507393A/en active Pending
- 1993-05-19 EP EP93914003A patent/EP0646236A4/en not_active Withdrawn
- 1993-05-19 AU AU43829/93A patent/AU672011B2/en not_active Ceased
- 1993-05-19 BR BR9306456A patent/BR9306456A/en not_active Application Discontinuation
- 1993-05-26 TR TR00435/93A patent/TR28391A/en unknown
- 1993-05-27 IL IL105814A patent/IL105814A/en not_active IP Right Cessation
- 1993-05-27 MX MX9303152A patent/MX9303152A/en not_active IP Right Cessation
- 1993-05-27 ZA ZA933728A patent/ZA933728B/en unknown
- 1993-05-29 CN CN93106223A patent/CN1080723A/en active Pending
- 1993-06-01 AR AR93325071A patent/AR248316A1/en active
- 1993-07-21 TW TW082105797A patent/TW227532B/zh active
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1994
- 1994-11-30 NO NO944597A patent/NO944597L/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4880120A (en) * | 1987-09-02 | 1989-11-14 | The Coca-Cola Company | Plastic container inspection process |
EP0578146A1 (en) * | 1992-07-09 | 1994-01-12 | Elpatronic Ag | Method and device for testing of bottles for contamination |
AU5557894A (en) * | 1992-12-03 | 1994-06-22 | Photovac Incorporated | System for the detection of noxious contaminants in beverage and potable water containers |
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EP0646236A1 (en) | 1995-04-05 |
RU94046340A (en) | 1997-04-20 |
AU4382993A (en) | 1993-12-30 |
KR950702028A (en) | 1995-05-17 |
NZ253476A (en) | 1995-11-27 |
AR248316A1 (en) | 1995-07-12 |
BR9306456A (en) | 1998-06-30 |
ZA933728B (en) | 1994-03-01 |
IL105814A (en) | 1997-07-13 |
KR0184531B1 (en) | 1999-05-15 |
WO1993024825A1 (en) | 1993-12-09 |
IL105814A0 (en) | 1993-09-22 |
HUT75420A (en) | 1997-05-28 |
CN1080723A (en) | 1994-01-12 |
CA2135878A1 (en) | 1993-12-09 |
TR28391A (en) | 1996-05-23 |
HU9403443D0 (en) | 1995-02-28 |
EP0646236A4 (en) | 1996-02-28 |
JPH07507393A (en) | 1995-08-10 |
RU2125721C1 (en) | 1999-01-27 |
NO944597D0 (en) | 1994-11-30 |
TW227532B (en) | 1994-08-01 |
MX9303152A (en) | 1994-06-30 |
NO944597L (en) | 1994-11-30 |
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