EP0824970B1 - Beschichtete Gasflaschen - Google Patents

Beschichtete Gasflaschen Download PDF

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Publication number
EP0824970B1
EP0824970B1 EP19970306321 EP97306321A EP0824970B1 EP 0824970 B1 EP0824970 B1 EP 0824970B1 EP 19970306321 EP19970306321 EP 19970306321 EP 97306321 A EP97306321 A EP 97306321A EP 0824970 B1 EP0824970 B1 EP 0824970B1
Authority
EP
European Patent Office
Prior art keywords
gas
cylinder
polymer
cylinders
polar
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.)
Expired - Lifetime
Application number
EP19970306321
Other languages
English (en)
French (fr)
Other versions
EP0824970A2 (de
EP0824970A3 (de
Inventor
Alan John Francis Paterson
John Irven
Segun Lateef Obadun
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Products and Chemicals Inc
Original Assignee
Air Products and Chemicals Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Publication of EP0824970A2 publication Critical patent/EP0824970A2/de
Publication of EP0824970A3 publication Critical patent/EP0824970A3/de
Application granted granted Critical
Publication of EP0824970B1 publication Critical patent/EP0824970B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C13/00—Details of vessels or of the filling or discharging of vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0607—Coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0639—Steels
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0646—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/03—Mixtures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/03—Mixtures
    • F17C2221/032—Hydrocarbons
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/05—Improving chemical properties

Definitions

  • the present invention relates to the use of a coating on the internal gas-contacting surface of a metal gas cylinder to improve the stability of gas mixtures contained in the cylinder.
  • GB-A-2075366 (corresponding to US-A-4311250) disclosed the use of a layer of an inert water-insoluble organic polymeric material with at least 75% of the layer formed from a monomer containing hydrophilic chemical groups to reduce carbon dioxide bubble nucleation on the internal walls of a container for liquid carbonated beverages.
  • the coatings would be of use, if applied to the internal surface of a metal gas cylinder, to maintain the standard of a calibration gas mixture within the cylinder. It refers to the use of poly(vinyl alcohol) (“PVA”) as a suitable hydrophilic polymer but states that PVA must be insolubilized by, for example, cross-linking before it is suitable for use.
  • PVA poly(vinyl alcohol)
  • JP-A-55115694 discloses the coating of internal surfaces of gas cylinders with poly(trifluorochloroethylene) ("PCTFE”) to stabilize calibration gas mixtures and JP-A-54134070 discloses the coating of the internal surfaces of gas cylinders with a wax also to stabilize calibration gas mixtures.
  • the exemplified waxes are Japan wax, ceresin wax, paraffin wax and silicon wax.
  • PCTFE and the exemplified waxes are hydrophobic and are non-polar (i.e. non-water-wettable) and were used only to prevent contact between the gas and cylinder walls.
  • the present invention is directed to stabilizing gas mixtures in a gas cylinder and has particular, but not exclusive, application to the storage of calibration gases. It has been found that stability of gas mixtures is significantly improved by coating the internal surfaces of gas cylinders with a film of a polar (i.e. water-wettable) film-forming polymer whereby non-polar organic molecules will not adhere to the polymer film.
  • a polar film-forming polymer whereby non-polar organic molecules will not adhere to the polymer film.
  • a polar film-forming polymer to form on an internal, gas-contacting surface of a metal gas cylinder a film to which non-polar organic molecules will not adhere to stabilize a gas mixture contained within the cylinder.
  • the polar polymer prevents, or at least tends to inhibit, condensation of polar organic compounds and nitrogen oxides on, or reaction of compounds with, the internal, gas-contacting surface of the cylinder.
  • the polar polymer is water-soluble, whereby it can be applied to the internal cylinder wall by contacting the wall surface with an aqueous solution of the polymer to coat the wall with the solution, and drying the coating to evaporate water from therefrom to leave a film on the wall surface. This process may be repeated to build up a second layer, or even more layers, on the gas-contacting surface.
  • the water-soluble polymer has multiple hydroxyl groups and suitably is a polymer of an alcohol, a glycol, or a polyhydroxyalcohol, for example poly(ethylene glycol) or, especially, (uncrosslinked) PVA.
  • the metal of the cylinder usually will be aluminium but may be, for example, steel.
  • Polyvinyl alcohol having a molecular weight of 25,000 in the form of chips was dissolved in hot water and allowed to cool. It is preferable to make the solution as concentrated as possible as the water has to be dried off later. It was found to be possible to dissolve 15% by weight (w/w) of PVA in water.
  • a quantity of the cooled solution was poured into a standard high quality aluminium gas cylinder in an amount sufficient to wet the entire internal, gas-contacting surface of the cylinder.
  • a torch was used to inspect the inside of the cylinder to ensure that the whole surface has been fully coated with the solution.
  • the gas cylinder was then be inverted to allow the excess solution to drain off and dry gas gently blown through the gas cylinder in order to evaporate water from the coating. This resulted in a gas cylinder which has a complete polymer film over the whole of its internal, gas-contacting surface.
  • the whole process may be repeated in order to build up a second coating layer.
  • further layers may be applied if desired.
  • Gas cylinders coated as described above provide for extremely stable storage of mixtures within the gas cylinder. This is particularly important where the gas mixture is used in a calibration method and is therefore stored for a considerable period of time.
  • the present invention derives its improved properties as follows.
  • An uncoated metal cylinder is covered with oxygen atoms at its surface and the surface may be slightly polar, especially if the oxide layer is thin and new.
  • larger organic molecules such as xylene tend to stick to, or condense on, the surface, thereby reducing the concentration of the molecules in the gas space in the cylinder.
  • the use of a polar polymer coating as proposed in the present invention, and particularly one which has multiple OH groups, causes the organic molecules to be repelled and thus prevents or inhibits the loss of the organic molecules from the gas space in the cylinder.
  • Nitric oxide mixtures are present in nitrogen because, in air, the nitric oxide reacts to form nitrogen dioxide.
  • the problem is that there are still traces of oxygen in nitrogen and the aluminium surface of the gas cylinder can promote a reaction.
  • Nitric oxide can be lost in two ways from an uncoated gas cylinder. In one mechanism, the nitric oxide reacts with gaseous oxygen, in which case the concentration of NO is lowered but the total NO x remains constant. In the second mechanism, the NO seems to react with the aluminium surface of an aluminium cylinder, but is retained so that the levels of NO and NO x both fall.
  • the metal surface of the gas cylinder either acts directly or as a catalyst in the mechanism, particularly in the case of an aluminium cylinder. Coating the surface of the cylinder with a substance which is not an oxide allows the concentration of NO to be stabilised.
  • OH groups can form a useful key to which other reactive compounds such as silanols could attach. This facilitates the provision of water-repellant coatings or other tailor made coatings for particular applications.
  • the present invention whilst described above with particular reference to aluminium gas cylinders, can also be applied to gas cylinders of other materials, for example steel.
  • the concentrations (ppb) of NO and NO x in gas mixtures stored the coated cylinders are compared with the concentrations (ppb) of NO and NO x in gas mixtures from the same source stored in the uncoated cylinders.
  • NO loss in the uncoated cylinders was between 15 and 30% within 21 ⁇ 2 months.
  • the gas mixture stored in the coated (invention) cylinders was stable to ⁇ 1.5% over a period of up to 11 ⁇ 2 years.
  • Hydrocarbons are often unstable and sometimes lost either when transfilled from one cylinder to another or when stored over a long period in a gas cylinder, especially at very low concentration. Component loss could be due to physical absorption onto metal surfaces or through chemical reaction and decomposition.
  • the four hydrocarbons the results for which are shown in Table 2 are chosen to be a fair representation of those that are often stable (e.g. propane) and those that are often unstable (e.g. isoprene and the C 8 and C 9 compounds).
  • the "Stability Ratio” is the quotient of the chromatographic peak area of a master cylinder component on day 0 and the chromatographic peak area of a target cylinder component on day x.
  • the “Reference Component” is a component that may be regarded as stable (such as propane).
  • the “Normalised Stability Ratio” is the quotient of the Stability Ratio of a component on day x and the stability ratio of the Reference Component on day x. In an ideal cylinder all the values would.be 1.00. Because of the decay shown by gas stored in the uncoated cylinders, no further measurements were made for those cylinders after 35 days. However, measurements were made for the coated cylinders for 394 days.

Landscapes

  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Paints Or Removers (AREA)

Claims (11)

  1. Verwendung eines polaren, filmbildenden Polymers, um auf einer inneren, mit dem Gas in Berührung kommenden Oberfläche eines Gaszylinders aus Metall einen Film zu bilden, an dem nicht-polare organische Moleküle nicht haften, um ein in dem Zylinder enthaltenes Gasgemisch zu stabilisieren.
  2. Verwendung nach Anspruch 1, wobei das polare Polymer wasserlöslich ist.
  3. Verwendung nach Anspruch 2, wobei das wasserlösliche Polymer Mehrfach-HydroxylGruppen enthält.
  4. Verwendung nach Anspruch 3, wobei das wasserlösliche Polymer ein Polymer eines Alkohols, eines Glykols oder eines Polyhydroxyalkohols ist.
  5. Verwendung nach Anspruch 4, wobei das Polymer Poly(Vinylalkohol) ist.
  6. Verwendung nach Anspruch 4, wobei das Polymer Poly(Ethylenglykol) ist.
  7. Verwendung nach einem der vorhergehenden Ansprüche, wobei der Gaszylinder aus Aluminium hergestellt ist.
  8. Verwendung nach einem der Ansprüche 1 bis 6, wobei der Gaszylinder aus Stahl hergestellt ist.
  9. Verwendung nach einem der vorhergehenden Ansprüche, wobei das Gasgemisch ein Eichgasgemisch ist.
  10. Verwendung nach Anspruch 9, wobei das Gasgemisch geeichte Spurenmengen von Stickoxid enthält.
  11. Verwendung nach Anspruch 9, wobei das Gasgemisch Spurenmengen von Kohlenwasserstoffen enthält.
EP19970306321 1996-08-19 1997-08-19 Beschichtete Gasflaschen Expired - Lifetime EP0824970B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9617368A GB9617368D0 (en) 1996-08-19 1996-08-19 Gas containers
GB9617368 1996-08-19

Publications (3)

Publication Number Publication Date
EP0824970A2 EP0824970A2 (de) 1998-02-25
EP0824970A3 EP0824970A3 (de) 2002-08-07
EP0824970B1 true EP0824970B1 (de) 2006-06-14

Family

ID=10798661

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19970306321 Expired - Lifetime EP0824970B1 (de) 1996-08-19 1997-08-19 Beschichtete Gasflaschen

Country Status (4)

Country Link
EP (1) EP0824970B1 (de)
DE (1) DE69736094T2 (de)
ES (1) ES2262171T3 (de)
GB (1) GB9617368D0 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3825434A (en) * 1972-10-27 1974-07-23 Goodrich Co B F Internally coated reaction vessel and process for coating the same
JPS55115694A (en) * 1979-02-26 1980-09-05 Nippon Sanso Kk Standard gas container and production thereof
US4311250A (en) * 1980-05-12 1982-01-19 The Continental Group, Inc. Container having internal wall surfaces modified to reduce carbonation loss

Also Published As

Publication number Publication date
ES2262171T3 (es) 2006-11-16
EP0824970A2 (de) 1998-02-25
GB9617368D0 (en) 1996-10-02
DE69736094D1 (de) 2006-07-27
DE69736094T2 (de) 2007-01-04
EP0824970A3 (de) 2002-08-07

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