WO2000036351A1 - Method and system for the production of cryogenic mixtures and the application of such mixtures - Google Patents

Method and system for the production of cryogenic mixtures and the application of such mixtures Download PDF

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Publication number
WO2000036351A1
WO2000036351A1 PCT/NO1999/000371 NO9900371W WO0036351A1 WO 2000036351 A1 WO2000036351 A1 WO 2000036351A1 NO 9900371 W NO9900371 W NO 9900371W WO 0036351 A1 WO0036351 A1 WO 0036351A1
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WO
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Patent type
Prior art keywords
cryogenic
mixture
liquid
carbon dioxide
characterised
Prior art date
Application number
PCT/NO1999/000371
Other languages
French (fr)
Inventor
Dag Eimer
Leif Kåre GRØNSTAD
Tore Haug-Warberg
Sigbjørn WIERSDALEN
Arne Hallvard ØYGARDEN
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Norsk Hydro Asa
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/02Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0275Construction and layout of liquefaction equipments, e.g. valves, machines adapted for special use of the liquefaction unit, e.g. portable or transportable devices
    • F25J1/0276Laboratory or other miniature devices
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/04Production of frozen sweets, e.g. ice-cream
    • A23G9/08Batch production
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A23B - A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/36Freezing; Subsequent thawing; Cooling
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A23B - A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/36Freezing; Subsequent thawing; Cooling
    • A23L3/37Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals
    • A23L3/375Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals with direct contact between the food and the chemical, e.g. liquid nitrogen, at cryogenic temperature
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/50Carbon dioxide
    • C01B32/55Solidifying
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/06Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/066Cooling mixtures; De-icing compositions
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/0002Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the fluid to be liquefied
    • F25J1/0012Primary atmospheric gases, e.g. air
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/0002Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the fluid to be liquefied
    • F25J1/0012Primary atmospheric gases, e.g. air
    • F25J1/0015Nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/003Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0035Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
    • F25J1/0037Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work of a return stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/003Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/004Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/003Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/005Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/003Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/006Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) characterised by the refrigerant fluid used
    • F25J1/007Primary atmospheric gases, mixtures thereof
    • F25J1/0072Nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/02Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0201Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using only internal refrigeration means, i.e. without external refrigeration
    • F25J1/0202Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using only internal refrigeration means, i.e. without external refrigeration in a quasi-closed internal refrigeration loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/02Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0203Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle (not used)
    • F25J1/0208Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle (not used) in combination with an internal quasi-closed refrigeration loop, e.g. with deep flash recycle loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/02Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0285Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings
    • F25J1/0288Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings using work extraction by mechanical coupling of compression and expansion of the refrigerant, so-called companders
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used)
    • F25J1/02Processes or apparatus for liquefying or solidifying gases or gaseous mixtures (not used) requiring the use of refrigeration, e.g. of helium or hydrogen Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0294Multiple compressor casings/strings in parallel, e.g. split arrangement
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B18/00Surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body
    • A61B18/02Surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body by cooling, e.g. cryogenic techniques
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00Surgical instruments, devices or methods, e.g. tourniquets
    • A61B2017/00743Type of operation; Specification of treatment sites
    • A61B2017/00747Dermatology
    • A61B2017/00774Wart
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/20Processes or apparatus using other separation and/or other processing means using solidification of components
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/60Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
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    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/90Mixing of components
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    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/80Carbon dioxide
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/40Separating high boiling, i.e. less volatile components from air, e.g. CO2, hydrocarbons
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    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/44Separating high boiling, i.e. less volatile components from nitrogen, e.g. CO, Ar, O2, hydrocarbons

Abstract

The present application concerns cryogenic mixtures, systems and methods for the production of such mixtures and applications of such mixtures.

Description

"Method and system for the production of cryogenic mixtures and the application of such mixtures"

The present invention concerns cryogenic mixtures, a system and method for producing such mixtures and the applications of such mixtures.

Carbon dioxide is sold and distributed largely as a refrigeration source for freezing purposes. Liquid nitrogen and local freezing systems are competing alternatives. Both the price of freezing and the quality of the end product are important parameters for the choice of alternative. At 1 atm, dry ice (CO2(s)) has a temperature of -79°C with an enthalpy content ΔH = 0.176 kWh/kg (the enthalpy content is relative to CO2(g) at 0°C and is indicated as "cold", i.e. without the minus sign). Distributed in liquid form, carbon dioxide usually has a pressure of 16 bar (abs), which corresponds to a temperature of -27°C and an enthalpy content ΔH = 0.096 kWh/kg.

With the present invention, it is possible to produce a cryogenic mixture which may consist of carbon dioxide in solid form and a cryogenic liquid such as, for example, nitrogen. This mixture will have a temperature of -196°C, while the enthalpy content may be ΔH = 0.214 kWh/kg, depending on the mixture ratio. In this way, the content of cold in the carbon dioxide may be increased significantly if the carbon dioxide is cooled to lower temperatures. This will result in large savings in transport costs and the cold mixture formed may have a number of interesting applications on account of its specific properties.

For example, the above mixture will have half the weight and take up a third of the space of the same quantity of cold in standard liquid carbon dioxide when transported. The mixture will thus have great potential in connection with the transport/storage of frozen/refrigerated products such as foods.

Moreover, it has been found that adding another component to the cryogenic mixture described above produces a cryogenic mixture or a cryogenic agent with very special properties.

US 5.368.105 describes the use of a slurry of carbon dioxide in liquid nitrogen to extinguish fires on refuse dumps. The flow properties of this mixture will be affected by the content of carbon dioxide, but it will be regarded as a liquid (slurry). When the nitrogen has evaporated, one is left with a lump of carbon dioxide or possibly carbon dioxide crystals. The patent specification also describes equipment for producing such a slurry comprising an inverted funnel in which carbon dioxide and nitrogen are mixed. The carbon dioxide is introduced in the uppermost part of the funnel, while liquid nitrogen is introduced at a lower level and in a tangentially manner with respect to the funnel.

US 4.305.205 describes the production of a cryogenic gel from a cryogenic liquid containing methane and concerns, in particular, the formation of gel in connection with liquefied natural gas (LNG). In this method, the liquid is converted into a mixture of cryogenic vapour and drops, after which a gelling agent is added to the mixture in a quantity which amounts to at least 0.1% weight of the cryogenic gel. The gelling agent has properties which cause it to form a chemical compound with methane and has a solid phase at the temperature of the cryogenic liquid and a liquid or gaseous phase at the ambient temperature. The mixture is separated and a condensed phase is collected in a container. The gelling agent may contain water or methyl alcohol or a mixture of the two.

Eutectic mixtures of dry ice in ethanol are widely known among those who work at chemically oriented laboratories. Temperatures of around -80°C can be achieved with such mixtures.

DE 195 08 475 describes a method for freeze-sealing pipes using CO2 pellets placed on the outside of the pipe. A device such as a sleeve is used to hold the pellets in place at the place at which the pipe is to be frozen.

It is common today to use liquefied nitrogen for the removal of warts. With this method, a pin with a wad of cotton wool at the end is dipped in liquid nitrogen and then applied to the wart. A disadvantage of this method is that the nitrogen evaporates rapidly so that the dipping/application must be repeated several times. The method is therefore time-consuming and labour-intensive. The method also requires care to ensure that the liquid nitrogen is not dripped onto or otherwise comes into contact with surfaces where it can cause major damage. This method will therefore not be adequate for the treatment of warts in the body's cavities such as in the oesophagus.

One embodiment of the present cryogenic mixture can produce an agent which can be used to simplify the treatment of warts. The mixture in this embodiment is produced from liquid nitrogen, carbon dioxide and ethanol. The cryogenic mixture has a stickiness or viscosity which is adapted to the application in question. Therefore, the risk of it coming into contact with surfaces which are not to be treated is reduced considerably. Moreover, the high viscosity contributes to making it possible for the mixture to be fixed in relation to the point (area) of application. Another advantageous feature is that the evaporation will be very slow compared with the above nitrogen-based method described above. In use, the treatment will thus be less labour-intensive and more effective as one application will normally be sufficient for each treatment. Moreover, the mixture contains well-known substances such as carbon dioxide, ethanol and liquid nitrogen for which there is good knowledge of the substances' effects on people, animals, and the environment.

When using the above mixture, also in other applications, the need for protective equipment will be less. The risks of accidents and the consequences of accidents will be less than with prior art products because the cream-like substance does not flow away in uncontrolled fashion like, for example, liquid nitrogen. This means that the likelihood of frost injuries when handling/using the proposed agent is less than that with prior art products. The stickiness of the substance is a further advantage in connection with the use of the mixture on the outside of objects which are to be frozen such as water pipes for temporary freeze-sealing; the need for formwork/sealing is less than when more liquid refrigerants are used.

Furthermore, the mixture is assumed to have future applications which are advantageous partly on account of its stickiness but also on account of its temperature. The mixture or agent can have a temperature which is, for example, higher than nitrogen but lower than a mixture of carbon dioxide and ethanol. For example, when freezing tissue, it will be advantageous for the temperature not to be extremely low.

The present invention will be described in further detail in the following using examples and with reference to the table and figures where:

Fig. 1 shows schematically a system for the production of a cryogenic mixture,

Fig. 2 shows a discharge/dosing device for a cryogenic mixture,

Fig. 3 shows schematically a system for effecting contact between

CO2 and liquid nitrogen, Fig. 4 shows schematically another embodiment of a system for the production of a cryogenic mixture,

Fig. 5 shows schematically a third embodiment of a system for the production of a cryogenic mixture,

Fig. 6 shows schematically a laboratory or a test equipment for the production of a cryogenic mixture,

Fig. 7 shows two flow diagrams of the production of a cryogenic mixture,

Fig. 8 shows a mixing device for the production of a cryogenic mixture,

Fig. 9 shows a table in which temperature and consistency are shown for various mixture ratios of a cryogenic mixture,

Fig. 10 shows a triangular diagram with a marked area which indicates the desired consistency of a cryogenic mixture.

The production system for a cryogenic mixture which is shown in Figure 1 is supplied with a first process flow 1 comprising liquid nitrogen (N2) or air, preferably through a spreading device 9, for example a nozzle, and a second process flow 2 comprising liquid or gaseous carbon dioxide (CO2). The inlet line for CO2 is insulated, preferably with a gas space purged with dry nitrogen gas to avoid the CO2 freezing in the pipe 3, which may comprise a nozzle 5 at the inlet to the contact chamber. When the flows 1 and 2 are mixed in the contact chamber or container 4, which may be a spray tower, a slurry is formed in which CO2 constitutes the solid while liquid nitrogen or air constitutes the continuum. The temperature in the container will be approximately -196°C if liquid nitrogen is used and slightly higher if air is used. In this embodiment, CO2 is supplied at a level which is below the level for the supply of the continuum. On account of temperature differences between the CO2 and the continuum, the CO2 will tend to rise in the contact chamber while the continuum will move downwards, which ensures a good mixture of the CO2 and the continuum. The base of the container is equipped with an outlet 6 at which the mixture of dry ice particles and liquid nitrogen can be removed. The angle 7 is under a maximum given by standard rules for removing powder and slurry from a container.

The cold requirement associated with the subcooling of CO2 is produced by evaporating nitrogen or air. This is handled by a line 8 being attached to the container 4 in its upper part.

By extrapolating the vapour pressure over carbon dioxide, which is known down to 145 K, to relevant temperatures, it is found that the carbon dioxide content in the gaseous phase will be lower than 1 ppm in flow 8. Therefore, it will be possible to recirculate nitrogen or air from the cooling chamber back into a refrigerating circuit without other measures than the installation of a drop collector (not shown) in the top of the chamber 4. A drop collector may also alternatively be fitted in another container placed in flow 8.

Figure 2 describes an expedient device 27 for storing and discharging/dosing a cryogenic mixture 38. The device comprises a tank 39 to receive the cryogenic mixture 38 through a line 26. An agitator 29 is fitted inside the tank 39. A feed device 37 is fitted in connection with the outlet when the consistency of the cryogenic mixture so requires. A pump 40 is then placed in the base of the tank 39. The pump 40 is equipped with an outlet line 35 with a valve 36. A bypass line 30 with a valve 31 can be arranged between the tank 39 and the line 35 in order to contribute to the agitation in the tank. The tank 39 and pump 40 are preferably enclosed in a jacket 28 for thermal insulation.

Figure 3 describes alternative methods of producing contact between CO2 and liquid nitrogen or air in order to produce a slurry of these two components. The design of the chamber 79 is only sketched in outline. The liquid outlet, which is not shown, must in practice be designed so that it is suitable for withdrawing a slurry as mentioned under Figure 1. Liquid nitrogen can be supplied either to the chamber's gaseous phase via line 70 and nozzle 80, from where it falls down onto the surface of the liquid 83, or by injection through line 72. Carbon dioxide can be introduced by direct injection into the liquid phase nitrogen through line 71 which is surrounded by an annular pipe 74 that constitutes dynamic thermal insulation using a flow of nitrogen gas or air 73 which can also bubble into the liquid phase. The chamber 79 can be equipped with a baffle 78 which divides the gaseous phase into sections to avoid any short-circuit between incoming CO2 gas and the discharge of exhaust gas 76 from the contactor. The exhaust gas 76 leaves the chamber 79 via a drop collector 81 which can be located in the actual outlet from the chamber 79 or in a separate container 82. Precipitated drops of liquid are returned to the liquid phase as flow 75 while the exhaust gas can expediently be returned to the attached liquefier.

Figure 4 shows a system for the production of a cryogenic mixture in which liquefied air is used. The process is based on an open air circuit in which air is taken in through an intake line 100 and conveyed to a compressor 101 where it may be compressed to a pressure of, for example, 5 bar. The compressed air is conveyed via line 102 to a unit 103 for the removal of water and carbon dioxide. The unit 103 may comprise molecular sieves 104, 104' connected in parallel as in a standard cryogenic air separation system. The treated air leaves the unit 103 via line 105 and is conveyed to a compressor 106 for a further increase in the pressure of the air. The size of this pressure increase will be such that it optimises the liquefier process

(see, for example, Randall F. Barron, Cryogenic Systems, 2nd ed., Oxford University Press, 1985). From compressor 106, the air is conveyed via line 107 to a compressor 108 which may be placed on the same axle as an expansion turbine 109 which will be described later. The compressed air leaves compressor 108 via line 110 which leads to a multi-flow heat exchanger 113. In the heat exchanger, the air is cooled to a suitable temperature before the flow is split in two; one part is conveyed via line 114 to the expansion turbine 109 to produce cold. The cold flow 124 from the expansion turbine 109 is conveyed to the heat exchanger 113 to balance out the cold requirement there. The other part of flow 110 is cooled further until the flow is completely or partially condensed and leaves the heat exchanger via line 115. The last temperature reduction may be produced using a Joule-Thomson valve 112, after which a single flash separation is carried out in a separator 111 , from where the gas part is returned to compressor 116 via cold recovery from flow 123 in the heat exchanger 113.

Liquid air leaves the separator 111 via line 117 and is sprayed via nozzle 125 into a contact chamber 122 which comprises a spray tower 118 which is constructed with a conical base which functions as an intermediate store for the slurry produced before it is transported onwards. The air is sprayed into the top of the spray tower 118 where it comes into contact with the carbon dioxide, which is conveyed into the tower via line 119. The carbon dioxide may, in this example, be introduced either as a gas or as a liquid, and line 119 may have a nozzle (not shown) adapted to the relevant aggregate state of the carbon dioxide. From the top of the spray tower 118, the exhaust gas is conveyed via line 120 through the heat exchanger 113 for cold recovery to compressor 116 or compressor 101. The gas which flows out of compressor 116 may, depending on the pressure, either be conveyed into compressor 106 on the intake side together with the gas flow 105 or it can be conveyed in together with flow 107 from the compressor 106.

The exhaust gas from the spray tower 118 is so cold that the content of carbon dioxide is negligible and the exhaust gas, which is nitrogen-enriched in relation to air, therefore does not need new treatment with molecular sieves before it is recompressed and recooled. An outlet with an outlet line 121 is arranged in the base of the spray tower for withdrawing the cryogenic mixture, which comprises a slurry consisting of solid phase carbon dioxide and liquid air. Air may be replaced with nitrogen gas in this process. If this nitrogen is sufficiently free of water and carbon dioxide, the cleaning unit 103 can be removed. Other changes will not be of such significance that the process description must be changed.

Figure 5 shows another embodiment of a system for producing a cryogenic mixture in which liquefied air is used and the refrigerating circuit is closed and the air circuit is open. In this system, air is taken in via intake line 150 by means of a compressor (possibly a fan) 151. A line 152 is arranged on the outlet side of the compressor and conveys the air to an adsorption unit 154 where water and C02 are removed to prevent refreezing of the air channels in a subsequent heat exchanger 155. The air is conveyed from the adsorption unit 154 to the heat exchanger 155 via line 156 where incoming air is mixed with recirculated air from compressor 175. In the heat exchanger, the air is cooled and liquefied before it is conveyed via line 157 and nozzle 178 into a contact chamber 172 which comprises a spray tower 158. The design of the spray tower is the same as that described in the previous example and will not therefore be described here.

The heat exchanger's need for cold is covered by a closed refrigerating circuit which expediently contains nitrogen as the refrigerant. The refrigerating circuit may comprise two or more compressor stages 159, 160, which are mutually connected by line 164; after compression the nitrogen is conveyed into the heat exchanger via line 165. Compressor 160 and turbine 161 (described in the following) are normally made as one mechanical unit. Cold production can be optimised by using two or more such compressor/turbine units in order to produce cold as close as possible to the temperature level at which the cold is required. In the heat exchanger, the flow is divided into two sub-flows; one goes via line 166 to an expansion turbine 161 and the other 167 is conveyed, after further cooling, to a flash separator 162 via a Joule-Thomson valve 163. The flash separator has a discharge line 168 in its base which is joined to a discharge line 169 from the expansion turbine 161 so that the entire flow is conveyed back through the heat exchanger and then conveyed via line 170 to the first compressor stage 159. Flows 169 and 168 can also be conveyed as separate flows through heat exchanger 155 and then be mixed afterwards. The flash separator has a vent line 171 which can be connected to the line from the expansion turbine 169 or possibly be conveyed separately back to compressor 159 via heat exchanger 155.

It should be noted that the above systems are only described in principle. Therefore, they may, for example, include more components than described here if required for reasons of efficiency or economy. Moreover, no pretreatment or tempering of carbon dioxide is described. However, such actions must naturally be performed if the available carbon dioxide is of a quality which makes such actions necessary. In terms of refrigeration, it is expedient for the carbon dioxide which is supplied in line 173 to have the greatest possible cold content on "arrival".

Figure 6 shows a laboratory or test equipment for the production of a cryogenic mixture. The equipment comprises a supply line 200 for liquid nitrogen. The supply line is equipped with a stop valve 201 and is connected to a pressurised tank 203 which will be described in further detail in the following. Liquid nitrogen is conveyed from the pressurised tank via line 204 into a contact chamber 218 which comprises a spray tower 206 with an open top. The nitrogen is atomised and sprayed downwards in a uniform shower using a nozzle 205 mounted at the end of line 204. Carbon dioxide gas is supplied to the spray tower from a container 207 via line 208 with valves 210, 209 and a nozzle 211 which extends into the spray tower 206. The carbon dioxide gas flows upwards from the nozzle 211 , even though the opening itself points downwards, and encounters the downward shower of nitrogen, whereupon a slurry is formed which falls down and is collected in an insulated bottle 217 arranged at the base of the spray tower. The equipment comprises a system for flushing with nitrogen gas. The nitrogen gas is supplied through a line 212 which has a branch 213 to supply nitrogen gas to an annular space 214 around the nozzle 211. The purpose of this is to be able to utilise the heat in the gas to prevent the carbon dioxide gas freezing in the nozzle so that the nozzle becomes clogged. Another branch 215 conveys nitrogen gas to the pressurised tank 203 to flush remnants of air or liquid nitrogen out of it and to regulate the pressure in the tank 203. The pressurised tank also has a vent line 216 which is connected to a safety valve (not shown).

Tests carried out with the equipment show that it is possible to create slurry of carbon dioxide gas and liquid nitrogen and that the consistency can be controlled by regulating the ratio between the supply of liquid nitrogen and the supply of carbon dioxide.

It was found that a cryogenic mixture or agent with a vaseline-like or cream-like consistency can be created by mixing the mixture of CO and liquid nitrogen (possibly liquid air) with ethanol.

The mixing sequences can be as illustrated in Figure 7, which shows that the end result is the same regardless of whether CO2 is first mixed in liquid nitrogen or air and ethanol is then added or a cold mixture with CO2 in solid form is made first and liquid nitrogen or air is subsequently added. The mixing will typically take place in a closed agitator reactor like that illustrated in Figure 8 which shows a closed container 251 with a concave base and top as well as an agitator 250 with a propeller. Other embodiments of the container and agitator may be used and flow breakers or similar may be fitted. An embodiment such as that shown in Figure 2 is also conceivable.

A test has been performed to establish which mixture ratio of the three ingredients

(LIN, CO2, EtOH) produces the desired consistency in the cryogenic mixture. The test will be described in the following as an example. In the example, the cryogenic mixture is produced from finely-crushed dry ice, ethanol and LIN (liquid N2). The mixture is produced by the dry ice being crushed and sieved so that the size of the particles is less than 0.85 mm. The crushed dry ice is weighed on scales and transferred to a cryo-container (insulated container). Absolute pure alcohol was cooled in advance by being poured into a beaker which was then lowered into a container with liquid N . The cooled alcohol was measured in a measuring cylinder and poured into the cryo-container. Liquid nitrogen was then weighed in a beaker on the scales and transferred to the cryo-container. The mixture was stirred with a wooden spatula. The temperature in the cryogenic mixture was read off using a temperature registration apparatus (Minitemp). It should be noted that the mixture can also be produced using liquid or gaseous CO2.

The results of the test are stated in Figure 9, Table 1 , which shows the weight of the ingredients in grammes and their percentage proportion of the mixture. The table also indicates the temperature of the mixture and a quantification of the consistency of the mixture.

Figure 10 shows a triangular diagram with a marked area which indicates composition of the mixture giving the desired consistency.

The mixture has a cream-like/vaseline-like consistency, even at -120°C. Tests show that in this connection nitrogen plays a role as a source of cold. It does not seem that liquid nitrogen as a chemical moderates the properties of the mixture. A mixture of EtOH and liquid nitrogen alone has been shown to become crystalline in a test. Basically, frozen alcohol was formed. This is ductile to a certain extent in a small range around freezing point, possibly because so-called denatured alcohol was used in this test so that the freezing point is not sharply defined. The addition of carbon dioxide is essential to achieve the special consistency described above. Without liquid nitrogen, the mixture does not become cold enough and the result is the known cold mixture of alcohol and CO2, the temperature of which is approximately -80°C. Without alcohol, a slurry of CO2 and N2 is achieved at the boiling point of the latter.

In the above example, absolute pure alcohol is used, as stated. This is pure ethanol and has its melting point at -117°C. A test was also carried out using ethanol with 2% MIBK (methyl isobutyl ketone), commonly called "iso-alcohol", "denatured alcohol" or "rectified alcohol". MIBK has a melting point of -80°C. The purpose of the test was to investigate whether the consistency of the mixture is different if ethanol with 2% MIBK added is used instead of pure ethanol. On the basis of the tests, no difference in consistency could be established between the mixture created using absolute alcohol and that created using rectified alcohol (iso-alcohol). Admittedly, the marking method used is coarse and imprecise, but any differences in the consistency of the mixture are assumed to be so small that they have no practical significance.

The mixture can be transported/stored in small doses or in syringes. The syringes should preferably have no constrictions towards the outlet. When used, the walls of the syringe can be warmed a little to cause the agent to flow when applied (not shown).

The cryogenic mixture can, on account of its stickiness, have other useful applications. One such application of the cryogenic mixture may be freeze-sealing of pipelines. This application is very useful in connection with water leaks in houses in which the stop cock may be located outside and may be defective or difficult to access after years without use. Prior art methods for freeze-sealing pipes require extensive formwork/sealing around the pipe so that the refrigerant does not flow away. With the present invention, a rag or similar will be sufficient in many cases to keep the refrigerant in place. In this application, the mixture will therefore represent a clear simplification in relation to prior art methods such as the CO2 pellets-based method described in DE 195 08 475.

Another application of the cryogenic mixture may be to cool samples, in particular laboratory samples, which require such treatment/preservation. The mixture described will be easier to transport in connection with fieldwork as splashing is eliminated and evaporation is reduced. Moreover, the refrigerant can be handled easily with a wooden spatula or similar without the major flashing which occurs when liquid nitrogen is to be scooped or poured from one container to another.

The use of the mixture is not limited to the above applications. Therefore, the mixture may be used within all specialist fields in which the properties of the mixture represent advantages versus other known refrigerants and methods for using them. The mixture is assumed to be able to replace dry ice in a number of areas with simple modifications of existing equipment and will result in rationalisation gains on account of its pumpability and its low weight/cold ratio. An application in which the mixture's good weight/cold properties can be utilised is in connection with the transportation/storage of frozen/refrigerated products such as foods.

Claims

Claims
1. A method for producing a cryogenic mixture containing carbon dioxide in solid form, where carbon dioxide is brought into contact with a cryogenic liquid in a contact chamber (4, 79, 118, 158, 218), and where the cryogenic liquid may be in an atomised and/or liquid state, characterised in that the carbon dioxide (5, 71, 119, 173, 211) is brought into the contact chamber at a level below the level of introducing the cryogenic liquid.
2. A method in accordance with claim 1 , where the cryogenic liquid is atomised by means of a nozzle (9, 80, 125, 178, 205), characterised in that the carbon dioxide is introduced to the contact chamber by means (5, 119, 173, 211 ) in atomised form at a level below the level at which the cryogenic liquid is atomised.
3. A method in accordance with claim 1 , where the cryogenic liquid is in liquid state, characterised in that the carbon dioxide is introduced into the chamber (79) via a line (71) at a level which is inside the cryogenic liquid
4. A method in accordance with claim 1 , characterised in that ethanol is added to the mixture.
5. A system for implementing the method in accordance with one or more of the above standing claims, comprising a contact chamber (4, 79, 118, 158, 218) into which the cryogenic liquid is introduced using an atomisation device or nozzle (9, 80, 125, 178, 205) and where the system further comprises a supply line or nozzle (5, 71 , 119, 173, 211 ), for introducing carbon dioxide to the chamber, characterised in that the carbon dioxide which is in a liquid state or in a gas state is introduced at a level which is below the level of introducing the cryogenic liquid.
6. A system in accordance with claim 5, characterised in that the carbon dioxide is introduced via line (71) into the chamber (79) at a level which is inside the cryogenic liquid.
7. A system in accordance with claims 5-6, characterised in that it comprises an agitator reactor (250) for mixing-in ethanol.
8. A system in accordance with claims 5-6, characterised in that it comprises a discharge device with a pump (40).
9. A cryogenic mixture consisting of a slurry comprising a cryogenic liquid and carbon dioxide in the form of particles, characterised in that the mixture further comprises ethanol.
10. A cryogenic mixture in accordance with claim 9, characterised in that the cryogenic liquid consists of liquid air.
11. A cryogenic mixture in accordance with claim 9, where the cryogenic liquid consists of liquid nitrogen, characterised in that the percentage weight of carbon dioxide in the mixture is 10-50%, the percentage weight of ethanol in the mixture is 20-60% and the percentage weight of nitrogen is 50-90%.
12. Application of the cryogenic mixture described in claims 9-11 for the removal of growths such as warts.
13. Application of the cryogenic mixture described in claims 9-11 for the temporary freeze-sealing of pipelines.
14. Application of the cryogenic mixture described in claims 9-11 for cooling or freezing products such as foods during transportation or storage.
15. Application of the cryogenic mixture described in claims 9-11 for cooling samples such as laboratory samples.
PCT/NO1999/000371 1998-12-11 1999-12-08 Method and system for the production of cryogenic mixtures and the application of such mixtures WO2000036351A1 (en)

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