US3400545A - Use of cold-carriers in liquefaction and regasification of gases - Google Patents

Use of cold-carriers in liquefaction and regasification of gases Download PDF

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US3400545A
US3400545A US55271266A US3400545A US 3400545 A US3400545 A US 3400545A US 55271266 A US55271266 A US 55271266A US 3400545 A US3400545 A US 3400545A
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carrier
cold
substance
liquid
particles
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Willem P Hendal
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Shell USA Inc
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Shell Oil Co
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Priority claimed from NL6512260A external-priority patent/NL6512260A/xx
Priority claimed from NL6514359A external-priority patent/NL6514359A/xx
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-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
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • 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
    • F17C9/00—Methods or apparatus for discharging liquefied or solidified gases from vessels not under pressure
    • F17C9/02—Methods or apparatus for discharging liquefied or solidified gases from vessels not under pressure with change of state, e.g. vaporisation
    • F17C9/04—Recovery of thermal energy
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/02—Pipe-line systems for gases or vapours
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0022—Hydrocarbons, e.g. natural gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0027—Oxides of carbon, e.g. CO2
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures 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
    • F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures 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 the cold stored in an external cryogenic component in an open refrigeration loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures 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
    • F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures 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 the cold stored in an external cryogenic component in an open refrigeration loop
    • F25J1/0223—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures 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 the cold stored in an external cryogenic component in an open refrigeration loop in combination with the subsequent re-vaporisation of the originally liquefied gas at a second location to produce the external cryogenic component
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures 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
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0275—Construction and layout of liquefaction equipments, e.g. valves, machines adapted for special use of the liquefaction unit, e.g. portable or transportable devices
    • F25J1/0277—Offshore use, e.g. during shipping
    • F25J1/0278—Unit being stationary, e.g. on floating barge or fixed platform
    • 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
    • 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
    • F17C2221/01—Pure fluids
    • F17C2221/013—Carbone dioxide
    • 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
    • F17C2221/033—Methane, e.g. natural gas, CNG, LNG, GNL, GNC, PLNG
    • 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
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0146—Two-phase
    • F17C2223/0153—Liquefied gas, e.g. LPG, GPL
    • F17C2223/0161—Liquefied gas, e.g. LPG, GPL cryogenic, e.g. LNG, GNL, PLNG
    • 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
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/03—Heat exchange with the fluid
    • 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
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0337—Heat exchange with the fluid by cooling
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/20—Processes or apparatus using other separation and/or other processing means using solidification of components
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/62—Ethane or ethylene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/64—Propane or propylene

Definitions

  • ABSTRACT OF THE DISCLOSURE Method of liquefying a natural gas by bringing the gas into heat exchange with a cooled cold-carrier which coldcarrier is formed by introducing a carrier liquid which remains fluid during the process of heat exchange and having a boiling point higher than a temperature which is just below ambient temperature, and having particles evenly dispersed the-rein of a substance distinct from the carrier fluid which, during the process of heat exchange, undergo a phase change, the said even dispersion being accomplished by the addition of an emulsifying agent for the system of carrier fluid and particles.
  • the invention relates to use of cold-carriers in liquefaction and regasification of gases, in particular of methane or natural gas.
  • the invention relates more in particular to such use of cold-carriers in the transportation or in peak-shaving of gases.
  • stage (t) At the production point the gas is cooled according to stage (a) by bringing it in heat exchange with the cold-carrier supplied according to stage (e).
  • the cold is thus passed back from the consumption point to the production point by means of a cold-carrier.
  • the production point is meant the place where the gas is liquefied for dispatch
  • the consumption point is meant the place where the liquefied gas is converted, on arrival, to the gaseous state for consumption.
  • the cold-carrier may also be used in the storage of gas, for example natural gas or methane, for peak-shaving purposes which may be described as follows.
  • gas for example natural gas or methane
  • this can be liquefied by passing it in heat exchange with the cold cold-carrier.
  • the methane or natural gas thus liquefied can then be stored in suitable heat-insulated reservoirs and in periods of large demand for natural gas or methane the liquefied methane or natural gas is regasified by passing it in heat exchange with the warmed up cold-carrier so that the cold-carrier is cooled down.
  • the cooled down cold-carrier is then stored temporarily in suitable heat-insulated reservoirs until a period of small demand for natural gas or methane arrives again.
  • the cold-carrier it is desirable for the cold-carrier to be able to absorb a large amount of cold per unit of volume, so that the reservoir space required for storing or transporting the cold-carrier can be small. To this end the cold-carrier should possess among others a relatively high specific heat and a relatively high specific gravity.
  • FIGURE 1 is a diagrammatic view of an arrangement according to the present invention.
  • FIGURE 2 is a schematic view of a detail of the arrangement of FIGURE 1.
  • natural gas may be transported in the liquid state between a production point and a consumption point.
  • the gas is introduced into a heat exchange at the gas producing area where it is cooled by contact with a cooled cold-carrier.
  • the liquefied gas is passed into a reservoir which is transported to the gas consuming area.
  • the liquefied natural gas is converted back to the gaseous state by bringing it into contact with a warm cold-carrier in a heat exchanger at the gas consumption area.
  • the natural gas is removed from the heat exchanger.
  • the cold-carrier consists of a cooled carrier liquid having solid particles evenly dispersed therein as will be explained further hereinbelow.
  • the cold-carrier cooled down as a result of the foregoing, is passed into a reservoir for transportation back to the production area where the cooled cold-carrier is brought into contact with the natural gas introduced into the heat exchanger at the production area.
  • a cold-carrier which is characterized by a carrierliquid not solidifying, i.e., remaining fluid, during the process of heat exchange and having a boiling point higher than, equal to or just below ambient temperature, i.e., a boiling point which is higher than a temperature which is just below ambient temperature, and containing particles of a substance, which, during the process of heat exchange, undergo a phase change.
  • the substance of the particles is of such a nature that, during the process of heat exchange, it entirely or partly melts or solidifies, said substance having a boiling point higher than, equal to, or just below ambient temperature.
  • the liquid of the particles which can be dispersed in the carrier-liquid, will solidify upon cooling, so that the heat of fusion thereof adds to the specific heat of the cold-carrier. Accordingly as more liquid solidifies, the effect will be larger.
  • the temperature of the coldcarrier remains constant. Heat is then transferred from the cold-carrier to the liquefied gas which is being regasified, without a simultaneous drop in temperature of the cold-carrier. This is favorable With respect to a high rate of the heat transfer.
  • the substance of the particles of the cold-carrier consists of water containing a freezing point depressant.
  • the temperature range in which the substance of the particles remains liquid is increased. This is favorable with respect to increasing the specific heat of the cold-carrier, because the specific heat of the particles in liquid condition is higher than that of the particles in solid condition.
  • Suitable freezing point depressants are ammonia, hydrochloric acid, an alcohol, a mixture of alcohols, a glycol, a mixture of glycols.
  • the cold-carrier can be converted into a stable emulsion.
  • a suspension is formed.
  • a manageable emulsion or suspension can also be obtained by stirring, for instance by means of a jet of liquid or with the aid of mechanical means.
  • a cold-carrier in which the particles, in addition, contain a solid capable of adsorbing or absorbing, i.e., picking up, the liquid of the particles.
  • a solid capable of adsorbing or absorbing, i.e., picking up, the liquid of the particles for this purpose use can be made of silica gel.
  • a heterogeneous cold-carrier of this type can be converted into a stable suspension.
  • a suitable liquid is for example isopentane. It is also possible to choose as a carrier-liquid a liquid containing a freezing point depressant. In this connection the eutectic mixtures of 88% isopentane and 12% normal pentane or 85% isopentane and 15% isohexane are attractive in view of their low melting point.
  • the cold-carrier is still pumpable if the dispersed particles contain not more than 50% of liquid based on the total volume of the cold-carrier.
  • the gas can be liquefied and be transported in a reservoir at a pressure of 1 atmosphere, but in many cases it may be desirable to employ a higher pressure.
  • the cold-carrier is heated up, for example to ambient temperature.
  • the heated-up cold-carrier can be used in the production point, for example in chemical industry. It is also possible for the heated-up cold carrier to be passed into a reservoir and thus to be transported to the consumption point, as illustrated in FIGURE 1. Generally, such transport will take place under a pressure of 1 atmosphere, but it is also possible to employ a higher pressure.
  • the cooled down cold-carrier can be transported from the consumption point to the production point in the same reservoir as that in which the liquefied gas has been transported in the opposite direction.
  • An advantage of this is that the reservoir always remains in cold condition. Owing to the high specific heat and the generally high specific weight of the cold-carrier according to the invention the reservoir that has been used for the transport of the liquefied gas is as a rule large enough for the transpoit of the cold cold-carrier in the opposite direction.
  • a cold-carrier in which the substance of the particles is of such a nature that, during the process of heat exchange, it shows one or more transitions between the solid-, the liquid-, or the vapor phase.
  • the temperature of the cold-carrier remains constant. Then heat is transferred from the cold-carrier to the liquefied gas which is being regasified or heat is transferred from the gas which is being liquefied to the coldcarrier without a simultaneous drop or rise in the temperature of the cold-carrier. This is favorable with respect to a high rate of heat transfer.
  • the temperature at which the substance of the particles displays a phase transition naturally in the first instance depends on the nature of said substance. Furthermore, to said substance a material may be added for lowering the temperature of the phase transition. As a result, more freedom on the point of the mode of operation of the process is obtained.
  • the substance of the particles consists of carbon dioxide.
  • carbon dioxide For the sublimation of carbon dioxide approximately 135 cal./g. are required, which is already considerably more than the heat of fusion of water (approximately cal./g.), so that a considerably larger amount of gas can be liquefied with a specific amount by weight of a cold-carrier comprising a carrierliquid containing particles of solid carbon dioxide than with the same amount by weight of a cold-carrier comprising a carrier-liquid containing particles of ice instead.
  • the ratio of the amount of useful load, i.e. the amount of liquefied methane or liquefied natural gas, to the amount of cold-carrier then becomes more favorable.
  • the coldcarrier comprises a carrier-liquid containing particles of ammonia.
  • the transition of solid ammonia into vapor requires approximately 400 cal./g.
  • a suitable substance for addition to the substance of the particles is methane.
  • the carbon dioxide which changes into vapor form
  • the carbon dioxide may then be used for a variety of purposes.
  • the bound carbon dioxide may be stored or be transported to the consumption point so that it, after liberation, may be used again as the substance of the particles in the coldcarrier.
  • Suitable compounds for binding the carbon dioxide are for instance bicarbonates or ammonium carbonate. These can be decomposed by little heat. It is advantageous if the ammonia, which during the cooling and liquefaction of the gas changes into vapor form, is bound and that in such a way that it may easily be decomposed again.
  • a suitable way of binding the ammonia is by catching the released ammonia in water.
  • the bound ammonia may be stored or be transported to the consumption point so that it, after liberation, may be used again as the substance of the particles in the cold-carrier.
  • Ammonia is valuable and may for example be further processed to fertilizer in the neighborhood of the production point of the methane or the natural gas.
  • the vapor that forms the substance for the particles of the cold-carrier in cooled condition should at the consumption point together with the carrier-liquid form a heterogeneous system.
  • a suitable process for obtaining this result is one by which during the heat exchange with the liquefied gas which is being regasified, first the carrierliquid of the cold-carrier is cooled and, next, the substance which is to form the particles is introduced in vapor form into the carrier-liquid, whereby said substance changes from the vapor phase into the liquidor into the solid phase so that an emulsion or a suspension, i.e., a non-homogeneous two-phase fiuid, is formed.
  • the temperature of the carrier-liquid of the cold-carrier will in generaly be so low, during the introduction in vapor form of the substance which is to form the particles, that condensation or solidification of that vapor occurs at once.
  • the introduction of said vapor into the carrier-liquid may take place for example by injecting the vapor into the carrier-liquid from one or more narrow openings and under pressure. Also, the vapor may already be cooled beforehand by heat exchange with the vaporizing natural gas or methane.
  • Various liquids can be used for the carrier-liquid of the cold-carrier.
  • An example is isopentane. It is also possible to select a liquid containing a freezing point depressant. In this connection the eutectic mixtures consisting of 88% isopentane and 12% normal pentane or 85% isopentane and 15% isohexane are attractive on account of their low melting points.
  • the cold-carrier In the liquefaction ofgas, such as natural gas or methane, the cold-carrier is raised in temperature, for instance to ambient temperature. If desired, the heatedup cold carrier may be used on the spot, for instance in a chemical industry. It is also possible for the components of the cold-carrier to be led to one or more reservoirs and thus to be transported to the consumption point.
  • the cooled down cold-carrier may be transported from the consumption point to the production point in the same reservoir as that in which the liquefied gas has been transported from the production point to the consumption point.
  • This has the advantage that the reservoir always remains cold. Owing to the high specific heat of the coldcarrier according to the inventon, the reservoir that has een used for the transport of the liquefied gas is more than sufficiently large for the transport of the coldcarrier in the opposite direction.
  • the reservoirs for the transport of the liquefied gas and/or cold-carrier may be built in or form part of a ship, a railway truck, a road truck or any other means of conveyance.
  • the method according to the invention may be used for the transportation or for peak-shaving of natural gas, methane, ethane, propane, butane or other gases.
  • a cold-carrier comprising said carrier-liquid in which the particles of said substance are present
  • these particles are evenly dispersed in the carrier-liquid. If this cold-carrier is prepared a long time before the cooling down of the cold-carrier takes place, and if the substance of the particles is in liquid condition, for the stabilization of the dispersion addition of an emulsifier will be required.
  • This addition of an emulsifier may have the disadvantage that the viscosity of the cold-carrier, in particular at low temperatures, will increase.
  • a carrier-liquid containing a sufiicient quantity of the dispersed substance will form only under elevated pressure and/ or with thorough stirring.
  • the substance for the particles is a liquid with a high vapor pressure
  • the vapor pressure of said substance will be considerably reduced, so that trouble encountered owing to vapor formation will be less.
  • the said substance is added to the carrier-liquid at the moment that the carrier-liquid has been cooled down to a temperature, equal to, or lower than the temperature at which said substance may, under the prevailing conditions, change into the liquid condition. Then, if the said substance is vapor, this will condense more easily when being brought into contact with the cooled down carrierliquid.
  • the said substance is added to the carrier-liquid at the moment that the carrierliquid has been cooled down to a temperature, equal to, or lower than the temperature at which said substance may, under the prevailing conditions, change into the solid condition.
  • the particles formed will hardly be in the liquid condition so that, even when a corrosive substance is used, the cold-carrier formed will have no corrosive properties and, hence the heat exchange apparatus used may be made of material meeting only low requirements as regards chemical resistance. In this case use of emulsifiers is not necessary.
  • vapors may be first converted to the liquid or the solid condition and then be added to the cooled down carrier-liquid.
  • At least some of the particles of the substance undergoing a phase change during the process of heat exchange are each enclosed within a wall.
  • the substance of the particles which absorbs or evolves the latent heat is present in enclosed spaces, this substance cannot come into contact with the walls of reservoirs, heat exchangers or other equipment. Also, any vapor that may have formed will remain confined within said enclosed spaces, so that no vaporization losses will occur. This results in a high degree of independence of both the boiling point and the corrosive properties of the substance of the particles. The degree of this indepedence may be controlled by the choice of the mechanical properties of the walls in which the particles are enclosed and the chemical resistance thereof.
  • the rate of heat transfer between the gas to be liquefied or to be regasified and the cold-carrier is determined partly by the rate of heat transfer through the walls of the particles.
  • the size of those walls as well as the shape thereof may be adapted to the requirements to be made in this respect.
  • a number of embodiments are of course possible. For instance a large number of hollow objects piled up in a reservoir in such a way that a good contact with the pumpable carrier-liquid is possible, may be used.
  • the particles may be advantageous to employ for the particles two or more different substances, for example a mixture of water and ammonia on the one hand and toluene on the other hand, which, each at a different temperature level can absorb or evolve latent heat, so that it is possible that the heat exchange with the gas to be liquefied or to be regasified takes place at various levels of constant or substantially constant temperature.
  • These different substances may together be enclosed within a Wall or walls. However, it is also possible for one or more of those substances or combinations thereof to be each enclosed by walls so that they are separate from each other and from the carrier-liquid. This may be desirable, for instance, if these substances interact physically or chemically.
  • the cold-carrier at least two reservoirs, each of which can contain, in addition to the carrier-liquid one of the said substances.
  • the contents of these reservoirs may then separately be subjected to heat exchange with the gas to be liquefied or to be regasified, for instance at different temperature levels.
  • the walls which enclose the substance or substances of the particles may be made of a metal with a high conductivity, for instance aluminum. This is promotive of a rapid heat transfer. It is also possible for these walls to be made of a polymer, for instance high-pressure polyethene. This material has the advantage of possessing a high chemical resistance.
  • the walls of the particles may also consist of two or more different materials, for instance of a plurality of layers of different material, of a coated material or a material containing reinforcing elements of another material; this may be of importance when the requirements concerning, for instance, the tightness, the strength and the chemical resistance cannot be met by one material without resort to a wall thickness that is unacceptably large in relation to the heat transfer.
  • a polymer may be used for obtaining a tight wall with a high chemical resistance, while the mechanical strength is increased with the aid of a layer of plate metal.
  • the material serving stiffening purposes need consist only of a grid or a gauze.
  • the substance of the particles may be contained in enclosed receptacles resembling capsules as illustrated in FIGURE 2.
  • Capsules enable a favorable ratio to be obtained between wall thickness and wall strength; they can be evenly distributed over the volume of a reservoir, while a close packing can also be obtained herewith in reservoirs which are shaped irregularly or which are provided on the inside with stiffening elements. They may also be suspended in the carrier-liquid and be introduced into the reservoir in suspended condition.
  • the carrierliquid may circulate between the gas and the substance of the particles which are enclosed within walls and may alternately be subjected to heat exchange therewith.
  • the carrier-liquid may contact the gas at different temperature levels and if more than one reservoir is employed, enter into heat exchange with said particles at different temperature levels.
  • the capsules may be suspended in the carrier-liquid during the process of heat exchange between the coldcarrier and the gas to be liquefied or regasified.
  • the cooled cold-carrier also may be transported from the consumption point to the production point in a reservoir in which liquefied gas has been transported to the consumption point. The advantage of this is that the reservoir always remains cold.
  • a method of transporting a gas selected from the group consisting of methane and natural gas, in liquefied condition comprising the following steps:
  • stage (f) cooling the gas at the production point according to stage (a) by bringing it in heat exchange with the coldcarrier supplied according to stage (0), the coldcarrier used being formed by introducing a carrierliquid which remains fluid during the process of heat exchange and: having a boiling point higher than a temperature which is just below ambient temperature, and having particles evenly dispersed therein of a substance, distinct from the carrier fluid which, during the process of heat exchange, undergo a phase change, the said even dispersion being accomplished by the addition of an emulsifying agent for the system of carrier fluid and particles.
  • step (t) The method of claim 12 in which the cold-carrier, after heating up according to step (t), is passed into a reservoir and is thus transported to the consumption point.
  • step (c) 16. The method of claim 12 in which the cold-carrier, after cooling down according to step (c), is transported from the consumption point to the production point in the same reservoir as that in which the liquefied gas has been transported from the production point to the consumption point.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Ocean & Marine Engineering (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Separation By Low-Temperature Treatments (AREA)
US55271266 1965-05-31 1966-05-25 Use of cold-carriers in liquefaction and regasification of gases Expired - Lifetime US3400545A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL6506843A NL6506843A (fr) 1965-05-31 1965-05-31
NL6512260A NL6512260A (fr) 1965-09-21 1965-09-21
NL6514359A NL6514359A (fr) 1965-11-05 1965-11-05

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US (1) US3400545A (fr)
JP (1) JPS4822892B1 (fr)
DE (1) DE1501749A1 (fr)
ES (1) ES327211A1 (fr)
FR (1) FR1481495A (fr)
GB (1) GB1082789A (fr)
SE (1) SE334634B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872682A (en) * 1974-03-18 1975-03-25 Northfield Freezing Systems In Closed system refrigeration or heat exchange
US4380907A (en) * 1980-07-14 1983-04-26 Cryoplants, Ltd. Method of boiling liquefied gas
US5214924A (en) * 1990-12-17 1993-06-01 Herco-Kuhltechnik Hermans & Co., Gmbh Method and apparatus for recovering solvents
US6298671B1 (en) 2000-06-14 2001-10-09 Bp Amoco Corporation Method for producing, transporting, offloading, storing and distributing natural gas to a marketplace
US20110297346A1 (en) * 2009-02-11 2011-12-08 Moses Minta Methods and Systems of Regenerative Heat Exchange
CN103899913A (zh) * 2014-03-24 2014-07-02 华南理工大学 一种利用余废热的移动式lng供气装置
FR3018111A1 (fr) * 2014-03-03 2015-09-04 Gdf Suez Procede et installation de transport et de liquefaction de gaz

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Publication number Priority date Publication date Assignee Title
FR2852590B1 (fr) * 2003-03-20 2005-06-17 Snecma Moteurs Alimentation en energie d'un terminal gazier a partir d'un navire transportant du gaz liquefie
CN109058767B (zh) * 2018-10-08 2023-10-03 江苏金合能源科技有限公司 一种核反应堆蒸汽存储与供热***

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US1472294A (en) * 1921-09-26 1923-10-30 Carbide & Carbon Chem Corp Process of purifying chlorine and other corrosive gases
US2449351A (en) * 1945-02-08 1948-09-14 Southern Steel Co Method of and apparatus for dispensing liquefied petroleum gas
US2496380A (en) * 1946-04-18 1950-02-07 Elliott Co Gas purifying method and apparatus
US2975604A (en) * 1956-05-07 1961-03-21 Little Inc A Method of distribution of condensable gases
US3018632A (en) * 1959-05-11 1962-01-30 Hydrocarbon Research Inc Cyclic process for transporting methane
US3034309A (en) * 1955-01-19 1962-05-15 Otto H Muck Method for transporting gas
US3224208A (en) * 1961-11-24 1965-12-21 Conch Int Methane Ltd Purification of natural gases
US3283521A (en) * 1960-03-09 1966-11-08 Conch Int Methane Ltd Separation of a gaseous mixture containing a solidifiable contaminant
US3306057A (en) * 1963-11-04 1967-02-28 Conch Int Methane Ltd Process for the cold separation of gaseous mixtures with solidliquid slurry heat exchange
US3331214A (en) * 1965-03-22 1967-07-18 Conch Int Methane Ltd Method for liquefying and storing natural gas and controlling the b.t.u. content

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1472294A (en) * 1921-09-26 1923-10-30 Carbide & Carbon Chem Corp Process of purifying chlorine and other corrosive gases
US2449351A (en) * 1945-02-08 1948-09-14 Southern Steel Co Method of and apparatus for dispensing liquefied petroleum gas
US2496380A (en) * 1946-04-18 1950-02-07 Elliott Co Gas purifying method and apparatus
US3034309A (en) * 1955-01-19 1962-05-15 Otto H Muck Method for transporting gas
US2975604A (en) * 1956-05-07 1961-03-21 Little Inc A Method of distribution of condensable gases
US3018632A (en) * 1959-05-11 1962-01-30 Hydrocarbon Research Inc Cyclic process for transporting methane
US3283521A (en) * 1960-03-09 1966-11-08 Conch Int Methane Ltd Separation of a gaseous mixture containing a solidifiable contaminant
US3224208A (en) * 1961-11-24 1965-12-21 Conch Int Methane Ltd Purification of natural gases
US3306057A (en) * 1963-11-04 1967-02-28 Conch Int Methane Ltd Process for the cold separation of gaseous mixtures with solidliquid slurry heat exchange
US3331214A (en) * 1965-03-22 1967-07-18 Conch Int Methane Ltd Method for liquefying and storing natural gas and controlling the b.t.u. content

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872682A (en) * 1974-03-18 1975-03-25 Northfield Freezing Systems In Closed system refrigeration or heat exchange
US4380907A (en) * 1980-07-14 1983-04-26 Cryoplants, Ltd. Method of boiling liquefied gas
US5214924A (en) * 1990-12-17 1993-06-01 Herco-Kuhltechnik Hermans & Co., Gmbh Method and apparatus for recovering solvents
US6298671B1 (en) 2000-06-14 2001-10-09 Bp Amoco Corporation Method for producing, transporting, offloading, storing and distributing natural gas to a marketplace
US20110297346A1 (en) * 2009-02-11 2011-12-08 Moses Minta Methods and Systems of Regenerative Heat Exchange
FR3018111A1 (fr) * 2014-03-03 2015-09-04 Gdf Suez Procede et installation de transport et de liquefaction de gaz
WO2015136182A3 (fr) * 2014-03-03 2015-12-17 Gdf Suez Procédé et installation de transport et de liquéfaction de gaz
CN106461318A (zh) * 2014-03-03 2017-02-22 法国Gdf Suez集团 输送和液化气体的方法和装置
CN103899913A (zh) * 2014-03-24 2014-07-02 华南理工大学 一种利用余废热的移动式lng供气装置

Also Published As

Publication number Publication date
GB1082789A (en) 1967-09-13
DE1501749A1 (de) 1969-11-27
JPS4822892B1 (fr) 1973-07-10
SE334634B (fr) 1971-05-03
FR1481495A (fr) 1967-05-19
ES327211A1 (es) 1967-07-16

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