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WO1994000713A1 - Procede et installation de transformation de gaz en hydrate - Google Patents

Procede et installation de transformation de gaz en hydrate Download PDF

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Publication number
WO1994000713A1
WO1994000713A1 PCT/NO1993/000102 NO9300102W WO9400713A1 WO 1994000713 A1 WO1994000713 A1 WO 1994000713A1 NO 9300102 W NO9300102 W NO 9300102W WO 9400713 A1 WO9400713 A1 WO 9400713A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrate
gas
chamber
temperature
medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NO1993/000102
Other languages
English (en)
Inventor
Tore Andreas Torp
Otto Skovholt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Equinor ASA
Original Assignee
Den Norske Stats Oljeselskap AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Den Norske Stats Oljeselskap AS filed Critical Den Norske Stats Oljeselskap AS
Priority to AU45153/93A priority Critical patent/AU4515393A/en
Priority to EP93915009A priority patent/EP0649508A1/fr
Publication of WO1994000713A1 publication Critical patent/WO1994000713A1/fr
Priority to FI946165A priority patent/FI946165A7/fi
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • 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
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]

Definitions

  • the present invention relates to a method for storing gas by generating hydrate.
  • the invention also relates to a method for subsequent extraction of gas from the generated hydrate.
  • the invention relates to a plant for storing and for extracting of gas.
  • the hydrate is generated in at least one chamber; as hydrate-forming gas is brought together with a finely distributed hydrate-generating liquid in the chamber at such temperature and pressure conditions that the hydrate will be formed. Later on an extraction of gas from said hydrate may be obtained by heating the hydrate.
  • Storing of gas is an efficient method both of adapting deliveries to variations in the market and to obtain a more efficient transportation of gas in pipes. Storage also secures against failure in gas supplies and is in this con ⁇ nection of the greatest importance when stores are located close to the consumers or close to the market.
  • Conventionally gas is stored in underground reservoirs such as emptied oil and gas reservoirs or in subterranean water magazines. Then a prerequisite is that extraordinary geological structures exist at the location where the store is to be placed. Storing of gas in subterranean salt strata has also been attempted, but then the salt deposits have to be present at the site where the gas is to be stored.
  • Hydrates can store large amounts of gas. In optimal conditions 1 m 3 of water may absorb approx. 180 3 natural gas, thus representing a considerable storage capacity. However, the storage capacity will vary according to the gas in question.
  • the object of the present invention is to provide a method and means for storing gas, especially, but not exclus ively, natural gas, in a place which can be chosen without many limitations as to choice of location, and without large investments for the control of pressure and temperature.
  • a further, important, object of the present invention i to produce a method for generating hydrate where the gas to be included in the hydrate and/or the liquid to be included in the hydrate, is not required to be cooled before the gas and/or the liquid is introduced into the generating chamber.
  • Further objects of the present invention are: to provide a method for temporary storage of gas near the consumer in reasonably priced, roughly hewn chambers in rock without special requirements regarding the surrounding rock, - to provide a method for storing gas by which it is not necessary to have any previous cooling or pressurising of th gas to be stored. to provide a method for storing and subsequent extrac ⁇ tion of gas by using naturally or artificially available col or hot water sources such as coolig water from gasworks or the like.
  • Fig. 1 illustrates the principles for a means for genera ing/storing/dissociating gas where the gas is fir converted to hydrate
  • fig. 2 shows a diagram which gives pressure/temperature ratios at the point of convertion from gas/liquid mixture to hydrate, for natural gas and water
  • an fig. 3 outlines how a series of caverns blasted from rock can be adapted and arranged for constructing a complete means according to the present invention
  • fig. 4 shows a means for generating hydrates for subse- quent transport or storage
  • fig. 5 shows a mobile "hydrate cannon", also according to the present invention.
  • the same reference numbers are used in all the drawings for components with the same function, where this is exped- ient.
  • the chamber 1 is a pressure chamber which is constructed to withstand the hydrate storing pressure concerned.
  • the temperature ought to lie between 0°C and the equilibrium curve for hydrate as shown in fig. 2, i.e. below ca. 15°C at the pressure concerned.
  • the pressure should preferably be about 30-50 barg and the temperature about 0- 12°C for natural gas.
  • the pressure/temperature region con ⁇ cerned is hatched in fig.
  • Forming of hydrates occurs when the chamber 1 is filled with gas 2 through a pipe 10 which is lead in at the top of the chamber.
  • the chamber 1 communicates directly with the gas which participates in the actual process. Neither pumps nor valves are required to bring the gas into or out of the chamber 1. This can be controlled exclusively by the level of pressure in the chamber 1.
  • the same pipe 10 is used during subsequent discharge of gas from the chamber.
  • a cold hydrate-forming liquid 3 with a tempera ⁇ ture of ca. 2° C is introduced into the chamber 1, and is spread and finely dispersed with the help of jets 4 which ar specially constructed to give finely dispersed drops of water.
  • Special jets might be used for this purpose, e.g. jets with mechanically vibrating elements, most likely with vibrations in the ultra sound region, in order to achieve small, mist-like drops which fall slowly down through the ga 2 in the chamber 1 when they are formed.
  • This medium 1 may be water and can if desired be introduced through the same pipe system as the hydrate-forming liquid 3 which also may be water.
  • this can if desired be supplied with certain additives, such as, for example, surfactants and crystallization nuclei particles.
  • additives such as, for example, surfactants and crystallization nuclei particles.
  • Such additives are intended to affect the size of the drops and the rate of crystallization and are therefore primarily of interest as additives to the hydrate-forming liquid.
  • the jets 6 which are specially equipped to attain a temperature regulation of the gas 2, have, however, a much greater transport capacity for liquid than the jets 4 and do not provide such a fine dispersement of the flow of liquid.
  • the supply pipes for the tempera ⁇ ture regulating medium 11 to jets 6 and supply pipes for the hydrate-forming liquid 3 to the jets 4 can be completely separate and that the liquids can even be different. This i not however a requirement, since in a simple and preferred embodiment a common pipe system and the same liquid are used through both jets. The latter embodiment is preferred preci sely because of its simplicity both with regard to construc ⁇ tion and running. Therefore both liquids are most often referred to as water.
  • a feature of the invention is that the cold water 3, 11 is sprayed right into the gas 2 which is taken directly and completely untreated from a supply system or a process sys ⁇ tem.
  • the hydrate 5 resembles snow or ice and is formed in the chamber 1 when cold water 3 comes in contact with cold gas 2.
  • the hydrate's specific gravity is a little lower tha that of water, and unused water collects at the bottom of th chamber 1.
  • a collection well 7 for superfluous liquid which is not included in the produc ⁇ tion of hydrate 5, and this extra liquid 11 can be made to circulate through a heat exchanger 8 which is placed outside the chamber, and from there the liquid, again cooled to abou 2°C, is sent back through a recirculation loop to the jets 4 and/or 6.
  • the amount of cooling water 11 necessary is about ten times the amount of water 3 which in the same time span is required to be supplied through the jets 4 for forming hydrate. It is therefore essential that that there are separate cooling water jets 6 which can supply larger amount of water than th hydrate-forming jets 4. All the water which is supplied and does not take part in the forming of hydrate, will gradually be collected at the bottom of the chamber l by drain pipe 7 and be circulated through the heat exchanger 8 for renewed cooling.
  • As external cooling medium 9 a natural source of cold water is preferrable or the heat exchanger can be con ⁇ nected to a refrigeration machine.
  • the shape of the store is important, since great height as mentioned in fig. 1, increases the time of contact betwee the cooled water and gas, and thereby increases the formatio of hydrate.
  • the storage condition i.e. hydrate form
  • the pressure is as given in the curve in fig. 2. It is only necessary to maintian the pressure in relation to the equilibrium diagram for the stored gases concerned. Such an equilibrium diagram for natural gas is shown in fig. 2 and as can be seen the tem ⁇ peratures in question will mean the storage pressure can be kept under ca. 80 barg.
  • a so-calle water curtain 12 can be used round storage chamber 1, to maintain the desired pressure conditions.
  • the effect of suc a, per se, known water curtain 12, is to increase the ground water pressure and thereby the prevailing pressure in the rock chamber 1, beyond the natural ground water pressure.
  • the amount of heat which has to be added in order to release gas corresponds to the amount of heat which was removed during the storing procedure.
  • the energy for heating can preferrably be taken from external, natural heat reservoirs, or the plant can be planned so that the store is located near a power station which in any case discharges cooling water, such as a gasworks or the like.
  • the pressure in the store it can be expedient to adjust to a lower level, in some cases right down to atmospheric pressure.
  • the means according to the present invention is special in that it is simple and requires very few control and steer ing systems. It is remarked that the gas which is to be stored is introduced into the storage rooms untreated and at the prevailing temperature conditions. A reduction in pres ⁇ sure can, however, be relevant if the pressure in the pipes is especially high. In this way large and expensive plants with necessary steering and control routines for cooling the gas to a suitable temperature are avoided. According to the present invention all cooling takes place inside the storage chamber 1 itself, and only by water 3 and 11 being circulate through the chamber and pervading the gass/hydrate. This gives an extremely simple and easily controlled transport of energy in the plant.
  • each chamber can have a length of 400-1000 i, a width o 15-20 m and a height of 40-60 m. Up to 20 such chambers can be included in one and the same plant.
  • the present invention is relevant both to a method for performing such production of hydrate as well as storing and discharge of gas, and a plant where this can be undertaken.
  • Fig. 4 shows an embodiment of the present invention where the hydrate 5 which is produced in the hydration cham ⁇ ber 1 does not necessarily remain in the chamber until the gas is to be used again, but where the hydrate 5 in the form of a loose, somewhat watery mass is taken out through an opening 14 near the bottom of the chamber 1.
  • the hydrate 5 can with advantage be driven out with the help of a transport screw 15 which is placed ob ⁇ liquely out through opening 14.
  • this transport screw 1 is in operation much of the water in the hydrate 5 runs back into the chamber 1, e.g. via the water discharge pipe 16 at the bottom of the transport screw 15, while the solids of th hydrate are driven out through the opening 14 of transport screw 15 to a suitable external store or a suitable transpor vehicle (not shown) .
  • a suitable external store or a suitable transpor vehicle not shown
  • a pressure regulator 18 at the gas intake 10 for ensuring that the gas 2 in the chamber 1 is maintained at a hydrate-forming pressure P even if the gas's process pressure out in the plant should differ somewhat fro this; as well as a pump 19 for circulating the temperature regulating medium 11.
  • the generating chambe can be constructed as a mobile or even a portable hydrate cannon 20.
  • the same reference numbers are used as earlier, and it will be understood that the hydrate 5 is produced continuously here inside the hydrate cannon 20 and is spraye continuously out of the same together with the superfluous cooling liquid 11 which enters via the jet 6.
  • hydrate 5 will not build up in the generating chamber 1, as hydrate 5 will immediately be carried out with the cooling medium 11 into a receiving system not shown which for exampl can filter the hydrate from the used cooling water 11 by means known per se.
  • the hydrate cannon 20 does not necessarily have to be held vertically, but can take any position desired.
  • hydrate cannon is shown equipped with a tapered mouth 23. This is primarily in order to ensure that the pressure inside the hydrate cannon 20 will be sufficien ⁇ tly high for the hydrate to be formed, even if the pressure of the surroundings is lower than the desired hydrate-formin pressure P.
  • a discharge apparatus is also shown, e.g. in the form of a passive or driven transport screw 25 at the opening. This, if required, is to ensure that hydrate 5 will not clog together at the discharge pipe 23 and make a barrier which cannot be bypassed.
  • the temperature regulating medium 11 When such a “hydrate cannon" is used, the temperature regulating medium 11 only functions as a cooling medium.
  • tapering 23 will not be necessary if the hydrate cannon 20 is used in a surrounding chamber 24 with regulated pressure.
  • Rapid cooling is also obtained because of direct contakt between the cold water and the hot gas, and at the same time the spray effect of the cold water causes strong movement in the gas which both expedites the cooling and hydrate generation in a simple and very effectiv manner.
  • the temperaure regulat ⁇ ing liquid 11 can be water with different additives, e.g. to adjust freezing point and/or crystallization capacity.
  • Seawater can also be used.
  • a suitable, freely chosen liquid can be used as the heating medium during the heating process.
  • both the hydrate-forming liquid and the temperature regulating medium are the same liquid and flow through a common pipe system.
  • the liquid and the medium do not have to be the same and neither do they have t be introduced from the same sources.
  • the jets for adding hydrate-forming liquid 3 and temper ature regulating medium 11 are different and have a differen construction even if the media are the same.
  • the most important principle of the invention is that all cooling, or at least the greater part of the necess ary cooling, of the gas which is to be included in the hyd ⁇ rate is undertaken by direct cooling as the volume of gas is sprayed through with forceful jets of water which has a temperature lower than the temperature at which the hydrate is formed.
  • This principle involves a series of important advantage such as rapid, effective, and inexpensive cooling, water is available as a possible transport medium for the hydrate produced, which can easily be collected by a filter as the cooling water flows through, and above all a simple method for extracting from the generating chamber all latent heat produced as the water and gas is changed to hydrate, is obtained.
  • This last mentioned feature is very important, as in previous plants there have been stoppages in hydrate production after a short time precisely because the latent heat released has not been removed quickly enough.
  • This cooling principle and heat transport principle will be just as useful for a chamber which is used exculusively for generating hydrate, but which is not intended to be used as a store for the ready made hydrate.
  • the main principle according to the present invention can be used both in connection with purely producing hydrate in a generating chamber and, as a principle for temporary storage of gas as the hydrate is kept stationary in the chamber where it is formed and not removed from this chamber at all in the form of hydrate, but is again changed to gas, primarily as a consequence of heating.
  • the hydrate can be produced directly in large tanks which either are an integral part of, or placed in large transport vehicles such as ships or trucks. It is thereby possible to transport the hydrate in light tanks which do not need to withstand higher pressure than from a few bar up to 10 bar, even if, as in the case of several gases, it must be produced at relatively high pressure such as up to 50 bar g. This has, as already mentioned, great positive effects on expense as well as security during the transport phase.
  • the generating chamber itself can be a small hydrate cannon wher the shape of the generating chamber together with the amount of gas and cooling liquid which passes through it gives a sufficiently increased pressure inside the cannon so that hydrate can be produced from all relevant gases, while the hydrate which is blown or washed out of the cannon can easily be separated from the cooling water and stored at low pres ⁇ sure.
  • a hydrate cannon operating inside a larger chamber which can be tightly closed and therefore maintain the necessary pressure for hydrate formation.
  • the hydrate cannon can simply be comprised of a cylindrical, cartridge-shaped hyd ⁇ rate cannon which is quite open without any narrowing of its open end, and with the necessary connections for gas, hyd ⁇ rate-forming liquid and cooling agent at its closed end.
  • the hydrate is generated in a chamber and remains there until the gas is needed again and is dissociated by heating the hydrate.
  • the hydrate is formed in the generating chamber and re ⁇ mains stationary in this chamber which, however, can be mobile. This means that the already generated hydrate can remain in the chamber which is transported to the place of consumption where the gas is released from the hydrate while the hydrate is still in the chamber where it was produced.
  • the gas is produced in a relatively small hydrate canno and is sprayed straight over into large storage tanks which can for example be perforated so that cooling water runs through. Then the hydrate can be transporte to the desired place in these transport tanks.
  • the hydrate can be produced in a chamber which operates exclusively as a generating chamber and be moved echan ically from the generating chamber to the desired trans port system for passage to the place of consumption.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de transformation en hydrate (5) d'un gaz à formation d'hydrate (2) à mesure que celui-ci se combine avec un liquide à formation d'hydrate (3) introduit dans le gaz sous forme finement dispersée, cela dans des conditions de pression et de température aptes à permettre la production d'hydrate. On a prévu un éventuel stockage et/ou transport ultérieurs dudit gaz (2) sous forme d'hydrate gazeux (5). Le processus de transformation s'effectue dans au moins une chambre (1), et comporte les étapes suivantes. On introduit le gaz (2) dans la chambre (1) à une pression apte à permettre la production d'hydrate, et de préférence égale à la pression de travail du gaz, ainsi qu'à une température aléatoire et de préférence égale à la température de travail du gaz. On introduit dans la partie remplie de gaz de ladite chambre (1) un milieu thermorégulateur (11) ayant de préférence une capacité calorifique élevée, cela à une température inférieure à la température de production d'hydrate dudit gaz (2), puis on extrait le milieu thermorégulateur (11) de la chambre (1) une fois qu'il est entré en contact direct avec ledit gaz (2) et ledit liquide finement dispersé (3) dans ladite chambre (1). Ainsi, le milieu emporte au moins une partie sensible de la chaleur latente dégagée au cours de la production dudit hydrate.
PCT/NO1993/000102 1992-06-29 1993-06-29 Procede et installation de transformation de gaz en hydrate Ceased WO1994000713A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU45153/93A AU4515393A (en) 1992-06-29 1993-06-29 Method and plant for converting gas into hydrate
EP93915009A EP0649508A1 (fr) 1992-06-29 1993-06-29 Procede et installation de transformation de gaz en hydrate
FI946165A FI946165A7 (fi) 1992-06-29 1994-12-29 Menetelmä ja laitteisto kaasun konvertoimiseksi hydraatiksi

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO922575A NO175656C (no) 1992-06-29 1992-06-29 Fremgangsmåte for lagring av gass, samt anlegg for gjennomföring av fremgangsmåten
NO922575 1992-06-29

Publications (1)

Publication Number Publication Date
WO1994000713A1 true WO1994000713A1 (fr) 1994-01-06

Family

ID=19895264

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NO1993/000102 Ceased WO1994000713A1 (fr) 1992-06-29 1993-06-29 Procede et installation de transformation de gaz en hydrate

Country Status (5)

Country Link
EP (1) EP0649508A1 (fr)
AU (1) AU4515393A (fr)
FI (1) FI946165A7 (fr)
NO (1) NO175656C (fr)
WO (1) WO1994000713A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996034227A1 (fr) * 1995-04-28 1996-10-31 Den Norske Stats Oljeselskap A.S Procede et installation de fabrication d'un produit sature en hydrocarbures et ce meme produit
WO1996034226A1 (fr) * 1995-04-28 1996-10-31 Den Norske Stats Oljeselskap A.S Procede et dispositif de fabrication d'un hydrocarbure, et produit ainsi fabrique
WO1997024550A1 (fr) * 1995-12-29 1997-07-10 Den Norske Stats Oljeselskap A/S Installation terminale destinee au stockage et a la regazeification de produit hydrocarbone et procede correspondant
US6653516B1 (en) 1999-03-15 2003-11-25 Mitsubishi Heavy Industries, Ltd. Production method for hydrate and device for proceeding the same
JP2016064947A (ja) * 2014-09-24 2016-04-28 株式会社Ihi オゾンハイドレート輸送容器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2399723A (en) * 1941-06-28 1946-05-07 Kellogg M W Co Gas hydration
US4920752A (en) * 1988-01-14 1990-05-01 Sulzer Brothers Limited Apparatus and process for storing hydrate-forming gaseous hydrocarbons
NO172080B (no) * 1990-01-29 1993-02-22 Gudmundsson Jon Steinar Framgangsmaate for framstilling av gasshydrater og apparattil utfoerelse av samme

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2399723A (en) * 1941-06-28 1946-05-07 Kellogg M W Co Gas hydration
US4920752A (en) * 1988-01-14 1990-05-01 Sulzer Brothers Limited Apparatus and process for storing hydrate-forming gaseous hydrocarbons
NO172080B (no) * 1990-01-29 1993-02-22 Gudmundsson Jon Steinar Framgangsmaate for framstilling av gasshydrater og apparattil utfoerelse av samme

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DERWENT'S ABSTRACT, No. 90-353271/47, week 9047; & SU,A,1535602 (AS KALA CHEM OIL), 15 January 1990 (15.01.90). *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996034227A1 (fr) * 1995-04-28 1996-10-31 Den Norske Stats Oljeselskap A.S Procede et installation de fabrication d'un produit sature en hydrocarbures et ce meme produit
WO1996034226A1 (fr) * 1995-04-28 1996-10-31 Den Norske Stats Oljeselskap A.S Procede et dispositif de fabrication d'un hydrocarbure, et produit ainsi fabrique
GB2315774A (en) * 1995-04-28 1998-02-11 Norske Stats Oljeselskap Method and plant for the manufacture of a hydrocarbon-saturated product as well as the product itself
GB2315773A (en) * 1995-04-28 1998-02-11 Norske Stats Oljeselskap Method and apparatus for the manufacture of a hydrocarbon product as well as the product itself
WO1997024550A1 (fr) * 1995-12-29 1997-07-10 Den Norske Stats Oljeselskap A/S Installation terminale destinee au stockage et a la regazeification de produit hydrocarbone et procede correspondant
US6653516B1 (en) 1999-03-15 2003-11-25 Mitsubishi Heavy Industries, Ltd. Production method for hydrate and device for proceeding the same
JP2016064947A (ja) * 2014-09-24 2016-04-28 株式会社Ihi オゾンハイドレート輸送容器

Also Published As

Publication number Publication date
EP0649508A1 (fr) 1995-04-26
FI946165A7 (fi) 1995-02-17
NO922575L (no) 1993-12-30
AU4515393A (en) 1994-01-24
NO175656B (fr) 1994-08-01
FI946165A0 (fi) 1994-12-29
NO175656C (no) 1994-11-09
NO922575D0 (no) 1992-06-29

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