# US 2013/0152608 A1 · Cryogenic injection compositions, systems and methods for cryogenically modulating flow in a conduit

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- Number: US 2013/0152608 A1
- Document ID: US20130152608A1
- Status: Published application
- Kind: A1
- Application number: 13/715,909
- Filed: 2012-12-14
- Published: 2013-06-20
- Earliest claimed: 2011-12-16
- Assignees: Biofilm IP, LLC
- Inventors: Daniel X. Wray
- Web page: https://patentgrep.com/patent/US20130152608A1

## CPC

- F17C 13/04: Arrangement or mounting of valves (valves per se F16K {; snap-coupling of nipples F16L37/00})
- C09K 5/04: the change of state being from liquid to vapour or vice versa
- F16L 55/1003: {by introduction of paste, powder, particles, or the like}
- F16L 55/103: by temporarily freezing liquid sections in the pipe
- 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 (storing fluids in natural or artificial cavities or chambers in the earth B65G5/00; construction or assembling of bulk storage containers employing civil-engineering techniques E04H7/00; variable-capacity gas-holders F17B; liquefaction or refrigeration machines, plants, or systems F25)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- F16L: PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL

## Abstract

Provided are cryogenic injection compositions, methods and systems to introduce a cryogenic injection composition into a fluid within a conduit such that at least a portion of the temperature of the fluid is reduced to a temperature below which at least a portion of the fluid becomes a solid thereby reversibly plugging the conduit. Also provided are methods and systems for cooling or freezing a conduit and a fluid therein using a pressurized fluid cryogen as a thermal transfer fluid for controlled removal of thermal energy from a thermal conducting metal conduit and a fluid contained therein.

## Claims

### Claim 1

A cryogenic injection composition, comprising:
a fluid cryogen selected from among liquid nitrogen, liquid oxygen, liquid helium, liquid neon, liquid methane, liquid natural gas, liquid argon, liquid nitrous oxide, liquid carbon dioxide, liquid chlorofluorocarbons and combinations thereof;
a material selected from among carbon fibers, carbon nanostructures, graphite, fused silica, ground granite, aluminum silicon carbide, aluminum graphite, aluminum nitride, silicon nitride ceramic, polyacetylene fibers and combinations thereof having a size of 100 μm or less in an amount of at or about 0.05% to at or about 90% based on the weight of the injection composition; and
a plurality of particles having a diameter of 10 μm or less in an amount of at or about 0.05% to at or about 90% based on the weight of the injection composition, wherein at least a portion of the particles comprise a material having a specific heat capacity (cp) of at or about 0.7 J·g−1K−1 or greater.

### Claim 2 (depends on 1)

The cryogenic injection composition of claim 1, wherein the particles comprise a material that has a specific heat capacity (cp) of at or about 1 J·g−1K−1 to at or about 3 J·g−1K−1.

### Claim 3 (depends on 1)

The cryogenic injection composition of claim 1, wherein:
(a) the particles comprise a material that has a heat of fusion greater than 20 cal/g; or
(b) the particles comprise a material that has a heat of sublimation greater than 500 J·g−1; or
(c) both (a) and (b).

### Claim 4 (depends on 1)

The cryogenic injection composition of claim 1, wherein the particles comprise a material selected from among a metal, a glass, a metal-coated glass, an oxide, a plastic, a metal-coated plastic, a ceramic, corian, diatomaceous earth, fiberglass, foam glass, gypsum, magnesite, magnesia fibers, mineral fibers, nylon, perlite, foamed plastic, expanded polystyrene, polyurethane, porcelain, PTFE, PVC, pyrex glass, silica, fused silica, amorphous silica, vermiculite, crushed stone, and sand and combinations thereof.

### Claim 5 (depends on 1)

The cryogenic injection composition of claim 1, wherein:
(a) the particles comprise or are coated with frozen water or solid carbon dioxide; or
(b) the particles comprise a thermally conductive material; or
(c) both (a) and (b).

### Claim 6 (depends on 1)

The cryogenic injection composition of claim 1, wherein the particles are of a material or contain a material selected from among silver, gold, tungsten, zinc, copper, and iron and a combination thereof.

### Claim 7 (depends on 1)

The cryogenic injection composition of claim 1, wherein:
(a) the particles have a density or morphology for suspending the particles in the injection composition; or
(b) the particles are hollow; or
(c) the particles contain entrapped gas.

### Claim 8 (depends on 1)

The cryogenic injection composition of claim 1, wherein:
the particles have a diameter between 1 μm and 10 μm; or
the particles have a diameter less than 1000 nm.

### Claim 9 (depends on 1)

The cryogenic injection composition of claim 1, wherein the particles are of a shape selected from among cubes, flakes, granules, cylinders, rings, rods, needles, prisms, disks, fibers, pyramids, spheres, spheroids, prolate spheroids, oblate spheroids, ellipsoids, ovoids and random non-geometric shapes and combinations of these shapes.

### Claim 10 (depends on 1)

The cryogenic injection composition of claim 1, wherein the particles have a specific surface area in a range from at or about 0.1 m2/g to at or about 500 m2/g.

### Claim 11 (depends on 1)

The cryogenic injection composition of claim 1, wherein the carbon nanostructures are selected from among carbon nanotubes, carbon buckyballs, carbon nanoribbons and carbon nanowires and combinations thereof.

### Claim 12 (depends on 1)

The cryogenic injection composition of any one of claim 1, wherein:
the particles are contained within a frozen bead comprising a solvent; or
the particles are contained on the surface of a frozen bead comprising a solvent; or
the particles are on the surface of and contained within a frozen bead comprising a solvent.

### Claim 13 (depends on 1)

The cryogenic injection composition of claim 1, wherein the frozen bead further comprises a material having a high latent heat of fusion or high heat of sublimation.

### Claim 14 (depends on 12)

The cryogenic injection composition of claim 12, wherein the frozen bead further comprises a surface active agent selected from among an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, a non-ionic surfactant and a silicone surfactant or a combination thereof.

### Claim 15 (depends on 1)

The cryogenic injection composition of claim 1, further comprising a solvent or frozen particles of solvent in an amount from at or about 0.05% to at or about 85% based on the weight of the injection composition.

### Claim 16 (depends on 1)

The cryogenic injection composition of claim 1, further comprising a surfactant selected from among cationic, anionic, non-ionic, amphoteric, zwitterionic and silicone surfactants or a combination thereof in an amount from at or about 0.1% to at or about 25% based on the weight of the composition.

### Claim 17 (depends on 1)

A thermal transfer system for modulating thermal energy within a thermally conducting conduit containing a fluid, comprising:
a liquid cryogen thermal transfer fluid selected from among liquid nitrogen, liquid oxygen, liquid helium, liquid neon, liquid methane, liquid natural gas, liquid argon, liquid nitrous oxide, liquid carbon dioxide and combinations thereof;
a jacket in thermal communication with the conduit;
an injector for introducing a cryogen or a cryogenic injection composition of claim 1 into the fluid in the conduit;
a pump;
a refrigeration system; and
a circuit through which the liquid cryogen thermal transfer fluid flows, wherein the circuit passes through or is enveloped by the evaporator chamber of the refrigeration system.

### Claim 18 (depends on 17)

The thermal transfer system of claim 17, as depicted in FIG. 1.

### Claim 19 (depends on 17)

The thermal transfer system of claim 17, wherein the injector further comprises one or more of a flow rate meter, a flow-control metering valve, an isolation valve, an emergency shut-off valve, an over-pressure valve, a diverter valve, a heating unit, and a thermal monitoring device.

### Claim 20 (depends on 17)

The thermal transfer system of claim 17, further comprising a housing that contains the thermal transfer system and isolates the thermal transfer system from the environment, wherein the housing includes a projection, a depression, a connector or a hook or a combination thereof that can be engaged and manipulated by a robotic arm of a subsea vehicle, a remotely operated vehicle or a remotely operable manipulation device.

### Claim 21 (depends on 17)

The thermal transfer system of claim 17, further comprising a computer module for automation of the system.

### Claim 22 (depends on 1)

A method for freezing or precipitating at least a portion of a flowing fluid in a conduit, comprising:
introducing negative thermal energy into the flowing fluid within the conduit by injecting via an injector a cryogenic injection composition of claim 1 into the fluid in the pipeline.

### Claim 23 (depends on 17, 22)

The method of claim 22, wherein the injector is part of a thermal transfer system of claim 17.

### Claim 24 (depends on 22)

The method of claim 22, wherein:
(a) the particles of the cryogenic injection composition create nucleation sites in the flowing fluid and localized modulation in fluid temperature and viscosity; or
(b) the particles of the cryogenic injection composition result in the precipitation of at least some portion of the fluid within the conduit onto the wall of the conduit or onto previously frozen fluid attached to a wall of the conduit; or
(c) both (a) and (b).

### Claim 25 (depends on 17)

A method for temporarily preventing flow of fluid in a pipeline, comprising:
activating a thermal transfer system of claim 17 attached to the pipeline so that the jacket is in thermal contact with at least one portion of the pipeline and the injector when activated introduces a material into the fluid in the pipeline,
wherein the activated thermal transfer system and the injected material remove sufficient thermal energy to cause the fluid in the pipeline to form a reversible plug attached to an inner surface of the pipeline that prevents the fluid from flowing through the pipeline.

### Claim 26 (depends on 1, 25)

The method of claim 25, wherein the material injected into the fluid by the injector is a cryogenic injection composition of claim 1.

### Claim 27 (depends on 25)

The method of claim 25, wherein the injector is positioned so that the introduction of the material into the fluid cools the fluid before the fluid reaches the area of the pipeline to which the jacket of the thermal transfer system is attached.

### Claim 28 (depends on 25)

The method of claim 25, wherein the method further includes as a step increasing the temperature of the jacket so that it donates thermal energy to the pipeline, thereby at least partially melting the frozen plug and restoring flow of the fluid through the pipeline.

### Claim 29 (depends on 25)

The method of claim 25, wherein the fluid within the conduit comprises a hydrocarbon.

### Claim 30

A method for modulating flow of a fluid in a conduit, comprising:
activating a heat transfer system affixed to at least a portion of the conduit to remove thermal energy from the conduit and the fluid within the conduit; and
activating an injection device affixed to the conduit to introduce into the fluid within the conduit:
(a) a surfactant and cryogen; or
(b) surfactant and frozen beads comprising solvent and micron or submicron-size particles of a thermally conductive material having a thermal conductivity of at least 1 Watt/m° C.; or
(c) surfactant, cryogen and frozen beads comprising solvent and micron or submicron-size particles of a thermally conductive material having a thermal conductivity of at least 1 Watt/m° C.,
wherein activating the heat transfer system and the injection device results in a reduction in thermal energy in the flowing fluid within the conduit thereby reducing or eliminating the flow of fluid through the conduit by precipitating or freezing at least a portion of the fluid within the conduit.

### Claim 31 (depends on 30)

The method of claim 30, wherein the injection device introduces frozen beads into the fluid, wherein the frozen beads comprise a material having a high latent heat of fusion or a high heat of sublimation and the solvent is selected to have a melting point below the initial temperature of the fluid flowing within the conduit.

### Claim 32 (depends on 30)

The method of claim 30, wherein the surfactant is selected from among an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, a non-ionic surfactant and a silicone surfactant or a combination thereof.

### Claim 33 (depends on 30)

The method of claim 30, wherein the injection device introduces frozen beads into the fluid, wherein the frozen beads comprise particles of a thermally conductive material selected from among an oxide, graphite, carbon fibers, carbon nanostructures, aluminum silicon carbide, aluminum graphite, aluminum nitride, silicon nitride ceramic, polyacetylene fibers, copper, brass, beryllium, cadmium, cobalt, chrome nickel steel, gold, graphite, silver, iridium, iron, lead, magnesium, molybdenum, nickel, platinum, tin, tungsten, zinc, carbon steel, stainless steel and any combination or alloy thereof.

### Claim 34 (depends on 33)

The method of claim 33, wherein the carbon nanostructures are selected from among carbon nanotubes, carbon buckyballs, carbon nanoribbons and carbon nanowires and combinations thereof.

### Claim 35 (depends on 33)

The method of claim 33, wherein:
the particles have a shape selected from among cubes, flakes, granules, cylinders, rings, rods, needles, prisms, disks, fibers, pyramids, spheres, spheroids, prolate spheroids, oblate spheroids, ellipsoids, ovoids and random non-geometric shapes and combinations of these shapes; and
the particles are hollow or contain entrapped gas.

### Claim 36 (depends on 30)

The method of claim 30, wherein the heat transfer system comprises a detachable housing having side portions for enclosing a section of the conduit and end portions for engaging in sealing relation with opposite ends of the conduit section, the side and end portions defining a cooling chamber when assembled around the conduit, the cooling chamber being operable when filled by discharging cryogen from a refrigerant supply module into the chamber, which confines a volume of the cryogen at least a portion of which is in its liquid phase in intimate contact with the exterior surface of the section of conduit enclosed by the housing, the detachable housing including an inlet port for admitting the cryogen from the refrigerant supply module into the cooling chamber and an exhaust port for discharging the spent cryogen out of the cooling chamber, wherein the side portions of the detachable housing comprise a first cylindrical half shell and a second cylindrical half shell, the first and second shells each including longitudinally extending flange portions which cooperate to permit mating engagement of the shells to each other to form a closed structure, the end portions of the housing comprising radially extending flange portions for mating engagement with opposite ends of the conduit section enclosed by the housing.

### Claim 37 (depends on 36)

The method of claim 36, wherein the inlet port comprises a first inlet for admitting a flow of the cryogenic fluid into a first region of the cooling chamber and a second inlet for admitting a flow of the cryogen into a second region of the cooling chamber.

### Claim 38 (depends on 36)

The method of any one of claim 36, wherein the refrigerant supply module comprises:
a reservoir containing a supply of the cryogen, wherein the cryogen is selected from among liquid argon, liquid nitrogen, liquid oxygen, liquid helium, liquid neon, liquid methane, liquid natural gas, liquid nitrous oxide, liquid carbon dioxide, liquid freon and combinations thereof;
pipes or tubes for providing fluid communication between the reservoir and the inlet port;
valves for controlling the rate of flow of cryogen into the cooling chamber;
pipes or tubes for providing fluid communication between the reservoir and the injector device; and
valves for controlling the rate of flow of cryogen to the injector device.

### Claim 39 (depends on 30)

The method of claim 30, wherein the injector device comprises a first injector and a second injector, wherein the first injector injects a surfactant and a second injector injects a cryogenic fluid simultaneously or consecutively into the fluid within the conduit, wherein the cryogenic fluid comprises (a) a liquid cryogen or (b) a cryogenic injector composition comprising frozen beads containing particles of a thermally conductive material and a liquid cryogen.

### Claim 40 (depends on 30)

The method of claim 30, further comprising as a step increasing the temperature of the thermal transfer system to transfer thermal energy to the conduit, thereby at least partially melting the frozen plug and restoring flow of the fluid through the conduit.