Patent Grant
9605896
This application is a National Phase Entry of International Application No. PCT/IB2011/051879, filed on Apr. 28, 2011, which claims priority to French Patent Application Serial No. 1053340, filed on Apr. 29, 2010, both of which are incorporated by reference herein.
The present invention relates to a cryogenic-type process for treating natural gas, with the aim of removing at least some of the carbon dioxide that it contains, in which the hydrocarbons normally lost as a result of the cryogenic treatment are largely recovered. The invention also relates to a plant suitable for implementing this process.
Within the context of producing natural gas or liquefied natural gas, it is necessary to purify said natural gas, originating from deposits, of a certain number of contaminants, primarily acidic gases such as hydrogen sulphide (H2S) and carbon dioxide (CO2). In particular, carbon dioxide can represent a major part of the gaseous mixture originating from a deposit of natural gas, up to more than 70% (in molar concentration). Several processes are known in the field for making it possible to reduce the carbon dioxide content of the natural gas.
The most usual treatment is based on the use of amine solvents. This method makes possible a separation of the CO2 that is very selective vis-à-vis hydrocarbons; it makes it possible to lower the concentration of CO2 below the threshold of 50 ppm. But this method requires high energy to regenerate the solvent. As a result, it is unsuitable if the original gas has a high concentration of CO2. Moreover, the regeneration is virtually atmospheric, and requires a compression that consumes a lot of energy if a reinjection of the separated CO2 is envisaged (which is to be envisaged more and more routinely in view of the environmental issues).
Another type of treatment is based on the use of semipermeable membranes. The uses of these membranes for gases with an average CO2 content have developed significantly in the last few years. Membrane treatment is advantageous for significant concentrations of CO2 and for a certain range of “feed-to-retentate” partial pressure ratios. However, when the CO2 specifications are relatively low, the associated losses of methane can become considerable. It is also possible to provide several stages of membranes for concentrating the CO2 in the permeate, which makes it necessary to provide intermediate compressions of the permeate. The reinjection of the CO2, if sought, requires an additional compression, from the low pressure of the final permeate, which further increases the energy bill for this type of process.
Cryogenic processes constitute another type of treatment. The higher the concentration of CO2 in the original gas, the greater their advantage in terms of energy. An example of a cryogenic process is shown in U.S. Pat. No. 4,152,129. However, due to the possible crystallization of the CO2 and/or the critical conditions at the head of the column, such a process does not allow stringent CO2 requirements to be met. A finishing treatment, for example of the amines type, is therefore essential if a strict CO2 specification is required.
Certain variants of cryogenic treatment have been presented more recently, in particular the process called “CFZ” (“Controlled Freeze Zone”), the particular feature of which is to allow a crystallization of the CO2 in the problematic zone of the column, which makes it possible to envisage very high specifications with very low treatment temperatures (about −90° or even −110° C.). On this point, reference may be made for example to U.S. Pat. No. 4,533,372.
Another variant of cryogenic treatment has been developed by Cool Energy Limited. This process, called “CryoCell”, makes it possible, by means of a cryogenic separation step, to meet specifications of about 2 to 3% CO2, starting from a gas pretreated by cryogenic distillation, or directly for crude gases with an average concentration of CO2 (typically 25 to 35%). This process uses a liquefaction of the gas under pressure, then an expansion of the fluid which creates an intense cold and a partial crystallization of the CO2. The liquid and solid fractions are recovered in a flask designed for certain methods of application, keeping the bottom temperature in the liquid range. WO 2007/030888, WO 2008/095258 and WO 2009/144275 illustrate this technique.
Another variant of cryogenic treatment is constituted by the family of so-called “Ryan Holmes” processes. These processes, which make possible a fairly complete recovery of the C3+ hydrocarbons, use 3 or 4 distillation columns, depending on the nature of the gas, and as a result prove to be relatively complex and costly in terms of investment and consumption.
A drawback of these cryogenic methods is that they separate the components according to their volatility and therefore, with the liquid CO2, trap virtually all of the C3+ hydrocarbons contained in the natural gas. This constitutes a sometimes very great handicap depending on the composition of the gas. It is estimated that 8 to 15% by mass of the hydrocarbons are generally lost when a separation of the CO2 by distillation is implemented; furthermore, the majority of the hydrocarbons lost are hydrocarbons with an intermediate molar mass, therefore the most valuable.
WO 99/01707 relates to a variant of the process called “CFZ”, in which some of the stream of liquid CO2 recovered at the foot of the distillation column is expanded, then used to cool the natural gas before it enters the distillation column in two successive heat exchangers. Between the two heat exchangers, the stream of CO2 undergoes a gas/liquid separation, only the liquid portion being expanded then guided to the second heat exchanger (the gaseous portion being compressed before finally being removed). At the outlet of the second heat exchanger, another gas/liquid separation is provided: the gaseous phase is compressed before finally being removed, while the liquid phase provides a recovery of the condensates trapped in the stream of CO2.
This technique makes it possible to limit the hydrocarbon losses in the stream of liquid CO2 and could be applied to any process for cryogenically separating the CO2 which traps C3+ hydrocarbons in the liquid CO2. On the other hand, a drawback of the technique proposed in this document is that the composition of the stream (mostly CO2) in the successive heat exchangers varies, the stream becoming progressively richer in heavy fractions. This leads to an increased risk of crystallization, in particular of the paraffinic hydrocarbons, and particularly in the last heat exchanger in the cold cycle, the temperature of which is the lowest. This is why the document provides the alternative of a rectification column for the natural gas at the inlet of the plant in order to avoid these problems, so as to remove some of the heavy compounds upstream. This method is extremely complex and difficult to implement, since it requires an additional fractionation of all of the gas.
There is therefore a real need to develop a treatment that makes it possible to effectively reduce the hydrocarbon losses for these types of cryogenic separation of CO2, in a manner that is simple to implement.
In the first place the invention relates to a process for treating a natural gas containing carbon dioxide in which:
According to an embodiment:
According to an embodiment:
According to an embodiment:
According to an embodiment:
Another subject of the invention is a plant for treating natural gas containing carbon dioxide comprising:
According to an embodiment:
According to an embodiment:
According to an embodiment:
According to an embodiment, the line for the second liquid phase or, if applicable, the line for the third liquid phase, feeds a condensate stabilization unit, at the outlet of which a line for liquid phase rich in hydrocarbons and a line for gaseous phase rich in carbon dioxide are connected, said line for gaseous phase rich in carbon dioxide preferably feeding the second separation flask or, if applicable, the third separation flask. According to an embodiment, the line for the first gaseous phase, the line for the second gaseous phase and, if applicable, the line for the third gaseous phase feed compression means and join in an outlet line for carbon dioxide, said outlet line for carbon dioxide preferably being equipped with cooling means and preferably joining a line for non-recycled carbon dioxide originating from the line for liquid carbon dioxide, in order to form a line for final carbon dioxide.
According to an embodiment, the plant comprises:
The present invention makes it possible to overcome the drawbacks of the state of the art. More particularly it provides a treatment for natural gas whereby the carbon dioxide content can be significantly reduced. Said treatment is implemented while limiting the losses of hydrocarbons, in particular the C3+ compounds trapped with the stream of liquid carbon dioxide.
This is achieved, on the one hand, by recycling at least some of the carbon dioxide originating from a distillation (or more generally from a cryogenic process) and by using this carbon dioxide rich in C3+ as a refrigerant in an open refrigeration cycle in order to produce the frigories necessary for the cryogenic process, i.e. by making a heat exchange necessary (in several steps) between the carbon dioxide used in the open refrigeration cycle and the natural gas; on the other hand, by recovering the hydrocarbons trapped in the carbon dioxide from the open refrigeration cycle by a simple gas/liquid separation after the heat exchange with the natural gas, the composition of the stream of carbon dioxide from the open refrigeration cycle remaining constant during the different steps of said heat exchange.
According to certain particular embodiments, the invention also has one or preferably several of the advantageous characteristics listed below.
The invention will now be described in greater detail and in a non-limitative fashion in the following description. All pressures are given in absolute values. All percentages are given as molar values, unless otherwise indicated. The terms “upstream” and “downstream” refer to the direction of flow of the fluids in the plant.
Plant
With reference to
The feed line for natural gas 1 feeds (indirectly) a cryogenic separation unit 35. By “cryogenic separation unit” is meant a set of means capable of separating carbon dioxide from methane with a supply of cold at an operating temperature below or equal to −40° C.
Preferably, the cryogenic separation unit 35 is a distillation unit and, more precisely, in the embodiment shown, it is a standard distillation column equipped with a reboiler 32 at the foot. Heat exchange means between the feed line for natural gas 1 and the reboiler 32 are provided; the feed line for natural gas 1 opens into a gas/liquid separator 31. Two lines for natural gas 33, 34, namely a line for gaseous fraction 33 and a line for liquid fraction 34, are connected at the outlet of the gas/liquid separator 31.
The line for gaseous fraction 33 and the line for liquid fraction 34 respectively open into the cryogenic separation unit 35, at different stages. Each of these two lines is equipped with expansion means; moreover, the line for gaseous fraction 33 passes successively through a first heat exchanger 36 and a second heat exchanger 37 before passing through the above-mentioned expansion means and opening into the cryogenic separation unit 35.
A line for liquid carbon dioxide 10 is connected at the foot of the cryogenic separation unit 35, and a line for natural gas 39, feeding a reflux system, is connected at the head of the cryogenic separation unit 35. More precisely, the line for natural gas 39 passes through a third heat exchanger 38 then feeds a gas/liquid separator 40. At the outlet of this gas/liquid separator 40, there are connected, at the foot on the one hand, a reflux line 41 equipped with pumping means and returning to the cryogenic separation unit 35 and, at the head on the other hand, a line for purified natural gas 99.
The line for purified natural gas 99 passes successively through the third heat exchanger 38, the second heat exchanger 37 and the first heat exchanger 36. On the diagram, the streams passing through the heat exchangers from left to right give off heat and the streams passing through the heat exchangers from right to left absorb heat. Thus, the cooling of the heat exchangers 36, 37, 38 is ensured by the line for purified natural gas 99 and by the open refrigeration cycle described below and containing a stream rich in carbon dioxide. The line for purified natural gas 99 can be followed by recompression means.
If necessary, additional treatment means (and in particular additional deacidification means) can be provided from the line for purified natural gas 99, if a finishing purification of the gas is necessary. Such additional treatment means (generally situated downstream of fractionation means) can comprise means for treating the carbon dioxide according to any one of the techniques known in the state of the art (for example scrubbing with amine solvent, separation by membrane, etc.). This can prove useful in the case of a gas comprising a very high CO2 content.
Downstream, this line for purified natural gas 99 can be linked to the gas transport and/or distribution network, or feed a natural gas liquefaction unit. Moreover, the line for liquid carbon dioxide 10 divides into two branches, namely a line for non-recycled carbon dioxide 11 and a line for recycled carbon dioxide 12. The line for recycled carbon dioxide 12 passes through the first heat exchanger 36. Then it divides into two branches, namely a line for the first portion 13 and a line for the second portion 42. The line for the second portion 42 passes through the second heat exchanger 37 then itself divides into two branches, namely a line for the third portion 16 and a line for the fourth portion 19. The line for the fourth portion 19 passes through the third heat exchanger 38 a first time.
Expansion means 43 are provided on the line for the first portion 13, which then passes through the first heat exchanger 36, before feeding a first separation flask 47. Similarly, expansion means 45 are provided on the line for the third portion 16, which then passes through the second heat exchanger 37, before feeding a second separation flask 48. Finally, the line for the fourth portion 19 passes through the third heat exchanger 38 a second time, expansion means 46 being provided on the line for the fourth portion 19 between its two passages through the heat exchanger 38; finally, the line for the fourth portion 19 feeds a third separation flask 49.
The three separation flasks 47, 48, 49 are suitable for carrying out a liquid/gas separation and they are connected in cascade. In other words, at the outlet of the first separation flask 47 there are connected a line for the first gaseous phase 15 (at the head) and a line for the first liquid phase 14 (at the foot), said line for the first liquid phase 14 feeding the second separation flask 48 after having passed through expansion means 58; similarly, at the outlet of the second separation flask 48 there are connected a line for the second gaseous phase 18 (at the head) and a line for the second liquid phase 17 (at the foot), said line for the second liquid phase 17 feeding the third separation flask 49 after passing through expansion means 59. At the outlet of the third separation flask 49 there are connected a line for the third gaseous phase 23 (at the head) and a line for the third liquid phase 20 (at the foot).
The line for the third liquid phase 20 is equipped with pumping means and feeds a condensate stabilization unit 55. This condensate stabilization unit 55 can be a distillation column or, preferably, a distillation half-column, i.e. a column equipped with a reboiler 56 at the foot, but without a cooling and reflux system at the head.
At the outlet of the condensate stabilization unit 55 there are connected, on the one hand, a line for liquid phase rich in hydrocarbons 21 at the foot and a line for gaseous phase rich in carbon dioxide 22 at the head. The line for gaseous phase rich in carbon dioxide 22 returns to the third separation flask 49. The line for liquid phase rich in hydrocarbons 21 can open into treatment means (for example fractionation means) and/or means for storing condensates.
The line for the third gaseous phase 23 feeds a first compressor 50, at the outlet of which a first intermediate line 24 is connected. This first intermediate line 24 is joined by the line for the second gaseous phase 18, at the inlet of a second compressor 51. A second intermediate line 25 is connected at the outlet of the second compressor 51. This second intermediate line 25 is joined by the line for the first gaseous phase 15, at the inlet of a third compressor 52. An outlet line for carbon dioxide 26 is connected at the outlet of the third compressor 52.
The outlet line for carbon dioxide 26 is equipped with cooling means 53 and joins the line for non-recycled carbon dioxide 11 in order to form a line for final carbon dioxide 27. Pumping means can be provided on this. The line for final carbon dioxide 27 can open into downstream treatment means, for example means for injection into an underground formation.
Process
The natural gas which is treated by the process according to the invention is a gaseous mixture (which may contain a minority liquid fraction) comprising at least methane and CO2. Preferably, this gaseous mixture comprises at least 5% methane, and generally at least 10% or at least 15% or at least 20% methane or at least 25% methane (molar proportions relative to the natural gas). Preferably, this gaseous mixture comprises at least 10% CO2, and generally at least 20% CO2 or at least 30% CO2 or at least 40% CO2 or at least 50% CO2 or at least 60% CO2 or at least 70% CO2 (molar proportions relative to the natural gas). The natural gas also contains C3+ hydrocarbons (comprising at least 3 carbon atoms), preferably in a proportion by mass greater than or equal to 1% or 2% or 3% or 4% or 5% relative to the methane.
The natural gas optionally undergoes one or more preliminary treatments (in the pretreatment unit 57) with the aim of removing its solid contaminants or its liquid fraction, dehydrating it and/or pre-cooling it and/or reducing its hydrogen sulphide content. According to a preferred embodiment, the natural gas does not undergo any treatment with the specific aim of reducing its CO2 content prior to the cryogenic separation. In the embodiment shown, the natural gas is first cooled by heat exchange in the reboiler 32 of the cryogenic separation unit 35, then it undergoes a separation into a gaseous phase and a liquid phase in the gas/liquid separator 31. These two phases are introduced at different stages of the cryogenic separation unit 35, after an expansion.
A stream of liquid carbon dioxide is recovered at the foot of the cryogenic separation unit 35 in the line for liquid carbon dioxide 10. By “stream of carbon dioxide” is meant, within the context of the present description, a mixture comprising mostly CO2 and comprising a minority proportion of other compounds, in particular C3+ hydrocarbons.
The cooling needed to implement the cryogenic separation is ensured by the multi-stage open refrigeration cycle (at least two heat exchangers) which is fed by at least one part of the liquid carbon dioxide (stream of recycled carbon dioxide). In the embodiment shown, the refrigeration is carried out in the three heat exchangers 36, 37, 38 operating at decreasing temperatures, the heat exchangers 36 and 37 typically functioning at between −40° C. and 0° C., and the heat exchanger 38 typically functioning at between −60° C. and −45° C. (temperature of the refrigeration fluid after expansion). More precisely, the gaseous phase of the natural gas is cooled in the first heat exchanger 36 and the second heat exchanger 37.
The third heat exchanger 38 serves to cool the reflux of the cryogenic separation, i.e. to cool the stream of natural gas leaving the cryogenic separation unit 35 at the head. After this cooling, the stream of natural gas undergoes a separation in the gas/liquid separator 40 producing a stream of liquid phase which is pumped and returned to the cryogenic separation (reflux line 41), and a stream of purified natural gas which is recovered in the line for purified natural gas 99. In the embodiment shown, the stream of purified natural gas is heated in the three heat exchangers 38, 37, 36 successively, which makes it possible to recover the frigories available therein.
With regard to the functioning of the refrigeration cycle, the stream of recycled carbon dioxide undergoes a first cooling in the first heat exchanger 36, then it is divided into two liquid streams, namely a first portion and a second portion. The first portion is cooled by expansion, and it then returns to the first heat exchanger 36, in which it absorbs heat originating from the natural gas upstream of the cryogenic separation (and also heat originating from the stream of recycled carbon dioxide before expansion). The second portion undergoes a second cooling in the second heat exchanger 37, then it is divided into two liquid streams, namely a third portion and a fourth portion. The third portion is cooled by expansion, and it then returns to the second heat exchanger 37, in which it absorbs heat originating from the natural gas upstream of the cryogenic separation (and also heat originating from the stream of recycled carbon dioxide before expansion). The fourth portion undergoes a third cooling in the third heat exchanger 38, then it is cooled by expansion, and it then returns to the third heat exchanger 38, in which it absorbs heat originating from the natural gas at the level of the reflux of the cryogenic separation (and also heat originating from the stream of recycled carbon dioxide before expansion).
A first, second and third stream of heated carbon dioxide are therefore recovered at the outlet of the first, second and third heat exchanger 36, 37, 38 respectively. A significant part of the C3+ hydrocarbons contained in these streams is recovered by liquid/gas separation carried out on these streams. The liquid/gas separation is carried out by means of the first, second and third separation flasks 47, 48, 49, operating at decreasing pressures. The typical operating pressures are 10 bar to 40 bar for the separation flasks 47 and 48, and bar to 10 bar for the separation flask 49.
Each separation flask (respectively the first, second or third) produces a liquid phase (respectively the first, second or third) and a gaseous phase (respectively the first, second or third). The heavy hydrocarbons (essentially C4+) are mostly in the liquid phase. The first liquid phase is expanded and sent to the second separation flask 48 operating at a lower pressure than the first, and similarly the second liquid phase is expanded and sent to the third separation flask 49 operating at a lower pressure than the second. Thus, the heavy hydrocarbons trapped in the stream of CO2 tend to concentrate in the bottom of the third separation flask 49 functioning at the lowest pressure, where they can easily be recovered in the third liquid phase.
An additional purification step (stabilization of the condensates) can be implemented, as shown, by means of the condensate stabilization column 55. A liquid phase rich in hydrocarbons is recovered at the foot thereof and a gaseous phase rich in carbon dioxide, which is returned to the separation flask at the lowest pressure, is recovered at the head. Each gaseous phase originating from the different separation flasks, depleted of heavy hydrocarbons, is compressed; these different gaseous phases are mixed, then the mixture is cooled and advantageously combined with the part of the liquid CO2 that is not recycled for refrigeration. The stream of final liquid CO2 can be pumped and injected into an underground formation, or else be used or otherwise turned to account.
Variants
The plant according to the invention and the process according to the invention can be varied from the embodiment described above in several ways. For example, it is possible to provide an additional line for carbon dioxide 54 equipped with a valve reaching from the outlet line for carbon dioxide 26 (typically downstream of the cooling means 53) to the line for recycled carbon dioxide 12. This characteristic makes it possible to compensate for any lack of refrigerant in the multi-stage refrigeration system, making it possible to recycle part of the CO2 stream used for the refrigeration.
It is also possible to provide an additional line for hydrocarbons 44 (optionally equipped with a valve) connected at the outlet of the third separation flask 49 at the foot, equipped with pumping means and returning to the line for the fourth portion 19, upstream of the first passage into the third heat exchanger 38. Thus, part of the third liquid phase can be recycled in the CO2 stream used for the refrigeration. This characteristic makes it possible to avoid any risk of crystallization at the coldest point, while enriching the expanded stream passing through the third heat exchanger 38 with hydrocarbons.
Moreover, the above description was made in relation to an open refrigeration cycle with three stages. This is the variant that makes an optimum functioning of the system possible. However, it is also possible to provide a cycle with two stages or, alternatively, with four or more stages.
In the case of a system with two stages, compared with the above description: the third heat exchanger 38 and the third separation flask 49 are omitted, as are the associated components, namely the line for the fourth portion 19, the line for the third gaseous phase 23, the first compressor 50 and the first intermediate line 24. The line for the second liquid phase 17 then merges with the line for the third liquid phase 20 and therefore directly feeds the condensate stabilization unit 55.
In the case of a system with four or more stages, compared with the above description, at least one additional heat exchanger (suitable for cooling the natural gas upstream of the cryogenic separation unit or in the reflux of the latter) and at least one additional separation flask are added; at least one additional division of the line originating from the line for recycled carbon dioxide 12, equipped with expansion means and feeding the additional separation flask are also added; and, at the outlet of the (or of each) additional separation flask, there are provided an additional line for gaseous phase, associated with an additional compressor, and an additional line for liquid phase, equipped with expansion means and feeding the following separation flask (i.e. operating at lower pressure).
Moreover, in the embodiment shown, the line for natural gas 33 passing into the first heat exchanger 36 and the second heat exchanger 37 originates from the gas/liquid separator 31 and feeds the cryogenic separation unit 35; and the natural gas line 39 passing into the third heat exchanger 38 forms part of the reflux system of the cryogenic separation unit 35, since it originates from the head of the cryogenic separation unit 35 and feeds the gas/liquid separator 40 to which the reflux line 41 is connected at the foot. However, this distribution can be modified according to, on the one hand, the number of heat exchangers and, on the other hand, the operating parameters of the plant.
For example, the line for natural gas 33 originating from the gas/liquid separator 31 and feeding the cryogenic separation unit 35 can pass through a single heat exchanger (in particular if the refrigeration cycle comprises only two heat exchangers, in which case the second heat exchanger can be associated with the reflux system of the cryogenic separation unit 35). Conversely, this line for natural gas 33 can pass through more than two heat exchangers. Another variant is for all of the heat exchangers to be associated with the line for natural gas 33 originating from the gas/liquid separator 31 and feeding the cryogenic separation unit 35, in which case the reflux system of the cryogenic separation unit 35 is equipped with additional cooling means (replacing the third heat exchanger described above).
The cryogenic separation unit 35 can be a standard distillation column, suitable for the cryogenic separation of CO2, as described above. But it can also be a distillation column suitable for functioning under solids-forming conditions (“CFZ”-type column, such as described for example in U.S. Pat. No. 4,533,372 or WO 99/01707). The cryogenic separation unit 35 can also comprise liquefaction means suitable for liquefying the gas under pressure, means for expanding the fluid suitable for creating an intense cold and a partial crystallization of the CO2, and means for recovering a liquid fraction and a solid fraction comprising a flask suitable for maintaining a bottom temperature in the liquid range (“cryocell”-type distillation unit as described for example in WO 2007/030888, WO 2008/095258 and WO 2009/144275). In this case, it is advantageous to provide a stabilization column on the line for liquid carbon dioxide 10, suitable for recovering the light hydrocarbons (in particular methane) present in the liquid CO2.
The following example illustrates the invention without limiting it. A numerical simulation was carried out in order to characterize the functioning of a plant corresponding to
It is noted in this example that only 10% of the C7 hydrocarbons (representing the heavy paraffins) present in the liquid CO2 pass through the coldest heat exchanger. This illustrates the impact of the process, compared with the state of the art, where a cascade refrigeration cycle would collect all of the heavy paraffins in the coldest heat exchanger.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 53340 | Apr 2010 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/IB2011/051879 | 4/28/2011 | WO | 00 | 10/24/2012 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2011/135538 | 11/3/2011 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2826266 | Hachmuth et al. | Mar 1958 | A |
| 3130026 | Becker | Apr 1964 | A |
| 4152129 | Trentham et al. | May 1979 | A |
| 4318723 | Holmes et al. | Mar 1982 | A |
| 4441900 | Swallow | Apr 1984 | A |
| 4533372 | Valencia et al. | Aug 1985 | A |
| 4710213 | Sapper et al. | Dec 1987 | A |
| 5950453 | Bowen | Sep 1999 | A |
| 6053007 | Victory | Apr 2000 | A |
| 7124605 | Parro et al. | Oct 2006 | B2 |
| 7332145 | Chretien | Feb 2008 | B2 |
| 7678951 | Chretien | Mar 2010 | B2 |
| Entry |
|---|
| Haut R.C., et al.; “Development and Application of the Controlled-Freeze-Zone Process;” SPE Production of Engineering, The Society, vol. 4, No. 3, Aug. 1, 1989, pp. 265-271. |
| Number | Date | Country | |
|---|---|---|---|
| 20130036765 A1 | Feb 2013 | US |
