• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The invention relates to a method for purifying and drying a stream of hydrofluoroolefin comprising a hydrofluoroolefin, water and impurities based on halogenated carbon compounds, characterized in that said stream is brought into contact with an adsorbent agent. .
    公开号:FR3041632A1
    申请号:FR1559002
    申请日:2015-09-24
    公开日:2017-03-31
    发明作者:Anne Pigamo；Dominique Deur-Bert；Laurent Wendlinger
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    PROCESS FOR PURIFYING AND DRYING A FLOW OF HYDROFLUOROOLEFINS
    FIELD OF THE INVENTION
    The present invention relates to a process for purifying and drying a stream of hydrofluoroolefins using an adsorbent. The present invention also relates to the use of an adsorbent for simultaneously drying and purifying a flow of hydrofluoroolefins.
    TECHNICAL BACKGROUND
    The Montreal Protocol for the Protection of the Ozone Layer led to the abandonment of the use of chlorofluorocarbons (CFCs). Substances that are less aggressive for the ozone layer, such as hydrofluorocarbons (HFCs) have replaced chlorofluorocarbons. However, these compounds contribute relatively significantly to the greenhouse effect. We have therefore looked for efficient substitution compounds with both a low ozone depletion potential (ODP) and a low GWP (global warming potential). Hydrofluoroolefins (HFOs) have been identified as desirable alternatives because of their low ODP and GWP values.
    Hydrofluorocarbons (HFCs) and in particular hydrofluoroolefins (HFOs), such as 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), are compounds known for their properties as refrigerants and heat-transfer fluids, extinguishers, propellants, foaming agents, blowing agents, gaseous dielectrics, polymerization medium or monomer, carrier fluids, abrasive agents, drying agents and fluids for power generation units. Unlike CFCs and HCFCs, which are potentially hazardous to the ozone layer, HFOs do not contain chlorine and therefore do not pose a problem for the ozone layer as part of their uses.
    It is known to produce hydrofluoroolefins or hydrofluorocarbons by fluorination of hydrochloro-olefins or hydrochlorocarbons in particular. This fluorination is generally a catalytic fluorination using hydrofluoric acid as fluorinating agent.
    This type of production process generally requires washing steps in columns provided for this purpose (water or basic aqueous solution) in order to eliminate certain undesirable products (residual HF in particular). These washing steps can lead to hydrofluoroolefin compositions comprising water and / or moisture.
    Therefore, the processes for making hydrofluoroolefin compositions generally comprise one or more drying steps after the washing steps, so as to render anhydrous or substantially anhydrous the streams that will be processed in the subsequent steps. Conventional methods used for drying are for example the use of a compound with dehydrating properties such as calcium chloride, magnesium sulphate, sodium sulphate, calcium sulphate, potassium hydroxide or oxide of calcium. Other well known methods involve the use of a molecular sieve, a silica gel or an activated carbon.
    In addition, the processes for producing hydrofluoroolefin compositions generally used lead to the formation of by-products (impurities) of hydrocarbon-type compounds which requires subsequent purification steps.
    JP2013241390 discloses a method for purifying a stream comprising 2,3,3,3-tetrafluoro-1-propene (1234yf) obtained by pyrolysis. WO 2013/115048 describes a process for purifying a flow of 1-chloro-3,3,3-trifluoropropene (1233zd) using a zeolite. In this document, separate washing and drying steps are carried out before the purification step can be carried out.
    There is therefore a need to simplify the process for producing hydrofluoroolefin compositions, for example by limiting the number of steps while maintaining an efficient process having a satisfactory yield, in particular for industrial applications.
    The present invention aims to propose a novel process for purifying and drying hydrofluoroolefin compositions which make it possible both to dry and to remove hydrocarbon-type impurities, in particular saturated halogenated hydrocarbons.
    SUMMARY OF THE INVENTION The invention relates first of all to a process for purifying and drying a stream of hydrofluoroolefin comprising a hydrofluoroolefin, water and impurities based on halogenated carbon compounds, characterized in that said stream is contacted with an adsorbent.
    According to one embodiment, the stream of hydrofluoroolefin comprising a hydrofluoroolefin, water and impurities comprises at least 50% by weight, preferably at least 70% by weight, preferably at least 90%, preferably at least 95% by weight, preferably at least 98% by weight, preferably at least 99% by weight of at least one hydrofluoroolefin, relative to the total weight of the stream comprising a hydrofluoroolefin, water and impurities.
    According to one embodiment of the invention, the adsorbent agent is a membrane and / or molecular sieves, preferably molecular sieves.
    Preferably, the molecular sieves have a pore opening with an average diameter ranging from 3 to 15 A, preferably from 5 to 10 A.
    Preferably, the molecular sieves are type X or A zeolites.
    According to one embodiment of the invention, the impurities based on halogenated carbon compounds comprise at least one compound chosen from chloromethane (F40), fluoromethane (F41), difluoromethane (F32), tetrafluoromethane (F14), trifluoromethane (F23), 1,1,1-trifluoroethane (F143a), 1,1-difluoroethane (F152a), pentafluoroethane (F125), chloropentafluoroethane (F115), 1,1,1,2-tetrafluoroethane ( F134a), pentafluoropropane (F245), monochlorotetrafluoropropene (F244), 1,3,3,3-tetrafluoropropene (F1234ze) isomer E or Z, 3,3,3-trifluoropropene (1243zf), 1,2, 3,3,3-pentafluoropropene (F1225ye), 3,3,3-trifluoropropyne, 1,3-dichloro-3,3-difluoropropene (F1232zd), 1,1-dichloro-3,3-difluoropropene (F1232za) ), 1,1-dichloro-1,3,3-trifluoropropane (F243fc), the cis isomer of 1-chloro-3,3,3-trifluoropropene (Z-1233zd).
    According to one embodiment of the invention, the stream of hydrofluoroolefin before contacting with the adsorbent comprises from 10 to 10,000 ppm by weight of water and / or the stream of hydrofluoroolefin before contact with the adsorbent agent comprises from 500 to 8000 mass ppm of impurities.
    According to a particular embodiment of the invention, the stream of hydrofluoroolefin is a stream of 1234yf. According to this embodiment, the adsorbent agent is preferably a type A zeolite having a pore diameter ranging from 3 A to 6 A. According to this embodiment, the impurities are preferably chosen from chloromethane (F40), tetrafluoromethane (F14), trifluoromethane (F23), 1,1-difluoroethane (F152a), alone or in admixture.
    According to another particular embodiment of the invention, the flow of hydrofluoroolefin is a stream of 1233zd, preferably a stream of 1233zd of configuration E. According to this embodiment, the adsorbent agent is preferably a zeolite of type X having a pore diameter ranging from 8 A to 12 A. According to this embodiment, the impurities are preferably chosen from pentafluoropropane (F245), 1,3,3,3-tetrafluoropropene (F1234ze), 1, 3-dichloro-3,3-difluoropropene (F1232zd), 1,1-dichloro-3,3-difluoropropene (F1232za), 1,1-dichloro-1,3,3-trifluoropropane (F243fc), alone or in mixture, preferably among pentafluoropropane (F245), 1,3,3,3-tetrafluoropropene (F1234ze), 1,3-dichloro-3,3-difluoropropene (F1232zd), 1,1-dichloro-3, 3-difluoropropene (F1232za), 1,1-dichloro-1,3,3-trifluoropropane (F243fc), 1-chloro-3,3,3-trifluoropropene Z (Z-1233zd), alone or as a mixture . The invention also relates to the use of an adsorbent for simultaneously drying and purifying a stream of hydrofluoroolefin comprising a hydrofluoroolefin, water and impurities based on halogenated carbon compounds.
    The process according to the invention is simple to implement, in particular on an industrial scale.
    The process according to the invention makes it possible to obtain a composition of hydrofluoroolefins of improved purity by a simplified process.
    The process according to the invention makes it possible to dry and purify a stream of hydrofluoroolefin in one and the same step.
    The process according to the invention is based on the surprising discovery that it is possible in a single step to dry and purify a stream of hydrofluoroolefin using an adsorbent. Indeed, until now, the drying and the purification were carried out in two distinct stages. It was generally recognized by those skilled in the art that in the presence of water or moisture, the adsorbent gorged itself with this water or moisture and became unusable for purification.
    DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows.
    The present invention provides a method for purifying and drying a hydrofluoroolefin comprising contacting a stream comprising a hydrofluoroolefin (species of interest), water and impurities based on halogenated compounds (other than species of interest), with an adsorbent.
    For the purposes of the present invention, the term "hydrofluoroolefin" is intended to mean a hydrocarbon compound comprising at least one unsaturation and at least one fluorine atom.
    According to one embodiment, the hydrofluoroolefin comprises at least 3 fluorine atoms.
    According to one embodiment, the hydrofluoroolefin is a compound of formula (I): wherein X, (i ranging from 1 to 6) independently of one another represents a hydrogen atom or a chlorine atom. or fluorine, it being understood that at least one of Xi represents a fluorine atom.
    According to one embodiment, the hydrofluoroolefin is chosen from 1-chloro-3,3,3-trifluoropropene (1233zd) or 2,3,3,3-tetrafluoropropene (1234yf).
    According to one embodiment of the invention, the stream comprising a hydrofluoroolefin (species of interest), water and impurities before contacting with the adsorbent agent comprises at least 50% by weight of at least a hydrofluoroolefin, preferably at least 70% by weight of at least one hydrofluoroolefin, more preferably at least 90% by weight of at least one hydrofluoroolefin, or even at least 95% by weight of at least one hydrofluoroolefin or at least at least 98% by weight of at least one hydrofluoroolefin or at least 99% by weight of at least one hydrofluoroolefin, relative to the total weight of the stream comprising a hydrofluoroolefin, water and impurities.
    "Impurity" means a species present in the stream comprising a hydrofluoroolefin, water and impurities in a minor amount, preferably in an amount of less than or equal to 5% by weight, relative to the weight total of said flow. The impurity (s) are different from the hydrofluoroolefin as a species of interest.
    The flow comprising a hydrofluoroolefin may be obtained by a method known to those skilled in the art, for example by a method as described in document US 2014/0296585 or WO 2015/104517.
    In the manufacture of the hydrofluoroolefins, washing steps are often necessary and cause the introduction of water or moisture into the stream of hydrofluoroolefin thus washed. In addition, by-products (impurities) are also obtained during the reaction to obtain the desired hydrofluoroolefin.
    According to one embodiment, the stream comprising a hydrofluoroolefin, water and impurities based on halogenated compounds comprises less than 5% by weight of water and impurities based on halogenated compounds, preferably less than 3%. by weight of water and impurities based on halogenated compounds, more preferably less than 2% by weight of water and impurities based on halogenated compounds, advantageously less than 1% by weight of water and of impurities based on halogenated compounds, with respect to the total weight of said flux.
    The impurities are generally based on halogenated, saturated or unsaturated compounds, for example based on halogenated compounds comprising one, two or three carbon atoms.
    Among the halogenated impurities containing one or two carbon atoms, mention may be made of chloromethane (F40), fluoromethane (F41), difluoromethane (F32), tetrafluoromethane (F14), trifluoromethane (F23), pentafluoroethane (F 125 ), chloropentafluoroethane (F115), 1,1,1,2-tetrafluoroethane (F134a), 1,1,1-trifluoroethane (F143a) and 1,1-difluoroethane (F152a). Other halogenated impurities containing 3 carbon atoms may also be formed, such as pentafluoropropane (F245), monochlorotetrafluoropropene (F244), 1,3,3,3-tetrafluoropropene (F1234ze), 3,3,3- trifluoropropene (1243zf), 1,2,3,3,3-pentafluoropropene (F1225ye), 3,3,3-trifluoropropyne, 1,3-dichloro-3,3-difluoropropene (F1232zd), -dichloro-3,3-difluoropropene (F1232za) and 1,1-dichloro-1,3,3-trifluoropropane (F243fc).
    When two isomers exist, one of the isomers may be considered as an impurity with respect to the other, in particular the cis isomer of 1-chloro-3,3,3-trifluoropropene may be mentioned in a flow containing predominantly trans 1-chloro-3,3,3-trifluoropropene or the cis isomer of 1,3,3,3-tetrafluoropropene in a stream containing predominantly trans-1,3,3,3-tetrafluoropropene.
    The method according to the invention makes it possible to obtain a stream both enriched in the hydrofluoroolefin, that is to say that the molar proportion of hydrofluoroolefin (product of interest) in the initial flow before purification and drying is less than the molar proportion of said hydrofluoroolefin in the stream after purification, and depleted of impurities.
    The flow comprising a hydrofluoroolefin, water and impurities based on halogenated compounds used in the process according to the invention may, before purification, comprise, for example: from 10 to 10,000 ppm by weight of water, preferably from 50 to 8000 ppm by weight of water, and from 500 to 8000 ppm by weight, preferably from 1000 to 6000 ppm by weight, of impurities based on halogenated compounds, relative to the total weight of the stream of hydrofluoroolefin.
    Preferably, the flow after purification and drying comprises from 5 to 100 ppm by weight of water and from 5 to 3000 ppm by weight of impurities. The water may for example be from a previous step of washing the stream of hydrofluoroolefins.
    The purification process according to the invention comprises contacting the stream comprising the hydrofluoroolefin, water and impurities with an adsorbent.
    Preferably, the adsorbent agent is chosen from a membrane and / or molecular sieves.
    Preferably, the adsorbent agent is chosen from molecular sieves.
    Molecular sieves, also called synthetic zeolites, are chemical compounds widely used in the industry as adsorbents, especially for drying gases or liquids. These are metal aluminosilicates which have a three-dimensional crystalline structure consisting of an assembly of tetrahedra. These tetrahedra are formed by four oxygen atoms which occupy the vertices, and which surround either a silicon atom or an aluminum atom placed in the center. These buildings usually contain cations to make the system electrically neutral, such as those derived from sodium, potassium or calcium.
    According to one embodiment of the invention, the adsorbent agent is a molecular sieve having a pore diameter ranging from 3 A to 15 A, preferably ranging from 5 A to 10 A.
    Suitable molecular sieves are preferably those of type A and type X.
    In the case of molecular sieves, called type A, the tetrahedra are assembled in such a way that they make up a truncated octahedron. These octahedra are themselves arranged in a simple cubic crystal structure, forming a network whose cavities have an approximate diameter of 11.5 A. These cavities are accessible through openings, or pores, which can be partially blocked by means of cations . When these cations are derived from sodium, these cavities have an aperture diameter of 4 A, and there is then a so-called "4 A" molecular sieve. The crystalline structure of such a sieve can be represented by the following chemical formula:
    Nai2 [(AIC> 2) i2 (SiC> 2) i2] .XH2C> wherein X which represents the number of water molecules belonging to the structure (water of crystallization) can reach 27, which represents 28.5% by weight of the anhydrous zeolite.
    The size of the openings (or pores) can be modified according to the different types of molecular sieve. Thus, by exchange of a large part of the sodium ions of a molecular sieve 4A with potassium ions, the molecular sieve 3 A is obtained, the pores of which have a diameter of approximately 3 A. The molecular sieve 5 A is produced by replacing the sodium ions with calcium ions, the effective pore diameter then being of the order of 5 A. The elementary cell of the zeolite X is a tetrahedron whose vertices are occupied by polyhedra of the same type as those present in zeolite A, each being connected to four other polyhedra through an octahedral substructure, formed by a double ring containing eight oxygen atoms. The center of each edge is always occupied by an oxygen atom, while the atoms of silicon and aluminum occupy the different vertices of the polyhedra. The empirical formula has a structure of Na88Al88 Si-10O4> 384.220H2O.
    According to one embodiment of the invention, the stream of hydrofluoroolefin is a stream of 2,3,3,3-tetrafluoropropene (1234yf) and the adsorbent is a type A zeolite having a pore diameter of 3 A to 6 A.
    According to this embodiment, the invention makes it possible to eliminate, in one and the same step, moisture or water as well as organic impurities, such as chloromethane (F40), tetrafluoromethane (F14), trifluoromethane ( F23) or 1,1-difluoroethane (F152a) contained in the initial flow.
    According to this embodiment, the initial hydrofluoroolefin stream may comprise from 90% to 99% by weight of 12,3,3,3-tetrafluoropropene (1234yf), from 0.05 to 3% by weight of water, from From 0.05% to 3% by weight of chloromethane (F40), from 0.05% to 3% by weight of tetrafluoromethane (F14), from 0.05% to 3% by weight of trifluoromethane (F23) and from 0, From 5% to 3% by weight of 1,1-difluoroethane (F152a), based on the total weight of the hydrofluoroolefin stream.
    According to another embodiment of the invention, the flow of hydrofluoroolefin is a flow of 1-chloro-3,3,3-trifluoropropene (1233zd) and the adsorbent is a type X zeolite having a pore diameter ranging from 8 A to 12 A.
    According to an embodiment, the invention makes it possible to eliminate in a single step, moisture or water and also organic impurities, such as pentafluoropropane (F245), 1,3,3,3- tetrafluoropropene (F1234ze), 1,3-dichloro-3,3-difluoropropene (F1232zd), 1,1-dichloro-3,3-difluoropropene (F1232za) or 1,1-dichloro-1,3,3 trifluoropropane (F243fc).
    Preferably, the flow of 1-chloro-3,3,3-trifluoropropene is a flow of 1-chloro-3,3,3-trifluoropropene E configuration (1233zd E). In this case, the 1-chloro-3,3,3-trifluoropropene configuration Z (1233zd Z) can be considered an impurity, completing the list of impurities mentioned above.
    According to this embodiment, the initial hydrofluoroolefin flow (before the purification and drying process) may comprise from 90% to 99% by weight of 1-chloro-3,3,3-trifluoropropene of configuration E (1233zd E), from 0.05 to 3% by weight of water, from 1% to 6% by weight of Z-configuration 1-chloro-3,3,3-trifluoropropene (1233Zd Z), from 0.1% to 2% by weight, weight of 1,3-dichloro-3,3-difluoropropene (F1232zd), from 0.05% to 2% by weight of pentafluoropropane (F245) and from 0.05% to 2% by weight of 1,1-dichloro- 3,3-difluoropropene (F1232za), based on the total weight of the hydrofluoroolefin stream.
    According to one embodiment of the invention, the contacting step is carried out at a temperature ranging from -20 ° C. to + 80 ° C., preferably from + 10 ° C. to + 40 ° C., and pressure of 100 to 2200 kPa, preferably at atmospheric pressure.
    According to one embodiment, the method according to the invention is implemented in the gas phase.
    The present invention also relates to the use of an adsorbent agent as defined above for simultaneously drying and purifying a flow of hydrofluoroolefins.
    The characteristics detailed above with respect to the process according to the invention apply to the use according to the invention.
    EXAMPLES
    Example 1: Purification of a stream of 1234vf 20g of NK20® zeolite (type A having a pore diameter of 5A) available from CECA are loaded into a reactor having a length of 70 cm and an inside diameter of 1 6 cm; the 20 g of zeolite cover about 16 cm of the height of the reactor. The zeolite is dried beforehand under an inert gas at a flow rate of 20 l / h at 120 ° C. for 10 hours.
    The purification test is then carried out at room temperature (25 ° C.) and at atmospheric pressure with a contact time of about 100 seconds and a space velocity of 0.3 cm / s.
    Several gaseous streams were tested and compared: Flux 1: 1234yf distilled (purity 98.64%) doped with 6000 ppm by mass of F40. Flux 2: crude product comprising 94.42% by weight of 1234yf and 245cb further comprising 8300 ppm by weight of F40. Stream 3: crude product comprising 94.55% by weight of 1234yf and 245cb further comprising 5700 ppm by weight of F40, said crude product undergoing a bubbling step in water at 18 ° C to obtain a flow gas saturated with water (approximately 5000 ppm by weight of water calculated from the saturation vapor pressure). Stream 4: crude product comprising 94.55% by weight of 1234yf and 245cb further comprising 4700 ppm by weight of F40, said crude product being bubbled in water at 25 ° C. in order to obtain a flow gas saturated with water (approximately 8000 ppm by weight of water calculated from the saturation vapor pressure).
    For each test, the contact time was maintained until saturation of the zeolite. The impurities F40 were removed immediately from the gas stream to reach a content of less than 20 mass ppm. Once the zeolite is saturated, the F40 content of the flux increases again since said F40 can no longer be removed.
    This type of test makes it possible to evaluate the adsorption capacity of the zeolite, expressed in g of F40 per 100 g of zeolite loaded in the reactor.
    The results are shown in Table 1 below.
    Table 1: Adsorption Capacity of the NK20® Molecular Sieve
    The results in Table 1 show that streams 3 and 4 comprising amounts of moisture can be purified, as well as streams 1 and 2 without detectable moisture. Indeed, the absorption capacity is respectively 4.0% and 3.3%, which effectively allows a satisfactory purification of organic impurities.
    Example 2 Purification of a stream of 1233zd (configuration E)
    Assays were performed using 50 g of molecular sieve and a 1233 zd E crude stream was contacted with the zeolite for 1 hour at a pressure of 0.5 bar and at room temperature (25 ° C). The compositions of the input and output streams were compared. The molar proportions in each of the constituents were determined by gas chromatographic analysis, which is well known to those skilled in the art.
    Table 2 below illustrates the results obtained with a G5 zeolite (type X having a pore diameter of 10 A) available from CECA. A test was also carried out with a flow of 1233Zd E which was previously bubbled into water at 25 ° C.
    Table 2: Purification of 1233zd E
    Table 2 above shows that a 1233zd stream can be purified using an adsorbent, such as a Type X zeolite.
    Surprisingly, the inventors have discovered that the test with zeolite G5 where the flow of 1233zd E comprises water (or moisture) makes it possible to purify the flow and thus obtain a flow of 1233zd E having a improved purity.
    Table 2 also shows that the process according to the invention makes it possible to separate two isomers, such as F1233zd E and F1233zd Z.
    Table 2 also shows that the process according to the invention makes it possible to eliminate the F1234ze Z while the F1234ze E remains intact and present in the F1233zd stream at the outlet.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    A process for purifying and drying a stream of hydrofluoroolefin comprising a hydrofluoroolefin, water and impurities based on halogenated carbon compounds, characterized in that said stream is contacted with an adsorbent.
    [2" id="c-fr-0002]
    The process according to claim 1, wherein the stream of hydrofluoroolefin comprising a hydrofluoroolefin, water and impurities comprises at least 50% by weight, preferably at least 70% by weight, preferably at least 90%, preferably at least 95% by weight, preferably at least 98% by weight, preferably at least 99% by weight of at least one hydrofluoroolefin, relative to the total weight of the stream comprising a hydrofluoroolefin, water and impurities.
    [3" id="c-fr-0003]
    3. The method of claim 1 or 2, wherein the adsorbent is a membrane and / or molecular sieves, preferably molecular sieves.
    [4" id="c-fr-0004]
    4. The process according to claim 3, wherein the molecular sieves have an average pore opening of 3 to 15 A, preferably 5 to 10 A.
    [5" id="c-fr-0005]
    The method of claim 3 or claim 4, wherein the molecular sieves are X or A type zeolites.
    [6" id="c-fr-0006]
    6. Method according to one of claims 1 to 5, wherein the impurities based on halogenated carbon compounds comprise at least one compound selected from chloromethane (F40), fluoromethane (F41), difluoromethane (F32), tetrafluoromethane (F14), trifluoromethane (F23), 1,1,1-trifluoroethane (F143a), 1,1-difluoroethane (F152a), pentafluoroethane (F125), chloropentafluoroethane (F115), 1,1,1 , 2-tetrafluoroethane (F134a), pentafluoropropane (F245), monochlorotetrafluoropropene (F244), 1,3,3,3-tetrafluoropropene (F1234ze) isomer E or Z, 3,3,3-trifluoropropene (1243zf), 1,2,3,3,3-pentafluoropropene (F1225ye), 3,3,3-trifluoropropyne, 1,3-dichloro-3,3-difluoropropene (F1232zd), 1,1-dichloro-3, 3-difluoropropene (F1232za), 1,1-dichloro-1,3,3-trifluoropropane (F243fc), the cis isomer of 1-chloro-3,3,3-trifluoropropene (Z-1233zd).
    [7" id="c-fr-0007]
    7. Method according to one of claims 1 to 6, wherein the flow of hydrofluoroolefin is a flow of 1234yf.
    [8" id="c-fr-0008]
    The process according to claim 7, wherein the adsorbent is a type A zeolite having a pore diameter ranging from 3 A to 6 A.
    [9" id="c-fr-0009]
    9. The method of claim 7 or 8, wherein the impurities are selected from chloromethane (F40), tetrafluoromethane (F14), trifluoromethane (F23), 1,1-difluoroethane (F152a), alone or in combination. mixed.
    [10" id="c-fr-0010]
    10. Method according to one of claims 1 to 6, wherein the flow of hydrofluoroolefin is a flow of 1233zd, preferably a stream of 1233zd configuration E.
    [11" id="c-fr-0011]
    The method of claim 10, wherein the adsorbent is an X-type zeolite having a pore diameter of from 8A to 12A.
    [12" id="c-fr-0012]
    The process according to claim 10 or 11, wherein the impurities are selected from pentafluoropropane (F245), 1,3,3,3-tetrafluoropropene (F1234ze), 1,3-dichloro-3,3-difluoropropene (F1232zd), 1,1-dichloro-3,3-difluoropropene (F1232za), 1,1-dichloro-1,3,3-trifluoropropane (F243fc), alone or in a mixture, preferably from pentafluoropropane (F245), 1, 3,3,3-tetrafluoropropene (F1234ze), 1,3-dichloro-3,3-difluoropropene (F1232zd), 1,1-dichloro-3,3-difluoropropene (F1232za), 1,1-dichloro-1, 3,3-trifluoropropane (F243fc), 1-chloro-3,3,3-trifluoropropene Z (Z-1233zd) configuration, alone or in admixture.
    [13" id="c-fr-0013]
    13. Method according to one of claims 1 to 12, wherein the stream of hydrofluoroolefin before contacting the adsorbent comprises from 10 to 10000 ppm by weight of water.
    [14" id="c-fr-0014]
    14. Process according to one of claims 1 to 13, wherein the flow of hydrofluoroolefin before contacting with the adsorbent agent comprises from 500 to 8000 mass ppm of impurities.
    [15" id="c-fr-0015]
    15. Use of an adsorbent for simultaneously drying and purifying a stream of hydrofluoroolefin comprising a hydrofluoroolefin, water and impurities based on halogenated carbon compounds.
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    同族专利:
    公开号 | 公开日
    US10633312B2|2020-04-28|
    CN108026003A|2018-05-11|
    JP2018528223A|2018-09-27|
    JP2021176882A|2021-11-11|
    US20180346396A1|2018-12-06|
    WO2017050686A1|2017-03-30|
    FR3041632B1|2020-01-10|
    EP3353140A1|2018-08-01|
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    WO2015125877A1|2014-02-20|2015-08-27|旭硝子株式会社|Method for purifying fluid that includes trifluoroethylene, and method for producing trifluoroethylene|FR3086287A1|2018-09-26|2020-03-27|Arkema France|STABILIZATION OF 1-CHLORO-3,3,3-TRIFLUOROPROPENE|
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    FR3094714B1|2019-04-03|2021-04-23|Arkema France|Process for the purification of 1-chloro-3,3,3-trifluoropropene|
    法律状态:
    2016-08-16| PLFP| Fee payment|Year of fee payment: 2 |
    2017-03-31| PLSC| Publication of the preliminary search report|Effective date: 20170331 |
    2017-08-10| PLFP| Fee payment|Year of fee payment: 3 |
    2018-08-13| PLFP| Fee payment|Year of fee payment: 4 |
    2019-08-15| PLFP| Fee payment|Year of fee payment: 5 |
    2020-08-12| PLFP| Fee payment|Year of fee payment: 6 |
    2021-08-12| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1559002A|FR3041632B1|2015-09-24|2015-09-24|PROCESS FOR PURIFYING AND DRYING A FLOW OF HYDROFLUOROOLEFINS|
    FR1559002|2015-09-24|FR1559002A| FR3041632B1|2015-09-24|2015-09-24|PROCESS FOR PURIFYING AND DRYING A FLOW OF HYDROFLUOROOLEFINS|
    CN201680054431.3A| CN108026003A|2015-09-24|2016-09-19|Purifying and the method for dry HF hydrocarbon logistics|
    US15/761,543| US10633312B2|2015-09-24|2016-09-19|Method for purifying and drying a hydrofluoroolefin stream|
    JP2018513874A| JP2018528223A|2015-09-24|2016-09-19|Process for purifying and drying a hydrofluoroolefin stream|
    EP16775511.5A| EP3353140A1|2015-09-24|2016-09-19|Method for purifying and drying a hydrofluoroolefin stream|
    PCT/EP2016/072142| WO2017050686A1|2015-09-24|2016-09-19|Method for purifying and drying a hydrofluoroolefin stream|
    JP2021121049A| JP2021176882A|2015-09-24|2021-07-21|Method of purifying and drying hydro-fluoro-olefin stream|
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