Patent Grant
11286221
The present invention relates to the production of hydrochlorofluoroolefins. More particularly, the present invention relates to the production of 1-chloro-3,3,3-trifluoropropene.
3,3,3-Trifluoro-1-chloropropene, or alternatively 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), exists in the form of two isomers: the cis isomer, namely Z-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdZ), and the trans isomer, namely E-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE). They have different boiling points of, respectively, 18.5° C. for the trans compound and 39.5° C. for the cis compound.
Fluids based on E-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE) have found numerous applications in varied industrial fields, in particular as heat transfer fluids, propellants, foaming agents, blowing agents, gaseous dielectrics, monomers or polymerization media, support fluids, abrasive agents, drying agents, and fluids for energy production units.
The manufacture of HCFO-1233zdE is accompanied by a multitude of byproducts having a boiling point close to HCFO-1233zdE. This results in purification steps which are relatively complex and costly. The difficulties encountered during the purification of HCFO-1233zdE generally entail an appreciable loss of target product. In addition, the byproducts may form azeotropic compositions with the HCFO-1233zdE, making separation by simple distillation very difficult, or even impossible.
U.S. Pat. No. 5,877,359 discloses a process for preparing HCFO-1233zdE from 1,1,3,3-tetrachloropropene in liquid phase and in the absence of catalyst. The molar HF/1230za ratio in the fluorination reactor is from 12 to 500. U.S. Pat. No. 9,643,903 also discloses a process for fluorinating 1,1,3,3-tetrachloropropene in liquid phase and in the absence of catalyst, in an HF-rich medium.
Furthermore, a not inconsiderable amount of overfluorinated byproducts are observed, linked to the presence of this HF in large amount. The presence of 245fa may bring about a loss of yield, it being known that this mixture forms an azeotropic mixture with the primary product, 1233zdE (see in particular US2017/174965). It will therefore be difficult to separate and will have to be removed in the form of an azeotropic mixture, thus bringing about a loss of yield. There is therefore a need for new processes which minimize the drawbacks described above.
The present invention relates to a process for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) comprising the steps of:
The present process makes it possible, by means of controlling the temperature of the liquid phase, to produce 1-chloro-3,3,3-trifluoropropene while at the same time minimizing the formation of overfluorinated coproducts or of heavy compounds (dimers or trimers of C3 compounds).
According to a preferred embodiment, during the implementation of step ii), the temperature of said liquid phase varies by a maximum of 2° C.
According to a preferred embodiment, said stirring means comprise a static mixer, a device for injecting an inert gas into said liquid phase, a device for recirculating the liquid phase, or a device for returning a flow of HF into said liquid phase, or a combination of two or more of these stirring means.
According to a preferred embodiment, the stirring means comprises a static mixer and the process comprises the steps of:
According to one embodiment, said stream A1 and said stream A2 are preheated before carrying out step i′) or ii).
According to a preferred embodiment, step ii) is carried out at a temperature of between 20° C. and 150° C.
According to a preferred embodiment, step ii) is carried out at a pressure of between 1 and 20 bara.
According to a preferred embodiment, the process is carried out in continuous mode in a single reactor.
According to a preferred embodiment, step ii) is carried out in the absence of catalyst.
According to a preferred embodiment, stream C is purified, preferably by distillation, to form a stream C1 comprising HCl and a stream C2 comprising 1-chloro-3,3,3-trifluoropropene and HF, said stream C2 itself being separated into a stream C3 comprising 1-chloro-3,3,3-trifluoropropene and a stream C4 predominantly comprising the HF recycled to step i′) or ii).
According to a preferred embodiment, said liquid phase is low in HF, advantageously said liquid phase comprises less than 15% by weight of HF, preferably less than 10% by weight of HF, more preferentially less than 8% by weight of HF.
According to a preferred embodiment, stream C is a gaseous stream.
According to a first aspect of the present invention, a process for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) is provided. The present process comprises the steps of:
Preferably, step ii) is carried out in a reactor provided with means for stirring said liquid phase. Said stirring means are suitable for keeping the temperature of said liquid phase substantially constant during step ii). The present process makes it possible, by means of controlling the temperature of the liquid phase, to produce 1-chloro-3,3,3-trifluoropropene while at the same time minimizing the formation of overfluorinated coproducts or of heavy compounds (dimers or trimers of C3 compounds).
The term “substantially constant” refers to a temperature which varies by a maximum of 3° C. in terms of absolute value, advantageously a maximum of 2.5° C. in terms of absolute value, preferably a maximum of 2° C. in terms of absolute value, more preferentially by a maximum of 1.5° C. in terms of absolute value, in particular by at most 1° C. in terms of absolute value, more particularly by at most 0.5° C. in terms of absolute value.
Thus, according to a preferred embodiment, during the implementation of step ii), the temperature of said liquid phase varies by a maximum of 3° C. in terms of absolute value, advantageously a maximum of 2.5° C. in terms of absolute value, preferably a maximum of 2° C. in terms of absolute value, more preferentially by a maximum of 1.5° C. in terms of absolute value, in particular by at most 1° C. in terms of absolute value, more particularly by at most 0.5° C. in terms of absolute value.
The temperature of said liquid phase is measured at several points within said phase in accordance with the methods known to those skilled in the art.
According to one particular embodiment, said low-HF liquid phase is a liquid phase comprising less than 15% by weight of HF, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferentially less than 6% by weight of HF, in particular less than 5% by weight of HF, more particularly less than 4% by weight of HF, favorably less than 2% by weight of HF, based on the total weight of said liquid phase.
According to an alternative embodiment, said liquid phase is rich in HF. Advantageously, in this alternative embodiment, said liquid phase comprises at least 25% by weight of HF, preferably at least 30% by weight of HF, more preferentially at least 35% by weight of HF. Thus, said liquid phase may comprise at least 25%, at least 26%, at least 27%, at least 28%, at least 29%, at least 30%, at least 31%, at least 32%, at least 33%, at least 34%, at least 35%, at least 36%, at least 37%, at least 38%, at least 39%, at least 40%, at least 41%, at least 42%, at least 43%, at least 44%, at least 45%, at least 46%, at least 47%, at least 48%, at least 49% or at least 50% by weight of HF.
The embodiment in which said liquid phase is poor in HF is nevertheless favored.
Said liquid phase may comprise at least 10% by weight of compounds of formula (I) C3HnFmClp (I) in which n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably, n is an integer from 0 to 8, m is an integer from 0 to 6, and p is an integer from 0 to 6. Compounds of formula (I) may, for example, be C3Cl6, C3H4Cl4 or C3H3Cl5. Said liquid phase may preferably comprise at least 10% by weight of compounds of formula (I) C3HnFmClp (I) in which n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably, n is an integer from 1 to 4, m is an integer from 0 to 3, and p is an integer from 2 to 4. The compounds of formula (I) may be propane- or propene-type compounds comprising one or more chlorine atoms and/or one or more fluorine atoms. Said liquid phase may preferably comprise at least 10% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F, C3H2Cl2F2, C3H3Cl5, C3H3Cl4F, C3H3Cl3F2, and C3H3Cl2F3. More particularly, said liquid phase may comprise at least 10% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F, and C3H2Cl2F2. Said liquid phase may comprise at least 15% by weight of compounds of formula (I) C3HnFmClp (I) in which n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably, n is an integer from 0 to 8, m is an integer from 0 to 6, and p is an integer from 0 to 6. Said liquid phase may in particular comprise at least 15% by weight of compounds of formula (I) C3HnFmClp (I) in which n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably, n is an integer from 1 to 4, m is an integer from 0 to 3, and p is an integer from 2 to 4. Said liquid phase may preferably comprise at least 15% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F, C3H2Cl2F2, C3H3Cl5, C3H3Cl4F, C3H3Cl3F2, and C3H3Cl2F3. In particular, said liquid phase may comprise at least 15% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F, and C3H2Cl2F2. Said liquid phase may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) C3HnFmClp (I) in which n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably, n is an integer from 0 to 8, m is an integer from 0 to 6, and p is an integer from 0 to 6. Said liquid phase may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) C3HnFmClp (I) in which n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably, n is an integer from 1 to 4, m is an integer from 0 to 3, and p is an integer from 2 to 4. Said liquid phase may preferably comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F, C3H2Cl2F2, C3H3Cl5, C3H3Cl4F, C3H3Cl3F2, and C3H3Cl2F3. In particular, said liquid phase may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F, and C3H2Cl2F2.
Preferably, said stream A2 comprises at least 10% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, based on the total weight of said stream A2. Advantageously, said stream A2 comprises at least 15% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, preferably at least 20% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, more preferentially at least 25% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, in particular at least 30% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, more particularly at least 35% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, favorably at least 40% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, advantageously favorably at least 45% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, preferentially favorably at least 50% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, and particularly favorably at least 55% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, based on the total weight of said stream A2.
Preferably, said stream A2 comprises at least 60% by weight or at least 65% by weight or at least 70% by weight or at least 75% by weight or at least 80% by weight or at least 85% by weight or at least 90% by weight or at least 95% by weight or at least 99% by weight of 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene, based on the total weight of said stream A2.
According to one embodiment, said stream A1 and said stream A2 are preheated before carrying out step i′) or ii).
According to a preferred embodiment, step ii) is carried out at a temperature of between 20° C. and 150° C., advantageously between 50° C. and 150° C., preferably between 80 and 120° C. and in particular between 90 and 110° C.
According to a preferred embodiment, step ii) is carried out at a pressure of between 1 and 20 bara, advantageously between 5 and 20 bara, preferably between 5 and 18 bara, more preferentially between 7 and 18 bara, in particular between 10 and 18 bara, more particularly between 12 and 18 bara, favorably between 12 and 15 bara.
According to a preferred embodiment, the process is carried out in continuous mode in a single reactor.
According to a preferred embodiment, step ii) is carried out in the absence of catalyst. Alternatively, step ii) may be carried out in the presence of a catalyst. The catalyst may be selected from the group consisting of TiCl4, SnCl4, TaCl5, SbCl3, AlCl3, SbCl5, and a mixture of these. The catalyst may be partially or totally fluorinated. Preferably, the implementation of step ii) in the absence of catalyst is favored in order to avoid problems of corrosion of the reactor.
According to a preferred embodiment, said stirring means comprise a static mixer, a device for injecting an inert gas into said liquid phase, a device for recirculating the liquid phase, a mechanical stirring device, or a device for returning a flow of HF into said liquid phase, or a combination of two or more of these stirring means. Preferably, said stirring means comprise a static mixer, a device for injecting an inert gas into said liquid phase, a device for recirculating the liquid phase, or a device for returning a flow of HF into said liquid phase, or a combination of two or more of these means.
According to another embodiment, the reactor 1 comprises, as stirring means, a device for recirculating the liquid phase. This embodiment is illustrated in
According to another embodiment, the reactor 1 comprises, as stirring means, a device from returning a flow of HF into the liquid phase. This embodiment is illustrated in
According to another embodiment, the reactor 1 comprises, as stirring means, a device for injecting an inert gas into the liquid phase. This embodiment is illustrated in
According to another embodiment, the reactor 1 comprises, as stirring means, a static mixer and a device for returning a flow of the HF into the liquid phase. This embodiment is illustrated in
According to another embodiment, the reactor 1 comprises, as stirring means, a device for recirculating the liquid phase and a static mixer. This embodiment is illustrated in
According to another embodiment, the reactor 1 comprises, as stirring means, a device for recirculating the liquid phase, a static mixer and a device for returning a flow of the HF into the liquid phase. This embodiment is illustrated in
More particularly, the stirring means comprises a static mixer. Thus, the present process for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprises the steps of:
Thus, according to one particular embodiment, the present process for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprises the steps of:
The use of a static mixer enables optimal control of the temperature of the liquid phase during the implementation of step ii). Thus, in this embodiment, the temperature of said liquid phase is substantially constant. Preferably, the use of a static mixer allows a variation of the temperature of the liquid phase by a maximum of 0.5° C.
Preferably, the static mixer is combined with one or more stirring means as defined in the present application. Thus, the reactor may comprise, in addition to the static mixer, a device for returning a flow of the HF into the liquid phase and/or a device for recirculating said liquid phase as defined in the present application, in particular in
In addition, the static mixer makes it possible to initiate the fluorination reaction between the hydrofluoric acid and the 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene. In said mixture B, the HF is in gaseous form or liquid form. In said mixture B, the 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene is in liquid form. Said mixture B may also comprise compounds having a degree of fluorination greater than that of 1,1,3,3-tetrachloropropene or 1,3,3,3-tetrachloropropene. The degree of fluorination corresponds to the number of fluorine atoms contained in the compound considered. For example, the mixture B may comprise trichlorofluoropropene (HCFO-1231) or dichlorodifluoropropene (HCFO-1232) compounds. It has thus been discovered, surprisingly, that the use of starting products such as 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene made it possible to produce 1-chloro-3,3,3-trifluoropropene more easily and more rapidly under operating conditions which are less constraining in terms of temperature and pressure. Thus, the use of starting products such as 1,1,3,3-tetrachloropropene and/or 1,3,3,3-tetrachloropropene in combination with the static mixer makes it possible to initiate the fluorination reaction as soon as they are put in contact in said static mixer. The HCl byproduct generated during initiation of the reaction contributes to the homogeneity of the mixture of starting materials. Thus, the implementation of the process is more efficient than with a starting product such as 1,1,1,3,3-pentachloropropane (HCC-240fa). The static mixer makes it possible in addition to control the diffusion of the mixture B into said liquid phase by limiting the formation of heavy compounds (as mentioned above).
The stream C is preferably in gaseous form. The stream C may also comprise organic compounds such as intermediates of the fluorination reaction or coproducts. Mention may in particular be made of dichlorodifluoropropene, trichloromonofluoropropene, fluorotetrachloropropane, pentafluoropropane, difluorotrichloropropane, dichlorotrifluoropropane and 1,3,3,3-tetrafluoropropene. Preferably, stream C comprises 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane. The molar content of 1,3,3,3-tetrafluoropropene in said stream C is less than 0.2 mol %. The molar content of 1,1,1,3,3-pentafluoropropane in said stream C is less than 0.5 mol %.
According to a preferred embodiment, stream C is purified, preferably by distillation, to form a stream C1 comprising HCl and a stream C2 comprising 1-chloro-3,3,3-trifluoropropene and HF, said stream C2 itself being separated, for example by cold settling, into a stream C3 comprising 1-chloro-3,3,3-trifluoropropene and a stream C4 comprising HF recycled to step i′) or ii). The cold settling step can be carried out at a temperature of −50° C. to 50° C., preferably of −30° C. to 0° C.
The examples that follow illustrate the invention without limiting it. The apparatus used consists of an autoclave having a capacity of 1 liter with a jacket, made of 316L stainless steel. It is provided with means for measuring temperature and pressure. Openings at the top of the autoclave allow the introduction of the reactants and the removal of the products. A condenser is provided at the top, as is a valve for regulating the pressure. The condenser is temperature controlled by means of a thermostatically controlled bath. Due to the pressure regulation, the reaction products are progressively extracted. Thus, the flow of outlet gas passes into a washing device which collects the hydracids HF and HCl, and is then cooled in liquid nitrogen. The molar distribution of the products of the outlet gas is analyzed periodically, by GC (gas chromatography). At the end of the test, the reaction medium is cooled to room temperature and depressurized.
An amount of HF of 150 g is introduced into the autoclave. The temperature of the reactor is adjusted to 90° C. in the liquid phase. The pressure is regulated at 13 bara. Once the temperature has stabilized, 135 g of 1230za are introduced into the reactor. The molar ratio of HF to the organic compound is therefore 10. The temperature of the liquid phase taken at the same time at two points is different. After two hours of reaction, the test is stopped and processed in accordance with the methods described above. The conversion of HCO-1230za is 69.2%. The amount of heavy compounds formed is estimated by the mass of organic products (other than 1230za) recovered from the reactor at the end of reaction divided by the mass of 1230za which has reacted. This is 9% by weight.
An amount of HF of 150 g is introduced into the autoclave. The reactor is equipped with a mechanical stirring means. The temperature of the reactor is adjusted to 90° C. in the liquid phase. The pressure is regulated at 13 bara. Once the temperature has stabilized, 136 g of 1230za are introduced into the reactor. The molar ratio of HF to the organic compound is therefore 10. The temperature of the liquid phase taken at the same time at two different points does not vary. After two hours of reaction, the test is stopped and processed in accordance with the methods described above. The conversion of HCO-1230za is 100%. The amount of heavy compounds formed is estimated by the mass of organic products (other than 1230za) recovered from the reactor at the end of reaction divided by the mass of 1230za which has reacted. This is 6% by weight.
The presence of a stirring means as provided by the present invention makes it possible to reduce the amount of heavy compounds formed during the fluorination reaction. As demonstrated by example 2, the presence of a stirring means makes it possible to reduce the content of heavy compounds to 6% by weight, compared to 9% in example 1 carried out in the absence of stirring.
The pilot apparatus used consists of a reactor with a capacity of 60 liters, made of 316L stainless steel. It is provided with means for measuring temperature, pressure, and liquid level. The two reactants are preheated. They are then mixed and fed into the reactor using a dip tube equipped with a static mixer and a diffuser at the end. An in-line withdrawal system allows the flow of outlet gas to be sampled, for which it is guided to a gas chromatograph. The reactants are fed in continuously, and the products are analyzed and collected continuously. An amount of 1230za of 25 liters is introduced into the reactor. The pressure regulation is adjusted to 15 bara. The reactants are then fed in at the following flow rates: 2.3 kg/h of HF and 3.2 kg/h of 1230za. The temperature of the liquid phase taken at the same time at five different points after 24 h of continuous operation of the reactor varies by a maximum of 0.5° C. The composition of the resulting gaseous organic flow is given: 95.4 mol % of HFCO-1233zdE, 4.17 mol % of HCFO-1233zdZ, 0.14 mol % of 1234ze (E+Z), 0.002 mol % of 245fa.
Example 3 is reproduced without a static mixer. The two reactants are fed to the reactor independently using two dip tubes. The temperature of the liquid phase taken at the same time at five different points in the reactor varies between 89° C. at the liquid surface and 94° C. at the bottom of the reactor. The composition of the resulting gaseous organic flow is given: 94.6 mol % of HFCO-1233zdE, 4.53 mol % of HCFO-1233zdZ, 0.18 mol % of 1234ze (E+Z), 0.025 mol % of 245fa.
The presence of a static mixer as stirring means also makes it possible to reduce the content of coproducts. Specifically, the content of 1234ze and 245fa decreases when the fluorination process is carried out in the presence of a stirring means such as the static mixer.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1855793 | Jun 2018 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2019/051520 | 6/21/2019 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2020/002800 | 1/2/2020 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2583812 | Briggs et al. | Jan 1952 | A |
| 2882243 | Milton | Apr 1959 | A |
| 4013566 | Taylor | Mar 1977 | A |
| 5616819 | Boyce et al. | Apr 1997 | A |
| 5684219 | Boyce et al. | Nov 1997 | A |
| 5705779 | Demmin et al. | Jan 1998 | A |
| 5877359 | Elsheikh | Mar 1999 | A |
| 6166274 | Chen et al. | Dec 2000 | A |
| 6403847 | Nakada et al. | Jun 2002 | B1 |
| 8404907 | Nair et al. | Mar 2013 | B2 |
| 8426656 | Merkel et al. | Apr 2013 | B2 |
| 8436217 | Wang et al. | May 2013 | B2 |
| 8704017 | Pokrovski et al. | Apr 2014 | B2 |
| 8877990 | Fukuju et al. | Nov 2014 | B2 |
| 9255045 | Pigamo et al. | Feb 2016 | B2 |
| 9643903 | Pokrovski et al. | May 2017 | B2 |
| 9834499 | Pigamo et al. | Dec 2017 | B2 |
| 10077221 | Bonnet et al. | Sep 2018 | B2 |
| 10227275 | Pigamo et al. | Mar 2019 | B2 |
| 10343963 | Bonnet | Jul 2019 | B2 |
| 10427998 | Pigamo et al. | Oct 2019 | B2 |
| 10532965 | Pigamo et al. | Jan 2020 | B2 |
| 10669465 | Rached | Jun 2020 | B2 |
| 10858561 | Abbas et al. | Dec 2020 | B2 |
| 11028027 | Wendlinger et al. | Jun 2021 | B2 |
| 11034635 | Wendlinger et al. | Jun 2021 | B2 |
| 11084768 | Wendlinger et al. | Aug 2021 | B2 |
| 20010014707 | Thomas et al. | Aug 2001 | A1 |
| 20100191025 | Perdrieux | Jul 2010 | A1 |
| 20110196178 | Nyberg | Aug 2011 | A1 |
| 20110197602 | Abbas et al. | Aug 2011 | A1 |
| 20110201853 | Tung et al. | Aug 2011 | A1 |
| 20110218370 | Elsheikh et al. | Sep 2011 | A1 |
| 20110245549 | Merkel et al. | Oct 2011 | A1 |
| 20110259828 | Bouvier et al. | Oct 2011 | A1 |
| 20120059199 | Pokrovski et al. | Mar 2012 | A1 |
| 20120172636 | Pokrovski | Jul 2012 | A1 |
| 20120190902 | Nyberg | Jul 2012 | A1 |
| 20120226081 | Elsheikh et al. | Sep 2012 | A1 |
| 20120256119 | Bouvier et al. | Oct 2012 | A1 |
| 20120256120 | Bouvier et al. | Oct 2012 | A1 |
| 20120271070 | Wang et al. | Oct 2012 | A1 |
| 20120329893 | Abbas | Dec 2012 | A1 |
| 20130037058 | Abbas | Feb 2013 | A1 |
| 20130211154 | Cottrell et al. | Aug 2013 | A1 |
| 20130261353 | Pokrovski et al. | Oct 2013 | A1 |
| 20130261354 | Merkel et al. | Oct 2013 | A1 |
| 20140213831 | Nyberg | Jul 2014 | A1 |
| 20140221704 | Tung et al. | Aug 2014 | A1 |
| 20140264173 | Merkel et al. | Sep 2014 | A1 |
| 20150152235 | Abbas | Jun 2015 | A1 |
| 20150197467 | Pigamo et al. | Jul 2015 | A1 |
| 20160023974 | Bonnet et al. | Jan 2016 | A1 |
| 20160115104 | Pigamo et al. | Apr 2016 | A1 |
| 20160272561 | Rached et al. | Sep 2016 | A1 |
| 20170050904 | Ondrus | Feb 2017 | A1 |
| 20170081263 | Klausmeyer et al. | Mar 2017 | A1 |
| 20170174965 | Tsuchiya et al. | Jun 2017 | A1 |
| 20170210686 | Pigamo et al. | Jul 2017 | A1 |
| 20180015407 | Vittenet et al. | Jan 2018 | A1 |
| 20180093934 | Pigamo et al. | Apr 2018 | A1 |
| 20180148394 | Pigamo et al. | May 2018 | A1 |
| 20180346396 | Pigamo et al. | Dec 2018 | A1 |
| 20180354875 | Bonnet | Dec 2018 | A1 |
| 20190048241 | Abbas et al. | Feb 2019 | A1 |
| 20190152883 | Pigamo et al. | May 2019 | A1 |
| 20190276721 | Rached | Sep 2019 | A1 |
| 20190375698 | Pigamo et al. | Dec 2019 | A1 |
| 20200407293 | Wendlinger et al. | Dec 2020 | A1 |
| 20210002188 | Wendlinger et al. | Jan 2021 | A1 |
| 20210002189 | Wendlinger et al. | Jan 2021 | A1 |
| 20210238112 | Pigamo et al. | Aug 2021 | A1 |
| Number | Date | Country |
|---|---|---|
| 101687735 | Mar 2010 | CN |
| 102216247 | Oct 2011 | CN |
| 0 940 382 | Sep 1999 | EP |
| 1 566 600 | Aug 2005 | EP |
| 2 035 117 | Mar 2009 | EP |
| 1 257 034 | Jan 1960 | FR |
| 2768727 | Mar 1999 | FR |
| 2 973 717 | Oct 2012 | FR |
| 2 973 809 | Oct 2012 | FR |
| 3 032 131 | Aug 2016 | FR |
| 3 041 632 | Mar 2017 | FR |
| 2000-95714 | Apr 2000 | JP |
| 2012-509324 | Apr 2012 | JP |
| WO 0181353 | Nov 2001 | WO |
| WO 2008127940 | Oct 2008 | WO |
| WO 2008149011 | Dec 2008 | WO |
| WO 2008149011 | Dec 2008 | WO |
| WO 2010059496 | May 2010 | WO |
| WO 2010063975 | Jun 2010 | WO |
| WO 2010111067 | Sep 2010 | WO |
| WO 2012067980 | May 2012 | WO |
| WO 2014116562 | Jul 2014 | WO |
| WO 2015175791 | Nov 2015 | WO |
| WO 2016146940 | Sep 2016 | WO |
| WO 2017031046 | Feb 2017 | WO |
| Entry |
|---|
| Ghanem, A. et al. “Static mixers: Mechanisms, applications,and characterization methods—A review” chemical engineering research and design 92 (2014 ) 205-228 (Year: 2014). |
| International Search Report (PCT/ISA/210) and translation and Written Opinion (PCT/ISA/237) dated Oct. 8, 219, by the European Patent Office as the International Searching Authority for International Application No. PCT/FR2019/051520. |
| Test No. 102: Melting point/Melting range, OECD guidelines for the testing of chemical products, Section 1, OECD Editions, Paris, 1995, available at http://dx.doi.org/10.1787/9789264069534-fr (with English translation) (17 pages). |
| Breck, Donald W., et al., “Zeolite Molecular Sieves”, John Wiley & Sons Eds, (1974), 159 pages. |
| Boutier, Jean-Christophe, et al., U.S. Appl. No. 17/280,547 entitled “Stabilization of 1-Chloro-3,3,3-Trifluoropropene,” filed in the U.S. Patent and Trademark Office filed Mar. 26, 2021. |
| Number | Date | Country | |
|---|---|---|---|
| 20210261485 A1 | Aug 2021 | US |
