Fluoride catalyst for catalyzing CFC-113a to synthesize CFC-1316mxx and preparation method thereof

Abstract

The invention relates to the technical field of fluoride catalysts, and particularly discloses a fluoride catalyst for catalyzing CFC-113a to synthesize CFC-1316mxx and a preparation method of the fluoride catalyst. The fluoride catalyst is prepared from a catalyst precursor, and the catalyst precursor comprises a transition metal salt and a fluoride carrier MFx, wherein the transition metal salt is selected from any one or more of ruthenium salt, rhodium salt, palladium salt, nickel salt and copper salt; the fluoride carrier MFx is selected from any one or more of sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride and aluminum fluoride. When the fluoride-based catalyst is used for catalyzing CFC-113a to synthesize CFC-1316mxx through hydrogenation coupling, the CFC-1316mxx selectivity and the CFC-113a conversion rate are remarkably high, and finally, the yield of the target product CFC-1316mxx reaches up to 91.98%.

Description

Technical Field

[0001] The present application relates to the technical field of fluoride catalysts, and further to a fluoride-based catalyst for catalyzing hydrogenation coupling reactions, and specifically to a fluoride catalyst for catalyzing the synthesis of CFC-1316mxx from CFC-113a and a preparation method thereof. Background Art

[0002] With growing concern about global warming, the issue of reducing hydrofluorocarbons (HFCs) due to their high global warming potential (GWP) has become a focus of international public opinion in recent years. 1,1,1,4,4,4-Hexafluoro-2-butene (HFO-1336mzz), with its zero ODP and short atmospheric lifetime, is considered a new, environmentally friendly alternative to chlorofluorocarbons (CFCs).

[0003] There are numerous methods for synthesizing HFO-1336mzz, but most routes suffer from issues such as limited raw material availability, low efficiency, and significant pollution. The two-step gas-phase reaction route for synthesizing HFO-1336mzz using 1,1,1-trifluorotrichloroethane (CFC-113a) offers readily available raw materials, high efficiency, and a clean, environmentally friendly process without the use of hazardous chemicals such as hydrogen fluoride and chlorine. CFC-113a is hydrocoupled to synthesize CFC-1316mxx, which can be converted to HFO-1336mzz via a simple hydrodechlorination reaction. Therefore, studying the synthesis of CFC-1316mxx is of great significance.

[0004] For example, prior art reports have shown that using 2% carbon-supported ruthenium as a catalyst, a liquid hourly space velocity of 2, a H2:CFC-113a molar ratio of 10:1, and a reaction temperature of 125°C, the conversion of the raw material CFC-113a is 100%, and the selectivity for the target product CFC-1316 is 58.22%. Some prior art reports using copper powder as a catalyst and a reaction temperature of 180°C achieve a 94% conversion of the raw material and an 88% selectivity for CFC-1316. While these patents offer high raw material conversion, they exhibit poor selectivity for the target product.

[0005] For example, some prior art catalysts use 2% Ru on a SiC carrier, achieving a CFC-113a conversion of 54.5% and a CFC-1316 selectivity of 85.68%. Alternatively, 5% of the total weight of ruthenium can be loaded onto an activated carbon carrier, resulting in a CFC-113a conversion of 60% and a CFC-1316 selectivity of 88%. Furthermore, platinum can be loaded onto activated carbon, gamma-alumina, silicon dioxide, magnesium fluoride, calcium fluoride, or tungsten carbide at 0.2-5% of the total catalyst weight, with rhodium, ruthenium, or rhenium as the catalyst additive. This results in a CFC-113a conversion of 55.10% and a CFC-1316 selectivity of 83.20%. These prior art catalysts have high selectivity for the target product but poor or even inferior raw material conversion. Summary of the Invention

[0006] To address the poor catalyst activity in existing technologies, this application provides a fluoride catalyst for catalyzing the synthesis of CFC-113a into CFC-1316mxx and its preparation method. This application utilizes a metal fluoride as a catalyst support, loading the active metal onto the fluoride support at a low concentration. By leveraging the fluoride support's strong thermal stability and acid corrosion resistance, as well as the interaction between the fluoride support, the catalytically active centers, and the substrate, the catalyst's catalytic activity in the CFC-113a hydrocoupling reaction is enhanced. This catalyst exhibits excellent catalytic activity and good stability in the CFC-113a hydrocoupling reaction to synthesize CFC-1316mxx.

[0007] This application involves the following:

[0008] 1. A fluoride catalyst for catalyzing the synthesis of CFC-1316mxx from CFC-113a, wherein the fluoride catalyst is prepared from a catalyst precursor comprising a transition metal salt and a fluoride carrier MF x ;

[0009] Wherein, the transition metal salt is selected from any one or more of ruthenium salt, rhodium salt, palladium salt, nickel salt and copper salt;

[0010] The fluoride carrier MF x Any one or more selected from sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, and aluminum fluoride.

[0011] 2. The fluoride catalyst according to item 1, wherein the transition metal element in the transition metal salt accounts for the transition metal salt and the fluoride carrier MF x 0.05-30 wt% of the total weight; preferably 1-25 wt%.

[0012] 3. A method for preparing the fluoride catalyst according to item 1 or 2, the preparation method comprising:

[0013] The transition metal salt and fluoride carrier MF x Mixing evenly and then drying to obtain the catalyst precursor;

[0014] The catalyst precursor is reduced and activated by hydrogen to obtain the fluoride catalyst.

[0015] 4. The preparation method according to item 3, wherein the drying comprises pre-drying and secondary drying;

[0016] Wherein, the pre-drying is to make the metal salt and fluoride carrier MF x The mixture is dried at 100-150°C;

[0017] The secondary drying conditions include: a drying temperature of 100-300°C;

[0018] And / or, the drying time of the secondary drying is 0.5-24 hours.

[0019] 5. According to the preparation method described in item 4, the secondary drying is carried out in an environment containing an inert gas; preferably, the inert gas is nitrogen.

[0020] Preferably, the process further comprises: mixing the metal salt and the fluoride carrier MF before drying. x The step of tableting the mixture and then crushing the obtained tablets.

[0021] 6. The preparation method according to any one of items 3 to 5, wherein the reduction activation temperature is 150-500° C.;

[0022] The reduction activation time is 1-100 h, preferably 6-12 h.

[0023] 7. The preparation method according to any one of items 3 to 5, wherein the reducing agent during the reduction activation is nitrogen;

[0024] Preferably, the volume ratio of nitrogen to hydrogen is 0.5-3:1.

[0025] 8. A method for catalyzing the synthesis of CFC-1316mxx from CFC-113a, the method comprising using the fluoride catalyst described in item 2 or 3 and / or the fluoride catalyst prepared by the preparation method described in any one of items 3 to 7.

[0026] 9. The method according to item 8, wherein when catalyzing CFC-113a to synthesize CFC-1316mxx, the reaction temperature is 150-350°C, preferably 210-290°C;

[0027] And / or, the reaction time is 1-40 s, preferably 10-30 s.

[0028] 10. The method according to item 8 or 9, wherein when catalyzing CFC-113a to synthesize CFC-1316mxx, the molar ratio of hydrogen to CFC-113a is 1-20:1, preferably 2-8:1.

[0029] Effects of the Invention

[0030] The fluoride-based catalyst disclosed in this application uses a transition metal salt as the catalytically active agent and a fluoride as the carrier. When catalyzing the hydrocoupling of CFC-113a to synthesize CFC-1316mxx, the fluoride-based catalyst has significantly high CFC-1316mxx selectivity and CFC-113a conversion rate, ultimately resulting in a yield of the target product CFC-1316mxx as high as 91.98%. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 .Life evaluation diagram of fluoride-based catalysts in the catalytic hydrocoupling reaction of CFC-113a to synthesize CFC-1316mxx.

[0032] Figure 2 .XRD diffraction pattern of the barium fluoride-based catalyst in Example 1.

[0033] Figure 3 . is the SEM image of the barium fluoride-based catalyst in Example 1.

[0034] Figure 4 .This is the TEM image of the barium fluoride-based catalyst in Example 1. DETAILED DESCRIPTION

[0035] It should be noted that certain terms are used in the specification and claims to refer to specific components. Those skilled in the art will understand that they may use different terms to refer to the same component. This specification and claims do not distinguish components based on differences in terms, but rather on differences in their functions.

[0036] Throughout the specification and claims, the words "including" or "comprising" are open-ended terms and should be interpreted as "including but not limited to." The specification subsequently describes preferred embodiments of the present application. However, the description is for the purpose of general principles of the specification and is not intended to limit the scope of the present application. The scope of protection of the present application shall be determined by the appended claims. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0037] It should be understood that the embodiments of the present application described herein include "consisting of" and / or "consisting essentially of" embodiments. Reference herein to "about" a value or parameter includes (and describes) variations with respect to that value or parameter itself. For example, a description referring to "about X" includes a description of "X."

[0038] As used herein, reference to an "other than" value or parameter generally means and describes an "other than" value or parameter. For example, the method is not for treating cancer type X, meaning that the method is for treating cancers other than type X.

[0039] As used herein, the term "about XY" has the same meaning as "about X to about Y."

[0040] As used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. It should also be noted that claims can be drafted to exclude any optional element. Thus, this statement is intended to serve as antecedent basis for use of exclusive terminology such as "only," "only" and the like in connection with the recitation of claim elements, or the use of a limitation such as "no."

[0041] As used herein, the term "and / or" in phrases such as "A and / or B" is intended to include both A and B; A or B; A (alone); and B (alone). Similarly, as used herein, the term "and / or" in phrases such as "A, B and / or C" is intended to include each of the following embodiments: A, B, and C; A, B, or C; A or C; A or B; B or C; A and C; A and B; B and C; A (alone); B (alone); and C (alone).

[0042] The present application provides a fluoride catalyst for catalyzing the synthesis of CFC-1316mxx from CFC-113a. The fluoride catalyst is prepared from a catalyst precursor, which comprises a transition metal salt and a fluoride carrier MF. x ;

[0043] Wherein, the transition metal salt is selected from any one or more of ruthenium salt, rhodium salt, palladium salt, nickel salt and copper salt;

[0044] The fluoride carrier MF x Any one or more selected from sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, and aluminum fluoride.

[0045] Among them, "fluoride carrier MF x " means: the basic composition of the catalyst carrier is MF x, where M refers to the metal atom, F refers to the fluorine atom, and x refers to the number of fluorine atoms corresponding to each metal atom (generally x can be 1, 2, 3, etc.). For example, the fluoride carrier MF x Specifically, it can be barium fluoride (BaF2), magnesium fluoride (MgF2), calcium fluoride (CaF2), strontium fluoride (SrF2), sodium fluoride (NaF), aluminum fluoride (AlF3) and potassium fluoride (KF). In some preferred embodiments, the fluoride carrier MF x is selected from any one or more of barium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, sodium fluoride and aluminum fluoride; in some more preferred embodiments, the fluoride carrier MF x Any one or more selected from barium fluoride, magnesium fluoride, strontium fluoride, sodium fluoride and aluminum fluoride. In some embodiments, the fluoride carrier MF x is barium fluoride; in some embodiments, the fluoride carrier MF x is magnesium fluoride; in some embodiments, the fluoride carrier MF x is strontium fluoride; in some embodiments, the fluoride carrier MF x is sodium fluoride; in some embodiments, the fluoride carrier MF x Aluminum fluoride.

[0046] In some embodiments, the transition metal salt is selected from any one or more of ruthenium salts, rhodium salts, palladium salts, nickel salts, and copper salts; for example, it can be ruthenium chloride, palladium chloride, rhodium chloride, copper chloride, or nickel chloride. In some preferred embodiments, the transition metal salt is ruthenium chloride or rhodium chloride.

[0047] In some embodiments, the fluoride carrier MF x is barium fluoride, and the transition metal salt is ruthenium chloride; in some embodiments, the fluoride carrier MF x is magnesium fluoride, and the transition metal salt is ruthenium chloride; in some embodiments, the fluoride carrier MF x is strontium fluoride, and the transition metal salt is ruthenium chloride; in some embodiments, the fluoride carrier MF x is sodium fluoride, and the transition metal salt is ruthenium chloride; in some embodiments, the fluoride carrier MF x is aluminum fluoride, and the transition metal salt is ruthenium chloride.

[0048] In the research of this application, it was found that the transition metal salt and fluoride carrier MF xWhen the catalyst is prepared and used to catalyze the reaction of hydrogenating and coupling CFC-113a to synthesize CFC-1316mxx, the selectivity for the substrate CFC 1316mxx is high, even as high as 100%. The selectivity for CFC 1316mxx is also maintained at a high level, as high as 95.67% or even higher. The final product yield is as high as 85.25%.

[0049] In this application, the calculation formulas for CFC 113a conversion %, CFC 1316mxx selectivity %, and CFC 1316mxx yield % are as follows:

[0050] CFC-113a conversion rate % = (the amount of the initial substance of CFC-113a - the amount of the remaining substance of CFC-113a) / the amount of the initial substance of CFC-113a × 100%;

[0051] CFC-1316mxx selectivity % = (amount of CFC-113a consumed to produce CFC-1316mxx / amount of CFC-113a consumed) × 100%;

[0052] CFC-1316mxx yield % = CFC-113a conversion % × CFC-1316mxx selectivity % × 100%.

[0053] In some embodiments, the transition metal element in the transition metal salt accounts for the transition metal salt and the fluoride carrier MF x The transition metal salt may be present in an amount of 0.05-30 wt%, 1-25 wt%, 1-20 wt%, 1-15 wt%, 1-10 wt%, 1-5 wt%, 1-2 wt% or any content range of 0.05-30 wt% of the total weight; for example, it may be 0.05 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 23 wt%, 26 wt%, 29 wt%, 30 wt% or any content range of 0.05-30 wt%. In some embodiments, the transition metal element in the transition metal salt accounts for 1% of the transition metal salt and the fluoride carrier MF. xWhen the content of the transition metal salt is within any range of 1-30wt%, 1-25wt%, 1-20wt%, 1-15wt%, 1-10wt%, 1-5wt%, 1-2wt% or 1-30wt% of the total weight of the catalyst, when the catalyst is used to catalyze the hydrocoupling of CFC-113a to synthesize CFC-1316mxx, the yield of the target product CFC-1316mxx remains at a high level of about 63-85%, or even as high as 87%, 89%, 92%, or even higher. In the present application, when the transition metal element in the transition metal salt is in the "transition metal salt and fluoride carrier MF x The proportion of the "sum of weight" is low. As understood by those skilled in the art, if the content of active metal with the main catalytic effect in the prepared catalyst is low, the conversion rate of the reaction raw materials will be low (for example, Example 11); However, it is also found that the catalyst prepared with a low content of transition metal salt still has a high selectivity for the target product CFC 1316mxx in the reaction of catalyzing the hydrogenation coupling of CFC-113a to synthesize CFC-1316mxx, maintaining at a level of about 85.84%. When the transition metal element in the transition metal salt is in the "transition metal salt and fluoride carrier MF x The proportion of "weight sum" is high, for example, 25%. Even if the selectivity of the target product CFC 1316mxx is reduced to a certain extent in the reaction of catalyzing the hydrocoupling of CFC-113a to synthesize CFC-1316mxx, the yield of the target product CFC 1316mxx is still maintained at a certain level, for example, higher than 63%.

[0054] The present application also provides a method for preparing the above-mentioned fluoride catalyst, the preparation method comprising:

[0055] The transition metal salt and fluoride carrier MF x Mixing evenly and then drying to obtain the catalyst precursor;

[0056] The catalyst precursor is reduced and activated by hydrogen to obtain the fluoride catalyst.

[0057] In some embodiments, the drying comprises pre-drying and secondary drying;

[0058] Wherein, the pre-drying is to make the metal salt and fluoride carrier MF x The mixture is dried at 100-150°C;

[0059] The secondary drying conditions include: a drying temperature of 100-300°C;

[0060] And / or, the drying time of the secondary drying is 0.5-24 hours.

[0061] Generally speaking, the transition metal salt and the fluoride carrier MF x When the mixture is evenly mixed, it is mixed in a solution state, which will result in a water-containing liquid mixed solution. Therefore, drying is required here. In pre-drying, a large amount of free water in the mixture (or adsorbed water adsorbed on the catalyst) is removed; in this process, a relatively low temperature drying (for example, 100-150°C) is used to avoid the oxygen in the environment from oxidizing the catalyst during high-temperature drying, which is more energy-efficient. In further secondary drying, a relatively high drying temperature (for example, 100-300°C) is selected to further remove the moisture in the catalyst that is more tightly bound to the catalyst.

[0062] In some embodiments, the pre-drying is to separate the transition metal salt and the fluoride carrier MF. x The mixture is dried at a temperature within the range of 100-150°C, 100-140°C, 100-130°C, 100-120°C, 100-110°C, 100-105°C, or 100-150°C; for example, the drying temperature is 100°C, 102°C, 105°C, 108°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, or any temperature within the range of 100-150°C. In some embodiments, the pre-drying can be carried out in an apparatus in the presence of oxygen or air, such as in an oven. In some embodiments, the pre-drying time is about 8-20 hours, or even longer; for example, overnight drying, such as drying for 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, or even longer. Those skilled in the art will understand that within a certain drying time, the drying effect (e.g., moisture content after drying) and drying time are linearly related; however, as the drying time is extended, the drying effect changes more slowly. There are no absolute restrictions on the drying temperature and drying time during the pre-drying process; the catalyst should be dried to a point where no moisture is visible on the catalyst surface.

[0063] In some embodiments, the drying temperature of the secondary drying is 100-300°C, 110-270°C, 120-240°C, 130-210°C, 130-170°C, or any temperature range within the range of 100-300°C; for example, the drying temperature is 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 220°C, 240°C, 250°C, 270°C, 300°C, or any temperature within the range of 100-300°C. The drying time of the secondary drying is any time range within the range of 0.5-24h, 1-22h, 1-20h, 1-18h, 1-16h, 1-15h, 1-13h, 1-9h, 1-6h, 1-3h, 1-2h, 2-3h or 0.5-24h; for example, the drying time is 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h or any time within the range of 0.5-24h. Those skilled in the art will appreciate that, when drying at a relatively low drying temperature (e.g., 110° C., 120° C., or 130° C.), a prolonged drying time (e.g., 4 h, 8 h, or even 10 h) can also achieve a better drying effect, resulting in a higher CFC-1316mxx yield (e.g., approximately 82%, such as approximately 85%, or even higher) when the catalyst is used to catalyze the hydrocoupling of CFC-113a to produce CFC-1316mxx. Similarly, when drying at a relatively short drying time (e.g., 0.5 h, 1 h) by increasing the drying temperature (e.g., 170° C., 190° C., or 210° C., or even higher drying temperatures) the catalyst can also achieve a better drying effect, resulting in a higher CFC-1316mxx yield (e.g., approximately 83%, such as approximately 85%, or even higher) when the catalyst is used to catalyze the hydrocoupling of CFC-113a to produce CFC-1316mxx. In actual production, those skilled in the art should understand that in order to obtain products more efficiently and / or energy-saving, based on this consideration, the secondary drying is carried out at the shortest possible drying time and / or the lowest possible drying temperature while ensuring a better catalytic effect of the precursor.

[0064] In some preferred embodiments, the secondary drying is performed in an environment containing an inert gas.

[0065] "Inert gas" in this application refers to the catalyst, the selected transition metal salt and the fluoride carrier MF under the dry conditions. xA non-reactive gas, such as nitrogen, is used. This inert gas environment prevents oxidation of the catalyst during the secondary drying, which can affect its catalytic activity. Furthermore, the gas quickly removes moisture during the drying process, making the drying process more efficient.

[0066] In some embodiments, the drying step further comprises: x The tableting step is to crush the obtained tablet after the mixture is tableted. In some embodiments, the tableting step is to crush the transition metal salt and the fluoride carrier MF x The mixture is pressed into tablets; this operation facilitates the subsequent crushing; of course, the metal salt and fluoride carrier MF can also be directly crushed x mixture.

[0067] In some embodiments, the reduction activation temperature is 150-500°C, 180-450°C, 200-400°C, 220-380°C, 200-350°C, 240-300°C, 260-300°C, or any temperature range within the range of 150-500°C; for example: 150°C, 170°C, 190°C, 210°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 370°C, 390°C, 420°C, 450°C, 470°C, 500°C, or any temperature within the range of 150-500°C.

[0068] In some embodiments, the reduction activation time is 1-100h, preferably any temperature range within the range of 1-90h, 2-80h, 3-70h, 5-80h, 6-80h, 6-70h, 6-60h, 6-50h, 6-40h, 6-30h, 6-20h, 6-12h, 8-12h, 10-12h or 1-100h; for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 18h, 25h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h or any reduction time within the range of 1-100h.

[0069] In some embodiments, the reducing agent during the reduction activation is nitrogen.

[0070] In some embodiments, the volume ratio of nitrogen to hydrogen is any ratio range in the range of 0.1-3:1, 0.5-3:1, 0.5-2:1, 1-2:1, or 0.1-3:1; for example, 0.1:1, 0.5:1, 0.8:1, 1:1, 1.3:1, 1.5:1, 1.8:1, 2:1, 2.5:1, 3:1, or any ratio in the range of 0.1-3:1.

[0071] Those skilled in the art will appreciate that the reduction temperature, reduction time, and volume ratio of nitrogen to hydrogen listed in the examples of this application should not be construed as limiting the conditions under which this application can be implemented. When reduction is performed at a lower reduction temperature (e.g., 240° C., 220° C., or 200° C.), by extending the reduction time (e.g., for 10 h, 15 h, or even 20 h) and / or reducing the volume ratio of nitrogen to hydrogen (e.g., a volume ratio of 1:1 or 0.5:1), a better reduction effect can be achieved, resulting in a higher CFC-1316mxx yield (e.g., approximately 65%, approximately 70%, or approximately 80%, or even higher) when the resulting catalyst catalyzes the hydrocoupling of CFC-113a to synthesize CFC-1316mxx. Similarly, at a shorter reduction time (e.g., 6 h, 4 h), by increasing the reduction temperature (e.g., 300° C., 320° C., or 340° C., or even higher reduction temperatures) and / or decreasing the volume ratio of nitrogen to hydrogen (e.g., 1:1, 0.5:1), a better reduction effect can be achieved. This results in a higher CFC-1316mxx yield (e.g., about 75%, about 80%, or even higher) when the prepared catalyst catalyzes the hydrocoupling of CFC-113a to synthesize CFC-1316mxx. Similarly, when the volume ratio of nitrogen to hydrogen is relatively large (e.g., a volume ratio of 3:1), the reduction temperature can be increased (e.g., 300° C., 320° C., or 340° C., or even higher) and / or the reduction time can be extended (e.g., 10 h, 15 h, or even 20 h) to achieve a better reduction effect, so that the resulting catalyst can achieve a higher yield of CFC-1316mxx (e.g., about 62%, about 70%, about 75%, about 80%, or even higher) when catalyzing the hydrocoupling of CFC-113a to synthesize CFC-1316mxx. It will be understood by those skilled in the art that in actual production, in order to obtain the product more efficiently and / or energy-efficiently, based on this consideration, the reduction activation operation is performed with the shortest possible reduction time and / or the lowest possible reduction temperature, while ensuring a good catalytic effect.

[0072] The present application also provides a method for catalyzing CFC-113a to synthesize CFC-1316mxx, which comprises using the above-mentioned fluoride catalyst and / or the fluoride catalyst prepared by the above-mentioned preparation method.

[0073] In some embodiments, when catalyzing CFC-113a to synthesize CFC-1316mxx, the reaction temperature is 150-350°C, 180-330°C, 190-300°C, 210-290°C, 250-270°C, or any temperature in the range of 150-350°C, preferably 210-290°C; for example, the reaction temperature can be 150°C, 170°C, 190°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 330°C, 350°C, or any temperature in the range of 150-350°C.

[0074] In some embodiments, when catalyzing CFC-113a to synthesize CFC-1316mxx, the reaction time is any time range within the range of 1-60 s, 2-35 s, 5-32 s, 10-30 s, 10-15 s, or 1-60 s, preferably 10-30 s; for example, it can be 1 s, 5 s, 8 s, 10 s, 12 s, 13 s, 15 s, 18 s, 19 s, 20 s, 22 s, 25 s, 28 s, 30 s, 35 s, 40 s, 50 s, 60 s, or any time range within the range of 1-60 s.

[0075] In some embodiments, when catalyzing CFC-113a to synthesize CFC-1316mxx, the molar ratio of hydrogen to CFC-113a is any molar ratio in the range of 1-20:1, 1-18:1, 1-15:1, 1-12:1, 1-8:1, 2-8:1, 4-8:1, or 1-20:1, preferably 2-8:1; for example, the molar ratio can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 15:1, 18:1, 20:1, or any molar ratio in the range of 1-20:1.

[0076] Those skilled in the art will appreciate that the reaction temperatures, reaction times, and molar ratios of hydrogen to CFC-113a listed in the examples herein should not be construed as limiting the embodiments of the present invention. When reacting at lower reaction temperatures (e.g., 210° C., 200° C.), by extending the contact time (e.g., 30 seconds, 60 seconds, or even longer) and / or increasing the molar ratio of hydrogen to CFC-113a (e.g., 8:1, 10:1), a better catalytic reduction effect can be achieved, resulting in a higher yield of CFC-1316mxx (e.g., approximately 80%, 85%, or even higher). Similarly, at shorter contact times (e.g., 10 s, 15 s), by increasing the reaction temperature (e.g., 270° C., 290° C., or 310° C., or even higher reduction reaction temperatures) and / or increasing the molar ratio of hydrogen to CFC-113a (e.g., 8:1, 10:1), a better catalytic reduction effect can be achieved, resulting in a higher CFC-1316mxx yield (e.g., approximately 80%, such as approximately 85%, or even higher). Similarly, when the molar ratio of hydrogen to CFC-113a is smaller (e.g., a molar ratio of 3:1), a better reduction effect can be achieved by increasing the reaction temperature (e.g., 270° C., 290° C., or 310° C., or even higher reduction reaction temperatures) and / or extending the contact time (e.g., 30 s, 60 s, or even longer contact times) to achieve a higher CFC-1316mxx yield (e.g., approximately 65%, such as approximately 70%, such as approximately 85%, or even higher). It should be understood by those skilled in the art that, in actual production, in order to obtain products more efficiently and / or energy-savingly, based on this consideration, the reaction is carried out with the shortest possible contact time and / or the lowest possible reduction reaction temperature while ensuring a good product yield.

[0077] When the catalyst prepared herein is used to catalyze the hydrocoupling of CFC-113a to synthesize CFC-1316mxx, the final yield of CFC-1316mxx remains at a level of at least approximately 75%, and can even reach as high as 92%, or even higher. Therefore, when used to catalyze the hydrocoupling of CFC-113a to synthesize CFC-1316mxx, the catalyst herein exhibits significantly high selectivity (at least 92%) and relatively high conversion (approximately 75%-95%).

[0078] Example

[0079] Specific embodiments of the present application will be described in more detail below with reference to the accompanying drawings. Although specific embodiments of the present application are shown in the accompanying drawings, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein. Rather, these embodiments are provided to enable a more thorough understanding of the present application and to fully convey the scope of the present application to those skilled in the art.

[0080] Example 1:

[0081] At room temperature, 0.41g of ruthenium chloride and 20.00g of barium fluoride (the mass ratio of Ru in RuCl3 / BaF2 is 1wt.%) are mixed evenly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is evenly mixed. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, the tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%RuCl3 / BaF2.

[0082] The catalyst precursor was pre-treated for activation. The pre-treatment process was as follows: 10.0 mL of 1 wt.% RuCl3 / BaF2 catalyst precursor was placed in a reactor, N2 was used as diluent (50 mL / min), and reduced at 280°C for 8 h under H2 atmosphere (25 mL / min) to obtain a 1% Ru / BaF2 catalyst. The XRD diffraction pattern of the catalyst is shown in FIG. Figure 2 , SEM images are shown in Figure 3 , TEM image see Figure 4 .

[0083] The above catalyst was used to catalyze the hydrocoupling of CFC-113a to synthesize CFC-1316mxx. The reaction conditions for the catalyst evaluation experiment were: 10.0 mL of 1% Ru / BaF2 catalyst was loaded into the constant temperature zone of the reaction tube, atmospheric pressure, a preheater temperature of 150°C, a reactor temperature of 230°C, a contact time of 20 seconds between reactants and catalyst, a material ratio of n(H2):n(CFC-113a) of 6:1, and an evaluation time of 9 hours. The conversion of CFC-113a and the selectivity for CFC-1316mxx are shown in Table 1.

[0084] Example 2:

[0085] At room temperature, 0.41g of ruthenium chloride and 20.00g of magnesium fluoride (the mass ratio of Ru in RuCl3 / MgF2 is 1wt.%) are mixed uniformly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is uniform. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, the tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%RuCl3 / MgF2.

[0086] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0087] Example 3:

[0088] At room temperature, 0.41g of ruthenium chloride and 20.00g of calcium fluoride (the mass ratio of Ru in RuCl3 / CaF2 is 1wt.%) are mixed uniformly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is uniform. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, the tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%RuCl3 / CaF2.

[0089] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0090] Example 4:

[0091] At room temperature, 0.41g of ruthenium chloride and 20.00g of strontium fluoride (the mass ratio of Ru in RuCl3 / SrF2 is 1wt.%) are mixed evenly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is evenly mixed. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, the tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%RuCl3 / SrF2.

[0092] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0093] Example 5:

[0094] At room temperature, 0.41g of ruthenium chloride and 20.00g of sodium fluoride (the mass ratio of Ru in RuCl3 / NaF is 1wt.%) are mixed uniformly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is uniform. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, the tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%RuCl3 / NaF.

[0095] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0096] Example 6:

[0097] At room temperature, 0.41g of ruthenium chloride and 20.00g of aluminum fluoride (the mass ratio of Ru in RuCl3 / AlF3 is 1wt.%) are mixed uniformly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is uniform. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, the tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%RuCl3 / AlF3.

[0098] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0099] Example 7:

[0100] At room temperature, 0.34g of palladium chloride and 20.00g of barium fluoride (the mass ratio of Pd in ​​PdCl2 / BaF2 is 1wt.%) are mixed uniformly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is uniform. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.% PdCl2 / BaF2.

[0101] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0102] Example 8:

[0103] At room temperature, 0.52g of rhodium chloride and 20.00g of barium fluoride (Rh mass ratio in RhCl3 / BaF2 is 1wt.%) are mixed uniformly, and then 0.63g of release agent graphite powder (graphite powder mass ratio in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is uniform. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.% RhCl3 / BaF2.

[0104] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0105] Example 9:

[0106] At room temperature, 0.43g of copper chloride and 20.00g of barium fluoride (Cu mass ratio in CuCl2 / BaF2 is 1wt.%) are mixed evenly, and then 0.63g of release agent graphite powder (graphite powder mass ratio in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is evenly mixed. The mixed catalyst sample is made into catalyst tablets by a powder tabletting machine, that is, tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%CuCl2 / BaF2.

[0107] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0108] Example 10:

[0109] At room temperature, 0.45g nickel chloride and 20.00g barium fluoride (Ni mass ratio in NiCl2 / BaF2 is 1wt.%) are mixed uniformly, and then 0.63g release agent graphite powder (graphite powder mass ratio in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is uniform. The mixed catalyst sample is made into catalyst tablets by a powder tabletting machine, that is, tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.% NiCl2 / BaF2.

[0110] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0111] Comparative Example 1:

[0112] At room temperature, 0.41g of ruthenium chloride and 20.00g of silicon carbide (the mass ratio of Ru in RuCl3 / SiC is 1wt.%) are mixed evenly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is evenly mixed. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, the tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%RuCl3 / SiC.

[0113] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0114] Comparative Example 2:

[0115] At room temperature, 0.41g of ruthenium chloride and 20.00g of silicon dioxide (the mass ratio of Ru in RuCl3 / SiO2 is 1wt.%) are mixed uniformly, and then 0.63g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3wt.%) is added and mechanically stirred for 30min until the mixture is uniform. The mixed catalyst sample is made into catalyst tablets by a powder tablet press, that is, the tableting is maintained at 30Mpa for 2min. Subsequently, the tablet catalyst is crushed and sieved to 40-60 mesh and dried in a 105°C oven overnight. The dried sample is dried at 150°C for 2h under N2 atmosphere (50mL / min) to obtain a catalyst precursor 1wt.%RuCl3 / SiO2.

[0116] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0117] Comparative Example 3:

[0118] 0.41g of ruthenium chloride was dissolved in 50.0mL of water at room temperature and heated with stirring until fully dissolved. 20.0g of Al2O3 (Ru content = 1 wt.%) was added to the solution and slowly stirred at 60°C for 4 hours. The filtrate was then filtered and removed. The sample was dried in a 105°C oven overnight. The dried sample was then dried at 150°C for 2 hours under a nitrogen atmosphere (50mL / min) to obtain a catalyst precursor, 1 wt.% RuCl3 / Al2O3.

[0119] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0120] Comparative Example 4:

[0121] 0.41g of ruthenium chloride was dissolved in 50.0mL of water at room temperature and heated with stirring until fully dissolved. 20.0g of 3A molecular sieve (Ru content: 1 wt.%) was added to the solution and slowly stirred at 60°C for 4 hours. The filtrate was then filtered and removed. The sample was dried in a 105°C oven overnight. The dried sample was then dried at 150°C under a nitrogen atmosphere (50mL / min) for 2 hours to obtain a catalyst precursor, 1 wt.% RuCl3 / 3A.

[0122] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 1.

[0123] Examples 11-15:

[0124] At room temperature, 0.21g, 0.84g, 2.05g, 6.15g, 10.25g of ruthenium chloride and 20.00g of barium fluoride (RuCl3 / BaF2 in a Ru mass ratio of 0.5wt.%, 2wt.%, 5wt.%, 15wt.%, 25wt.%) were mixed uniformly, and then graphite powder (the mass ratio of graphite powder in the mixture was 3wt.%) was added as a release agent and mechanically stirred for 30min until the mixture was uniform. The mixed catalyst sample was obtained by a powder tabletting machine to obtain catalyst tablets, i.e., tableting was maintained at 30Mpa for 2min. Subsequently, the tablet catalyst was crushed and sieved to 40-60 mesh and dried overnight in a 105°C oven. The dried samples were dried at 150°C for 2 h under N2 atmosphere (50 mL / min) to obtain catalyst precursors 0.5 wt.% RuCl3 / BaF2, 2 wt.% RuCl3 / BaF2, 5 wt.% RuCl3 / BaF2, 15 wt.% RuCl3 / BaF2 and 25 wt.% RuCl3 / BaF2.

[0125] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as those in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 2.

[0126]

[0127] As shown in Table 1, compared to other supports (SiC, SiO2, Al2O3, and 3A molecular sieve), the fluoride-based catalyst of the present invention exhibits the highest activity in the hydrocoupling reaction of CFC-113a to synthesize CFC-1316mxx, achieving CFC-113a conversion and CFC-1316mxx selectivity exceeding 80.00%. Different fluoride-based catalysts exhibit varying activity, with BaF2 as the support exhibiting the highest activity, achieving a CFC-113a conversion of 89.43% and a CFC-1316mxx selectivity of 95.33%.

[0128] Examples 16-18:

[0129] Examples 16-18 investigate the effect of drying temperature on catalyst activity during the preparation of catalyst precursors. At room temperature, 0.41 g of ruthenium chloride and 20.00 g of barium fluoride (Ru mass ratio of Ru in RuCl3 / BaF2 is 1 wt.%) were mixed uniformly, and then 0.63 g of release agent graphite powder (the mass ratio of graphite powder in the mixture is 3 wt.%) was added and mechanically stirred for 30 min until the mixture was uniformly mixed. The mixed catalyst sample was obtained by a powder tabletting machine to obtain catalyst tablets, i.e., tableting was maintained at 30 MPa for 2 min. Subsequently, the tablet catalyst was crushed and sieved to 40-60 mesh and dried in a 105 ° C oven overnight. The dried sample was dried for 2 h at 130 ° C, 170 ° C and 250 ° C using N2 atmosphere (50 mL / min) to obtain a catalyst precursor.

[0130] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as in Example 1. Catalysts 16#, 17#, and 18# were obtained. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 2.

[0131] Examples 19-20:

[0132] Example 19-20 investigates the effect of drying time on catalyst activity during the preparation of a catalyst precursor. At room temperature, 0.41 g of ruthenium chloride and 20.00 g of barium fluoride (RuCl3 / BaF2 in a mass ratio of 1 wt.%) were mixed uniformly, and then 0.63 g of a release agent graphite powder (the mass ratio of graphite powder in the mixture was 3 wt.%) was added and mechanically stirred for 30 min until the mixture was uniformly mixed. The mixed catalyst sample was obtained by a powder tabletting machine to obtain catalyst tablets, i.e., tableting was maintained at 30 MPa for 2 min. Subsequently, the tablet catalyst was crushed and sieved to 40 to 60 meshes and dried in a 105 ° C oven overnight. The dried sample was dried at 150 ° C for 1 h and 3 h, respectively, using a N2 atmosphere (50 mL / min) to obtain a catalyst precursor.

[0133] The activation pretreatment of the catalyst precursor and the evaluation method of the catalyst were the same as in Example 1. Catalysts 19# and 20# were obtained. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 2.

[0134] Examples 21-23:

[0135] The preparation of the catalyst precursor is the same as that in Example 1.

[0136] Examples 21-23 investigated the effect of reduction temperature on catalyst activity during catalyst precursor activation. 10.0 mL of 1 wt.% RuCl3 / BaF2 catalyst precursor was charged into a reactor and reduced at 240°C, 260°C, and 300°C for 12 h, 8 h, and 8 h, respectively, under a nitrogen diluent (50 mL / min) and hydrogen atmosphere (25 mL / min). Catalysts 21#, 22#, and 23# were obtained, as shown in Table 2.

[0137] The catalyst evaluation method was the same as in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 2.

[0138] Examples 24-26:

[0139] The preparation of the catalyst precursor is the same as that in Example 1.

[0140] Examples 24-26 investigated the effect of reduction time on catalyst activity during catalyst precursor activation. 10.0 mL of 1 wt.% RuCl3 / BaF2 catalyst precursor was charged into a reactor and reduced at 280°C under a nitrogen dilution gas (50 mL / min) and a hydrogen atmosphere (25 mL / min) for 6, 10, and 12 hours, respectively, to obtain catalysts 24#, 25#, and 26#.

[0141] The catalyst evaluation method was the same as in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 2.

[0142] Examples 27-28:

[0143] The preparation of the catalyst precursor is the same as that in Example 1.

[0144] Examples 27-28 investigated the effect of the N2:H2 ratio on catalyst activity during catalyst precursor activation. 10.0 mL of a 1 wt.% RuCl3 / BaF2 catalyst precursor was charged into a reactor with N2 as the diluent (50 mL / min). Reduction was carried out at 280°C for 8 h and 12 h at N2:H2 ratios of 1:1 (H2: 50 mL / min) and 3:1 (H2: 17 mL / min), respectively, to produce Catalysts 27# and 28#.

[0145] The catalyst evaluation method was the same as in Example 1. The conversion of CFC-113a and the selectivity of CFC-1316mxx are shown in Table 2.

[0146]

[0147] As shown in Table 2, when the active component loading is low, the catalyst activity is poor. When the active component loading is too high, the feedstock conversion rate will increase slightly, but excessive active metal will cause agglomeration, thereby reducing the selectivity of the target product to a certain extent. Low drying temperature and insufficient drying time will cause residual moisture on the catalyst surface, resulting in poor catalyst activity. Low activation temperature, insufficient activation time, and an excessively high ratio of inert gas to reducing gas will lead to insufficient reduction of ruthenium chloride and poor catalyst activity. The fluoride-based catalyst with the best catalytic activity was obtained under the optimal preparation conditions.

[0148] Examples 29-32:

[0149] The preparation and activation pretreatment methods of the catalyst precursor are the same as those in Example 1.

[0150] Examples 29-32 investigated the effect of reaction temperature on catalyst activity among process parameters. The above-mentioned catalyst was used to catalyze the hydrocoupling of CFC-113a to synthesize CFC-1316mxx. The reaction conditions for the catalyst evaluation experiments were: 10.0 mL of 1% Ru / BaF2 catalyst was loaded into the constant temperature zone of the reaction tube, atmospheric pressure, a preheater temperature of 150°C, and reactor temperatures of 210°C, 250°C, 270°C, and 290°C, respectively. The contact time between the reactants and the catalyst was 20 seconds, the material ratio n(H2):n(CFC-113a) was 6:1, and the evaluation time was 18 hours. The conversion of CFC-113a and the selectivity for CFC-1316mxx are shown in Table 3.

[0151] Examples 33-35:

[0152] The preparation and activation pretreatment methods of the catalyst precursor are the same as those in Example 1.

[0153] Examples 32-34 investigated the effect of the process parameter material ratio n(H2):n(CFC-113a) on catalyst activity. The catalyst was used to catalyze the hydrocoupling of CFC-113a to synthesize CFC-1316mxx. The catalyst evaluation conditions were: 10.0 mL of 1% Ru / BaF2 catalyst was loaded into the constant temperature zone of the reaction tube, atmospheric pressure, a preheater temperature of 150°C, a reactor temperature of 250°C, and contact times of 20, 20, and 30 seconds. The material ratios n(H2):n(CFC-113a) were 8:1, 4:1, and 2:1, respectively, and the evaluation period was 18 hours. The conversion of CFC-113a and the selectivity for CFC-1316mxx are shown in Table 3.

[0154] Examples 36-38:

[0155] The preparation and activation pretreatment methods of the catalyst precursor are the same as those in Example 1.

[0156] Examples 35-37 investigated the effect of contact time on catalyst activity among process parameters. The above-mentioned catalyst was used to catalyze the hydrocoupling of CFC-113a to synthesize CFC-1316mxx. The reaction conditions for the catalyst evaluation experiments were: 10.0 mL of 1% Ru / BaF2 catalyst was loaded into the constant temperature zone of the reaction tube, atmospheric pressure, a preheater temperature of 150°C, a reactor temperature of 250°C, contact times of 30, 15, and 10 seconds, respectively; a material ratio of n(H2):n(CFC-113a) of 6:1, and an evaluation period of 18 hours. The conversion of CFC-113a and the selectivity for CFC-1316mxx are shown in Table 3.

[0157] Table 3 Effect of different process parameters on the synthesis of CFC-1316mxx by hydrogenation coupling of CFC-113a

[0158]

[0159] As shown in Table 3, different process parameters significantly influence the reaction. The purpose of this section of the examples was to determine the optimal process conditions for the hydrocoupling of CFC-113a to synthesize CFC-1316mxx using a fluoride-based catalyst, thereby enabling the subsequent evaluation of catalyst stability. To achieve the product with the highest possible efficiency and energy conservation, the reaction was conducted with the shortest possible contact time and the lowest possible reaction temperature, while ensuring a good product yield. Therefore, the optimal process conditions were a reactor temperature of 250°C, a contact time of 15 seconds between reactants and catalyst, and a material ratio of n(H2):n(CFC-113a) of 6:1. Under these optimal conditions, a CFC-113a conversion of 93.21% and a CFC-1316mxx selectivity of 96.04% were achieved.

[0160] Example 39:

[0161] The service life of fluoride-based catalysts in the hydrocoupling reaction of CFC-113a to synthesize CFC-1316mxx was evaluated under optimal reaction conditions.

[0162] The reaction conditions for the catalyst life evaluation experiment were: 10.0 mL of 1% Ru / BaF2 catalyst was loaded into the constant temperature zone of the reaction tube, atmospheric pressure, a preheater temperature of 150°C, a reactor temperature of 250°C, a contact time of 15 seconds between the reactants and the catalyst, a material ratio of n(H2):n(CFC-113a) of 6:1, and an evaluation time of 100 hours. The time-dependent changes in CFC-113a conversion and CFC-1316mxx selectivity are shown in the following figure. Figure 1 shown.

[0163] Depend on Figure 1It can be seen that the fluoride-based catalyst of the present invention has good stability in the reaction of hydrogenating and coupling CFC-113a to synthesize CFC-1316mxx. After continuous use for 100 hours, the conversion rate can still reach 70.00% and the selectivity can reach 95.21%.

[0164] The description of the present disclosure is provided for purposes of illustration and description and is not intended to be exhaustive or to limit the disclosure to the disclosed form. Many modifications and variations will be apparent to those skilled in the art. The embodiments are selected and described in order to better illustrate the principles and practical applications of the present disclosure and to enable those skilled in the art to understand the present disclosure and design various embodiments with various modifications suitable for specific applications.

Claims

1. A fluoride catalyst for catalyzing the synthesis of CFC-1316mxx from CFC-113a, wherein the fluoride catalyst is prepared from a catalyst precursor comprising a transition metal salt and a fluoride carrier MF x ; in, The transition metal salt is selected from any one or more of ruthenium salts, rhodium salts, palladium salts, nickel salts, and copper salts; The fluoride carrier MF x Any one or more selected from sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, and aluminum fluoride.

2. The fluoride catalyst according to claim 1, wherein the transition metal element in the transition metal salt accounts for x 0.05-30 wt% of the total weight; preferably 1-25 wt%.

3. A method for preparing the fluoride catalyst according to claim 1 or 2, comprising: The transition metal salt and fluoride carrier MF x Mixing evenly and then drying to obtain the catalyst precursor; The catalyst precursor is reduced and activated by hydrogen to obtain the fluoride catalyst.

4. The preparation method according to claim 3, wherein the drying comprises pre-drying and secondary drying; in, The pre-drying process is to combine the transition metal salt and the fluoride carrier MF. x The mixture is dried at 100-150°C; The secondary drying conditions include: a drying temperature of 100-300°C; And / or, the drying time of the secondary drying is 0.5-24 hours.

5. The preparation method according to claim 4, wherein the secondary drying is performed in an environment containing an inert gas; preferably, the inert gas is nitrogen.

6. The preparation method according to any one of claims 3 to 5, wherein the reduction activation temperature is 150-500°C; The reduction activation time is 1-100 h, preferably 6-12 h.

7. The preparation method according to any one of claims 3 to 5, wherein the reducing agent during the reduction activation is nitrogen; Preferably, the volume ratio of nitrogen to hydrogen is 0.5-3:

1.

8. A method for catalyzing the synthesis of CFC-1316mxx from CFC-113a, the method comprising using the fluoride catalyst according to claim 1 or 2 and / or the fluoride catalyst prepared by the preparation method according to any one of claims 3 to 7.

9. The method according to claim 8, wherein when catalyzing CFC-113a to synthesize CFC-1316mxx, the reaction temperature is 150-350°C, preferably 210-290°C; And / or, the reaction time is 1-40 s, preferably 10-30 s.

10. The method according to claim 8 or 9, wherein when catalyzing CFC-113a to synthesize CFC-1316mxx, the molar ratio of hydrogen to CFC-113a is 1-20:1, preferably 2-8:1.

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