CN110563547A - preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene - Google Patents
preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07C17/00—Preparation of halogenated hydrocarbons
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- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
Abstract
the invention discloses a preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene, which is characterized by comprising the following steps: the preparation method comprises the following preparation steps: (1) under the action of a catalyst, reacting 1,1, 1-trifluorotrichloroethane serving as a raw material with hydrogen to obtain a first product 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene; (2) reacting the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene obtained in the step (1) with hydrogen under the action of a catalyst to obtain a second product 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene; (3) carrying out gas-phase dehydrochlorination on the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene obtained in the step (2) under the action of a catalyst to obtain a third product of hexafluoro-2-butyne; (4) and carrying out selective hydrogenation reaction on the hexafluoro-2-butyne under the action of a catalyst to obtain a final product 1,1,1,4,4, 4-hexafluoro-2-butene. The preparation method disclosed by the invention has the advantages that the required raw materials are more conventional and easily obtained, the process is simple, the operation is convenient, the preparation process is more environment-friendly, the pollution is less, the preparation method is suitable for industrial production, and the prepared 1,1,1,4,4, 4-hexafluoro-2-butene has excellent selectivity and conversion rate.
Description
Technical Field
The invention relates to the field of synthesis of fluoroolefin, and particularly relates to a preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene.
background
1,1,1,4,4, 4-hexafluoro-2-butene, which is a cis isomer and a trans isomer, is a colorless and odorless gas in general, and can be used as a novel foaming agent, a refrigerant and a fire extinguishing agent. The hexafluoro-2-butene is considered as one of ideal substitutes of the foaming agent HCFC-141b, the foaming agent product is environment-friendly, has remarkable heat insulation and preservation characteristics, is nonflammable, does not consume ozone, can replace other liquid foaming agents at low conversion cost, and has wide application prospect.
Currently, 1,1,1,4,4, 4-hexafluoro-2-butene mainly has the following synthesis methods:
A method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene is disclosed in U.S. Pat. No. 5, 2011288349A1, published as 2011, 11 months and 24 days, and uses hexafluoropropylene and trichloromethane as raw materials to synthesize the 1,1,1,4,4, 4-hexafluoro-2-butene. Hexafluoropropylene and trichloromethane are subjected to addition reaction to generate 1,1, 1-trichloro-2, 2,3,4,4, 4-hexafluorobutane, the 1,1,2, 2,3,4,4, 4-nonafluorobutane is obtained through fluorination, dehydrofluorination and reduction dehalogenation are carried out on the 1,1,1,4,4, 4-hexafluoro-2-butene. The synthesis method has multiple synthesis steps and complex process.
A production process of hexafluoro-2-butene, disclosed as WO2011119388A2, disclosed as 29/09/2011, adopts carbon tetrachloride and ethylene as raw materials to synthesize 1,1,1,4,4, 4-hexafluoro-2-butene. The addition reaction of carbon tetrachloride and ethylene produces 1,1,1, 4-tetrachloropropane, the dehydrochlorination of 1,1,1, 4-tetrachloropropane, the addition of 1,1,1,2,4,4, 4-heptachlorobutane and carbon tetrachloride produces 1,1,1,2,4,4, 4-heptachlorobutane, which is fluorinated and dehydrochlorinated to produce 1,1,1,4,4, 4-hexafluoro-2-butene with total yield of 69%. The synthesis method has long synthesis steps, complex process and low yield.
A production method of a fluorine-containing olefin compound is disclosed as JP2010001244, wherein the publication date is 2010, 01-month and 07-year, and 1,1, 1-trifluoro-2-bromo-2-chloroethane is adopted as a raw material to synthesize 1,1,1,4,4, 4-hexafluoro-2-butene. 1,1, 1-trifluoro-2-bromo-2-chloroethane is coupled by zinc powder to obtain 1,1,1,4,4, 4-hexafluoro-2, 3-chlorobutane, and the 1,1,1,4,4, 4-hexafluoro-2-butene is obtained by dechlorinating with zinc powder, wherein the yield is 42-69%. The synthesis method has the advantages of difficult obtainment of required raw materials and low yield.
Disclosure of Invention
the technical problem to be solved by the invention is to provide a preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene, which has the advantages of simple process route, small pollution and excellent conversion rate and selectivity.
in order to solve the technical problems, the invention is realized by the following technical scheme:
A preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene comprises the following preparation steps:
(1) Under the action of a catalyst, reacting 1,1, 1-trifluorotrichloroethane and hydrogen at the temperature of 125-300 ℃, wherein the molar ratio of the hydrogen to the 1,1, 1-trifluorotrichloroethane is 0.5-5: 1, and then separating and recovering to obtain a first product 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene;
(2) Reacting the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene obtained in the step (1) with hydrogen at the temperature of 125-300 ℃ under the action of a catalyst, wherein the molar ratio of the hydrogen to the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 1-10: 1, the contact time of the hydrogen and the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 20-80 s, and then separating and recovering to obtain a second product 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene;
(3) Carrying out gas-phase dehydrochlorination on the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene obtained in the step (2) under the action of a catalyst, wherein the reaction temperature is 200-400 ℃, and the reaction space velocity is 100h < -1 > to 600h < -1 >, so as to obtain a third product of hexafluoro-2-butyne;
(4) Carrying out selective hydrogenation reaction on hexafluoro-2-butyne under the action of a catalyst, wherein the reaction temperature is 150-250 ℃, the molar ratio of hydrogen to hexafluoro-2-butyne is 1-15: 1, and the contact time of the hydrogen and the hexafluoro-2-butyne is 5-40 s, so as to obtain a final product 1,1,1,4,4, 4-hexafluoro-2-butene;
in the step (1), the main active component of the catalyst is platinum, the cocatalyst component is rhodium, ruthenium or rhenium, the carrier is one of activated carbon, gamma-alumina, silica, magnesium fluoride, calcium fluoride and tungsten carbide, and the platinum is loaded on the carrier by a loading amount of 0.2-5% of the total weight of the catalyst;
the catalyst component in the step (2) is one or the combination of more than two of cobalt, zinc, copper, osmium or iridium, the carrier is alumina, and the catalyst component is loaded on the carrier by 0.3-5 percent of the total weight of the catalyst;
The catalyst component in the step (3) is one or the combination of more than two of iron, cobalt, nickel, magnesium, potassium, cesium and barium, the carrier is coconut shell activated carbon, and the catalyst component is loaded on the carrier by 1-20% of the total weight of the catalyst;
The catalyst in the step (4) is palladium modified by porous aluminum fluoride supported lead or bismuth, the supported amount of the palladium is 1-10% of the total weight of the catalyst, and the supported amount of the lead or bismuth is 0.1-5% of the total weight of the catalyst.
Preferably, in the step (1), the carrier is tungsten carbide, and the platinum is supported on the carrier at a loading amount of 0.5-2.5% of the total weight of the catalyst.
preferably, the catalyst component in the step (2) is supported on the carrier in an amount of 0.5 to 25% by weight based on the total weight of the catalyst.
preferably, the catalyst component in the step (3) is supported on the carrier in an amount of 5% to 15% by weight based on the total weight of the catalyst.
preferably, the loading amount of the palladium in the step (4) is 3 to 5 percent of the total weight of the catalyst; the loading amount of the lead or the bismuth is 0.5 to 3 percent of the total weight of the catalyst.
Preferably, in the step (1), the reaction temperature is 175-225 ℃, and the molar ratio of hydrogen to 1,1, 1-trifluorotrichloroethane is 1-3: 1; in the step (2), the reaction temperature is 175-225 ℃, the molar ratio of hydrogen to 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 4-8: 1, and the contact time of the hydrogen and the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 30-60 s; in the step (3), the reaction temperature is 250-350 ℃, and the reaction space velocity is 300-1-500 h-1; in the step (4), the reaction temperature is 180-200 ℃, the molar ratio of hydrogen to hexafluoro-2-butyne is 5-10: 1, and the contact time of the hydrogen and the hexafluoro-2-butyne is 10-30 s.
Preferably, the catalyst in the steps (1) to (4) is prepared by an impregnation method, and the impregnation solvent is deionized water or ethanol or acetone.
preferably, a competitive adsorbent is added to the impregnation solvent, and the competitive adsorbent is citric acid, tartaric acid, oxalic acid, hydrochloric acid or lactic acid.
The invention has the beneficial effects that: the preparation method disclosed by the invention has the advantages that the required raw materials are more conventional and easily obtained, the process is simple, the operation is convenient, the preparation process is more environment-friendly, the pollution is less, and the preparation method is suitable for industrial production, and in the preparation process, the selectivity of the product generated in each step is high, so that the final product 1,1,1,4,4, 4-hexafluoro-2-butene has excellent selectivity and conversion rate.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
example 1
A preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene comprises the following preparation steps:
(1) filling Pt-Rh/WC catalyst in an alloy reactor, wherein Pt is loaded on WC in a loading amount of 0.2 percent of the total weight of the catalyst, firstly introducing hydrogen at the speed of 100ml/min, simultaneously raising the temperature of the bed layer to 140 ℃, stabilizing the temperature for 30min, changing the hydrogen flow to 50ml/min, raising the temperature of the bed layer to 220 ℃, stabilizing for 60min, feeding hydrogen and 1,1, 1-trifluorotrichloroethane at a molar ratio of 3:1, reacting for 2h, separating and recovering to obtain a first product 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene, and sampling and analyzing by GC detection, wherein the conversion rate of the 1,1, 1-trifluorotrichloroethane is 52.18 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 82.36 percent;
(2) Co-Zn-Os/Al is filled into the alloy reactor2O3Catalyst, Co-Zn-Os loaded on Al in 0.3% of total weight of catalyst2O3Firstly, introducing hydrogen at the rate of 100ml/min, simultaneously raising the temperature of the bed layer to 140 ℃, stabilizing the temperature for 30min, changing the flow rate of the hydrogen to 50ml/min, raising the temperature of the bed layer to 210 ℃, stabilizing the temperature for 60min, and setting the molar ratio of the hydrogen to the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene to be 30s and the retention time4, feeding the raw materials at the ratio of 1:1, reacting for 2 hours, separating and recovering to obtain a second product 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, and sampling and analyzing by GC detection, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 86.52%, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 92.54%;
(3) Filling an alloy reactor with an Ni-Cs/C catalyst and 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, wherein the Ni-Cs is loaded on the C by 5 percent of the total weight of the catalyst, the hydrogen flow is 20ml/min at 120 ℃, the activation treatment is carried out for 12h, the reaction temperature is 350 ℃, the space velocity is 400h < -1 >, a third product of hexafluoro-2-butyne is obtained after the reaction is carried out for 2h, and the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 97.85 percent and the selectivity of the hexafluoro-2-butyne is 95.43 percent by sampling and analyzing through GC detection;
(4) Filling a Pd-Bi/PAF catalyst and hexafluoro-2-butyne into an alloy reactor, wherein the load of Pd is 1% of the total weight of the catalyst, the load of Bi is 5% of the total weight of the catalyst, introducing hydrogen and nitrogen in an amount of 1:1 at 100 ℃, carrying out activation treatment for 2 hours, the reaction temperature is 180 ℃, the retention time is 30s, the molar ratio of hydrogen to hexafluoro-2-butyne is 10:1, obtaining a final product of 1,1,1,4,4, 4-hexafluoro-2-butene after reacting for 2 hours, and analyzing by sampling and GC detection, the conversion rate of hexafluoro-2-butyne is 99.62%, and the selectivity of 1,1,4,4, 4-hexafluoro-2-butene is 96.57%.
example 2
A preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene comprises the following preparation steps:
(1) filling Pt-Ru/SiO into alloy reactor2catalyst, Pt is loaded on SiO in a loading amount of 2.5 percent of the total weight of the catalyst2Firstly, introducing hydrogen at the rate of 100ml/min, raising the temperature of a bed layer to 125 ℃, stabilizing the temperature for 30min, changing the hydrogen flow rate to 50ml/min, raising the temperature of the bed layer to 225 ℃, stabilizing for 60min, starting feeding with the molar ratio of the hydrogen to the 1,1, 1-trifluorotrichloroethane being 0.5:1, separating and recovering after reacting for 2h to obtain a first product 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene, and sampling and analyzing by GC detection, wherein the conversion rate of the 1,1, 1-trifluorotrichloroethane is 51.05 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 80.26 percent;
(2) filling Co-Cu-Ir/Al into an alloy reactor2O3Catalyst, Co-Cu-Ir 0.5% of total weight of catalyst is loaded on Al2O3Firstly, introducing hydrogen at the rate of 100ml/min, simultaneously raising the temperature of the bed layer to 125 ℃, stabilizing the temperature for 30min, changing the hydrogen flow rate to 50ml/min, raising the temperature of the bed layer to 225 ℃, stabilizing for 60min, feeding the mixture with a retention time of 60s and a molar ratio of 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene of 1:1, reacting for 2h, separating and recovering to obtain a second product 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, sampling and analyzing by GC detection, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 83.86%, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 90.21%;
(3) filling an Fe-K/C catalyst and 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene into an alloy reactor, wherein the Fe-K is loaded on the C by 15 percent of the total weight of the catalyst, the hydrogen flow is 20ml/min at 120 ℃, the activation treatment is carried out for 12h, the reaction temperature is 200 ℃, the space velocity is 100h < -1 >, a third product of hexafluoro-2-butyne is obtained after the reaction is carried out for 2h, and a sample is sampled and analyzed by GC (gas chromatography) detection, so that the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 96.75 percent, and the selectivity of the hexafluoro-2-butyne is 94.26 percent;
(4) Filling a Pd-Pb/PAF catalyst and hexafluoro-2-butyne into an alloy reactor, wherein the load of Pd is 5% of the total weight of the catalyst, the load of Pb is 0.5% of the total weight of the catalyst, introducing hydrogen and nitrogen in an amount of 1:1 at 100 ℃, carrying out activation treatment for 2 hours, the reaction temperature is 150 ℃, the residence time is 10s, the molar ratio of hydrogen to hexafluoro-2-butyne is 1:1, obtaining a final product of 1,1,1,4,4, 4-hexafluoro-2-butene after reacting for 2 hours, and analyzing by sampling through GC detection, the conversion rate of hexafluoro-2-butyne is 99.62%, and the selectivity of 1,1,4,4, 4-hexafluoro-2-butene is 95.55%.
Example 3
A preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene comprises the following preparation steps:
(1) Filling Pt-Re/CaF into an alloy reactor2catalyst, Pt is loaded on CaF with a load of 0.5 percent of the total weight of the catalyst2first, hydrogen was introduced at a rate of 100ml/min while the bed temperature was raised to 175 deg.CThe temperature is stabilized for 30min, the hydrogen flow is changed to 50ml/min, the bed temperature is increased to 300 ℃, the bed temperature is stabilized for 60min, the feeding is started with the molar ratio of the hydrogen to the 1,1, 1-trifluorotrichloroethane being 5:1, after the reaction is carried out for 2h, the separation and the recovery are carried out to obtain a first product 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene, the sampling is detected and analyzed by GC, the conversion rate of the 1,1, 1-trifluorotrichloroethane is 55.10 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 83.20 percent;
(2) Filling Co-Zn-Cu/Al into an alloy reactor2O3catalyst, Co-Zn-Cu is loaded on Al by 5 percent of the total weight of the catalyst2O3Firstly, introducing hydrogen at the rate of 100ml/min, simultaneously raising the temperature of the bed layer to 175 ℃, stabilizing the temperature for 30min, changing the hydrogen flow rate to 50ml/min, raising the temperature of the bed layer to 300 ℃, stabilizing for 60min, feeding the mixture with the retention time of 80s and the molar ratio of the hydrogen to the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene of 10:1, reacting for 2h, separating and recovering to obtain a second product 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, sampling and analyzing by GC detection, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 87.12 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 93.24 percent;
(3) Filling an alloy reactor with a Ni-Co/C catalyst and 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, wherein the Ni-Co is loaded on the C by 1 percent of the total weight of the catalyst, the hydrogen flow is 20ml/min at 120 ℃, the activation treatment is carried out for 12h, the reaction temperature is 400 ℃, the space velocity is 600h < -1 >, a third product of hexafluoro-2-butyne is obtained after the reaction is carried out for 2h, and the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 98.15 percent and the selectivity of the hexafluoro-2-butyne is 95.88 percent by sampling and GC detection and analysis;
(4) filling a Pd-Bi/PAF catalyst and hexafluoro-2-butyne into an alloy reactor, wherein the loading of Pd is 3% of the total weight of the catalyst, the loading of Bi is 0.1% of the total weight of the catalyst, introducing hydrogen and nitrogen in an amount of 1:1 at 100 ℃, carrying out activation treatment for 2 hours, the reaction temperature is 250 ℃, the residence time is 40s, the molar ratio of hydrogen to hexafluoro-2-butyne is 15:1, obtaining a final product of 1,1,1,4,4, 4-hexafluoro-2-butene after reacting for 2 hours, and analyzing by sampling and GC detection, the conversion rate of hexafluoro-2-butyne is 99.62%, and the selectivity of 1,1,4,4, 4-hexafluoro-2-butene is 97.66%.
Example 4
A preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene comprises the following preparation steps:
(1) Filling Pt-Ru/MgF into an alloy reactor2Catalyst, Pt is loaded on MgF with a load of 3 percent of the total weight of the catalyst2Firstly, introducing hydrogen at the rate of 100ml/min, raising the temperature of a bed layer to 150 ℃, stabilizing the temperature for 30min, changing the hydrogen flow rate to 50ml/min, raising the temperature of the bed layer to 210 ℃, stabilizing for 60min, starting feeding with the molar ratio of the hydrogen to the 1,1, 1-trifluorotrichloroethane being 1:1, after reacting for 2h, separating and recovering to obtain a first product 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene, and sampling and analyzing by GC detection, wherein the conversion rate of the 1,1, 1-trifluorotrichloroethane is 51.25 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 80.45 percent;
(2) Filling Cu-Ir-Zn/Al into an alloy reactor2O3catalyst, Cu-Ir-Zn is loaded on Al by 10 percent of the total weight of the catalyst2O3Firstly, introducing hydrogen at the rate of 100ml/min, simultaneously raising the temperature of the bed layer to 160 ℃, stabilizing the temperature for 30min, changing the hydrogen flow rate to 50ml/min, raising the temperature of the bed layer to 200 ℃, stabilizing for 60min, feeding the mixture with a retention time of 20s and a molar ratio of hydrogen to 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene of 8:1, reacting for 2h, separating and recovering to obtain a second product 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, sampling and analyzing by GC detection, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 83.66 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 90.45 percent;
(3) Filling an alloy reactor with Fe-Mg/C catalyst and 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, wherein the Fe-Mg is loaded on the C by 20 percent of the total weight of the catalyst, the hydrogen flow is 20ml/min at 120 ℃, the activation treatment is carried out for 12h, the reaction temperature is 250 ℃, the space velocity is 300h < -1 >, a third product of hexafluoro-2-butyne is obtained after the reaction is carried out for 2h, and a sample is sampled and analyzed by GC detection, so that the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 96.25 percent, and the selectivity of the hexafluoro-2-butyne is 94.05 percent;
(4) Filling a Pd-Pb/PAF catalyst and hexafluoro-2-butyne into an alloy reactor, wherein the load of Pd is 10% of the total weight of the catalyst, the load of Pb is 1% of the total weight of the catalyst, hydrogen and nitrogen are introduced in a ratio of 1:1 at 100 ℃, activation treatment is carried out for 2 hours, the reaction temperature is 200 ℃, the retention time is 5s, the molar ratio of hydrogen to hexafluoro-2-butyne is 5:1, a final product of 1,1,1,4,4, 4-hexafluoro-2-butene is obtained after reaction for 2 hours, and the conversion rate of hexafluoro-2-butyne is 99.48% and the selectivity of 1,1,1,4,4, 4-hexafluoro-2-butene is 95.45% by sampling and GC detection analysis.
Example 5
A preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene comprises the following preparation steps:
(1) filling Pt-Ru/gamma-Al into the alloy reactor2O3catalyst, Pt is loaded on gamma-Al with the loading amount of 5 percent of the total weight of the catalyst2O3Firstly, introducing hydrogen at the rate of 100ml/min, raising the temperature of a bed layer to 140 ℃, stabilizing the temperature for 30min, changing the hydrogen flow rate to 50ml/min, raising the temperature of the bed layer to 220 ℃, stabilizing for 60min, starting feeding with the molar ratio of the hydrogen to the 1,1, 1-trifluorotrichloroethane being 2:1, after reacting for 2h, separating and recovering to obtain a first product 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene, and sampling and analyzing by GC detection, wherein the conversion rate of the 1,1, 1-trifluorotrichloroethane is 51.05 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 80.26 percent;
(2) Co-oS/Al fill into the alloy reactor2O3catalyst, Co-oS was supported on Al in an amount of 20% by weight based on the total weight of the catalyst2O3Firstly, introducing hydrogen at the rate of 100ml/min, simultaneously raising the temperature of the bed layer to 150 ℃, stabilizing the temperature for 30min, changing the hydrogen flow rate to 50ml/min, raising the temperature of the bed layer to 210 ℃, stabilizing for 60min, feeding the materials with the retention time of 50s and the molar ratio of the hydrogen to the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene of 6:1, reacting for 2h, separating and recovering to obtain a second product 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, sampling and analyzing by GC detection, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 83.05 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 90.05 percent;
(3) Filling an alloy reactor with a Ni-Ba/C catalyst and 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, wherein the Ni-Ba is loaded on the C by 10 percent of the total weight of the catalyst, the hydrogen flow is 20ml/min at 120 ℃, the activation treatment is carried out for 12h, the reaction temperature is 250 ℃, the space velocity is 5000h < -1 >, a third product of hexafluoro-2-butyne is obtained after the reaction is carried out for 2h, and a sample is sampled and analyzed by GC detection, so that the conversion rate of the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene is 96.95 percent, and the selectivity of the hexafluoro-2-butyne is 94.80 percent;
(4) filling a Pd-Bi/PAF catalyst and hexafluoro-2-butyne into an alloy reactor, wherein the load of Pd is 4% of the total weight of the catalyst, the load of Pb is 3% of the total weight of the catalyst, introducing hydrogen and nitrogen in an amount of 1:1 at 100 ℃, carrying out activation treatment for 2 hours, the reaction temperature is 190 ℃, the retention time is 20s, the molar ratio of hydrogen to hexafluoro-2-butyne is 6:1, obtaining a final product of 1,1,1,4,4, 4-hexafluoro-2-butene after reacting for 2 hours, and sampling and analyzing by GC detection, wherein the conversion rate of hexafluoro-2-butyne is 99.25%, and the selectivity of 1,1,4,4, 4-hexafluoro-2-butene is 95.05%.
further, the catalysts used in the above examples 1 to 3 were all prepared by an impregnation method, and the impregnation solvent was deionized water or ethanol or acetone.
further, in the preparation process of the catalyst used in the above examples 1 to 3, a competitive adsorbent is added to the impregnation solvent, and the competitive adsorbent is citric acid, tartaric acid, oxalic acid, hydrochloric acid or lactic acid.
the embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (8)
1. A preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene is characterized in that: the preparation method comprises the following preparation steps:
(1) under the action of a catalyst, reacting 1,1, 1-trifluorotrichloroethane and hydrogen at the temperature of 125-300 ℃, wherein the molar ratio of the hydrogen to the 1,1, 1-trifluorotrichloroethane is 0.5-5: 1, and then separating and recovering to obtain a first product 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene;
(2) reacting the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene obtained in the step (1) with hydrogen at the temperature of 125-300 ℃ under the action of a catalyst, wherein the molar ratio of the hydrogen to the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 1-10: 1, the contact time of the hydrogen and the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 20-80 s, and then separating and recovering to obtain a second product 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene;
(3) under the action of a catalyst, the 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene obtained in the step (2) is subjected to gas-phase dehydrochlorination reaction at the reaction temperature of 200-400 ℃ and the reaction space velocity of 100h-1～600h-1To obtain a third product of hexafluoro-2-butyne;
(4) carrying out selective hydrogenation reaction on hexafluoro-2-butyne under the action of a catalyst, wherein the reaction temperature is 150-250 ℃, the molar ratio of hydrogen to hexafluoro-2-butyne is 1-15: 1, and the contact time of the hydrogen and the hexafluoro-2-butyne is 5-40 s, so as to obtain a final product 1,1,1,4,4, 4-hexafluoro-2-butene;
In the step (1), the main active component of the catalyst is platinum, the cocatalyst component is rhodium, ruthenium or rhenium, the carrier is one of activated carbon, gamma-alumina, silica, magnesium fluoride, calcium fluoride and tungsten carbide, and the platinum is loaded on the carrier by a loading amount of 0.2-5% of the total weight of the catalyst;
The catalyst component in the step (2) is one or the combination of more than two of cobalt, zinc, copper, osmium or iridium, the carrier is alumina, and the catalyst component is loaded on the carrier by 0.3-5 percent of the total weight of the catalyst;
The catalyst component in the step (3) is one or the combination of more than two of iron, cobalt, nickel, magnesium, potassium, cesium and barium, the carrier is coconut shell activated carbon, and the catalyst component is loaded on the carrier by 1-20% of the total weight of the catalyst;
The catalyst in the step (4) is palladium modified by porous aluminum fluoride supported lead or bismuth, the supported amount of the palladium is 1-10% of the total weight of the catalyst, and the supported amount of the lead or bismuth is 0.1-5% of the total weight of the catalyst.
2. the process for producing 1,1,1,4,4, 4-hexafluoro-2-butene according to claim 1, wherein: in the step (1), the carrier is tungsten carbide, and the platinum is loaded on the carrier by 0.5-2.5% of the total weight of the catalyst.
3. The process for producing 1,1,1,4,4, 4-hexafluoro-2-butene according to claim 1, wherein: in the step (2), the catalyst component is loaded on the carrier by 0.5-25% of the total weight of the catalyst.
4. The process for producing 1,1,1,4,4, 4-hexafluoro-2-butene according to claim 1, wherein: in the step (3), the catalyst component is loaded on the carrier by 5-15% of the total weight of the catalyst.
5. the process for producing 1,1,1,4,4, 4-hexafluoro-2-butene according to claim 1, wherein: the load amount of the palladium in the step (4) is 3-5% of the total weight of the catalyst; the loading amount of the lead or the bismuth is 0.5 to 3 percent of the total weight of the catalyst.
6. The process for producing 1,1,1,4,4, 4-hexafluoro-2-butene according to any one of claims 1 to 5, wherein: in the step (1), the reaction temperature is 175-225 ℃, and the molar ratio of hydrogen to 1,1, 1-trifluorotrichloroethane is 1-3: 1; in the step (2), the reaction temperature is 175-225 ℃, the molar ratio of hydrogen to 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 4-8: 1, and the contact time of the hydrogen and the 1,1,1,4,4, 4-hexafluoro-2, 3-dichloro-2-butene is 30-60 s; in the step (3), the reaction temperature is 250-350 ℃, and the reaction space velocity is 300h-1～500h-1(ii) a In the step (4), the reaction temperature is 180-200 ℃, the molar ratio of hydrogen to hexafluoro-2-butyne is 5-10: 1, and the contact time of the hydrogen and the hexafluoro-2-butyne is 10-30 s.
7. The process for producing 1,1,1,4,4, 4-hexafluoro-2-butene according to claim 1, wherein: the catalysts in the steps (1) to (4) are all prepared by adopting an impregnation method, and the impregnation solvent is deionized water or ethanol or acetone.
8. The process for producing 1,1,1,4,4, 4-hexafluoro-2-butene according to claim 7, wherein: a competitive adsorbent is added into the impregnation solvent, and the competitive adsorbent is citric acid, tartaric acid, oxalic acid, hydrochloric acid or lactic acid.
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| CN110950735A (en) * | 2019-10-22 | 2020-04-03 | 浙江巨化技术中心有限公司 | Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by gas phase method |
| CN111574321A (en) * | 2020-06-17 | 2020-08-25 | 广东电网有限责任公司电力科学研究院 | Preparation method of trans-1, 1,1,4,4, 4-hexafluoro-2-butene |
| CN111604041A (en) * | 2020-06-18 | 2020-09-01 | 大连九信精细化工有限公司 | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesis of 1,1, 3-trichloropropene |
| CN114436759A (en) * | 2020-11-04 | 2022-05-06 | 浙江省化工研究院有限公司 | Gas phase preparation method of 1,1,1,2,4,4, 4-heptafluoro-2-butene |
| CN114716297A (en) * | 2021-01-06 | 2022-07-08 | 浙江省化工研究院有限公司 | Preparation method of E-1,1,1,4,4, 4-hexafluoro-2-butene |
| CN116037120A (en) * | 2023-03-31 | 2023-05-02 | 北京宇极科技发展有限公司 | E-1, 4-hexafluoro-2-butene and Z-preparation method of 1, 4-hexafluoro-2-butene |
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| CN110950735A (en) * | 2019-10-22 | 2020-04-03 | 浙江巨化技术中心有限公司 | Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by gas phase method |
| CN111574321A (en) * | 2020-06-17 | 2020-08-25 | 广东电网有限责任公司电力科学研究院 | Preparation method of trans-1, 1,1,4,4, 4-hexafluoro-2-butene |
| CN111604041A (en) * | 2020-06-18 | 2020-09-01 | 大连九信精细化工有限公司 | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesis of 1,1, 3-trichloropropene |
| CN111604041B (en) * | 2020-06-18 | 2023-04-07 | 大连九信精细化工有限公司 | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 1, 3-trichloropropene |
| CN114436759A (en) * | 2020-11-04 | 2022-05-06 | 浙江省化工研究院有限公司 | Gas phase preparation method of 1,1,1,2,4,4, 4-heptafluoro-2-butene |
| CN114436759B (en) * | 2020-11-04 | 2023-10-27 | 浙江省化工研究院有限公司 | Gas phase preparation method of 1,2, 4-heptafluoro-2-butene |
| CN114716297A (en) * | 2021-01-06 | 2022-07-08 | 浙江省化工研究院有限公司 | Preparation method of E-1,1,1,4,4, 4-hexafluoro-2-butene |
| CN114716297B (en) * | 2021-01-06 | 2023-10-27 | 浙江省化工研究院有限公司 | Preparation method of E-1, 4-hexafluoro-2-butene |
| CN116037120A (en) * | 2023-03-31 | 2023-05-02 | 北京宇极科技发展有限公司 | E-1, 4-hexafluoro-2-butene and Z-preparation method of 1, 4-hexafluoro-2-butene |
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