CN112645793B - Process system and method for producing trans-1-chloro-3, 3-trifluoropropene - Google Patents
Process system and method for producing trans-1-chloro-3, 3-trifluoropropene Download PDFInfo
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Abstract
The invention discloses a process system and a method for producing trans-1-chloro-3, 3-trifluoropropene, wherein hydrogen fluoride and 1, 3-pentachloropropane undergo liquid phase fluorination reaction in a liquid phase catalytic reactor, the trans-1-chloro-3, 3-trifluoropropene is synthesized, and cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane are by-produced. In the gas phase catalytic reactor, the by-products cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane react with HCl and are further converted into trans-1-chloro-3, 3-trifluoropropene. The method can produce trans-1-chloro-3, 3-trifluoropropene with high yield, realize the optimized conversion of materials and the cycle conversion of main byproducts into target products, and avoid the separation problem of an approximate azeotrope HCFO-1233zd (Z) and HCFC-244 fa.
Description
Technical Field
The invention relates to a method for producing trans-1-chloro-3, 3-trifluoropropene, in particular to a method for producing trans-1-chloro-3, 3-trifluoropropene in high yield by using hydrogen fluoride and 1, 3-pentachloropropane as raw materials and passing through two reactors.
Background
Trans-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (E)) has the boiling point of 18.7 ℃, the potential value of ozone loss is about zero, the potential value of greenhouse effect is 7.0, the environment-friendly performance is excellent, the toxicity is low, the foaming system is non-inflammable under normal state, the use is safe, the rigid polyurethane foam plastic synthesized by adopting the HCFO-1233zd (E) foaming system has good comprehensive performance and excellent heat insulation performance, can meet the requirements of the heat insulation and heat preservation industry, has more excellent heat conductivity and the energy consumption level of the whole machine compared with the existing foaming system, and is considered as an ideal substitute of 1, 1-dichloro-1-fluoroethane (HCFC-141 b) and 1, 3-pentafluoropropane (HFC-245 fa).
HCFO-1233zd (E) is generally synthesized by gas phase fluorination or liquid phase fluorination using hydrogen fluoride and 1, 3-pentachloropropane (HCC-240 fa) as raw materials. Chinese patent CN1166479A discloses a composite material made of Cr-Ni/AlF 3 As a catalyst, HCC-240fa was fluorinated in the gas phase in a tubular reactor to synthesize HCFO-1233zd (E) at 250 ℃ with a contact time of 2s and a HF/HCC-240fa molar ratio of 14, 100% conversion of HCC-240fa, 72% selectivity, and the major by-products were over-fluoride (8.2% trans-1, 3-tetrafluoropropene (HFO-1234 ze (E)) and 8.5% HFC-245 fa).
The synthesis of HCFO-1233zd (E) with high selectivity cannot be realized due to the characteristics of the reaction, the reaction selectivity of HCFO-1233zd (E) is generally not more than 90%, and the main byproducts are HFC-245fa, HCFC-244fa, HFO-1234ze, HCFO-1233zd (Z) and the like. Accordingly, the literature suggests a process for the co-production of HFC-245fa or HFO-1234ze from HCFO-1233zd (E). Chinese patent No. 103429558A discloses an integrated process for the co-production of HCFO-1233zd (E), HFO-1234ze (E) and HFC-245fa. The chemical process involves the steps of: (1) Reacting HCC-240fa with excess anhydrous HF in a liquid phase catalytic reactor in such a way as to produce primarily HCFO-1233zd (E) and 3-chloro-1, 3-tetrafluoropropane (HCFC-244 fa) in combination (plus byproduct HCl); (2) The HCFC-244fa stream is then used to directly produce any of three desired products, including dehydrochlorination to produce HFO-1234ze (E), dehydrofluorination to produce HCFO-1233zd (E), or fluorination to produce HFC-245fa. The products from this process are HCFO-1233zd (E), HFO-1234ze (E), and HFC-245fa. Considering that HFC-245fa is hydrofluorocarbon, the potential value of greenhouse effect is high, and the HFC-1234 ze (E) is eliminated by the international society, but the application of HFO-1234ze (E) is limited, and the market demand is very small, so that a large amount of HFC-245fa and HFO-1234ze (E) with low byproduct value can be produced by a co-production process, and HCFO-1233zd (E) is difficult to produce on a large scale, namely the technical problem of producing HCFO-1233zd (E) with high yield is still not solved.
Disclosure of Invention
The invention aims to overcome the defects in the background art and provide a process system and a method for producing trans-1-chloro-3, 3-trifluoropropene with high yield.
In order to realize the technical task of the invention, the invention adopts the following technical scheme to realize:
a process system for producing trans-1-chloro-3, 3-trifluoropropene comprises at least two reactors and a separation system, wherein the two reactors are respectively a liquid phase catalytic reactor and a gas phase catalytic reactor, the liquid phase catalytic reactor and the gas phase catalytic reactor share one set of separation system, HCl required by the gas phase catalytic reactor comes from the liquid phase catalytic reactor, and HF generated by the gas phase catalytic reactor is circulated to the liquid phase catalytic reactor;
introducing reaction raw materials into a liquid phase catalytic reactor, and carrying out liquid phase fluorination reaction to obtain reaction products of HCl, HF, trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane;
the separation system comprises multistage separation devices which are connected in series with each other and are used for separating and removing HCl and HF from reaction products obtained by the liquid phase catalytic reactor to obtain a heavy component mixture of trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, recovering a target product of trans-1-chloro-3, 3-trifluoropropene and introducing the heavy component mixture into the gas phase catalytic reactor;
in a gas phase catalytic reactor, under the condition of HCl, 3-chloro-1, 3-tetrafluoropropane in a heavy component mixture is promoted to carry out dehydrofluorination reaction to obtain trans-1-chloro-3, 3-trifluoropropene and HF, cis-1-chloro-3, 3-trifluoropropene carries out isomerization reaction to obtain the trans-1-chloro-3, 3-trifluoropropene, a reaction product obtained by the gas phase catalytic reactor is circularly fed back to a separation system, then enters the gas phase catalytic reactor through the separation system, and HF generated by the gas phase catalytic reactor is circularly fed back to a liquid phase catalytic reactor.
The invention further discloses a method for producing trans-1-chloro-3, 3-trifluoropropene, comprising the steps of:
(1) In a liquid phase catalytic reactor, hydrogen fluoride and 1, 3-pentachloropropane are taken as raw materials to carry out liquid phase fluorination reaction in the presence of a liquid phase fluorination catalyst, to obtain HCl, HF and a reaction product of trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, wherein the liquid phase fluorination catalyst is of the general formula Q + [Sb x Ti y F 5x+4y+1 ] - Ionic salt of, cation Q + Is a quaternary ammonium cation, wherein x + y is more than 1 and less than or equal to 2, x is more than or equal to 0 and less than or equal to 1<y≤2；
(2) Introducing a reaction product obtained by liquid phase catalytic reaction into a separation system, separating, sequentially separating and removing HCl and HF to obtain a heavy component mixture of trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, recovering a target product of trans-1-chloro-3, 3-trifluoropropene, and introducing the heavy component mixture into a gas phase catalytic reactor;
(3) Introducing HCl into a gas phase catalytic reactor, under the condition of existence of a solid catalyst, promoting 3-chloro-1, 3-tetrafluoropropane in a heavy component mixture to carry out dehydrofluorination reaction to obtain trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and HF, then circularly feeding reaction products obtained by the gas phase catalytic reactor back to a separation system, then feeding the reaction products into the gas phase catalytic reactor through the separation system, and circulating the HF generated by the gas phase catalytic reactor into a liquid phase catalytic reactor to finally obtain the high-selectivity trans-1-chloro-3, 3-trifluoropropene.
Further, the solid catalyst selected in the gas phase catalytic reactor is AlF containing one of Zn, ni, fe or Cr 3 Or MgF 2 。
Further, in the liquid phase fluorination reaction, the molar ratio of hydrogen fluoride to 1, 3-pentachloropropane is 4-10: 1; in the gas-phase catalytic reaction, the molar ratio of hydrogen chloride to the heavy component mixture is 1-10: 1.
the liquid phase fluorination catalyst of the invention is of the general formula Q + [Sb x Ti y F 5x+4y+1 ] - Ionic salt of, cation Q + Is a quaternary ammonium cation, wherein x + y is more than 1 and less than or equal to 2, x is more than or equal to 0 and less than or equal to 1<y is less than or equal to 2, the cation Q + Tripropylammonium, tetrabutylammonium, 1-butyl-3-methylimidazolium, 1-benzyl-3-methylimidazolium, 1-hexyl-2, 3-dimethylimidazolium or N-hexylpyridinium.
The solid catalyst selected in the gas phase catalytic reactor is Zn/AlF 3 、Ni/AlF 3 、Cr/MgF 2 Or Fe/MgF 2 。
The preferred steps of the process of the present invention for producing trans-1-chloro-3, 3-trifluoropropene are:
(1) In a liquid phase catalytic reactor, hydrogen fluoride and 1, 3-pentachloropropane are taken as raw materials, the reaction temperature is 110 ℃, the reaction pressure is 1.5Mpa, the molar ratio of the hydrogen fluoride to the 1, 3-pentachloropropane is 6:1, fluorination of catalyst [ 1-butyl-3-methylimidazolium salt in liquid-liquid phase][SbTi 0.25 F 7 ]Liquid phase fluorination in the presence of HCl, HF and trans-1-chloro-3, 3-trifluoropropene to obtain a reaction product comprising HCl, HF and cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane;
(2) Introducing a reaction product obtained by liquid phase catalytic reaction into a separation system, separating, sequentially separating and removing HCl and HF to obtain a heavy component mixture of trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, recovering part of the target product trans-1-chloro-3, 3-trifluoropropene, and introducing the heavy component mixture into a gas phase catalytic reactor;
(3) Introducing HCl into a gas phase catalytic reactor and adding Ni/AlF serving as a solid catalyst 3 In the presence of the catalyst, 3-chloro-1, 3-tetrafluoropropane in the heavy component mixture is promoted to have dehydrofluorination reaction to obtain trans-1-chloro-3, 3-trifluoropropene and HF, cis-1-chloro-3, 3-trifluoropropene has isomerization reaction to obtain trans-1-chloro-3, 3-trifluoropropene, the reaction temperature is 150 ℃, the reaction pressure is 1.0MPa, and the molar ratio of hydrogen chloride to the heavy component mixture is 5:1, the residence time is 10 seconds, then the reaction product obtained by the gas phase catalytic reactor is fed back to a separation system circularly, enters the gas phase catalytic reactor through the separation system, and HF generated by the gas phase catalytic reactor is circulated to a liquid phase catalytic reactor, and finally trans-1-chloro-3, 3-trifluoropropene with high selectivity is obtained.
In particular, the HCl required for the gas phase catalytic reaction of the present invention comes from the liquid phase catalytic reactor and the HF produced by the gas phase catalytic reaction is recycled to the liquid phase catalytic reactor.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) Provides a production process for preparing HCFO-1233zd (E) with high yield, and the process only obtains HCFO-1233zd (E) product and realizes the circulation and conversion of main by-products into target products.
(2) The liquid phase catalytic reactor and the gas phase catalytic reactor share one separation system, the process is simple, hydrogen chloride required by the gas phase catalytic reactor comes from the liquid phase catalytic reactor, hydrogen fluoride generated by the gas phase catalytic reactor is circulated to the liquid phase catalytic reactor, the optimized conversion of materials is realized, and the separation problem of approximate azeotrope HCFO-1233zd (Z) and HCFC-244fa is avoided.
Drawings
FIG. 1 is a process flow diagram of trans-1-chloro-3, 3-trifluoropropene of one embodiment of the present invention.
FIG. 2 shows the results of chromatographic analysis of the organic at the reaction outlet as a function of time for the liquid phase fluorination of HF with HCC-240fa carried out in step (1) in a continuous process according to example 15, wherein the top line is HCFO-1233zd (E), the middle line is HCFC-244fa, and the bottom line is HCFO-1233zd (Z).
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings, without limiting the scope of the invention.
The process system and the method for producing the trans-1-chloro-3, 3-trifluoropropene of the invention share a set of separation system with the liquid phase catalytic reactor and the gas phase catalytic reactor, simultaneously realize the self-circulation of reactants and reaction products of the whole process system, realize the optimal conversion of materials and avoid the difficult problem of separating HCFO-1233zd (Z) and HCFC-244fa which are similar to azeotrope.
The key reaction mechanism involved in the present invention is as follows:
in the liquid phase catalytic reaction, hydrogen fluoride and 1, 3-pentachloropropane are taken as raw materials, and a liquid phase fluorination catalyst is adopted and has a general formula of Q + [Sb x Ti y F 5x+4y+1 ] - Ionic salt of, cation Q + Is a quaternary ammonium cation, wherein x + y is more than 1 and less than or equal to 2, x is more than or equal to 0 and less than or equal to 1<y is less than or equal to 2. To obtain reaction products of HCl, HF, trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene, and 3-chloro-1, 3-tetrafluoropropane;
the specific reaction process is as follows:
the separation system comprises multistage separation devices which are connected in series with each other and are used for separating and removing HCl and HF from reaction products obtained by the liquid phase catalytic reactor to obtain a heavy component mixture of trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, recovering a target product of trans-1-chloro-3, 3-trifluoropropene and introducing the heavy component mixture into the gas phase catalytic reactor;
the separation system passes through one or a combination of a plurality of devices of a rectifying tower, a phase separator and a water/alkali washing tower. After part of target product trans-1-chlorine-3, 3-trifluoropropene is recovered, HCFO-1233zd (Z) and HCFC-244fa have similar boiling points and form approximate azeotrope, and the two are difficult to be effectively separated by conventional rectification.
In a gas phase catalytic reactor, under the condition of HCl, 3-chloro-1, 3-tetrafluoropropane in a heavy component mixture is promoted to have dehydrofluorination reaction to obtain trans-1-chloro-3, 3-trifluoropropene and HF, cis-1-chloro-3, 3-trifluoropropene has isomerization reaction to obtain trans-1-chloro-3, 3-trifluoropropene, then the reaction product obtained by the gas phase catalytic reactor is fed back to the separation system circularly, then enters the gas phase catalytic reactor through the separation system, and HF generated by the gas phase catalytic reactor is circulated to the liquid phase catalytic reactor, and finally trans-1-chloro-3, 3-trifluoropropene with high selectivity is obtained.
The specific reaction process is as follows:
in a gas phase catalytic reactor, under the action of an acid catalyst, HCFO-1233zd (Z), HCFO-1233zd (E), HCFC-244fa, HCl and the like are in chemical equilibrium, the existence of HCl inhibits the dehydrochlorination of HCFC-244fa to HFO-1234ze, and the isomerization of HCFO-1233zd (Z) changes a direct isomerization path through an addition and removal mechanism, so that the isomerization reaction rate of HCFO-1233zd (Z) is improved. That is, in the catalytic reaction system constructed by the invention, HCFO-1233zd (Z) and HCFC-244fa are efficiently converted into HCFO-1233zd (E), so that compared with the disclosed patent literature scheme, HCFO-1233zd (Z) is isomerized independently, or HCFC-244fa is dehydrohalogenated independently, the method has higher selectivity and simpler process. The technical scheme of the invention fully realizes the conversion of byproducts HCFO-1233zd (Z) and HCFC-244fa into the target product HCFO-1233zd (E), so that the whole process only produces HCFO-1233zd (E) one product, thereby realizing the production of HFO-1234ze (E) with high yield.
The invention discloses a liquid phase fluorination catalyst with the general formula of Q + [Sb x Ti y F 5x+4y+1 ] - Ionic salt of, cation Q + Is quaternary ammonium cation, wherein x + y is more than 1 and less than or equal to 2, x is more than or equal to 0 and less than or equal to 1, and y is more than 0 and less than or equal to 2. The liquid phase fluorination catalyst may be prepared from Q + [SbF 6 ] – And TiF 4 Obtained by direct reaction and can also be obtained by Q + [SbF x Cl 6-x ] – And TiCl 4 Obtained by reaction in hydrogen fluoride and optionally Q + [SbF 6 ] – And Q + [Ti n F 4n+1 ] - Obtained by anion exchange reaction. Q designed by the invention + [Sb x Ti y F 5x+4y+1 ] - The catalyst overcomes the anion [ Sb ] x F 5x+1 ] – Instability of [ Ti ] y F 4y+1 ] - The problem of low catalytic reaction activity of anions is solved, a proper acidic catalyst is obtained by modulating the cation type and the anion composition, the high efficiency of the reaction (a) is realized while the high selectivity is realized, and the feeding load of HCC-240fa can reach 200-300 gL during continuous feeding -1 (reaction solution) h -1 。
Further, the liquid phase fluorination catalyst cation Q of the present invention + Tetraalkylammonium, dialkylimidazolium, trialkylimidazolium, N-alkylpyridinium, N-alkyl-N-methylpyrrolidinium or N-alkyl-N-methylpiperidinium, etc. Particularly preferred cations Q + Is tripropylammonium [ NHPr 3 ]Tetrabutylammonium [ NBu ] 4 ]1-butyl-3-methylimidazolium ([ BMIm)]) 1-benzyl-3-methylimidazolium [ PhCH ] 2 MIm]) 1-hexyl-2, 3-dimethylimidazolium ([ HMMIm)]) Or N-hexylpyridinium ([ HPy ]])。
Furthermore, the solid catalyst selected in the gas phase catalytic reactor is AlF containing one of Zn, ni, fe or Cr 3 Or MgF 2 . The solid catalyst is preferably Zn/AlF 3 ，Ni/AlF 3 ，Cr/MgF 2 Or Fe/MgF 2 One ofAnd (4) seed selection.
Referring to FIG. 1, a process flow diagram for trans-1-chloro-3, 3-trifluoropropene of the present invention.
The liquid phase catalytic reaction is a kettle type stirring reactor, a rectifying column and a condenser are arranged on the reactor and are used for refluxing entrained catalyst, raw materials and intermediate fluorinated products, and the fluorinated products with target compositions are obtained by adjusting the pressure and the temperature at the top of the tower. The reactor is preferably constructed of a material resistant to the corrosive effects of HF and catalyst, such as carbon steel, hastelloy-C, inconel, monel, or fluoropolymer-lined steel vessels.
The gas phase catalytic reactor is a fixed bed tubular reactor, and adopts heat conduction oil or molten salt for heating. The reactor is preferably constructed of materials resistant to the corrosive effects of HF and catalyst, such as carbon steel, inconel, hastelloy-C, monel, and the like.
As a practical scheme without specific limitation, FIG. 1 shows a process scheme for producing trans-1-chloro-3, 3-trifluoropropene, which is described as follows:
(a) HCC-240fa and hydrogen fluoride enter a liquid phase catalytic reactor to react, the reaction temperature is 110 ℃, the reaction pressure is 1.5Mpa, and the molar ratio of the hydrogen fluoride to the HCC-240fa is 6:1, continuous liquid phase fluorination synthesis to obtain reaction products containing HCl, HF, HCFO-1233zd (E), HCFO-1233zd (Z) and HCFC-244 fa;
(b) The reaction product of the liquid phase catalytic reactor enters a T101 rectifying tower for separation, HCl is arranged at the top of the T101 rectifying tower, one part of HCl is discharged to the outside, and the other part of HCl is used as a raw material and enters a gas phase catalytic reactor; the tower bottom of the T101 rectifying tower is a mixture of HF and organic, and enters a T102 rectifying tower;
(c) The material at the top of the T102 rectifying tower is an azeotrope of HF and organic matters, the HF phase returns to the liquid phase catalytic reactor after phase separation by the phase separator, the organic phase enters the T201 tower after being washed by water and alkali, and the HF and the catalyst are circulated to the liquid phase catalytic reactor at the bottom of the T102 rectifying tower.
(d) The material at the top of the T201 rectifying tower is low-boiling-point substance and is discharged to the outside, and the material at the bottom of the T201 rectifying tower enters a T202 rectifying tower; the material at the top of the T202 rectifying tower is HCFO-1233zd (E) product, and the material at the bottom of the T202 rectifying tower enters a T203 rectifying tower; the material at the top of the T203 rectifying tower is a heavy component mixture of HCFO-1233zd (E), HCFO-1233zd (Z) and HCFC-244fa, and enters a gas phase catalytic reactor, and the material at the bottom of the T203 rectifying tower is a high-boiling-point substance and is discharged to the outside;
(e) The material at the top of the T203 rectifying tower and HCl enter a gas phase catalytic reactor to react, the reaction temperature is 150 ℃, the reaction pressure is 1.0Mpa, and the molar ratio of hydrogen chloride to mixed heavy components is 5:1, the residence time is 10 seconds, and the continuous gas phase synthesis obtains a mixture containing HCl, HF, HCFO-1233zd (E) and HCFO-1233zd (Z), and circularly and repeatedly enters a T102 tower until a high-selectivity single product trans-1-chloro-3, 3-trifluoropropene is obtained.
The preferred steps of the process of the present invention for producing trans-1-chloro-3, 3-trifluoropropene are:
(1) In a liquid phase catalytic reactor, hydrogen fluoride and 1, 3-pentachloropropane are taken as raw materials, the reaction temperature is 110 ℃, the reaction pressure is 1.5Mpa, the molar ratio of the hydrogen fluoride to the 1, 3-pentachloropropane is 6: fluorination of catalyst [ 1-butyl-3-methylimidazolium ] in liquid-liquid phase][SbTi 0.25 F 7 ]In the presence of a liquid phase fluorination reaction to produce a reaction product comprising HCl, HF and trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene, and 3-chloro-1, 3-tetrafluoropropane;
(2) Introducing a reaction product obtained by liquid phase catalytic reaction into a separation system, separating, sequentially separating and removing HCl and HF to obtain a heavy component mixture of trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, recovering a target product of trans-1-chloro-3, 3-trifluoropropene, and introducing the heavy component mixture into a gas phase catalytic reactor;
(3) Introducing HCl into a gas phase catalytic reactor and adding Ni/AlF serving as a solid catalyst 3 In the presence of the catalyst, 3-chloro-1, 3-tetrafluoropropane in the heavy component mixture is promoted to have dehydrofluorination reaction to obtain trans-1-chloro-3, 3-trifluoropropene and HF, cis-1-chloro-3, 3-trifluoropropene has isomerization reaction to obtain trans-1-chloro-3, 3-trifluoropropene, the reaction temperature is 150 ℃, the reaction pressure is 1.0MPa, and the molar ratio of hydrogen chloride to the heavy component mixture is 5:1, residence time 10 seconds, and then recycling the reaction product obtained from the gas-phase catalytic reactorFeeding back to the separation system, then feeding the reaction product into the gas phase catalytic reactor through the separation system, and circulating HF generated by the gas phase catalytic reactor into the liquid phase catalytic reactor to finally obtain the high-selectivity trans-1-chloro-3, 3-trifluoropropene.
Example 1
This example illustrates the batch operation of the liquid phase fluorination reaction of HF with HCC-240fa in step (1) of the generation process of the present invention. Batch liquid phase fluorination was carried out in a stirred 300ml lnconel autoclave. Sequentially charging catalyst [ BMIm ] into the reaction vessel][SbTi 0.25 F 7 ]65.9g, 75.5g of HF and 35.7 g of HCC-240fa, wherein the reaction temperature is 110 ℃, the pressure is discharged through a gas phase port in the reaction process, the pressure of a stable reactor is 1.5MPa, and the temperature is reduced after the reaction is carried out for 2 hours. The discharged gas material is put into a water washing bottle in a low-temperature bath tank at the temperature of-5 ℃ for removing acid, and then the gas material is kept stand for phase separation, and about 16.2g of organic phase at the lower layer is collected. The organic phase was analyzed by gas chromatography and the results indicated that the selectivity to HCFO-1233zd (E) was 90.8%, the selectivity to HCFO-1233zd (Z) was 3.3%, the selectivity to HCFC-244fa was 4.9%, and the others (including primarily HFO-1234ze, HFC-245fa, HCFC-243fa, etc.) were 1%.
Examples 2 to 10
Examples 2-10 describe formation processes of the invention the liquid phase fluorination of HF with HCC-240fa in step (1) is similar to that of example 1 except that the liquid phase fluorination catalyst is changed and the results are shown in table 1.
TABLE 1 results of liquid phase fluorination of HF with HCC-240fa over various catalysts
Note: others include primarily HFO-1234ze, HFC-245fa, HCFC-243fa, and the like.
Examples 11 to 14
The liquid phase fluorination of HF to HCC-240fa in step (1) of the formation process of the invention described in examples 11-14 is similar to that of example 1 except that the operating conditions are changed and the results are shown in Table 2.
TABLE 2 results of liquid phase fluorination of HF with HCC-240fa under different reaction conditions
Note: others include primarily HFO-1234ze, HFC-245fa, HCFC-243fa, and the like.
Example 15
This example illustrates the liquid phase fluorination of HF with HCC-240fa in step (1) of the production process of the invention operated continuously. Continuous liquid phase fluorination is carried out in a 2L stainless steel stirring autoclave, a distillation tower and a reflux condenser are arranged above the autoclave, the bottom of the autoclave is heated by an oil kettle, and materials at the top of the autoclave are collected in a low-temperature bath tank at the temperature of minus 20 ℃ after being washed with water and subjected to alkaline deacidification. 562.5g of [ BMIm ] was put into the reactor in this order][SbF 6 ]，46.5gTiF 4 500g HF, gradually heating to 110 ℃, keeping the temperature for 24h, and preparing the catalyst [ BMIm ]][SbTi 0.25 F 7 ]. HCC-240fa and HF were then continuously fed into the reactor by means of a metering pump at a feed rate of 280g/h HCC-240fa, a feed rate of-155 g/h HF, a molar ratio of HF to HCC-240fa of 6:1, the reaction temperature is 105-115 ℃, and the reaction pressure is 1.4-1.6 MPA. The composition of the overhead gas phase material, i.e., the reaction product, was analyzed, and the reaction results are shown in FIG. 2. As can be seen from FIG. 2, the HCFO-1233zd (E) average selectivity is 89% in the continuous operation of 800h, and the catalyst keeps good stability in the reaction process. In the case of continuous feeding, the volume of the reactor contents was estimated to be about 1000ml, at which point the feed rate of HCC-240fa reached 280g L -1 (reaction solution) h -1 。
Example 16
This example illustrates the sequential separation of the HCFO-1233zd (E) product and the mixture of heavy components entering the gas phase catalytic reactor by rectification columns T201, T202 and T203 in fig. 1. An intermittent rectifying tower is adopted in the verification experiment, the diameter of the rectifying tower is 25mm, the height of the filler is 1m, theta ring stainless steel filler with the diameter of 3 is filled in the rectifying tower, and a coil condenser is arranged at the top of the rectifying tower. The HCl and HF removed crude product of HCFO-1233zd (E) obtained in example 15 was added to the bottom of the rectification column, about 1000g of crude product was added at one time, and after the temperature was raised, it was continuously and slowly withdrawn, and fractions were collected in stages, the results of which are shown in the following Table. The process sends the front cut fraction to the outside, and the heavy component mixture enters a gas phase catalytic reactor to continue to react to generate HCFO-1233zd (E), so the real yield of HCFO-1233zd (E) in the whole process is 98.7%.
TABLE 3 crude isolation of HCFO-1233zd (E)
Note: the light impurities mainly comprise HFO-1234ze and HFC-245fa, and the heavy impurities mainly comprise HCFC-243fa, HCFC-242fa and the like
Example 17
This example illustrates the gas phase reaction of hydrogen chloride in step (2) with the heavy components mixture of step (2). 30mL of Zn/AlF is measured 3 The catalyst is loaded into a stainless steel reaction tube, after the reaction temperature is stabilized at 150 ℃, HCl and a heavy component mixture (component analysis: 1233zd (E) 35.0%,1233zd (Z) 23.3%, 244fa39.7%) are respectively introduced, the contact time of the materials is calculated to be 10s, the molar ratio of the HCl to the heavy component mixture is calculated to be 10, the reaction product is stably operated for 24h, and after the acid is removed by washing, the gas chromatography is used for analysis: 1233zd (E) 90.1%,1233zd (Z) 7.5%,244fa2.4%.
Example 18
The procedures of examples 18 to 24 were similar to those of example 17 except that the catalyst was changed and the reaction temperature and molar ratio were adjusted, and the reaction results are shown in Table 4.
TABLE 4 gas phase reaction results of hydrogen chloride with heavy component mixtures
Note: others include primarily HFO-1234ze, HFC-245fa, and the like.
Claims (5)
1. A process for producing trans-1-chloro-3, 3-trifluoropropene, comprising the steps of:
(1) In a liquid phase catalytic reactor, with hydrogen fluoride and 1,1,13, 3-pentachloropropane as a raw material is subjected to liquid phase fluorination reaction in the presence of a liquid phase fluorination catalyst to obtain a reaction product of HCl, HF, trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, wherein the liquid phase fluorination catalyst is represented by the general formula Q + [Sb x Ti y F 5x+4y+1 ] - Ionic salt of, cation Q + Is quaternary ammonium cation, wherein 1 is more than x + y is less than or equal to 2<x≤1，0<y<2；
(2) Introducing a reaction product obtained by liquid phase catalytic reaction into a separation system, separating, sequentially separating and removing HCl and HF to obtain a heavy component mixture of trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, recovering a target product of trans-1-chloro-3, 3-trifluoropropene, and introducing the heavy component mixture into a gas phase catalytic reactor;
(3) Introducing HCl into a gas phase catalytic reactor, promoting 3-chloro-1, 3-tetrafluoropropane in a heavy component mixture to perform dehydrofluorination reaction in the presence of a solid catalyst to obtain trans-1-chloro-3, 3-trifluoropropene and HF, and performing isomerization reaction on the cis-1-chloro-3, 3-trifluoropropene to obtain the trans-1-chloro-3, 3-trifluoropropene, and then the reaction product obtained by the gas-phase catalytic reactor is fed back to the separation system in a circulating manner, then enters the gas-phase catalytic reactor through the separation system, and HF generated by the gas-phase catalytic reactor is circulated into the liquid-phase catalytic reactor to finally obtain the high-selectivity trans-1-chloro-3, 3-trifluoropropene, wherein the solid catalyst is a combination of AlF3 or MgF2 and one of Zn, ni, fe and Cr.
2. The process for producing trans-1-chloro-3, 3-trifluoropropene according to claim 1, wherein the liquid phase fluorination reaction comprises a molar ratio of hydrogen fluoride to 1, 3-pentachloropropane of from 4 to 10:1; in the gas-phase catalytic reaction, the molar ratio of hydrogen chloride to the heavy component mixture is 1 to 10:1.
3. the process for producing trans-1-chloro-3, 3-trifluoropropene according to claim 1, wherein,the solid catalyst selected in the gas phase catalytic reactor is Zn/AlF 3 、Ni /AlF 3 、Cr/MgF 2 Or Fe/MgF 2 。
4. The process for producing trans-1-chloro-3, 3-trifluoropropene according to any one of claims 1 to 3, comprising the steps of:
(1) In a liquid phase catalytic reactor, hydrogen fluoride and 1, 3-pentachloropropane are taken as raw materials, the reaction temperature is 110 ℃, the reaction pressure is 1.5Mpa, the molar ratio of the hydrogen fluoride to the 1, 3-pentachloropropane is 6: fluorination of catalyst in liquid phase [ 1-butyl-3-methylimidazolium salt ]][SbTi 0.25 F 7 ]Liquid phase fluorination in the presence of HCl, HF and trans-1-chloro-3, 3-trifluoropropene to obtain a reaction product comprising HCl, HF and cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane;
(2) Introducing a reaction product obtained by liquid phase catalytic reaction into a separation system, separating, sequentially separating and removing HCl and HF to obtain a heavy component mixture of trans-1-chloro-3, 3-trifluoropropene, cis-1-chloro-3, 3-trifluoropropene and 3-chloro-1, 3-tetrafluoropropane, recovering a target product of trans-1-chloro-3, 3-trifluoropropene, and introducing the heavy component mixture into a gas phase catalytic reactor;
(3) Introducing HCl into a gas phase catalytic reactor and adding Ni/AlF serving as a solid catalyst 3 In the presence of the catalyst, 3-chloro-1, 3-tetrafluoropropane in the heavy component mixture is promoted to have dehydrofluorination reaction to obtain trans-1-chloro-3, 3-trifluoropropene and HF, cis-1-chloro-3, 3-trifluoropropene has isomerization reaction to obtain trans-1-chloro-3, 3-trifluoropropene, the reaction temperature is 150 ℃, the reaction pressure is 1.0MPa, and the molar ratio of hydrogen chloride to the heavy component mixture is 5: and 1, the retention time is 10 seconds, then a reaction product obtained by the gas phase catalytic reactor is fed back to the separation system circularly, enters the gas phase catalytic reactor through the separation system, and circulates HF generated by the gas phase catalytic reactor into the liquid phase catalytic reactor to finally obtain the high-selectivity trans-1-chloro-3, 3-trifluoropropene.
5. The process for producing trans-1-chloro-3, 3-trifluoropropene according to claim 4, wherein: HCl required by the gas-phase catalytic reaction comes from the liquid-phase catalytic reactor, and HF generated by the gas-phase catalytic reaction is circulated to the liquid-phase catalytic reactor.
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| US11795125B2 (en) * | 2022-01-26 | 2023-10-24 | Honeywell International Inc. | Integrated process for making 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from a mixture of high-boiling fluorinated components |
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