Preparation and continuous preparation method of fluoroacetyl halide

Abstract

The invention relates to a preparation and continuous preparation method of fluoroacetyl halide, which comprises the following steps: chloroacetyl chloride and anhydrous hydrofluoric acid are subjected to fluoridation by taking antimony pentachloride as a catalyst to generate the fluoroacetyl halide. According to the technical scheme, the SbCl5 is used as the catalyst, the reaction condition is mild, continuous preparation can be carried out by adopting processes of continuous feeding, continuous fluorination and continuous rectification, the yield of continuous production is high, the overall three-waste amount is small, the cost is low, and the conversion rate is high.

Description

Technical Field

[0001] The present application relates to the field of fluorine chemical industry, and in particular to a preparation and continuous preparation method of fluoroacetyl halide. Background Art

[0002] As an important chemical intermediate, fluoroacetyl halide has downstream products such as trifluoroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate, 1-methyl-3-difluoromethyl-4-pyrazole acid, ethyl difluoroacetate, difluoroacetone and difluoroethanol. It is widely used in the fields of cleaning agents and etching agents in the electronics industry, pesticide intermediates, fluorine-containing material monomers, etc. These extended compounds are widely used in important fluorine-containing fine chemicals, pesticides, and medicines.

[0003] According to the technology provided by patent CN102218304 A: tetrafluoroethyl alkyl ether is used as raw material for high temperature catalytic cracking to obtain difluoroacetyl fluoride, and its catalyst is aluminum fluoride after fluorination treatment. The reaction process requires high temperature, which is difficult to operate; and the by-product is monofluoroalkane, which is difficult to recover, resulting in a large amount of three wastes. The technical route is:

[0004]

[0005] According to the technology provided by patents CN1282723A, CN1935757A, US3725475A, etc.: trichloroethylene is used as a raw material to generate 1,1,1-trifluoro-2-chloroethane through HF fluorination, and then chlorine gas is used to generate 1,1,1-trifluoro-2,2-dichloroethane, and finally trifluoroacetyl chloride is prepared by reacting with SO3 under the catalysis of mercuric sulfate. The use of mercuric sulfate is extremely harmful to the environment and human body, and the by-product sulfonyl chloride is difficult to recover, resulting in a large amount of three wastes generated by the entire route and difficult to handle. The technical route is:

[0006]

[0007] CN 111995516A uses dichloroacetyl chloride and inorganic fluoride to generate difluoroacetyl fluoride under the action of chromium complex catalyst. The inorganic metal fluoride used as the fluorination agent will produce solid waste after the reaction; and the preparation process of the Cr complex catalyst is complicated. Its technical route is:

[0008]

[0009] CN 1121064A uses trifluoroacetyl chloride as raw material to generate trifluoroacetyl fluoride by high temperature gas phase catalytic reaction under the action of chromium magnesium catalyst. The high temperature gas phase catalytic reaction of HF with trichloroacetyl chloride under pressure has high risk factor and is difficult to operate. In addition, the catalyst is easily sintered and poisoned under high temperature environment, causing the catalyst to lose activity, thereby affecting the catalytic efficiency and effect. Its technical route is:

[0010]

[0011] CN 114105766A uses tetrachloroethylene as raw material, and high-temperature oxidation and fluorination are carried out under the joint action of HF, O2 and chromium complex catalyst to prepare trifluoroacetyl fluoride. The preparation process of the chromium complex catalyst used is complicated, and pulping, water washing, recrystallization and other operations are required in the catalyst preparation process to remove residual chloride ions, and a large amount of wastewater will be generated in this process. Its technical route is:

[0012] Summary of the invention

[0013] In view of the above problems, the present application provides a simple production process, mild reaction conditions, simple operation, high product yield and easy industrialization. Although anhydrous hydrofluoric acid is used in excess, it can be recycled and reused, and the by-product hydrogen chloride can also be recycled, and the overall amount of three wastes is small.

[0014] The present application provides a method for preparing fluoroacetyl halide, comprising the following steps: chloroacetyl chloride and anhydrous hydrofluoric acid undergo fluorination reaction with antimony pentachloride as a catalyst to generate fluoroacetyl halide.

[0015] The reaction formula is shown in Formula 1:

[0016]

[0017] When Y is H, Z is H; when Y is Cl, Z is F.

[0018] Different from the prior art, the above technical solution provides a fluorination reaction using chloroacetyl chloride as a raw material, anhydrous HF as a fluorination reagent, and SbCl5 as a catalyst to generate fluoroacetyl halide; the SbCl5 catalyst will be SbCl5 during the reaction. a F 5-a The reaction conditions are mild and the by-product is hydrogen chloride, which is easy to handle and can also be recycled.

[0019] Furthermore, the chloroacetyl chloride includes dichloroacetyl chloride and trichloroacetyl chloride; the fluoroacetyl halide includes difluoroacetyl fluoride and trifluoroacetyl fluoride.

[0020] Furthermore, when the chloroacetyl chloride is dichloroacetyl chloride, the fluoroacetyl halide is difluoroacetyl fluoride.

[0021] Furthermore, when the chloroacetyl chloride is trichloroacetyl chloride, the fluoroacetyl halide is trifluoroacetyl fluoride.

[0022] Furthermore, the molar ratio of the anhydrous hydrofluoric acid to the chloroacetyl chloride is 5-30: 1. The anhydrous hydrofluoric acid is in an excess state, which is conducive to the full fluorination reaction and the increase of the reaction rate.

[0023] Furthermore, the molar ratio of the antimony pentachloride to the chloroacetyl chloride is 5-100:100.

[0024] Furthermore, the fluorination reaction temperature is 5-105°C.

[0025] The present application also provides a continuous preparation method of fluoroacetyl halide, comprising the following steps: continuously feeding chloroacetyl chloride and anhydrous hydrofluoric acid into a reactor containing antimony pentachloride to undergo a continuous fluorination reaction to generate fluoroacetyl halide and hydrochloric acid; continuously distilling the mixture obtained by the continuous fluorination reaction in the reactor to separate fluoroacetyl fluoride; and returning the chloroacetyl chloride, anhydrous hydrofluoric acid and the intermediate product fluoroacetyl chloride separated by distillation to the reactor to continue the continuous fluorination reaction.

[0026] Different from the prior art, the technical scheme uses chloroacetyl chloride as a starting material, anhydrous HF as a fluorination agent, and SbCl5 as a catalyst to carry out a fluorination reaction to generate fluoroacetyl halide, and adopts a process of continuous feeding, continuous fluorination and continuous distillation. The above continuous production of fluoroacetyl halide has high purity and high yield; the overall amount of three wastes is small, the cost is low, and the conversion rate is high.

[0027] Furthermore, the antimony pentachloride is returned to the reactor after distillation to continue the continuous fluorination reaction.

[0028] Furthermore, in the process of preparing fluorinated acetyl fluoride from chloroacetyl chloride, an intermediate product fluorinated acetyl chloride is generated. The intermediate product of difluoroacetyl fluoride is difluoroacetyl chloride; the intermediate product of trifluoroacetyl fluoride is trifluoroacetyl chloride.

[0029] Further, the following steps are included:

[0030] The dichloroacetyl chloride and anhydrous hydrofluoric acid are continuously fed into a reaction kettle containing antimony pentachloride to undergo a continuous fluorination reaction to generate difluoroacetyl fluoride, hydrochloric acid and difluoroacetyl chloride;

[0031] The first mixture obtained by the continuous fluorination reaction in the reactor is subjected to primary distillation to obtain a first gas phase mixture and a first liquid phase mixture; the first liquid phase mixture includes dichloroacetyl chloride, difluoroacetyl chloride and anhydrous hydrofluoric acid, and the first liquid phase mixture is returned to the reactor to continue the continuous fluorination reaction; the first gas phase mixture includes difluoroacetyl fluoride and hydrochloric acid; the first gas phase mixture is subjected to secondary distillation to separate difluoroacetyl fluoride liquid.

[0032] Furthermore, the first liquid phase mixture also includes antimony pentachloride.

[0033] Further, the following steps are included:

[0034] Trichloroacetyl chloride and anhydrous hydrofluoric acid are continuously fed into a reaction kettle containing antimony pentachloride to undergo a continuous fluorination reaction to generate trifluoroacetyl fluoride, hydrochloric acid and trifluoroacetyl chloride;

[0035] The second mixture obtained by the continuous fluorination reaction in the reactor is subjected to primary distillation to obtain a second gas phase mixture and a second liquid phase mixture; the second liquid phase mixture includes trifluoroacetyl chloride, trichloroacetyl chloride and anhydrous hydrofluoric acid, and the second liquid phase mixture is returned to the reactor to continue the continuous fluorination reaction; the second gas phase mixture includes trifluoroacetyl fluoride and hydrochloric acid; the second gas phase mixture is subjected to secondary distillation to separate trifluoroacetyl fluoride liquid.

[0036] Furthermore, the second liquid phase mixture also includes antimony pentachloride.

[0037] Further, the following steps are included:

[0038] The dichloroacetyl chloride, trichloroacetyl chloride and anhydrous hydrofluoric acid are continuously fed into a reaction kettle containing antimony pentachloride to undergo a continuous fluorination reaction to generate difluoroacetyl fluoride, trifluoroacetyl fluoride, hydrochloric acid, difluoroacetyl chloride and trifluoroacetyl chloride;

[0039] The third mixture obtained by the continuous fluorination reaction in the reactor is subjected to primary distillation to obtain a third gas phase mixture and a third liquid phase mixture; the third liquid phase mixture includes dichloroacetyl chloride, difluoroacetyl chloride, trichloroacetyl chloride and anhydrous hydrofluoric acid, and the third liquid phase mixture is returned to the reactor to continue the continuous fluorination reaction; the third gas phase mixture includes trifluoroacetyl chloride, difluoroacetyl fluoride, trifluoroacetyl fluoride and hydrochloric acid;

[0040] The third gas phase mixture is subjected to secondary distillation to separate difluoroacetyl fluoride liquid and a fourth gas phase mixture; the fourth gas phase mixture comprises trifluoroacetyl chloride, trifluoroacetyl fluoride and hydrochloric acid;

[0041] The fourth gas phase mixture is subjected to three-stage distillation to separate trifluoroacetyl chloride liquid and a fifth gas phase mixture; the trifluoroacetyl chloride liquid is returned to the reactor to continue the continuous fluorination reaction; the fifth gas phase mixture includes trifluoroacetyl fluoride and hydrochloric acid;

[0042] The fifth gas phase mixture is subjected to a fourth-stage distillation to separate trifluoroacetyl fluoride liquid.

[0043] Furthermore, the third liquid phase mixture also includes antimony pentachloride.

[0044] Furthermore, the fluorination reaction temperature is 5-105°C.

[0045] Furthermore, the chloroacetyl chloride includes dichloroacetyl chloride and trichloroacetyl chloride; the fluoroacetyl halide includes difluoroacetyl fluoride and trifluoroacetyl fluoride.

[0046] Furthermore, when the chloroacetyl chloride is dichloroacetyl chloride, the fluoroacetyl halide is difluoroacetyl fluoride.

[0047] Furthermore, when the chloroacetyl chloride is trichloroacetyl chloride, the fluoroacetyl halide is trifluoroacetyl fluoride.

[0048] Furthermore, the molar ratio of the anhydrous hydrofluoric acid to the chloroacetyl chloride is 5-30: 1. The anhydrous hydrofluoric acid is in an excess state, which helps the fluorination reaction to be sufficient and the reaction rate to increase. The feed ratio of chloroacetyl chloride and anhydrous hydrofluoric acid can be controlled by a flow meter.

[0049] Furthermore, the molar ratio of the antimony pentachloride to the chloroacetyl chloride is 5-100:100.

[0050] The above-mentioned records related to the invention content are only an overview of the technical solution of the present application. In order to enable ordinary technicians in the field to more clearly understand the technical solution of the present application, and then implement it according to the written contents of the specification, and to make the above-mentioned purpose and other purposes, features and advantages of the present application easier to understand, the specific implementation methods of the present application are explained below. DETAILED DESCRIPTION

[0051] In order to explain the technical content, structural features, achieved objectives and effects of the technical solution in detail, the following is a detailed description in conjunction with specific embodiments.

[0052] In order to explain in detail the possible application scenarios, technical principles, specific schemes that can be implemented, and the purposes and effects that can be achieved, the following is a detailed description in conjunction with the specific embodiments listed. The embodiments described herein are only used to more clearly illustrate the technical solutions of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0053] Reference to "embodiment" herein means that the specific features, structures or characteristics described in conjunction with the embodiment may be included in at least one embodiment of the present application. The term "embodiment" appearing in various places in the specification does not necessarily refer to the same embodiment, nor does it particularly limit its independence or association with other embodiments. In principle, in the present application, as long as there is no technical contradiction or conflict, the various technical features mentioned in the embodiments can be combined in any way to form a corresponding implementable technical solution.

[0054] Unless otherwise defined, the technical terms used in this document have the same meanings as those generally understood by those skilled in the art to which this application belongs; the use of relevant terms in this document is only for describing specific embodiments and is not intended to limit this application.

[0055] In the description of this application, the term "and / or" is an expression used to describe the logical relationship between objects, indicating that three relationships may exist, for example, A and / or B, which means: A exists, B exists, and A and B exist at the same time. In addition, the character " / " in this article generally indicates that the objects before and after are in an "or" logical relationship.

[0056] In the present application, terms such as “first” and “second” are merely used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship of quantity, priority or sequence between these entities or operations.

[0057] Without further limitations, in this application, the words "include", "comprises", "has" or other similar expressions used in the sentences are intended to cover non-exclusive inclusion. These expressions do not exclude the presence of additional elements in the process, method or product including the elements, so that the process, method or product including a series of elements may include not only those limited elements, but also other elements not explicitly listed, or also include elements inherent to such process, method or product.

[0058] Similar to the understanding in the Examination Guidelines, in this application, expressions such as "greater than", "less than", "exceed" and the like are understood to exclude the number itself; expressions such as "above", "below", "within" and the like are understood to include the number itself. In addition, in the description of the embodiments of this application, "multiple" means more than two (including two), and similar expressions related to "multiple" are also understood in this way, such as "multiple groups", "multiple times", etc., unless otherwise clearly and specifically limited.

[0059] In this embodiment, two or more distillation towers connected in series on the reactor are used to carry out continuous distillation in coordination with the continuous fluorination reaction. The reaction raw materials dichloroacetyl chloride, trichloroacetyl chloride, anhydrous hydrofluoric acid, the intermediate products difluoroacetyl chloride, trifluoroacetyl chloride, and the catalyst antimony pentachloride are returned to the reactor after distillation separation to continue the continuous fluorination reaction.

[0060] It should be noted that in order to prevent water in the reactor from affecting the fluorination reaction, the reactor is purged with N2 before use. Therefore, in the initial stage of the fluorination reaction, the distilled gas mixture still contains a small amount of nitrogen, which finally enters the tail gas quenching device together with hydrogen chloride.

[0061] Example 1: Preparation of difluoroacetyl fluoride (purity 89.1%, yield 87.9%)

[0062] Antimony pentachloride SbCl5 (37.38 g, 0.125 mol, molar ratio to dichloroacetyl chloride 0.05) was added into the reactor, the flow rate of anhydrous HF was controlled at 50.03 g / h by a flow meter, and 73.69 g / h of dichloroacetyl chloride was continuously introduced into the reactor, and the temperature was raised to 95-105°C for continuous fluorination reaction.

[0063] As the fluorination reaction proceeds, the first mixture in the reactor is continuously fed into a primary distillation tower to obtain a first gas phase mixture and a first liquid phase mixture, and the first liquid phase mixture (anhydrous HF, difluoroacetyl chloride, dichloroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the first gas phase mixture (HCl and difluoroacetyl fluoride) is subjected to secondary distillation, and the difluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower, and the by-product hydrogen chloride enters the tail gas quenching device.

[0064] After fluorination reaction for 5 hours, the collected difluoroacetyl fluoride was analyzed by GC after derivatization, with a purity of 89.1% and a yield of 87.9%.

[0065] Example 2: Preparation of difluoroacetyl fluoride (purity 92.5%, yield 89.6%)

[0066] SbCl5 (57.25 g, 0.25 mol, molar ratio to dichloroacetyl chloride 0.1) was added into the reactor, the flow rate of anhydrous HF was controlled at 100.05 g / h by a flow meter, and 73.69 g / h of dichloroacetyl chloride was continuously introduced into the reactor, and the temperature was raised to 80-90°C for continuous fluorination reaction.

[0067] As the fluorination reaction proceeds, the first mixture in the reactor is continuously fed into a primary distillation tower to obtain a first gas phase mixture and a first liquid phase mixture, and the first liquid phase mixture (anhydrous HF, difluoroacetyl chloride, dichloroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the first gas phase mixture (HCl and difluoroacetyl fluoride) is subjected to secondary distillation, and the difluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower, and the by-product hydrogen chloride enters the tail gas quenching device.

[0068] After fluorination reaction for 5 hours, the collected difluoroacetyl fluoride was analyzed by GC after derivatization, with a purity of 92.5% and a yield of 89.6%.

[0069] Example 3: Preparation of difluoroacetyl fluoride (purity 94.1%, yield 88.5%)

[0070] SbCl5 (747.53 g, 2.5 mol, molar ratio to dichloroacetyl chloride 0.5) was added into the reactor, the flow rate of anhydrous HF was controlled at 50.03 g / h by a flow meter, and 73.69 g / h of dichloroacetyl chloride was continuously introduced into the reactor, and the temperature was raised to 65-75°C for continuous fluorination reaction.

[0071] As the fluorination reaction proceeds, the first mixture in the reactor is continuously fed into a primary distillation tower to obtain a first gas phase mixture and a first liquid phase mixture, and the first liquid phase mixture (anhydrous HF, difluoroacetyl chloride, dichloroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the first gas phase mixture (HCl and difluoroacetyl fluoride) is subjected to secondary distillation, and the difluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower, and the by-product hydrogen chloride enters the tail gas quenching device.

[0072] After fluorination reaction for 5 hours, the collected difluoroacetyl fluoride was analyzed by GC after derivatization, with a purity of 94.1% and a yield of 88.5%.

[0073] Example 4: Preparation of difluoroacetyl fluoride (purity 91.4%, yield 87.3%)

[0074] SbCl5 (1495.05 g, 5 mol, molar ratio of SbCl5 to dichloroacetyl chloride: 1) was added to the reactor, the flow rate of anhydrous HF was controlled to be 100.05 g / h by a flow meter, and 73.69 g / h of dichloroacetyl chloride was continuously introduced into the reactor. The mixture was heated to 50-60°C for continuous fluorination reaction.

[0075] As the fluorination reaction proceeds, the first mixture in the reactor is continuously fed into a primary distillation tower to obtain a first gas phase mixture and a first liquid phase mixture, and the first liquid phase mixture (anhydrous HF, difluoroacetyl chloride, dichloroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the first gas phase mixture (HCl and difluoroacetyl fluoride) is subjected to secondary distillation, and the difluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower, and the by-product hydrogen chloride enters the tail gas quenching device.

[0076] After fluorination for 5 hours, the collected difluoroacetyl fluoride was analyzed by GC after derivatization, with a purity of 91.4% and a yield of 87.3%.

[0077] Example 5: Preparation of difluoroacetyl fluoride (purity 93.1%, yield 87.1%)

[0078] SbCl5 (149.6 g, 0.5 mol, molar ratio to dichloroacetyl chloride 0.1) was added to the reactor, the flow rate of anhydrous HF was controlled by a flow meter to be 200.1 g / h, and 73.69 g / h of dichloroacetyl chloride was continuously introduced into the reactor. The mixture was heated to 35-45°C for continuous fluorination reaction.

[0079] As the fluorination reaction proceeds, the first mixture in the reactor is continuously fed into a primary distillation tower to obtain a first gas phase mixture and a first liquid phase mixture, and the first liquid phase mixture (anhydrous HF, difluoroacetyl chloride, dichloroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the first gas phase mixture (HCl and difluoroacetyl fluoride) is subjected to secondary distillation, and the difluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower, and the by-product hydrogen chloride enters the tail gas quenching device.

[0080] After fluorination reaction for 10 hours, the collected difluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of difluoroacetyl fluoride was 93.1% and the yield was 87.1%.

[0081] Example 6: Preparation of difluoroacetyl fluoride (90.5%, yield 85.2%)

[0082] SbCl5 (747.53 g, 2.5 mol, molar ratio to dichloroacetyl chloride 0.5) was added to the reactor, the flow rate of anhydrous HF was controlled at 300.15 g / h by a flow meter, and 73.69 g / h of dichloroacetyl chloride was continuously introduced into the reactor. The reaction temperature was controlled at 20-30°C to carry out continuous fluorination reaction.

[0083] As the fluorination reaction proceeds, the first mixture in the reactor is continuously fed into a primary distillation tower to obtain a first gas phase mixture and a first liquid phase mixture, and the first liquid phase mixture (anhydrous HF, difluoroacetyl chloride, dichloroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the first gas phase mixture (HCl and difluoroacetyl fluoride) is subjected to secondary distillation, and the difluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower, and the by-product hydrogen chloride enters the tail gas quenching device.

[0084] After fluorination reaction for 10 hours, the collected difluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of difluoroacetyl fluoride was 90.5% and the yield was 85.2%.

[0085] Example 7: Preparation of difluoroacetyl fluoride (purity 90.1%, total yield 85.3%)

[0086] SbCl5 (747.53 g, 2.5 mol, molar ratio to dichloroacetyl chloride 0.5) was added to the reactor, the flow rate of anhydrous HF was controlled at 300.15 g / h by a flow meter, and 73.69 g / h of dichloroacetyl chloride was continuously introduced into the reactor. The reaction temperature was controlled at 5-15°C to carry out continuous fluorination reaction.

[0087] As the fluorination reaction proceeds, the first mixture in the reactor is continuously fed into a primary distillation tower to obtain a first gas phase mixture and a first liquid phase mixture, and the first liquid phase mixture (anhydrous HF, difluoroacetyl chloride, dichloroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the first gas phase mixture (HCl and difluoroacetyl fluoride) is subjected to secondary distillation, and the difluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower, and the by-product hydrogen chloride enters the tail gas quenching device.

[0088] After fluorination reaction for 10 hours, the collected difluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of difluoroacetyl fluoride was 90.1% and the total yield was 85.3%.

[0089] Example 8: Preparation of trifluoroacetyl fluoride (purity 97.5%, yield 97.8%)

[0090] SbCl5 (37.38 g, 0.125 mol, molar ratio to trichloroacetyl chloride 0.05) was added into the reactor, the flow rate of anhydrous HF was controlled at 50.03 g / h by a flow meter, 90.92 g / h of trichloroacetyl chloride was continuously introduced into the reactor, and the temperature was raised to 95-105°C for continuous fluorination reaction.

[0091] As the fluorination reaction proceeds, the second mixture in the reactor is continuously fed into the primary distillation tower to obtain a second gas phase mixture and a second liquid phase mixture, and the second liquid phase mixture (anhydrous HF, trichloroacetyl chloride, trifluoroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the second gas phase mixture (HCl, trifluoroacetyl fluoride) is subjected to secondary distillation. The trifluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower. The byproduct hydrogen chloride enters the tail gas quenching device.

[0092] After fluorination reaction for 5 hours, the collected trifluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of trifluoroacetyl fluoride was 97.5% and the yield was 97.8%.

[0093] Example 9: Preparation of trifluoroacetyl fluoride (purity 98.9%, yield 95.9%)

[0094] SbCl5 (57.25 g, 0.25 mol, molar ratio to trichloroacetyl chloride 0.1) was added into the reactor, the flow rate of anhydrous HF was controlled at 100.05 g / h by a flow meter, 90.92 g / h of trichloroacetyl chloride was continuously introduced into the reactor, and the temperature was raised to 80-90°C for continuous fluorination reaction.

[0095] As the fluorination reaction proceeds, the second mixture in the reactor is continuously fed into the primary distillation tower to obtain a second gas phase mixture and a second liquid phase mixture, and the second liquid phase mixture (anhydrous HF, trichloroacetyl chloride, trifluoroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the second gas phase mixture (HCl, trifluoroacetyl fluoride) is subjected to secondary distillation. The trifluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower. The byproduct hydrogen chloride enters the tail gas quenching device.

[0096] After fluorination reaction for 5 hours, the collected trifluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of trifluoroacetyl fluoride was 98.9% and the yield was 95.9%.

[0097] Example 10: Preparation of trifluoroacetyl fluoride (purity 98.7%, yield 96.2%)

[0098] SbCl5 (747.53 g, 2.5 mol, molar ratio to trichloroacetyl chloride 0.5) was added into the reactor, the flow rate of anhydrous HF was controlled at 50.03 g / h by a flow meter, 90.92 g / h of trichloroacetyl chloride was continuously introduced into the reactor, and the temperature was raised to 65-75°C for continuous fluorination reaction.

[0099] As the fluorination reaction proceeds, the second mixture in the reactor is continuously fed into the primary distillation tower to obtain a second gas phase mixture and a second liquid phase mixture, and the second liquid phase mixture (anhydrous HF, trichloroacetyl chloride, trifluoroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the second gas phase mixture (HCl, trifluoroacetyl fluoride) is subjected to secondary distillation. The trifluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower. The byproduct hydrogen chloride enters the tail gas quenching device.

[0100] After fluorination reaction for 10 hours, the collected trifluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of trifluoroacetyl fluoride was 98.7% and the yield was 96.2%.

[0101] Example 11: Preparation of trifluoroacetyl fluoride (purity 97.9%, yield 95.7%)

[0102] SbCl5 (1495.05 g, 5 mol, molar ratio to trichloroacetyl chloride 1) was added into the reactor, the flow rate of anhydrous HF was controlled at 100.05 g / h by a flow meter, 90.92 g / h of trichloroacetyl chloride was continuously introduced into the reactor, and the temperature was raised to 50-60°C for continuous fluorination reaction.

[0103] As the fluorination reaction proceeds, the second mixture in the reactor is continuously fed into the primary distillation tower to obtain a second gas phase mixture and a second liquid phase mixture, and the second liquid phase mixture (anhydrous HF, trichloroacetyl chloride, trifluoroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the second gas phase mixture (HCl, trifluoroacetyl fluoride) is subjected to secondary distillation. The trifluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower. The byproduct hydrogen chloride enters the tail gas quenching device.

[0104] After fluorination reaction for 10 hours, the collected trifluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of trifluoroacetyl fluoride was 97.9% and the yield was 95.7%.

[0105] Example 12: Preparation of trifluoroacetyl fluoride (purity 96.5%, yield 95.4%)

[0106] SbCl5 (149.6 g, 0.5 mol, molar ratio to trichloroacetyl chloride 0.1) was added into the reactor, the flow rate of anhydrous HF was controlled at 200.1 g / h by a flow meter, 90.92 g / h of trichloroacetyl chloride was continuously introduced into the reactor, and the temperature was raised to 35-45°C for continuous fluorination reaction.

[0107] As the fluorination reaction proceeds, the second mixture in the reactor is continuously fed into the primary distillation tower to obtain a second gas phase mixture and a second liquid phase mixture, and the second liquid phase mixture (anhydrous HF, trichloroacetyl chloride, trifluoroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the second gas phase mixture (HCl, trifluoroacetyl fluoride) is subjected to secondary distillation. The trifluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower. The byproduct hydrogen chloride enters the tail gas quenching device.

[0108] After fluorination reaction for 10 hours, the collected trifluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of trifluoroacetyl fluoride was 96.5% and the yield was 95.4%.

[0109] Example 13: Preparation of trifluoroacetyl fluoride (purity 96.1%, yield 95.0%)

[0110] SbCl5 (747.53 g, 2.5 mol, molar ratio to trichloroacetyl chloride 0.5) was added to the reactor, and the flow rate of anhydrous HF was controlled to 300.15 g / h by a flow meter, and 90.92 g / h of trichloroacetyl chloride was continuously introduced into the reactor. The reaction temperature was controlled at 20-30°C to carry out a continuous fluorination reaction.

[0111] As the fluorination reaction proceeds, the second mixture in the reactor is continuously fed into the primary distillation tower to obtain a second gas phase mixture and a second liquid phase mixture, and the second liquid phase mixture (anhydrous HF, trichloroacetyl chloride, trifluoroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the second gas phase mixture (HCl, trifluoroacetyl fluoride) is subjected to secondary distillation. The trifluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower. The byproduct hydrogen chloride enters the tail gas quenching device.

[0112] After fluorination reaction for 10 hours, the collected trifluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of trifluoroacetyl fluoride was 96.1% and the yield was 95.0%.

[0113] Example 14: Preparation of trifluoroacetyl fluoride (purity 95.1%, yield 94.8%)

[0114] SbCl5 (747.53 g, 2.5 mol, molar ratio to trichloroacetyl chloride 0.5) was added into the reactor, the flow rate of anhydrous HF was controlled at 300.15 g / h by a flow meter, 90.92 g / h of trichloroacetyl chloride was continuously introduced into the reactor, the reaction temperature was controlled at 5-15°C, and a continuous fluorination reaction was carried out.

[0115] As the fluorination reaction proceeds, the second mixture in the reactor is continuously fed into the primary distillation tower to obtain a second gas phase mixture and a second liquid phase mixture, and the second liquid phase mixture (anhydrous HF, trichloroacetyl chloride, trifluoroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the second gas phase mixture (HCl, trifluoroacetyl fluoride) is subjected to secondary distillation. The trifluoroacetyl fluoride is collected in a storage tank at the bottom of the secondary distillation tower. The byproduct hydrogen chloride enters the tail gas quenching device.

[0116] After fluorination reaction for 5 hours, the collected trifluoroacetyl fluoride was analyzed by GC after derivatization, and the purity of trifluoroacetyl fluoride was 95.1% and the yield was 94.8%.

[0117] Example 15 Combined preparation of difluoroacetyl fluoride and trifluoroacetyl fluoride

[0118] SbCl5 (2990.1 g, 10 mol, with a total molar ratio of 1 to dichloroacetyl chloride and trichloroacetyl chloride) was added into the reactor, and the flow rate of anhydrous HF was controlled by a flow meter to be 400.2 g / h, dichloroacetyl chloride, 73.69 g / h, and trichloroacetyl chloride, 90.92 g / h were continuously introduced into the reactor, and the reaction temperature was controlled at 60-80°C to carry out continuous fluorination reaction.

[0119] As the fluorination reaction proceeds, the third mixture in the reactor is continuously fed into a primary distillation tower to obtain a third gas phase mixture and a third liquid phase mixture, and the third liquid phase mixture (anhydrous HF, difluoroacetyl chloride, dichloroacetyl chloride, trichloroacetyl chloride, SbCl5) is returned to the reactor to continue the reaction; the third gas phase mixture (HCl, difluoroacetyl fluoride, trifluoroacetyl fluoride, trifluoroacetyl chloride) is subjected to secondary distillation; a fourth gas phase mixture and difluoroacetyl fluoride liquid are obtained, and the difluoroacetyl fluoride product is collected in a storage tank at the bottom of the secondary distillation tower.

[0120] The fourth gas phase mixture (HCl, trifluoroacetyl chloride, trifluoroacetyl fluoride) is subjected to three-stage distillation, and trifluoroacetyl chloride is collected as an intermediate in a storage tank at the bottom of the three-stage distillation tower and returned to the reactor to continue the reaction; while the fifth gas phase mixture (HCl, trifluoroacetyl fluoride) enters the fourth stage distillation separation, and finally trifluoroacetyl fluoride is collected as a product in a storage tank at the bottom of the four-stage distillation tower. The by-product hydrogen chloride enters the tail gas quenching device,

[0121] After fluorination reaction for 10 hours, the collected fluoroacetyl halide products were analyzed by GC after derivatization. The fluoroacetyl halide products difluoroacetyl fluoride had a purity of 91.4% and a yield of 85.4%; the purity of trifluoroacetyl fluoride had a purity of 95.1% and a yield of 92.3%.

[0122] It can be seen from the above examples that the purity of difluoroacetyl fluoride in the obtained fluoroacetyl halide product is above 89% and the yield is above 85%; the purity of trifluoroacetyl fluoride is above 95% and the yield is above 92%.

[0123] Finally, it should be noted that although the above embodiments have been described in the text of the specification of this application, this does not limit the scope of patent protection of this application. All technical solutions generated by replacing or modifying equivalent structures or equivalent processes based on the essential concept of this application using the contents recorded in the text of the specification of this application, as well as directly or indirectly implementing the technical solutions of the above embodiments in other related technical fields, are included in the scope of patent protection of this application.

Claims

1. A method for preparing a fluoroacetyl halide, characterized in that: The following steps are involved: Chloroacetyl chloride reacts with anhydrous hydrofluoric acid with antimony pentachloride as a catalyst to produce fluoroacetyl fluoride.

2. The preparation method according to claim 1, characterized in that: The chloroacetyl chloride includes dichloroacetyl chloride and trichloroacetyl chloride; the fluoroacetyl halide includes difluoroacetyl fluoride and trifluoroacetyl fluoride.

3. The preparation method according to claim 1, characterized in that: If the chloroacetyl chloride is dichloroacetyl chloride, the fluoroacetyl halide is difluoroacetyl fluoride.

4. The preparation method according to claim 1, characterized in that: If the chloroacetyl chloride is trichloroacetyl chloride, the fluoroacetyl halide is trifluoroacetyl fluoride.

5. The preparation method according to claim 1, characterized in that: The molar ratio of the anhydrous hydrofluoric acid to the chloroacetyl chloride is 5-30:

1.

6. The preparation method according to claim 1, characterized in that: The molar ratio of the antimony pentachloride to the chloroacetyl chloride is 5-100:

100.

7. A continuous preparation method of fluoroacetyl halide, characterized in that: The method comprises the following steps: continuously feeding chloroacetyl chloride and anhydrous hydrofluoric acid into a reaction kettle containing antimony pentachloride to carry out a continuous fluorination reaction to generate fluoroacetyl halide and hydrochloric acid; continuously rectifying the mixture obtained by the continuous fluorination reaction in the reaction kettle to separate fluoroacetyl fluoride; and returning the chloroacetyl chloride, anhydrous hydrofluoric acid and the intermediate product fluoroacetyl chloride separated by rectification to the reaction kettle to continue the continuous fluorination reaction.

8. The continuous preparation method according to claim 7, characterized in that: The method comprises the following steps: continuously feeding dichloroacetyl chloride and anhydrous hydrofluoric acid into a reactor containing antimony pentachloride to carry out a continuous fluorination reaction; performing primary distillation on a first mixture obtained by the continuous fluorination reaction in the reactor to obtain a first gas phase mixture and a first liquid phase mixture; the first liquid phase mixture comprises dichloroacetyl chloride, difluoroacetyl chloride and anhydrous hydrofluoric acid, and the first liquid phase mixture is returned to the reactor to continue the continuous fluorination reaction; the first gas phase mixture comprises difluoroacetyl fluoride and hydrochloric acid; and performing secondary distillation on the first gas phase mixture to separate difluoroacetyl fluoride liquid.

9. The continuous preparation method according to claim 7, characterized in that: The following steps are involved: Trichloroacetyl chloride and anhydrous hydrofluoric acid are continuously fed into a reactor containing antimony pentachloride to carry out a continuous fluorination reaction; a second mixture obtained by the continuous fluorination reaction in the reactor is subjected to primary distillation to obtain a second gas phase mixture and a second liquid phase mixture; the second liquid phase mixture includes trifluoroacetyl chloride, trichloroacetyl chloride and anhydrous hydrofluoric acid, and the second liquid phase mixture is returned to the reactor to continue the continuous fluorination reaction; the second gas phase mixture includes trifluoroacetyl fluoride and hydrochloric acid; the second gas phase mixture is subjected to secondary distillation to separate trifluoroacetyl fluoride liquid.

10. The continuous preparation method according to claim 7, characterized in that: The method comprises the following steps: continuously feeding dichloroacetyl chloride, trichloroacetyl chloride and anhydrous hydrofluoric acid into a reactor containing antimony pentachloride to carry out a continuous fluorination reaction; performing a primary distillation on a third mixture obtained by the continuous fluorination reaction in the reactor to obtain a third gas phase mixture and a third liquid phase mixture; the third liquid phase mixture comprises dichloroacetyl chloride, difluoroacetyl chloride, trichloroacetyl chloride and anhydrous hydrofluoric acid, and the third liquid phase mixture is returned to the reactor to continue the continuous fluorination reaction; the third gas phase mixture comprises trifluoroacetyl chloride, difluoroacetyl fluoride, trifluoroacetyl fluoride and hydrochloric acid; The third gas phase mixture is subjected to secondary distillation to separate difluoroacetyl fluoride liquid and a fourth gas phase mixture; the fourth gas phase mixture comprises trifluoroacetyl chloride, trifluoroacetyl fluoride and hydrochloric acid; The fourth gas phase mixture is subjected to three-stage distillation to separate trifluoroacetyl chloride liquid and a fifth gas phase mixture; the trifluoroacetyl chloride liquid is returned to the reactor to continue the continuous fluorination reaction; the fifth gas phase mixture includes trifluoroacetyl fluoride and hydrochloric acid; The fifth gas phase mixture is subjected to a fourth-stage distillation to separate trifluoroacetyl fluoride liquid.

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