CN103880588B - Method for preparing perfluoroalkyl iodine through catalytic distillation telomerization - Google Patents
Method for preparing perfluoroalkyl iodine through catalytic distillation telomerization Download PDFInfo
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- CN103880588B CN103880588B CN201410067621.1A CN201410067621A CN103880588B CN 103880588 B CN103880588 B CN 103880588B CN 201410067621 A CN201410067621 A CN 201410067621A CN 103880588 B CN103880588 B CN 103880588B
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Abstract
The invention discloses a method for preparing perfluoroalkyl iodine through catalytic distillation telomerization. A catalytic distillation tower adopted for preparation consists of a rectifying section, a reaction section, a stripping section and a tower vessel which are sequentially connected from a tower top to a tower bottom, and the reaction section is filled with a phosphor bronze gauze packing which serves as a catalyst; the preparation method comprises the following steps: (a) respectively continuously adding pentafluoroethyl iodide and tetrafluoroethylene from the rectifying section and the stripping section into the catalytic distillation tower for reaction at the reaction temperature of 70-100DEG C under the reaction pressure of 0.5-1.4MPa, wherein the mole ratio of pentafluoroethyl iodide to tetrafluoroethylene is 1:(2-10); and (b) continuously guiding a reaction product of the tower vessel out, to obtain the perfluoroalkyl iodine product. The method has the advantages of being simple in production equipment, easily controllable for technology parameters, good in operation safety, high in reaction efficiency, easy for product separation.
Description
Technical field
The present invention relates to the preparation method of fluoride-containing PMMA intermediate, particularly a kind of catalytic distillation telomerizes the method preparing perfluoroalkyl iodides.
Background technology
Perfluoroalkyl iodides is the key intermediate producing fluoride-containing PMMA.Usually with C
2f
5i is end group thing, TFE (tetrafluoroethylene) for telomerizing monomer, telomerization under initiator or High Temperature High Pressure or metal-based catalysts exist and obtaining.All there is production in fluorine chemical production firm main in the world, and deep processing is the fluorine surfactant of the various trade mark, is widely used in chemistry, machinery, weaving and paper industry, and printing ink paint is industrial and fire-fighting domain.In recent years, there is comparatively quantum jump in each company in initiator improvement, type of reactor improvement, the control of telomer molecular weight distribution and yield raising etc., is proposed respective new technology of preparing, facilitates the progress of perfluoroalkyl iodides synthetic technology.
Catalytic distillation technology carries out in catalytic distillation tower, due to achieve reaction and rectifying while carry out, make material reaction all the time forward carry out, the transformation efficiency of material almost reaches 100%, significantly reduces cost and improves efficiency.The successful Application of catalytic distillation technology on methyl tertiary butyl ether (MTBE) device is especially for solid foundation has been established in the deep processing of C4.
China Patent Publication No. CN1535258A, publication date on October 6th, 2004, denomination of invention: the method for continuous production of perfluoroalkyl iodide telomer, this application case discloses a kind of continuous seepage by general formula R
f(CF
2cF
2)
nthe method of the full-fluorine alkyl iodide that I represents, wherein R
ffor C
1-
6perfluoroalkyl, n is the integer of 1 ~ 4, and described method comprises provides full-fluorine alkyl iodide as by general formula R continuously
fthe telogen that I represents, wherein R
fas above, be added in tubular reactor using tetrafluoroethylene as taxogen, described reactor charge has the metal catalyst comprising powdery spherical metal or sintering metal in definition; And telomerization is carried out under temperature is 60 DEG C ~ 160 DEG C and pressure is 0.1 ~ 5MPa (gauge pressure).Weak point to be discharged in the product of reactor containing a large amount of catalyzer with liquid state, need carry out solid-liquor separation, and catalyzer can not recycle, and cost is high, and tubular reactor easily causes the accumulation of reaction heat, makes telomerization control difficulty.
US Patent No. 5571193 with the metal fluoride of strong oxidizing property for catalyzer, rhythmic reaction mode prepares perfluoroalkyl iodides, initiator used has CrF3, CrF4, CrF5, Co Fa, M nFa, CeF4, XeF4, KCo F4, NaCoF4, VF5 etc., temperature of reaction 20 ~ 180 DEG C, reaction pressure is self-generating pressure at this temperature.Reaction product produces tensio-active agent and oil-proofing agent effectively.Weak point is this handicraft product carbochain wider distribution.
Reaction preparation unites two into one with rectifying separation by US Patent No. 59292927, adopts rectification process technique continuous production perfluoroalkyl iodides.This method can avoid product carbon number distribution wide, or prepares a certain intermediate product that can react further with raw material.Its technique is: perfluoro ethyl iodide (C
2f
5i) 738g adds packing type rectifying column reactor distilling period, and heating direct reaches 75 DEG C to charging opening temperature, pressure 6kg/cm (G); Add from tower top the perfluoro-ethyl iodine solution that concentration is the diisopropyl peroxydicarbonate of 2%, add TFE gas in the middle part of rectifying column, flow is respectively 25.75g/h, 25g/h, terminates reinforced after 30min.Weak point is that this technique has hydrogeneous by product to generate, and not easily purifies.
What above patent and known technology adopted telomerizes technique, all has weak point: or adopt tubular reactor, and reaction efficiency is low, and operation easier is large; Or employing tank reactor, telomerization is restive, and product carbon number distribution is wide; Or adopting peroxide initiator simultaneously, hydrogeneous by-products content is large; Or use copper powder catalyst particle little, can the shortcomings such as bed resistance is large be caused, have influence on the normal operation of full scale plant.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, provide a kind of production unit simple, processing parameter is easily controlled, good operation safety, and reaction efficiency is high, and the segregative catalytic distillation of product telomerizes the method preparing perfluoroalkyl iodides.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of catalytic distillation telomerizes the method preparing perfluoroalkyl iodides, prepared by employing catalytic distillation tower, described catalytic distillation tower is made up of the rectifying section connected successively, conversion zone, stripping section and tower reactor at the bottom of from tower top to tower, described conversion zone is filled with the phosphor bronze wire corrugated wire gauze packing as catalyzer, and described preparation method comprises the following steps:
A PFEI and tetrafluoroethylene are added catalytic distillation tower from rectifying section and stripping section simultaneously react by () respectively continuously, the mol ratio of described PFEI and tetrafluoroethylene is 1: 2 ~ 10, reaction pressure is 0.5 ~ 1.4MPa, and temperature of reaction is 70 ~ 100 DEG C;
B tower reactor reaction product is drawn and is namely obtained perfluoroalkyl iodides product by () continuously.
Described conversion zone is preferably divided into 1 ~ 5 section.
Described phosphor bronze wire corrugated wire gauze packing by mass percentage content composition is preferably: tin 2 ~ 8%, phosphorus 0.1 ~ 0.4%, and plumbous 0.05 ~ 0.1%, all the other are copper.
The specific surface area of described phosphor bronze wire corrugated wire gauze packing is preferably 125-500m
2/ m
3.
Described PFEI and the mol ratio of tetrafluoroethylene are preferably 1: 3 ~ 5, and reaction pressure is preferably 0.5 ~ 0.8MPa, and temperature of reaction is preferably 80 ~ 95 DEG C.
The present invention adopts catalytic distillation tower as the production equipment of telomerization, with PFEI (C
2f
5i) and tetrafluoroethylene as raw material, carry out continuous catalyst distillation reaction, the conversion zone of catalytic distillation tower filling phosphor bronze wire corrugated wire gauze packing, this filler uses as copper-based catalysts.Containing the low boiler cut of tetrafluoroethylene by overhead extraction.Product perfluoroalkyl iodides is discharged continuously by tower reactor, obtains perfluoroalkyl iodides crude product, and perfluoroalkyl iodides crude product as after rectifying, can obtain more highly purified perfluoroalkyl iodides product through follow-up this area regular refiner operation.Phosphor bronze wire corrugated wire gauze packing in the present invention can adopt commercially available prod, as the phosphor bronze wire corrugated wire gauze packing product that star chemical industry equipment filler company limited of Pingxiang City China produces.
Compared with prior art, the present invention has the following advantages:
1, reaction efficiency is high, product is easily separated, use regular phosphor bronze wire corrugated wire gauze packing good as catalyst activity, reaction efficiency is high, avoid the generation because of the hydrogeneous by product using peroxide initiator to bring, product is easily separated, and uses regular phosphor bronze wire corrugated wire gauze packing as catalyzer, easy installing/dismounting, avoids the shortcoming that the powdered catalysts such as copper powder cause the large and solid-liquid separation difficulty of bed resistance;
2, product composition distributes, and avoid product carbon number distribution wide, C4 ~ C8 product content is more than 97%;
3, production unit is simple, and processing parameter is easily controlled, good operation safety, and adopt catalytic distillation tower as the device of continuous production perfluoroalkyl iodides, facility investment is low, and throughput is large, is suitable for industrialization scale operation.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
In figure, rectifying section 1, conversion zone 2, stripping section 3 and tower reactor 4
Embodiment
In the present invention, adopt catalytic distillation tower to prepare perfluoroalkyl iodides, catalytic distillation tower is made up of the rectifying section 1 connected successively, conversion zone 2, stripping section 3 and tower reactor 4 at the bottom of from tower top to tower, and conversion zone 1 is filled with the phosphor bronze wire corrugated wire gauze packing as catalyzer.
The technological process of production is: PFEI is added catalytic distillation tower continuously from rectifying section 1, gas phase tetrafluoroethylene adds catalytic distillation tower continuously from stripping section 3, low boiler cut containing tetrafluoroethylene is concentrated to tower top, by overhead extraction by conversion zone 2 and rectifying section 1.Product perfluoroalkyl iodides concentrates at the bottom of tower, is discharged continuously by tower reactor 4, obtains perfluoroalkyl iodides crude product, and perfluoroalkyl iodides crude product as after rectifying, can obtain more highly purified perfluoroalkyl iodides product through the operation of follow-up this area conventional purification.
By the following examples more specific description is carried out to the present invention, but the present invention is not limited to described embodiment.
Embodiment 1
Catalytic distillation tower internal diameter is φ 1000mm, and conversion zone 2 is divided into three sections, every section of filling phosphor bronze wire corrugated wire gauze packing duckweed
star chemical industry equipment filler company limited of China of city of townshipproduce, model 125, specific surface area 125m
2/ m
3, content consists of by mass percentage: tin 2%, phosphorus 0.4%, and plumbous 0.08%, all the other are copper) and 2m is high, C
2f
5i adds continuously from conversion zone 2 upper rectifying section 1, and gas phase tetrafluoroethylene adds continuously from the stripping section 3 of conversion zone 2 bottom.Reaction conditions is: C
2f
5i and tetrafluoroethylene mol ratio are 1: 5; Reaction pressure 1.0MPa; Conversion zone temperature 70 C, containing the low boiler cut of tetrafluoroethylene by overhead extraction, perfluoroalkyl iodides crude product is discharged continuously by tower reactor 4.Sampling analysis, reaction result is in table 1.
Embodiment 2
Catalytic distillation tower internal diameter is φ 1000mm, and conversion zone 2 is divided into five sections, every section of filling phosphor bronze wire corrugated wire gauze packing duckweed
star chemical industry equipment filler company limited of China of city of townshipproduce, model 250, specific surface area 250m
2/ m
3, content consists of by mass percentage: tin 3%, phosphorus 0.3%, and plumbous 0.05%, all the other are copper) and 1m is high, C
2f
5i adds continuously from conversion zone 2 upper rectifying section 1, and gas phase tetrafluoroethylene adds continuously from the stripping section 3 of conversion zone 2 bottom.Reaction conditions is: C
2f
5i and tetrafluoroethylene mol ratio are 1: 3; Reaction pressure 0.8MPa; Conversion zone temperature 80 DEG C, containing the low boiler cut of tetrafluoroethylene by overhead extraction, perfluoroalkyl iodides crude product is discharged continuously by tower reactor 4.Sampling analysis, reaction result is in table 1.
Embodiment 3
Catalytic distillation tower internal diameter is φ 1000mm, and conversion zone 2 is divided into one section, every section of filling phosphor bronze wire corrugated wire gauze packing duckweed
star chemical industry equipment filler company limited of China of city of townshipproduce, model 500, specific surface area 500m
2/ m
3, content consists of by mass percentage: tin 4%, phosphorus 0.2%, and plumbous 0.1%, all the other are copper) and 5m is high, C
2f
5i adds continuously from conversion zone 2 upper rectifying section 1, and gas phase tetrafluoroethylene adds continuously from the stripping section 3 of conversion zone 2 bottom.Reaction conditions is: C
2f
5i and tetrafluoroethylene mol ratio are 1: 7; Reaction pressure 0.6MPa; Conversion zone temperature 85 DEG C, containing the low boiler cut of tetrafluoroethylene by overhead extraction, perfluoroalkyl iodides crude product is discharged continuously by tower reactor 4.Sampling analysis, reaction result is in table 1.
Embodiment 4
Catalytic distillation tower internal diameter is φ 1000mm, and conversion zone 2 is divided into two sections, every section of filling phosphor bronze wire corrugated wire gauze packing duckweed
star chemical industry equipment filler company limited of China of city of townshipproduce, model 325, specific surface area 325m
2/ m
3, content consists of by mass percentage: tin 5%, phosphorus 0.2%, and plumbous 0.1%, all the other are copper) and 2.5m is high, C
2f
5i adds continuously from conversion zone 2 upper rectifying section 1, and gas phase tetrafluoroethylene adds continuously from the stripping section 3 of conversion zone 2 bottom.Reaction conditions is: C
2f
5i and tetrafluoroethylene mol ratio are 1: 4; Reaction pressure 0.5MPa; Conversion zone temperature 90 DEG C, containing the low boiler cut of tetrafluoroethylene by overhead extraction, perfluoroalkyl iodides crude product is discharged continuously by tower reactor 4.Sampling analysis, reaction result is in table 1.
Embodiment 5
Catalytic distillation tower internal diameter is φ 1000mm, and conversion zone 2 is divided into four sections, every section of filling phosphor bronze wire corrugated wire gauze packing duckweed
star chemical industry equipment filler company limited of China of city of townshipproduce, model 125, specific surface area 125m
2/ m
3, content consists of by mass percentage: tin 6%, phosphorus 0.1%, and plumbous 0.1%, all the other are copper) and 1.2m is high, C
2f
5i adds continuously from conversion zone 2 upper rectifying section 1, and gas phase tetrafluoroethylene adds continuously from the stripping section 3 of conversion zone 2 bottom.Reaction conditions is: C
2f
5i and tetrafluoroethylene mol ratio are 1: 8; Reaction pressure 0.7MPa; Conversion zone temperature 95 DEG C, containing the low boiler cut of tetrafluoroethylene by overhead extraction, perfluoroalkyl iodides crude product is discharged continuously by tower reactor 4.Sampling analysis, reaction result is in table 1.
Embodiment 6
Catalytic distillation tower internal diameter is φ 1000mm, and conversion zone 2 is divided into one section, every section of filling phosphor bronze wire corrugated wire gauze packing duckweed
star chemical industry equipment filler company limited of China of city of townshipproduce, model 125, specific surface area 125m
2/ m
3, content consists of by mass percentage: tin 8%, phosphorus 0.1%, and plumbous 0.1%, all the other are copper) and 4m is high, C
2f
5i adds continuously from conversion zone 2 upper rectifying section 1, and gas phase tetrafluoroethylene adds continuously from the stripping section 3 of conversion zone 2 bottom.Reaction conditions is: C
2f
5i and tetrafluoroethylene mol ratio are 1: 10; Reaction pressure 1.2MPa; Conversion zone temperature 100 DEG C, containing the low boiler cut of tetrafluoroethylene by overhead extraction, perfluoroalkyl iodides crude product is discharged continuously by tower reactor 4.Sampling analysis, reaction result is in table 1.
Table 1 embodiment 1 ~ 6 reaction result
Claims (4)
1. a catalytic distillation telomerizes the method preparing perfluoroalkyl iodides, prepared by employing catalytic distillation tower, described catalytic distillation tower is made up of the rectifying section connected successively, conversion zone, stripping section and tower reactor at the bottom of from tower top to tower, described conversion zone is filled with the phosphor bronze wire corrugated wire gauze packing as catalyzer, described phosphor bronze wire corrugated wire gauze packing by mass percentage content consists of: tin 2 ~ 8%, phosphorus 0.1 ~ 0.4%, plumbous 0.05 ~ 0.1%, all the other are copper, it is characterized in that described preparation method comprises the following steps:
A PFEI and tetrafluoroethylene are added catalytic distillation tower from rectifying section and stripping section simultaneously react by () respectively continuously, the mol ratio of described PFEI and tetrafluoroethylene is 1: 2 ~ 10, reaction pressure is 0.5 ~ 1.4MPa, and temperature of reaction is 70 ~ 100 DEG C;
B tower reactor reaction product is drawn and is namely obtained perfluoroalkyl iodides product by () continuously.
2. catalytic distillation according to claim 1 telomerizes the method preparing perfluoroalkyl iodides, it is characterized in that described conversion zone is divided into 1 ~ 5 section.
3. catalytic distillation according to claim 1 telomerizes the method preparing perfluoroalkyl iodides, it is characterized in that the specific surface area of described phosphor bronze wire corrugated wire gauze packing is 125-500m
2/ m
3.
4. catalytic distillation according to claim 1 telomerizes the method preparing perfluoroalkyl iodides, and it is characterized in that the mol ratio of described PFEI and tetrafluoroethylene is 1: 3 ~ 5, reaction pressure is 0.5 ~ 0.8MPa, and temperature of reaction is 80 ~ 95 DEG C.
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| CN101306977A (en) * | 2008-05-23 | 2008-11-19 | 巨化集团公司 | Process for preparing perfluoroalkyl group by telomerization |
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