CN105399598A - 1,1,1,3,3-perfluoropropane preparation device and preparation method - Google Patents
1,1,1,3,3-perfluoropropane preparation device and preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
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- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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Abstract
The invention discloses a 1,1,1,3,3-perfluoropropane preparation device and preparation method. The preparation method comprises a vaporizer, a liquid phase fluorination reactor, a superheater, a gaseous phase fluorination reactor, a compression pump, a first rectifying tower, a second rectifying tower, a third rectifying tower, a water washing tower, an alkaline washing tower and a product rectifying tower which are connected sequentially, wherein an overhead distillate output end of the second rectifying tower returns to the preceding stage through a pipeline and is connected with an input end of the gaseous phase fluorination reactor for a reaction, and a tower bottom component output end of the third rectifying tower returns to the preceding stage and is connected with a raw material input end of the vaporizer. According to the preparation method, 1,1,1,3,3-perfluoropropane is synthesized through a one-step liquid phase and a one-step gaseous phase; multi-tower separation is adopted, and the preparation device and the preparation method have the advantages that the liquid phase reaction efficiency is high, the reactor corrosion is small, the life of a catalyst is long, the gaseous phase reaction conversion rate and yield are high, the production cost is low and the like.
Description
Technical field
The present invention relates to a kind of preparation facilities of 1,1,1,3,3-pentafluoropropane, and the preparation method of 1,1,1,3,3-pentafluoropropane, particularly relate to one with 1,1,1,3,3 – pentachloropropane are raw material, two step lines synthesis 1,1,1,3, the method for 3 – pentafluoropropanes.
Background technology
1,1,1,3,3-pentafluoropropane (HFC-245fa) is a kind of fluorinated hydrocarbon compounds to atmospheric ozone layer safety, its ozone depletion latent energy value (ODP) is zero, and Greenhouse effect value (GWP) is low, does not fire, toxicity is low, main as trifluorochloromethane (CFC-11) and 1 at present, the substitute of 1,1-trichlorofluoroethane (HCFC-141b) whipping agent, is also widely used in solvent, propellant, fire-fighting medium and dry etching agent.
The preparation method of 1,1,1,3,3-pentafluoropropane is mainly with 1,1,1,3,3-pentachloropropane and anhydrous hydrogen fluoride are raw material, and Liquid preparation methods forms, vapor phase process route seldom adopts, and 1,1,1,3, the selectivity of 3-pentafluoropropane is not high, and liquid phase method generally adopts the muriate of Sb, Sn or Ti to make catalyzer, reaction later stage 1-chloro-1,3, the content of 3,3 – tetrafluoropropane increases, and affects reaction effect, is difficult to continue to fluoridize into 1 in same reactor, 1,1,3,3-pentafluoropropane.
China Patent Publication No. CN103214342A, publication date on July 24th, 2013, denomination of invention: a kind of synthetic method of 1,1,1,3,3-pentafluoropropane.Which disclose under the effect of chromium-based catalysts, by 1, 1, 1, 3, 3-pentachloropropane (HCC-240) and anhydrous hydrogen fluoride, HFC-245fa is produced by two step gas phase catalytic fluorination reactions, the first step reaction product contains HCFC-1233zd and HFC-1234ze of generation, a small amount of target product HFC-245fa, by product HCl and unreacted raw material, then the product of liquid phase fluorination reactor is directly entered gas phase fluorination device to react, obtain containing HFC-245fa, a small amount of unreacted HFC-1234ze, HCFC-1233zd and HF, the product of by product HCl, target product HFC-245fa is obtained after separating impurity.
Chinese patent Authorization Notice No. CN100546959C, authorized announcement date on October 7th, 2009, denomination of invention: the preparation method of 1,1,1,3,3-pentafluoropropane.Which disclose a kind of 1,1,1,3, the production method of 3-pentafluoropropane, under chromium-based catalysts exists, by 1,1,1,3,3-pentachloropropane and anhydrous hydrogen fluoride, produce HFC-245fa by two step gas phase catalytic fluorination reactions, and the first step resultant of reaction HCFC-1233zd, HFC-1234ze, a small amount of object product HFC-245fa, by product HCl and unreacted raw material are after " HCl knockout tower " removes HCl, separate HCC-240fa through raw material knockout tower again and return the first step reaction, all the other organic materialss enter second step reaction.Although this invention is by carrying out separating treatment to intermediate product, make the selectivity of final product good, yield is high, by product is few, separating treatment is carried out to second step reaction product simultaneously, allow raw materials recovery utilize, this technique is more optimized, can production cost be reduced, also meet the policy of China's less energy-consumption, environment protection clean production.But this invention is separated the HCl that the first step is reacted, step is complicated, and energy efficiency is low, facility investment is large.
In addition, in existing liquid phase fluorination reaction, adopt antimony pentachloride single mass system catalyzer, catalyst effect is strong, and reaction may produce more 1,1 in earlier stage, 1,3,3-pentafluoropropane, the reaction later stage has a lot of 3-chloro-1,1,1,3 – tetrafluoropropane (R224fa), be easy to assemble and make the coking inactivation of catalyzer on a catalyst, reduce the work-ing life of catalyzer, and equipment corrosion is serious.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of preparation facilities of 1,1,1,3,3-pentafluoropropane, adopt multitower to be separated, liquid phase reaction efficiency is high, reactor corrosion is little, and catalyst life is long.
The present invention also provides a kind of preparation method of 1,3,3,3-tetrafluoeopropene, gas-phase reaction transformation efficiency and yield high, production cost is low, and the selectivity of 1,1,1,3,3-pentafluoropropane is high, and production efficiency is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A kind of preparation facilities of 1,1,1,3,3-pentafluoropropane, comprises the vaporizer connected successively, liquid phase fluorination reactor, superheater, gas phase fluorination device, compression pump, the first rectifying tower, Second distillation column, the 3rd rectifying tower, and connection line, wherein:
Vaporizer is provided with raw material input terminus, the output terminal of vaporizer is connected with the input terminus of liquid phase fluorination reactor by pipeline, the output terminal of liquid phase fluorination reactor is connected via the input terminus of superheater with gas phase fluorination device, the output terminal of gas phase fluorination device is connected with the first rectifying tower input terminus via compression pump, the tower reactor component output terminal of the first rectifying tower is connected with the input terminus of Second distillation column, the overhead fraction output terminal of the first rectifying tower connects absorption by Hydrochloric Acid system, the overhead fraction output terminal of Second distillation column is connected via the input terminus of pipeline with gas phase fluorination device, the tower reactor component output terminal of Second distillation column is connected with the 3rd rectifying tower input terminus, the tower reactor component output terminal of the 3rd rectifying tower is connected with the raw material input terminus of vaporizer, the overhead fraction output terminal of the 3rd rectifying tower obtains target product 1, 1, 1, 3, 3-pentafluoropropane.
Preferably, the overhead fraction (1,1 of described 3rd rectifying tower, 1,3,3-pentafluoropropane) output terminal is connected with water wash column and soda-wash tower successively by pipeline, carries out liquid phase washing, alkali cleaning process, soda-wash tower is connected via the input terminus of pipeline with product rectifying tower, the target product 1,1,1 of purifying is obtained by product rectifying tower tops output terminal, 3,3-pentafluoropropane.
The preparation facilities of 1,1,1,3,3-pentafluoropropane of the present invention, adopt multitower to be separated, have that liquid phase reaction efficiency is high, reactor corrosion is little, catalyst life is long.
The preparation method of a kind of 1,1,1,3,3-pentafluoropropane of the present invention, comprises the following steps:
Comprise the following steps:
(a) by fresh hydrogen fluoride and 1,1,1,3,3 – pentachloropropane enter into liquid phase fluorination reactor via vaporizer, under the effect of catalyzer, liquid phase reaction occur, described hydrogen fluoride and 1,1, the mol ratio of 1,3,3 – pentachloropropane is 4 ~ 30:1, and temperature of reaction is 40 ~ 100 DEG C, reaction pressure is 0.5 ~ 1.2MPa, obtains containing a large amount of 1-chloro-3,3,3 ,-trifluoropropene, a small amount of 1,3,3,3-tetrafluoeopropene, a small amount of 1,1, the mix products of 1,3,3-pentafluoropropane, HF and HCL;
B mix products that liquid phase fluorination reactor exports by (), after superheater heating and gasifying, enters into gas phase fluorination device,
And pumping into the first rectifying tower by compression pump pressurization, the first rectifying tower tops obtains HCL, and HCL being connected absorption by Hydrochloric Acid system can obtain hydrochloric acid;
(c) first the tower reactor component of rectifying tower carry out rectifying separation by Second distillation column, Second distillation column overhead fraction is 1,3,3,3-tetrafluoeopropene, 1,3,3,3-tetrafluoeopropene returns prime gas phase fluorination device, continues to participate in gas-phase reaction under the effect of catalyzer;
Described gas phase fluorination device due to the liquid reactive HF of the first step excessive larger, so second step gas-phase reaction no longer adds fresh HF, temperature of reaction is 250 ~ 380 DEG C, and air speed is 500 ~ 1000h-1, HF and 1-chloro-3,3,3-trifluoro propene, 1,3,3, the mol ratio of 3 – tetrafluoeopropenes is 1 ~ 10:1
Owing to there being Second distillation column overhead fraction to be the gas-phase reaction that 1,3,3,3-tetrafluoeopropene participates in prime, in gas phase fluorination device, therefore obtain the mix products containing 1,1,1,3,3-pentafluoropropane, 1,3,3,3-tetrafluoeopropene, HF and HCL;
D () will pass into the first rectifying tower containing the mix products of 1,1,1,3,3-pentafluoropropane, 1,3,3,3-tetrafluoeopropene, HF and HCL and carry out rectifying separation, overhead fraction is HCl, and HCl otherwise processed can be obtained hydrochloric acid;
E the tower reactor component of the first rectifying tower is led to Second distillation column and is carried out rectifying separation by (), overhead fraction is 1,3,3,3-tetrafluoeopropene, returns gas phase fluorination device and continues to participate in reaction;
F logical for the tower reactor component of Second distillation column the 3rd rectifying tower is carried out rectifying separation by (), overhead fraction is thick 1,1,1,3,3-pentafluoropropane, and tower reactor component obtains HF and returns liquid phase fluorination reactor and continue to participate in reaction again;
G () is by thick 1,1,1,3,3-pentafluoropropane enters follow-up water wash column, soda-wash tower and carries out liquid phase washing, alkali cleaning process respectively, by 1 after depickling, 1,1,3, the mix products of 3-pentafluoropropane passes into product rectifying tower again and carries out rectifying, the target product 1,1,1 of purifying is obtained after distillation operation, 3,3-pentafluoropropane.
Preferably, the hydrogen fluoride HF and 1 described in described step (a), the mol ratio of 1,1,3,3 – pentachloropropane is 5 ~ 8:1, and temperature of reaction is 45 ~ 60 DEG C, and reaction pressure is 0.7 ~ 1.0MPa.
Preferably, the catalyzer described in described step (a) is the mixture of antimony pentachloride and tin tetrachloride, and catalyst quality ratio is 2 ~ 4:1.
Preferably, the gas phase fluorination device temperature of reaction described in described step (c) is 280 ~ 310 DEG C, HF and 1-chloro-3,3,3 ,-trifluoropropene, 1, and the mol ratio of 3,3,3 – tetrafluoeopropenes is 1 ~ 3:1, and air speed is 600 ~ 800h-1.
Preferably, by mass percentage, it consists of the catalyzer described in described step (c): zinc oxide 50 ~ 80%, and aluminum oxide is 20 ~ 50%.
Preferably, described in described step (f), temperature of reaction is 10 ~ 30 DEG C, and reaction pressure is 0.3 ~ 1.0MPa.
Excellent effect of the present invention:
The present invention with 1,1,1,3,3-pentachloropropane (HCC-240) and anhydrous hydrogen fluoride (HF) are raw material, fluoridize synthesis 1 through two-step catalysis, 1,1,3,3-pentafluoropropane (HFC-245fa), the first step is reacted with 1, and 1,1,3,3-pentachloropropane and anhydrous hydrogen fluoride are raw material, under the effect of antimony pentachloride and stannic chloride catalyst, liquid phase reaction occur, hydrogen fluoride and 1,1,1,3, the mol ratio of 3 – pentachloropropane is 4 ~ 20:1, temperature of reaction is 40 ~ 100 DEG C, and reaction pressure is 0.5 ~ 1.2MPa, and the control of temperature and pressure can improve
The selectivity of 1-chloro-3,3,3 ,-trifluoropropene.
Gas phase fluorination device be liquid phase fluorination reactor is exported containing 1-chloro-1,3,3, pass into after the mix products preheating of 3 – tetrafluoeopropenes, under the effect of zinc oxide+aluminium oxide catalyst, carry out gas-phase reaction, temperature of reaction is 250 ~ 380 DEG C, hydrogen fluoride and HCFC-1233zd and 1-chloro-3,3,3-trifluoro propene and 1,3,3, the mol ratio of both 3 – tetrafluoeopropenes mixture is 1 ~ 10:1, and air speed is 500 ~ 1000h
-1, obtain the mix products containing 1,1,1,3,3-pentafluoropropane.Reaction is easy to carry out, and the selectivity of 1,1,1,3,3-pentafluoropropane can reach 100%.
Accompanying drawing explanation
Accompanying drawing described herein is in order to provide a further understanding of the present invention, and form the part of the present patent application, schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the process flow sheet of an embodiment of the present invention.
In figure:
1, vaporizer,
2, liquid phase fluorination reactor
3, superheater,
4, gas phase fluorination device,
5, compression pump,
6, the first rectifying tower
7, Second distillation column,
8, the 3rd rectifying tower,
21, water wash column
22, soda-wash tower
23, product rectifying tower
9,10,11,12,13,14,15,16,17,18,19 is pipeline.
Embodiment
Below by way of particular specific embodiment, technology contents of the present invention is described, the content that those skilled in the art can be disclosed by this specification sheets understands other advantage of the present invention and effect easily.The present invention is also implemented by other different specific embodiment or is applied, and the every details in this specification sheets also based on different viewpoints and application, can carry out various modification and change under spirit of the present invention.
For the ease of understanding, abbreviation below and chemical name contrast as follows:
1,1,1,3,3 – pentachloropropane are called for short HCC-240
1,1,1,3,3-pentafluoropropane is called for short HFC-245fa,
1-chloro-3,3,3 ,-trifluoropropene is called for short HCFC-1233zd,
1,3,3,3-tetrafluoeopropene is called for short HCFC-1234ze,
Below in conjunction with accompanying drawing, the present invention is further detailed explanation.
A kind of preparation facilities of 1,1,1,3,3-pentafluoropropane, comprise the vaporizer 1 connected successively, liquid phase fluorination reactor 2, superheater 3, gas phase fluorination device 4, compression pump 5, first rectifying tower 6, Second distillation column 7, the 3rd rectifying tower 8, and connection line 9-19, wherein:
Vaporizer 1 is provided with raw material input terminus, raw material enters vaporizer 1 by pipeline 9, the output terminal of vaporizer 1 is connected with the input terminus of liquid phase fluorination reactor 2 by pipeline 10, the output terminal of liquid phase fluorination reactor 2 is by pipeline 11, be connected via the input terminus of superheater 3 with gas phase fluorination device 4, the output terminal of gas phase fluorination device 4 is connected with the first rectifying tower 6 input terminus via via pipeline 12 compression pump 5, the tower reactor component output terminal of the first rectifying tower 6 is connected with the input terminus of Second distillation column 7 by pipeline 13, the overhead fraction output terminal of the first rectifying tower 6 connects absorption by Hydrochloric Acid system, the overhead fraction output terminal of Second distillation column 7 is connected via the input terminus of pipeline 15 with gas phase fluorination device 4, the tower reactor component output terminal of Second distillation column 7 is connected with the 3rd rectifying tower 8 input terminus by pipeline 14, the tower reactor component output terminal of the 3rd rectifying tower 8 is connected with the raw material input terminus of vaporizer 1 by pipeline 17, the overhead fraction output terminal of the 3rd rectifying tower 8 obtains target product 1, 1, 1, 3, 3-pentafluoropropane.
Preferably, the overhead fraction (1,1 of described 3rd rectifying tower, 1,3,3-pentafluoropropane) output terminal is connected with water wash column 21 by pipeline 16, water wash column 21 is connected by pipeline 18 soda-wash tower 22, carry out liquid phase washing, alkali cleaning process, soda-wash tower 22 is connected via the input terminus of pipeline 19 with product rectifying tower 23, is obtained the target product 1 of purifying by product rectifying tower 23 overhead fraction output terminal, 1,1,3,3-pentafluoropropane.
The flow process of the preparation method of one 1,1,1,3,3-pentafluoropropane of the present invention as shown in Figure 1.
Fresh HF and 1, 1, 1, 3, 3 – pentachloropropane and HCC-240 are after pipeline 9 is heat vaporized by vaporizer 1, enter liquid phase fluorination reactor 2 by pipeline 10 to react, such as: reactor size can be 5L, be obtained by reacting containing 1-chloro-1, 3, 3, the mix products of 3 – tetrafluoeopropenes, gas phase fluorination device 4 is entered after superheater 3, react under the mixed catalyst effect of antimony pentachloride and tin tetrachloride, reacted material is through pipeline 12, and pump into the first rectifying tower 6 by compression pump 5 pressurization, the tower top of the first rectifying tower 6 obtains HCL, the tower reactor component of the first rectifying tower 6 enters Second distillation column 7 through pipeline 13, after Second distillation column 7 is separated, the unreacted 1-of tower top chloro-1 of Second distillation column 7, 3, 3, 3 – tetrafluoeopropenes enter gas phase fluorination device 4 again through pipeline 15, continue to participate in reaction.
The tower reactor component of Second distillation column 7 enters the 3rd knockout tower 8 through pipeline 14 and carries out rectifying, 3rd knockout tower 8 overhead fraction is thick 1,1,1,3,3-pentafluoropropane, enters follow-up water wash column 21, soda-wash tower 22 carries out liquid phase washing, alkali cleaning depickling process, is obtained the target product 1 of purifying by product rectifying tower 23 tops fraction output terminal, 1,1,3,3-pentafluoropropane.3rd knockout tower 8 tower reactor obtain HF return liquid phase fluorination reactor 2 continue again participate in reaction.
In the liquid phase reaction of liquid phase fluorination reactor 2, if antimony pentachloride single mass system catalyzer, catalyst effect is strong, more 1 may be produced, 1,1,3,3-pentafluoropropane, the reaction later stage has a lot of 1-chloro-1,3,3,3 – tetrafluoropropane (R224fa), it is more difficult to fluoridize at same reactor, if adopt the mixed catalyst of antimony pentachloride and tin tetrachloride, 1-chloro-3,3,3-trifluoro propene select selectivity very high, catalyst life is long.
In the gas-phase reaction of gas phase fluorination device 4, the catalyzer preferential oxidation zinc+aluminium oxide catalyst of fluoridation.This catalyzer can adopt coprecipitation method well known in the art to prepare, such as: in proportion zinc salt and auxiliary salt are mixed with certain density solution, add precipitation agent reaction, slurries after filtration, washing, oven dry, roasting, then compression molding, loading reactor, passes into anhydrous HF and nitrogen carries out fluoridizing obtained catalyzer.
Below by embodiment, the preparation method to one 1,1,1,3,3-pentafluoropropane of the present invention is described in further detail, but the present invention is not limited to described embodiment.
Embodiment 1 ~ 8 is the resultant of differential responses condition, is specifically shown in two forms below, does to illustrate below for the reaction corresponding to two forms:
Add in liquid phase fluorination reactor 2 by the antimony pentachloride of certain mass ratio and the mixture catalyzer of tin tetrachloride, control temperature of reaction 40 ~ 100 DEG C, the mol ratio of pressure 0.5 ~ 1.2MPa, HF and HCC-240 is 4 ~ 20:1.
Reaction mixture in liquid phase fluorination reactor 2 is passed in the gas phase fluorination device 4 that 10ml50 ~ 80% zinc oxide+20 ~ 50% aluminium oxide catalyst is housed, reactor passes into HF and activates 50 hours, temperature of reaction 250 ~ 380 DEG C, HF and HCFC-1233zd i.e. 1-chloro-3,3,3 ,-trifluoropropene and 1,3, the mol ratio of both 3,3 – tetrafluoeopropenes mixture is 1 ~ 10:1, and air speed is 500 ~ 1000h
-1.Connect a bypass in the outlet of liquid phase fluorination reactor and gas phase fluorination reactor, carry out sampling analysis, before analyzing, product is washed, alkali cleaning, with the composition of chromatographic organic product, the results are shown in Table 1, table 2.
Described in above form and above step, the preparation method of one 1,1,1,3,3-pentafluoropropane of the present invention is preferably as follows preferably protection domain:
1, preferred, the described hydrogen fluoride and 1 described in described preparation method's step (a), the mol ratio of 1,1,3,3 – pentachloropropane is 5 ~ 8:1, and temperature of reaction is 45 ~ 60 DEG C, and reaction pressure is 0.7 ~ 1.0MPa.
2, preferred, the catalyzer described in described preparation method's step (a) is the mixture of antimony pentachloride and tin tetrachloride, and catalyst quality ratio is 2 ~ 4:1.
3, preferred, gas phase fluorination device temperature of reaction described in described preparation method's step (c) is 280 ~ 310 DEG C, HF and HCFC-1233zd i.e. 1-chloro-3,3,3-trifluoro propene and 1,3,3, the mol ratio of both 3 – tetrafluoeopropenes mixture is 1 ~ 3:1, and air speed is 600 ~ 800h-1.
4, preferred, by mass percentage, it consists of the catalyzer described in described preparation method's step (c): zinc oxide 50 ~ 80%, and aluminum oxide is 20 ~ 50%.
5, preferred, described in described preparation method's step (f), temperature of reaction is 10 ~ 30 DEG C, and reaction pressure is 0.3 ~ 1.0MPa.
Although this patent is explained with reference to preferred embodiment and accompanying drawing, but above-mentioned explanation should be considered as illustrative and non-limiting, and the change that person's spirit according to the present invention of being familiar with technique is made and amendment, all should belong to the protection domain of this patent.
Claims (8)
1. the preparation facilities of a pentafluoropropane, is characterized in that:
Comprise the vaporizer connected successively, liquid phase fluorination reactor, superheater, gas phase fluorination device, compression pump, the first rectifying tower, Second distillation column, the 3rd rectifying tower, and connection line, wherein:
Vaporizer is provided with raw material input terminus, the output terminal of vaporizer is connected with the input terminus of liquid phase fluorination reactor by pipeline, the output terminal of liquid phase fluorination reactor is connected via the input terminus of superheater with gas phase fluorination device, the output terminal of gas phase fluorination device is connected with the first rectifying tower input terminus via compression pump, the tower reactor component output terminal of the first rectifying tower is connected with the input terminus of Second distillation column, the overhead fraction output terminal of the first rectifying tower connects absorption by Hydrochloric Acid system, the overhead fraction output terminal of Second distillation column is connected via the input terminus of pipeline with gas phase fluorination device, the tower reactor component output terminal of Second distillation column is connected with the 3rd rectifying tower input terminus, the tower reactor component output terminal of the 3rd rectifying tower is connected with the raw material input terminus of vaporizer, the overhead fraction output terminal of the 3rd rectifying tower obtains target product 1, 1, 1, 3, 3-pentafluoropropane.
2. the preparation facilities of one 1,1,1,3, the 3-pentafluoropropane according to claim, is characterized in that:
The overhead fraction (1 of described 3rd rectifying tower, 1,1,3,3-pentafluoropropane) output terminal is connected with water wash column and soda-wash tower successively by pipeline, carry out liquid phase washing, alkali cleaning process, soda-wash tower is connected via the input terminus of pipeline with product rectifying tower, is obtained the target product 1 of purifying by product rectifying tower tops output terminal, 1,1,3,3-pentafluoropropane.
3. the preparation method of a pentafluoropropane, is characterized in that:
Comprise the following steps:
(a) by fresh hydrogen fluoride and 1,1,1,3,3 – pentachloropropane enter into liquid phase fluorination reactor via vaporizer, under the effect of catalyzer, liquid phase reaction occur, described hydrogen fluoride and 1,1, the mol ratio of 1,3,3 – pentachloropropane is 4 ~ 30:1, and temperature of reaction is 40 ~ 100 DEG C, reaction pressure is 0.5 ~ 1.2MPa, obtains containing a large amount of 1-chloro-3,3,3 ,-trifluoropropene, a small amount of 1,3,3,3-tetrafluoeopropene, a small amount of 1,1, the mix products of 1,3,3-pentafluoropropane, HF and HCL;
B mix products that liquid phase fluorination reactor exports by (), after superheater heating and gasifying, enters into gas phase fluorination device,
And pumping into the first rectifying tower by compression pump pressurization, the first rectifying tower tops obtains HCL, and HCL being connected absorption by Hydrochloric Acid system can obtain hydrochloric acid;
(c) first the tower reactor component of rectifying tower carry out rectifying separation by Second distillation column, Second distillation column overhead fraction is 1,3,3,3-tetrafluoeopropene, 1,3,3,3-tetrafluoeopropene returns prime gas phase fluorination device, continues to participate in gas-phase reaction under the effect of catalyzer;
Described gas phase fluorination device due to the liquid reactive HF of the first step excessive larger, so second step gas-phase reaction no longer adds fresh HF, temperature of reaction is 250 ~ 380 DEG C, and air speed is 500 ~ 1000h-1, HF and 1-chloro-3,3,3-trifluoro propene, 1,3,3, the mol ratio of 3 – tetrafluoeopropenes is 1 ~ 10:1
Owing to there being Second distillation column overhead fraction to be the gas-phase reaction that 1,3,3,3-tetrafluoeopropene participates in prime, in gas phase fluorination device, therefore obtain the mix products containing 1,1,1,3,3-pentafluoropropane, 1,3,3,3-tetrafluoeopropene, HF and HCL;
D () will pass into the first rectifying tower containing the mix products of 1,1,1,3,3-pentafluoropropane, 1,3,3,3-tetrafluoeopropene, HF and HCL and carry out rectifying separation, overhead fraction is HCl, and HCl otherwise processed can be obtained hydrochloric acid;
E the tower reactor component of the first rectifying tower is led to Second distillation column and is carried out rectifying separation by (), overhead fraction is 1,3,3,3-tetrafluoeopropene, returns gas phase fluorination device and continues to participate in reaction;
F logical for the tower reactor component of Second distillation column the 3rd rectifying tower is carried out rectifying separation by (), overhead fraction is thick 1,1,1,3,3-pentafluoropropane, and tower reactor component obtains HF and returns liquid phase fluorination reactor and continue to participate in reaction again;
G () is by thick 1,1,1,3,3-pentafluoropropane enters follow-up water wash column, soda-wash tower and carries out liquid phase washing, alkali cleaning process respectively, by 1 after depickling, 1,1,3, the mix products of 3-pentafluoropropane passes into product rectifying tower again and carries out rectifying, the target product 1,1,1 of purifying is obtained after distillation operation, 3,3-pentafluoropropane.
4. according to claim 31,1,1, the preparation method of 3,3 – pentafluoropropanes, is characterized in that:
Described hydrogen fluoride HF and 1 described in described step (a), the mol ratio of 1,1,3,3 – pentachloropropane is 5 ~ 8:1, and temperature of reaction is 45 ~ 60 DEG C, and reaction pressure is 0.7 ~ 1.0MPa.
5. according to claim 31,1,1, the preparation method of 3,3 – pentafluoropropanes, is characterized in that:
Catalyzer described in described step (a) is the mixture of antimony pentachloride and tin tetrachloride, and catalyst quality ratio is 2 ~ 4:1.
6. according to claim 31,1,1, the preparation method of 3,3 – pentafluoropropanes, is characterized in that:
Gas phase fluorination device temperature of reaction described in described step (c) is 280 ~ 310 DEG C, HF and 1-chloro-3,3,3 ,-trifluoropropene, 1, and the mol ratio of 3,3,3 – tetrafluoeopropenes is 1 ~ 3:1, and air speed is 600 ~ 800h-1.
7. according to claim 31,1,1, the preparation method of 3,3 – pentafluoropropanes, is characterized in that:
By mass percentage, it consists of catalyzer described in described step (c): zinc oxide 50 ~ 80%, and aluminum oxide is 20 ~ 50%.
8. according to claim 31,1,1, the preparation method of 3,3 – pentafluoropropanes, is characterized in that:
Described in described step (f), temperature of reaction is 10 ~ 30 DEG C, and reaction pressure is 0.3 ~ 1.0MPa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652159A (en) * | 2017-10-18 | 2018-02-02 | 山东华安新材料有限公司 | A kind of device and method for preparing 2,3,3,3 tetrafluoropropenes |
| CN110066295A (en) * | 2019-04-28 | 2019-07-30 | 衢州康鹏化学有限公司 | A kind of preparation method of five fluorine ethoxy basic ring, three phosphonitrile |
| CN110746265A (en) * | 2019-10-09 | 2020-02-04 | 浙江大学 | Method for continuously producing fluorinated alkane in pipeline manner by liquid phase method |
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| CN113499741A (en) * | 2021-08-10 | 2021-10-15 | 聊城氟尔新材料科技有限公司 | Difluoromethane reaction gas separation device and method and application thereof |
| CN113501743A (en) * | 2021-08-19 | 2021-10-15 | 山东华安新材料有限公司 | Preparation method of 1,1,1,3, 3-pentafluoropropane |
| CN115043701A (en) * | 2022-08-12 | 2022-09-13 | 山东澳帆新材料有限公司 | Preparation method of cis-1-chloro-3, 3, 3-trifluoropropene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078172A (en) * | 1992-02-26 | 1993-11-10 | 帝国化学工业公司 | fluorination catalyst and fluorination process |
| JPH10101594A (en) * | 1996-09-25 | 1998-04-21 | Asahi Glass Co Ltd | Production of 1,1,1,3,3-pentafluoropropane |
| CN1266045A (en) * | 2000-01-21 | 2000-09-13 | 浙江省化工研究院 | Process for preparation of 1,1,1,3,3-pentafluoropropane |
| CN1849282A (en) * | 2003-08-08 | 2006-10-18 | 霍尼韦尔国际公司 | Low temperature production of 1-Chloro-3,3,3-trifluoropropene (HCFC-1233zd) |
-
2015
- 2015-11-23 CN CN201510807627.2A patent/CN105399598A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078172A (en) * | 1992-02-26 | 1993-11-10 | 帝国化学工业公司 | fluorination catalyst and fluorination process |
| JPH10101594A (en) * | 1996-09-25 | 1998-04-21 | Asahi Glass Co Ltd | Production of 1,1,1,3,3-pentafluoropropane |
| CN1266045A (en) * | 2000-01-21 | 2000-09-13 | 浙江省化工研究院 | Process for preparation of 1,1,1,3,3-pentafluoropropane |
| CN1849282A (en) * | 2003-08-08 | 2006-10-18 | 霍尼韦尔国际公司 | Low temperature production of 1-Chloro-3,3,3-trifluoropropene (HCFC-1233zd) |
Non-Patent Citations (2)
| Title |
|---|
| 徐桂花等: "1,1,1,3,3-五氟丙烷的合成研究", 《有机氟化工》 * |
| 赵卫娟等: ""制备1,1,1,3,3-五氟丙烷的研究进展"", 《浙江化工》 * |
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|---|---|---|---|---|
| CN107652159A (en) * | 2017-10-18 | 2018-02-02 | 山东华安新材料有限公司 | A kind of device and method for preparing 2,3,3,3 tetrafluoropropenes |
| CN110066295A (en) * | 2019-04-28 | 2019-07-30 | 衢州康鹏化学有限公司 | A kind of preparation method of five fluorine ethoxy basic ring, three phosphonitrile |
| CN110066295B (en) * | 2019-04-28 | 2021-10-26 | 衢州康鹏化学有限公司 | Preparation method of pentafluoroethoxy cyclotriphosphazene |
| CN110746265A (en) * | 2019-10-09 | 2020-02-04 | 浙江大学 | Method for continuously producing fluorinated alkane in pipeline manner by liquid phase method |
| CN110746265B (en) * | 2019-10-09 | 2021-02-26 | 浙江大学 | Method for continuously producing fluorinated alkane in pipeline manner by liquid phase method |
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| CN113501743A (en) * | 2021-08-19 | 2021-10-15 | 山东华安新材料有限公司 | Preparation method of 1,1,1,3, 3-pentafluoropropane |
| CN113501743B (en) * | 2021-08-19 | 2024-03-29 | 山东华安新材料有限公司 | Preparation method of 1, 3-pentafluoropropane |
| CN115043701A (en) * | 2022-08-12 | 2022-09-13 | 山东澳帆新材料有限公司 | Preparation method of cis-1-chloro-3, 3, 3-trifluoropropene |
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