KR20190083347A - How to dry HCFO-1233ZD - Google Patents

Abstract

The present invention relates to a process for the preparation of 1-chloro-3,3,3-trifluoropropene (HCFO) which enables improved recovery of 1-chloro-3,3,3-trifluoropropene during or after the manufacturing process -1233zd) azeotrope-like composition of an azeotropic or azeotrope-like composition. Such a recovery or separation process provides a highly pure composition of 1-chloro-3,3,3-trifluoropropene while providing a high yield of 1-chloro-3,3,3-trifluoropropene With the various combinations of separation techniques (e.g., distillation and decanting), the unique properties of an azeotropic or azeotrope-like composition can be exploited. Such highly pure compositions of 1-chloro-3,3,3-trifluoropropene can find useful applications in polymer technology as monomers or comonomers.

Description

How to dry HCFO-1233ZD

Cross-reference to related application

This application is a continuation-in-part (CIP) application to US patent application Ser. No. 15 / 046,591 filed on February 18, 2016, which is a continuation-in-part application filed on March 19, 2015, Claim domestic priority from 62 / 135,282; This application is also a continuation-in-part of U.S. Patent Application No. 14 / 929,657, filed November 2, 2015, which is a continuation of U.S. Application No. 13 / 298,452, filed November 17, 2011, 9,175,200, filed on October 26, 2009, which is a continuation-in-part of U.S. Patent Application No. 12 / 605,609, now U.S. Patent No. 8,163,196, entitled Priority 61 / 109,007 of U.S. Provisional Patent Application No. 61 / U.S. Patent No. 7,935,268, which is a continuation-in-part of U.S. Application No. 12 / 259,694, filed October 28, 2008, the disclosure of which is incorporated herein by reference in its entirety.

Technical field

In the commercial production of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), the crude product from the process requires an aqueous wash to remove HF, HCl, and other acid components . The present invention relates to an azeotrope-like composition of HFO-1233zd and water, and to the processing of such compositions.

Commercial applications for HCFO-1233zd (1233zd) include foam blowing agents and solvent applications. In such applications, rigorous control of moisture content is typically required to meet customer requirements. Occasionally, due to process problems, the moisture level in 1233zd may exceed the specification limit.

A variety of 1233zd manufacturing processes have been disclosed. One example is shown in U.S. Patent No. 8,921,621, which discloses a process for the preparation of HCFO-1233zd comprising the steps of: (a) reacting HCC-240 and HF in a high pressure liquid phase reactor; and "overhead crude HCFO- Step (h) of feeding the 1233zd stream to a caustic scrubber to remove any remaining acidity and drying the scrubbed stream to a desiccant.

In the process of U.S. Patent No. 8,921,621, one objective is to provide sufficient desiccant to remove water in the process stream, and to be prepared for the overhead crude HCFO-1233zd vapor stream to be completely saturated with water. In such a case, it is estimated that for every 1,000 pounds of HCFO-1233zd vapor produced, it may be necessary to remove more than 4 pounds of water. Thus, when using a typical molecular sieve desiccant capable of adsorbing up to about 15 weight percent moisture, it will be necessary to use less than about 27 pounds of molecular sieve for every 1,000 pounds of HCFO-1233zd produced in the process. Embodiments of the present invention considerably reduce the desiccant consumption required for such a process and have the additional advantage of utilizing the azeotropic or azeotropic mixture-like composition of 1-chloro-3,3,3-trifluoropropene and water .

The present invention relates to a process for the preparation of 1-chloro-3,3,3-trifluoropropene (HCFO) which enables improved recovery of 1-chloro-3,3,3-trifluoropropene during or after the manufacturing process ≪ / RTI > -1233zd) in an azeotropic or azeotropic mixture-like composition. Such a recovery or separation process provides a highly pure composition of 1-chloro-3,3,3-trifluoropropene while providing a high yield of 1-chloro-3,3,3-trifluoropropene With the various combinations of separation techniques (e.g., distillation and decanting), the unique properties of an azeotropic or azeotrope-like composition can be exploited. Such highly pure compositions of 1-chloro-3,3,3-trifluoropropene can find useful applications in polymer technology as monomers or comonomers.

The method for recovering 1-chloro-3,3,3-trifluoropropene includes, or consists essentially of, 1-chloro-3,3,3-trifluoropropene and water, Or an azeotrope-like composition, transferring the formed azeotropic or azeotropic mixture-like composition into a separator, and recovering the organic layer comprising 1-chloro-3,3,3-trifluoropropene Step < / RTI > In various embodiments, the composition comprises about 70% by weight of 1-chloro-3,3,3-trifluoropropene, 86% by weight of 1-chloro-3,3,3-trifluoropropene, 90 % By weight of 1-chloro-3,3,3-trifluoropropene, 98.5% by weight of 1-chloro-3,3,3-trifluoropropene, 99% by weight of 1- -3,3,3-trifluoropropene, 99.95% by weight of 1-chloro-3,3,3-trifluoropropene, or any of the values defined above between any two of the foregoing values (For example, 70 wt% of 1-chloro-3,3,3-trifluoropropene to 99.95 wt% of 1-chloro-3,3,3-trifluoropropene) , And 0.05 weight percent water, 2.5 weight percent water, 10 weight percent water, or 14 weight percent water, 20 weight percent water, 30 weight percent water, Any range defined between any two values (e.g., For example, from 0.05% by weight to 30% by weight of water). In some embodiments, the composition may have a boiling point of about 17.4 DEG C +/- 1 DEG C at a pressure of about 14.7 psia.

A variety of methods may also be used to produce additional steps such as, for example, decanting the water layer, returning the organic layer to the distillation column, and / or distillation from 1-chloro-3,3,3-trifluoropropene Separating the water in the organic layer.

Providing a mixture of 1-chloro-3,3,3-trifluoropropene and water, the mixture comprising an organic layer predominantly comprising 1-chloro-3,3,3-trifluoropropene and an aqueous layer Decanting a portion of the aqueous layer from the mixture, transferring the organic layer to a distillation column, forming an azeotropic mixture of 1-chloro-3,3,3-trifluoropropene and water in the distillation column , Removing the azeotrope as an overhead stream from the distillation column, and removing substantially pure 1-chloro-3,3,3-trifluoropropene from the bottom of the distillation column Lt; / RTI >

In various embodiments, some methods, upon removal from the distillation column, can produce substantially pure 1-chloro-3,3,3-trifluoropropene, which results in less than about 100 ppm water , Or may contain less than about 50 ppm water by weight, or may contain less than about 40 ppm water by weight. In some embodiments, the substantially pure 1-chloro-3,3,3-trifluoropropene can be removed from the distillation column at less than about 10 ppm, 11 ppm, 15 ppm, or 20 ppm, 25 ppm , 30 ppm, 40 ppm, 50 ppm, 100 ppm, or any range (e.g., 10 ppm to 40 ppm) defined between any two values of the foregoing values.

The azeotropic mixture contains about 70% by weight of 1-chloro-3,3,3-trifluoropropene, 86% by weight, based on the total weight of water and 1-chloro-3,3,3-trifluoropropene, Chloro-3,3,3-trifluoropropene, 90% by weight of 1-chloro-3,3,3-trifluoropropene, 98.5% by weight of 1-chloro-3 , 3,3-trifluoropropene, 99% by weight of 1-chloro-3,3,3-trifluoropropene, 99.95% by weight of 1-chloro-3,3,3-trifluoropropene (E.g., 70 wt% of 1-chloro-3,3,3-trifluoropropene to 99.95 wt% of 1, defined between any two of the above values -Chloro-3,3,3-trifluoropropene), and an amount of 0.05 weight% water, 2.5 weight% water, 10 weight% water, or 14 weight% water, 20 weight % Water, as much as 30 wt% water, or any of the above values Two values a certain range that is defined between (e.g., 0.05% by weight of water to 30% by weight of water) can have a volume of less than. The azeotropic mixture may have a boiling point of about 17.4 DEG C +/- 1 DEG C at a pressure of about 14.7 psia.

An azeotropic or azeotrope-like composition with 1-chloro-3,3,3-trifluoropropene and water is also disclosed. In some embodiments, the composition may consist solely of water and 1-chloro-3,3,3-trifluoropropene.

The composition comprises about 70% by weight of 1-chloro-3,3,3-trifluoropropene, 86% by weight of 1-chloro-3,3,3-trifluoropropene, 90% Chloro-3,3,3-trifluoropropene, 98.5% by weight of 1-chloro-3,3,3-trifluoropropene, 99% by weight of 1-chloro-3,3, 3-trifluoropropene, 99.95% by weight of 1-chloro-3,3,3-trifluoropropene, or any range defined between any two of the above values (e.g., Chloro-3,3,3-trifluoropropene to 99.95% by weight of 1-chloro-3,3,3-trifluoropropene) and 0.05% by weight of Water, 2.5 weight percent water, as little as 10 weight percent water, or as much as 14 weight percent water, 20 weight percent water, 30 weight percent water, or any two of the above values Any range defined (e.g., 0.05 wt% water To 30% by weight of water). In various embodiments, the composition may have a boiling point of about 17.4 DEG C +/- 1 DEG C at a pressure of about 14.7 psia.

BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other features and objects of the present invention and the manner of accomplishing them will become more apparent by reference to the following description of exemplary embodiments of the invention taken in conjunction with the accompanying drawings, will be.
Figure 1 is a process diagram for the recovery of 1-chloro-3,3,3-trifluoropropene.
Figure 2 is a flow diagram of an exemplary method for recovering 1-chloro-3,3,3-trifluoropropene.
Although the drawings illustrate embodiments of the invention, the drawings are not necessarily drawn to scale, and certain features may be exaggerated to better illustrate and describe the invention. The examples set forth herein illustrate exemplary embodiments of the invention in various forms, and such examples should not be construed as limiting the scope of the invention in any way.

As described briefly above, the present invention relates to a separation technique using an azeotropic or azeotrope-like composition of 1-chloro-3,3,3-trifluoropropene (HCFC-1233zd) and water, Chloro-3,3,3-trifluoropropene (HCFC-1233zd) from an azeotropic or azeotrope-like composition comprising 3,3-trifluoropropene and water .

1-Chloro-3,3,3-trifluoropropene forms azeotropic and azeotrope-like compositions or mixtures with water, and more particularly, to heterogeneous azeotropic and azeotrope-like compositions or mixtures with water .

1-Chloro-3,3,3-trifluoropropene has a boiling point of about 19 DEG C and a vapor pressure of about 1516 hPa at about 30 DEG C, and has the following structure:

As used herein, the modifier "about" used in connection with an amount includes the stated value and has the meaning indicated by the context (e.g., including at least the degree of error associated with a particular amount of measurement do). When used in the context of a range, the modifier "about" should also be regarded as initiating a range defined by the absolute value of the two endpoints. For example, a range of "about 2 to about 4" also discloses a range of "2 to 4 ".

As described above, U.S. Patent No. 8,921,621 discloses a process for the preparation of commercial scale 1-chloro-3,3,3-tri (tert-butoxycarbonyl) propane by reaction of 1,1,1,3,3-pentachloropropane (HCC- A method for producing fluoropropene (HCFC-1233zd) is described.

In one embodiment of the process of U.S. Patent No. 8,921,621, HCC-240fa and HF are fed to a liquid phase reactor operating at high pressure. The resulting product stream of 1233zd, HCl, HF, and other byproducts is partially condensed and HF is recovered by phase separation. The recovered HF phase is recycled to the reactor. HCl is scrubbed from the vapor stream and recovered as an aqueous solution. The remaining organic components, including the desired HCFC-1233zd, are scrubbed, dried and distilled to meet commercial product specifications.

Figure 1 is a process diagram for the recovery of 1-chloro-3,3,3-trifluoropropene from water. In one embodiment, the wet and acid-free 1233zd (HCFO-1233zd) crude vapors from the corrosive scrubber outlet are condensed in the condenser. The condensed wet 1233zd will then flow into the distillation pump tank or the decantering tank 12 (illustrated as the flow stream 11 in FIG. 1) where the water will settle to the top layer (first aqueous layer 14) And 1233zd will settle as a bottom layer (first organic layer 16). At a production rate of 1000 to 1500 lb / hr of 1233 zd including free scrubber liquid entrainment, about 2 gal / hr of free water will be accumulated in the distillation pump tank (capacity of 19,000 gallons) It is expected. Thus, it is assumed that the tank 12 is capable of easily handling at least about 4,000 gallons of free water, at least temporarily.

During commercial processing of 1233zd, it is not necessary to pay attention to such water for up to three months at a crude 1233zd production rate of 1,500 lb / hr, and when water is removed, water can be removed as the first strip stream 18 It is expected. Removal of water as the first strip stream 18 can be accomplished by decanting, selective pumping, or other liquid-liquid separation processes. Monitoring programs have been developed to track such water volume and its acidity content, for example, to prevent any corrosion or overspill incident. The water is expected to contain about 2,000 ppm crude 1233 zd, or about 0.03 lb / hr organic matter. As used herein, the term "ppm" or "fraction of a million" will be understood to be the mass fraction unless otherwise explicitly stated. Such water can be recycled to the caustic scrubber for organic material recovery and disposal.

The first organic layer 16 may then be further processed, such as distilling the first organic layer. Thus, the first organic layer 16 may flow into the distillation column 20 through the distillation inlet 22, wherein the 1-chloro-3,3,3-trifluoropropene and water are separated from the azeotropic mixture Lt; RTI ID = 0.0 > of < / RTI >

As used herein, distillation column 20 is understood to include a fractionation column that uses distillation to separate the mixture into component portions or fractions based on any conventional fractionation column or difference in volatility . Thus, the first organic layer 16 can be distilled in the distillation column to yield the bottoms 24 of the intrinsically pure 1-chloro-3,3,3-trifluoropropene, while the overhead 26 May be condensed and sent to the first separator 12 and / or the second phase separator 30. In various embodiments, the upper vapor fraction or overhead 26 may be an azeotropic or azeotrope-like composition of 1-chloro-3,3,3-trifluoropropene and water.

In some embodiments, other organics and / or impurities (e.g., 1,3,3,3-tetrafluoropropene (HFO-1234ze)) may also be present and / or water in the overhead of the distillation column It should be noted that an azeotropic mixture can also be formed. In some embodiments, other organics and / or impurities in the composition that form an azeotrope mixture with water by itself are not only water that enters the primary azeotropic mixture of 1-chloro-3,3,3-trifluoropropene and water, Can be used to further advantageously withdraw additional water from the contents of the distillation column 21, and the 1233zd collected product is further dried and purified. Additionally, impurities of relatively low boiling points can nevertheless be volatilized and removed in the overhead stream, even if they can not form an azeotropic mixture with water by itself. Thus, in the present method, both the water-containing azeotrope of the impurities and / or the non-azeotrope composition of the impurities can be withdrawn from the 1233zd in the distillation column 20 to improve the purity of the recovered 1233zd.

Moreover, in some embodiments, an excess of 1-chloro-3,3,3-trifluoropropene may be present in the azeotropic mixture composition in the overhead due to, for example, tray inefficiency or distillation column inefficiency.

The thermodynamic state of a fluid is defined by its pressure, temperature, liquid composition and vapor composition. For true azeotropic compositions, the liquid composition and the vapor phase are essentially the same at a given temperature and pressure range. From a practical standpoint, this means that the components can not be separated during the phase change. As disclosed herein, an azeotrope is a liquid mixture that exhibits a maximum or minimum boiling point relative to the boiling point of the surrounding mixture compositions. Also, as used herein, the term "azeotropic mixture-like" refers to compositions that behave in a strictly azootropic composition and / or generally behave like an azeotrope.

An azeotropic mixture or an azeotropic mixture-like composition is a mixture of two or more different components boiling at a substantially constant temperature when in liquid form under a given pressure, and this temperature may be higher or lower than the boiling temperature of the individual components, Lt; RTI ID = 0.0 > vapor composition < / RTI >

As used herein, an azeotropic composition may be defined as comprising an azeotropic mixture-like composition wherein the azeotropic mixture-like composition has a constant boiling behavior or behaves like an azeotropic mixture, Or have a tendency not to be discerned upon evaporation. Thus, the composition of the vapor formed during boiling or evaporation is the same or substantially the same as the original liquid composition. Thus, during boiling or evaporation, the liquid composition will vary only to a minimum or negligible extent, even if varied. This contrasts with non-azeotropic mixture-like compositions in which the liquid composition varies considerably during boiling or evaporation.

An essential feature of the azeotropic mixture or the azeotrope-like composition is therefore that at a given pressure, the boiling point of the liquid composition is fixed and the composition of the vapor on the boiling composition is essentially that of the boiling liquid composition, Fractional distillation of the components of the reaction mixture does not occur. If both the azeotropic mixture or the azeotropic mixture-like liquid composition are boiled at different pressures, the weight percentage and boiling point of each component of the azeotropic composition may vary. Thus, the azeotropic mixture or the azeotropic mixture-like composition may be used in the context of the relationship existing between its components or in terms of the composition range of the components, or of the exact composition of each component of the composition characterized by a fixed boiling point at a specified pressure Can be defined in terms of weight percentages.

In various embodiments of the present invention, there is provided a composition comprising an effective amount of 1-chloro-3,3,3-trifluoropropene and water to form an azeotropic or azeotrope-like composition. As used herein, the term "effective amount" is the amount of each component that, when combined with other ingredients, forms an azeotrope or an azeotrope-like mixture.

The composition preferably comprises or consists essentially of a combination of 1-chloro-3,3,3-trifluoropropene and water or a mixture of 1-chloro-3,3,3-trifluoropropene and Water. ≪ / RTI > As used herein, the term "consisting essentially of" refers to an azeotropic mixture-like composition or mixture of components, wherein the composition contains the indicated components in an azeotrope-like ratio, Means that it may contain additional components if it does not form a similar system. For example, an azeotrope-like mixture consisting essentially of two compounds will optionally form a bidentate azeotrope that can include one or more additional components, provided that the additional component is a non-azeotropic mixture And does not form an azeotropic mixture with either or both of the compounds (e.g., does not form a 3-membered azeotropic mixture).

As used herein, the terms " heteroazeotrope "and" heterogeneous azeotropic mixture "refer to an azeotrope-like composition comprising a vapor phase coexisting with two liquid phases.

The present invention also includes isolating the azeotrope from impurities after producing an azeotropic or azeotrope-like composition of 1-chloro-3,3,3-trifluoropropene and water. The present invention also includes steps for separating and purifying 1-chloro-3,3,3-trifluoropropene from an azeotrope, as discussed in more detail below.

1-Chloro-3,3,3-trifluoropropene can be prepared using one or more methods known in the art, wherein 1-chloro-3,3,3-trifluoropropene is a Or more of the impurities contained in the reaction mixture.

After purification, the constituent part of the azeotropic mixture of 1-chloro-3,3,3-trifluoropropene and water was added to a purified form of 1-chloro-3,3,3-trifluo It may also be desirable to separate by rope. As used herein, "essentially water-free" or "water-free" means a composition of 1-chloro-3,3,3-trifluoropropene containing less than 1.0% Quot; For example, a composition of 1-chloro-3,3,3-trifluoropropene and water having less than 0.4% water by weight, or less than 0.1% water by weight will be considered water-free.

The separation method may include any method generally known in the art. In one embodiment, for example, the excess water can be removed from 1-chloro-3,3,3-trifluoropropene by liquid-liquid phase separation, but other alternatives include distillation or scrubbing. The remaining water is then purified by distillation and / or by using one or more drying media or drying agents such as molecular sieves, calcium sulfate, silica, alumina, and combinations thereof to yield 1-chloro-3,3,3-trifluoro- Propene. ≪ / RTI >

Exemplary methods, such as those illustrated in the flow chart of FIG. 2, can be used to recover 1-chloro-3,3,3-trifluoropropene. Recovery method 1 comprises the steps of forming an azeotropic or azeotrope-like composition essentially consisting of 1-chloro-3,3,3-trifluoropropene and water (step 2), contacting the formed azeotropic or azeotrope- (Step 3), and recovering an organic layer comprising 1-chloro-3,3,3-trifluoropropene (step 4).

For example, with continued reference to FIG. 1, the overhead can be divided into light organics purge 25 and overhead product stream 26 before condensation or after condensation, And 1-chloro-3,3,3-trifluoropropene, may be condensed and sent to the second phase separator 30. In some embodiments, the hard organic spill can be part of the second phase separator 30. The hard organic sparging can be used to remove hard organic matter present in the manufacturing system, and can include 1,3,3,3-tetrafluoropropene (HFO-1234ze) isomers, 1,1,1,3,3-pentafluoro (HFC-245fa), and in some cases, some of HFO-1233zd.

Here, when the overhead product stream 26 flows into the separator 30, the second aqueous phase 34 and the second organic layer 36 may be formed. The second aqueous phase 34 can be decanted and discarded (as illustrated by the second waste stream 38) or recycled (entirely or partially) to the first phase separator 12 via the recycle stream 32 . In various embodiments, exemplary process 10 can enable a greater yield of higher purity 1-chloro-3,3,3-trifluoropropene. In some embodiments, the second organic layer 36 may have other organic compounds besides 1-chloro-3,3,3-trifluoropropene. For example, in some embodiments, the reflux stream 40 from the second organic layer comprises a substantial amount of 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,1,3, (E.g., about 70 wt% HFO-1234ze, about 15 wt% HFC-245fa, and about 15 wt% 1-chloro- 3,3,3-trifluoropropene). ≪ / RTI >

Less than 50 ppm, less than 40 ppm, less than 25 ppm, less than 20 ppm, or less than 10 ppm of purified 1-chloro-3,3,3-trifluoropropene removed as distillation column (20) ppm or less water, or in another embodiment, between 10 ppm, 15 ppm, or 20 ppm water, 25 ppm, 40 ppm, or 50 ppm water, or any two of the above values Water < / RTI > The purified 1-chloro-3,3,3-trifluoropropene (1233zd) can be used as a final product such as a refrigerant, blowing agent, propellant, or diluent for gas sterilization, or it can be used as a monomer, , Or else can be further processed for the production of alternative HFO or similar compounds.

In addition, the purified azeotrope does not have an ozone depletion potential and contributes little to greenhouse global warming and meets the needs of the art for nonflammable mixtures. Such mixtures may be used in a wide variety of applications, including, but not limited to, refrigerants, foaming agents, propellants, and diluents for gas sterilization. The azeotropic mixture may be provided in combination with other useful additives or ingredients for such purposes.

Example

Example 1 - Processing of 1,000 lbs of crude HCFO-1233zd

1,000 lbs of wet and acid-free crude HCFO-1233zd vapor from the corrosive scrubber outlet are condensed in the condenser. The condensed wet HCFO-1233zd will then flow into the decanter. The water will settle as an upper layer, while HCFO-1233zd will settle as a lower layer.

The upper water layer is discharged, which is expected to contain about 4 lbs of water and contain about 2,000 ppm or 0.008 lb of dissolved HCFO-1233zd. Such water can be recycled or discarded as a corrosive scrubber for organic recovery.

The lower HCFO-1233zd organic layer is discharged, which is expected to contain about 1,000 lb of HCFO-1233zd and about 400 ppm or 0.4 lb of dissolved water. The resulting HCFO-1233zd stream is then dried with a drying agent such as molecular sieve 3A or 4A, activated alumina, silica gel, CaSO _4, and the like.

Using a commercial 3A molecular sieve desiccant capable of adsorbing up to 15% moisture, this improved process would have consumed only 2.7 pounds of molecular sieve per 1,000 pounds of processed HCFO-1233zd. The water content is about 10 ppm after this treatment.

In view of this low desiccant consumption rate, the drying equipment size can be made much smaller than that used in prior art processes. Moreover, considering that the molecular sieve can be regenerated, the final desiccant consumption can be minimized.

Example 2 - Processing of 1,000 lbs of crude HCFO-1233zd

1,000 lbs of liquid crude HCFO-1233zd containing 10 lbs of HF acid was mixed with about 300 lbs of water and / or a dilute caustic solution and then washed to remove the acid at the subcooled temperature while maintaining the mixture in a liquid phase do. The resulting wet and acid-free HCFO-1233zd will then flow into the decanter. The water or caustic solution will settle as an upper layer, while HCFO-1233zd will settle as a lower layer. The above can be carried out stepwise (e. G., By first rinsing with water, decanting, then washing with aqueous caustic and decanting, etc.).

The top water or caustic layer is discharged, which is expected to contain about 300 lbs of water and contain about 2,000 ppm or 0.6 lbs of dissolved HCFO-1233zd. Such water or caustic solutions may be subsequently heated or stripped to recover or discard valuable organics.

The lower HCFO-1233zd organic layer is discharged, which is expected to contain about 1,000 lb of HCFO-1233zd and about 400 ppm or 0.4 lb of dissolved water. The resulting HCFO-1233zd stream is then dried with a drying agent such as molecular sieve 3A or 4A, activated alumina, silica gel, CaSO _4, and the like.

Using a commercial 3A molecular sieve desiccant capable of adsorbing up to 15% moisture, this improved process would have consumed only 2.7 pounds of molecular sieve per 1,000 pounds of processed HCFO-1233zd. The water content is about 10 ppm after this treatment.

In view of this low desiccant consumption rate, the drying equipment size can be made much smaller than that used in prior art processes. Moreover, considering that the molecular sieve can be regenerated, the final desiccant consumption can be minimized.

Example 3 - Processing of tempered 1233zd in a pilot plant (Pilot Plant)

100 lbs of wet and acid-free crude HCFO-1233zd vapor from the corrosive scrubber outlet are condensed in the condenser. Condensed wet HCFO-1233zd will then flow into the decanter. The water will settle as an upper layer, while HCFO-1233zd will settle as a lower layer.

The upper water layer is drained and discarded.

The lower HCFO-1233zd organic layer is drained. The resulting HCFO-1233zd stream is then dried with a drying agent such as molecular sieve 3A or 4A, activated alumina, silica gel, CaSO _4, and the like.

Using a commercial 3A molecular sieve desiccant capable of adsorbing up to 15% moisture, this improved process would have consumed only 2.7 pounds of molecular sieve per 1,000 pounds of processed HCFO-1233zd. The water content is about 10 ppm after this treatment.

Alternatively, the organic layer may be further processed, for example, by forming an azeotropic or azeotrope-like composition to further separate water and 1-chloro-3,3,3-trifluoropropene.

For Example 4 and Example 5 below, 1,000 lb / hr of wet and acid-free 1-chloro-3,3,3-trifluoropropene vapor was condensed in the condenser. The condensed 1-chloro-3,3,3-trifluoropropene was combined with a wet azo ratio of 100 lb / hr from the distillation column with 1-chloro-3,3,3-trifluoropropene and water . The resulting mixture was then sent to a phase separator. Water was settled as the top layer while 1-chloro-3,3,3-trifluoropropene was settled as the bottom (organic) layer. The water layer contained 2,000 ppm crude 1-chloro-3,3,3-trifluoropropene or about 0.2 lb / hr organic matter. The water layer containing 1-chloro-3,3,3-trifluoropropene was then processed as follows according to Examples 4 and 5 below.

Example 4 - Recovery of 1-chloro-3,3,3-trifluoropropene from Water

A mixture of crude 1-chloro-3,3,3-trifluoropropene and 1,100 lb / hr of 0.4 lb / hr of water was fed into the distillation column where essentially all of the water was added to about 1 lb / hr of 1 -Chloro-3,3,3-trifluoropropene. ≪ / RTI > The overhead was found to be an azeotropic mixture of 1-chloro-3,3,3-trifluoropropene and water.

This overhead mixture was then sent to a phase separator or caustic scrubber to re-separate the water from the 1-chloro-3,3,3-trifluoropropene contained in the overhead.

The bottom stream yielded about 1,000 lb / hr crude 1-chloro-3,3,3-trifluoropropene containing less than about 50 ppm water.

Example 5 - Recovery of 1-chloro-3,3,3-trifluoropropene from Water

1,100 lb / hr of crude 1-chloro-3,3,3-trifluoropropene and 0.4 lb / hr of water were fed into the distillation column, where 0.4 lb / hr of water and about 100 lb / hr of azeotropic Essentially all of the crude 1-chloro-3,3,3-trifluoropropene was contained in the overhead. The overhead azeotropic mixture was then sent to a second phase separator to form an aqueous phase and an organic phase. The top layer was found to contain 0.4 lb / hr of water and may be recycled back to the first phase separator, discarded, or partially recycled. The phases of the first phase separator can also be discarded or sent for further processing. The organic phase was then returned to the distillation column as reflux. When used in conjunction with the second phase separator, the bottom appeared to yield approximately 100% of 1-chloro-3,3,3-trifluoropropene while the reflux stream 40 contained approximately 50 ppm of water Respectively.

In a further test run, the composition of the bottoms stream could be controlled to yield water at about 11 ppm by weight to about 90 ppm water by weight. Thus, the substantially pure, dry 1-chloro-3,3,3-trifluoropropene was removed from the distillation column.

Thus, as can be seen from the above examples, the use of an azeotropic or azeotropic mixture-like composition of 1-chloro-3,3,3-trifluoropropene and water in an economical manner yields 1-chloro-3,3 , 3-trifluoropropene can be recovered.

Example 6 - EZ data for 1-chloro-3,3,3-trifluoropropene and water

An ebulliometer consisting of a vacuum jacketed tube with a condenser on top, with a further quartz thermometer, was used. Approximately 10 cc of trans-HFO-1233zd was charged to the boiling point apparatus and then water was added in small measured increments. The temperature drop when adding water was observed, indicating that a binary minimum boiling point mixture was formed. By more than 0 wt.% To about 30 wt.% Water,

The point varies from less than about 0.5 DEG C at ambient pressure.

As used herein, the singular forms "a," "an," and "the" include plural unless the context clearly dictates otherwise. Furthermore, when an amount, concentration, or other value or parameter is given as a range, a preferred range, or a list of preferred upper and lower preferred values, it is understood that any upper limit range or any desired value and any It should be understood that specifically all ranges forming from any pair of lower limit limits or preferred values are disclosed.

Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include all its integers and fractions within its range, and its range. The scope of the present invention is not intended to be limited to the specific values recited when defining the scope.

From the foregoing it will be appreciated that although specific embodiments have been described herein for purposes of illustration, various modifications may be made without departing from the spirit or scope of the invention. Accordingly, the foregoing detailed description is intended to be regarded in an illustrative rather than a restrictive sense, and to be understood as being intended to particularly point out and distinctly claim the essence of the following claims (including all equivalents).

Claims (10)

As a method for recovering 1-chloro-3,3,3-trifluoropropene,
Forming an azeotrope-like composition comprising an azeotrope or an azeotrope-like composition comprising 1-chloro-3,3,3-trifluoropropene and water;
Transferring the formed azeotropic or azeotropic mixture-like composition into a separator; And
Recovering an organic layer comprising 1-chloro-3,3,3-trifluoropropene
/ RTI > The composition of claim 1, wherein the composition comprises from about 0.05% to about 30% water by weight, based on the total weight of water and 1-chloro-3,3,3-trifluoropropene, and from about 70% 99.95 wt.% Of 1-chloro-3,3,3-trifluoropropene. 2. The method of claim 1, wherein the composition has a boiling point of about 17.4 DEG C +/- 1 DEG C at a pressure of about 14.7 psia. Providing a mixture of 1-chloro-3,3,3-trifluoropropene and water;
Separating the mixture into an aqueous layer and an organic layer predominantly comprising 1-chloro-3,3,3-trifluoropropene;
Decanting a portion of the aqueous layer from the mixture;
Transferring the organic layer to a distillation column;
Forming an azeotropic mixture of 1-chloro-3,3,3-trifluoropropene and water in said distillation column;
Removing the azeotrope as an overhead stream from the distillation column; And
Removing substantially pure 1-chloro-3,3,3-trifluoropropene from the bottom of the distillation column
/ RTI > 5. The process of claim 4, wherein the substantially pure 1-chloro-3,3,3-trifluoropropene removed from the distillation column contains less than about 100 ppm water by weight. 6. The process of claim 5, wherein the substantially pure 1-chloro-3,3,3-trifluoropropene removed from the distillation column contains less than about 40 ppm water by weight. 7. The process of claim 6, wherein the substantially pure 1-chloro-3,3,3-trifluoropropene removed from the distillation column contains less than about 20 ppm water by weight. 5. The process of claim 4, wherein the azeotrope comprises from about 0.05% to about 30% water by weight and from about 70% to about 70% by weight, based on the total weight of water and 1-chloro-3,3,3- About 99.95% by weight of 1-chloro-3,3,3-trifluoropropene. 11. The method of claim 10, wherein the azeotrope comprises from about 0.05% to about 14% water by weight and from about 86% to about 86% by weight, based on the total weight of water and 1-chloro-3,3,3- About 99.95% by weight of 1-chloro-3,3,3-trifluoropropene. 10. The method of claim 9, wherein the azeotrope has a boiling point of about 17.4 DEG C +/- 1 DEG C at a pressure of about 14.7 psia.

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