Method for removing acidic impurities from halogenated propylene

Abstract

This application relates to a method for removing acidic impurities from halogenated propenes. The present invention relates to a method for removing acidic impurities from halogenated olefins, especially a method for removing acidic impurities from halogenated propenes, and even more particularly relates to a method for removing acidic impurities from 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), 1-chloro-3,3,3-trifluoro-1-propene (HCFO-1233zd) and 2-chloro-3,3,3-trifluoro-1-propene (HCFO-1233xf). The method is carried out by passing a halogenated olefin stream in liquid or gaseous form through a bed of solid adsorbent containing at least one acid-reactive reagent.

Description

[0001] Cross - reference to related applications

[0002] This application is a divisional application of the patent application for invention titled "Method for Removing Acidic Impurities from Halopropene" with the application date of August 15, 2016, application number 201680060958.7. This application claims the domestic priority of the co - owned and co - pending US Provisional Patent Application Serial No. 62 / 206,916 filed on August 19, 2015, the disclosure of which is incorporated herein by reference. Technical field

[0003] The present invention relates to a method for removing acidic impurities from halogenated olefins, particularly a method for removing acidic impurities from halopropenes, and even more particularly to a method for removing acidic impurities from 1,3,3,3 - tetrafluoro - 1 - propene (HFO - 1234ze), 2,3,3,3 - tetrafluoro - 1 - propene (HFO - 1234yf), 1 - chloro - 3,3,3 - trifluoro - 1 - propene (HCFO - 1233zd), and 2 - chloro - 3,3,3 - trifluoro - 1 - propene (HCFO - 1233xf). Background art

[0004] Chlorofluorocarbons (CFCs), such as trichlorofluoromethane and dichlorodifluoromethane, have been used as refrigerants, blowing agents, and diluents for gas sterilization. In recent years, there has been a general concern that certain chlorofluorocarbons may be detrimental to the Earth's ozone layer. Therefore, efforts are being made worldwide to use halogenated hydrocarbons with fewer or no chlorine substituents.

[0005] Accordingly, the production of hydrofluorocarbons or compounds containing only carbon, hydrogen, and fluorine has become an increasingly concerned topic to provide environmentally friendly and ideal products for use as solvents, blowing agents, refrigerants, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire - extinguishing compositions, and working fluids for power cycles. In this regard, trans - 1,3,3,3 - tetrafluoropropene (trans - 1234ze or 1234zeE), trans - 1 - chloro - 3,3,3 - trifluoropropene (trans - 1233zd or 1233zdE), and 2,3,3,3 - tetrafluoropropene (1234yf) are part of many products that have been or are being commercialized for various applications.

[0006] There are many methods related to the preparation of fluorinated organic compounds and compositions containing such compounds. Many such methods involve the reaction of an organic compound (such as a chloroalkane or chloroolefin) with hydrogen fluoride (HF) in the presence of a fluorination catalyst. In many such methods, water is present in one or more reaction product streams containing the desired fluorinated organic compound. Such water may be generated as an impurity in the reactants or other starting materials. Water can also be formed as a by-product of the reaction process, including the reaction of HF with the catalyst, and / or as a product of the catalyst regeneration process. In addition, water may be entrained from upstream unit operations (such as a caustic scrubber where acid gases are neutralized and removed).

[0007] To remove water contained in a hydrofluorocarbon and / or hydrochlorofluorocarbon stream free of acid, concentrated sulfuric acid is often used as a drying agent because it has a very strong affinity for water. Absorbing water into sulfuric acid can be achieved in a typical dry acid system, which generally consists of a drying tower, an acid pump sump, an acid pump, an acid cooler, piping, and instrumentation and controls. A typical drying tower is a vertical cylindrical vessel designed to bring the process gas into contact with strong sulfuric acid (93%-98.5% H 2 SO4).

[0008] Recently, the present applicant has unexpectedly found that certain halopropenes react with sulfuric acid to produce small amounts of acids, including but not limited to HF and HCl, which can corrode downstream processing equipment (such as distillation towers, pumps, storage tanks, etc.). Non-limiting examples of such halopropenes include 1,3,3,3-tetrafluoropropene (1234ze), 1-chloro-3,3,3-trifluoropropene (1233zd), and 2-chloro-3,3,3-trifluoropropene (1233xf). The first two can be used as end products, while the third is a useful intermediate for the preparation of 2,3,3,3-tetrafluoropropene. Accordingly, there is a need for means to remove one or more acids present in various halopropene streams using cost-effective methods. SUMMARY OF THE INVENTION

[0009] The present inventors have recognized a need in the art for methods to remove acidic impurities contained in halopropenes, including but not limited to 1,3,3,3-tetrafluoropropene (1234ze), 2,3,3,3-tetrafluoro-1-propene (1234yf), 1-chloro-3,3,3-trifluoropropene (1233zd), and 2-chloro-3,3,3-trifluoropropene (1233xf). Non-limiting examples of acidic impurities include hydrogen fluoride (HF), hydrogen chloride (HCl), sulfuric acid (H 2 SO 4 ), trifluoroacetic acid (CF 3 COOH), and mixtures of two or more of such acids.

[0010] It has been found that this need can be met by passing a stream of halogenated propene in liquid or gaseous form through a bed of solid adsorbent containing at least one acid-reactive reagent. The acid-reactive reagent can be selected from metal oxides (such as alumina), alkaline earth metal oxides, alkali metal oxides, metal hydroxides (such as aluminum hydroxide), alkaline earth metal hydroxides and alkali metal hydroxides, aluminosilicate minerals (such as andalusite, kyanite, sillimanite, calcium aluminosilicate, sodium aluminosilicate), silica and various combinations thereof.

[0011] In view of the fact that water may be produced by the reaction between the acid and the acid-reactive reagent, preferably, the solid adsorbent bed also contains a water absorbent. The water absorbent can be selected from inorganic salts (such as magnesium sulfate, calcium sulfate (Drierite) and calcium chloride), molecular sieves (molsiv) (such as 3A, 4A, 5A, AW500, XH-7, XH-9 and 13X), silica gel, activated carbon and various combinations thereof. Preferably, the solid adsorbent bed contains the acid-reactive reagent at the top and the water absorbent at the bottom, and the halogenated propene stream enters the solid adsorbent bed from the top. In a preferred embodiment, activated alumina is used as the acid-reactive reagent and 3A or XH-9 is used as the water absorbent. By applying this teaching, a halogenated propene stream substantially free of acid can be obtained.

[0012] Accordingly, one embodiment of the present invention is a method for removing acidic impurities from a halogenated olefin, which comprises contacting a stream containing the halogenated olefin in liquid or gaseous form with a bed of solid adsorbent containing at least one acid-reactive reagent by passing the stream through the bed of solid adsorbent, wherein the solid adsorbent bed also contains a water absorbent; and wherein the acidic impurities are selected from hydrogen fluoride (HF), hydrogen chloride (HCl), sulfuric acid (H 2 SO 4 ), trifluoroacetic acid (CF 3 COOH) and mixtures of two or more of these acids.

[0013] One embodiment of the present invention is a method for removing acidic impurities from a halogenated olefin, which comprises contacting a stream containing the halogenated olefin in liquid or gaseous form with a bed of solid adsorbent containing at least one acid-reactive reagent and at least one water absorbent by passing the stream through the bed of solid adsorbent;

[0014] wherein the acidic impurities are selected from hydrogen fluoride (HF), hydrogen chloride (HCl), sulfuric acid (H 2 SO 4 ), trifluoroacetic acid (CF 3 COOH) and mixtures of two or more of these acids; and

[0015] Wherein the haloolefin includes a halopropene selected from 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), 1-chloro-3,3,3-trifluoro-1-propene (HCFO-1233zd), and 2-chloro-3,3,3-trifluoro-1-propene (HCFO-1233xf).

[0016] In certain embodiments, the acid-reactive reagent is selected from:

[0017] (a) metal oxides, alkaline earth metal oxides, alkali metal oxides, and mixtures thereof;

[0018] (b) metal hydroxides, alkaline earth metal hydroxides, alkali metal hydroxides, and mixtures thereof;

[0019] (c) aluminosilicate minerals selected from andalusite, kyanite, sillimanite, calcium aluminosilicate, sodium aluminosilicate, and mixtures thereof;

[0020] (d) silicon oxide; and

[0021] (e) activated alumina.

[0022] In certain embodiments, the water absorbent is selected from:

[0023] (a) inorganic salts, magnesium sulfate, calcium sulfate, calcium chloride, and combinations thereof;

[0024] (b) molecular sieves 3A, 4A, 5A, AW500, XH-7, XH-9, 13X, and combinations thereof; and

[0025] (c) silica gel, activated carbon, and combinations thereof.

[0026] One of ordinary skill in the art to which the present invention pertains should understand that any feature of any particular aspect and / or embodiment of the present invention described herein can be combined with one or more of any other features of any other aspect and / or embodiment of the present invention described herein, with modifications made as appropriate to ensure compatibility of the combination. Such combinations are considered to be part of the present invention contemplated by the present disclosure.

[0027] It should be understood that the foregoing summary and the following detailed description are merely exemplary and illustrative, and not restrictive of the claimed invention. Other embodiments will be apparent to those skilled in the art in view of the specification and practice of the invention disclosed herein. Detailed Description

[0028] The present invention can generally be described as a method for removing acidic impurities present in a liquid or gaseous stream of a halogenated propene by passing the liquid or gaseous stream of the halogenated propene through a bed of a solid adsorbent containing at least an acid-reactive reagent, the acidic impurities non-exclusively including hydrogen fluoride (HF), hydrogen chloride (HCl), sulfuric acid (H 2 SO 4 ) and trifluoroacetic acid (CF 3 COOH), and the halogenated propene being non-exclusively selected from 1,3,3,3-tetrafluoropropene (1234ze), 2,3,3,3-tetrafluoro-1-propene (1234yf), 1-chloro-3,3,3-trifluoropropene (1233zd) and 2-chloro-3,3,3-trifluoropropene (1233xf).

[0029] In some embodiments of the present invention, the organic portion of the halogenated propene stream is a purified product containing a single halogenated propene (e.g., trans-1234ze, trans-1233zd, 1233xf or 1234yf). In some embodiments of the present invention, the organic portion of the halogenated propene stream is a crude product containing one or more halogenated propenes and one or more halogenated propane (e.g., a mixture of trans-1234ze, cis-1234ze, 245fa, etc.). In some embodiments of the present invention, the passage of the halogenated propene stream through the solid adsorbent bed is a once-through process, in which the organic stream passes through the adsorbent bed only once. In some embodiments of the present invention, the passage of the halogenated propene stream through the solid adsorbent bed is a cyclic process, in which the organic stream circulates through the adsorbent bed multiple times.

[0030] The acid-reactive reagent can be selected from metal oxides (such as alumina), alkaline earth metal oxides, alkali metal oxides, metal hydroxides (such as aluminum hydroxide), alkaline earth metal hydroxides and alkali metal hydroxides, aluminosilicate minerals (such as andalusite, kyanite, sillimanite, calcium aluminosilicate, sodium aluminosilicate), silica and various combinations thereof. In some preferred embodiments, alumina is used as the acid-reactive reagent. In some even more preferred embodiments, activated alumina is used. Activated alumina is a porous granular material and can be prepared from aluminum hydroxide by dehydroxylating the aluminum hydroxide to produce a highly porous material. Activated alumina can have a surface area significantly greater than 200 m 2 / g.

[0031] Since water may be produced by the reaction between an acid and an acid-reactive reagent, preferably, the solid adsorbent bed further contains a water absorbent. The water absorbent may be selected from inorganic salts (such as magnesium sulfate, calcium sulfate (Drierite), and calcium chloride), molecular sieves (such as 3A, 4A, 5A, AW500, XH-7, XH-9, and 13X), silica gel, activated carbon, and various combinations thereof.

[0032] In some preferred embodiments, a molecular sieve is used as the water absorbent. A molecular sieve is a material containing very small pores with precise and uniform sizes. These pores are small enough to block large molecules while allowing small molecules to pass through. In an even more preferred embodiment, 3A is used for a once-through process. In another more preferred embodiment, XH-9 is used for a recycle process.

[0033] When both an acid-reactive reagent and a water absorbent are present in the solid adsorbent bed, preferably, the acid-reactive reagent is at the top and the water absorbent is at the bottom, and the halopropene stream enters the solid adsorbent bed from the top (in other words, the acid-reactive reagent first contacts the organic stream). The amount of the water absorbent layer relative to the acid-reactive reagent layer can be determined experimentally or based on their adsorption capacities. In some embodiments of the present invention, the volume of the water absorbent layer is 10-60%. In some embodiments of the present invention, the volume of the water absorbent layer is 30-50%.

[0034] The contact between the halopropene stream and the acid-reactive reagent (or both the acid-reactive reagent and the water absorbent) can be carried out in any suitable container or reactor, which should preferably be constructed of a material resistant to the corrosive action of various acids, including stainless steel, Hastelloy, Inconel, Incoloy, Monel, or lined with a fluoropolymer.

[0035] In some embodiments of the present invention, the temperature during the contact step is from about -20°C to about 200°C. In some embodiments of the present invention, the temperature during the contact step is from about 0°C to about 100°C. In some embodiments of the present invention, the temperature during the contact step is from about 10°C to about 50°C. In some embodiments of the present invention, the temperature during the contact step is about room temperature. The pressure during the contact step is not critical and can be from about 10 kPa to about 3000 kPa.

[0036] During the contacting step, the mixture of halopropene and acidic impurities is washed with an acid-reactive reagent in a contacting vessel, and the acidic impurities are removed. In some embodiments of the present invention, the concentration of at least one acidic impurity in the mixture is reduced to 0.5 ppm or less. In some embodiments of the present invention, the concentration of at least one acidic impurity in the mixture is reduced to 0.1 ppm or less. In some embodiments of the present invention, the concentration of at least one acidic impurity in the mixture is reduced to 0.05 ppm or less. In some embodiments of the present invention, the amount of at least one acidic impurity in the mixture is reduced by at least about 50% by weight relative to the amount initially present. In some embodiments of the present invention, the amount of at least one acidic impurity in the mixture is reduced by at least about 80% by weight relative to the amount initially present. In some embodiments of the present invention, the amount of at least one acidic impurity in the mixture is reduced by at least about 95% by weight relative to the amount initially present.

[0037] The halopropene having a reduced concentration of acidic impurities obtained from the contacting step can be recovered using techniques well known in the art (such as condensation or distillation). In some embodiments of the present invention, the halopropene obtained from the contacting step can be further purified by fractional distillation. Examples

[0038] The following non-limiting examples are used to illustrate the present invention.

[0039] Example 1 - Removal of one or more acids contained in crude 1234zeE via various solid adsorbents

[0040] 15 ml of 95% H 2 SO 4 was charged into a PFA reactor vessel, and the vessel was heated to 38 °C using an oil bath. The temperature was maintained at this set point for 30 minutes before starting the addition of the organic matter to ensure that the H 2 SO 4 was uniformly heated to this set point. Magnetic stirring was applied to the reactor vessel throughout the experiment to ensure a constant temperature and the mixing of the organic matter and H 2 SO 4 . The outlet of the reactor was connected to a solid adsorbent column and then to a PFA trap containing 20 ml of deionized water to absorb the acid (if any). At the end of the experiment, the contents of the PFA - H 19 SO 2 reactor vessel were analyzed by 4 F-NMR, and the contents of the deionized water trap were analyzed by IC.

[0041] In this embodiment, the organic matter is crude 1234zeE, which contains 45 - 60% of 1234zeE, 30 - 45% of 245fa, and 5 - 15% of 1234zeZ. The tested solid adsorbents include silica gel, alumina, molecular sieve XH-9, molecular sieve 3A, and molecular sieve 4A. As shown in Table 1, HF is indeed formed in the sulfuric acid reactor. Nevertheless, the level of HF in the deionized water trap (i.e., at the outlet of the solid adsorbent column) is significantly lower. Calculate the concentration of HF in the organic stream after the solid adsorption column and list it in the last column of Table 1. It can be seen that when using alumina, molecular sieve 3A, or molecular sieve 4A, a negligible amount of HF is detected.

[0042] Table 1

[0043]

[0044] 1 The acidity is most likely generated by the hydrolysis of SiF 4 (proven by the presence of silicon ions in deionized water).

[0045] Example 2 - Removal of one or more acids contained in crude 1234zeE via alumina

[0046] Load 15 ml of 95% H 2 SO 4 into a PFA reactor vessel and heat the vessel to 38 °C using an oil bath. Keep the temperature at this set point for 30 minutes before starting to deliver the organic matter at an average flow rate of 106 g / h to ensure that H 2 SO 4 is evenly heated to this set point. Apply magnetic stirring to the reactor vessel throughout the experiment to ensure a constant temperature and the mixing of the organic matter and H 2 SO 4 Connect the outlet of the reactor vessel to an activated alumina column containing 20 ml (15.1 g) of alumina, and then connect it to a PFA trap containing 40 ml of deionized water to "wash" the reactor gas effluent. During the experiment, regularly collect samples of the reactor effluent (i.e., the inlet sample of the alumina column) and the deionized water sample (i.e., the outlet sample of the alumina column), and analyze them by IC to determine the HF levels at the inlet and outlet of the alumina column.

[0047] In this embodiment, the organic matter is crude 1234zeE, which contains 45 - 60% of 1234zeE, 30 - 45% of 245fa, and 5 - 15% of 1234zeZ. As shown in Table 2, although the average HF concentration in the inlet of the alumina column was about 22 ppm, a negligible amount of HF was detected at the column outlet, again indicating that alumina effectively removes HF. Calculations using the total amount of organic matter passing through the alumina column and the average HF concentrations at the inlet and outlet of the alumina column showed that the amount of adsorbed HF reached 9.2% of the weight of the alumina after 25 days of production.

[0048]

[0049] Example 3 - Removal of one or more acids contained in the 1234zeE product

[0050] 15 ml of 95% H 2 SO 4 was charged into a PFA reactor vessel, and the vessel was heated to 38 °C using an oil bath. The temperature was maintained at this set point for 30 minutes before starting to deliver the organic matter at an average flow rate of 35 g / h to ensure that H 2 SO 4 was uniformly heated to this set point. Magnetic stirring was applied to the reactor vessel throughout the experiment to ensure a constant temperature and the mixing of the organic matter and H 2 SO 4 . The outlet of the reactor vessel was connected to a combined column of 20 ml of alumina / 20 ml of molecular sieve XH - 9, and then to a PFA trap containing 20 ml of deionized water to absorb the acid (if any). At the end of the experiment (which lasted 59 hours), the contents of the deionized water trap were analyzed by IC.

[0051] In this embodiment, the organic matter is a 1234zeE product with a purity of 99.9 + %. The IC analysis results showed that a negligible amount of HF (<0.1 ppm) was present in the deionized water.

[0052] Example 4 - Removal of one or more acids contained in the 1233xf intermediate

[0053] 15 ml of 95 - 98% H 2 SO 4 was charged into a PFA reactor vessel, and the vessel was heated to 38 °C using an oil bath. The temperature was maintained at this set point for 30 minutes before starting to deliver the organic matter at an average flow rate of 30 g / h to ensure that H 2 SO 4 was uniformly heated to this set point. Magnetic stirring was applied to the reactor vessel throughout the experiment to ensure a constant temperature and the mixing of the organic matter and H2 SO 4 Mixing. Connect the outlet of the reactor vessel to a combined column of 20 ml alumina / 20 ml molecular sieve 3A, and then to a PFA trap containing 20 ml deionized water to absorb the acid (if any). During the experiment, reactor effluent samples (i.e., alumina column inlet samples) and deionized water samples (i.e., alumina column outlet samples) were collected periodically and analyzed by IC to determine the HF levels at the inlet and outlet of the alumina column.

[0054] In this example, the organic matter is a 99+% pure 1233xf intermediate. The IC analysis results showed that the average concentrations of HF and HCl at the inlet of the alumina / 3A column were approximately 1 ppm and 65 ppm, respectively, but negligible amounts (<0.1 ppm) of HF and HCl were detected at the column outlet.

[0055] This application may include the following technical solutions.

[0056] 1. A method for removing acidic impurities from a halogenated olefin, comprising contacting a liquid or gas stream containing the halogenated olefin with a solid adsorbent bed containing at least one acid-reactive reagent and at least one water absorbent; and wherein the acidic impurities are selected from hydrogen fluoride (HF), hydrogen chloride (HCl), sulfuric acid (H 2 SO 4 )), trifluoroacetic acid (CF 3 COOH), and mixtures of two or more of these acids.

[0057] 2. The method of aspect 1, wherein the halogenated olefin comprises a halogenated propene selected from 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), 1-chloro-3,3,3-trifluoro-1-propene (HCFO-1233zd), and 2-chloro-3,3,3-trifluoro-1-propene (HCFO-1233xf).

[0058] 3. The method of aspect 1, wherein the acid-reactive reagent is selected from metal oxides, alkaline earth metal oxides, alkali metal oxides, and mixtures thereof.

[0059] 4. The method of aspect 1, wherein the acid-reactive reagent is selected from metal hydroxides, alkaline earth metal hydroxides, alkali metal hydroxides, and mixtures thereof.

[0060] 5. The method of aspect 1, wherein the acid-reactive reagent comprises aluminosilicate minerals selected from andalusite, kyanite, sillimanite, calcium aluminosilicate, sodium aluminosilicate, and mixtures thereof.

[0061] 6. The method of Scheme 1, wherein the acid-reactive reagent comprises silica.

[0062] 7. The method of Scheme 1, wherein the acid-reactive reagent comprises activated alumina.

[0063] 8. The method of Scheme 1, wherein the water absorbent is selected from inorganic salts, magnesium sulfate, calcium sulfate, calcium chloride, and combinations thereof.

[0064] 9. The method of Scheme 1, wherein the water absorbent is selected from molecular sieves 3A, 4A, 5A, AW500, XH-7, XH-9, 13X, and combinations thereof.

[0065] 10. The method of Scheme 1, wherein the water absorbent is selected from silica gel, activated carbon, and combinations thereof.

[0066] As used herein, unless the context clearly indicates otherwise, the singular forms "a", "an", and "the" include the plural. Further, when an equivalent, concentration, or other value or parameter is given as a range, preferred range, or a series of upper preferred values and lower preferred values, this should be understood to specifically disclose all ranges formed by any pair of any upper range limit or preferred value and any lower range limit or preferred value, whether or not the ranges are separately disclosed. When a numerical range is recited herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within the range. When defining a range, it is not intended that the scope of the invention be limited to the specific values recited.

[0067] From the above, it can be understood that although specific embodiments are described herein for purposes of illustration, various modifications can be made without departing from the spirit or scope of the present disclosure. Accordingly, it is intended that the above detailed description be considered illustrative rather than restrictive, and it should be understood that what is particularly pointed out and distinctly claimed is the subject matter of the appended claims (including all equivalents).

Claims

1. A method for preparing at least one halogenated olefin selected from 1,3,3,3 - tetrafluoro - 1 - propene (HFO - 1234ze), 2,3,3,3 - tetrafluoro - 1 - propene (HFO - 1234yf), 1 - chloro - 3,3,3 - trifluoro - 1 - propene (HCFO - 1233zd) and 2 - chloro - 3,3,3 - trifluoro - 1 - propene (HCFO - 1233xf), the method comprises: Removing water from the acid-free stream of the at least one haloolefin with concentrated sulfuric acid to produce a composition comprising the at least one haloolefin and at least one acid impurity selected from trifluoroacetic acid (CF 3 COOH), hydrogen fluoride (HF), hydrogen chloride (HCl), and mixtures thereof; and removing the at least one acid impurity, wherein removing the one acid impurity comprises passing a liquid or gas stream of the composition through a solid adsorbent bed comprising at least one acid - reactive reagent and at least one water absorbent; wherein the water absorbent is selected from inorganic salts, molecular sieves 3A, 4A, 5A, AW500, XH - 7, XH - 9, 13X, silica gel, activated carbon and combinations thereof; and wherein the acid - reactive reagent is selected from metal oxides, metal hydroxides, and mixtures thereof, or wherein the acid - reactive reagent comprises aluminosilicate minerals selected from andalusite, kyanite, sillimanite, calcium aluminosilicate, sodium aluminosilicate and mixtures thereof, or wherein the acid - reactive reagent comprises silica and / or activated alumina.

2. The method of claim 1, wherein the inorganic salt is selected from magnesium sulfate, calcium sulfate, calcium chloride and combinations thereof.

3. The method of claim 1, wherein the metal oxide is selected from alkaline earth metal oxides, alkali metal oxides and combinations thereof; and wherein the metal hydroxide is selected from alkaline earth metal hydroxides, alkali metal hydroxides and combinations thereof.

4. The method of claim 1, wherein the at least one halogenated olefin is selected from 1,3,3,3 - tetrafluoro - 1 - propene (HFO - 1234ze) and 1 - chloro - 3,3,3 - trifluoro - 1 - propene (HCFO - 1233zd).

5. The method of claim 4, wherein the at least one halogenated olefin comprises 1,3,3,3 - tetrafluoro - 1 - propene (HFO - 1234ze).

6. The method of claim 4, wherein the halogenated olefin comprises 1 - chloro - 3,3,3 - trifluoro - 1 - propene (HCFO - 1233zd).

7. The method of claim 1, wherein the water absorbent is an inorganic salt.

8. The method of claim 7, wherein the inorganic salt is selected from magnesium sulfate, calcium sulfate, calcium chloride and combinations thereof.

9. The method of claim 1, wherein the water absorbent is selected from molecular sieves 3A, 4A, 5A, AW500, XH - 7, XH - 9, 13X and combinations thereof.

10. The method of claim 1, wherein the water absorbent is selected from silica gel, activated carbon and combinations thereof.

11. The method of claim 1, wherein the acid - reactive reagent contacts the liquid or gas stream of the composition before the at least one water absorbent contacts the liquid or gas stream of the composition.

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