WO2025019752A2

WO2025019752A2 - Hcl recovery in fluorochemical processes to produce high quality anhydrous hcl or aqueous hcl of specific concentration

Info

Publication number: WO2025019752A2
Application number: PCT/US2024/038694
Authority: WO
Inventors: Sheng Peng; Michael A. Bradley; William H. Zimmerman
Original assignee: Chemours Co FC LLC
Current assignee: Chemours Co FC LLC
Priority date: 2023-07-20
Filing date: 2024-07-19
Publication date: 2025-01-23
Anticipated expiration: 2026-01-20
Also published as: WO2025019752A3; CN121464119A

Abstract

The invention relates to HCl recovery and purification from fluorochemical raw product streams.

Description

HCL RECOVERY IN FLUOROCHEMICAL PROCESSES TO PRODUCE HIGH QUALITY ANHYDROUS HCL OR AQUEOUS HCL OF SPECIFIC CONCENTRATION

FIELD

[0001] The invention relates to HCI recovery and purification of process streams from fluorochemical processes which are subjected to purification to produce anhydrous HCI or aqueous HCI suitable for use in the chemical, food, electrical and pharmaceutical industries, as well as HCI/HF-fluorochemical compositions.

BACKGROUND

[0002] Fluorochemicals, including, but not limited to, hydrofluoroolefins (HFOs) have been produced by fluorination, dehydrochlorination, hydrodechlorination and hydrogenation, and result in compounds with low ozone depletion potential (ODP) and low global warming potential (GWP). Hydrofluoroolefins (HFOs) have been replacing saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons) in a variety of applications for several years, as well as hydrofluorocarbons which tend to have high GWP values. As a result, the low ODP and GWP fluorochemicals are being used as refrigerants, solvents, foam expansion agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishants, and power cycle working fluids, as well as starting materials.

[0003] To meet these increasing demands, new manufacturing techniques continue to be developed and additional manufacturing plants and suppliers come on-line. Often fluorochemicals of interest are produced from starting materials such as hydrochlorofluorocarbons and hydrochlorofluoroolefins. As a result HCI is a common byproduct made in the fluorochemical processes, and it is desirable to recover HCI either as gas or aqueous solution at high purity for use in the chemical, food, electrical and pharmaceutical industries. However, HCI produced in these reactions often contain trace amounts of HF, acid fluorides or lower boiling organic compounds, and these impurities could negatively impact the quality of the recovered HCI, and therefore, impede its end use, leading to disposing it as waste. Thus a need exists to provide more effective and efficient HCI recovery in fluorochemical processes for environmental pollution reduction, and help improving process economics.

SUMMARY

[0004] The invention relates to HCI recovery and purification from fluorochemical processes for producing anhydrous HCI or aqueous HCI for use in the chemical, food, electrical and pharmaceutical industries. See https://balchem.com/performance- qases/products/anhvdrous- hcl/#:~:text=lt%20is%20used%20in%20chemical,electronic%20components%20and%2 0soap%20refinino and https://labproinc.com/bloqs/chemicals-and-solvents/top-5-uses- of-hvdrochloric-acid, the disclosure of each incorporated herein by reference in its entirety.

[0005] The present invention relates to recovering HCI from fluorochemical process product mixtures which comprises, consist essentially of, or consist of desired products, reaction intermediates, organic byproducts, HCI, trace HF and other impurities, by separatory techniques to produce anhydrous HCI and/or aqueous HCI stream of desired concentrations for use in the chemical, food, electrical and pharmaceutical industries.

[0006] In certain embodiments of the invention disclosed herein the desired products includes one of 3,3,3-trifluoropropene, 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (E), 2,4-dichloro- 1 ,1 ,1 ,4,4,4hexafluoro-2-butene(E) and 2,4-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene(Z), 2,3,3,3-tetrafluoropropene, 2-choro-1 ,1,1 ,4-tetrafluoropropane and 1 , 1 ,1 , 4,4,4- hexafluoro-2-butene (E).

[0007] In certain embodiments of the invention disclosed herein the fluorochemical processes include, but not limited to,

(1) fluorination of 1 ,1 ,1 ,3-tetrachoropropane to 3,3,3-trifluropropene:

CCI3CH2CH2CI + HF — > CF₃CH=CH₂ + HCI;

(2) catalytic coupling of 1 ,1 ,1-trifluorotrichloroethane in the presence of hydrogen:

2

SUBSTITUTE SHEET (RULE 26) (3) Dehydrochlorination of 2-chloro-1 ,1,1,2-tetrafluoropropane — 2, 3, 3, 3- tetrafluoropropene

CF3CCIFCH3 — CF₃CF=CH₂ + HCI;

(4) fluorination of 2,3-dichloro-1 ,1 ,1-trifluoropropane to 2-chloro-1 ,1 ,1 ,3 tetrafluoropropane:

CF3CCIHCH2CI +HF -^CF₃CHCICH₂F + HCI

(5) fluorination of 1,1, 1, 3-tetrachloro-4,4,4-trifluorobutane (343jfd) — trans- 1,1,1,4,4,4-hexafluoro-2-butene + 4 HCI:

CF₃CCIHCH₂CCI₃ + HF -^CF₃CH=CHCF₃ + 4 HCI.

[0008] In one embodiment 1 ,1 ,1,3-tetrachoropropane contacts HF to form a product mixture including 3,3,3-trifluropropene, as disclosed in U.S. Patent Pub. No.

20210317055, the disclosure of which is incorporated by reference in its entirety and the mixture is treated to obtain HCI.

[0009] In another embodiment 2-chloro-3,3,3-trifluoropropene contacts HF to form a reaction mixture comprising 2-chloro- 1,1 , 1 ,2-tetrafluoropropene (244bb) or 1, 1 ,2,3- tetrachloropropene (HCC-1230xa) contacts hydrogen fluoride to form a product mixture comprising 2-chloro-3,3,3-trifluoropropene (1233xf), HF and HCI as disclosed in International Publication WO2020247423 the disclosure of which is incorporated by reference in its entirety, and mixtures containing HF and HCI are treated to recover HCI and remove HF.

[0010] In one embodiment the 2-chloro-1 ,1,1 ,2-tetrafluoropropane contacts HF to form a product mixture including 2,3,3,3-tetrafluoropropene and HCI and the mixture is treated to obtain HCI.

[0011] In one embodiment 1,1 ,2,4-tetrachloropropene contacts hydrogen to form a product mixture comprising at least 2-chloro-3,3,3-trifluoropropene ad HCI, as disclosed in U.S. Patent No. 9,943,717, the disclosure of which is incorporated by reference in its entirety and the mixture is treated to obtain HCI. [0012] In one embodiment 2, 3-dichloro-1 , 1,1 -trifluoropropane contacts HF to form a product mixture comprising 2-chloro-1 ,1 ,1 ,3 tetrafluoropropane and HCI, and the mixture is treated to obtain HCI.

[0013] In one embodiment the 1 ,1 ,3-trichloro-4,4,4-trifluorobut-1-ene contacts HF, as disclosed in, for example, International Publication No. WO 2019/11305, the disclosure of which is incorporated herein by reference in its entirety, and the product mixture including E-1336mzz and 1333azd, 1336mt, 346mdf, 13351zz, Z-1336mzz, 356mff, 1326mxz and HCI is treated to obtain HCI.

[0014] In one embodiment the product mixture from the hydrogenation of 1,1 ,1 - trifluorotrichloroethane (HCFC-113a), such as that disclosed in U.S. Patent Publication US 2016/0347694, the disclosure of which is incorporated herein by reference in its entirety, including HCI, E-1336, 356mff, 1345czf, Z-1336mzz, 346mdf, 1316mxx and 1326mxz is treated to obtain HCI.

[0015] In the fluorochemical processes disclosed herein involving hydrogenation or contact with HF, the HCI in the product mixture(stream) is treated to form anhydrous HCI, which can be used to make aqueous HCI at desired concentration and substantially free of HF and organics.

[0016] The present invention relates to processes where the product mixture from a fluorochemical process includes reactor effluent containing reaction products, reaction intermediates, organic byproducts, HCI and trace HF which can be sent to one or more distillation columns for separation. High boilers are separated at the bottom of the column and can be sent to another separation train, and the HCI and lower boilers that are separated at the top of the column can pass through one or more absorbent beds, including, but not limited to, silica gel (amorphous silica including pyrogenic silica, precipitated silica and silica gel) or alumina to remove HF and low boiling organics such as COF2, and obtain anhydrous HCI at >99% purity, >99.5% purity, and substantially free of HF, and substantially free organics, e.g., <20 ppm, <10, ppm, <5 ppm.

[0017] In another embodiment disclosed herein the anhydrous HCI stream withdrawn from the one of more absorbers can be sent to an HCI absorber to make aqueous HCI at desired concentration which is substantially free of HF and organics. [0018] In certain embodiments of the invention disclosed herein treatment operations for HCI bearing streams include, but are not limited to, distillation, decantation, absorption, adsorptions, etc.

[0019] In certain embodiments of the invention disclosed herein treatment operations for HCI bearing streams include membrane separation. In one such embodiment, there is a process comprising contacting a fluorochemical product stream containing at least one of a fluoroolefin, fluorochloroolefin, HCFO, HFC, HCO, HCFC, chloroolefin product, HCI, HF and optionally COF2 and moisture with a membrane. The membrane may be an ion exchange membrane, particularly a fluorinated ion-exchange membrane. Membrane separation may comprise using a fluorinated ion-exchange membranes. Fluorinated ion exchange membranes include those commercially available, such as those sold under the Nation™, FORBLUE™, FLEMION™ names.

[0020] In certain embodiments of the invention disclosed herein unit operations include, a reactor, plus one or more of the following units: at least one distillation column, a least one decanter, at least one absorber, and at least one sparging unit..

[0021] In another embodiment the anhydrous HCI stream can be sent to an HCI absorber to make aqueous HCI at desired concentration and substantially free of HF and organics.

[0022] In a still further embodiment the product mixture is removed from the reactor and sent to a HCI quench tank Decanting, the high boilers from the bottom of the tank are removed for additional purification. Volatile organics are collected for additional purification. HCI solution is sent to a separate tank with gas sparging to remove the remaining organics. Optionally CaCl2 in the tank is added to remove HF and obtain aqueous HCI at the desired concentration and substantially free of HF and organics.

[0023] Certain embodiments disclosed herein relate to compositions comprising HCI, HF and two or more, three or more additional compounds selected from one of 346mdf, 1336mzz(E), 1336mzz(Z), 356mff, 133a,1327mz, 1336ft, 1243zf, 1242zf, 254eb, 254fb, 253fb, 113a, 123, 133a, 1316mxx(E), 1316mxx(Z), 1326mxz(E), 1326mxz(Z), 1234ze(Z), 1234ze(E), 1234yf, 244bb,1233xf, 1233zd(E), 1233zd(Z), 245fa, optionally COF2, and CO₂. [0024] Certain embodiments disclosed herein relate to compositions comprising HCI, HF plus two more or three more of the following 346mdf, 1336mzz(E), 1336mzz(Z), 356mff, 133a,1327mz, 1336ft, 1243zf, 1242zf, 254eb, 254fb, 253fb, 113a, 123, 133a, 1316mxx(E), 1316mxx(Z), 1326mxz(E), 1326mxz(Z), 1234ze(Z), 1234ze(E), 1234yf, 1233xf, 1233zd(E), 1233zd(Z), 245fa, optionally COF2 and/or CO₂.

[0025] Certain embodiment disclosed herein relate to compositions comprising ., 346mdf, 1336mzz(E), 1336mzz(Z), HCI, HF, 356mff, 133a,1327mz, and optionally COF2, CO₂ wherein the amount of HCI present <500 ppm, <400ppm, or <300 ppm.

[0026] Certain embodiment disclosed herein relate to compositions which comprise, consist essentially of, or consists of 346mdf, 1336mzz(E), 1336mzz(Z), greater than 100 ppm and <500 ppm HCI, HF, 356mff, 133a,1327mz, optionally CO2 and/or COF2.

[0027] Certain embodiment disclosed herein relate to compositions which comprise, consist essentially of, or consists of one or more of 346mdf, 1336mzz(E), 356mff, 133a,1327mz and 1336mzz(Z), greater than 100 ppm and <500 ppm HCI, HF, and optionally CO2 and/or COF₂.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 depicts a first treatment scenario of the invention.

[0030] Figure 2 depicts a second treatment scenario of the invention.

[0031] Figure 3 depicts a third treatment scenario of the invention. DETAILED DESCRIPTION

[0032] The present invention relates fluorochemical processes which are conducted in the reaction zone of a reactor a product mixture/stream which includes the product of interest, reaction intermediates, organic byproducts, starting materials, HCI and trace HF. The Product mixture is sent to a distillation column. High boilers are separated at the bottom of the column and sent to another separation train. HCI and lower boilers separated at the top of the column optionally pass through an absorbent bed (silica gel (amorphous silica including pyrogenic silica, precipitated silica and silica gel), or alumina)) to obtain anhydrous HCI at >99% purity and substantially free of HF and organics.

[0033] In another embodiment the anhydrous HCI stream from the top of the column can be sent to an HCI absorber to make aqueous HCI at desired concentration and substantially free of HF, and organics .

[0034] In another embodiments first sent to a HCI quench tank. The high boilers at the bottom are decanted, removed and sent for additional purification. Volatile organics are collected for additional purification, HCI solution is sent to a separate tank with gas sparging to remove remain organics. HF is optionally removed by contact with CaCh.

[0035] Before addressing details of embodiments described herein, some terms are defined or clarified as follows.

[0036] Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. Moreover, all ranges set forth herein are intended to include not only the particular ranges specifically described, but also any combination of values therein, including the minimum and maximum values recited.

[0037] The term “compound” as used herein is meant to include all stereoisomers, geometric isomers, tautomers, and isotopes of the structures or chemical described. Compounds herein identified by name or structure as one particular tautomeric form are intended to include other tautomeric forms unless otherwise specified. [0038] The term “hydrohaloalkane,” as used herein means a molecule containing hydrogen, carbon, fluorine and/or chlorine and/or bromine and/or iodine, with no carboncarbon double bond (halo=fluoro, chloro, bromo, iodo). Examples are described throughout the instant specification.

[0039] The term “hydrohaloalkene” is intended to mean a chemical compound selected from the classes of hydrofluoroolefms (HFOs) and hydrochlorofluoroolefins (HCFOs) which include a double bond between adjacent carbon atoms and can contain 1 to 8 carbon atoms.

[0040] The term “dehydrohalogenation,” as used herein, means loss of HX from a hydrohaloalkane, where X=F, Cl, Br, I, where H and X are on adjacent carbons in the hydrohaloalkane. For example, the term “dehydrofluorination,” “dehydrofluorinating” or “dehydrofluorinated,” as used herein, means a process during which hydrogen and fluorine on adjacent carbons in a molecule are removed; the term “dehydrochlorination,” “dehydrochlorinating,” or “dehydrochlorinated,” as used herein, means a process during which hydrogen and chlorine on adjacent carbons in a molecule are removed.

[0041] Typically a heated reactor is used in the hydrogenation or fluorochemical processes described herein. A number of reactor configurations are possible including packed bed tube or column reactors, operated in batch, semi-batch or continuous modes. In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed and effluent lines, units associated with mass transfer, contacting vessels (pre-mixers), distillation columns, absorbers, and valving associated with reactors, heat exchangers, vessels, columns, and units that are used in the processes of various embodiments disclosed herein should be constructed of materials resistant to corrosion

[0042] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B is true (or present).

[0043] The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0044] The transitional phrase “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term ‘consisting essentially of’ occupies a middle ground between “comprising” and ‘consisting of.’

[0045] Where applicants have defined an invention or a portion thereof with an open- ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of’ or “consisting of.”

[0046] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0047] As used herein, the term “substantially free” means that less than about 0.0005 percent by weight is present (5 ppm), most preferably less than 1 ppm.

[0048] As used herein the term “about” in certain embodiments can mean ± 1%, ± 2%, ± 3% and up to and including ±10% of an identified value, including all whole numbers and fractions thereof. [0049] As used herein the term “substantially,” “main” or “major” and should be construed to mean at least 51 percent.

[0050] As used herein the terms Non-Condensable Gas (NCG) is meant to gases such as oxygen and nitrogen (air), carbon dioxide, argon and carbon monoxide. Nonabsorbable gas (NAG), non-condensable gas (NCG), or simply non-condensables are all terms used to reference gases such as air, nitrogen, argon, carbon dioxide, and oxygen.

[0051] As used herein impurities comprise, but are not limited to moisture (water), non-absorbable gas (NAG), non-condensable gas (NCG), or simply non-condensables are all terms used to reference gases such as air, nitrogen, argon, carbon dioxide, and oxygen, and chlorine containing HCC, HCFC, HCFO and HCO compounds.

[0052] Compounds referred to in this disclosure may be referred to by code, based on fluorochemical naming convention, chemical structure and/or chemical name. For convenience and reference, selected compounds with codes, structures and chemical names are listed in Table 1.

TABLE 1

Code Name-ASHRAE Designation Formula

R-123 2,2-dichloro-l,l,l-trifluoroethane (HCFC-123)

R-143a 1,1,1-trifluoroethane (HFC-143a)

R-346mdf 2-chloro-l,l,l,l,4,4,4-hexafluorobutane (HCFC-346mdf)

R-356mff l,l,l,4,4,4-hexafluorobutane (HFC-356mff) CF3CH2CH2CF3

R-1130a 1,1-dichloroethene (HCO-1130a) CCI₂=CH₂

E-2-chloro-l,l,l,4,4,4-hexafluoro -2-butene (HCFO- E-CF₃CCI=CH₂CF₃

R-1326 1326mxz(E),

Z-2-chloro-l,l,l,4,4,4-hexafluoro -2-butene (HCFO- Z-CF₃CCI=CH₂CF3

R-1326 1326mxz(Z),

R-1327me l,l,l,2,4,4,4-hexafluoro-2-butene (HFO-1327me) CF₃CF=CH₂CF₃

R-1336mzz(E) E-1,1,1,4,4,4 hexafluoro-2-butene (HFO-1336mzz(E)) E-CF₃CH=CHCF₃

R-1336mzz(Z) Z-1,1,1,4,4,4 hexafluoro-2-butene (HFO-1336mzz(Z)) Z-CF₃CH=CHCF₃ EXAMPLES

Example 1

[0053] HCI recovery as anhydrous

Cat. /HF

CF3CHCICH2CCI3 - ⁱ

1336mzz(E)

[0054] In the first scenario, illustrated in Fig. 1, raw product feed 1 containing products, reaction intermediates, organic byproducts, HCI and trace HF (e.g., raw feed comprising, e.g., 346mdf, 1336mzz(E), 1336mzz(Z), , HCI, HF, COF2, 356mff, 133a,1327mz, CO2 can be sent to a distillation column, and high boilers are separated at the bottom of the column and removed through (2) and sent to another separation train (not shown). HCI and lower boilers are separated at the top of the column in line (3) and optionally passes through an absorbent bed (silica gel (amorphous silica including pyrogenic silica, precipitated silica and silica gel), or alumina) to obtain anhydrous HCI at >99% purity and substantially free of HF and organics as stream (4). Before passing through the silica gel, stream (3) may contain HF < 500 ppm, organic < 500 ppm. After passing the silica gel, the amount of HF< 50 ppm, < 10 ppm, < 5 ppm, < 1 ppm, organic < 50 ppm, < 5 ppm < 1 ppm.

[0055] Alternatively, in scenario 2 shown in Fig. 2, the anhydrous HCI stream (4) can be sent to an HCI absorber to make aqueous HCI at desired concentrations and substantially free of HF and organics as stream (5).

[0056] Alternatively, in scenario 3 shown in Fig. 3, the raw production mixture (feed) from reaction (1) is first sent to a HCI quench tank to decant the high boilers which are removed from the bottom of the tank through line (6) for additional purification. Volatile organics (7) are collected for additional purification and HCI solution (8) is sent to a separate tank with gas sparging to remove remain organics (9), optionally adding CaCh (10) (not shown) to remove HF to obtain aqueous HCI stream (11) at desired concentration and substantially free of HF and organics. Example 1A

[0057] HCI recovery as aqueous HCI:

[0058] Anhydrous hydrogen chloride (AHCI) made from Example 1 can be sent to a tank to make aqueous HCI solution in desired concentration.

Example 2

[0059] HCI recovery as aqueous solution via distillation

1316mxx(E) 13t6mxx Z)

(H)

[0060] Trichlorotrifluoroethane( CFC-113a, CCI3CF3) is converted to a mixture of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (a mixture of the (E) and (Z) isomers (E- HCFO-1316mxx and Z-HCFO-1316mxx)) by contacting trichlorotrifluoroethane with hydrogen in the presence of a hydrogenation catalyst according to the reaction scheme (II). The crude reaction product comprises 113a, 123, 143a, 1316mxx(Z), 1316mzz(E), trace HF, HCI, H2 is sent to a distillation column. 1316mxx(E) or 1316mxx(Z), 113a, H2, reaction byproducts such as 123 are separated at the bottom of the column and sent to another purification column. HCI containing trace amount of HF and low boiling organics , e.g., H2,143a are distilled off from the top of the column, and optionally pass through silica gel (amorphous silica including pyrogenic silica, precipitated silica or silica gel) to remove HF and COF2, followed by going through an aqueous HCI absorber for HCI collection. The final aqueous HCI purity is greater than 99% with HF < 20 ppm.

Example 2A

[0061] HCI recovery as aqueous solution from a Quench Tank

[0062] HCI recovery as aqueous solution: The reaction product mixture is sent to an aqueous quench tank. While 1316mxx(E) or 1316mxx(Z), 113a, reaction byproducts such as 123 are separated at the bottom of the reactor and sent to another purification column after drying. H2, 143a will be recycled after drying. Aqueous HCI is sparged for organic removal, optionally adding CaCI2 to remove HF. The final aqueous HCI purity is greater than 99% with HF < 20 ppm.

Example 3

[0063] HCI recovery as aqueous solution via distillation

¹243z^f _{(| | |)}

[0064] 1,1,1,3-Tetrachloropropane ( HCC-250fb, CCI3CH2CH2CI) is converted to a mixture of 3,3,3-trifluoroproene by contacting 250fb with Anhydrous HF in the presence of a fluorination catalyst according to the reaction scheme (III). The raw reaction product comprises 1243zf, 253fb, 1242zf, 1233zd, 1233zd(E), 1233zd(Z), 1233xf HF, HCI, optionally COF2, and/or CO2 ) is sent to a distillation column. 1243zf, 253fb, 1242zf, , 1233zd(E), 1233zd(Z), 1233xf, 254eb and 254fb HF are separated at the bottom of the column and sent to another purification column. HCI containing trace amount of HF and trace low boiling organics , e.g., 1243zf are distilled off from the top of the column, and optionally pass through silica gel (amorphous silica including pyrogenic silica, precipitated silica or silica gel) to remove HF and COF2, followed by going through an aqueous HCI absorber for HCI collection. The final aqueous HCI purity is greater than 99% with HF < 20 ppm.

CLAIM EMBODIMENTS:

[0065] A process embodiment comprising passing a fluorochemical product stream containing at least two of a fluoroolefin, fluorochloroolefin, HCFO, HFC, HCO, HCFC, chloroolefin product, HCI, HF and optionally COF2 and moisture to at least one distillation column, withdrawing an overhead stream from the column comprising at least HCI, HF and optionally COF2 and moisture, contacting the overhead stream with an absorber adapted to remove HF, moisture and optionally COF2, and withdrawing anhydrous HCI. [0066] A process embodiment comprising passing a fluorochemical product stream containing at least HCI, HF, and at least three of a fluoroolefin, fluorochloroolefin, HCFO, HFC, HCO, HCFC, chloroolefin and optionally one of CO2 COF2 to at least one distillation column, withdrawing an overhead stream from the column comprising at least HCI, HF and optionally COF2 and moisture, contacting the overhead stream with an absorber adapted to remove HF, moisture and optionally COF2, and withdrawing anhydrous HCI.

[0067] A composition embodiment comprising greater than 100 ppm and <500 ppm of HCI and/or HF, at least one of 346mdf, 1336mzz(E), 1336mzz(Z), 356mff, 133a,1327mz, and optionally one of COF2 and CO2.

[0068] A composition embodiment comprising greater than 100 ppm and <500 ppm of HCI and/or HF, at least two of 346mdf, 1336mzz(E), 1336mzz(Z), 356mff, 133a,1327mz, and optionally one of COF2 and CO2.

[0069] A composition embodiment comprising greater than 100 ppm and <500 ppm of HCI and/or HF, at least three of 346mdf, 1336mzz(E), 1336mzz(Z), 356mff, 133a,1327mz, and optionally one of COF2 and CO2.

[0070] A composition embodiment comprising greater than 100 ppm and <500 ppm of HCI and/or HF, at least four of 346mdf, 1336mzz(E), 1336mzz(Z), 356mff, 133a,1327mz, and optionally one of COF2 and CO2.

[0071] A composition embodiment comprising greater than 100 ppm and <500 ppm of HCI and/or HF, at least five of 346mdf, 1336mzz(E), 1336mzz(Z), 356mff, 133a,1327mz, and optionally one of COF2 and CO2.

[0072] A composition embodiment comprising 113a, 123, 143a, 1316mxx(Z), 1316mzz(E), HF, HCI, H₂

[0073] A composition embodiment consists essentially of at least one, two or three of 346mdf, 1336mzz(E),1336mzz(Z) 356mff, 133a,1327mz, at least one of HCI and HF, and optionally COF2 or CO2

[0074] A composition embodiment comprising HCI, trace amounts of HF, H2,143a and COF2. [0075] A composition embodiment comprising at least one of 1243zf, 253fb, 1242zf, 1233zd, 1233zd(E), 1233zd(Z), and 1233xf, HF, HCI, and optionally COF₂, and/or CO₂.

[0076] A composition embodiment comprising at least one of 1243zf, 253fb, 1242zf, 1233zd(E), 1233zd(Z), 1233xf, 254eb and 254fb, and HF.

[0077] A composition embodiment comprising 1243zf, 253fb, 1242zf, 1233zd, 1233zd(E), 1233zd(Z), and 1233xf, HF, HCI, and optionally COF2, and/or CO2 ).

[0078] A composition embodiment comprising 1243zf, 253fb, 1242zf, 1233zd(E), 1233zd(Z), 1233xf, 254eb and 254fb, and HF.

[0079] A process embodiment 1 comprising passing a fluorochemical product stream containing at least one of a fluoroolefin, fluorochloroolefin, HCFO, HFC, HCO, HCFC, chloroolefin product, HCI, HF and optionally COF₂ and moisture to at least one distillation column, withdrawing an overhead stream from the column comprising at least HCI, HF and optionally COF₂ and moisture, contacting the overhead stream with an absorber adapted to remove HF, moisture and optionally COF₂, and withdrawing anhydrous HCI.

[0080] The process embodiment Iwherein the HCI stream is substantially free of moisture and HF.

[0081] The process embodiment Iwherein the HCI stream includes less than 20 ppm of HF.

[0082] The process embodiment Iwherein the HCI stream includes less than 10 ppm of HF.

[0083] The process embodiment 1 wherein the HCI stream includes less than 1 ppm of HF.

[0084] Any process embodiment 1 wherein the HCI stream is anhydrous HCI.

[0085] Any process embodiment 1 wherein the absorber is silica gel comprising one of: amorphous silica, pyrogenic silica, precipitated silica and silica gel.

[0086] Any process embodiment 1 where the absorber is an alumina compound. [0087] Any process embodiment 1 where the absorber amorphous silica.

[0088] Any process embodiment 1 wherein there are two of more distillation columns.

[0089] The process embodiment 1 wherein distillation columns are in one of series or parallel.

[0090] The process embodiment 1 wherein and the overhead stream from a first distillation column is further purified to form a second overhead stream comprising HCI.

[0091] Any process embodiment wherein the absorber removes HF, moisture and COF₂.

[0092] A composition embodiment consisting essentially substantially pure of HCI containing between greater than 0 and <20 ppm, <10 ppm, <1 ppm, 0..1 ppm organics.

[0093] A composition embodiment of substantially pure HCI containing between greater than O and <20 ppm, <10 ppm, 1 ppm or 0.1 ppm organics.

[0094] An HCI composition embodiment containing > 99%, >99.5% or >99.9% HCI and between 0 and<20 ppm organics, between 0 and<10 ppm organics, between 0 and<5 ppm organics, between 0 and<1 ppm organics, or between 0 and<0.1 ppm organics

Claims

CLAIMS What is claimed is:

1. A process comprising passing a fluorochemical product stream containing at least one of a fluoroolefin, fluorochloroolefin, HCFO, HFC, HCO, HCFC, chloroolefin product, HCI, HF and optionally COF2 and moisture to at least one distillation column, withdrawing an overhead stream from the column comprising at least HCI, HF and optionally COF2 and moisture, contacting the overhead stream with an absorber adapted to remove HF, moisture and optionally COF2, and withdrawing anhydrous HCI.

2. The process of claim 1 wherein the HCI stream is substantially free of moisture and HF.

3. The process of claim 1 wherein the HCI stream includes less than 20 ppm of HF.

4. The process of claim 3 wherein the HCI stream includes less than 10 ppm of HF.

5. The process of claim 4 wherein the HCI stream includes less than 1 ppm of HF.

6. The process of any of claims 1-4 wherein the HCI stream is anhydrous HCI.

7. The process of claim 1 wherein the absorber is silica gel comprising one of: amorphous silica, pyrogenic silica, precipitated silica and silica gel.

8. The process of claim 1 with the absorber is an alumina compound.

9. The process of claim 1 where the absorber amorphous silica.

10. The process of claim 1 wherein there are two of more distillation columns.

11. The process of claim 11 wherein the distillation columns are in one of series or parallel.

12. The process of claim 1 wherein and the overhead stream from the first distillation column is further purified to form a second overhead stream comprising HCI.

13. The process of any of claims 1 and 7-9 wherein the absorber removes HF, moisture and COF2.

14. A system comprising, a. fluorochemical process reactor, b. first and second reactant flow lines connected to said reactor, wherein the first flow line is connected to and in fluid communication with a contained source of HF or hydrogen and the second flowline is connected in flow communication with a source chloro(fluoro)organic material., and a discharge line for withdrawing the reactor product mixture, c. at least one of a distillation column and/or a decanter, said discharge line being connected directly to one said distillation column or decanter, wherein the distillation column comprises an overhead line, d. optionally at least one absorber unit connected to and in flow communication with said overhead line of said distillation column., e. optional purification units connected to and in flow communication with said overhead line of said distillation column, wherein said absorber includes one of silica gel, alumina or and optionally at least one of moisture and COF2.

15. The system for performing the process of claim 1 including a distillation column and an absorber unit comprising an alumina compound.

16. The system for performing the process of claim 1 including a distillation column and an absorber unit comprising amorphous silica.

17. The system for performing the process of claim 1 including a distillation column and a unit absorber comprising a silica gel compound selected from one of amorphous silica, pyrogenic silica, precipitated silica and silica gel.

18. The system for performing the process of claim 8 wherein the are at least two different absorber units selected from silica gel, or alumina are present.

19. The system for performing the process of claim 7 wherein the fluorochemical process comprises fluorination of 1 ,1 ,1 ,3-tetrachoropropane to 3,3,3- trifluropropene and HCI

20. The process of claim 1 wherein the fluorochemical process comprises catalytic hydrogenation of 1 ,1 ,1-trifluoro-2-2-2-trichloroethane to 2,4-dichloro-1 , 1 , 1 ,4,4,4— hexafluoro-2-butene (E) and 1,1,1,4,4,4-hexafluoro-2-butene and 2,4-dichloro- 1,1 ,1,4,4,4-hexafluoro-2-butene (Z) and HCI.

21. The process of claim 1 wherein the fluorochemical process comprises catalytic fluorination of 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene and HCI

22. The process of claim 1 wherein the fluorochemical process comprises catalytic fluorination of 2,3-dichloro-1 ,1 ,1 -trifluoropropane to 2-chloro-1 ,1 ,1 ,3 tetrafluoropropane:.

23. The process of claim 1 wherein the fluorochemical process comprises catalytic fluorination of 1 ,1,3-trichloro-4,4,4-trifluorobut-1-ene (343jfd) to trans-1, 1 ,1, 4,4,4- hexafluoro-2-butene and HCI.

24. The process of any of claims 1-13 wherein the HCI is anhydrous HCI having a purity of at least 98% by weight.

25. The process of any of claims 1-13 wherein the HCI is anhydrous HCI having a purity of at least 99% by weight.

26. The process of any of claims 1-13 wherein the HCI is anhydrous HCI having a purity of >99.5% or greater than 99.9% by weight.

27. The process of any of claims 1-13 wherein the HCI is anhydrous HCI and is converted to aqueous HCI at a concentration selected from one of 10%, 20%, 30%, 40%, or 50%.

28. A composition comprising greater than 100 ppm and <500 ppm of HCI and/or HF, at least one of 346mdf, 1336mzz(E), 1336mzz(Z), 356mff, 133a,1327mz, and optionally one of COF2 and CO2.

29. A composition comprising 113a, 123, 143a, 1316mxx(Z), 1316mzz(E), HF, HCI, H₂

30. A composition consists essentially of at least one, two or three of 346mdf, 1336mzz(E),1336mzz(Z) 356mff, 133a,1327mz, at least one of HCI and HF, and optionally COF2.

31. A composition comprising HCI, trace amounts of HF, H2,143a and optionally COF₂.

32. A composition consisting essentially of HCI substantially free of organics to < 20 ppm.

33. The composition of claim 32, with less than 10ppm organics.

34. The composition of claim 32, with less than 5 ppm organics.

35. A process comprising contacting a fluorochemical product stream containing at least one of a fluoroolefin, fluorochloroolefin, HCFO, HFC, HCO, HCFC, chloroolefin product, HCI, HF and optionally COF2 and moisture with a membrane.

36. The process of claim 35, wherein the membrane is an ion exchange membrane.

37. The process of claim 36, wherein the ion exchange membrane is a fluorinated ion exchange membrane.