Treatment of waste water containing fluorine species

Abstract

The present invention describe a waste water treatment process to obtain clean water from waste water containing fluorine species from fluorochemical processes.

Description

TREATMENT OF WASTE WATER CONTAINING FLUORINE SPECIES

[0001] The present invention describes a waste water treatment process to obtain clean water from waste water containing fluorine species.BACKGROUND

[0002] The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents and propellants. These new compounds, such as HFC refrigerants, HFC-134a and HFC-125 being the most widely used at this time, have zero ozone depletion potential but generally have relatively highly global warming potentials.

[0003] Since there is a new for have low ODP and GWP properties certain hydrofluoroolefins are believed to meet both goals. Thus, there is a need for manufacturing processes that provide hydrofluoroolefins or hydrochlorofluoroolefines that also have a low global warming potential.

[0004] In addition, fluoro(chloro)olefins such as TFE, CTFE, vinylidene fluoride, vinyl fluoride, etc. are monomers to make fluorinated polymer. Furthermore, fluorinated molecules are widely used in pharmaceutical and agrochemicals. Processes for producing fluorinated molecules include both vapor phase and liquid phase reactions.

[0005] In the liquid phase process or gas phase process of fluorinated products, it often involves the use of aqueous solution, either as part of reaction media, or scrubber solution in downstream purification, etc. The waste-water generated in these processes usually contains fluorine species such as fluoride and other water soluble fluorinated molecules or salts, these fluorine species pose significant environmental concerns. Although attempts have been made to remove the fluorinated species using, for example, Ca(2+) ion organic fluoride species aredifficult to remove. One example is reported in US20130161264A1 which uses brine containing both calcium salt and magnesium salt. Other attempts to provide clean waste water using absorbent have been tried, but are not as successful as hoped. However, these methods do not work well with water soluble fluorinated small molecules such as fluorinated acids, fluorinated ketone, fluorinated esters or fluorinated alcohol have not been successful. Other attempts using ion exchange technology can be effective in some cases but it is expensive. Thus, there remains a need to be able to remove water soluble and organic fluorine containing species including fluorinated esters or fluorinated ketones.SUMMARY

[0006] The present invention relates to waste water treatment processes to obtain clean water free or substantially free of fluorine species.

[0007] The present invention processes for obtaining clean water from waste water which contains one or more fluorine species having 1 to 6 carbon atoms.

[0008] The present invention processes for obtaining clean water from waste water which contains fluorine species. The fluorine species may comprise, but is not limited to one or more of: E- and / or Z-1 ,1 ,1 ,4,4,4-hexafluoro-2-chloro-2-butene (E- and / or Z-HFCO-1326mxz), E- and / or Z-2,3-dichloro-1, 1 ,1 , 4,4, 4-hexafluoro-2-butene (E- and / or Z-1316mxx), 2-chloro-1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb), 2- chloro-3,3,3-trifluoropropene (HCFO-1233xf), Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z), E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), 2-chloro- 1 , 1 ,1 ,4,4,4-hexafluorobutane (HFC-346mdf ), 2,3-dichloro-1 ,1 , 1 ,4,4,4- hexafluorobutane (HCFC-336mdd), hexafluoroacetone, trifluoroacetone, perfluoro(2- methyl-3-pentanone).

[0009] The present invention processes for obtaining clean water from waste water which contains fluorine species. The fluorine species may comprise, but is not limited to one or more of:HFO-1327mz (1,1 ,1 ,2,4,4,4-heptafluorobut-2-ene),HFO-1325lxz (1 ,2-dichloro-1,1 ,4,4,4-pentafluorobut-2-ene),HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane),HFC-336maf (2,2-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane),HFC-336lbf (1 ,2-dichloro-1 ,1 ,2,4,4,4-hexafluorobutane),HFC-337mbf (2-chloro-1 ,1 ,1 ,2,4,4,4-heptafluorobutane),HFC-337mde (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobutane),HFC-356mff (1 ,1 ,1 ,4,4,4-hexafluorobutane),HFC-346mdf (2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane),HFC-338mf (1 ,1 ,1 ,2,2,4,4,4-octafluorobutane,HCFC-1122 (2-chloro-1 ,1-difluoroethylene),H C FC- 124 (2-ch loro- 1 , 1 , 1 , 2-tetra f I uoroethane) ,CFC-114 (1 ,2-dichloro-1 , 1 ,2,2-tetrafluoroethane),CFC-113 (1 , 1 ,2-trichloro- 1 ,2,2-trifluoroethane),CFC-133a (2-chloro-1 ,1 ,1-trifluoroethane),CFC-123 (2, 2-dichloro-1 , 1 ,1 -trifluoroethane),CFC-123a (1 ,2-dichloro-1 ,1 ,2-trifluoroethane),CFC-122 (1 , 2, 2-trichloro-1 , 1 -difluoroethane),CFC-112a (1 ,1 ,1 ,2-tetrachloro-2,2-difluoroethane),HCFC-224db (1 ,1,1 ,3-tetrafluoro-2,3,3-trichloropropane,HFC-225da (1 ,2-dichloro-1 , 1 ,3,3,3-pentafluoropropane),HFC-235da (2-chloro-1 ,1 ,1 ,3,3-pentafluoropropane),HFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane),HFC-236fa (1 ,1 ,1 ,3,3, 3-hexafluoropropane), andE- and Z-CFO-1317mx (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobut-2-ene).E-1 ,2,3-trichloro-1 ,1 ,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx);Z-1 , 2 ,3-trichloro- 1 ,1 ,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx);E-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (E-CFC-1314kxx); andZ-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (Z-CFC-1314kxx).

[0010] One embodiment of the invention relates to a waste water treatment process which comprises phase separation, treatment of the water with base and heating in a batch reactor or a CSTR. The fluorinated waste is converted into nontoxic trifluoroacetate or fluoride or the mixture thereof. The final step is to remove the F- by calcium ion.

[0011] In certain embodiment the base is selected from alkali metal bases, wherein the metal comprises one of sodium, potassium, cesium, rubidium or combinations thereof, preferably KOH and NaOH, including alkaline earth hydroxides such as calcium hydroxide, lithium hydroxide, magnesium hydroxide.

[0012] In one embodiment disclosed herein the pH of fluorochemical process waste water is determined and then optionally separated into organic and aqueous phase, provided an organic layer is present. In the presence of organics, the separation involves decanting gross organics, and recycling the organic back to the reactor, or sending the organics to a thermal converter. If a gross organic layer is not present the waste water liquid is sparged with air or N2 sparging and the overhead containing volatile organics are fed to a thermal converter.

[0013] One embodiment disclosed herein relates to processes of obtaining a liquid waste water phase, adjusting the pH of the phase with a base and forming an aqueous mixture having a pH of between 9 and 14, heating the aqueous mixture to a temperature of 80°C and 100°C and then adding sufficient HCI to adjust the pH of 8.5.

[0014] In another embodiment the 8.5 adjusted pH mixture is brought into contact with an alkaline earth halide to remove fluoride ions CaCh, Ca(OAc).

[0015] In another embodiment the 8.5 adjusted pH mixture is brought into contact with an alkaline earth halide selected from calcium chloride to remove fluoride ions, and then separating the solid CaCh reaction product to produce clean water substantially free of fluorine ions.

[0016] The various embodiments of the invention can be used alone or in combinations with each other. The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.DETAILED DESCRIPTION

[0017] Before addressing details of embodiments described herein, some terms are defined or clarified as follows.

[0018] 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.

[0019] The term “hydrohaloalkane,” as used herein means a molecule containing hydrogen, carbon, fluorine and / or chlorine and / or bromine and / or iodine, with no carbon-carbon double bond (halo=fluoro, chloro, bromo, iodo). Examples are described throughout the instant specification.

[0020] 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.

[0021] As used herein TOC (total organic carbon) is defined consistent with5310: TOTAL ORGANIC CARBON (TOC) at pages 5-19- to 5-20, and High-Temperature Combustion Method 5310-B pages 5-21 to 5-23 are respectively incorporated herein by reference in its entirety.

[0022] 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 composition, 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 composition, process, method, article, or apparatus. Further, unless expressly statedto 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 are true (or present).

[0023] 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.

[0024] 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.”

[0025] 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.”

[0026] 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.

[0027] As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value). All measurements reported herein are understood to be modified by the term “about,” whether or not the term is explicitly used, unless explicitly stated otherwise, 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.

[0028] As used herein, the term “substantially free” means that less than about 0.0005 percent by weight is present (5 ppm).

[0029] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. 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.

[0030] In one embodiment disclosed herein the pH of fluorochemical process waste water is determined and then separated into organic and aqueous phase.

[0031] In one embodiment disclosed herein the pH of fluorochemical process waste water is determined and then separated into organic and aqueous phase and the pH of the separated aqueous waste water is adjusted to 13.5. In one embodiment a sufficient amount of an alkali metal hydroxide is added to adjust the pH to 13.5. In one embodiment the alkali metal comprises sodium or potassium.

[0032] In another embodiment the pH of fluorochemical process waste water is determined and then separated into organic and aqueous phase and the pH of the separated aqueous waste water is adjusted to a pH range 12 to 14, 13 to 14,13.5 to 14, and all values and ranges therebetween, e.g., a pH of 12, 12,5, 13, 13.5, or 14.

[0033] In one embodiment, an alkali metal hydroxide is added to adjust the pH adjusted and the resulting mixture is heated to between to 80°C and 100°C. In one embodiment, heating is conducted at a temperature of about 90°C for a period of at least 30 minutes up to about 120 minutes.

[0034] In another embodiment the pH of fluorochemical process waste water is determined and then separated into organic and aqueous phase and the pH of the separated aqueous waste water is adjusted to 13.5. In one embodiment, an alkali metal hydroxide is added to adjust the pH adjusted and the resulting mixture isheated to between to 80°C and 100°C. In one embodiment, heating is conducted at a temperature of about 90°C for a period of at least 30 minutes up to about 90 minutes and then HCI is added to adjust the heated mixture pH to a range of 7-9, 8-9 and all values and ranges therebetween, e.g., 7, 7.5, 8, or 8.5,.

[0035] In another embodiment the pH of fluorochemical process waste water is determined and then separated into organic and aqueous phase and the pH of the separated aqueous waste water is adjusted to 13.5. In one embodiment, an alkali metal hydroxide is added to adjust the pH adjusted and the resulting mixture is heated to between to 80°C and 100°C. In one embodiment, heating is conducted at a temperature of about 90°C for a period of at least 30 minutes up to about 90 minutes and then HCI is added to adjust the heated mixture pH to 8.5, an alkaline earth halide is used to removed fluoride ions.EXAMPLESExample 1

[0036] KOH aqueous solution (120 mL, 1.2 mol) was added to the mixture of Z- 1326 / E-1326mxz (E- and / or Z- 1 ,1, 1 ,4, 4, 4-hexafluoro-2-chloro-2-butene ((E- and / or Z-HFCO-1326mxz)) (200 g, 1 mol) and water (180 mL) in the presence of 35 g fresh KCI and Aliquat® 336 (5.3 g, 0.01325 mol) at 35°C. The reaction temperature was raised to 50°C after the addition, and gas chromatography was used to monitor the reaction. The reaction was completed after 1. hour and 70 g product (conversion: 50%; yield: 87%) was collected in a dry ice trap. The reaction mixture was phase separated into two layers. The organic layer was used for recycling. The aqueous layer was subjected to the treatment involving one or more of basic pH adjustment, heating, sparging and pH readjustment, followed by contact with an alkaline halide and filtration.

[0037] The wastewater generated from the above containing fluoride, water soluble small organic molecules trifluoroacetone, 1326mxz(E), 1326mxz which was subjected for wastewater treatment.1) Measure pH of waste water2) Separate both organic and aqueous phase as needed3) Adjust the waste water pH to 13.5 with KOH (or NaOH)4) Heat the waste water to 90°C for 1 hr5) Adjust the pH to 8.5 with HCI6) Add CaCh solution to precipitate F- out of solution7) Filter the solution and adjust the pH to neutral

[0038] Control 1 : the waste water above went through the following steps:1) Measure pH of waste water2) Separate both organic and aqueous phase as needed3) Adjust pH to 8.5 with HCI4) Add CaC solution to precipitate F- out of solution5) Filter the solution and adjust the pH to neutralExample 2

[0039] KOH aqueous solution (120 mL, 1.2 mol) was added to the mixture of Z- 1326 / E-1326mxz (E- and / or Z- 1 ,1, 1 ,4, 4, 4-hexafluoro-2-chloro-2-butene ((E- and / or Z-HFCO-1326mxz)) (200 g, 1 mol) and water (180 mL) in the presence of 35 g fresh KCI and Aliquat® 336 (5.3 g, 0.01325 mol) at 35°C. The reaction temperature was raised to 50°C after the addition, and gas chromatography was used to monitor the reaction. The reaction was completed after 1. hour and 58 g product (conversion: 40%; yield: 90%) was collected in a dry ice trap. The reaction mixture was phase separated into two layers. The organic layer was used for recycling. The aqueous layer was subjected to the treatment involving one or more of basic pH adjustment, heating, sparging and pH readjustment, followed by contact with an alkaline halide and filtration.

[0040] The wastewater generated from the above containing fluoride, water soluble small organic molecules trifluoroacetone, 1326mxz(E), 1326mxz which was subjected for wastewater treatment.1. M eas u re p H of waste wate r2. Separate both organic and aqueous phase as needed3. Adjust the waste water pH to 13.5 with KOH (or NaOH)4. Heat the waste water to 90°C for 1 hr5. Adjust the pH to 8.5 with HCI6. Add CaC solution to precipitate F’ out of solution7. Filter the solution and adjust the pH to neutralControl 2: the waste water above went through the following steps:1 ) M eas u re p H of waste wate r2) Separate both organic and aqueous phase as needed3) adjust pH to 8.5 with HCI4) sparging the aqueous solution via N2 for 60 minutes5) Add CaCh solution to precipitate F- out of solution6) Filter the solution and adjust the pH to neutral

[0041] Date from Examples 1 and 2, as well as Controls 1 and 2, are provided in the table below

[0042] The data above has shown that just by neutralization, fluoride removal, or in combination with inert gas sparging, sparging has minimum impact on TOC and inorganic carbon reduction. The most effective treatment involves pH adjustment , heating, fluoride removal.CLAIM EMBODIMENTS (D- (N)

[0043] (1) A process embodiment (1) comprising, a. providing a fluorochemical waste water stream, b. optionally separating the waste water stream into an aqueous phase or an organic phase,c. adjusting the aqueous phase to a basic pH, d. heating the pH adjusted phase to a temperature of 50 to 100 to form a heated mixture, e. adjusting the pH of the heated mixture with HCI, f. contacting the pH adjusted mixture with an alkaline earth metal halide, g. recovering substantially F ion free water from step f. wherein the waste water is optionally sparged prior to heating, during heating or after heating to remove volatile organics which are passed to a thermoconverter.

[0044] (2) The process embodiment (1) wherein the TOC of the fluorochemical waste water stream and water recovered from step g are measured.

[0045] (3) The process embodiment (1) wherein the TOC of the fluorochemical waste water stream and water recovered from step g are measured.

[0046] (4) Any of the process embodiments (1) -(3) the TOC is reduced by over60%.

[0047] (5) The process embodiment (1) wherein fluoride ion content is reduced by99%.

[0048] (6) Any of the process embodiments (1 )-(5) wherein step d, the heating is conducted at a temperature of between 50°C and 100°C.

[0049] (7) Any of the process embodiments (1 )-(6) wherein step d, the heating is conducted at a temperature of about 90°C.

[0050] (8) Any of the process embodiments (1 )-(7) step f, wherein the alkaline earth metal comprises at least one of Ca and Mg

[0051] (9) Any of the process embodiments (1 )-(8) step f, wherein the halide of the alkaline earth metal is a halide selected from one of Cl, Br or I, preferably Cl.

[0052] (10) Any of the process embodiments (1 )-(9) wherein the TOC of the fluorochemical waste water stream and water recovered from step g are measured.

[0053] (11) Any of the process embodiments (1 )-(10) wherein the TOC is reduced by over 60%.

[0054] (12) The process embodiment 1 wherein fluoride ion content is reduced to less than 10 ppm, preferably 1 ppm, most preferably less than 0.1 ppm.

[0055] (13) The process of claim 13 wherein fluoride ion content is reduced to less than 10 ppm, preferably 1 ppm, most preferably less than 0.1 ppm.

[0056] (14) The process embodiment Iwherein the waste water is sparged prior to heating.

[0057] (15) The process embodiment 1 wherein the waste water is sparged during heating.

[0058] (16) The process embodiment Iwherein the waste water is sparged after heat heating.

[0059] (17) Any of the process embodiments (14)-(16) wherein sparging is conducted with on or air or nitrogen.

[0060] (18) The process embodiment 17 wherein the sparging produces organic volatiles which are withdrawn.

[0061] (19) The process embodiment 18 wherein the withdrawn organic volatiles are passed to a thermoconverter.

[0062] (20) Any of the process embodiments (1 )-(19) , wherein the basic pH of step “(c)”is selected from one of a pH range 12 to 14, a pH range of 13 to 14, a pH range of 13.5 to 14, or a pH of about 12, about 12,5, about 13, about 13.5, or about 14, or a pH of 12, or 12,5, or 13, or 13.5, or 14.

[0063] (21) Any of the process embodiments (1 )-(20) , wherein the pH of step“(e)”is selected from one of a pH range of 7-9, a pH range of 8-9 , a pH of about 7, about 7.5, about 8, or about 8.5, or a pH of 7, 7.5, 8, or 8.5.

[0064] (22) Any of the process embodiments (1 )-(21 ) , wherein the fluorine species comprises one or more of: E- and / or Z- 1,1, 1 ,4,4, 4-hexafluoro-2-chloro-2- butene (E- and / or Z-HFCO-1326mxz).

[0065] (23) The process of embodiments (22), wherein the fluorine species comprises E-1 ,1 ,1 ,4,4,4-hexafluoro-2-chloro-2-butene (E-HFCO-1326mxz).

[0066] (24) The process of embodiments (22), wherein the fluorine species comprises Z-1 ,1 ,1 ,4,4,4-hexafluoro-2-chloro-2-butene (Z-HFCO-1326mxz).

[0067] (25) The process of embodiments (22), wherein the fluorine species comprises E-1 ,1 ,1 ,4,4,4-hexafluoro-2-chloro-2-butene (E-HFCO-1326mxz) and Z-1 .1 .1 .4.4.4-hexafluoro-2-chloro-2-butene (Z-HFCO-1326mxz).

[0068] (26) Any of the process embodiments (1 )-(21 ) , wherein the fluorine species comprises one or more of: E- and / or Z-2,3-dichloro-1 ,1, 1 ,4,4,4-hexafluoro-2- butene (E- and / or Z-HCFO-1316mxx), 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC- 244bb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Z-1-chloro-3,3,3- trifluoropropene (HCFO-1233zd(Z), E-1-chloro-3,3,3-trifluoropropene (HCFO- 1233zd(E)), 2-chloro-1 ,1 , 1,4,4,4-hexafluorobutane (HFC-346mdf ), 2,3-dichloro-1.1.1.4.4.4-hexafluorobutane (HCFC-336mdd), hexafluoroacetone, trifluoroacetone, perfluoro(2-methyl-3-pentanone).

[0069] (27) The process of embodiment (26), wherein the fluorine species comprises one or more of: E- and / or Z-1 ,1 ,1 ,4,4,4-hexafluoro-2,3-dichloro-2-butene (E- and / or Z-HFCO-1316mxx).

[0070] (28) The process of embodiments (27), wherein the fluorine species comprises E-1 ,1 ,1 ,4,4,4-hexafluoro-2,3-dichloro-2-butene (E-HFCO-1316mxx).

[0071] (29) The process of embodiments (27), wherein the fluorine species comprises Z-1 ,1 ,1 ,4,4,4-hexafluoro-2,3-dichloro-2-butene (Z-HFCO-1316mxx).

[0072] (30) The process of embodiments (27), wherein the fluorine species comprises E-1 ,1 ,1 ,4,4,4-hexafluoro-2,3-dichloro-2-butene (E-HFCO-1316mxx) and Z-1 , 1 ,1 ,4,4,4-hexafluoro-2,3-dichloro-2-butene (Z-HFCO-1316mxx).

[0073] (31) The process of embodiment (26) wherein the fluorine species comprises 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC-244bb).

[0074] (32) The process of embodiment (26) wherein the fluorine species comprises 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0075] (33) The process of embodiment (26) wherein the fluorine species comprises Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z).

[0076] (34) The process of embodiment (26) wherein the fluorine species comprises E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)).

[0077] (36) The process of embodiment (26) wherein the fluorine species comprises 2-chloro-1,1 ,1 ,4,4,4-hexafluorobutane (HFC-346mdf ).

[0078] (36) The process of embodiment (26) wherein the fluorine species comprises 2,3-dichloro-1 ,1 ,1,4,4,4-hexafluorobutane (HCFC-336mdd).

[0079] (37) The process of embodiment (26) wherein the fluorine species comprises hexafluoroacetone.

[0080] (38) The process of embodiment (26) wherein the fluorine species comprises trifluoroacetone.

[0081] (39) The process of embodiment (26) wherein the fluorine species comprises perfluoro(2-methyl-3-pentanone).

[0082] (40) Any of the process embodiments (1 )-(21 ) , wherein the fluorine species comprises one or more of:HFO-1327mz (1 ,1 ,1 ,2,4,4,4-heptafluorobut-2-ene),HFO-1325lxz (1 ,2-dichloro-1 ,1 ,4,4,4-pentafluorobut-2-ene),HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),HFC-336maf (2,2-dichloro-1 ,1,1 ,4,4,4-hexafluorobutane),HFC-336lbf (1 ,2-dichloro-1 , 1 ,2,4,4,4-hexafluorobutane),HFC-337mbf (2-chloro-1,1 ,1 ,2,4,4,4-heptafluorobutane),HFC-337mde (2-chloro-1 ,1,1 ,3,4,4,4-heptafluorobutane),HFC-356mff (1,1,1 ,4,4,4-hexafluorobutane),HFC-338mf (1 ,1 ,1 ,2,2,4,4,4-octafluorobutane,HCFO-1122 (2-chloro-1 , 1-difluoroethylene),HCFC-124 (2-chloro-1,1 ,1 ,2-tetrafluoroethane),CFC-114 (1 ,2-dichloro-1 , 1 ,2,2-tetrafluoroethane),CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane),C FC- 133a (2- chi oro- 1 , 1 , 1 -trif I uoroethane) ,CFC-123 (2, 2-dichloro- 1 ,1 ,1 -trifluoroethane),CFC-123a (1 ,2-dichloro-1 ,1 ,2-trifluoroethane),CFC-122 (1 , 2, 2-trichloro-1 , 1 -difluoroethane),CFC-112a (1 ,1 ,1 ,2-tetrachloro-2,2-difluoroethane),HCFC-224db (1 ,1,1 ,3-tetrafluoro-2,3,3-trichloropropane,HFC-225da (1 ,2-dichloro-1, 1 ,3,3,3-pentafluoropropane),HFC-235da (2-chloro-1 ,1 ,1 ,3,3-pentafluoropropane),HFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane),HFC-236fa (1 ,1 ,1 ,3,3, 3-hexafluoropropane),E- and Z-CFO-1317mx (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobut-2-ene).E-1 ,2,3-trichloro-1 ,1 ,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx);Z-1 ,2,3-trichloro-1 ,1 ,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx);E-1 , 1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (E-CFC-1314kxx); and Z-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (Z-CFC-1314kxx).

[0083] (41) The process of embodiment (40) wherein the fluorine species comprises HFO-1327mz (1 ,1 ,1 ,2,4,4,4-heptafluorobut-2-ene),

[0084] (42) The process of embodiment (40) wherein the fluorine species comprises HFO-1325lxz (1 , 2-dichloro- 1 , 1 ,4,4,4-pentafluorobut-2-ene)

[0085] (43) The process of embodiment (40) wherein the fluorine species comprisesHFO-1325dx (1 ,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene).

[0086] (44) The process of embodiment (40) wherein the fluorine species comprises HFC-336maf (2,2-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane).

[0087] (45) The process of embodiment (40) wherein the fluorine species comprises HFC-336lbf (1 ,2-dichloro-1 , 1 ,2,4,4,4-hexafluorobutane).

[0088] (46) The process of embodiment (40) wherein the fluorine species comprises HFC-337mbf (2-chloro-1 ,1 ,1 ,2,4,4,4-heptafluorobutane).

[0089] (47) The process of embodiment (40) wherein the fluorine species comprises HFC-337mde (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobutane).

[0090] (48) The process of embodiment (40) wherein the fluorine species comprises HFC-356mff (1 ,1 ,1 ,4,4,4-hexafluorobutane).

[0091] (49) The process of embodiment (40) wherein the fluorine species comprises HFC-338mf (1,1,1 ,2,2,4,4,4-octafluorobutane.

[0092] (50) The process of embodiment (40) wherein the fluorine species comprises HCFO-1122 (2-chloro-1,1 -difluoroethylene).

[0093] (51) The process of embodiment (40) wherein the fluorine species comprises HCFC-124 (2-chloro-1 ,1,1 ,2-tetrafluoroethane).

[0094] (52) The process of embodiment (40) wherein the fluorine species comprises CFC-114 (1 ,2-dichloro-1 ,1 ,2,2-tetrafluoroethane).

[0095] (53) The process of embodiment (40) wherein the fluorine species comprises CFC-113 (1 ,1,2-trichloro-1,2,2-trifluoroethane).

[0096] (54) The process of embodiment (40) wherein the fluorine species comprises CFC-133a (2-chloro-1 ,1,1-trifluoroethane).

[0097] (55) The process of embodiment (40) wherein the fluorine species comprises CFC-123 (2,2-dichloro-1,1 ,1-trifluoroethane).

[0098] (56) The process of embodiment (40) wherein the fluorine species comprises CFC-123a (1,2-dichloro-1,1,2-trifluoroethane).

[0099] (57) The process of embodiment (40) wherein the fluorine species comprises CFC-122 (1 ,2,2-trichloro-1,1-difluoroethane).

[0100] (58) The process of embodiment (40) wherein the fluorine species comprises CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane).

[0101] (59) The process of embodiment (40) wherein the fluorine species comprises HCFC-224db (1,1,1 ,3-tetrafluoro-2,3,3-trichloropropane.

[0102] (60) The process of embodiment (40) wherein the fluorine species comprises HFC-225da (1,2-dichloro-1 ,1 ,3,3,3-pentafluoropropane).

[0103] (61) The process of embodiment (40) wherein the fluorine species comprises HFC-235da (2-chloro-1 ,1 ,1,3,3-pentafluoropropane).

[0104] (62) The process of embodiment (40) wherein the fluorine species comprises HFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane).

[0105] (63) The process of embodiment (40) wherein the fluorine species comprises HFC-236fa (1 ,1 ,1 ,3,3,3-hexafluoropropane).

[0106] (64) The process of embodiment (40) wherein the fluorine species comprises E- and Z-CFO-1317mx (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobut-2-ene).

[0107] (65) The process of embodiment (40) wherein the fluorine species comprises E-1 ,2,3-trichloro-1 ,1 ,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx).

[0108] (66) The process of embodiment (40) wherein the fluorine species comprises Z-1 ,2,3-trichloro-1 ,1 ,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx).

[0109] (67) A purified water composition produced by any of the process embodiments (1)-(20).

[0110] (68) The process embodiment (20) wherein sparging the media at temperatures greater than 60°C is achieved either by heating the media or sparging with hot inert gas such as N2.

[0111] Although certain aspects, embodiments and principals have been described above, it is understood that this description is made only way of example and not as limitation of the scope of the invention or appended claims. The foregoing various aspects, embodiments and principals can be used alone and in combinations with each other.

Claims

CLAIMSWhat is claimed is:

1. A process comprising, a. providing a fluorochemical waste water stream, b. optionally separating the waste water stream into an aqueous phase or an organic phase, c. adjusting the aqueous phase to a basic pH, d. heating the pH adjusted phase to a temperature of 50 to 100 to form a heated mixture, e. adjusting the pH of the heated mixture with HCI, f. contacting the pH adjusted mixture with an alkaline earth metal halide, g. recovering substantially F ion free water from step f. wherein the waste water is optionally sparged prior to heating, during heating or after heating to remove volatile organics which are passed to a thermoconverter.

2. The process of claim 1 wherein the TOC of the fluorochemical waste water stream and water recovered are measured.

3. The process of claim 1 wherein the TOC of the fluorochemical waste water stream and water recovered from step g are measured.

4. The process of claim 2 wherein the TOC is reduced by over 60%.

5. The process of claim 1 wherein fluoride ion content is reduced by 99%6. The process of step d wherein the heating is conducted at a temperature of between 50°C and 100°C.

7. The process of step d wherein the heating is conducted at a temperature of about 90°C.

8. The process of step f wherein the alkaline earth metal comprises at least one of Ca and Mg.

9. The process of step f wherein the halide of the alkaline earth metal is a halide selected from one of Cl, Br or I, preferably Cl.

10. The process of claim 9 wherein the TOC of the fluorochemical waste water stream and water recovered from step g are measure.

11. The process of claim 10 wherein the TOC of the fluorochemical waste water stream and water recovered from step are measured.

12. The process of claim 11 wherein the TOC is reduced by over 60%.

13. The process of claim 13 wherein fluoride ion content is reduced to less than 10 ppm, preferably 1 ppm, most preferably less than 0.1 ppm.

14. The process of claim 1 wherein the waste water is sparged prior to heating.

15. The process of claim 1 wherein the waste water is sparged during heating.

16. The process of claim 1 wherein the waste water is sparged after heat heating.

17. The process of any of claims 14-16 wherein sparging is conducted with on or air or nitrogen.

18. The process of 17 wherein the sparging produces organic volatiles which are withdrawn.

19. The process of 18 wherein the withdrawn organic volatiles are passed to a thermoconverter.

20. The process of any of claims 1-19, wherein the basic pH of step “(c)”is selected from one of a pH range 12 to 14, a pH range of 13 to 14, a pH range of 13.5 to 14, or a pH of about 12, about 12,5, about 13, about 13.5, or about 14, or a pH of 12, or 12,5, or 13, or 13.5, or 14.

21. The process of any of claims 1-20, wherein the pH of step “(e)”is selected from one of a pH range of 7-9, a pH range of 8-9 , a pH of about 7, about 7.5, about 8, or about 8.5, or a pH of 7, 7.5, 8, or 8.5.

22. The process of any of claims 1-21, wherein, wherein the fluorine species comprises one or more of: E- and / or Z-1 , 1,1 , 4,4, 4-hexafluoro-2-chloro-2- butene (E- and / or Z-HFCO-1326mxz).

23. The process of claim 22, wherein the fluorine species comprises E- 1,1 ,1,4,4,4-hexafluoro-2-chloro-2-butene (E-HFCO-1326mxz).

24. The process of claim 22, wherein the fluorine species comprises Z-1,1 ,1,4,4,4-hexafluoro-2-chloro-2-butene (Z-HFCO-1326mxz).

25. The process of claim 22, wherein the fluorine species comprises E-1,1 ,1,4,4,4-hexafluoro-2-chloro-2-butene (E-HFCO-1326mxz) and Z-1.1.1.4.4.4-hexafluoro-2-chloro-2-butene (Z-HFCO-1326mxz).

26. The process of any of claims 1-21, wherein the fluorine species comprises one or more of: E- and / or Z-2,3-dichloro-1,1 ,1 ,4,4,4-hexafluoro-2-butene (E- and / or Z-HCFO-1316mxx), 2-chloro-1 ,1,1 ,2-tetrafluoropropane (HCFC- 244bb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Z-1-chloro-3,3,3- trifluoropropene (HCFO-1233zd(Z), E-1-chloro-3,3,3-trifluoropropene (HCFO- 1233zd(E)), 2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346mdf ), 2,3- dichloro-1 , 1 , 1 ,4,4,4-hexafluorobutane (HCFC-336mdd), hexafluoroacetone, trifluoroacetone, perfluoro(2-methyl-3-pentanone).

27. The process of claim 26, wherein the fluorine species comprises one or more of: E- and / or Z-1 , 1 , 1 ,4,4,4-hexafluoro-2,3-dichloro-2-butene (E- and / or Z- HFCO-1316mxx).

28. The process of claim 27, wherein the fluorine species comprises E-1.1.1.4.4.4-hexafluoro-2,3-dichloro-2-butene (E-HFCO-1316mxx).

29. The process of claim 27, wherein the fluorine species comprises Z-1,1 ,1 ,4,4,4-hexafluoro-2,3-dichloro-2-butene (Z-HFCO-1316mxx).

30. The process of claim 27, wherein the fluorine species comprises E-1,1 ,1,4,4,4-hexafluoro-2,3-dichloro-2-butene (E-HFCO-1316mxx) and Z-1,1 ,1 ,4,4,4-hexafluoro-2,3-dichloro-2-butene (Z-HFCO-1316mxx).

31. The process of claim 26, wherein the fluorine species comprises 2-chloro- 1,1 ,1 ,2-tetrafluoropropane (HCFC-244bb).

32. The process of claim 26, wherein the fluorine species comprises 2-chloro- 3,3,3-trifluoropropene (HCFO-1233xf).

33. The process of claim 26, wherein the fluorine species comprises Z-1-chloro- 3,3,3-trifluoropropene (HCFO-1233zd(Z).

34. The process of claim 26, wherein the fluorine species comprises E-1-chloro- 3,3,3-trifluoropropene (HCFO-1233zd(E)).

35. The process of claim 26, wherein the fluorine species comprises 2-chloro- 1,1 ,1 ,4,4,4-hexafluorobutane (HFC-346mdf ).

36. The process of claim 26, wherein the fluorine species comprises 2,3-dichloro- 1,1 ,1 ,4,4,4-hexafluorobutane (HCFC-336mdd) .

37. The process of claim 26, wherein the fluorine species comprises hexafluoroacetone.

38. The process of claim 26, wherein the fluorine species comprises trifluoroacetone.

39. The process of claim 26, wherein wherein the fluorine species comprises perfluoro(2-methyl-3-pentanone) .

40. The process of any of claims 1-21, wherein the fluorine species comprises one or more of:HFO-1327mz (1,1,1 ,2,4,4,4-heptafluorobut-2-ene),HFO-1325lxz (1,2-dichloro-1 ,1,4,4,4-pentafluorobut-2-ene), HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene), HFC-336maf (2,2-dichloro-1,1,1 ,4,4,4-hexafluorobutane), HFC-336lbf (1,2-dichloro-1 ,1,2,4,4,4-hexafluorobutane), HFC-337mbf (2-chloro-1 ,1 ,1 ,2,4,4,4-heptafluorobutane), HFC-337mde (2-chloro-1 ,1 ,1,3,4,4,4-heptafluorobutane), HFC-356mff (1,1,1 ,4,4,4-hexafluorobutane), HFC-338mf (1,1 , 1,2, 2,4,4, 4-octafluorobutane, HCFO-1122 (2-chloro-1 , 1 -difluoroethylene), HCFC- 124 (2-chl oro- 1,1 ,1 ,2-tetrafl uoroethane) , CFC-114 (1 ,2-dichloro-1 , 1 ,2,2-tetrafluoroethane), CFC-113 (1 ,1 , 2-trich loro- 1 ,2,2-trifluoroethane), CFC-133a (2-chloro-1,1,1-trifluoroethane),CFC-123 (2, 2-dichloro-1, 1 ,1 -trifluoroethane),CFC-123a (1 ,2-dichloro-1,1 ,2-trifluoroethane),CFC-122 (1 ,2,2-trichloro-1,1-difluoroethane),CFC-112a (1 ,1 ,1 ,2-tetrachloro-2,2-difluoroethane),HCFC-224db (1 ,1 ,1 ,3-tetrafluoro-2,3,3-trichloropropane,HFC-225da (1 ,2-dichloro-1 , 1 ,3,3,3-pentafluoropropane),HFC-235da (2-chloro-1 , 1 ,1 ,3,3-pentafluoropropane),HFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane),HFC-236fa (1 ,1 ,1 ,3,3,3-hexafluoropropane),E- and Z-CFO-1317mx (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobut-2-ene).E-1 ,2 , 3-trichlo ro- 1 , 1 ,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx);Z-1 ,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx);E-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (E-CFC-1314kxx); andZ-1 ,1 ,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (Z-CFC-1314kxx).

41. The process of claim 40, wherein the fluorine species comprises HFO- 1327mz (1,1,1 ,2,4,4,4-heptafluorobut-2-ene),42. v the fluorine species comprises HFO-1325lxz (1,2-dichloro-1 , 1,4, 4,4- pentafluorobut-2-ene)43. The process of claim 40, wherein the fluorine species comprisesHFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene).

44. The process of claim 40, wherein the fluorine species comprises HFC-336maf (2,2-dichloro-1 ,1,1 ,4,4,4-hexafluorobutane).

45. The process of claim 40, wherein the fluorine species comprises HFC-336lbf (1 ,2-dichloro-1 , 1 ,2,4,4,4-hexafluorobutane).

46. The process of claim 40, wherein the fluorine species comprises HFC-337mbf (2-chloro-1 ,1 ,1,2,4,4,4-heptafluorobutane).

47. The process of claim 40, wherein the fluorine species comprises HFC- 337mde (2-chloro-1 ,1,1 ,3,4,4,4-heptafluorobutane).

48. The process of claim 40, wherein the fluorine species comprises HFC-356mff (1,1,1 ,4,4,4-hexafluorobutane).

49. The process of claim 40, wherein the fluorine species comprises HFC-338mf (1,1 ,1 ,2,2,4,4,4-octafluorobutane.

50. The process of claim 40, wherein the fluorine species comprises HCFO-1122 (2-chloro-1 ,1 -difluoroethylene).

51. The process of claim 40, wherein the fluorine species comprises HCFC-124 (2-chloro-1 ,1,1 ,2-tetrafluoroethane).

52. The process of claim 40, wherein the fluorine species comprises CFC-114 (1 ,2-dichloro-1 , 1 ,2,2-tetrafluoroethane).

53. The process of claim 40, wherein the fluorine species comprises CFC-113 (1 , 1 ,2-trichloro- 1 ,2,2-trifluoroethane).

54. The process of claim 40, wherein the fluorine species comprises CFC-133a (2-chloro-1 ,1 ,1 -trifluoroethane).

55. The process of claim 40, wherein the fluorine species comprises CFC-123 (2,2-dichloro-1 , 1 , 1-trifluoroethane).

56. The process of claim 40, wherein the fluorine species comprises CFC-123a (1 ,2-dichloro-1 , 1 ,2-trifluoroethane).

57. The process of claim 40, wherein the fluorine species comprises CFC-122 (1,2,2-trichloro-1 ,1-difluoroethane).

58. The process of claim 40, wherein the fluorine species comprises CFC-112a (1,1,1 ,2-tetrachloro-2,2-difluoroethane).

59. The process of claim 40, wherein the fluorine species comprises HCFC-224db (1,1,1 ,3-tetrafluoro-2,3,3-trichloropropane.

60. The process of claim 40, wherein the fluorine species comprises HFC-225da (1 ,2-dichloro-1 , 1 ,3,3,3-pentafluoropropane).

61. The process of claim 40, wherein the fluorine species comprises HFC-235da (2-chloro-1 ,1 ,1, 3,3-pentafluoropropane).

62. The process of claim 40, wherein the fluorine species comprises HFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane).

63. The process of claim 40, wherein the fluorine species comprises HFC-236fa (1,1,1 ,3,3,3-hexafluoropropane).

64. The process of claim 40, wherein the fluorine species comprises E- and Z- CFO-1317mx (2-chloro-1 ,1,1,3,4,4,4-heptafluorobut-2-ene).

65. The process of claim 40, wherein the fluorine species comprises E-1 ,2,3- trichloro-1 ,1 ,4,4, 4-pentafluoro-2-butene (E-CFC-1315lxx).

66. The process of claim 40, wherein the fluorine species comprises Z-1 ,2,3- trichloro-1 ,1 ,4,4, 4-pentafluoro-2-butene (Z-CFC-1315lxx).

67. A purified water composition produced by any of claims 1-21 .

68. The process of claim 20 wherein sparging the media at temperatures greater than 60°C is achieved either by heating the media or sparging with hot inert gas such as N2.

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