Materials and methods for abatement of halide species in process streams

Abstract

To provide materials and methods for mitigating the effects of halide species contained in a process stream.SOLUTION: The halide-containing process stream may be contacted with an abatement material combined with a solid, porous substrate comprising an active metal oxide and a non-acidic, high surface area support. The halide species in the process stream may react with the abatement material to produce a process stream that is essentially free of neutralized halide salts and halides. The neutralized salt can be attracted to and retained on the solid porous substrate.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The subject matter disclosed herein relates to mitigating the effects of undesirable halide species in process streams within industrial process facilities. [Background technology]

[0002] Related Applications This application claims the benefit of and priority to U.S. Provisional Patent Application No. 62 / 377,294, filed August 19, 2016, and U.S. Provisional Patent Application No. 62 / 378,059, filed August 22, 2016, the disclosures and contents of which are incorporated herein by reference in their entireties.

[0003] Undesirable halide species are found in industrial process streams and can cause corrosion, contamination, and poisoning within process equipment and the equipment and media contained therein. Such undesirable halide species are acidic in nature and include chlorides, bromides, fluorides, and iodides. Commonly undesirable halide species in industrial process equipment streams are chloride compounds.

[0004] Alumina-based molecular sieves have been used to mitigate the effects of undesirable halide species in process streams. Molecular sieves are available from companies such as UOP, Axens, and Criterion, and may be used to treat process streams with halide species concentrations up to 15 ppm, as measured by spectrometer. Molecular sieves generally contain activated alumina, which reacts with the halide species to form aluminum halide species. While the halide species are rejected, the resulting aluminum halide species provide sites for reaction to form other undesirable species. Among these undesirable species are hydrocarbons known as green oils. Green oils and other undesirable species can cause severe contamination of process equipment and poison the media they contain.

[0005] Also commercially available, for example from Johnson Matthey, are guard materials that are basic in nature. These materials generally consist of sodium oxide or sodium hydroxide on substrates such as alumina and silica. A bed of these materials can neutralize acidic halide species at concentrations up to 5,000 ppm. In doing so, the generation of undesirable species, including green oil and green oil precursors, is avoided, but the neutralized species can cause contamination of process equipment and media.

[0006] Such commercially available abatement materials are limited in that they cannot handle concentrations of acidic halide species greater than about 15-5000 ppm, they form undesirable species such as green oils, and they lack the ability to retain neutralized species. Improvements in this area are therefore desirable. Summary of the Invention

[0007] The subject matter disclosed herein provides various specific embodiments of materials and methods for mitigating the effects of halide species contained in process streams.

[0008] In certain specific embodiments, a method for treating undesirable halide species in a process stream is provided. The process stream can be contacted with a medium comprising a reactant and a retainer. The retainer can be a solid porous substrate retainer. The process stream may be a non-acidic substrate retainer. Acidic halide species in the process stream can react with reactants in the medium to produce a halide-free process stream and neutralized halide salts. The neutralized halide salts may be attracted to and retained on the retainer via sorption. The reactants may include one or more active oxides of Group 1 or Group 2 metals. The reactants may include one or more active oxides of Group 1 or Group 2 metals and at least one non-acidic high surface area carrier. The active oxides of Group 1 or Group 2 metals may include one or more phosphates of sodium, potassium, magnesium, and calcium. The active oxide may include tribasic potassium phosphate. The carrier may include titanium dioxide. The reactants may be mixed or combined with a liquid carrier to form a slurry. The liquid carrier may include water. The slurry may include an amount of a slurry binder. The process stream may contain up to 3% by weight (30,000 ppm) of acidic species. The non-acidic, high surface area support may have a surface area of ​​up to 300 square meters per gram. The reactants or slurry may be disposed on the surface of or impregnated within the substrate retainer. The physical composition of the substrate may include the reactants or slurry. The reactants or slurry may comprise the entire composition of the substrate. The substrate may be a reticulate, a monolith, a fibrous solid, or a particle bonded solid.

[0009] In certain specific embodiments, a medium for treating halide species in a process stream is provided. The medium may include a reactant and a retainer. The retainer may be a solid porous substrate retainer. The reactant may include one or more active oxides of a Group 1 or Group 2 metal. The reactant may include one or more active oxides of a Group 1 or Group 2 metal and a non-acidic high surface area support. The reactant may be combined with a liquid to form a slurry. The reactant or slurry may be incorporated into the surface of the substrate retainer. The physical composition of the substrate may include the reactant or slurry. The active oxide may include one or more phosphates of sodium, potassium, magnesium, and calcium. The active oxide may include tribasic potassium phosphate. The non-acidic high surface area support may include titanium dioxide. The halide may include chloride, bromide, fluoride, and / or iodide.

[0010] While particular embodiments of the presently disclosed subject matter will be described in connection with the presently specific embodiments set forth herein, it will be understood that it is not intended to limit the invention to such aspects, but rather to cover all alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.

[0011] A better understanding of the present invention will be obtained when the following detailed description of the preferred embodiments is considered in conjunction with the following drawings. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is an image of a solid porous substrate material in the form of a reticulated ceramic foam disc according to an embodiment of the present disclosure. [Figure 2] 1 is a graph showing molecular analysis of experimental test results according to aspects of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0013] In accordance with the subject matter disclosed herein, various specific embodiments of materials and methods are described for improved mitigation of the effects of undesirable halide species in process streams within industrial process facilities.

[0014] In certain specific embodiments, a medium is provided that includes a reactant and a retainer. The reactant may include one or more active oxides of Group 1 or Group 2 metals whose function is to neutralize halides. The reactant may also include one or more non-acidic, high surface area supports. The non-acidic nature of the support prevents the formation of undesirable species such as green oil. The high surface area of ​​the support promotes increased reactive sites for the active metal oxides.

[0015] In certain specific embodiments, the retainer may comprise a solid porous substrate, the function of which is to attract and retain neutralized halide species that would otherwise lead to contamination of process equipment and media.

[0016] In certain specific embodiments, the medium can mitigate the impact of halide species in process streams with water contents not exceeding 1% and concentrations of halide species up to 3% (30,000 ppm) while preventing the formation of undesirable species such as green oil and green oil precursors. In certain specific embodiments, the presently disclosed subject matter can mitigate the impact of halide species in process streams containing high concentrations of halide species by converting the halide species to non-reactive, neutralized species (e.g., salts). Use of this medium does not result in the formation of undesirable species such as green oil and / or its precursors. This conversion can occur at ambient temperature and pressure (e.g., standard sea level conditions between 45° South and 45° North) and with little or no temperature increase. The resulting process stream will be essentially halide-free, and the retainer will attract and retain neutralized halide species.

[0017] In certain specific embodiments, the active metal oxide component of the reactants comprises oxides of Group 1 and Group 2 metals, including phosphates of sodium, potassium, magnesium, and calcium, all of which are basic. Of particular interest are the tribasic phosphates, which are highly basic yet have a high capacity to neutralize acidic species.

[0018] In certain specific embodiments, non-acidic, high surface area supports may be utilized. The non-acidic nature avoids the formation of undesirable species such as green oil, while the high surface area promotes increased reactive sites for the active metal oxide(s). Non-acidic, high surface area supports may include oxides of titanium, aluminum, and zirconium. In certain specific embodiments, the non-acidic, high surface area materials will have a surface area of ​​up to 70 square meters per gram. In certain specific embodiments, the non-acidic, high surface area materials will have a surface area of ​​up to 150 square meters per gram. In certain specific embodiments, the non-acidic, high surface area materials will have a surface area of ​​up to 300 square meters per gram.

[0019] In certain specific embodiments, reactants comprising a mixture of one or more active metal oxides and one or more non-acidic high surface area materials may form with an active metal oxide(s) content of about 10 to about 50%.

[0020] In certain specific embodiments, a slurry may be prepared. The slurry may include reactants, a liquid, and a slurry binder in amounts. The liquid should be inert and promote the formation of a uniform slurry. Water is a preferred liquid. The medium containing the slurry as a component may need to be dried at a suitable temperature and for a suitable time in certain specific embodiments.

[0021] In certain specific embodiments, the retainer may include porous ceramics or metals (including reticulated materials such as foams), honeycomb monoliths, fibrous meshes or solids, particle-bound solids, and any carrier having sufficient capacity to attract and retain large amounts of neutralized halide species and withstand the process conditions to which it will be exposed.

[0022] In certain specific embodiments, the medium may include a solid porous substrate retainer comprised entirely of the reactants or slurry. The medium may comprise a solid porous substrate partially combined with the reactants or slurry. The medium may also comprise a solid porous substrate coated or impregnated with the reactants or slurry. The retainer may be comprised entirely of the reactants or the slurry. The subject matter disclosed herein can be utilized in a variety of process industries, including continuous and / or batch processes. For example, the process industries may include, but are not limited to, one or more of the refining, processing, and production of petroleum products, biofuels, and biolubricants, petrochemicals, chemicals, and natural gas and its components.

[0023] In certain specific embodiments, the process stream may be a liquid, a gas, a combination of the two, or a mixture of the two. The process stream may enter, exit, and / or be within the vessels, piping, and other ancillary equipment that make up an industrial process facility.

[0024] In certain specific embodiments, a method for mitigating halide species in a process stream is provided. The process stream may be contacted with a medium comprising a reactant combined with a retainer.

[0025] In certain specific embodiments, the reactants may include one or more active metal oxides mixed with one or more non-acidic high surface area supports. In certain specific embodiments, the mixture may be combined with a solid porous substrate retainer. Acidic halide species may be essentially eliminated by reaction with the reactants to produce an essentially halide-free process stream and neutralized halide species, generally salts. The neutralized halide species may be attracted to and retained by the solid porous substrate retainer.

[0026] In certain specific embodiments, methods are provided for treating halide species in a process stream and mitigating the undesirable effects of the halide species, which can result in both neutralized halide salts retained in contact with a medium and a process stream that is essentially free of halide.

[0027] In certain aspects, process streams containing halide species contain very small amounts of free water. Free water contents greater than about 1% will deactivate the active components of the reactants in certain specific embodiments. Process streams containing halide species may contain up to 3% by weight of halide species.

[0028] The reactants may include one or more active metal oxides combined with one or more non-acidic high surface area supports. The active metals may include oxides of Group 1 or Group 2 metals. An example of an active metal oxide may be tribasic potassium phosphate. An example of a non-acidic high surface area support may be titanium dioxide. The reactants may be mixed with a liquid to form a slurry. The liquid may be water. The slurry may further include an amount of a slurry binder.

[0029] In certain specific embodiments, the reactants or slurries may be coated onto the surface of or impregnated into the solid porous substrate retainer, or may be included in the formation of the solid porous substrate retainer, which may be entirely comprised of the reactants or slurries.

[0030] Neutralization of halide species by contacting a process stream containing the halide species with a medium can occur at near ambient conditions and with little or no significant exothermic reaction. Attraction and retention of the neutralized halide species can occur on a solid porous substrate retainer. Operation of this method does not result in the formation of undesirable species such as green oil or its precursors.

[0031] In certain specific embodiments, a medium for mitigating halide species in a process stream is provided, which may be a solid porous substrate retainer having a reactant or slurry disposed thereon or therewith.

[0032] To better understand the subject matter disclosed herein, the following examples of specific embodiments are given. The following examples should not be read to limit or define the scope of the subject matter disclosed herein. [Example]

[0033] Test vehicles were prepared according to the following procedure: A mixture of 50% tribasic potassium phosphate and 50% titanium dioxide was combined with an equal volume of water to form a slurry. Actigel slurry binder was added. A solid porous substrate in the form of a reticulated ceramic foam disc (Figure 1), 2 inches in diameter and 0.5 inches high, was impregnated with the slurry. The slurry-coated disc was dried at 300°C for 30 minutes.

[0034] Three hydrocarbon test liquids were prepared, each containing approximately 1% of a different acidic chloride species: hydrochloric acid, benzoyl chloride, and carbon tetrachloride. The test media (i.e., dried slurry-coated disks) were impregnated with the three test liquids. Test conditions were ambient temperature and pressure. Neutralization of the chloride species to form potassium chloride salts occurred essentially instantaneously, with no significant increase in the temperature of the reaction mixture. Laboratory analysis indicated that the treated test liquids were chlorine-free. When the salt was filtered through a mesh disk, the color of the disk changed from nearly white to a yellowish color. When the slurry-coated disk was tapped on a laboratory bench, a fine white powder material fell off. Upon analysis, the powder contained inactive potassium chloride salts, unreacted titanium dioxide, elemental phosphorus, and hydrocarbons, as shown in Figure 2.

[0035] These experimental results demonstrate that desired improvements over existing technology have been achieved: [i] significant concentrations of halide species can be converted to inert salts utilizing novel media; [ii] the conversion can be carried out at ambient conditions and is not significantly exothermic; [iii] the solid porous substrate offers a large capacity to attract and retain neutralized halide species; [iv] the resulting product is essentially halide-free; and [v] the mitigation of halide species can be achieved without the formation of undesirable species such as green oil or its precursors.

[0036] Although the disclosed subject matter has been described in detail in connection with numerous embodiments, it is not limited to such disclosed embodiments. Rather, the disclosed subject matter may be modified to encompass numerous other variations, alterations, substitutions, or equivalent arrangements not previously described, which are equivalent to the scope of the disclosed subject matter. Furthermore, while various embodiments of the disclosed subject matter have been described, it should be understood that aspects of the disclosed subject matter may include only some of the described embodiments. Therefore, the disclosed subject matter should not be understood to be limited by the foregoing description, but only by the scope of the claims.

Claims

1. 1. A method for treating halide species in a process stream comprising: contacting the process stream with a medium comprising reactants and a solid porous substrate retainer; reacting halide species in the process stream with a medium to produce a halide-free process stream and a neutralized halide salt; and attracting and retaining the neutralized halide salt on a solid porous substrate retainer.

2. The method of claim 1 , wherein the reactants comprise one or more active oxides of Group 1 or Group 2 metals.

3. 10. The method of claim 1, wherein the reactants comprise one or more active oxides of a Group 1 or Group 2 metal and at least one non-acidic, high surface area support.

4. 3. The method of claim 2, wherein the active oxide of a Group 1 or Group 2 metal comprises one or more phosphates of sodium, potassium, magnesium, and calcium.

5. The method of claim 2 wherein the active oxide comprises tribasic potassium phosphate.

6. 4. The method of claim 3, wherein the non-acidic high surface area support comprises titanium dioxide.

7. The method of claim 1 , wherein the reactants are combined with a liquid to form a slurry.

8. The method of claim 7 , wherein the liquid comprises water.

9. The method of claim 7 wherein the slurry includes an amount of a slurry binder.

10. 10. The method of claim 1, wherein the process stream contains up to 3 wt.% halide species.

11. 4. The method of claim 3, wherein the non-acidic, high surface area support has a surface area of ​​up to 300 square meters per gram.

12. The method of claim 1 , wherein the reactant or slurry is disposed on or impregnated into a surface of the substrate retainer.

13. The method of claim 1 , wherein the physical composition of the substrate retainer comprises a reactant or a slurry.

14. The method of claim 1 , wherein the reactant or slurry comprises the entire substrate retainer.

15. The method of claim 1 , wherein the substrate retainer is a mesh.

16. The method of claim 1 , wherein the substrate retainer is a monolith.

17. The method of claim 1 , wherein the substrate retainer is a fibrous solid.

18. The method of claim 1 , wherein the substrate retainer is a particle-bonded solid.

19. 1. A medium for treating halide species in a process stream, the medium comprising reactants and A medium comprising a solid porous substrate retainer, wherein the reactants comprise one or more active oxides of Group 1 or Group 2 metals.

20. 20. The reaction medium of claim 19, wherein the reactants further comprise at least one non-acidic high surface area support.

21. 20. The reaction medium of claim 19, wherein the reactants are combined with a liquid to form a slurry.

22. 20. The medium of claim 19, wherein the reactant or slurry is incorporated into the surface of the substrate retainer.

23. 20. The reaction medium of claim 19, wherein the physical composition of the substrate retainer comprises a reactant or a slurry.

24. 20. The reaction medium of claim 19, wherein the reactant or slurry comprises the entire substrate retainer.

25. 20. The reaction medium of claim 19, wherein the active oxide comprises one or more phosphates of sodium, potassium, magnesium, and calcium.

26. 26. The reaction medium of claim 25, wherein the active oxide comprises tribasic potassium phosphate.

27. 20. The reaction medium of claim 19, wherein the non-acidic high surface area support comprises titanium dioxide.

28. 20. The method of claim 19, wherein the halide comprises one or more of chloride, bromide, fluoride, and iodide.

Images