Materials and methods for reducing halide species in process flow

Abstract

To provide materials and methods for mitigating the effects of halide species contained in process streams.SOLUTION: A halide-containing process stream can be contacted with mitigation materials comprising active metal oxides and a non-acidic high surface area carrier, combined with a solid porous substrate. The halide species in the process stream can be reacted with the mitigation materials to produce neutralized halide salts and a process stream that is essentially halide-free. The neutralized salts can be attracted and retained on the solid porous substrate.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The subject matter disclosed herein relates to reducing the impact of undesirable halide species in a process stream within industrial process equipment.

Background Art

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

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

[0004] Molecular sieves of alumina substrate have already been utilized to reduce the impact of undesirable halide species in a process stream. Molecular sieves are sold by companies such as UOP, Axens, and Criterion and may be used to treat process streams having halide species at concentrations up to 15 ppm measured by a spectrometer. Molecular sieves generally contain activated alumina that reacts with halide species to form aluminum halide species. Although the halide species are removed, the resulting aluminum halide species provide sites for reactions that form other undesirable species. Among these undesirable species are hydrocarbons known as green oil. Green oil and other undesirable species can cause severe contamination of process equipment and poisoning of the media contained therein.

[0005] Furthermore, commercially available materials from Johnson Matthey, for example, are inherently basic guard materials. These materials generally consist of sodium oxide or sodium hydroxide on a substrate such as alumina and silica. Beds of these materials can neutralize acidic halide species at concentrations up to 5,000 ppm. Doing so avoids the formation of undesirable species, including green oil and green oil precursors, although the neutralized species may contaminate process equipment and media.

[0006] Such commercially available mitigation materials have limitations in that they cannot handle acidic halide species at concentrations higher than approximately 15–5000 ppm, they form undesirable species such as green oil, and they lack the ability to retain neutralized species. Therefore, improvements in this area are desired. [Overview of the Initiative]

[0007] According to the subject matter disclosed herein, various specific embodiments of materials and methods for mitigating the influence of halide species present in process flows are provided.

[0008] In certain specific embodiments, a method for treating undesirable halide species in a process stream is provided. The process stream can be brought into contact with a medium containing reactants and a retainer. The retainer is a solid porous substrate retainer. An orous substrate retainer may be present. Acidic halide species in the process stream may react with reactants in the medium to produce a process stream free of halide species 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 activated oxides of Group 1 or Group 2 metals. The reactants may include one or more activated oxides of Group 1 or Group 2 metals and at least one non-acidic high surface area carrier. The activated oxides of Group 1 or Group 2 metals may include one or more phosphates of sodium, potassium, magnesium, and calcium. The activated oxides 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 a quantity of slurry binder. The process flow may contain up to 3% by weight (30,000 ppm) of acidic species. Non-acidic, high-surface-area carriers may have a surface area of ​​up to 300 square meters per gram. The reactant or slurry can be placed on the surface of the substrate retainer or impregnated into it. The physical composition of the substrate may include the reactant or slurry. The reactant or slurry may constitute the entire composition of the substrate. The substrate may be a reticulate, monolith, fibrous solid, or particle-bonded solid.

[0009] In certain specific embodiments, a medium is provided for processing halide species in a process stream. The medium may include reactants and a retainer. The retainer may be a solid porous substrate retainer. The reactants may include one or more activated oxides of Group 1 or Group 2 metals. The reactants may include one or more activated oxides of Group 1 or Group 2 metals and a non-acidic high-surface-area support. The reactants may be combined with a liquid to form a slurry. The reactants or slurry may be incorporated into the surface of the substrate retainer. The physical composition of the substrate may include the reactants or slurry. The activated oxides may include one or more phosphates of sodium, potassium, magnesium, and calcium. The activated oxides may include tribasic potassium phosphate. The non-acidic high-surface-area support may include titanium dioxide. The halides may include chlorides, bromides, fluorides, and / or iodides.

[0010] While specific embodiments of the subject matter of this disclosure will be described in relation to the current specific embodiments shown herein, it will be understood that the invention is not intended to be limited to such embodiments. Rather, it is intended to cover all modifications, alterations and equivalents that may fall within the spirit and scope of the invention as defined by the claims.

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

[0012] [Figure 1] This is an image of a solid porous substrate material in the form of a mesh ceramic foam disc according to an aspect of the present disclosure. [Figure 2] This graph shows the molecular analysis of experimental test results according to the embodiments of this disclosure. [Modes for carrying out 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 flows within industrial process equipment.

[0014] In certain specific embodiments, a medium comprising reactants and retainers is provided. The reactants may include one or more active oxides of Group 1 or Group 2 metals whose function is to neutralize halides. The reactants may also include one or more non-acidic, high-surface-area supports. The non-acidic nature of the supports prevents the formation of undesirable species such as green oil. The high surface area of ​​the supports promotes an increase in reaction sites for the active metal oxides.

[0015] In certain specific embodiments, the retainer may include a solid porous substrate whose function is to attract and retain neutralized halide species, without which contamination of process equipment and media would occur.

[0016] In certain specific embodiments, the medium can reduce the influence of halide species in process streams with a water content not exceeding 1% and a halide species concentration 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 subject disclosed herein can reduce the influence of halide species in process streams containing high concentrations of halide species by converting the halide species to unreactive, neutralized species (e.g., salts). The 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°S and 45°N), with little to no temperature increase. The resulting process stream is essentially halide-free, and the retainer will attract and retain the neutralized halide species.

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

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

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

[0020] In certain specific embodiments, a slurry may be prepared. This slurry may contain reactants, a liquid, and a slurry binder. The liquid should be inert and should promote the formation of a uniform slurry. Water is a suitable liquid. The medium containing the slurry as an ingredient will 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 a porous ceramic or metal (including reticulated materials such as foams), a honeycomb monolith, a fibrous mesh or solid, a particulate-bound solid, and any carrier that attracts and holds a large amount of neutralized halide species and has sufficient ability to withstand the process conditions to which it is exposed.

[0022] In certain specific embodiments, the medium may include a solid porous substrate retainer that is entirely composed of reactants or slurries. The medium may be composed of a solid porous substrate that is partially combined with reactants or slurries. The medium may also be composed of a solid porous substrate coated or impregnated with reactants or slurries. The retainer may be entirely composed of reactants or slurries. The subject matter disclosed herein can be utilized in various process industries including continuous and / or batch processes. For example, process industries may include, but are not limited to, one or more of the refining, processing, and manufacturing 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 vessels, piping, and other ancillary equipment that make up industrial process facilities.

[0024] In certain specific embodiments, a method for reducing halide species contained in a process stream is provided. The process stream may be contacted with a medium containing reactants 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 carriers. In certain specific embodiments, the mixture may be combined with a solid porous substrate retainer. Acidic halide species can be essentially eliminated by reaction with the reactants to produce a process stream essentially free of halides 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, a method is provided for treating halide species in a process stream and reducing the undesirable effects of the halide species. The halide species in the process stream can result in both a neutralized halide salt retained in contact with a medium and a process stream essentially free of halides.

[0027] In certain aspects, the process stream containing halide species contains a very small amount of free water. A free water content exceeding about 1% will inactivate the active components of the reactants in certain specific embodiments. The process stream containing halide species can contain up to 3 wt% of halide species.

[0028] The reactants may include one or more active metal oxides combined with one or more non-acidic high-surface-area carriers. The active metal may include oxides of Group 1 or Group 2 metals. An example of an active metal oxide may be tripotassium tribasic phosphate. An example of a non-acidic high-surface-area carrier may be titanium dioxide. The reactants can 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 reactant or slurry may be coated onto the surface of a solid porous substrate retainer or impregnated into it. Alternatively, the reactant or slurry may be incorporated into the formation of the solid porous substrate retainer. The solid porous substrate retainer can be composed entirely of the reactant or slurry.

[0030] Neutralization of halide species by contacting a process flow containing the halide species with a medium can occur under near-environmental conditions and with little to no significant exothermic reaction. Attraction and retention of the neutralized halide species may occur on solid porous substrate retainers. Operation by 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 is provided for reducing halide species in the process flow. The medium may be a solid porous substrate retainer containing the reactants or slurry, placed on or with them.

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

[0033] The test medium was prepared according to the following procedure: A slurry was formed by combining a mixture of 50% tribasic potassium phosphate and 50% titanium dioxide with an equal volume of water. Actigel slurry binder was added. A solid porous substrate in the form of a mesh ceramic foam disc (Figure 1) with a diameter of 2 inches and a height of 0.5 inches was impregnated into the slurry. The slurry-coated discs were 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 three test liquids were impregnated into a test medium (i.e., a disc coated with a dry slurry). Test conditions were ambient temperature and pressure. The neutralization of the chloride species to form potassium chloride salt occurred essentially instantaneously, and there was no significant rise in the temperature of the reaction mixture. Laboratory analysis showed that the treated test liquids were chlorine-free. When the salt was filtered through a mesh disc, the disc's color changed from nearly white to a yellowish color. When the slurry-coated disc was tapped on a laboratory bench, a fine white powdery substance fell off. Analysis revealed that the powder contained inert potassium chloride salt, unreacted titanium dioxide, phosphorus, and hydrocarbons, as shown in Figure 2.

[0035] These experimental results demonstrate that the desired improvements to existing technologies have been achieved: [i] significant concentrations of halide species can be converted to inert salts using a novel medium; [ii] the conversion can be carried out under environmental conditions and without significant exothermic reactions; [iii] the porous solid substrate provides a great capacity to attract and retain the neutralized halide species; [iv] the resulting product is essentially halide-free; and [v] the reduction of halide species can be achieved without forming undesirable species such as green oil or its precursors.

[0036] The disclosed subject matter has been described in detail in relation to numerous aspects, but is not limited to such aspects of disclosure. Rather, the disclosed subject matter may be modified to include many other variations, alterations, substitutions, or equivalent configurations not previously described, but these are equal to the scope of the disclosed subject matter. Furthermore, while various aspects of the disclosed subject matter have been described, it should be understood that aspects of the disclosed subject matter may only include some of the described aspects. Therefore, the disclosed subject matter should not be understood as being limited by the foregoing description, but only by the scope of the claims.

Claims

1. A method for treating chloride species in a process stream: A process flow containing hydrocarbon fluids and chloride species is brought into contact with a medium containing a reactant comprising tribasic potassium phosphate and titanium dioxide support, and a solid porous substrate retainer; The process stream is reacted with the medium to produce a process stream free of halogens and a neutralized chloride salt; and This includes attracting and retaining the neutralized chloride salt on the substrate retainer, Here, the solid porous substrate retainer includes a mesh-like ceramic material having a surface area of ​​up to 300 square meters per gram. method.

2. The method according to claim 1, wherein the reactant further comprises tribasic calcium phosphate.

3. The method according to claim 1, wherein the reactant is coated on the surface of the solid porous substrate retainer.

4. The method according to claim 1, wherein the reactant is impregnated into the solid porous substrate retainer.

5. The method according to claim 1, wherein the solid porous substrate retainer is composed entirely of the reactant.

6. The method according to claim 1, wherein the medium can reduce the influence of chloride species in a process stream having a water content not exceeding 1% and a chloride species concentration of up to 3%.

Images