U.S. patent application number 17/515813 was filed with the patent office on 2022-02-17 for materials and methods for mitigating halide species in process streams.
This patent application is currently assigned to CRYSTAPHASE PRODUCTS, INC.. The applicant listed for this patent is CRYSTAPHASE PRODUCTS, INC.. Invention is credited to UMAKANT PRAVINCHANDRA JOSHI.
Application Number | 20220047967 17/515813 |
Document ID | / |
Family ID | |
Filed Date | 2022-02-17 |
United States Patent
Application |
20220047967 |
Kind Code |
A1 |
JOSHI; UMAKANT
PRAVINCHANDRA |
February 17, 2022 |
MATERIALS AND METHODS FOR MITIGATING HALIDE SPECIES IN PROCESS
STREAMS
Abstract
Materials and methods for mitigating the effects of halide
species contained in process streams are provided. 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 material 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.
Inventors: |
JOSHI; UMAKANT PRAVINCHANDRA;
(SPRING, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CRYSTAPHASE PRODUCTS, INC. |
Houston |
TX |
US |
|
|
Assignee: |
CRYSTAPHASE PRODUCTS, INC.
HOUSTON
TX
|
Appl. No.: |
17/515813 |
Filed: |
November 1, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16258286 |
Jan 25, 2019 |
11161056 |
|
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17515813 |
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15485943 |
Apr 12, 2017 |
10258902 |
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16258286 |
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62378059 |
Aug 22, 2016 |
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62377294 |
Aug 19, 2016 |
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International
Class: |
B01D 15/08 20060101
B01D015/08; B01J 20/28 20060101 B01J020/28; B01J 20/32 20060101
B01J020/32; C10G 53/14 20060101 C10G053/14; C10G 19/00 20060101
C10G019/00; B01D 53/68 20060101 B01D053/68; B01D 53/70 20060101
B01D053/70; B01J 20/04 20060101 B01J020/04; C10G 25/00 20060101
C10G025/00; B01D 15/36 20060101 B01D015/36; B01J 20/06 20060101
B01J020/06; B01J 20/30 20060101 B01J020/30 |
Claims
1. A method of treating chloride species in a process stream, the
method comprising: contacting the process stream with a medium
comprising a reactant and a solid porous substrate retainer,
wherein the process stream comprises a hydrocarbon fluid and
chloride species, and wherein the reactant comprises tribasic
potassium phosphate and a titanium dioxide carrier; reacting the
halide species in the process stream with the medium to produce a
halide-free process stream and neutralized chloride salts; and
attracting and retaining the neutralized chloride salts on the
substrate retainer.
Description
RELATED APPLICATIONS
[0001] This application is a continuation application and claims
the benefit, and priority benefit, of U.S. patent application Ser.
No. 16/258,286, filed Jan. 25, 2019, which claims the benefit, and
priority benefit, of U.S. patent application Ser. No. 15/485,943,
filed Apr. 12, 2017, now issued as U.S. Pat. No. 10,258,902, which
claims the benefit, and priority benefit, of U.S. Provisional
Patent Application Ser. No. 62/377,294, filed Aug. 19, 2016, and
U.S. Provisional Patent Application Ser. No. 62/378,059, filed Aug.
22, 2016, the disclosures and contents of which are incorporated by
reference herein in their entirety.
BACKGROUND
Field of the Invention
[0002] The presently disclosed subject matter relates to mitigating
the effects of undesired halide species in process streams within
industrial process facilities.
Description of the Related Art
[0003] Undesired halide species can be found in industrial process
streams and can cause corrosion, fouling and poisoning in process
facilities and the equipment and media contained therein. Such
undesired halide species are, by nature, acidic and include
chlorides, bromides, fluorides and iodides. Common undesired halide
species in industrial process facility streams are chloride
compounds.
[0004] Alumina-based molecular sieves have previously been utilized
to mitigate the effects of undesired halide species in process
streams. The molecular sieves are commercially available from
companies such as UOP, Axens and Criterion, and can be used to
treat process streams having halide species concentrations up to 15
ppm measured by spectrometer. The molecular sieves typically
contain activated alumina which reacts with halide species to form
aluminum halide species. While halide species are removed, the
resulting aluminum halide species provide sites for reactions to
form other undesirable species. Among these undesired species are
hydrocarbons known as green oil. Green oil and other undesirable
species can cause severe fouling of process equipment and poisoning
of media contained therein.
[0005] Also available commercially from, for example, Johnson
Matthey, are guard materials which are basic in nature. These
materials are typically composed of sodium oxide or sodium
hydroxide on supports such as alumina and silica. Beds of these
materials can neutralize acidic halide species in concentrations up
to 5,000 ppm. In doing so, creation of undesired species including
green oil and green oil precursors are avoided but neutralized
species can cause fouling in process facilities and media.
[0006] These commercially available mitigation materials are
limited due to their inability to handle acidic halide species at
concentrations above about 15 to 5,000 ppm, their formation of
undesired species such as green oil, and their lack of capacity to
retain neutralized species. Improvements in this field are
therefore desired.
SUMMARY
[0007] In accordance with the presently disclosed subject matter,
various illustrative embodiments are provided of materials and
methods for mitigating the effects of halide species contained in
process streams.
[0008] In certain illustrative embodiments, a method of treating
undesired 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 acidic halide species in the process stream can be
reacted with the reactant in the medium to produce a halide
species-free process stream and neutralized halide salts. The
neutralized halide salts can be attracted and retained, via
sorption, on the retainer. The reactant can include one or more
active oxides of Group 1 or Group 2 metals. The reactant can
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 and Group 2 metals can include phosphates of one
or more of sodium, potassium, magnesium and calcium. The active
oxide can include tribasic potassium phosphate. The carrier can
include titanium dioxide. The reactant can be mixed or combined
with a liquid carrier to form a slurry. The liquid carrier can
include water. The slurry can include an amount of a slurry binder.
The process stream can contain up to 3 wt % (30,000 ppm) acidic
species. The non-acidic, high surface area carrier can have a
surface area of up to 300 square meters per gram. The reactant or
slurry can be disposed on or impregnated into the surface of the
substrate retainer. The physical composition of the substrate can
include the reactant or slurry. The reactant or slurry can comprise
the entirety of the composition of the substrate. The substrate can
be a reticulate, a monolith, a fibrous solid or a particle bonded
solid.
[0009] In certain illustrative embodiments, a medium for treating
halide species in a process stream is provided. The medium can
include a reactant and a retainer. The retainer can be a solid,
porous substrate retainer. The reactant can include one or more
active oxides of Group 1 or Group 2 metals. The reactant can
include one or more active oxides of a Group 1 or Group 2 metals
and a non-acidic, high surface area carrier. The reactant can be
combined with a liquid to form a slurry. The reactant or slurry can
be incorporated onto the surface of the substrate retainer. The
physical composition of the substrate can include the reactant or
the slurry. The active oxides can include phosphates of one or more
of sodium, potassium, magnesium and calcium. The active oxide can
include tribasic potassium phosphate. The non-acidic, high surface
area carrier can include titanium dioxide. The halides can include
chlorides, bromides, fluorides and/or iodides.
[0010] While certain embodiments of the presently disclosed subject
matter will be described in connection with the present
illustrative embodiments shown herein, it will be understood that
it is not intended to limit the invention to those embodiments. On
the contrary, it is intended to cover all alternatives,
modifications, and equivalents, as may be included within the
spirit and scope of the invention as defined by the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] A better understanding of the present invention can be
obtained when the following detailed description of the preferred
embodiment is considered in conjunction with the following
drawings, in which:
[0012] FIG. 1 is an image of a solid, porous substrate material in
the form of a reticulated ceramic foam disk according to an
embodiment of the present disclosure; and
[0013] FIG. 2 is a graph showing a molecular analysis of
experimental test results according to an embodiment of the present
disclosure.
DETAILED DESCRIPTION
[0014] In accordance with the presently disclosed subject matter,
various illustrative embodiments of materials and methods are
described for improved mitigation of the effects of undesired
halide species in process streams within industrial process
facilities.
[0015] In certain illustrative embodiments, a medium is provided
comprising a reactant and a retainer. The reactant can comprise one
or more active oxides of Group 1 or Group 2 metals whose functions
are to neutralize halide species. The reactant can also comprise
one or more non-acidic, high surface area carriers. Carrier
non-acidity prevents creation of undesirable species such as green
oil. Carrier high surface area facilitates proliferation of
reaction sites for the active metal oxides.
[0016] In certain illustrative embodiments, the retainer can
include a solid, porous substrate whose function is to attract and
retain neutralized halide species which otherwise would contribute
to fouling of process facilities and media.
[0017] In certain illustrative embodiments, the medium is capable
of mitigating the effects of halide species in process streams
having water content not exceeding 1% and halide species
concentrations up to 3% (30,000 ppm) while preventing the formation
of undesired species such as green oil and green oil precursors. In
certain illustrative embodiments, the presently disclosed subject
matter is able to mitigate the effects of halide species in process
streams with high concentrations of halide species by converting
the halide species to non-reactive, neutralized species (such as
salts). Use of this medium does not result in creation of undesired
species such as green oil and/or its precursors. The conversion can
occur at ambient temperature and pressure (e.g., normal sea level
conditions between Earth latitudes 45.degree. South and 45.degree.
North) and with little or no temperature increase. The resulting
process stream is essentially halide-free and the retainer will
have attracted and retained the neutralized halide species.
[0018] In certain illustrative embodiments, the active metal oxide
components of the reactant include oxides of Group 1 and Group 2
metals including phosphates of sodium, potassium, magnesium and
calcium, all of which are basic in nature. Of special interest are
tribasic phosphates which are highly basic and have a high capacity
to neutralize acidic species.
[0019] In certain illustrative embodiments, non-acidic, high
surface area carriers can be utilized. Non-acidity avoids creation
of undesired species such as green oil and high surface area
facilitates proliferation of reaction sites for the active metal
oxide(s). The non-acidic, high surface area carriers can include
oxides of titanium, aluminum and zirconium. In certain illustrative
embodiments, the non-acidic, high surface area materials will have
a surface area of up to 70 square meters per gram. In certain
illustrative embodiments, the non-acidic, high surface area
materials will have a surface area of up to 150 square meters per
gram. In certain illustrative embodiments, the non-acidic, high
surface area materials will have a surface area of up to 300 square
meters per gram.
[0020] In certain illustrative embodiments, a reactant comprising a
mixture of the one or more active metal oxides and the one or more
non-acidic, high surface area carriers can be formed with the
content of the active metal oxide(s) being from about 10 to about
50%.
[0021] In certain illustrative embodiments, a slurry can be
prepared. The slurry can comprise the reactant, a liquid and an
amount of slurry binder. The liquid should be inert and should
facilitate formation of a uniform slurry. Water is a preferred
liquid. Any medium including slurry as a component will require
drying at an appropriate temperature for an appropriate period of
time, in certain illustrative embodiments.
[0022] In certain illustrative embodiments, the retainer can
include porous ceramics or metals (including reticulated materials
such as foams), honeycomb monoliths, fibrous meshes or solids,
particle-bonded solids and any carrier with sufficient capability
to attract and retain large quantities of neutralized halide
species and to tolerate the process conditions to which they are
exposed.
[0023] In certain illustrative embodiments, the medium can comprise
a solid, porous substrate retainer composed in its entirety by the
reactant or the slurry. The medium can be composed of the solid,
porous substrate combined in part with the reactant or the slurry.
The medium can also be composed of the solid, porous substrate
coated or impregnated with the reactant or the slurry. The retainer
can be composed entirely by the reactant or by the slurry. The
presently described subject matter may be utilized in a variety of
process industries including continuous and/or batch processes. For
example, and without limitation, the process industry can comprise
one or more of refining, processing and manufacturing of: petroleum
products, biofuels and biolubricants, petrochemicals, chemicals and
natural gas and its components.
[0024] In certain illustrative embodiments, the process streams can
be liquid or vapor, combinations of the two or mixtures of the two.
The process streams can be entering, exiting and/or within vessels,
piping and other ancillary equipment comprising industrial process
facilities.
[0025] In certain illustrative embodiments, a method of mitigating
halide species contained in a process stream is provided. The
process stream can be contacted with a medium which includes a
reactant combined with a retainer.
[0026] In certain illustrative embodiments, the reactant can
include one or more active metal oxides mixed with one or more
non-acidic, high surface area carriers. In certain illustrative
embodiments, the mixture can be combined with a solid porous
substrate retainer. The acidic halide species can be essentially
eliminated by reaction with the reactant to produce an essentially
halide-free process stream and neutralized halide species,
typically salts. The neutralized halide species can be attracted to
and retained on the solid, porous substrate retainer.
[0027] In certain illustrative embodiments, a method of treating
halide species in a process stream and mitigating the undesired
effects of the halide species is provided. The halide species in
the process stream can be contacted with a medium to produce both
retained neutralized halide salts and a process stream that is
essentially halide-free.
[0028] In certain aspects, the halide species-containing process
stream contains very little free water. Free water contents in
excess of about 1% will deactivate the active components of the
reactant, in certain illustrative embodiments. The halide
species-containing process stream can contain up to 3 wt % halide
species.
[0029] The reactant can include one or more active metal oxides
combined with one or more non-acidic, high surface area carriers.
The active metal oxides can include oxides of Group 1 or Group 2
metals. An example of an active metal oxide can be tribasic
potassium phosphate. An example of a non-acidic, high surface area
carrier can be titanium dioxide. The reactant can be mixed with a
liquid to form a slurry. The liquid can be water. The slurry can
further comprise an amount of a slurry binder.
[0030] In certain illustrative embodiments, the reactant or slurry
can be coated on or impregnated in the surfaces of the solid,
porous substrate retainer. The reactant or r slurry can also be
included in the formation of the solid, porous substrate retainer.
The solid, porous substrate retainer can be composed entirely by
the reactant or the slurry.
[0031] Neutralization of halide species by contacting the halide
species-containing process stream with the medium can occur at near
ambient conditions and with no or little noticeable exotherm.
Attraction and retention of neutralized halides species can be on
the surfaces of the solid, porous substrate retainer. Operation of
the method does not lead to formation of undesired species such as
green oil or its precursors.
[0032] In certain illustrative embodiments, a medium for mitigating
halide species in a process steam is provided. The medium can be a
solid, porous substrate retainer with a reactant or slurry disposed
thereon or therewith.
[0033] To facilitate a better understanding of the presently
disclosed subject matter, the following example of a particular
embodiment is given. In no way should the following example be read
to limit, or define, the scope of the presently disclosed subject
matter.
[0034] Example #1--A test medium was 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. Solid, porous
substrate materials in the form of reticulated ceramic foam disks 2
inches in diameter by 0.5 inches high (See FIG. 1) were immersed in
the slurry. The slurry-coated disks were dried at 300.degree. C.
for 30 minutes.
[0035] Three hydrocarbon test liquids were prepared each containing
about 1% of a different acidic chloride species, namely:
hydrochloric acid, benzoyl chloride and carbon tetrachloride,
respectively. The test medium (that is, the dried slurry-coated
disks) was immersed in the three test liquids. Test conditions were
ambient temperature and pressure. Neutralization of the chloride
species to form potassium chloride salt was essentially
instantaneous with no noticeable increase in the temperature of the
reaction mixture. Laboratory analysis showed the treated test
liquids to be chlorine-free. When the salts filtered into the
reticulated disks, the coloration of the disks changed from
near-white to yellowish. Tapping the slurry-coated disks on the
laboratory table released a fine, white powdery substance. Upon
analysis, the powder included inert potassium chloride salt,
unreacted titanium dioxide, elemental phosphorous and hydrocarbon,
as indicated in FIG. 2.
[0036] These experimental results demonstrate that desired
improvements to the existing art have been achieved, namely: [i]
halide species in significant concentrations can be converted to
inert salts utilizing a novel medium; [ii] the conversion can be
carried out at ambient conditions and with no noticeable reaction
exotherm; [iii] solid, porous substrates provide large capability
to attract and retain neutralized halide species; [iv] a product is
produced that is essentially halide-free; and [v] mitigation of
halide species can be achieved without the formation of undesired
species such as green oil or its precursors.
[0037] While the disclosed subject matter has been described in
detail in connection with a number of embodiments, it is not
limited to such disclosed embodiments. Rather, the disclosed
subject matter can be modified to incorporate any number of
variations, alterations, substitutions or equivalent arrangements
not heretofore described, but which are commensurate with the scope
of the disclosed subject matter. Additionally, while various
embodiments of the disclosed subject matter have been described, it
is to be understood that aspects of the disclosed subject matter
may include only some of the described embodiments. Accordingly,
the disclosed subject matter is not to be seen as limited by the
foregoing description, but is only limited by the scope of the
claims.
* * * * *