WO2014174473A1 - Procédé et appareil d'élimination d'oxygène à partir d'un produit chimique - Google Patents

Procédé et appareil d'élimination d'oxygène à partir d'un produit chimique Download PDF

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Publication number
WO2014174473A1
WO2014174473A1 PCT/IB2014/060960 IB2014060960W WO2014174473A1 WO 2014174473 A1 WO2014174473 A1 WO 2014174473A1 IB 2014060960 W IB2014060960 W IB 2014060960W WO 2014174473 A1 WO2014174473 A1 WO 2014174473A1
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Prior art keywords
chemical
oxygen
vessel
scavenging
recirculation loop
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PCT/IB2014/060960
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English (en)
Inventor
Roland Schmidt
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Saudi Basic Industries Corporation
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Publication of WO2014174473A1 publication Critical patent/WO2014174473A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/0005—Degasification of liquids with one or more auxiliary substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/21—Organic compounds not provided for in groups B01D2251/206 or B01D2251/208
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1122—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/30—Controlling by gas-analysis apparatus

Definitions

  • the present disclosure relates to a method and apparatus for removing oxygen from a chemical.
  • the R 1 and R 2 groups of peroxide can potentially be many different chemical atoms or groups, inorganic or organic. If the R 1 and R 2 groups are organic groups, then the peroxide is an organic peroxide. To form a hydroperoxide, the R group is hydrogen. To form an organic hydroperoxide, the R 1 is organic and R 2 is hydrogen.
  • the present invention relates to a method for removing oxygen from a chemical; comprising:
  • the method does not comprise substantially any of an additive for scavenging a peroxide or for preventing peroxide formation.
  • An additional related aspect of the invention described herein relates to an apparatus for removing oxygen from a chemical; comprising:
  • the vessel is used to contain a chemical
  • the vessel has one or more inlets and one or more outlets for an inert gas
  • recirculation loop apparatus comprises:
  • a pump wherein the pump transports the chemical or the inert gas, or a mixture thereof, from the vessel through the recirculation apparatus; ii. a monitoring device, wherein the monitoring device measures the
  • FIG. 1 shows a schematic diagram of one aspect of an apparatus constructed in accordance with the teachings of the present invention.
  • Ranges may be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. In some particular aspects of the inventions described herein and the terminology used to describe them herein, the word “about” can mean a variation of + 10% of the value specified in the range.
  • chemical as used herein is any chemical that can be stored, transported, or used for its intended purpose.
  • the term "vessel” can be any vessel suitable for the transport and/or storage of a chemical.
  • peroxide-forming compound is intended to refer to a compound that by its intrinsic chemical nature has the tendency to form a peroxide when exposed to oxygen gas for any period of time.
  • oxygen scavenger relates to any device that is designed for scavenging oxygen molecules from a gas or liquid, including a device that comprises a chemical agent that can remove or scavenge oxygen molecules from a gas or liquid by contact, and/or chemical reaction, or by any other suitable means.
  • monitoring device is any analytical device capable of detecting the level of oxygen (0 2 ) and/or water in a sample of the substance being monitored.
  • the term "Acceptable oxygen level” as used herein is a concentration of oxygen (0 2 ) gas dissolved in a chemical or mixture of chemicals, or in the inert gas in contact with a chemical or mixture of chemicals, that in the judgment of the producers or sellers of the chemical and/or their customers suitably slows or prevents the formation of peroxides in the chemical or mixture of chemicals.
  • inert gas is a gas or mixture of gases which are inert to chemical reactivity with air, water, the compounds being stored or transported, or other substances likely to be encountered during shipment and storage of the chemicals.
  • chemical additive refers to a chemical compound which is added to another chemical compound to improve or preserve the chemical and physical properties of the compound to which it is added.
  • One aspect of the present invention relates to a method for removing oxygen from a chemical; comprising:
  • the method does not comprise substantially any of an additive for scavenging a peroxide or preventing peroxide formation.
  • the chemical can be solid, liquid or gas. In a further aspect, the chemical can be a gas or a vapor. In another aspect, the chemical can be an organic, an inorganic, or an organometallic compound. In yet another aspect, the chemical is an organic liquid. In an even further aspect, the chemical comprises an olefin, a diene or an ether. In one aspect, the chemical is an olefin.
  • the chemical is ethylene. In another aspect, the chemical is a diene. In a further aspect, the chemical is butadiene or cyclopentadience. In an even further aspect, the chemical comprises an ether. In a yet further aspect, the chemical comprises tetrahydrofuran (THF), diethyl ether, or methyl tertiary-butyl ether (MTBE), or a mixture thereof.
  • THF tetrahydrofuran
  • MTBE methyl tertiary-butyl ether
  • the chemical comprises dialkyl ethers of ethylene glycol, diethylene glycol, or triethylene glycol, or a mixture thereof.
  • the chemical comprises an aromatic or a hetero aromatic, or a mixture thereof.
  • the chemical comprises pyridine, benzene, toluene, styrene, acrylate, or cyanoacrylate.
  • the chemical is part of a subgenus of chemicals that are known in the art as being susceptible to the formation of peroxides.
  • the chemical forms at least one peroxide in the presence of oxygen.
  • Such substances often contain carbon-hydrogen bonds that neighbor other functional groups, which "activate" those carbon-hydrogen bonds toward attack by either free radicals, such as for example oxygen (0 2 ) gas, which is a relatively stable free radical.
  • Such substances often contain electron rich moieties such as an unsaturated bond, (a double or triple bond) found in alkene (olefin) and alkyne, and C-0 bond found in ether or carboxylic acid.
  • Well known peroxide forming compounds include an olefin such as styrene, butadiene, ethylene and the like; and ether such as tetrahydrofuran (THF), diethyl ether, methyl tertiary- butyl ether (MTBE), and the like.
  • olefin such as styrene, butadiene, ethylene and the like
  • ether such as tetrahydrofuran (THF), diethyl ether, methyl tertiary- butyl ether (MTBE), and the like.
  • THF tetrahydrofuran
  • MTBE methyl tertiary- butyl ether
  • the oxygen is removed by purging a vessel containing a chemical with an inert gas.
  • the vessel and/or recirculation loop apparatus are typically purged with the inert gases.
  • One or more inlets and outlets for the inert gas are attached to the vessel in one or more suitable locations. If the chemical to be stored and purged is a liquid, the inlet for the inert gas can be placed either above or below the surface of the liquid chemical. Purging employs the inert gases to physically sweep oxygen or water from the vessel and/or chemical contents.
  • purging of the vessel occurs after solid or liquid chemicals have been added to the vessel, so as to simultaneously sweep oxygen and/or air from both the vessel or entrained or dissolved in the chemical.
  • Purging can occur before, after, or during the filling of the vessel with the solid, liquid, or gaseous chemical to be stored, and may continue during storage or transport.
  • the vessel can be suitable for the transport and/or storage of a chemical.
  • the vessel can be a railroad tank car, a steel drum, a plastic drum, a tanker truck trailer, an Intermediate Bulk Container (IBC), a semi-permanent storage tank, or a permanent storage tank.
  • IBC Intermediate Bulk Container
  • a vessel designed for the transport of flammable and reactive organic chemicals can be employed in many aspects of the inventions, and those which are opaque to UV/visible light can be employed in many aspects of the inventions.
  • Such vessels can be fitted with boundary walls and inlet and outlet ports or devices that can be closed, so the vessel can be "closed” so as to substantially exclude penetration of atmospheric gases or water.
  • the steps employed in the method described herein includes the step of "purging a vessel for a chemical with an inert gas.”
  • the vessel employed in such methods can employ many sizes, shapes, number, kind, placement of openings, and materials of construction for the vessels.
  • the vessel can be designed so as to enable "closure” of the vessel so as to enable exclusion of undesired contamination by external materials, for example, oxygen, air, or water, or a mixture thereof.
  • the vessel walls can be constructed from material commonly used in the art that is capable of effectively containing the chemical, while simultaneously excluding oxygen, water, or air.
  • the vessel contains sealable openings for inlet, outlet, or circulation of the inert gases and/or the chemicals to be stored.
  • the inert gas is a gas or a mixture of gases which are inert to chemical reactivity with air, water, the compounds being stored or transported, or other substances likely to be encountered during shipment and storage of the chemicals.
  • inert gases include inflammable gases such as nitrogen, argon, helium and the like.
  • the inert gas comprises nitrogen or argon, or a mixture thereof.
  • the inert gases may contain small amounts of vapors from the gaseous or liquid chemicals being stored, but the presence of small amounts of vapors of the chemicals being stored does not necessarily exclude the mixed inert gases and vapors from being described as "inert.”
  • the method comprises circulating the chemical or the inert gas, or a mixture thereof, from the vessel through a recirculation loop apparatus.
  • the chemical remains in the vessel, while the inert gas is circulated through a recirculation loop apparatus.
  • the chemical is circulated through a recirculation loop apparatus.
  • the chemical and the inert gas are both circulated through the recirculation loop apparatus.
  • the chemical when the chemical is circulated through the loop, the chemical is a gas.
  • the chemical and/or the inert gas can be circulated through the recirculation loop apparatus.
  • the circulation time will be monitored by the monitoring device. Once the monitoring device shows acceptable levels, then the circulation can be terminated.
  • the method comprises a recirculation loop apparatus that comprises monitoring the oxygen level and scavenging the oxygen.
  • the monitoring occurs by using a monitoring device.
  • the monitoring device is any analytical device capable of detecting the level of oxygen (0 2 ) and/or water in a sample of the substance being monitored.
  • the device can be capable of measuring the oxygen concentration.
  • the device can also be capable of measuring the water concentration.
  • a single monitoring device can measure both oxygen
  • two monitoring devices can be used with one device to measure oxygen concentration and another device to measure water concentration.
  • oxygen monitoring devices are commercially available; for example, the optical sensor FDOTM 700 IQ supplied by WTW Inc., PO Box 9010,151 Graham Road College Station, Texas 77842, or the InPro6950i G from Mettler-Toledo Inc., 1900 Polaris Parkway, Columbus OH 43240.
  • the oxygen monitoring device can have as few fittings, parts and connectors as possible.
  • the oxygen monitoring device can comprise one overall device.
  • the monitoring the oxygen level precedes the scavenging of the oxygen. In another aspect, the scavenging the oxygen precedes the monitoring of the oxygen level.
  • the scavenging the oxygen occurs using an oxygen scavenger.
  • the oxygen scavenger relates to any device that is designed for scavenging oxygen molecules from a gas or liquid.
  • the oxygen scavenger can include a device that comprises a chemical agent that can remove or scavenge oxygen molecules from a gas or liquid by contact, and/or chemical reaction, or by any other suitable means.
  • the oxygen scavenging comprises an activated metal that can react rapidly and directly with oxygen.
  • the oxygen scavenging comprises an activated metal that can react rapidly and directly with oxygen at high temperatures.
  • the activated metal can comprise finely divided or dispersed copper or iron.
  • the activated metal can comprise oxides of copper or iron.
  • the finely divided spent copper oxide scavenger can be reactivated by treatment of the dispersed copper oxide with hydrogen/copper mixtures at elevated temperature.
  • suitable oxygen scavengers can include columns or cartridges that contain organic compounds that can function as reducing agents for oxygen.
  • the organic compound can comprise a bis-hydroxy aromatic.
  • the organic compound can comprise hydroquinone, catechol, or substituted variations of such bisphenols, or a mixture thereof.
  • Such bisphenols / hydroquinones can easily give up electrons and/or hydrogen atoms, in order to reduce other compounds, including oxygen, and thereby become oxidized to form benzoquinones or napthoquinones.
  • the electrons and hydrogen ions can be furnished by organic reducing agents.
  • the organic reducing agent can be hydroquinone and similar di- hydroxyaromatic that can reduce 0 2 to H 2 0, and thereby serve as oxygen scavengers, which can potentially be regenerated by treatment with reducing agents and sources of hydrogen ions.
  • the oxygen scavengers can also optionally comprise a variety of agents for removing water or water vapor from the chemicals, regardless of whether the water was present in the chemical when it was synthesized, or was formed by the oxygen scavenger by reduction of oxygen to form water.
  • Oxygen scavengers can also comprise a transition metal such as copper, iron, or iron salts, for example, those disclosed in US 8,226,850, hereby incorporated herein by reference for its teaching of oxygen scavengers.
  • Oxygen scavengers can also comprise noble metal catalysts, bisulfites, dithionites, hydrazines, guanidines, semicarbazides,
  • the oxygen scavenging agents can optionally be dispersed on supports that can be constructed from various suitable materials such as high surface area objects made from metals, inorganic oxides or suitable organic polymers.
  • the device can be designed so that the components of the column or cartridge are replaceable, can be removed after use, and can optionally be renewed and recharged by chemical means.
  • the method comprises transporting the chemical or the inert gas, or a mixture thereof, from the vessel through the recirculation loop apparatus.
  • the chemical or the inert gas, or a mixture thereof are transported, circulated, or re-circulated from the vessel and though the loop, and back into the vessel, after at least some scavenging of oxygen and/or water has been achieved, or until an acceptable oxygen level has been reached in the chemicals in the vessel.
  • selection of acceptable oxygen levels in a particular chemical of interest requires consideration of many factors, and is ordinarily selected in the context of one chemical of interest to the manufacturer or consumer of the chemical.
  • one or more chemicals or mixtures of chemicals can be contained in the vessel and/or recirculated through the recirculation loop apparatus.
  • Those chemicals can be gases or mixtures of gases or vapors, or can be liquids or mixtures of liquid, or can be solids or mixtures of solids.
  • the chemical is a gas or vapor, such as, for example, ethylene above its normal boiling point of -103.7 °C.
  • the chemical is a liquid, such as for example ethylene below its normal boiling point of -103.7 °C.
  • butadiene with a normal boiling point of -4.4 °C, can recirculated and/or oxygen scavenged as either a gas or liquid.
  • the chemical can be a solid in contact with its own liquid or vapor, as well as in contact with the inert gas.
  • the chemical is an organic liquid.
  • the chemical is a solid.
  • the method comprises transporting the chemical or the inert gas, or a mixture thereof, from the vessel through the recirculation loop apparatus until an acceptable oxygen level has been reached.
  • the acceptable oxygen level is a concentration of oxygen (0 2 ) gas dissolved in a chemical or mixture of chemicals, or in the inert gas in contact with a chemical or mixture of chemicals, that in the judgment of the producers or sellers of the chemical and/or their customers suitably slows or prevents the formation of peroxides in the chemical or mixture of chemicals. Many factors must be considered in order to choose an acceptable oxygen level for a chemical of interest.
  • An acceptable oxygen level can be empirically determined or chosen by one of ordinary skill in the art using known technical and analytical methods, for each individual chemical or mixture of chemicals to be stored, depending upon their individual chemical and physical properties, and likely anticipated conditions and length of storage. In some cases, a suitable oxygen level can be dictated by customer requirements as a specification. For example, in some aspects and for some chemicals, acceptable oxygen levels in the range of about 1 part per million (ppm) to about 1 mole % can be suitable and desirable.
  • acceptable oxygen levels can often be in the range of from about 1 ppm to about 200 ppm, including exemplary values of 5 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, and 190 ppm.
  • the acceptable oxygen level can be in the range of from 1 ppm to 10 ppm. In some aspects of the inventions, acceptable oxygen levels can be below about 10 ppm, or below about 5 ppm, or below about 1 ppm.
  • the method does not comprise substantially any of an additive for scavenging a peroxide or for preventing peroxide formation. In a further aspect, the method does not comprise any of an additive for scavenging a peroxide or for preventing peroxide formation. In a further aspect, the method does not comprise an additive for scavenging a peroxide or for preventing peroxide formation because the oxygen has been removed, preventing peroxide formation. As such, an additive for scavenging a peroxide or for preventing peroxide formation does not need to be added to the method.
  • the term additive refers to a chemical additive.
  • the term additive refers to anything directly added that decomposes or prevents peroxides from forming.
  • the chemical additive does not include preventing peroxide formation by removing the oxygen.
  • the present invention prevents peroxide formation by removing the oxygen.
  • the chemical additive comprises a chemical compound.
  • the chemical additive is a chemical compound that can be added to the chemical.
  • the chemical additive is present in the chemical in an amount generally less than about 5 weight percent (wt%), to improve or preserve the chemical and physical properties of the compound to which it is added. Improvements include greater stability towards air oxidation, inhibition of undesired polymerization or other undesired side reactions, the scavenging and decomposing peroxides that can form, and the like.
  • additives which scavenge peroxides and/or hydroperoxides once they have formed, and such additives are often bases and/or reducing agents, which can deprotonate and/or reduce hydroperoxides, or scavenge free radicals that form from the self- decomposition of peroxides.
  • Sterically hindered phenols such as a butylated hydroxytoluene (BHT) are well known as anti-oxidant additive that added to many air-oxidizable chemical products.
  • BHT butylated hydroxytoluene
  • the method when the method does not comprise substantially any of an additive for scavenging a peroxide or preventing peroxide formation, can comprise an additive in an amount ranging from 0 wt % to 1 wt %, including exemplary values of 0.001 wt%, 0.01 wt%, 0.1 wt %, 0.15 wt %, 0.20 wt %, 0.25 wt %, 0.30 wt %, 0.35 wt %, 0.40 wt %, 0.45 wt %, 0.5 wt %, 0.55 wt %, 0.6 wt %, 0.65 wt %, 0.7 wt %, 0.75 wt %, 0.8 wt %, 0.85 wt %, 0.9 wt %, and 0.95 wt %.
  • the range can be derived from any two exemplary values.
  • the method when the method does not comprise substantially any of an additive for scavenging a peroxide or preventing peroxide formation, the method can comprise an additive in an amount ranging from 0 wt % to 0.5 wt %.
  • the apparatus does not comprise, or the method or chemical does not comprise use of an additive for scavenging peroxides from the chemicals or preventing the formation of peroxides, including hydroperoxides.
  • an additive for scavenging peroxides from the chemicals or preventing the formation of peroxides, including hydroperoxides.
  • Such additives can be added in small amounts to many chemicals, but can be undesirable to down-stream users and customers, and must sometimes be removed from the chemicals prior to their end use.
  • Use of the methods and apparatuses described herein can however avoid the need for the use of such additives, and the associated purity issues or downstream use issues, and thus unexpectedly solves a long-standing problem in the art.
  • the vessel is used to contain a chemical
  • the vessel has one or more inlets and one or more outlets for an inert gas
  • recirculation loop apparatus comprises:
  • a pump wherein the pump transports the chemical or the inert gas, or a mixture thereof, from the vessel through the recirculation apparatus;
  • a monitoring device wherein the monitoring device measures the oxygen level;
  • the chemical can be solid, liquid or gas. In a further aspect, the chemical can be a gas or a vapor. In another aspect, the chemical can be an organic, an inorganic, and an organometallic compound. In yet another aspect, the chemical is an organic liquid. In an even further aspect, the chemical comprises an olefin, a diene or an ether. In one aspect, the chemical is an olefin.
  • the chemical is ethylene. In another aspect, the chemical is a diene. In a further aspect, the chemical is butadiene or cyclopentadience. In an even further aspect, the chemical comprises an ether. In a yet further aspect, the chemical comprises tetrahydrofuran (THF), diethyl ether, or methyl tertiary-butyl ether (MTBE), or a mixture thereof.
  • THF tetrahydrofuran
  • MTBE methyl tertiary-butyl ether
  • the chemical comprises dialkyl ethers of ethylene glycol, diethylene glycol, or triethylene glycol, or a mixture thereof.
  • the chemical comprises an aromatic or a hetero aromatic, or a mixture thereof.
  • the chemical comprises pyridine, benzene, toluene, styrene, acrylate, or cyanoacrylate.
  • the chemical is part of a sub-genus of chemicals that are known in the art as being susceptible to the formation of peroxides.
  • the chemical forms at least one peroxide in the presence of oxygen.
  • Such substances often contain carbon-hydrogen bonds that neighbor other functional groups, which "activate" those carbon-hydrogen bonds toward attack by either free radicals, such as for example oxygen (02) gas, which is a relatively stable free radical.
  • Such substances often contain electron rich moieties such as an unsaturated bond, (a double or triple bond) found in alkene (olefin) and alkyne, and C-0 bond found in ether or carboxylic acid.
  • Well known peroxide forming compounds include an olefin such as styrene, butadiene, ethylene and the like; and ether such as tetrahydrofuran (THF), diethyl ether, methyl tertiary- butyl ether (MTBE), and the like.
  • olefin such as styrene, butadiene, ethylene and the like
  • ether such as tetrahydrofuran (THF), diethyl ether, methyl tertiary- butyl ether (MTBE), and the like.
  • THF tetrahydrofuran
  • MTBE methyl tertiary- butyl ether
  • the vessel is used to contain a chemical.
  • the vessel can be suitable for the transport and/or storage of a chemical.
  • the vessel can be a railroad tank car, a steel drum, a plastic drum, a tanker truck trailer, an Intermediate Bulk Container (IBC), a semi-permanent storage tank, or a permanent storage tank.
  • IBC Intermediate Bulk Container
  • a vessel designed for the transport of flammable and reactive organic chemicals can be employed in many aspects of the inventions, and those which are opaque to UV/visible light can be employed in many aspects of the inventions.
  • Such vessels can be fitted with boundary walls and inlet and outlet ports or devices that can be closed, so the vessel can be "closed” so as to substantially exclude penetration of atmospheric gases or water.
  • the vessel comprises a railroad tank car, a tanker trailer, a drum, an intermediate bulk container (IBC), or a storage container.
  • the vessel has one or more inlets and one or more outlets for an inert gas.
  • One or more inlets and outlets for the inert gas can be attached to the vessel in one or more suitable locations. If the chemical to be stored and purged is a liquid, the inlet for the inert gas can be placed either above or below the surface of the liquid chemical.
  • Purging employs the inert gases to physically sweep oxygen or water from the vessel and/or chemical contents. Often purging of the vessel occurs after solid or liquid chemicals have been added to the vessel, so as to simultaneously sweep oxygen and/or air from both the vessel or entrained or dissolved in the chemical. Purging can occur before, after, or during the filling of the vessel with the solid, liquid, or gaseous chemical to be stored, and may continue during storage or transport.
  • the apparatus comprises a recirculation loop apparatus to and from the vessel.
  • a recirculation loop apparatus is attached to at least one inlet and at least one outlet of the vessel, so as to allow recirculation and/or transport of either the chemical, or the inert gas, or a mixture of both the chemical and inert gas, out of the bulk space of the vessel, through the recirculation loop apparatus, and back into the bulk space of the vessel.
  • One or more inlets and outlets for the recirculation loop device can be placed in one or more configurations either below or above the fill level of solid or liquid chemicals to be stored in the container, so as to enable recirculation of the chemicals, the inert gases, or mixtures of both.
  • the combination of the vessel and recirculation loop apparatus can be considered to form a "closed" loop, in the sense that it enables recirculation of the chemical and/or gases within the loop formed by the combination of the vessel and the recirculation loop apparatus.
  • the recirculation loop apparatus can be designed and constructed in many ways, either as integrated devices or as separate component devices within the recirculation loop apparatus connected by smaller vessels, pipes, or other devices.
  • the recirculation loop device can be mounted internally to the vessel, and/or external to the vessel. It should be noted that temperatures and pressures inside the recirculation loop device can be different in the recirculation loop device than they are in the vessel, and can be controlled so as to better optimize oxygen scavenging activity inside the recirculation loop device than might be obtainable under the conditions inside the vessel.
  • the temperature of the apparatus is ambient temperature. In a further aspect, the temperature of the apparatus is room temperature.
  • the recirculation loop device including its components such as an oxygen monitoring device, an oxygen scavenging device, a pump, etc., are external to the vessel, and can be removable and interchangeable from one vessel to another, or from one recirculation loop device to another.
  • the recirculation loop apparatus at least comprises devices or sensors for oxygen monitoring, and a device for oxygen scavenging or containing oxygen scavenging materials.
  • a pump wherein the pump transports the chemical or the inert gas, or a mixture thereof, from the vessel through the recirculation loop apparatus.
  • the recirculation loop apparatus can also comprise a pump for transporting the chemical or the inert gas from the vessel and through the recirculation loop device.
  • Many types of pumps can be employed in the recirculation loop device, and one of ordinary skill in the art can select a suitable pump in consideration of flows, and pressures needed, the chemical and physical properties of the chemical being circulated, and the need to minimize contact of the chemical being circulated with external air or water or sealing fluids or substances from the pump itself.
  • the inert gas comprises nitrogen or argon, or a mixture thereof.
  • the recirculation loop apparatus can also comprise an optional device or agent for scavenging water from the chemical, for example, if the devices or agents for oxygen scavenging produce water as a product of the oxygen scavenging.
  • an optional device or agent for scavenging water from the chemical for example, if the devices or agents for oxygen scavenging produce water as a product of the oxygen scavenging.
  • agents for scavenging water can be employed, such as for example small pore inorganic molecular sieves, clays, or zeolites, or strongly basic materials such as calcium hydride and the like.
  • the relative placement of the devices within the recirculation loop device, within the flow path for the chemical are not typically critical, though the oxygen level monitoring device is often placed prior to the pump, oxygen scavenger, or water scavenger.
  • the oxygen scavenger is placed prior to the water scavenger, so as to allow removal of water that can be generated in the oxygen scavenger.
  • the oxygen level monitoring precedes the oxygen scavenging.
  • the rate and duration of recirculation of the chemical and/or inert gas can be determined by the speed and/or volume of output of the pump, which can be either manually or automatically varied in response to the measurement signals from the oxygen level monitoring device.
  • the pump, recirculation loop apparatus, oxygen scavenger, and monitoring device are external to the vessel. In a further aspect, the pump, recirculation loop apparatus, oxygen scavenger, and monitoring device are internal to the vessel.
  • the pump, recirculation loop apparatus, oxygen scavenger, and monitoring device are removable and interchangeable from one vessel to another.
  • reaction conditions e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.
  • FIG. 1 An example of one of the various aspects of the methods and apparatuses described and/or claimed herein, can be illustrated by FIG. 1, showing that the problem of peroxide formation when storing chemical compounds can be solved by storage of the compounds in a vessel (20) which is fitted with an external recirculation loop apparatus comprising a pump (18), monitoring device (22) and oxygen scavenger (24), wherein the recirculation loop apparatus circulates the chemical contents of the vessel without exposure to outside atmosphere.
  • an external recirculation loop apparatus comprising a pump (18), monitoring device (22) and oxygen scavenger (24), wherein the recirculation loop apparatus circulates the chemical contents of the vessel without exposure to outside atmosphere.
  • the inlet for the recirculation loop apparatus at the top would transfer inert gas and/or vapors from the liquid toward the monitoring device and/or oxygen scavengers, then recirculate the gas into the bottom of the vessel, to purge and/or mix the liquid chemical with the deoxygenated and/or dehydrated gas.
  • the chemical was a gas (such as ethylene above its boiling point)
  • the chemical would be re-circulated by the recirculation loop apparatus.
  • Various arrangements of the inlets and outlets of the recirculation loop apparatus can be implemented by those of ordinary skill in the art to circulate the chemicals and/or inert gases or phases thereof.
  • the vessel is also fitted with an inlet (16) and outlet (14) port which permits purging of the vessel, recirculation loop apparatus, and/or chemical with a positive pressure stream of an inert gas, e.g., nitrogen, through the apparatus and/or chemical.
  • an inert gas e.g., nitrogen
  • the remaining air space is purged by introduction of the inert gas into the system for a time sufficient to displace the oxygen present. This time is shortened by the use of the circulating loop system which removes oxygen dissolved in the liquid.
  • the circulation can be discontinued and the vessel sealed with a slight positive pressure of inert gas. It is envisioned that the vessel, while now protected from exposure to the atmospheric oxygen, will be fitted with safety relief valves which would relieve any undo buildup of pressure within the vessel.
  • normal operating temperatures are from about -20 °C to about 150 °C; for example from about 10 °C to about 80 °C or from about 15 °C to about 65 °C.
  • the methods and apparatus for removing oxygen from a chemical disclosed herein include at least the following embodiments:
  • Embodiment 1 A method for removing oxygen from a chemical; comprising: (1) purging a vessel containing a chemical with an inert gas; (2) circulating the chemical or the inert gas, or a mixture thereof, from the vessel through a recirculation loop apparatus that performs the steps comprising: i. monitoring the oxygen level; and ii. scavenging the oxygen; and (3) transporting the chemical or the inert gas, or a mixture thereof, from the vessel through the recirculation loop apparatus until an acceptable oxygen level has been reached; wherein the method does not comprise substantially any of an additive for scavenging a peroxide or preventing peroxide formation.
  • Embodiment 2 The method of embodiment 1, wherein the chemical forms at least one peroxide in the presence of oxygen.
  • Embodiment 3 The method of any of embodiments 1-2, wherein the chemical is a gas or vapor.
  • Embodiment 4 The method of any of embodiments 1-2, wherein the chemical is a liquid.
  • Embodiment 5 The method of any of embodiments 1-2 or 4, wherein the chemical is an organic liquid.
  • Embodiment 6 The method of any of embodiments 1-5 wherein the monitoring the oxygen level precedes the scavenging the oxygen.
  • Embodiment 7 The method of any of embodiments 1-6, wherein the chemical comprises an olefin, a diene or an ether.
  • Embodiment 8 The method of any one of embodiments 1-7, wherein the chemical is an olefin.
  • Embodiment 9 The method of any one of embodiments 1-7, wherein the chemical is ethylene.
  • Embodiment 10 The method of any one of embodiments 1-7, wherein the chemical is a diene.
  • Embodiment 11 The method of any one of embodiments 1-7, wherein the chemical is butadiene.
  • Embodiment 12 The method of any one of embodiments 1-7, wherein the chemical comprises an ether.
  • Embodiment 13 The method of any one of embodiments 1-7, wherein the chemical comprises tetrahydrofuran (THF), diethyl ether, or methyl tertiary-butyl ether (MTBE), or a mixture thereof.
  • THF tetrahydrofuran
  • diethyl ether diethyl ether
  • MTBE methyl tertiary-butyl ether
  • Embodiment 14 The method of any one of embodiments 1-13, wherein the inert gas comprises nitrogen or argon, or a mixture thereof.
  • Embodiment 15 The method of any one of embodiments 1- 14, wherein the scavenging the oxygen comprises using an activated metal.
  • Embodiment 16 The method of any of embodiments 1-15, wherein the scavenging the oxygen comprises using a support.
  • Embodiment 17 The method of any one of embodiments 1-16, wherein the scavenging the oxygen comprises using an organic compound with oxygen scavenging properties.
  • Embodiment 18 The method of embodiment 17, wherein the organic compound with oxygen scavenging properties comprises a hydroquinone.
  • Embodiment 19 An apparatus for removing oxygen from a chemical
  • a vessel comprising: (1) a vessel, wherein the vessel is used to contain a chemical; wherein the vessel has one or more inlets and one or more outlets for an inert gas; and (2) a recirculation loop apparatus to and from the vessel, wherein the recirculation loop apparatus comprises: i. a pump, wherein the pump transports the chemical or the inert gas, or a mixture thereof, from the vessel through the recirculation loop apparatus; ii. a monitoring device, wherein the monitoring device measures the oxygen level; and iii. an oxygen scavenger.
  • Embodiment 20 The apparatus of embodiment 19, wherein the chemical forms at least one peroxide in the presence of oxygen.
  • Embodiment 21 The apparatus of any of embodiments 19-20, wherein the pump, recirculation loop apparatus, oxygen scavenger, and monitoring device are external to the vessel.
  • Embodiment 22 The apparatus of any of embodiments 19-21, wherein the pump, recirculation loop apparatus, oxygen scavenger, and monitoring device are removable and interchangeable from one vessel to another.
  • Embodiment 23 The apparatus of any of embodiments 19-22, wherein the vessel comprises a railroad tank car, a tanker trailer, a drum, an intermediate bulk container (IBC), or a storage container.
  • the vessel comprises a railroad tank car, a tanker trailer, a drum, an intermediate bulk container (IBC), or a storage container.
  • IBC intermediate bulk container

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  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

L'invention concerne des procédés et des appareils pour l'élimination d'oxygène à partir d'un produit chimique. Dans un aspect, le procédé d'élimination d'oxygène à partir d'un produit chimique comprend : (1) purger un récipient contenant un produit chimique par un gaz inerte ; (2) mettre en circulation le produit chimique ou le gaz inerte, ou un mélange de ceux-ci, à partir du récipient à travers un appareil de boucle de recirculation qui effectue les étapes comprenant : i. surveiller le taux d'oxygène ; et ii. piéger l'oxygène ; et (3) transporter le produit chimique ou le gaz inerte, ou un mélange de ceux-ci, à partir du récipient à travers l'appareil de boucle de recirculation jusqu'à ce qu'un taux d'oxygène acceptable ait été atteint ; le procédé ne comprenant substantiellement pas n'importe lequel parmi un additif pour piéger un peroxyde ou empêcher la formation de peroxyde.
PCT/IB2014/060960 2013-04-24 2014-04-24 Procédé et appareil d'élimination d'oxygène à partir d'un produit chimique WO2014174473A1 (fr)

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US61/815,320 2013-04-24

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1048757A1 (fr) * 1998-11-09 2000-11-02 Ebara Corporation Procede de metallisation et dispositif
WO2002028714A1 (fr) * 2000-10-02 2002-04-11 L'air Liquide, Society Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Inertage d'un reservoir a carburant d'aeronef
US20080099618A1 (en) * 2006-10-17 2008-05-01 Honeywell International Inc. Oxygen removal system
US20100050393A1 (en) * 2008-08-27 2010-03-04 Bp Corporation North America Inc. Apparatus and method of use for an inert gas rebreather used in furnace operations
US8226850B1 (en) 2009-09-22 2012-07-24 Clemson University Research Foundation Thermally enhanced oxygen scavengers including a transition metal and a free radical scavenger

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1048757A1 (fr) * 1998-11-09 2000-11-02 Ebara Corporation Procede de metallisation et dispositif
WO2002028714A1 (fr) * 2000-10-02 2002-04-11 L'air Liquide, Society Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Inertage d'un reservoir a carburant d'aeronef
US20080099618A1 (en) * 2006-10-17 2008-05-01 Honeywell International Inc. Oxygen removal system
US20100050393A1 (en) * 2008-08-27 2010-03-04 Bp Corporation North America Inc. Apparatus and method of use for an inert gas rebreather used in furnace operations
US8226850B1 (en) 2009-09-22 2012-07-24 Clemson University Research Foundation Thermally enhanced oxygen scavengers including a transition metal and a free radical scavenger

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
D.E. CLARK, CHEMICAL HEALTH & SAFETY, October 2001 (2001-10-01), pages 18
D.E. CLARK: "Chemical Health & Safety", October 2001, pages: 18
DONALD E. CLARK, PEROXIDES AND PEROXIDE-FORMING COMPOUNDS, CHEMICAL HEALTH AND SAFETY, September 2001 (2001-09-01), pages 12 - 22
INFORMATION ON PEROXIDE-FORMING COMPOUNDS, 23 July 2008 (2008-07-23)
MALCOLM A. KELLAND: "Oxygen Scavengers", 2009, CRC PRESS, article "Production Chemicals for the Oil and Gas Industry"

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