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Title:
PHOTOCHEMICAL DEOXYGENATION SYSTEMS AND METHODS FOR THE STORAGE OF LIQUID THAT GENERATES PEROXIDE
Document Type and Number:
WIPO Patent Application WO/2019/175700
Kind Code:
A1
Abstract:
A photochemical deoxygenation system is used for storing peroxide generating liquids. Singlet oxygen is generated by exposing a singlet oxygen precursor to a light source. The generated singlet oxygen reacts with atmospheric oxygen in the storage tank and forms peroxide. The formed peroxide is then transferred outside of the storage tank and broken down back to singlet oxygen and atmospheric oxygen by a second light source. The regenerated oxygen is then released. By using the photochemical deoxygenation system and method, the oxygen is effectively removed from the storage tank, thereby preventing the liquid from generating peroxide.

Inventors:
BODAS VIJAY DINKAR (SA)
PAUL SOMAK (SA)
AL OTAIBE SULTAN (SA)
Application Number:
PCT/IB2019/051628
Publication Date:
September 19, 2019
Filing Date:
February 28, 2019
Export Citation:
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Assignee:
SABIC GLOBAL TECHNOLOGIES BV (NL)
International Classes:
B01J19/00; B01J19/12; B65D90/00
Foreign References:
US20120245245A12012-09-27
JPH05200391A1993-08-10
CN103723803A2014-04-16
JP2016179956A2016-10-13
JP3851372B22006-11-29
CN105130928A2015-12-09
US20170051417A12017-02-23
US4775626A1988-10-04
DE102011119146A12013-05-23
Other References:
None
Download PDF:
Claims:
CLAIMS

1. A method of storing a liquid that generates peroxide, the method comprising:

disposing the liquid in a first area of a storage tank; disposing singlet oxygen in a second area of the storage tank so that the singlet oxygen reacts with atmospheric oxygen within the storage tank and thereby form peroxide; and removing the formed peroxide from the storage tank.

2. The method of claim 1, wherein the step of disposing singlet oxygen in the second area of the storage tank comprises: generating singlet oxygen outside of the storage tank; transferring the singlet oxygen to the second area of the storage tank; and retaining the singlet oxygen in the storage tank for a period so that the singlet oxygen reacts with the atmospheric oxygen within the storage tank and thereby form the peroxide.

3. The method of claim 1, wherein the step of disposing singlet oxygen in a second area of the storage tank comprises: generating singlet oxygen within the second area of the storage tank; and retaining the singlet oxygen in the storage tank for a period so that the singlet oxygen reacts with the atmospheric oxygen within the storage tank and thereby forms peroxide.

4. The method of any of claims 2 and 3, wherein the generating comprises:

exposing a singlet oxygen precursor to light of a wavelength sufficient to cause the singlet oxygen precursor to generate singlet oxygen.

5. The method of any of claims 1 to 3, further comprising:

exposing the removed peroxide to light of a wavelength sufficient to cause the removed peroxide to breakdown to regenerated singlet oxygen and regenerated atmospheric oxygen.

6. The method of claim 5, further comprising: transferring regenerated singlet oxygen to the second area of the storage tank so that the regenerated singlet oxygen reacts with atmospheric oxygen within the storage tank and thereby forms peroxide.

7. The method of claim 4, wherein a flowrate of the singlet oxygen precursor is at least 23.26 m3/hr.

8. The method of claim 4, wherein the singlet oxygen precursor has an activation energy in a range of 21 to 25 kcal/mol.

9. The method of claim 4, wherein the singlet oxygen precursor comprises a class (III) flammable liquid in packing group I under 49 C.F.R. 173.120 with a boiling point within 20° F of a boiling point of the liquid disposed in the first area of the storage tank.

10. The method of claim 4, wherein the singlet oxygen precursor is selected from the group consisting of 1, 4-dimethyl naphthalane, 9, lO-dimethyl anthracene, tetracene, l,2,3,4,5,6,7,8-octahydro l,l,4,4,5,5,8,8-octamethyl anthracene, and combinations thereof.

11. The method of any of claims 1 to 3, wherein the liquid disposed in the first area of the storage tank comprises a class (III) flammable liquid in packing group I under 49 C.F.R. 173.120 with a vapor space there above classified as non-hazardous under International Electrotechnical Commission 60079-1-1.

12. The method of any of claims 1 to 3, wherein the liquid disposed in the first area of the storage tank is not autopolymerizing.

13. The method of any of claims 1 to 3, wherein the liquid disposed in the first area of the storage tank is selected from the group consisting of 2-ethyl-hexanol, lauryl alcohol, capric alcohol, caprylic alcohol, isononanol, isobutanol, n-butanol, aldehydes thereof, and combinations thereof.

14. The method of any of claims 1 to 3, wherein the storage tank is selected from the group consisting of a mobile storage tank, a stationary storage tank, a rail car tank, a truck tank, and a ship cargo tank.

15. The method of any of claims 1 to 3, wherein the singlet oxygen reacts with the atmospheric oxygen at a rate of at least 75.6 nm3/hr oxygen from 360 nm3/hr air.

16. A photochemical deoxygenation system for storing a first liquid, the system comprising:

a storage tank that comprises: a first area configured to store the first liquid; and a second area comprising an area above the first liquid; and a first light source configured to expose the second liquid to light from the first light source.

17. The photochemical deoxygenation system of claim 16, wherein the second area comprises a first container configured to contain a second liquid.

18. The photochemical deoxygenation system of any of claims 16 and 17, wherein the first light source is configured to emit light of a wavelength of 210 nm to 280 nm.

19. The photochemical deoxygenation system of any of claims 16 to 17, further comprising:

a recovery container disposed outside of the storage tank and in fluid communication with the first container in the second area; and a second light source configured to expose a liquid in the recovery container to light from the second light source.

20. The photochemical deoxygenation system of claim 19, wherein the second light source is configured to emit light of a wavelength of 1200 nm to 1300 nm.

Description:
PHOTOCHEMICAL DEOXYGENATION SYSTEMS AND METHODS FOR THE STORAGE OF LIQUID THAT GENERATES PEROXIDE

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Patent

Application No. 62/642,545, filed March 13, 2018, which is hereby incorporated by reference in its entirety.

FIELD OF INVENTION

[0002] The present invention generally relates to systems and methods for storing a liquid. More specifically, the present invention relates to photochemical deoxygenation systems and methods for storing a liquid that generates peroxide when exposed to oxygen. BACKGROUND OF THE INVENTION

[0003] Peroxides are formed when peroxide forming compounds react with oxygen.

The rate of forming peroxide can greatly increase when the peroxide forming compounds are exposed to air, moisture, metal contamination, light shock, or thermal shock. For example, for stored liquids that have peroxide forming compounds, the formed peroxides directly react with the stored liquid, or generate free radicals to initiate radical chain reactions with the stored liquid, thereby causing deterioration of the stored liquid. Thus, liquids stored in open air ventilated metal tanks can be seriously contaminated by peroxides, even if the concentrations of peroxide forming compounds in these liquids are low, due to the chain reactions and resulting increased peroxide forming rate. Furthermore, some stored liquids can react with atmospheric oxygen and form peroxide crystals that can cause explosion when they are exposed to thermal or mechanical shock. Therefore, preventing liquids from forming peroxides in storage tanks is imperative.

[0004] Current solutions to peroxide contamination include purging the storage tank with inert gas to protect the stored liquid from oxygen. However, this method demands heavy duty gas compression equipment and/or air tight storage vessels, normally applied to storing highly flammable, highly explosive and/or volatile liquids. Thus, when the stored liquids are non-explosive and have high boiling points, using storage vessels purged with inert gas can significantly increase the costs for storing such liquids. Moreover, the heavy duty equipment used for purging the vessels and maintaining inert gas in the storage vessels can limit the mobility of the storage system because this equipment can be heavy and voluminous, thereby taking up a large space of transportation vehicles. Therefore, an improved system for storing peroxide forming liquids is desired.

BRIEF SUMMARY OF THE INVENTION

[0005] A method has been discovered for storing a liquid that generates peroxide. By using singlet oxygen to react with atmospheric oxygen in a storage tank, the liquid can be stored with little or no contact to peroxides. Advantages of this method include reduced transportation costs due to small footprint of the equipment and reduced process costs due to recycling of the singlet oxygen.

[0006] Embodiments of the invention include a method for storing a liquid that generates peroxide. The method may comprise disposing the liquid in a first area of a storage tank. Singlet oxygen may be disposed in a second area of the storage tank so that the singlet oxygen reacts with atmospheric oxygen within the storage tank, thereby forming peroxide. The method may further include removing the formed peroxide from the storage tank.

[0007] Embodiments of the invention include a method for storing a liquid that generates peroxide. The method may include disposing the liquid in a first area of a storage tank and generating singlet oxygen within a second area of the storage tank. The generating may comprise exposing a singlet oxygen precursor to light of a wavelength sufficient to cause the singlet oxygen precursor to generate singlet oxygen. The method may further include retaining the singlet oxygen in the storage tank for a period so that the singlet oxygen reacts with atmospheric oxygen within the storage tank and thereby forms peroxide. The formed peroxide is removed from the storage tank. The removed peroxide may be exposed to light of a wavelength sufficient to cause the removed peroxide to breakdown to form regenerated singlet oxygen and regenerated atmospheric oxygen.

[0008] Embodiments of the invention include a photochemical deoxygenation system for storing a first liquid. The system comprises a storage tank. The storage tank may comprise a first area configured to store the first liquid and a second area comprising an area above the first liquid. A first container may be disposed in the second area, where the first container is configured to contain a second liquid. The second liquid is a precursor to singlet oxygen. The system may further include a first light source disposed over the second area configured to expose the second liquid to light therefrom. [0009] Embodiments of the invention include a photochemical deoxygenation system for storing a first liquid. The system may comprise a storage tank. The storage tank may comprise a first area configured to store the first liquid and a second area comprising an area above the first liquid. A first container may be disposed in the second area configured to contain a second liquid. The system may further include a first light source configured to expose the second liquid to light therefrom. The system may further include a recovery container disposed outside of the storage tank and in fluid communication with the second area. Further still, the system may include a second light source configured to expose a content in the recovery container to the light therefrom. [0010] The following includes definitions of various terms and phrases used throughout this specification.

[0011] The terms “about” or“approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%.

[0012] The terms“wt.%,”“vol.%” or“mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol.% of component. [0013] The term“substantially” and its variations are defined to include ranges within

10%, within 5%, within 1%, or within 0.5%.

[0014] The terms“inhibiting” or“reducing” or“preventing” or“avoiding” or any variation of these terms, when used in the claims and/or the specification, include any measurable decrease or complete inhibition to achieve a desired result. [0015] The term“effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0016] The use of the words“a” or“an” when used in conjunction with the term

“comprising,”“including,”“containing,” or“having” in the claims or the specification may mean“one,” but it is also consistent with the meaning of“one or more,”“at least one,” and “one or more than one.”

[0017] The words“comprising” (and any form of comprising, such as“comprise” and

“comprises”),“having” (and any form of having, such as“have” and“has”),“including” (and any form of including, such as“includes” and“include”) or“containing” (and any form of containing, such as“contains” and“contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0018] The process of the present invention can“comprise,”“consist essentially of,” or“consist of’ particular ingredients, components, compositions, etc., disclosed throughout the specification.

[0019] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which: [0021] FIG. 1 shows a schematic diagram of a photochemical deoxygenation system for storing a liquid, according to embodiments of the invention; and

[0022] FIG. 2 shows a schematic flowchart for a method of storing a liquid that generates peroxide when exposed to oxygen, using a photochemical deoxygenation system, according to embodiments of the invention. DETATEED DESCRIPTION OF THE TNVENTTON

[0023] A method has been discovered for storing a liquid that generates peroxide when exposed to oxygen. Singlet oxygen may be used to react with atmospheric oxygen in the storage tank to form peroxide. By removing the formed peroxide, the stored liquid is protected from atmospheric oxygen, thereby preventing the stored liquid from forming peroxide. The singlet oxygen may be recovered by applying light of a wavelength sufficient to break down the formed peroxides back to singlet oxygen and atmospheric oxygen. This method requires minimal equipment to be added to the storage tank. Therefore, the method is suitable for storing liquid both in storage equipment at fixed locations and mobile storage equipment.

[0024] With reference to FIG. 1, a schematic diagram is shown as photochemical deoxygenation system 100 for storing a liquid that generates peroxide when exposed to oxygen. As shown in FIG. 1, photochemical deoxygenation system 100 may include storage tank 101 that may comprise first area 102 for storing liquid 112 and second area 103 in which singlet oxygen is disposed. Ventilation device 104 may be installed on storage tank 101. In embodiments of the invention, ventilation device 104 may be a flame arrester. Gas 133 in second area 103 may comprise primarily air and vapor of liquid 112. First light source 105 may be disposed in second area 103. In embodiments of the invention, first light source 105 may be configured to emit light of a wavelength that causes singlet oxygen precursor 113 in second area 103 to generate singlet oxygen. First light source 105 may be disposed over singlet oxygen precursor 113 in second area 103. Singlet oxygen precursor 113 may be disposed in first container 123, located in second area 103. According to embodiments of the invention, first container 123 may be an open-top container, such as a tray.

[0025] Photochemical deoxygenation system 100 may further comprise a recovery system for recovering singlet oxygen from peroxide that is formed by singlet oxygen reacting with atmospheric oxygen. The recovery system may comprise pump 106 in fluid communication with second area 103, recovery container 107 in fluid communication with pump 106, and second light source 108 disposed over recovery container 107. Second light source 108 may be configured to expose the peroxide in recovery container 107 to light of a wavelength sufficient to breakdown the peroxide back to singlet oxygen and atmospheric oxygen. In embodiments of the invention, pump 106 may be configured to reversibly transfer the singlet oxygen precursor from recovery container 107 of the recovery system to second area 103 of storage tank 101.

[0026] In embodiments of the invention, first light source 105 and singlet oxygen precursor 113 may be disposed outside of storage tank 101. And singlet oxygen may be generated by exposing singlet oxygen precursor 113 to the light emitted from first light source 105 outside of storage tank 101. Then generated singlet oxygen may be transferred to second area 103 to react with atmospheric oxygen in storage tank 101.

[0027] The conventional system used for storing a flammable and/or explosive liquid includes heavy duty equipment for purging the storage tank with inert gas in order to use the inert gas to isolate the liquid from atmospheric oxygen. The heavy duty equipment is heavy and bulky, and thereby significantly increases the cost of liquid storage and liquid transportation. Photochemical deoxygenation system 100 includes minimal equipment in addition to storage tank 101, thus the overall system can be lightweight and compact. In this way, photochemical deoxygenation system 100 may remedy deficiencies of the conventional systems used for liquid storage. In embodiments of the invention, storage tank 101 may include, but is not limited to a mobile storage tank, a stationary storage tank, a rail car tank, and a ship cargo tank.

[0028] FIG. 2 shows a schematic flowchart for method 200 of storing a liquid that generates peroxide when exposed to atmospheric oxygen. Method 200 may be implemented by photochemical deoxygenation system 100 as shown in FIG. 1. Method 200 may include disposing liquid 112 in first area 102 of storage tank 101, as shown in block 201. The storage tank may be ventilated to open air via ventilation device 104 installed on the storage tank. In embodiments of the invention, the ventilation device may be a flame arrester.

[0029] Liquid 112 may be a non-explosive and non-autopolymerizing liquid that has a high boiling point. In embodiments of the invention, liquid 112 may be a Class III flammable liquid in packing group I under 49 C.F.R. 173.120. A vapor space above liquid 112 may be classified as non-hazardous under International Electrotechnical Commission 60079-1-1. Furthermore, the liquid may generate peroxide when exposed to oxygen. The peroxide generating rate may be sufficiently low to avoid forming explosive peroxide. In embodiments of the invention, exemplary liquids stored in storage tank 101 may include, but are not limited to, one or more of 2-ethyl hexanol, SUPERBUTOL™ (Saudi Arabian Oil Company), dodecanol (lauryl alcohol), l-decanol (capric alcohol), octanol (caprylic alcohol), isononanol, isobutanol, n-butanol, or aldehydes thereof.

[0030] Block 202 shows that method 200 may further include disposing singlet oxygen in second area 103 of storage tank 101 so that the singlet oxygen reacts with atmospheric oxygen that is in gas 133 ( e.g . air and/or vapor of liquid 112) within storage tank 101 and thereby forms peroxide. Second area 103 may be an area above liquid 112. The singlet oxygen may react with the atmospheric oxygen at a rate of at least 75.6 nm 3 oxygen per hour from 360 nm 3 per hour of air. In embodiments of the invention, the a tank volumetric purge rate may be determined by one or more safety standards. Non-limiting examples of the safety standards may include NFPA 69 (National Fire Protection Association) and API-2000 (American Petroleum Institute). In embodiments of the invention, the step of disposing singlet oxygen may comprise generating singlet oxygen within second area 103 of storage tank 101 as shown in block 203, and retaining the singlet oxygen in storage tank 101 for a period so that the singlet oxygen reacts with atmospheric oxygen that is in gas within the storage tank and thereby forming peroxide, as shown in block 204. In embodiments of the invention, the singlet oxygen may be generated outside of storage tank 101 and then transferred into second area 103 of storage tank 101.

[0031] In embodiments of the invention, the generating in block 203 may comprise exposing singlet oxygen precursor 113 to light of a wavelength sufficient to cause singlet oxygen precursor 113 to generate singlet oxygen. The light may be from first light source 105 disposed above second area 103. Singlet oxygen precursor 113 may be disposed in first container 123, located in second area 103. The singlet oxygen precursor may have an activation energy in a range of 21 to 25 kcal/mol and all ranges and values there between, including 21 to 21.2 kcal/mol, 21.2 to 21.4 kcal/mol, 21.4 to 21.6 kcal/mol, 21.6 to 21.8 kcal/mol, 21.8 to 22.0 kcal/mol, 22.0 to 22.2 kcal/mol, 22.2 to 22.4 kcal/mol, 22.4 to 22.6 kcal/mol, 22.6 to 22.8 kcal/mol, 22.8 to 23.0 kcal/mol, 23.0 to 23.2 kcal/mol, 23.2 to 23.4 kcal/mol, 23.4 to 23.6 kcal/mol, 23.6 to 23.8 kcal/mol, 23.8 to 24.0 kcal/mol, 24.0 to 24.2 kcal/mol, 24.2 to 24.4 kcal/mol, 24.4 to 24.6 kcal/mol, 24.6 to 24.8 kcal/mol, or 24.8 to 25.0 kcal/mol.

[0032] In embodiments of the invention, singlet oxygen precursor 113 may comprise a class (III) flammable liquid in packing group I under 49 C.F.R. 173.120. A flammable liquid (Class III) under 49 C.F.R. 173.120 may be a liquid having a flash point of not more than 60.5° C (141° F), or any material in a liquid phase with a flash point at or above 37.8° C (100° F). Singlet oxygen precursor 113 may have a boiling point within 11.1° C (20° F) of a boiling point of the liquid disposed in first area 102 of storage tank 101. A vapor above the singlet oxygen precursor disposed in second area 103 of storage tank 101 may be classified as non-hazardous under International Electrotechnical Commission 60079-1-1. In embodiments of the invention, singlet oxygen precursor 113 may be less flammable and have a higher boiling point than the liquid stored in first area 102 of storage tank 101. Exemplary singlet oxygen precursors may include, but are not limited to, 1, 4-dimethyl naphthalane, 9,10- dimethyl anthracene, tetracene, l,2,3,4,5,6,7,8-octahydro l,l,4,4,5,5,8,8-octamethyl anthracene, or combinations thereof. The boiling points and flash points for these singlet oxygen precursors are shown in Table 1.

Table 1. Boiling points and flash points of singlet oxygen precursors

[0033] In embodiments of the invention, the wavelength sufficient to cause singlet oxygen precursor 113 to generate singlet oxygen may be 210 nm to 280 nm and all ranges and values there between including 210 to 215 nm, 215 to 220 nm, 220 to 225 nm, 225 to 230 nm, 230 to 235 nm, 235 to 240 nm, 240 to 245 nm, 245 to 250 nm, 250 to 255 nm, 255 to 260 nm, 260 to 265 nm, 265 to 270 nm, 270 to 275 nm, and 275 to 280 nm. The generated singlet oxygen from singlet oxygen precursor 113 may react with atmospheric oxygen to form peroxide in first container 123 in the second area.

[0034] As shown in block 205, the peroxide formed in block 202 may be removed from second area 103 of storage tank 101. In embodiments of the invention, the peroxide may be removed by pump 106 that is in fluid communication with recovery container 107 and first container 123. Peroxide along with unreacted singlet oxygen and/or unreacted singlet oxygen precursor in second area 103 may be pumped into recovery container 107. Block 206 shows that the peroxide removed from storage tank 101 and placed in recovery container 107 may be exposed to light of a wavelength sufficient to cause the removed peroxide to breakdown back to regenerated singlet oxygen precursor and the atmospheric oxygen (regenerated atmospheric oxygen). Therefore, the peroxide forming reaction from singlet oxygen and atmospheric oxygen may be reversed.

[0035] In embodiments of the invention, the light in block 206 may be from second light source 108. The wavelength of the light sufficient to cause the removed peroxide to breakdown may be in a range of 1200 nm to 1300 nm and all ranges and values there between including ranges of 1200 to 1205 nm, 1205 to 1210 nm, 1210 to 1215 nm, 1215 to 1220 nm, 1220 to 1225 nm, 1225 to 1230 nm, 1230 to 1235 nm, 1235 to 1240 nm, 1240 to 1245 nm,

1245 to 1250 nm, 1250 to 1255 nm, 1255 to 1260 nm, 1260 to 1265 nm, 1265 to 1270 nm,

1270 to 1275 nm, 1275 to 1280 nm, 1280 to 1285 nm, 1285 to 1290 nm, 1290 to 1295 nm, and 1295 to 1300 nm. The activation energy for singlet oxygen precursor 113 may be in a range of 21-25 kcal/mol as described above, for the peroxide forming process to be reversible, thereby setting up a redox cycle.

[0036] According to embodiments of the invention, the regenerated singlet oxygen may be transferred back to second area 103 of storage tank 101. The regenerated singlet oxygen may be reused to react with atmospheric oxygen in storage tank 101, thereby saving the cost of using the photochemical oxygenation system to store liquid. The regenerated atmospheric oxygen may be released outside of storage tank 101. In embodiments of the invention, singlet oxygen precursor 113 may have a flowrate of at least 23.26 m 3 /hr. In embodiments of the invention, an amount of singlet oxygen precursor and/or singlet oxygen may be supplied to first container 123 to make up the loss of the singlet oxygen precursor and/or singlet oxygen during the process of method 200.

[0037] In summary, embodiments of the invention involve a method of storing a liquid that forms peroxide when exposed to oxygen in a storage tank. The method uses a singlet oxygen precursor to generate singlet oxygen when exposed to light of wavelength of 210 nm to 280 nm. The generated singlet oxygen reacts with atmospheric oxygen in the storage tank and forms peroxide with the atmospheric oxygen. The peroxide may breakdown to release the oxygen and regenerate singlet oxygen under light of a wavelength in a range of 1200 nm to 1300 nm, thereby removing the oxygen and recycling the singlet oxygen. Embodiments of the invention utilize a system that has light weight and small volume. Therefore, implementing embodiments of the invention can be cost effective for liquid storage in both fixed location and during transportation.

[0038] Although embodiments of the present invention have been described with reference to blocks of FIG. 2, it should be appreciated that operation of the present invention is not limited to the particular blocks and/or the particular order of the blocks illustrated in FIG. 2. Accordingly, embodiments of the invention may provide functionality as described herein using various blocks in a sequence different than that of FIG. 2.

[0039] As part of the disclosure of the present invention, specific examples are included below. The examples are for illustrative purposes only and are not intended to limit the invention. Those of ordinary skill in the art will readily recognize parameters that can be changed or modified to yield essentially the same results.

EXAMPLES

Example 1

(Tests for Dissolved Oxygen and Aldehyde Content)

[0040] To study the correlation between dissolved oxygen level and aldehyde level,

2-ethylhexanol samples were collected from ALB (S-324)) at 0 hour and 120 hours (day 5). 2-ethylhexanol samples are collected from shore tank (255-F) at 1600 hours. The dissolved oxygen or peroxide contents were analyzed using ASTM E 299-08 standard. The aldehyde contents were analyzed using BS 4583: 1991 standard. The results are shown in Table 2.

Table 2 Exemplary results for dissolved oxygen and aldehyde contents

[0041] The results indicate that dissolved oxygen or peroxide content increased more than 18 times between samples from March 20, 2016 and samples from July 20, 2016. The aldehyde content increased about 13 times between the same two samples. This could be caused by peroxide initiated free radical reactions that oxidize alcohol. The free radical reactions may be triggered by radiation or thermal agitation. The required oxygen removal rate to prevent generating peroxide in the liquid was then calculated based on 7517 MT of stored 2-ethyl hexanol on sampled date turns out to be 2.36 normal m 3 /hr for the storage tanks listed in Table 2. For the photochemical removal system disclosed herein, the required removal rate was 75.6 nmVhour from 360 nmVhour air. The singlet oxygen precursor flowrate was calculated based on the assumption that the singlet oxygen precursor has an oxygen carrying ability of normal hemoglobin loaded blood. The resulted flowrate for singlet oxygen precursor was 23.26 m 3 /hour.

[0042] In the context of the present invention, embodiments 1-20 are described. Embodiment 1 is a method of storing a liquid that generates peroxide. The method includes disposing the liquid in a first area of a storage tank. The method also includes disposing singlet oxygen in a second area of the storage tank so that the singlet oxygen reacts with atmospheric oxygen within the storage tank and thereby form peroxide. In addition, the method includes removing the formed peroxide from the storage tank. Embodiment 2 is the method of embodiment 1, wherein the step of disposing singlet oxygen in the second area of the storage tank includes generating singlet oxygen outside of the storage tank, transferring the singlet oxygen to the second area of the storage tank, and retaining the singlet oxygen in the storage tank for a period so that the singlet oxygen reacts with the atmospheric oxygen within the storage tank and thereby form the peroxide. Embodiment 3 is the method of embodiment 1, wherein the step of disposing singlet oxygen in a second area of the storage tank includes generating singlet oxygen within the second area of the storage tank. The method also includes retaining the singlet oxygen in the storage tank for a period so that the singlet oxygen reacts with the atmospheric oxygen within the storage tank and thereby forms peroxide. Embodiment 4 is the method of either of embodiments 2 or 3, wherein the generating includes exposing a singlet oxygen precursor to light of a wavelength sufficient to cause the singlet oxygen precursor to generate singlet oxygen. Embodiment 5 is the method of any of embodiments 1 to 4, further including exposing the removed peroxide to light of a wavelength sufficient to cause the removed peroxide to breakdown to regenerated singlet oxygen and regenerated atmospheric oxygen. Embodiment 6 is the method of embodiment 5, further including transferring regenerated singlet oxygen to the second area of the storage tank so that the regenerated singlet oxygen reacts with atmospheric oxygen within the storage tank and thereby forms peroxide. Embodiment 7 is the method of any of embodiments 4 to 6, wherein a flowrate of the singlet oxygen precursor is at least 23.26 m 3 /hr. Embodiment 8 is the method of any of embodiments 4 to 7, wherein the singlet oxygen precursor has an activation energy in a range of 21 to 25 kcal/mol. Embodiment 9 is the method of any of embodiments 4 to 8, wherein the singlet oxygen precursor comprises a class (III) flammable liquid in packing group I under 49 C.F.R. 173.120 with a boiling point within 20° F of a boiling point of the liquid disposed in the first area of the storage tank. Embodiment 10 is the method of any of embodiments 4 to 9, wherein the singlet oxygen precursor is selected from the group consisting of 1, 4-dimethyl naphthalane, 9, lO-dimethyl anthracene, tetracene, l,2,3,4,5,6,7,8-octahydro 1, 1,4, 4, 5, 5,8,8- octamethyl anthracene, and combinations thereof. Embodiment 11 is the method of any of embodiments 1 to 10, wherein the liquid disposed in the first area of the storage tank comprises a class (III) flammable liquid in packing group I under 49 C.F.R. 173.120 with a vapor space there above classified as non-hazardous under International Electrotechnical Commission 60079-1-1. Embodiment 12 is the method of any of embodiments 1 to 11, wherein the liquid disposed in the first area of the storage tank is not autopolymerizing. Embodiment 13 is the method of any of embodiments 1 to 12, wherein the liquid disposed in the first area of the storage tank is selected from the group consisting of 2-ethyl-hexanol, lauryl alcohol, capric alcohol, caprylic alcohol, isononanol, isobutanol, n-butanol, aldehydes thereof, and combinations thereof. Embodiment 14 is the method of any of embodiments 1 to 13, wherein the storage tank is selected from the group consisting of a mobile storage tank, a stationary storage tank, a rail car tank, a truck tank, and a ship cargo tank. Embodiment 15 is the method of any of embodiments 1 to 14, wherein the singlet oxygen reacts with the atmospheric oxygen at a rate of at least 75.6 nm 3 /hr oxygen from 360 nm 3 /hr air.

[0043] Embodiment 16 is a photochemical deoxygenation system for storing a first liquid. The system includes a storage tank that has a first area configured to store the first liquid and a second area that is an area above the first liquid. The system also includes a first light source configured to expose the second liquid to light from the first light source. Embodiment 17 is the photochemical deoxygenation system of embodiment 16, wherein the second area includes a first container configured to contain a second liquid. Embodiment 18 is the photochemical deoxygenation system of either of embodiments 16 or 17, wherein the first light source is configured to emit light of a wavelength of 210 nm to 280 nm. Embodiment 19 is the photochemical deoxygenation system of any of embodiments 16 to 18, further including a recovery container disposed outside of the storage tank and in fluid communication with the first container in the second area. The photochemical deoxygenation system also includes a second light source configured to expose a liquid in the recovery container to light from the second light source. Embodiment 20 is the photochemical deoxygenation system of embodiment 19, wherein the second light source is configured to emit light of a wavelength of 1200 nm to 1300 nm.

[0044] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.