EP3802474A1

EP3802474A1 - Reducing oxidized oxo alcohols for quality improvement

Info

Publication number: EP3802474A1
Application number: EP19737893.8A
Authority: EP
Inventors: Somak PAUL; Vijay BODAS; Abdullah Saad DUGHAITHER-AL; Asraf A. ALI; Ganesh Bhat
Original assignee: SABIC Global Technologies BV
Current assignee: SABIC Global Technologies BV
Priority date: 2018-06-04
Filing date: 2019-05-23
Publication date: 2021-04-14
Also published as: WO2019234545A1

Abstract

Methods for the storage and/or transportation of an auto-oxidizable alcohol in commercial quantities and methods for distilling an auto-oxidizable alcohol are disclosed. For storage and/or transportation of an auto-oxidizable alcohol, a reducing agent is added in the alcohol to reduce oxidized alcohol products, thereby improving the quality of the auto-oxidizable alcohol. For distilling an auto-oxidizable alcohol, a reducing agent is combined in the feed stream of the distillation column for the auto-oxidizable alcohol to reduce the oxidized alcohol products and prevent oxidation process, resulting in higher quality of the distilled alcohol product.

Description

REDUCING OXIDIZED OXO ALCOHOLS FOR QUALITY IMPROVEMENT

CROSS REFERENCE TO RELATED APPLICATIONS

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

No. 62/680,129, filed June 4, 2018, which is hereby incorporated by reference in its entirety.

FIELD OF INVENTION

[0002] The present invention generally relates to the reduction of oxidized alcohols. More specifically, the present invention relates to a processes for reducing oxidized oxo alcohols in storage containers and/or during distillation processes.

BACKGROUND OF THE INVENTION

[0003] Oxo alcohols are alcohols produced by adding carbon monoxide and hydrogen to an olefin. Oxo alcohols can be used as solvents or as precursors of plasticizers ( e.g ., phthalates). When it is in contact with an oxidant, such as oxygen presented in the atmosphere, an oxo alcohol can be oxidized to form undesirable or even harmful aldehydes or other carbonyls. These formed aldehydes or carbonyls can further oxidize oxo alcohols resulting in significant decrease in product quality.

[0004] Further, when oxo alcohols are utilized and/or purified in a chemical process that requires high operating temperature, a large amount of oxo alcohols can be oxidized during the process, resulting in low productivity and/or high purification cost for the target product. Hence, maintaining product quality of high purity oxo alcohols during storing and transporting processes and in chemical processing, especially at high ambient temperatures, is imperative.

[0005] Conventionally, nitrogen blanketing is used to store and transport oxo alcohols. However, this method requires either air tight containers or periodic replenishing of nitrogen, thereby increasing the storing and/or transporting cost. Furthermore, when nitrogen blanketing is applied, a high pressure of nitrogen gas is generally required, which can increase the complexity of handling the storage containers during transportation. Moreover, for a chemical process that involves oxo alcohol, it is difficult to apply nitrogen blanketing to the oxo alcohols as the oxo alcohols are moving among different operation units.

[0006] Overall, while conventional methods of reducing oxo alcohol oxidation exist, the need for improvement in this field persists in light of at least the aforementioned drawbacks.

[0007] A solution to at least some of the above-mentioned problems associated with reduction of oxidation of oxo alcohols has been discovered. The solution resides in a process that includes adding a reducing agent in oxo alcohols to reduce any oxidized oxo alcohols that exist with the oxo alcohols. Notably, the process can be applied in a storage container for storing and transporting oxo alcohols, and to a chemical process that involves oxo alcohols, where the reducing agent can be directly dosed into any processing stream. This can be beneficial because adding the reducing agent to oxo alcohol reduces and/or eliminates the need of high pressure nitrogen blanketing in a storage container of oxo alcohol, thereby reducing the cost of storing and transporting oxo alcohols. Adding a reducing agent to a processing stream that contains an oxo alcohol can also solve the technical difficulties of minimizing oxidation of oxo alcohol during a chemical process. Therefore, the process of the present invention provides a solution to at least some of the problems associated with the currently available methods for preventing oxo alcohol from oxidation and/or reducing oxidized oxo alcohols.

[0008] Embodiments of the invention include a process for storage and/or transportation of an auto-oxidizable alcohol in commercial quantities. The process comprises obtaining a container holding an auto-oxidizable alcohol in an amount of greater than 50 kilograms and in a purity of greater than 98% by weight and with between 1 ppm and less than 500 ppm of aldehyde corresponding to auto-oxidizable product of the alcohol. The process further comprises adding a reducing agent to the alcohol in the container. The reducing agent is added in an amount effective for maintaining less than 500 ppm of aldehyde corresponding to auto- oxidizable product of the alcohol.

[0009] Embodiments of the invention include a process for producing a plasticizer or acrylate product. The process comprises obtaining a stabilized composition of 2-ethylhexanol. The process further includes reacting 2-ethylhexanol from the stabilized composition of 2- ethylhexanol with additional feedstocks to produce a plasticizer or acrylate product. The stabilized composition of 2-ethylhexanol in the process is prepared according to a method that comprises obtaining a container holding 2-ethylhexanol in an amount of greater than 50 kilograms and in a purity of greater than 98% by weight and with between 1 ppm and less than 500 ppm of 2-ethyl-hexaldehyde. The process further includes adding sodium borohydride to the 2-ethylhexanol in the container and maintaining the 2-ethylhexanol in the container for at least two days. The sodium borohydride is added in an amount effective for maintaining less than 500 ppm 2-ethyl-hexaldehyde in the 2-ethylhexanol. [0010] Embodiments of the invention include a reductive distillation process for the purification of a primary or secondary alcohol composition having an aldehyde, peroxide, and/or ketone contaminant. The process comprises providing a stream comprising a primary or secondary alcohol and an aldehyde, peroxide, and/or ketone contaminant wherein the contaminant is present at between 15 ppm and 2000 ppm. The process further comprises providing a reducing agent to the alcohol and contaminant stream to form a combined feed stream. The process further comprises feeding the combined feed stream to a distillation apparatus. The process further still comprises distilling the combined feed stream. The process further still comprises collecting a purified primary or secondary alcohol, the primary or secondary alcohol having an aldehyde, peroxide, and/or ketone content of less than 15 ppm. The process occurs at a scale selected from at least 50 kilograms of purified primary or secondary alcohol as a batch process, or at least a rate of 50 kilograms per hour of purified primary or secondary alcohol as a continuous process.

[0011] The following includes definitions of various terms and phrases used throughout this specification.

[0012] 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%.

[0013] The terms“wt.%,”“vol.%” or“mol.%” refer 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.

[0014] The term“substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0015] 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.

[0016] The term“effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0017] 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.”

[0018] 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.

[0019] The process of the present invention can“comprise,”“consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc., disclosed throughout the specification.

[0020] The term“primarily,” as that term is used in the specification and/or claims, means greater than any of 50 wt. %, 50 mol. %, and 50 vol. %. For example,“primarily” may include 50.1 wt. % to 100 wt. % and all values and ranges there between, 50.1 mol. % to 100 mol. % and all values and ranges there between, or 50.1 vol. % to 100 vol. % and all values and ranges there between.

[0021] 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

[0022] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

[0023] FIG. 1 shows a schematic flowchart of a process for storage and/or transportation of an auto-oxidizable alcohol, according to embodiments of the invention; [0024] FIG. 2 shows a schematic flowchart of a reductive distillation process for the purification of a primary or secondary alcohol, according to embodiments of the invention; and

[0025] FIG. 3 shows a schematic diagram of a system for purifying 2-ethylhexanol from a crude alcohol, according to embodiments of the invention.

DFTATFFD DESCRIPTION OF TTTF TNVFNTTON

[0026] Currently, auto-oxidizable alcohol stored in a storage container is protected from oxidation using a nitrogen blanketing method. The nitrogen blanketing method requires the storage container to be air tight and involves applying high nitrogen pressure in the container, which increases storing costs and further complicates the transportation of the auto-oxidizable alcohol. Furthermore, it is difficult and economically challenging to apply the nitrogen blanketing method in a chemical process that involves auto-oxidizable alcohol. The present invention provides a solution to these problems. The solution is premised on a process that includes adding a reducing agent in the auto-oxidizable alcohol in a storage container or in a processing stream of a chemical process to reverse the oxidation of the auto-oxidizable alcohol. The process does not need to have extra pressure added or specialized equipment ( e.g air-tight storage containers), resulting in a reduced cost and simplified steps for reducing oxidized auto- oxidizable alcohols in the auto-oxidizable alcohols. These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. Process for storage and/or transportation of auto-oxidizable alcohol

[0027] In embodiments of the invention, the process for storage and/or transportation of an auto-oxidizable alcohol may include steps of preventing the oxidation of the auto-oxidizable alcohols and/or reducing any oxidized auto-oxidizable alcohols. With the reference to FIG. 1, a schematic flowchart is shown of process 100 for storage and/or transportation of an auto- oxidizable alcohol in commercial quantities without need of conventional nitrogen blanketing of the auto-oxidizable alcohol.

[0028] According to embodiments of the invention, process 100 may include obtaining a container holding an auto-oxidizable alcohol in an amount of greater than 50 kilograms and in a purity of greater than 98% by weight and with between 1 ppm and less than 500 ppm of aldehyde corresponding to auto-oxidizable product of the auto-oxidizable alcohol, as shown in block 101. In embodiments of the invention, the auto-oxidizable alcohol may be an oxo alcohol. Non-limiting examples of the auto-oxidizable alcohol include 2-ethylhexanol, butanol, 2-methyl-2 -butanol, 2-propylheptanol, isononyl alcohol, and combinations thereof. In embodiments of the invention, the container may include stainless steel container, epoxy coated container, carbon steel container, or combinations thereof. In embodiments of the invention, the aldehyde includes 2-ethylhexaldehyde, heptanone, butyraldehyde, isobutyraldehyde, 2- propylheptaldehyde, or combinations thereof.

[0029] In embodiments of the invention, process 100 may further include adding a reducing agent to the auto-oxidizable alcohol in the container, as shown in block 102. In embodiments of the invention, the reducing agent is capable of reducing the aldehyde to form the auto- oxidizable alcohol. In embodiments of the invention, the reducing agent is a hydride reducing agent. Non-limiting examples of the hydride reducing agent may include sodium borohydride, lithium aluminum hydride, sodium cayanoborohydride, and combinations thereof.

[0030] According to embodiments of the invention, the reducing agent may be added in neat form. Additionally or alternatively, the reducing agent is contained in diatomaceous earth pellets when it is added to the auto-oxidizable alcohol. In embodiments of the invention, a concentration of the reducing agent in the container may be in a range of 0.005 wt. % to 1 wt. % and all ranges and values there between including ranges of 0.005 to 0.010 wt.%, 0.010 to 0.1 wt.%, 0.1 to 0.2 wt.%, 0.2 to 0.3 wt.%, 0.3 to 0.4 wt.%, 0.4 to 0.5 wt.%, 0.5 to 0.6 wt.%, 0.6 to 0.7 wt.%, 0.7 to 0.8 wt.%, 0.8 to 0.9 wt.%, and 0.9 to 1.0 wt.%. In embodiments of the invention, the adding of the reducing agent at block 102 does not affect the quality of the auto- oxidizable alcohol.

[0031] In embodiments of the invention, process 100 may further include maintaining the auto-oxidizable alcohol in the container for at least two days, as shown in block 103. According to embodiments of the invention, the reducing agent is added in an amount effective for maintaining less than 500 ppm of aldehyde corresponding to auto-oxidizable product of the alcohol. In embodiments of the invention, the amount of the reducing agent effective for maintaining less than 500 ppm of aldehyde may be in a range of 0.005 wt. % to 1 wt. % and all ranges and values there between including ranges of 0.005 to 0.010 wt.%, 0.010 to 0.1 wt.%, 0.1 to 0.2 wt.%, 0.2 to 0.3 wt.%, 0.3 to 0.4 wt.%, 0.4 to 0.5 wt.%, 0.5 to 0.6 wt.%, 0.6 to 0.7 wt.%, 0.7 to 0.8 wt.%, 0.8 to 0.9 wt.%, and 0.9 to 1.0 wt.%. Additional or alternatively, in embodiments of the invention, process 100 may be used for controlling peroxide impurities in the auto-oxidizable alcohol. Non-limiting examples of peroxide impurities include hydrogen peroxide, oxo radical, peroxo radicals, or combinations thereof. In embodiments of the invention, process 100 is capable of controlling peroxide impurities in a range of 0.25 ppm to 25 ppm and all ranges and values there between. [0032] According to embodiments of the invention, process 100 may be implemented to a method for producing a plasticizer or acrylate product. In embodiments of the invention, the method may include obtaining a stabilized composition of 2-ethylhexanol. The stabilized composition of 2-ethylhexanol may be prepared according to process 100. In embodiments of the invention, the stabilized composition of 2-ethylhexanol contains less than 500 ppm oxidized 2-ethylhexanol and does not further produce oxidized 2-ethylhexanol under storage and transportation conditions. The method may further include reacting the 2-ethylhexanol from the stabilized composition of 2-ethylhexanol with additional feedstocks to produce a plasticizer or acrylate product. In embodiments of the invention, the additional feedstock may include phthalic anhydride, terephthalic acid, trimellitic acid, acrylic acid, or combinations thereof. In embodiments of the invention, the plasticizer or acrylate product may include diester bis(2- ethylhexyl) phthalate, dioctyl terephthalate, 2-ethykhexyl acrylate, Tricotyl trimellitate, or combinations thereof.

B. Reductive distillation process for purification of alcohol

[0033] A reductive distillation process has been discovered to purify a primary or secondary alcohol by minimizing aldehyde, peroxide, and/or ketone contaminants in the final alcohol product. As shown in FIG. 2, embodiments of the invention include reductive distillation process 200 for the purification of a primary and/or secondary alcohol composition having an aldehyde, peroxide, and/or ketone contaminant. According to embodiments of the invention, reductive distillation process 200 may include providing a stream comprising a primary or secondary alcohol and an aldehyde, a peroxide and/or a ketone contaminant, as shown in block 201. In embodiments of the invention the contaminant is between 15 ppm and 2000 ppm and all ranges and values there between including ranges of 15 ppm to 20 ppm, 20 ppm to 40 ppm, 40 ppm to 60 ppm, 60 ppm to 80 ppm, 80 ppm to 100 ppm, 100 ppm to 200 ppm, 200 ppm to 300 ppm, 300 ppm to 400 ppm, 400 ppm to 500 ppm, 500 ppm to 600 ppm, 600 ppm to 700 ppm, 700 ppm to 800 ppm, 800 ppm to 900 ppm, 900 ppm to 1000 ppm, 1000 ppm to 1100 ppm, 1100 ppm to 1200 ppm, 1200 ppm to 1300 ppm, 1300 ppm to 1400 ppm, 1400 ppm to 1500 ppm, 1500 ppm to 1600 ppm, 1600 ppm to 1700 ppm, 1700 ppm to 1800 ppm, 1800 ppm to 1900 ppm, and 1900 ppm to 2000 ppm.

[0034] In embodiments of the invention, the primary or second alcohol may comprise 2- ethylhexanol (2-EH), butanol, isobutyl alcohol, 2-methyl-2-butanol, 2-propylheptanol, isononyl alcohol,, or combinations thereof. The aldehyde, peroxide and/or ketone contaminant may include 2-ethyl-3 -propyl acrolein (EPA), 2-ethylhexaldehyde, 2-ethylhexanal, organic peroxide, or combinations thereof. In embodiments of the invention, reductive distillation process 200 may include providing a reducing agent to the stream comprising primary or secondary alcohol and aldehyde and/or ketone contaminant to form a combined feed stream, as shown in block 202. In embodiments of the invention, the reducing agent may include sodium borohydride, LiAlH₄, sodium cyanoborohydrydide, or combinations thereof. In embodiments of the invention, in the combined feed stream, the reducing agent may have a concentration in a range of 0.005 wt. % to 1 wt. % and all ranges and values there between.

[0035] In embodiments of the invention, reductive distillation process 200 may further include feeding the combined feed stream to a distillation apparatus, as shown in block 203. According to embodiments of the invention, the distillation apparatus may include one or more distillation columns. In embodiments of the invention, reductive distillation process 200 may further include distilling the combined feed stream, as shown in block 204. In embodiments of the invention, the reducing agent may be separated from the primary or secondary alcohol during the distilling at block 204.

[0036] According to embodiments of the invention, reductive distillation process 200 may include collecting a purified primary or secondary alcohol having an aldehyde, peroxide, and/or ketone content of less than 15 ppm, as shown in block 205. In embodiments of the invention, purified primary or secondary alcohol may be stored or transported according to process 100. In embodiments of the invention, reductive distillation process 200 is performed at a scale selected from at least 50 kilograms of purified primary or secondary alcohol as a batch process, and/or at least a rate of 50 kilograms per hour of purified primary or secondary alcohol as a continuous process. In embodiments of the invention, the operating temperature of the distillation apparatus is in a range of 50 to 175 °C and all range and values there between including ranges of 50 to 60 °C, 60 to 70 °C, 70 to 80 °C, 80 to 90 °C, 90 to 100 °C, 100 to 110 °C, 110 to 120 °C, 120 to 130 °C, 130 to 140 °C, 140 to 150 °C, 150 to 160 °C, 160 to 170 °C, and 170 to 175 °C. The operating pressure of the distillation apparatus is in a range of 0 to 5.2 bar and all ranges and values there between including 0 to 0.4 bar, 0.4 to 0.8 bar, 0.8 to 1.2 bar, 1.2 to 1.6 bar, 1.6 to 2.0 bar, 2.0 to 2.4 bar, 2.4 to 2.8 bar, 2.8 to 3.2 bar, 3.2 to 3.6 bar, 3.6 to 4.0 bar, 4.0 to 4.4 bar, 4.4 to 4.8 bar, and 4.8 to 5.2 bar.

System and method for purification of 2-ethylhexanol from crude alcohol

[0037] In embodiments of the invention, reductive distillation process 200 may be implemented in a 2-ethylhexanol purification system. In embodiments of the invention, the 2- ethylhexanol purification system can include a plurality of distillation columns. With reference to FIG. 2, a schematic diagram is shown of 2-ethylhexanol recovering system 300 that is capable of recovering 2-ethylhexanol from crude alcohol.

[0038] In embodiments of the invention, 2-ethylhexanol purification system 300 may include first distillation column 301 configured to receive and distill crude alcohol stream 31 to form first distillate stream 32 and first bottom stream 33. In embodiments of the invention, crude alcohol stream 31 may be from a 2-EH production reactor configured to react synthesis gas and propylene to produce the crude alcohol, which includes 2-EH. In embodiments of the invention, the crude alcohol may further include 2-ethyl hexanal (EHA), 2-ethyl, 3 -propyl acrolein (EPA), butanol, and/or heavy hydrocarbons. In embodiments of the invention, crude alcohol stream 31 comprises at least 80 mol.% 2-EH. In embodiments of the invention, first distillate stream 32 may comprise at least 35 mol.% 2-EH, at least 27 mol.% lower alcohol (alcohol lighter than 2-EH), and at most 31 mol.% water. In embodiments of the invention, first bottom stream 33 comprises 97.5 to 99.5 mol.% 2-EH and all ranges and values there between including ranges of 97.5 to 97.7 mol.%, 97.7 to 97.9 mol.%

[0039] In embodiments of the invention, an overhead outlet of first distillation column 301 may be in fluid communication with an inlet of second distillation column 302 such that first distillate stream 32 flows from first distillation column 301 to second distillation column 302. According to embodiments of the invention, second distillation column 302 may include an overhead outlet disposed on the top half of second distillation column 302. Second distillate stream 34 from distillation column 302 may contain butanol or other lower alcohol (lower than 2-EH), and/or water. Second distillate stream 34 may be purged to waste liquid fuel. Second bottom stream 36 may be a light recycle stream configured to recycle to a reactor that produces the crude alcohol. In embodiments of the invention, second bottom stream 36 may include 80 to 90 mol.% 2-EH, and/or 2.0 to 3.0 mol.% lower alcohol (lower than 2-EH).

[0040] In embodiments of the invention, a bottom outlet of first distillation column 301 may be in fluid communication with an inlet of third distillation column 303 such that first bottom stream 33 flows from first distillation column 301 to third distillation column 303. In embodiments of the invention, first bottom stream 33 from first distillation column 301 may include 95 to 99 mol. % 2-EH and all ranges and values there between. In embodiments of the invention, third distillation column 303 may include an overhead outlet and a bottom outlet. In embodiments of the invention, third distillation column 303 may be configured to receive and distill first bottom stream 33 to form third distillate stream 37 flowing from the overhead outlet thereof and third bottom stream 38 flowing from the bottom outlet thereof.

[0041] In embodiments of the invention, a reducing agent may be added in first bottom stream 33. In embodiments of the invention, the reducing agent may include sodium borohydride, lithium aluminum hydride, sodium bisulphite, sodium cyanoborohydride, or combinations thereof. In embodiments of the invention, the reducing agent may have a concentration of 0.005 wt. % to 1 wt. % in first bottom stream 33. In embodiments of the invention, the reducing agent is configured to reduce aldehyde, peroxides, and/or ketone contaminants during the distillation process in third distillation column 303.

[0042] In embodiments of the invention, the aldehyde, peroxides, and/or ketone contaminants may include EHA. In embodiments of the invention, third distillation column 303 may have an operating temperature of 130 to 175 °C and all ranges and values there between including ranges of 130 to 133 °C, 133 to 136 °C, 136 to 139 °C, 139 to 142 °C, 142 to 145 °C, 145 to 148 °C, 148 to 151 °C, 151 to 154 °C, 154 to 157 °C, 157 to 160 °C, 160 to 163 °C, 163 to 166 °C, 166 to 169 °C, 169 to 172 °C, and 172 to 175 °C. Third distillation column 303 may have an operating pressure of 0.1 to 1.5 absolute bar and all ranges and values there between including 0.2 bara, 0.3 bara, 0.4 bara, 0.5 bara, 0.6 bara, 0.7 bara, 0.8 bara, 0.9 bara, 1.0 bara, 1.2 bara, 1.3 bara, and 1.4 bara.

[0043] In embodiments of the invention, third distillate stream 37 may include 99.5 to 99.8 wt.% 2-ethylhexanol and all ranges and values there between. In embodiments of the invention, third distillate stream 37 may include less than 15 ppm of aldehyde, peroxide, and/or ketone content. According to embodiments of the invention, third distillate stream 37 may be collected, stored, and/or transported according to process 100. Additionally or alternatively, third distillate stream 37 may be further purified.

[0044] In embodiments of the invention, third bottom stream 38 may comprise heavy products of reduction reaction of reducing agents, the reducing agent from first bottom stream 33, or combinations thereof. Third bottom stream 38 may be further distilled in fourth distillation column 104 to form fourth distillate stream 39a comprising heavy ether recycle for hydrogenolysis and fourth bottom stream 39b comprising glycol esters and the reducing agent.

[0045] Although embodiments of the present invention have been described with reference to blocks of FIGS. 1 and 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 FIGS. 1 and 2. Accordingly, embodiments of the invention may provide functionality as described herein using various blocks in a sequence different than that of FIGS. 1 and 2.

[0046] 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

(Reduction of oxidized product in 2-EH without distillation)

[0047] A series of mixtures of 2-ethylhexanol and sodium borohydride (NaBH₄) were prepared at room temperature. For each mixture sample, about 500 ml 2-ethylhexanol (2-EH) was used. Table 1 shows the comparison between the initial aldehyde concentration in each 2- EH sample before it was admixed with NaBH₄, and the aldehyde concentration at 1 hour after it was admixed with NaBH₄ in the corresponding 2-EH sample. The tested NaBH₄ concentrations in the 2-EH samples were 0.05 wt.%, 0.1 wt.%, and 0.5 wt.%. The concentrations of the aldehyde were determined by gas chromatography. As shown in Table 1, the aldehyde level in each of the 2-EH sample was significantly reduced due to the use of NaBH_4. About 0.05 wt.% NaBH₄ in the 2-EH sample was capable of reducing 278 ppm aldehyde to less than 5 ppm aldehyde within one hour.

Table 1. Aldehyde concentrations in 2-EH mixed with NaBH₄

Example 2

(Reduction of oxidized 2-EH product during distillation ) [0048] About 500 ml of 2-EH was admixed with 0.05 wt.% NaBH₄ at room temperature. The mixture was stirred for one hour and then decanted to obtain a first final sample. A second sample of about 500 ml 2-EH was admixed with 0.05 wt.% NaBH₄ at room temperature and the 2-EH was then distilled and collected to obtain a second final sample. The aldehyde concentrations in both initial samples and final samples were analyzed using gas chromatography. The results are shown in Table 2.

[0049] As shown in Table 2, in the non-distilled 2-EH sample, 0.05 wt.% NaBH₄ reduced the aldehyde in the 2-EH sample from 278 ppm to 5 ppm. In the distilled 2-EH sample, 0.05 wt.% NaBH₄ reduced the aldehyde in the 2-EH sample from 278 ppm to 11 ppm. Therefore, a reducing agent such as NaBH₄ is effective in reducing oxidized products in auto-oxidative alcohols during a chemical process.

Table 2. Aldehyde concentrations in distilled (first row) and non-distilled (second row) samples

[0050] In the context of the present invention, embodiments 1-17 are described. Embodiment l is a process for the storage and/or transportation of an auto-oxidizable alcohol in commercial quantities. The process includes obtaining a container holding an auto- oxidizable alcohol in an amount of greater than 50 kilograms and in a purity of greater than 98% by weight and with between 1 ppm and less than 500 ppm of aldehyde corresponding to auto-oxidizable product of said alcohol. The process further includes adding a reducing agent to the alcohol in said container and maintaining said alcohol in said container for at least two days, wherein the reducing agent is added in an amount effective for maintaining less than 500 ppm of aldehyde corresponding to auto-oxidizable product of said alcohol. Embodiment 2 is the process of embodiment 1, wherein the auto-oxidizable alcohol includes 2-ethylhexanol, butanol, 2-methyl-2-butanol, 2-propylheptanol, isononyl alcohol, or combinations thereof. Embodiment 3 is the process of either of embodiments 1 or 2, wherein the reducing agent is a hydride. Embodiment 4 is the process of embodiment 3, wherein the hydride reducing agent includes NaBH4, LiAlH4, sodium cyanoborohydride, or combinations thereof. Embodiment 5 is the process of any of embodiments 1 to 4, wherein the aldehyde includes heptanone, butyraldehyde, isobutyraldehyde, 2-propylheptaldehyde, or combinations thereof. Embodiment 6 is the process of any of embodiments 1 to 5, wherein the amount of the reducing agent effective for maintaining aldehyde concentration under 500 ppm is in a range of 0.005 wt. % to 1 wt. %.

[0051] Embodiment 7 is a process for producing a plasticizer or acrylate product. The process includes obtaining a stabilized composition of 2-ethylhexanol prepared according to the process of any of embodiments 1 to 6. The process further includes reacting 2-ethylhexanol from the stabilized composition of 2-ethylhexanol with additional feedstocks to produce a plasticizer or acrylate product. Embodiment 8 is the process of embodiment 7, wherein the additional feedstock includes phthalic anhydride, terephthalic acid, trimellitic acid, acrylic acid, or combinations thereof. Embodiment 9 is the process of embodiment 7, wherein the plasticizer or acrylate product include diester bis(2-ethylhexyl) phthalate, dioctyl terephthalate, 2-ethylhexyl acrylate, tricotyl timellitate,, or combinations thereof.

[0052] Embodiment 10 is a reductive distillation process for the purification of a primary or secondary alcohol composition having an aldehyde and/or ketone contaminant. The process includes providing a stream comprising a primary or secondary alcohol and an aldehyde and/or ketone contaminant, wherein said contaminant is present at between 15 ppm and 2000 ppm. The process also includes providing a reducing agent to the alcohol and contaminant stream to form a combined feed stream. The process further includes feeding the combined feed stream to a distillation apparatus. In addition, the process includes distilling the combined feed stream and collecting a purified primary or secondary alcohol, said alcohol having an aldehyde and/or ketone content of less than 15 ppm, wherein said process occurs at a scale selected from at least 50 kilograms of purified primary or secondary alcohol as a batch process, or at least a rate of 50 kilograms per hour of purified primary or secondary alcohol as a continuous process. Embodiment 11 is the reductive distillation process of embodiment 10, wherein the primary or secondary alcohol includes 2-ethylhexanol, butanol, isobutanol, 2-propylheptanol, or combinations thereof. Embodiment 12 is the reductive distillation process of embodiment 11, wherein the 2-ethylhexanol is purified via distilling a crude alcohol that is produced by reacting synthesis gas and propylene. Embodiment 13 is the reductive distillation process of embodiment 12, wherein the aldehyde and/or ketone contaminant includes 2-ethyl-3 -propyl acrolein (EPA), 2-ethylhexaldehyde. 2-ethylhexanal, or combinations thereof. Embodiment 14 is the reductive distillation process of either of embodiments 12 or 13, wherein the crude alcohol is distilled in a series of distillation columns, where an overhead stream from a first distillation column feeds to a second distillation column, and a bottom stream from the first distillation column feeds to a third distillation column, and wherein the reducing agent is provided to the bottom stream from a first distillation column to form the combined feed stream. Embodiment 15 is the reductive distillation process of any of embodiments 10 to 14, wherein the reducing agent includes sodium borohydride, lithium aluminum hydride, sodium bisulphite, sodium cyanoborohydride, or combinations thereof. Embodiment 16 is the reductive distillation process of any of embodiments 10 to 15, wherein the operating temperature of the distillation apparatus is in a range of 50 to 175 °C. Embodiment 17 is the reductive distillation process of any of embodiments 10 to 16, wherein the operating pressure of the distillation apparatus is in a range of 0 to 5.2 bar.

[0053] 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.

Claims

1. A process for the storage and/or transportation of an auto-oxidizable alcohol in commercial quantities comprising:

obtaining a container holding an auto-oxidizable alcohol in an amount of greater than 50 kilograms and in a purity of greater than 98% by weight and with between 1 ppm and less than 500 ppm of aldehyde corresponding to auto-oxidizable product of said alcohol;

adding a reducing agent to the alcohol in said container; and

maintaining said alcohol in said container for at least two days;

wherein the reducing agent is added in an amount effective for maintaining less than 500 ppm of aldehyde corresponding to auto-oxidizable product of said alcohol.

2. The process of claim 1, wherein the auto-oxidizable alcohol comprises 2-ethylhexanol, butanol, 2-methyl-2-butanol, 2-propylheptanol, isononyl alcohol, or combinations thereof.

3. The process of any of claims 1 or 2, wherein the reducing agent is a hydride.

4. The process of claim 3, wherein the hydride reducing agent comprises NaBH₄, LiAlTL, sodium cyanoborohydride, or combinations thereof.

5. The process of any of claims 1 or 2, wherein the aldehyde includes heptanone, butyraldehyde, isobutyraldehyde, 2-propylheptaldehyde, or combinations thereof.

6. The process of any of claims 1 or 2, wherein the amount of the reducing agent effective for maintaining aldehyde concentration under 500 ppm is in a range of 0.005 wt. % to 1 wt. %.

7. A process for producing a plasticizer or acrylate product, the process comprising: obtaining a stabilized composition of 2-ethylhexanol prepared according to the process of any of claims 1 or 2; and

reacting 2-ethylhexanol from the stabilized composition of 2-ethylhexanol with additional feedstocks to produce a plasticizer or acrylate product.

8. The process of claim 7, wherein the additional feedstock comprises phthalic anhydride, terephthalic acid, trimellitic acid, acrylic acid, or combinations thereof.

9. The process of claim 7, wherein the plasticizer or acrylate product include diester bis(2- ethylhexyl) phthalate, dioctyl terephthalate, 2-ethylhexyl acrylate, tricotyl timellitate,, or combinations thereof.

10. A reductive distillation process for the purification of a primary or secondary alcohol composition having an aldehyde and/or ketone contaminant, the process comprising: providing a stream comprising a primary or secondary alcohol and an aldehyde and/or ketone contaminant, wherein said contaminant is present at between 15 ppm and 2000 ppm;

providing a reducing agent to the alcohol and contaminant stream to form a combined feed stream;

feeding the combined feed stream to a distillation apparatus;

distilling the combined feed stream; and

collecting a purified primary or secondary alcohol, said alcohol having an aldehyde and/or ketone content of less than 15 ppm,

wherein said process occurs at a scale selected from at least 50 kilograms of purified primary or secondary alcohol as a batch process, or at least a rate of 50 kilograms per hour of purified primary or secondary alcohol as a continuous process.

11. The reductive distillation process of claim 10, wherein the primary or secondary alcohol comprises 2-ethylhexanol, butanol, isobutanol, 2-propylheptanol, or combinations thereof.

12. The reductive distillation process of claim 11, wherein the 2-ethylhexanol is purified via distilling a crude alcohol that is produced by reacting synthesis gas and propylene.

13. The reductive distillation process of claim 12, wherein the aldehyde and/or ketone contaminant includes 2-ethyl-3 -propyl acrolein (EPA), 2-ethylhexaldehyde. 2- ethylhexanal, or combinations thereof.

14. The reductive distillation process of any of claims 12 and 13, wherein the crude alcohol is distilled in a series of distillation columns, where an overhead stream from a first distillation column feeds to a second distillation column, and a bottom stream from the first distillation column feeds to a third distillation column; wherein the reducing agent is provided to the bottom stream from a first distillation column to form the combined feed stream.

15. The reductive distillation process of any of claims 10 to 13, wherein the reducing agent comprises sodium borohydride, lithium aluminum hydride, sodium bisulphite, sodium cyanoborohydride, or combinations thereof.

16. The reductive distillation process of any of claims 10 to 13, wherein the operating temperature of the distillation apparatus is in a range of 50 to 175 °C.

17. The reductive distillation process of any of claims 10 to 13, wherein the operating pressure of the distillation apparatus is in a range of 0 to 5.2 bar.