WO2016026675A1 - Détermination quantitative d'analyte pour analyse de carbonyle en ligne - Google Patents

Détermination quantitative d'analyte pour analyse de carbonyle en ligne Download PDF

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Publication number
WO2016026675A1
WO2016026675A1 PCT/EP2015/067686 EP2015067686W WO2016026675A1 WO 2016026675 A1 WO2016026675 A1 WO 2016026675A1 EP 2015067686 W EP2015067686 W EP 2015067686W WO 2016026675 A1 WO2016026675 A1 WO 2016026675A1
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Prior art keywords
reagent
analyte
sample
carbonyl
alcohol
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PCT/EP2015/067686
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English (en)
Inventor
Charles Yarbrough
Carl Beck
Jorg Weber
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Exxonmobil Chemical Patents Inc.
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Publication of WO2016026675A1 publication Critical patent/WO2016026675A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour

Definitions

  • the invention relates to an analytical technique for the quantitative determination of an analyte, in particular to an on-line analytical technique for the quantitative determination of carbonyl content in alcohols produced by the hydrogenation of aldehydes.
  • Hydro formylation is a well-known process in which an olefin is reacted with carbon monoxide and hydrogen in the presence of a catalyst to form aldehydes and/or alcohols containing one carbon atom more than the feed olefin. It is also known as the Oxo process, or as the oxonation process. The commercially important Oxo process produces such alcohols, which find uses in plastics, soaps, lubricants, and other products.
  • hydro formylation of ethylene yields propionaldehyde and propylene yields a mixture of n- and iso-butyraldehyde (with the n- isomer usually predominating), followed by catalytic hydrogenation to the corresponding alcohols, e.g. n-propanol and n-butanol.
  • Synthetic alcohols particularly those in the range of about 8 to 13 carbon atoms (C8-C13), are used as plasticizers for poly(vinyl chloride) and the like.
  • the important plasticizer alcohol 2-ethylhexanol
  • 2-ethylhexanol is made by alkali-catalyzed condensation of n-butyraldehyde to yield the unsaturated aldehyde, 2-ethyl-hex-2-enal, which is then hydrogenated to yield the desired 2-ethylhexanol.
  • Synthetic alcohols are typically plagued with the problem of undesirable color and color forming impurities, e.g., aldehydes and ketones.
  • Many methods have been tried to mitigate the problem, for example, treatment with reducing agents, such as hydrogen in the presence of a catalyst such as zinc and copper catalyst, Raney nickel catalyst, zirconium promoted nickel-kieselguhr catalyst, or the like, treatment with borohydrides such as sodium borohydride, and also ozone treatments. See, for instance, U.S. Patent Nos. 3,642,915 and 3,232,848.
  • the crude alcohol product from the hydrogenation section of the Oxo Process containing color and color-forming impurities, is passed through a finishing section, where it is treated with sodium borohydride.
  • the reactivity of sodium borohydride towards aldehydes and ketones (if present) is much greater than the reactivity of sodium borohydride with the active hydrogen of the alcohol or the ester carbonyl.
  • Sodium borohydride reduces aldehydes and ketones to the corresponding alcohols.
  • the amount of agent to use in the finishing section will depend on the amount of aldehydes and ketones in the crude product. Excess sodium borohydride leads to the formation of particulates in the product alcohol. It can also slow down the reaction to form plasticizers in the next production step. It may also lead to a decrease in resistivity in products used for wire and cable insulation. In the case where hydrogen is used in the finishing section, excess use of hydrogen is disadvantageous at least because of the expense.
  • the amount of residual aldehydes and ketones may be expressed as a carbonyl number.
  • the theoretical carbonyl number (TCBN) of a material is traditionally reported in mg
  • TCBN (FWKOH/FW CARBONYL COMPOUND) X (NCARBONYL COMPOUND) X 1000 mg/g
  • FW is the formula weight of the species specified in the equation.
  • N is the number of active carbonyl groups in the carbonyl compound.
  • the TCBN for pure 2-octanone, typically used as a calibration standard, is 438.
  • the carbonyl number (CBN) for a standard is expressed by the following formula:
  • the CBN value for an unknown sample may be obtained via direct titration, by way of example, with hydroxylammoniumchloride to form an oxime and free hydrochloric acid followed by pontentiometric titration of the free hydrochloric acid with an alcoholic solution of tetra-n-butyl ammonium hydroxide or an inferential technique using, by way of example, an extractive method followed by spectrophotometric determination as set forth, for instance, by Lohman, Spectroscopic Determination of Carbonyl Oxygen, Analytical Chemistry, Vol. 30, No. 5, May 1958, pp.
  • a reagent comprising an alcoholic solution of 2,4-dinitrophenylhydrazine (DNPH) and sulfuric acid has previously been described for qualitative analysis using Thin Layer Chromatography (TLC). See Organikum, pp. 70-71, 16, VEB Verlag, Berlin 1986. This technique, however, is inapplicable to quantitative determination.
  • DNPH 2,4-dinitrophenylhydrazine
  • TLC Thin Layer Chromatography
  • a subsequent technique described in U.S. Patent App. Pub. No. 2006/0145065 similarly suffers from several disadvantages. That publication describes a fast analysis method in which a sample to be analyzed is combined with a strong reagent solution of DNPH and sulfuric acid and subsequently reacted with a KOH mixture before undergoing analysis by a spectroscopic technique to determine the carbonyl content of the sample. This technique utilizes unstable reagents necessitating frequent replacement, and requires manual laboratory filtration due to precipitation of an insoluble salt requiring regular filter replacement.
  • KOH mixture comprising ethanol, water, and KOH
  • the KOH slowly catalyzes oxidation of ethanol into acetaldehyde. This slow change in the KOH mixture causes uncontrolled variation in measurement results unless the KOH mixture is changed regularly and frequently.
  • the present inventors surprisingly have found a new process that overcomes the noted drawbacks of existing methods including the carbonyl analysis process described in U.S. Patent App. Pub. No. 2006/0145065, thus providing a wet chemical method adapted to run in an on-line analyzer, potentially in conjunction with an Oxo alcohol finishing process.
  • the inventive process greatly improves response time for unit operations, helps insure product quality, and reduces necessary manpower.
  • On-line analysis additionally allows for carbonyl treatment processes to be controlled in real time, thereby reducing the usage and corresponding cost of treatment reagents, such as sodium borohydride, and preventing product overtreatment which can result in unsafe levels of free hydrogen or require additional hydrogen removal processes.
  • the invention is in part directed to a process for quantitative analysis of an analyte (species of interest, e.g., carbonyl containing species) in a sample which includes (1) mixing the sample with a first reagent to form a reaction mixture, wherein the first reagent mixture comprises a phenylhydrazine and an acid catalyst, and wherein the acid catalyst catalyzes a reaction of the analyte and the phenylhydrazine faster than HC1; (2) mixing a portion of the reaction mixture with a second reagent and a third reagent to form a final mixture containing a measurable species corresponding to the analyte, wherein the second reagent comprises a strong base and water, and the third reagent comprises an alcohol and water; (3) determining the quantity of the measurable species in the final mixture using a non- extractive spectrophotometric technique; and (4) determining the quantity of analyte present in the sample by correlation to the determined quantity of the
  • the phenylhydrazine may be 2,4-dinitrophenylhydrazine.
  • the strong base may be NaOH.
  • the third reagent may comprise ethanol and water.
  • the acid catalyst is H 2 SO 4 .
  • the second and third reagents may be stored separately until mixing with the reaction mixture. The final mixture does not need to be filtered before the quantity of the measurable species is determined using the non-extractive spectrophotometric technique.
  • the invention is in part directed to a process for quantitative analysis of an analyte in a sample which includes (1) mixing the sample with a first reagent to form a reaction mixture, wherein the first reagent mixture comprises a phenylhydrazine and an acid catalyst, and wherein the acid catalyst catalyzes a reaction of the analyte and the phenylhydrazine faster than HCl; (2) mixing a portion of the reaction mixture with a second reagent and a third reagent to form a final mixture containing a measurable species corresponding to the analyte, wherein the second reagent comprises a strong base and water, and the third reagent comprises an alcohol and water; (3) determining the quantity of the measurable species in the final mixture using a non-extractive spectrophotometric technique; and (4) determining the quantity of analyte present in the sample by correlation to the determined quantity of the measurable species.
  • analyte means the species that is being quantitatively analyzed, i.e. a carbonyl containing species including but not limited to aldehydes and/or ketones in a sample comprising C3-C20 alcohols.
  • the quantitative analytical technique according to the invention is conveniently and advantageously adapted to a commercial hydro formylation process (i.e., oxonation process, or "Oxo Process") finishing section.
  • the sample may be taken from an alcohol mixture containing alcohol and optionally carbonyl-containing compounds.
  • the alcohol may be a branched or linear C3-C20 alcohol, aromatic or cyclic alcohol, or various mixtures thereof.
  • the carbonyl containing compounds, which are the analyte in the alcohol mixture may be ketones, aldehydes, or mixtures thereof.
  • the sample may be taken from an unfinished alcohol stream, for example from downstream of a hydrogenation step and distillation step, but upstream from a hydro finishing step.
  • the sample may alternatively be taken downstream from a hydro finishing step, or even parallel to a hydro finishing step.
  • Such hydro finishing may entail catalyzed hydrogenation or chemical treatment such as treatment with sodium borohydride.
  • the process according to the invention is useful for quantitative analysis, e.g., carbonyl number determination on any sample by the addition of the reagents according to the present invention followed by potentiometric titration or spectrophotometric techniques using extractive or non-extractive methods, and is also useful for the determination of other analytes, i.e., those analytes which react with the reagent according to the present invention to form a moiety which may be quantitatively analyzed by spectroscopic (or spectrophotometric; the terms are used interchangeably herein), chromatographic, or other quantitative techniques.
  • the first reagent may include a phenylhydrazine and an acid catalyst in solution.
  • the phenylhydrazine may form a colored entity with the analyte, which may comprise aldehydes and ketones, whereby the analyte may be quantitatively determined by quantitative determination of the entity, either alone without further reaction (e.g., by non-extractive or extractive analysis such as set forth in Bartkiewicz et al, or Lohman, respectively, referred to above) or by reaction of the entity with yet another compound, e.g., a strong base, to generate a measurable species which may subsequently be quantitatively determined by techniques such as any spectroscopic method.
  • the phenylhydrazine may have electron-withdrawing substituents, e.g., a nitro group, such as a dinitrophenylhydrazine, including without limitation 2,4-dinitrophenylhydrazine.
  • DNPH refers specifically to the species 2,4- dinitrophenylhydrazine. DNPH will form a colored entity with aldehydes and ketones which will then react with a strong base, such as NaOH, to form a species that may be analyzed by spectrophotometric techniques, including without limitation the yellowness color index measure according to ASTM E-313. The yellowness color index is per se well-known; see, for instance, U.S. Patent No. 3,972,854. Other techniques such as those in ASTM D1500 and ASTM D6045 may also be applicable.
  • the acid catalyst present in the first reagent catalyzes the reaction between the phenylhydrazine and the analyte faster than HC1.
  • a DNPH-HCl complex has been used in the prior art but the present inventors have discovered that a more robust reaction is necessary in order to provide for an on-line analysis.
  • Sulfuric acid is a suitable acid.
  • the first reagent may be a highly concentrated solution of acid catalyst and DNPH.
  • the reagent may comprise a solution containing 10 vol. % or more acid and about 1 part by weight DNPH to about 5 parts by volume concentrated acid.
  • the acid may be an acid that catalyzes the reaction of the analyte, if present, and the DNPH faster than HC1.
  • the reagent may comprise 10 vol. % or more concentrated (i.e., between 90-100%) sulfuric acid and about 1 g DNPH per 5 mL sulfuric acid in an aqueous alcoholic solvent, which may comprise ethanol.
  • the solvent for the first reagent may comprise a mixture of water and ethanol.
  • the alcohol may be denatured alcohol and the water may be deionized water.
  • a mixed solvent useful in the present invention may be a solution having a ratio of ethanohwater of from about 4: 1 to about 1 : 1, or the solvent may comprise about 3 parts ethanol to about 1 part water.
  • a suitable denatured alcohol is available from EMD Millipore as product AX0445E-1 OmniSolv®, a high purity solvent consisting of approximately 95 parts by volume of specialty denatured ethyl alcohol formula 3A (200 proof), methanol (in the amount of about 4.3 vol. % in the final high purity solvent) and 5 parts by volume isopropyl alcohol (IP A).
  • the first reagent solution comprises 2-3 wt% DNPH; 20-30 wt% H 2 S0 4 ; 20-30 wt% H 2 0; and 40-60 wt% denatured ethanol.
  • the exact amounts of each component used in preparing the first reagent may be determined by one of ordinary skill in the art in possession of the present disclosure.
  • the first reagent With regard to preparation of the first reagent, it will be understood by one of ordinary skill in the art wishing to follow safe laboratory practice that a small amount of the acid stronger than HC1 is slowly added to the aqueous alcohol solution.
  • the phenylhydrazine e.g., DNPH
  • This first reagent solution is of high color and becomes darker in the presence of the sample.
  • This reagent solution may be prepared well ahead of the time at which the analysis will occur. Note that the first reagent solution is light sensitive and will typically degrade over time. It has been found that, for instance, wrapping a bottle containing the solution in aluminum foil will prolong the useful life of the reagent solution for several months.
  • This DNPH solution should be predominately free of particulates before use.
  • the second reagent solution may comprise a strong base in aqueous solution.
  • the strong base does not form an abundant amount of precipitant when in contact with the acid catalyst of the first reagent solution, and may be, by way of non-limiting example NaOH.
  • the second reagent may comprise 1.8M NaOH solution in water. This base is used to neutralize the acid of the first addition and thereby reduces the high color of the DNPH sample solution. The resulting solution's carbonyl chromophore becomes the desired measureable species.
  • the third reagent solution may include alcohol and water.
  • the third reagent solution is used to insure solubilization of the neutralized acid species and dilutes the mixture to the spectroscopically desired concentration.
  • the third reagent may comprise 70% alcohol and 30% water.
  • the alcohol may be denatured ethanol.
  • the third reagent may be the same as the alcohol solvent for the first reagent solution. The exact amounts used in preparing the second and third reagents may be determined by one of ordinary skill in the art in possession of the present disclosure.
  • An aspect of the inventive process is carried out by first combining the sample containing the analyte with the first reagent.
  • the first reagent is mixed with the sample, a highly colored entity is formed due to the reaction between the carbonyl containing compounds, if any are present in the sample, and the DNPH in the first reagent.
  • the first reagent is combined with the sample in a ratio so that there is a reasonable excess of DNPH to the expected carbonyl content, with which the DNPH will react. It is necessary to have at least a 100% stoichiometric amount of DNPH in order to get an accurate reading of carbonyl content, however a large excess of DNPH may negatively impact the signal to noise ratio and variability of the analysis results.
  • a volume ratio of first reagent solution to sample between 1 : 1 and 0.4: 1 provides an excess of DNPH, with a volume ratio of 0.4: 1 providing the best reduction in result variability.
  • 4 ml of first reagent solution may be combined with 10 ml of sample.
  • the resultant reaction mixture is well-mixed.
  • the reaction mixture may be mixed for 1-5 minutes.
  • a portion of the reaction mixture is then combined with the second and third reagents to form a final mixture.
  • the second and third reagents When combined with the reaction mixture, the second and third reagents together cause a reaction with the species formed from the reaction of the DNPH and the aldehyde and/or ketone, to form an ionic species that may be analyzed by spectrophotometric techniques.
  • the second and third reagents Before being combined with the reaction mixture, the second and third reagents are stored separately and not combined.
  • the reaction mixture, second reagent, and third reagent may be combined in a volume ratio of about 1 : 16:48. For example, 0.125 ml of reaction mixture may be combined with 2 ml of second reagent and 6 ml of third reagent.
  • the resulting final mixture is again well-mixed. For example, the final mixture may be mixed for 1-5 minutes.
  • the final mixture comprises a measurable species, which (without wishing to be bound by theory) is believed to be the "chinoidal anion" shown below:
  • Ri and R 2 are groups that were attached to the carbonyl in the carbonyl-containing compounds present in the sample.
  • This species may be analyzed by spectrophotometric techniques, including without limitation by colorimetry, uv spectroscopy, infrared spectroscopy, near-infrared spectroscopy, or by the yellowness color index measure according to ASTM E-313. Once the quantity of measurable species is found, the quantity of carbonyl- containing species may be correlated by well-known methods. For example, the final mixture may be measured using a spectrometer at a specified wavelength window appropriate for the carbonyl chromophore. The window is chosen based on its sensitivity to the carbonyl- hydrazine moiety.
  • Quantitation is determined by comparison to known standards using methods typically used for spectrometric methods.
  • the process described above may be performed in an on-line analyzer in connection with a commercial hydro formylation finishing system.
  • the sample may be provided to the analyzer by use of a fast transfer loop from the finishing system.
  • the on-line analyzer may be of the flow injection type. This allows the addition of the reagents sequentially and at appropriate timing.
  • a color- forming entity i.e., the phenylhydrazine
  • an analyte comprising a moiety of interest other than an aldehyde or ketone and which may also be analyzed by a spectroscopic technique, e.g., carboxylic acid groups by IR spectroscopy, and the like.
  • carbonyl derivatives having the formula X-C(0)-Y (where X and Y, which may be the same or different, are independently selected from H, F, CI, Br, I, OR, SR, SeR, NRR, PRR, CRR'R", SiRR'R', BRR, A1RR', where R, R * , and R", which may be the same or different, are independently selected from H, B, Al, C, Si, N, P, O, S, Se, F, CI, Br, I) will react with DNPH, to form derivatives that can be analyzed using extraction or non-extractive quantitative analysis by chromatographic (e.g., GC, HPLC, or Super Critical Fluid Chromatography (SFC)) and/or spectroscopic techniques (e.g., IR, UV- vis, Raman, NMR, or colorimetry).
  • chromatographic e.g., GC, HPLC, or Super Critical Fluid Chromatography (SFC)
  • spectroscopic techniques e.
  • Example 1-8 10 ml of the corresponding Sample (from Table 1) was combined with 4 ml of DNPH solution in a mixing vessel to form a reaction mixture.
  • the DNPH solution constituted 2.6 wt% DNPH, 24.3 wt% sulfuric acid, 21.1% water, and 52.0 wt% water.
  • the reaction mixture was mixed for 1 minute.
  • 2.0 ml of 1.8M NaOH solution and 6 ml of ethanol solution were combined with 0.125 ml of reaction mixture in a cuvette to form a final mixture.
  • the ethanol solution constituted 70% denatured ethanol and 30% water.
  • the final mixture was mixed for 3 minutes and allowed to rest before undergoing UV spectroscopy analysis with examination of absorbance at 590 nm.
  • the results were correlated to carbonyl number (CN) using a calibration sample of 1-octanone in 0.0 CN 1-octanol.
  • the results of the CN analysis for Examples 1-8 are set forth in Table 2.
  • Example results show that the analysis method has good sensitivity, and good reproducibility. Additionally, each Example took from 5-10 minutes to ascertain results. Thus, this analysis method could be performed up to 12 times per hour, whereas it has been found that the Comparative Method can only be performed 1-3 times per hour.
  • the present invention provides for an improved analytical method for quantitative determination of carbonyl number.
  • the method is not limited to the Oxo Process, as applied to the Oxo Process, it provides for an improved product by way of, inter alia, a more uniform product quality, whether sodium borohydride or catalytic hydrogenation is used to remove residual carbonyl-containing moieties.
  • the present invention also allows for real time measurement of carbonyl number allowing for accurate, real time control over a hydro finishing process. As stated in copending US patent application No. 62/040,827, such control over the hydro finishing process makes it possible to produce a low carbonyl number Oxo alcohol product and avoiding overtreatment, which may create dangerous hydrogen levels in a finished product or require additional hydrogen-removal processes.
  • Trade names used herein are indicated by aTM symbol or ® symbol, indicating that the names may be protected by certain trademark rights, e.g., they may be registered trademarks in various jurisdictions.

Abstract

L'invention concerne un procédé d'analyse quantitative d'un analyte dans un échantillon, qui consiste (1) à mélanger l'échantillon avec un premier réactif pour former un mélange de réaction ; (2) à mélanger une partie du mélange de réaction avec un deuxième réactif et un troisième réactif pour former un mélange final contenant une espèce mesurable correspondant à l'analyte ; (3) à déterminer la quantité de l'espèce mesurable dans le mélange final à l'aide d'une technique spectrophotométrique non-extractive ; et (4) à déterminer la quantité d'analyte présente dans l'échantillon par corrélation avec la quantité déterminée de l'espèce mesurable. Le procédé d'analyse quantitative est aisément et avantageusement adapté à la mesure de nombre de carbonyle en lien avec une section de finition de processus d'hydroformylation commerciale.
PCT/EP2015/067686 2014-08-22 2015-07-31 Détermination quantitative d'analyte pour analyse de carbonyle en ligne WO2016026675A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464775A (en) * 1991-09-16 1995-11-07 Chimera Research And Chemical, Inc. Method of detecting adulterant in urine
US20030219832A1 (en) * 1996-03-11 2003-11-27 Klein Elliott S. Synthesis and use of retinoid compounds having negative hormone and/or antagonist activities
US20060105464A1 (en) * 2004-11-12 2006-05-18 Weber Jorg Friedrich W Quantitative determination of analyte

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464775A (en) * 1991-09-16 1995-11-07 Chimera Research And Chemical, Inc. Method of detecting adulterant in urine
US20030219832A1 (en) * 1996-03-11 2003-11-27 Klein Elliott S. Synthesis and use of retinoid compounds having negative hormone and/or antagonist activities
US20060105464A1 (en) * 2004-11-12 2006-05-18 Weber Jorg Friedrich W Quantitative determination of analyte

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