WO2011159418A2 - Procédés de désodorisation de glycols à source renouvelable - Google Patents

Procédés de désodorisation de glycols à source renouvelable Download PDF

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Publication number
WO2011159418A2
WO2011159418A2 PCT/US2011/036719 US2011036719W WO2011159418A2 WO 2011159418 A2 WO2011159418 A2 WO 2011159418A2 US 2011036719 W US2011036719 W US 2011036719W WO 2011159418 A2 WO2011159418 A2 WO 2011159418A2
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WO
WIPO (PCT)
Prior art keywords
glycol product
renewable source
odor
deodorized
product
Prior art date
Application number
PCT/US2011/036719
Other languages
English (en)
Other versions
WO2011159418A3 (fr
Inventor
Paul D. Bloom
Chicheng Ma
Original Assignee
Archer Daniels Midland Company
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Filing date
Publication date
Application filed by Archer Daniels Midland Company filed Critical Archer Daniels Midland Company
Publication of WO2011159418A2 publication Critical patent/WO2011159418A2/fr
Publication of WO2011159418A3 publication Critical patent/WO2011159418A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/02—Purification; Separation; Stabilisation; Use of additives by treatment giving rise to a chemical modification
    • 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
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound

Definitions

  • Propylene glycol and ethylene glycol are examples of important commodity chemicals which have been targeted for replacement by renewable source-based equivalents.
  • propylene glycol is a three carbon diol with a steriogenic center at the central carbon atom.
  • Propylene glycol is commonly used in a variety of consumer products and food products, including deodorants, pharmaceuticals, moisturizing lotions, and fat-free ice cream and sour cream products. It also finds uses in hydraulic fluids, and as a solvent.
  • Ethylene glycol and propylene glycol are used to make antifreeze and de-icing solutions for cars, airplanes, and boats; to make polyester compounds; and as solvents in the paint and plastics industries.
  • Ethylene glycol, a two-carbon compound is also an ingredient in photographic developing solutions, hydraulic brake fluids and in inks used in stamp pads, ballpoint pens, and print shops.
  • Propylene glycol and ethylene glycol are produced on a commodity scale today by the hydration of propylene oxide and ethylene oxide, respectively.
  • Propylene oxide and ethylene oxide in turn are produced by the oxidation of propylene and ethylene, and propylene and ethylene are byproducts of petroleum oil refining and natural gas processing operations.
  • US Patent 5,206,927 describes a homogeneous process for hydrocracking carbohydrates in the presence of a soluble, transition metal catalyst to produce polyols/polyhydric alcohols inclusive of propylene glycol.
  • a carbohydrate is contacted with hydrogen in the presence of a soluble transition metal catalyst and a strong base at a temperature of from about 25°C to about 200°C and a pressure of from about 15 to about 3000 psi.
  • US Patents 5,276, 181 and 5,214,219 describe a process for the hydrogenolysis of glycerol using a copper and zinc catalyst in addition to a sulfided ruthenium catalyst at a pressure over 2100 psi and temperature between 240-270°C.
  • US Patent 5,616,817 describes a process of preparing 1 ,2 propanediol (propylene glycol) by catalytic hydrogenolysis of glycerol at elevated temperature and pressure using a catalyst comprising the metals cobalt, copper, manganese and molybdenum.
  • German Patent DE 541362 describes the hydrogenolysis of glycerol with a nickel catalyst
  • US Patent 4,476,331 describes a two stage method of hydrocracking carbohydrates (for example glucose), wherein a modified ruthenium catalyst is used for hydrocracking sorbitol to produce glycerol derivatives.
  • renewable source-based glycols otherwise appear to be directly substitutable for the corresponding fossil fuels-based glycols, nevertheless we have found that even high purity, pharmaceutical grade renewable source-based glycols produced according to the above-described methods can possess a characteristic odor that is not found in the fossil fuels- based glycols. While not unpleasant, the presence of an odor not found in the fossil fuels-based glycols is undesirable in certain replacement contexts, and might result in the renewable source-based glycols not being found suitable for certain conventional uses - so that non-renewable resources would unfortunately continue to be relied upon.
  • the present invention concerns processes for deodorizing renewable source-based glycols, and especially renewable source-based propylene glycol and ethylene glycol products which have been derived through hydrogenolysis from one or more of glycerol, 5- and 6-carbon sugars and sugar alcohols, wherein odor-causing materials in the renewable source-based glycol products are reactively neutralized or are removed by liquid-liquid extraction methods.
  • otherwise commercially acceptable renewable source-based glycol products including glycol products meeting pharmaceutical grade purity requirements, are deodorized by means of a process described in greater detail below, though generally the processes of the present invention may be performed on glycol products that require further processing in some other fashion to be ready for sale or direct commercial use (for example, decolorization).
  • a renewable source-based glycol product is combined with a weak base under conditions whereby an acidic, higher odor profile impurity will react with the weak base to form a salt having a lower odor profile.
  • the thus-treated glycol product is then distilled to remove the additional water formed in the acid-base reaction and to provide a deodorized glycol product.
  • a renewable source-based glycol product is contacted with an extractant-impregnated resin that will remove odor-causing materials from the glycol product through a combination of reactive extraction and adsorption mechanisms, or is contacted with a weak base-functionalized ion exchange resin that will remove odor-causing materials by the interaction of the weak base functional groups on the resin with .acidic, higher odor profile impurities in the glycol product.
  • Deodorization of a renewable source-based glycol product by means of liquid-liquid extraction will use solvents which have high affinities for the odor-causing materials but in which the desired glycol(s) are substantially insoluble.
  • Suitable solvents are identified below which are effective in reducing levels of the odor-causing materials and in deodorizing renewable source-based propylene glycol, for example, to compare with propylene glycol derived from non-renewable sources.
  • beneficialally, several effective solvents have been found which are commonly present already in facilities processing agricultural products and providing the glycerol and five and six carbon sugars and/or sugar alcohol feeds for making the renewable source-based glycol products of interest.
  • the deodorization processes of the present invention are in a preferred context applied to deodorizing propylene glycol and ethylene glycol products derived from renewable sources such as from glycerol and five and six carbon sugars and/or sugar alcohols.
  • renewable sources such as from glycerol and five and six carbon sugars and/or sugar alcohols.
  • biobased propylene glycol and/or ethylene glycol may be made from such sources, as indicated above, though the deodorization processes of the present invention are expected to have general applicability to renewable source-based glycol products made from such feeds by these and other methods, whether presently known or still to be developed.
  • the deodorization processes of the present invention are applied to deodorizing a propylene glycol product from the hydrogenolysis of refined glycerol; an example of such a process is found in United States Patent No. 6,841 ,085 to Werpy et al., wherein glycerol is converted to products including propylene glycol, in the presence of a rhenium-containing catalyst.
  • Deodorizing the propylene glycol product so made according to one approach involves "reactive neutralization” of the odor-causing materials, though it will be understood that "neutralization” as used herein (in the term “reactive neutralization”) may involve more than an acid-base reaction to a neutral or near-neutral pH.
  • a renewable source-based glycol product is combined with a weak base (or a plurality of weak bases) under conditions whereby an acidic, higher odor profile impurity (or a plurality of such impurities) will react with the weak base to form a salt having a lower odor profile.
  • the thus- treated glycol product is then distilled to remove the additional water formed in the acid-base reaction and to provide a deodorized glycol product.
  • Weak bases useful for deodorizing a propylene glycol product stream as produced from glycerol according to a process generally as described in the '085 patent include sodium borohydride (NaBH4), calcium carbonate, calcium oxide, and sodium bicarbonate. Of these, sodium bicarbonate is especially preferred, having been found to be effective with small addition amounts as demonstrated by the examples below at producing a deodorized propylene glycol product, through neutralizing acid impurities.
  • the deodorization process can be carried out on a batch, semi-batch or continuous basis, at atmospheric pressure and modest temperature conditions, e.g., about 100 degrees Celsius as in the examples below.
  • a renewable source-based glycol product such as a biobased propylene glycol product from the ⁇ 85 patented process
  • an extractant-impregnated resin that removes odor- causing materials from the glycol product through a combination of reactive extraction and adsorption mechanisms.
  • Extractant impregnated resin (EIR) technology has been evaluated for several contexts of use previously, wherein certain impurities present in aqueous solutions particularly in already low concentrations must nevertheless be effectively removed or recovered to a very high degree.
  • the reduction of heavy metals in aqueous effluents from industrial processes has been an exemplary application of the technology, though EIR technology has been evaluated for other uses, including for removing aldehydes, phenols, flavonoids, carboxylic acids and amino acids from aqueous streams.
  • EIRs The concept of EIRs is based on the incorporation of a selective extractive reagent into a porous particle by physical impregnation.
  • a suitable EIR for deodorizing propylene glycol product from the ⁇ 85 process would utilize a primary amine as the reactive extractant for reactively neutralizing residual carbonyl impurities in forming a stable Schiff base.
  • a weak base-functionalized ion exchange resin could be used for deodorizing the propylene glycol product.
  • a primary amine functionalized macroporous styrene-divinylbenzene resin can provide the primary amine for forming the stable Schiff base with the aldehyde or ketone impurities.
  • deodorization of a renewable source- based glycol product will be accomplished by means of liquid-liquid extraction using solvents which have high affinities for the odor-causing materials but in which the desired glycol(s) are substantially insoluble. Regardless of whether the reactive neutralization method or the liquid-liquid extraction approach is used, preferably the levels of the odor-causing materials left in the glycol product will be reduced to an extent whereby the deodorized glycol product will have no more of an odor than an equivalent glycol product that has been derived from nonrenewable sources.
  • odor-causing materials identified by gas chromatography-olfactometry or other conventional methods are the same in the renewable source-based glycol product and its nonrenewable source-based/fossil-based analog, preferably the amounts of one or more, and more preferably of most to all of the odor-causing materials in common between the two glycol products will be reduced in the deodorized, renewable source- based product.
  • the refined, bleached, deodorized soybean oil can be in the form of a liquid oil at ambient temperatures, or can be supplied in the form of fully hydrogenated soybean oil flakes which are heated to melting for providing the organic solvent into which the odor-causing materials are extracted. After the odor-causing materials are partitioned into the fully-hydrogenated soybean oil, the flakes can be regenerated by allowing the fully-hydrogenated soybean oil with odor-causing materials to cool, whereupon the deodorized glycol product can be recovered by a solids-liquid separation. Because of concerns regarding possible fouling and plugging with the fully- hydrogenated soybean oil flakes, in general it is expected that a refined, bleached, deodorized liquid soybean oil will be preferred over the flakes.
  • the organic solvent and the deodorized glycol product are separated from one another by allowing the immiscible glycol product and solvent to phase-separate, and then separating the two phases by decanting or the like.
  • the solvent containing the odor-causing materials is preferably then regenerated by distilling to remove the odor-causing materials, while the glycol product stream is preferably passed through a carbon bed or other adsorbent or is itself distilled to remove any of the organic solvent transferring into the deodorized glycol product stream.
  • the soybean oil can be regenerated by a steam deodorization using the same deodorizing capabilities as used originally.
  • the bottom layer containing water and the deodorized PG was collected, for later combining in the same way with the deodorized PG of Example 2 for gas chromatographic/mass spectrometric analysis.
  • the bottom layer exhibited a reduced odor profile for the extracted propylene glycol product as compared to the propylene glycol product as received, comparable to the odor profile and intensity of an equivalent fossil fuel-derived propylene glycol product.
  • EXAMPLE 2 A mixture of 55 grams of a distilled propylene glycol product from the hydrogenolysis of glycerol according to the US ⁇ 85 patent to Werpy et al. and 30 ml of heptane was shaken in a separatory funnel. The mixture was allowed to separate into two layers. The bottom layer containing propylene glycol product and a trace amount of heptane was drawn off, and the trace heptane was removed under vacuum. The deodorized propylene glycol product was then combined with the deodorized propylene glycol product of Example 1 , and analyzed by gas chromatography/mass spectrometry.
  • the top layer containing heptane and the odor-causing materials was concentrated by evaporation to remove most of the heptane, and the odor concentrate thus formed was combined with the odor concentrate of Example 1 and analyzed by gas chromatography/mass spectrometry.
  • the starting propylene glycol hydrogenolysis product was also analyzed for comparison, by gas
  • EXAMPLE 3 £0035] A mixture of 18 grams of a distilled propylene glycol product from the hydrogenolysis of glycerol according to the US '085 Werpy et al. patent and 2.3 grams of fully hydrogenated soybean oil flake was heated to 120 degrees Celsius with stirring. After 10 minutes, the soy flake was melted and the mixture was allowed to stir at temperature for a further 10 minutes. The mixture was then allowed to cool to room temperature. The soy flake became solid again and was filtered out. The recovered propylene glycol product, exhibiting a reduced odor, was then passed through a carbon column to remove trace amounts of soy flake and provide a deodorized glycol product.
  • EXAMPLE 4 A mixture of 9.75 grams of a distilled propylene glycol product from the hydrogenolysis of g)ycero ⁇ according to the US ⁇ 85 Werpy et al. patent and of 9.87 grams of refined, bleached, deodorized soybean oil was shaken in a centrifuge tube, then centrifuged for 3 minutes at 3000 rpm. Two layers were observed, the top layer containing soybean oil and the odor-causing materials, and the bottom layer containing deodorized propylene glycol product and a trace amount of soybean oil, which was removed by passing the deodorized propylene glycol product portion through a carbon column.
  • the propylene glycol product extracted with the refined, bleached, deodorized soybean oil had a less pronounced odor compared to the distilled propylene glycol product feed, though a stronger odor than the propylene glycol product portions deodorized with either ethyl acetate or heptane.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne des procédés de désodorisation d'un produit de glycol à base de source renouvelable préparé à partir de sucres à cinq ou six atomes de carbone et de polyols issus de la biomasse, notamment un produit de glycol distillé ou autrement purifié de pureté pharmaceutique. Dans un mode de réalisation, des matériaux plus acides au profil d'odeur plus prononcé réagissent avec une base faible pour former des sels au profil d'odeur moins prononcé. Dans une autre approche, les matériaux produisant les odeurs dans le produit de glycol à base de source renouvelable sont éliminés par extraction liquide-liquide.
PCT/US2011/036719 2010-06-16 2011-05-17 Procédés de désodorisation de glycols à source renouvelable WO2011159418A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35517410P 2010-06-16 2010-06-16
US61/355,174 2010-06-16

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WO2011159418A2 true WO2011159418A2 (fr) 2011-12-22
WO2011159418A3 WO2011159418A3 (fr) 2012-04-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9796948B2 (en) 2016-01-13 2017-10-24 The Procter & Gamble Company Laundry detergent compositions comprising renewable components

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5426249A (en) * 1992-11-14 1995-06-20 Degussa Aktiengesellschaft Process for the simultaneous production of 1,2- and 1,3-propanediol
US5616817A (en) * 1994-11-26 1997-04-01 Basf Aktiengesellschaft Preparation of 1,2-propanediol
WO2009149047A1 (fr) * 2008-06-05 2009-12-10 Huntsman Petrochemical Corporation Procédé de production et de purification de propylèneglycol

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2614105B2 (ja) * 1989-01-30 1997-05-28 三菱化学株式会社 エチレングリコールの脱臭方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5426249A (en) * 1992-11-14 1995-06-20 Degussa Aktiengesellschaft Process for the simultaneous production of 1,2- and 1,3-propanediol
US5616817A (en) * 1994-11-26 1997-04-01 Basf Aktiengesellschaft Preparation of 1,2-propanediol
WO2009149047A1 (fr) * 2008-06-05 2009-12-10 Huntsman Petrochemical Corporation Procédé de production et de purification de propylèneglycol

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9796948B2 (en) 2016-01-13 2017-10-24 The Procter & Gamble Company Laundry detergent compositions comprising renewable components
US10465145B2 (en) 2016-01-13 2019-11-05 The Procter & Gamble Company Laundry detergent compositions comprising renewable components
US10738265B2 (en) 2016-01-13 2020-08-11 The Procter & Gamble Company Laundry detergent compositions comprising renewable components

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