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WO2013090078A1 - Déshydroxylation d'acides polyhydroxycarboxyliques en acides polycarboxyliques aliphatiques en utilisant un catalyseur à base d'halogène - Google Patents

Déshydroxylation d'acides polyhydroxycarboxyliques en acides polycarboxyliques aliphatiques en utilisant un catalyseur à base d'halogène Download PDF

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Publication number
WO2013090078A1
WO2013090078A1 PCT/US2012/067839 US2012067839W WO2013090078A1 WO 2013090078 A1 WO2013090078 A1 WO 2013090078A1 US 2012067839 W US2012067839 W US 2012067839W WO 2013090078 A1 WO2013090078 A1 WO 2013090078A1
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WO
WIPO (PCT)
Prior art keywords
acid
halogen
moles
polyhydroxy carboxylic
aliphatic polycarboxylic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/US2012/067839
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English (en)
Inventor
Raj Deshpande
Paul Davis
Vandana Pandey
Nitin Kore
John R. Briggs
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of WO2013090078A1 publication Critical patent/WO2013090078A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups

Definitions

  • This invention relates generally to the field of dehydroxylation of poly hydroxy carboxylic acids. More particularly, it is a process to accomplish dehydroxylation of a biorenewable material to obtain aliphatic polycarboxylic acids.
  • Adipic acid also referred to as 1,6-hexanedioc acid
  • 1,6-hexanedioc acid is an important aliphatic polycarboxylic acid and a major commodity chemical in the world today.
  • the bulk of production representing billions of kilograms annually, is used primarily as a precursor for the production of nylon.
  • Other uses include as a monomer for polyurethanes and a plasticizer for polyvinyl chlorides. Small quantities of total production are also used for medical and food applications.
  • adipic acid The most common method of producing adipic acid is via oxidation. Frequently a mixture of cyclohexanol and cyclohexanone, called ketone-alcohol oil ("KA oil”), is oxidized with nitric acid, via a multi-step pathway. Side products of the method include glutaric and succinic acids. Other processes for producing adipic acid start from cyclohexanol alone. The cyclohexanol is generally obtained by hydrogenation of phenol.
  • WO 2010/144862 A2 discloses production of adipic acid and its derivatives from carbohydrate-containing materials, particularly glucose.
  • the patent discusses catalytic approaches for the conversion of glucose to glucaric acid and also conversion of glucaric acid to adipic acid, in the presence of hydrogen and a heterogeneous or homogeneous catalyst.
  • WO1995007996 discusses the conversion of carbohydrate sources to cis-cis muconic acid, an intermediate, which is then hydrogenated to adipic acid.
  • US 4400468 discloses a process for the conversion of biomass to adipic acid. The biomass is hydrolyzed to form 5-hydroxymethyl furfural, which is then hydrogenated to 2,5-tetrahydrofuran dimethanol in the presence of a catalyst. The 2,5-tetrahydrofuran dimethanol is catalytically hydrogenated to 1,6-hexanediol. Oxidation of the 1,6-hexanediol is conducted in the presence of microorganisms to form adipic acid.
  • the biomass may be a waste product of paper-making, or wood, cornstalks, or a logging residue.
  • this invention is a process for producing an aliphatic polycarboxylic acid comprising subjecting a polyhydroxy carboxylic acid to dehydroxylation conditions in the presence of a halogen-based catalyst containing at least one halogen atom, the dehydroxylation conditions including a reductive or non-reductive gas at a pressure of from 1 pound per square inch gauge ( ⁇ 6.89 kilopascals) to 2000 pound per square inch gauge ( ⁇ 13.79 megapascals), a temperature within a range of from 50 °C to 250 °C, a liquid reaction medium, and a ratio of moles of the polyhydroxy carboxylic acid to moles of the halogen atoms ranging from 1 : 10 to 100: 1 ; such that an aliphatic polycarboxylic acid is formed.
  • a halogen-based catalyst containing at least one halogen atom
  • the dehydroxylation conditions including a reductive or non-reductive gas at a pressure of from 1 pound per square inch gauge ( ⁇ 6.
  • a halogen-based catalyst contains at least one halogen atom and ionizes at least partially in an aqueous solution by losing one proton. It is important to note that the definition of "halogen-based” is applied to the catalyst at the point at which it catalyzes the dehydroxylation of the crude alcohol stream. Thus, it may be formed in situ in the liquid reaction medium beginning with, for example, a molecular halogen, e.g., molecular iodine (I 2 ), or may be introduced into the reaction as a halide acid, for example, as pre-prepared HI.
  • a molecular halogen e.g., molecular iodine (I 2 )
  • I 2 molecular iodine
  • Non-limiting examples include molecular iodine (I 2 ), hydroiodic acid (HI), iodic acid (HIO 3 ), lithium iodide (Lil), and combinations thereof.
  • the term "catalyst" is used in the conventionally understood sense, to clarify that the halogen-based compound takes part in the reaction but is regenerated thereafter and does not become part of the final product.
  • the halogen-based catalyst is at least partially soluble in the liquid reaction medium.
  • HI is selected as the halogen- based catalyst
  • it may be prepared as it is frequently prepared industrially, i.e., via the reaction of I 2 with hydrazine, which also yields nitrogen gas, as shown in the following equation.
  • Equation 1 When performed in water, the HI must be distilled. Alternatively, HI may be distilled from a solution of Nal or another alkali iodide in concentrated hypophosphorous acid. Another way to prepare HI is by bubbling hydrogen sulfide steam through an aqueous solution of iodine, forming hydroiodic acid (which must then be distilled) and elemental sulfur (which is typically filtered).
  • HI can be prepared by simply combining H 2 and I 2 . This method is usually employed to generate high purity samples.
  • polyhydroxy carboxylic acid is used to define a compound having any number of carbon atoms as a main chain, preferably from 4 to 20 carbon atoms, more preferably from 4 to 12, still more preferably from 4 to 8, and most preferably from 5 to 6 carbon atoms. These compounds have at least one carboxyl (COOH) functional group, and in many cases are diacids, i.e., they contain two COOH groups.
  • Non- limiting examples may include glucaric acid (also called saccharic acid), mucic acid (also called galactaric acid), xylaric acid (also called trihydroxy glutaric acid), and combinations thereof. Isomers of the above are also examples of polyhydroxy carboxylic acids.
  • the starting material may be glucaric acid, which may be obtained by a simple oxidation of glucose. Because glucose is a biorenewable material, the invention offers convenient sourcing as well as relatively mild conditions. Oxidation of glucose to glucaric acid may be carried out by, for example, oxidizing glucose by reacting it with nitric acid.
  • the starting material and the catalyst are desirably proportioned for optimized conversion of the starting material to at least one desired aliphatic polycarboxylic acid product.
  • a ratio of moles of starting material to moles of halogen atoms ranging from 1:10 to 100:1 is preferred. More preferred is a molar ratio ranging from 1:1 to 100: 1; still more preferably from 4:1 to 27:1; and most preferably from 4:1 to 8:1.
  • Alteration of the proportion of the catalyst to starting material will alter conversion of starting material to the corresponding aliphatic polycarboxylic acid(s), which may be, for example, a diacid.
  • corresponding is meant that the aliphatic polycarboxylic acid has the same carbon atom number as the starting polyhydroxy carboxylic acid.
  • Temperature parameters employed in the invention may vary within a range of from 50 °C to 250 °C, but are preferably from 100 °C to 210 °C. Those skilled in the art will be aware that certain temperatures may be preferably combined with certain molar ratios of material and catalyst to obtain optimized olefin yield. For example, a temperature of at least 180 °C combined with a molar ratio of starting material to halogen atoms of 6: 1 may result, in some embodiments, in particularly desirable yields. Other combinations of temperature and ratio of moles of starting material to moles of halogen atoms may also yield desirable conversions.
  • temperature may be varied especially within the preferred range of 100 °C to 210 °C, to obtain a range of conversion at a fixed time, e.g., 3 hours.
  • a fixed time e.g. 3 hours.
  • the conditions may also include a reaction time, typically within a range of from 1 hour to 10 hours. While a time longer than 10 hours may be selected, such may tend to favor formation of intermediates or of less stable aliphatic polycarboxylic acid products, neither of which is usually desirable. Intermediates formation may be more prevalent in a batch reactor than in a continuous process. Conversely, a time shorter than 1 hour may reduce overall product yield.
  • the inventive process may be carried out as either a reductive dehydroxylation or a non-reductive dehydroxylation.
  • gaseous hydrogen may be employed in essentially pure form as the reductant, but also may be included in mixtures further comprising, for example, carbon dioxide, carbon monoxide, nitrogen, methane, and any combination of hydrogen with one or more the above.
  • the hydrogen itself may therefore be present in the atmosphere, generally a gas stream, in an amount ranging from 1 weight percent (wt ) to 100 wt .
  • the atmosphere/gas stream is desirably substantially or, preferably, completely hydrogen-free.
  • gases including but not limited to nitrogen, carbon dioxide, carbon monoxide, methane, and combinations thereof, may be employed. Any constituent therefore may be present in amounts ranging from 1 wt to 100 wt , but the total atmosphere is desirably at least 98 wt , preferably 99 wt , and more preferably 100 wt , hydrogen-free.
  • the hydrogen-containing (reductive) or non-reductive atmosphere is useful in the present invention at a gas pressure sufficient to promote conversion of, for example, molecular halogen to halide, for example, I 2 to an iodide, preferably hydroiodic acid (HI, also known as "hydrogen iodide").
  • the pressure is desirably from 1 psig (—6.89 KPa) to 2000 psig (-13.79 MPa), and preferably from 50 psig (-344.5 KPa) to 200 psig (-1.38 MPa).
  • a gas pressure within the above ranges, especially the preferred range is often favorable for efficient conversion of molecular halide to the corresponding acid iodide.
  • gas pressures in excess of 2000 psig (—13.79 MPa) provide little or no discernible benefit and may simply increase cost of the process.
  • the conversion to an aliphatic polycarboxylic acid may be accomplished using many of the equipment and overall processing parameter selections that are generally known to those skilled in the art.
  • the starting material may function as both the compound(s) to be converted and the liquid reaction medium wherein the conversion will take place, or if desired, an additional solvent such as water, acetic acid, or another organic may be included.
  • Acetic acid may help to dissolve the halogen formed as part of the catalytic cycle and act as a leaving group, thereby facilitating the cycle.
  • Organic solvents may be helpful in removing any water accumulated during the course of the reaction.
  • Dialkyl ethers may also be selected.
  • Reactor with a glass insert.
  • Reaction commences as seen from a drop in the pressure of the reactor, and monitor against time. Continue the reaction in this fashion for a period of 3 hours. Fill with hydrogen intermittently to make up for the consumption of hydrogen in the reactor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Selon la présente invention, des acides polyhydroxycarboxyliques sont convertis en acides polycarboxyliques aliphatiques, tels que l'acide adipique, dans des conditions de déshydroxylation réductrices ou non réductrices, en présence d'un catalyseur à base d'halogène. Les conditions de procédé relativement douces comprennent une pression de gaz de 1 psig (~6,89 KPa) à 2000 psig (~13,79 MPa), une température de 50 °C à 250 °C, un milieu de réaction liquide, et un rapport molaire de l'acide polyhydroxycarboxylique, tel que l'acide glucarique, aux atomes d'halogène de 1:10 à 100:1.
PCT/US2012/067839 2011-12-15 2012-12-05 Déshydroxylation d'acides polyhydroxycarboxyliques en acides polycarboxyliques aliphatiques en utilisant un catalyseur à base d'halogène Ceased WO2013090078A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161570973P 2011-12-15 2011-12-15
US61/570,973 2011-12-15

Publications (1)

Publication Number Publication Date
WO2013090078A1 true WO2013090078A1 (fr) 2013-06-20

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PCT/US2012/067839 Ceased WO2013090078A1 (fr) 2011-12-15 2012-12-05 Déshydroxylation d'acides polyhydroxycarboxyliques en acides polycarboxyliques aliphatiques en utilisant un catalyseur à base d'halogène

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015084265A1 (fr) * 2013-12-04 2015-06-11 Agency For Science, Technology And Research Procédé chimique pour convertir l'acide mucique en acide adipique
WO2016032403A1 (fr) * 2014-08-28 2016-03-03 Agency For Science, Technology And Research Synthèse d'acide polycarboxylique aliphatique
CN108383717A (zh) * 2018-04-18 2018-08-10 中国石油大学(华东) 一种生物质基丙二酸的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400468A (en) 1981-10-05 1983-08-23 Hydrocarbon Research Inc. Process for producing adipic acid from biomass
WO1995007996A1 (fr) 1993-09-16 1995-03-23 Purdue Research Foundation Synthese de l'acide adipique a partir de sources carbonees derivees de la biomasse
WO2010144862A2 (fr) 2009-06-13 2010-12-16 Rennovia, Inc. Production d'acide adipique et de dérivés de celui-ci à partir de matières contenant des glucides
WO2010144871A2 (fr) * 2009-06-13 2010-12-16 Rennovia, Inc. Production d'acide glutarique et de dérivés à partir de matières contenant des glucides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400468A (en) 1981-10-05 1983-08-23 Hydrocarbon Research Inc. Process for producing adipic acid from biomass
WO1995007996A1 (fr) 1993-09-16 1995-03-23 Purdue Research Foundation Synthese de l'acide adipique a partir de sources carbonees derivees de la biomasse
WO2010144862A2 (fr) 2009-06-13 2010-12-16 Rennovia, Inc. Production d'acide adipique et de dérivés de celui-ci à partir de matières contenant des glucides
WO2010144871A2 (fr) * 2009-06-13 2010-12-16 Rennovia, Inc. Production d'acide glutarique et de dérivés à partir de matières contenant des glucides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015084265A1 (fr) * 2013-12-04 2015-06-11 Agency For Science, Technology And Research Procédé chimique pour convertir l'acide mucique en acide adipique
CN105899484A (zh) * 2013-12-04 2016-08-24 新加坡科技研究局 将粘酸转化为己二酸的化学方法
WO2016032403A1 (fr) * 2014-08-28 2016-03-03 Agency For Science, Technology And Research Synthèse d'acide polycarboxylique aliphatique
CN108383717A (zh) * 2018-04-18 2018-08-10 中国石油大学(华东) 一种生物质基丙二酸的制备方法
CN108383717B (zh) * 2018-04-18 2021-05-11 中国石油大学(华东) 一种生物质基丙二酸的制备方法

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