WO2020007808A1 - Production d'esters alkyliques d'acide acrylique - Google Patents

Production d'esters alkyliques d'acide acrylique Download PDF

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Publication number
WO2020007808A1
WO2020007808A1 PCT/EP2019/067632 EP2019067632W WO2020007808A1 WO 2020007808 A1 WO2020007808 A1 WO 2020007808A1 EP 2019067632 W EP2019067632 W EP 2019067632W WO 2020007808 A1 WO2020007808 A1 WO 2020007808A1
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WIPO (PCT)
Prior art keywords
derivatives
acrylic acid
lactic acid
process according
alkyl esters
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Ceased
Application number
PCT/EP2019/067632
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English (en)
Inventor
Simon David BISHOPP
Jean Paul Andre Marie Joseph Ghislain LANGE
Johannes Michael Maria Veerman
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Shell Internationale Research Maatschappij BV
Shell USA Inc
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Shell Internationale Research Maatschappij BV
Shell Oil Co
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Publication of WO2020007808A1 publication Critical patent/WO2020007808A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form

Definitions

  • the present invention generally relates to a process of producing alkyl esters of acrylic acid from alkyl esters of lactic acid.
  • alkyl esters of acrylic acid from alkyl esters of lactic acid involves the removal of a hydroxyl group from an alpha carbon atom and a hydrogen atom from the adjacent beta carbon atom (forming a water molecule), i.e. a dehydration reaction.
  • the general reaction is indicated by the equation below:
  • Alkyl esters of lactic acid such as methyl lactate
  • have many uses such as a solvent, a starting material for the manufacture of polylactic acid, or a starting material for numerous other reactions.
  • alkyl esters of lactic acid can be used as an intermediate in lactic acid purification, and as building block in the synthesis of chiral components, e.g., pesticides, and as a starting material for lactide manufacture.
  • Alkyl esters of lactic acid are also used in the manufacture of alkyl esters of acrylic acid, such as methyl acrylate, which is a starting material for the manufacture of acrylate polymers. Additionally, alkyl esters of acrylic acid are a suitable starting material for acrylic acid and other esters like ethyl acrylate and butyl acrylate.
  • Acrylic acid, acrylic acid derivatives, or mixtures thereof have a variety of industrial uses, typically in the form of polymers.
  • these polymers are commonly used in the manufacture of, among other things, adhesives, binders, coatings, paints, polishes, detergents, flocculants, dispersants, thixotropic agents, sequestrants, and superabsorbent polymers (SAP), which are used in disposable absorbent articles, including diapers and hygienic products, for example.
  • Acrylic acid has been commonly made from fossil resources. For example, acrylic acid has long been prepared by catalytic oxidation of propylene. These and other methods of making acrylic acid from fossil sources are described in the Kirk-Othmer Encyclopedia of Chemical Tech., Vol. 1, pgs.
  • Fossil-derived acrylic acid contributes to greenhouse emissions due to its high fossil-derived carbon content.
  • fossil resources become scarce, more expensive, and subject to regulations for C02 emissions, there exists a growing need for bio-based acrylic acid, acrylic acid derivatives, or mixtures thereof that can serve as an alternative to fossil-derived acrylic acid, acrylic acid derivatives, or mixtures thereof.
  • Known processes for producing of alkyl esters of acrylic acid start with alkyl esters of lactic acid which are subjected to a dehydration reaction in the presence of a catalyst to form alkyl esters of acrylic acid.
  • the process is typically carried out in the gas phase in the presence of excess steam.
  • the reaction temperature is, e.g., 300-500°C.
  • Reaction pressure is, e.g., in the range of 0.5-3 bar, and suitably atmospheric.
  • An inert gas may be added to reduce the partial pressure by dilution.
  • Suitable catalysts include dehydrogenation catalysts known in the art.
  • the invention provides a process for producing a mixture of alkyl esters of acrylic acid, the process including the step of contacting a mixture of an alkyl ester of lactic acid and a solvent over a dehydration catalyst to produce the mixture of alkyl esters of acrylic acid, wherein the density of the solvent ranges from about 10 to about 500 kg/m3 under operating conditions.
  • Fig. 1 is a graphical representation of conversion/yields for embodiments of the invention operating at different regimes.
  • the present invention is directed to a process for manufacturing alkyl esters of acrylic acid from alkyl esters of lactic acid. More preferably, the present invention is directed to a method for manufacturing methyl acrylate from methyl lactate.
  • Embodiments of the present invention include a method of making alkyl esters of acrylic acid by contacting alkyl esters of lactic acid with a dehydration catalyst.
  • the alkyl esters of acrylic acid may also include acrylic acid, acrylic acid derivatives, or mixtures thereof.
  • the alkyl esters of lactic acid may also include lactic acid, lactic acid derivatives, or mixtures thereof.
  • Non-limiting examples of alkyl esters of lactic acid are methyl lactate, ethyl lactate, butyl lactate, 2-ethylhexyl lactate, or mixtures thereof.
  • a non-limiting example of cyclic dimers of lactic acid is dilactide.
  • Lactic acid can be L-lactic acid, D-lactic acid, or mixtures thereof.
  • Lactic acid derivatives can be lactic acid oligomers, cyclic dimers of lactic acid, lactic acid anhydride, 2-alkoxypropoanoic acids or their alkyl esters, 2-aryloxypropanoic acids or their alkyl esters, 2-acyloxypropanoic acids or their alkyl esters, or a mixture thereof.
  • Non-limiting examples of metal salts of lactic acid are sodium lactate, potassium lactate, and calcium lactate.
  • Non-limiting examples of 2-alkoxypropoanoic acids are 2- methoxypropanoic acid and 2-ethoxypropanoic acid.
  • a non-limiting example of 2- aryloxypropanoic acid is 2-phenoxypropanoic acid.
  • a non-limiting example of 2- acyloxypropanoic acid is 2-acetoxypropanoic acid.
  • the alkyl esters of lactic acid originate from converting a renewable feedstock into the alkyl ester of lactic acid.
  • the renewable feedstock may be from at least one of a sugar source selected from at least one of sucrose, glucose, xylose or fructose, or a carbohydrate and their isomers.
  • the renewable feedstock may be from at least one of a sugar source selected from at least one of dimeric and oligomeric sugars such cellobiose, starch, cellulose, hemicellulose, pectin, etc.
  • the sugars source may be a triose source such as dihydroxyacetone and dihydroxypropanal.
  • Non-limiting examples of alkyl esters of acrylic acid are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, or mixtures thereof.
  • Acrylic acid derivatives can be metal or ammonium salts of acrylic acid, acrylic acid oligomers, or mixtures thereof.
  • Non-limiting examples of metal salts of acrylic acid are sodium acrylate, potassium acrylate, and calcium acrylate.
  • Embodiments of the present invention provide a stream comprising alkyl esters of lactic acid in a liquid stream.
  • the liquid stream can include the alkyl esters of lactic acid and a solvent (diluent).
  • the solvent include water, methanol, ethanol, acetone, C3 to C8 linear and branched alcohols, C3 to C8 esters (e.g. ethyl acetate, methyl propionate), ethers (including dimethyl ether, diethyl ether, diphenyl ether), and mixtures thereof.
  • the solvent may have an atmospheric boiling point below 300°C, below 250°C, or below 200°C and an atmospheric boiling point above 50°C, above 100°C, or above l50°C.
  • the solvent may have a high solvency for methyl lactate at l50°C, 100°C, 50°C, 25°C, while remaining in the liquid phase.
  • the solvent comprises methanol.
  • high solvency may refer to the solvent being able dissolve >5 w%
  • the liquid stream includes between about 2 wt % to about 95 wt % alkyl esters of lactic acid based on the total weight of the liquid stream. In another embodiment of the present invention, the liquid stream includes between about 5 wt % to about 50 wt % alkyl esters of lactic acid, based on the total weight of the liquid stream. In yet another embodiment of the present invention, the liquid stream includes between about 10 wt % to about 25 wt % alkyl esters of lactic acid, based on the total weight of the liquid stream. In even yet another embodiment of the present invention, the liquid stream includes about 20 wt % alkyl esters of lactic acid, based on the total weight of the liquid stream.
  • the liquid stream comprises a solution of alkyl esters of lactic acid.
  • the liquid stream includes greater than 5 wt%, greater than l0wt%, greater than l5wt% and greater than 20wt% alkyl esters of lactic acid, based on the total weight of the liquid stream.
  • the liquid stream includes less than 95wt%, less than 75wt%, less than 50wt% or less than 25wt% alkyl esters of lactic acid, based on the total weight of the liquid stream.
  • suitable dehydration catalysts include catalysts known in the art.
  • the catalyst may be an oxide or mixed oxide having amphoteric or mildly basic properties.
  • the mixed oxides may include an acidic oxide from Groups 13-15 (e.g. oxide of Al, Si, P, S), oxides from Groups 1-3 (e.g. oxide of K, Mg, Ca), or mixtures.
  • the mixed oxide can be mixed throughout the bulk of the catalyst or may consist of Groups 1 -3 metal oxides deposited on the surface of Groups 13-15 metal oxides.
  • the mixed oxide may be crystalline or amorphous. Crystalline mixed oxides may include crystalline alumino-silicates also called zeolites.
  • the metal of Groups 1-3 may then be exchanged or deposited in the zeolite.
  • Some examples include catalysts based on calcium sulphate, calcium phosphate, calcium pyrophosphate, and combinations thereof. Suitable promoters include sodium sulphate, copper sulphate, manganese sulphate, iron sulphate, magnesium sulphate, aluminium sulphate, sodium nitrate, sodium phosphate, and potassium phosphate.
  • the dehydration catalyst may be one or more of Na2S04, Na3P04, NaN03, Na2Si03, Na4P207, NaH2P04, Na2HP04, Na2HAs04, NaC3H503, NaOH, Cs2S04, KOH, CsOH, and LiOH.
  • the dehydration catalyst may be selected from one or more of ZSM-5 molecular sieves modified with aqueous alkali (such as NaOH, and Na2C03) or a phosphoric acid salt (such as NaH2P04, Na2HP04,
  • catalysts to be considered may include magnesium oxide, nickel oxide, zirconium oxide, calcium phosphates, barium phosphates, magnesium phosphate, bismuth phosphate, cobalt oxide, lithium aluminate, calcium sulfate, calcium carbonate, proprietary commercial molecular sieves, barium sulfate, strontium sulfate, lanthanum phosphate, barium fluoride, barium chloride, aluminum phosphate, zinc sulfate, calcium metasilicate, calcium zirconate, calcium titanate, calcium stannate, calcium aluminate, strontium carbonate, magnesium carbonate, calcium selenite, calcium borates and nickel sulfate, These materials were used alone, or as mixtures with others and promoters, and supported on extended surface materials such as alumina, silica gel, graphite and agents such as sodium and potassium mono and dihydrogen phosphates or organic agents such asphenothiazine.
  • the operating conditions of the reactor provide a density of the feed solution ranging from about 10 to about 500 kg/m3. In other embodiments, the operating conditions of the reactor provide a density of the feed solution ranging from about 50 to about 400 kg/m3. In still other embodiments, the operating conditions of the reactor provide a density of the feed solution ranging from about 100 to about 300 kg/m3. In some embodiments, the density of the feed solution is greater than 10 kg/m3, greater than 50 kg/m3, greater than 100 kg/m3, or greater than 150 kg/m3. In other embodiments, the density of the feed solution is less than 500 kg/m3, less than 300 kg/m3, or less than 200 kg/m3.
  • the contacting of the stream comprising alkyl esters of lactic acid with the dehydration catalyst may be earned out at supercritical conditions of the solvent, which is defined as above the critical pressure and critical temperature of the solvent.
  • the stream comprising alkyl esters of lactic acid contacts the dehydration catalyst at a pressure between about 73 psig (5 barg) and about 1305 psig (90 barg). In another embodiment of the present invention, the stream comprising alkyl esters of lactic acid contacts the dehydration catalyst at a pressure of about 290 psig (20 barg). In some embodiments, the pressure is greater than 5 bar, greater than 10 bar, greater than 20 bar, or greater than 30 bar and less than 200 bar, less than 150 bar, less than 100 bar, less than 80 bar, or less than 60 bar.
  • the reaction occurs at a temperature between about 80°C and about 700°C.
  • the contacting of the stream comprising alkyl esters of lactic acid with the dehydration catalyst is earned out at a temperature between about 100°C and about 500°C.
  • the contacting of the stream comprising alkyl esters of lactic thereof with the dehydration catalyst is carried out at a temperature between about 120°C and about 400°C.
  • the contacting of the stream comprising alkyl esters of lactic acid with the dehydration catalyst is earned out at a temperature between about l80°C and about 250°C.
  • the contacting of the stream comprising alkyl esters of lactic acid with the dehydration catalyst is carried out at a temperature of about 300°C.
  • the temperature is greater than 200, greater than 250°C, greater than 275°C, greater than 300°C, greater than 325°C or greater than 350°C and less than 500°C, less than 450°C, less than 400°C, or less than 375°C.
  • a 35 ml microflow reactor unit having a packed bed of hydroxyapatite catalyst with a BET surface area of about 65m2/g was fed a stream of reactants of about 20 wt% methyl lactate and 80 wt% methanol.
  • the hydroxyapatite catalyst was synthesized by the method described in Ghantani et ah, Green Chem., 2013, Vol.15, pagesl2l 1-1217.
  • the feed line can optionally be preheated.
  • the reactor itself has a volume of 35mL and is situated in an electrically heated furnace having three separate heating zones. Post reactor there is a condenser followed by a gas-liquid separator.
  • the back pressure in the unit is controlled by use of a standard back pressure regulator on the off-gas line, and additionally via the liquid product sample valve.
  • the initial reactor pressure was 20 bar.
  • the pressure of the reactor was raised to 90 bar, lowered to 1 bar, and then increased back to 90 bar.
  • the density of the solvent was also increased and decreased in response to the pressure change.
  • the density of the solvent at 20 bar was about 12 kg/m3, at 90 bar about 55 kg/m3 and at 1 bar about 0.62 kg/m3.
  • the density was conservatively calculated using the ideal gas law and adjusting for the molar mass of methanol, for the density of gases is known to increase more steeply than dictated by the ideal gas law when approaching and exceeding the critical pressure (i.e. 80 bar in the case of methanol).
  • the highest pressure applied provided a supercritical atmosphere in the reactor.
  • the resulting product stream included methyl acrylate (MA), methyl propanoate (MP), and 2-methoxy methyl propanoate (2-MMP).
  • MA methyl acrylate
  • MP methyl propanoate
  • 2-MMP 2-methoxy methyl propanoate
  • the catalyst showed moderate activity, with yield to the desired product, methyl acrylate, reaching a maximum of 14% ( Figure 1).
  • Figure 1 the MA yield remains stable around 10% for some 150 hours on stream when operating at 90 bar.
  • the yield of MA immediately drops to 10 % and further decreased to ⁇ 1 % within a day.
  • the catalyst activity appears to be restored based on the increase of the methyl acrylate in the product to 10% yield.
  • the catalyst further maintained this high activity for the following 150 hours of operation until the run was interrupted.
  • catalyst activity may be maintained for longer periods of time thus increasing catalyst lifetime and removing the need for separate decoking steps of the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'un mélange comprenant de l'acide acrylique ou des dérivés de celui-ci, le procédé comprenant une étape consistant à mettre en contact un mélange d'acide lactique ou de dérivés de celui-ci et un solvant sur un catalyseur de déshydratation pour produire un mélange comprenant des esters alkyliques d'acide acrylique, la densité du solvant étant comprise entre environ 10 et environ 500 kg/m3 dans des conditions de fonctionnement.
PCT/EP2019/067632 2018-07-02 2019-07-01 Production d'esters alkyliques d'acide acrylique Ceased WO2020007808A1 (fr)

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US201862692916P 2018-07-02 2018-07-02
US62/692,916 2018-07-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020099430A1 (fr) * 2018-11-14 2020-05-22 Shell Internationale Research Maatschappij B.V. Régénération de catalyseur pour la déshydratation d'acide lactique
CN114409927A (zh) * 2022-01-24 2022-04-29 安徽省纳胜生物科技有限公司 万吨级高粘速溶超高分子量聚丙烯酸钠及其制备方法与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2859240A (en) 1956-01-12 1958-11-04 Minnesota Mining & Mfg Production of acrylates by catalytic dehydration of lactic acid and alkyl lactates
US9422222B2 (en) 2012-04-11 2016-08-23 The Procter & Gamble Company Process for production of acrylic acid or its derivatives from hydroxypropionic acid or its derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2859240A (en) 1956-01-12 1958-11-04 Minnesota Mining & Mfg Production of acrylates by catalytic dehydration of lactic acid and alkyl lactates
US9422222B2 (en) 2012-04-11 2016-08-23 The Procter & Gamble Company Process for production of acrylic acid or its derivatives from hydroxypropionic acid or its derivatives

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Kirk-Othmer Encyclopedia of Chemical Tech.", vol. 1, 2004, JOHN WILEY & SONS, INC., pages: 342 - 369
AIDA T M ET AL: "Dehydration of lactic acid to acrylic acid in high temperature water at high pressures", THE JOURNAL OF SUPERCRITICAL FLUIDS, ELSEVIER, AMSTERDAM, NL, vol. 50, no. 3, 1 October 2009 (2009-10-01), pages 257 - 264, XP026395883, ISSN: 0896-8446, [retrieved on 20090623] *
CARL T. LIRA ET AL: "Conversion of lactic acid to acrylic acid in near-critical water", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 32, no. 11, 1 November 1993 (1993-11-01), pages 2608 - 2613, XP055271769, ISSN: 0888-5885, DOI: 10.1021/ie00023a025 *
GHANTANI ET AL., GREEN CHEM., vol. 15, 2013, pages 1211 - 1217
ZHANG J ET AL: "Evaluation of Catalysts and Optimization of Reaction Conditions for the Dehydration of Methyl Lactate to Acrylates", CHINESE JOURNAL OF CHEMICAL ENGINEERING, CHEMICAL INDUSTRY PRESS, BEIJING, CN, vol. 16, no. 2, 1 April 2008 (2008-04-01), pages 263 - 269, XP022856567, ISSN: 1004-9541, [retrieved on 20080401], DOI: 10.1016/S1004-9541(08)60073-7 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020099430A1 (fr) * 2018-11-14 2020-05-22 Shell Internationale Research Maatschappij B.V. Régénération de catalyseur pour la déshydratation d'acide lactique
CN114409927A (zh) * 2022-01-24 2022-04-29 安徽省纳胜生物科技有限公司 万吨级高粘速溶超高分子量聚丙烯酸钠及其制备方法与应用

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