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WO2017176669A1 - Procédés de production d'acides carboxyliques α,β-insaturés et de sels de ceux-ci - Google Patents

Procédés de production d'acides carboxyliques α,β-insaturés et de sels de ceux-ci Download PDF

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Publication number
WO2017176669A1
WO2017176669A1 PCT/US2017/025837 US2017025837W WO2017176669A1 WO 2017176669 A1 WO2017176669 A1 WO 2017176669A1 US 2017025837 W US2017025837 W US 2017025837W WO 2017176669 A1 WO2017176669 A1 WO 2017176669A1
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WIPO (PCT)
Prior art keywords
solid oxide
treated
alumina
metal
unsaturated carboxylic
Prior art date
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PCT/US2017/025837
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English (en)
Inventor
Mark HLAVINKA
Max Mcdaniel
Original Assignee
Chevron Phillips Chemical Company Lp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US15/091,794 external-priority patent/US9725393B2/en
Application filed by Chevron Phillips Chemical Company Lp filed Critical Chevron Phillips Chemical Company Lp
Priority to CN202211087783.2A priority Critical patent/CN115433075A/zh
Priority to CN201780022267.2A priority patent/CN109071398B/zh
Priority to EP17718237.5A priority patent/EP3426627A1/fr
Publication of WO2017176669A1 publication Critical patent/WO2017176669A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters

Definitions

  • Processes for producing an ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof are disclosed herein. These processes represent an improvement over homogeneous processes that result in poor yields and have challenging separation/isolation procedures, due in part to the reaction being conducted in an organic solvent, making isolation of the desired ⁇ , ⁇ - unsaturated carboxylic acid (e.g., acrylic acid) difficult.
  • the processes disclosed herein utilize a solid promoter (or solid activator, such as a treated solid oxide), providing a heterogeneous system that has a distinct advantage in ease of separation of the desired product from the catalytic promoter.
  • the solid promoters can result in surprisingly high yields of the desired acrylate or ⁇ , ⁇ -unsaturated carboxylic acid, such as acrylic acid.
  • one such process for producing an ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof can comprise:
  • a process for producing an ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof is provided, and in this aspect, the process can comprise:
  • a solid promoter e.g., a treated solid oxide
  • a process for performing a metallalactone elimination reaction is provided, and in this aspect, the process can comprise:
  • a solid promoter e.g., a treated solid oxide
  • the processes disclosed herein can be used to produce, for instance, acrylic acid or a salt thereof.
  • compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components or steps, unless stated otherwise.
  • a step in certain processes consistent with the present invention can contact components comprising a metallalactone, a diluent, and a treated solid oxide; alternatively, can contact components consisting essentially of a metallalactone, a diluent, and a treated solid oxide; or alternatively, can contact components consisting of a metallalactone, a diluent, and a treated solid oxide.
  • groups of elements are indicated using the numbering scheme indicated in the version of the periodic table of elements published in Chemical and Engineering News, 63(5), 27, 1985.
  • a group of elements can be indicated using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.
  • hydrocarbon refers to a compound containing only carbon and hydrogen.
  • Other identifiers may be utilized to indicate the presence of particular groups in the hydrocarbon, for instance, a halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon.
  • the term“ ⁇ , ⁇ -unsaturated carboxylic acid” and its derivatives refer to a carboxylic acid having a carbon atom of a carbon-carbon double bond attached to the carbonyl carbon atom (the carbon atom bearing the double bonded oxygen atom).
  • the ⁇ , ⁇ -unsaturated carboxylic acid may contain other functional groups and/or heteroatoms.
  • any name or structure presented is intended to encompass all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that may arise from a particular set of substituents, unless otherwise specified.
  • the name or structure also encompasses all enantiomers, diastereomers, and other optical isomers (if there are any) whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan, unless otherwise specified.
  • a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane; and a general reference to a butyl group includes a n-butyl group, a sec-butyl group, an iso-butyl group, and a t-butyl group.
  • substituted when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe the compound or group wherein any non-hydrogen moiety formally replaces hydrogen in that group or compound, and is intended to be non-limiting.
  • a compound or group can also be referred to herein as “unsubstituted” or by equivalent terms such as“non-substituted,” which refers to the original group or compound.
  • “substituted” is intended to be non-limiting and include inorganic substituents or organic substituents as specified and as understood by one of ordinary skill in the art.
  • the terms“contact product,”“contacting,” and the like, are used herein to describe compositions and methods wherein the components are combined or contacted together in any order, in any manner, and for any length of time, unless otherwise specified.
  • the components can be contacted by blending or mixing.
  • the contacting of any component can occur in the presence or absence of any other component of the compositions and methods described herein. Combining additional materials or components can be done by any suitable method.
  • the term“contact product” includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. Although“contact product” can, and often does, include reaction products, it is not required for the respective components to react with one another.
  • the term“contacting” is used herein to refer to materials which can be blended, mixed, slurried, dissolved, reacted, treated, or otherwise combined or contacted in some other manner.
  • the present invention is directed generally to methods for forming ⁇ , ⁇ -unsaturated carboxylic acids, or salts thereof.
  • An illustrative example of a suitable ⁇ , ⁇ -unsaturated carboxylic acid is acrylic acid.
  • the heterogeneous processes of this invention can provide a distinct advantage over homogeneous systems in the ease of separation (e.g., solid-liquid separation techniques) of the desired reaction product from the solid catalytic promoter (e.g., the treated solid oxide).
  • the processes of this invention are also advantageous in that an additional or auxiliary liquid base (e.g., an alkoxide, hydride, or amine) is not needed to perform the disclosed processes.
  • an additional or auxiliary liquid base e.g., an alkoxide, hydride, or amine
  • a transition metal complex that is covalently bound or immobilized on a solid support e.g., with a linking moiety
  • heterogeneous base comprising an organic basic moiety that is covalently bound or immobilized on a solid support (e.g., with a linking moiety) is not needed to perform the disclosed processes.
  • a consumable heterogeneous alkalinity reservoir e.g., NaH
  • an aryloxide e.g., a fluorophenolate
  • the solid promoter used in the processes disclosed herein can comprise (or consist essentially of, or consist of) a solid oxide, a clay or pillared clay, or combinations thereof.
  • a solid oxide e.g., a clay or pillared clay, or combinations thereof.
  • mixtures or combinations of two or more solid promoters can be employed in certain aspects of the invention.
  • solid promoter is used interchangeably herein with solid activator.
  • the solid promoter can comprise a basic promoter, for instance, a solid promoter that can act as a base.
  • basic promoters can include alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina- titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, and the like, as well as combinations thereof.
  • the solid promoter can comprise a Lewis acid promoter.
  • Lewis acid promoters can include silica, alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania- zirconia, and the like, as well as combinations thereof.
  • the solid promoter can comprise a Br ⁇ nsted base promoter.
  • Br ⁇ nsted base promoters can include alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania- zirconia, and the like, as well as combinations thereof.
  • the solid promoter can comprise a Br ⁇ nsted base and Lewis acid promoter.
  • Br ⁇ nsted base and Lewis acid promoters can include alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc- aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, and the like, as well as combinations thereof.
  • the solid promoter can comprise (or consist essentially of, or consist of) a solid oxide.
  • the solid oxide can comprise oxygen and one or more elements selected from Group 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or comprise oxygen and one or more elements selected from the lanthanide or actinide elements (See: Hawley's Condensed Chemical Dictionary, 11 th Ed., John Wiley & Sons, 1995; Cotton, F.A., Wilkinson, G., Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6 th Ed., Wiley-Interscience, 1999).
  • the solid oxide can comprise oxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, Zr, Na, K, Cs, Ca, Ba, and Li.
  • solid oxides that can be used as solid promoters as described herein can include, but are not limited to, Al 2 O 3 , B 2 O 3 , BeO, Bi 2 O 3 , BaO, MgO, CaO, CdO, Ce 2 O 3, Co 3 O 4 , Cr 2 O 3 , CuO, Fe 2 O 3 , Ga 2 O 3 , K 2 O, La 2 O 3 , Mn 2 O 3 , MoO 3 , Na 2 O, NiO, P 2 O 5 , Sb 2 O 5 , SiO 2 , SnO 2 , SrO, ThO 2 , TiO 2, V 2 O 5 , WO 3 , Y 2 O 3 , ZnO, ZrO 2 , and the like, including mixed oxides thereof, and combinations thereof.
  • solid oxide is meant to encompass carbonates and hydroxides of the above elements, either alone or in combination.
  • Illustrative and non-limiting examples of carbonates include sodium carbonate, sodium bicarbonate, potassium carbonate
  • the solid oxide can comprise silica, alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica- boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, and the like, or a combination thereof; alternatively, silica; alternatively, alumina; alternatively, titania; alternatively, zirconia; alternatively, magnesia; alternatively, boria; alternatively, calcia; alternatively, zinc oxide; alternatively, silica- alumina; alternatively, silica-coated
  • the solid oxide can comprise magnesium aluminate, calcium aluminate, zinc aluminate, zirconium aluminate, sodium aluminate, magnesium zirconium oxide, sodium zirconium oxide, calcium zirconium oxide, lanthanum chromium oxide, barium titanium oxide, and the like, or a combination thereof; alternatively, magnesium aluminate; alternatively, calcium aluminate; alternatively, zinc aluminate; alternatively, zirconium aluminate; alternatively, sodium aluminate; alternatively, magnesium zirconium oxide; alternatively, sodium zirconium oxide; alternatively, calcium zirconium oxide; alternatively, lanthanum chromium oxide; or alternatively, barium titanium oxide.
  • the solid oxide can comprise silica-coated alumina, as described in U.S. Patent No. 7,884,163 (e.g., Sasol Siral ® 28 or Sasol Siral ® 40).
  • silica-coated alumina solid oxide materials often are alumina-rich, with the weight ratio of alumina to silica (alumina:silica) in the silica-coated alumina typically falling in a range from 1.05:1 to 50:1, from 1.1:1 to 25:1, from 1.2:1 to 12:1, from 1.2:1 to 4:1, from 1.3:1 to 6:1, or from 1.3:1 to 3:1.
  • the solid promoter can comprise (or consist essentially of, or consist of) a clay or a pillared clay.
  • the clay or pillared clay materials that can be employed as a solid promoter in the disclosed processes can encompass clay materials either in their natural state or that have been treated with various ions by wetting, ion exchange, pillaring, or other processes.
  • the clay or pillared clay material can comprise clays that have been ion exchanged with large cations, including polynuclear, highly charged metal complex cations.
  • the clay or pillared clay material can comprise clays that have been ion exchanged with simple salts, including, but not limited to, salts of Al(III), Fe(II), Fe(III), and Zn(II) with ligands such as halide, acetate, sulfate, nitrate, nitrite, and the like.
  • the clay or pillared clay material can comprise a pillared clay.
  • pillared clay can be used to refer to clay materials that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations. Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometallates, and other large ions.
  • pillaring generally refers to a simple exchange reaction in which the exchangeable cations of a clay material can be replaced with large, highly charged ions, such as Keggin ions.
  • the clay or pillared clay can comprise montmorillonite, bentonite, nontronite, hectorite, halloysite, vermiculite, mica, fluoromica, chlorite, sepiolite, attapulgite, palygorskite, illite, saponite, allophone, smectite, kaolinite, pyrophyllite, and the like, or any combination thereof.
  • the clay or pillared clay can comprise montmorillonite; alternatively, bentonite; alternatively, nontronite; alternatively, hectorite; alternatively, halloysite; alternatively, vermiculite; alternatively, mica; alternatively, fluoromica; alternatively, chlorite; alternatively, sepiolite; alternatively, attapulgite; alternatively, palygorskite; alternatively, illite; alternatively, saponite; alternatively, allophone; alternatively, smectite; alternatively, kaolinite; or alternatively, pyrophyllite.
  • montmorillonite alternatively, bentonite; alternatively, nontronite; alternatively, hectorite; alternatively, halloysite; alternatively, vermiculite; alternatively, mica; alternatively, fluoromica; alternatively, chlorite; alternatively, sepiolite; alternatively, attapulgite; alternatively, palygorskite
  • the solid promoter can comprise silica, alumina, silica-alumina, aluminum phosphate, alumina-boria, silica-magnesia, silica-titania, zirconia, magnesia, magnesium aluminate, sepiolite, titania, palygorskite, montmorillonite, talc, kaolinite, halloysite, pyrophyllite, and the like, as well as combinations thereof.
  • the solid promoter can comprise silica, alumina, silica- alumina, aluminum phosphate, alumina-boria, silica-magnesia, silica-titania, zirconia, magnesia, magnesium aluminate, titania, and the like, as well as combinations thereof.
  • the solid promoter can comprise sepiolite, palygorskite, montmorillonite, talc, kaolinite, halloysite, pyrophyllite, and the like, as well as combinations thereof.
  • the solid promoter can comprise alumina, zirconia, magnesia, magnesium aluminate, sepiolite, and the like, as well as combinations thereof; alternatively, alumina; alternatively, zirconia; alternatively, magnesia; alternatively, magnesium aluminate; or alternatively, sepiolite.
  • the solid promoters contemplated herein can have any suitable surface area, pore volume, and particle size, as would be recognized by those of skill in the art.
  • the solid promoter can have a pore volume in a range from 0.1 mL/g to 2.5 mL/g, or alternatively, from 0.5 mL/g to 2.5 mL/g.
  • the promoter can have a pore volume from 1 mL/g to 2.5 mL/g, or from 0.1 mL/g to 1.5 mL/g.
  • the pore volume can be from 0.1 mL/g to 1.0 mL/g, or from 0.2 mL/g to 1.0 mL/g.
  • the solid promoter can have a BET surface area in a range from 10 m 2 /g to 750 m 2 /g; alternatively, from 100 m 2 /g to 750 m 2 /g; alternatively, from 100 m 2 /g to 500 m 2 /g; or alternatively, from 30 m 2 /g to 200 m 2 /g.
  • the solid promoter can have a surface area of from 20 m 2 /g to 500 m 2 /g, from 30 m 2 /g to 350 m 2 /g, from 100 m 2 /g to 400 m 2 /g, from 200 m 2 /g to 450 m 2 /g, or from 150 m 2 /g to 350 m 2 /g.
  • the average particle size of the solid promoter can vary greatly depending upon the process specifics, however, average particle sizes in the range of from 5 microns to 500 microns, from 10 microns to 250 microns, or from 25 microns to 200 microns, are often employed. Alternatively, 1/8 inch to 1/4 inch pellets or beads can be used.
  • the calcining step can be conducted at a variety of temperatures and time periods, and in a variety of atmospheres (an inert atmosphere, an oxidizing atmosphere, a reducing atmosphere).
  • the calcining step can be conducted at a peak calcining temperature in a range from 150 °C to 1000 °C; alternatively, from 250 °C to 1000 °C; alternatively, from 200 °C to 750 °C; alternatively, from 200 °C to 600 °C; alternatively, from 250 °C to 950 °C; alternatively, from 250 °C to 750 °C; alternatively, from 400 °C to 700 °C; alternatively, from 300 °C to 650 °C; or alternatively, from 400 °C to 600 °C.
  • these temperature ranges also are meant to encompass circumstances where the calcining step is conducted at a series of different temperatures (e.g., an initial calcining temperature, a peak calcining temperature), instead of at a single fixed temperature, falling within the respective ranges.
  • the calcining step can start at an initial calcining temperature, and subsequently, the temperature of the calcining step can be increased to the peak calcining temperature, for example, a peak calcining temperature in a range from 500 °C to 1000 °C, or from 250 °C to 750 °C.
  • the duration of the calcining step is not limited to any particular period of time.
  • the calcining step can be conducted, for example, in a time period ranging from as little as 15-45 minutes to as long as 12-24 hours, or more.
  • the appropriate calcining time can depend upon, for example, the initial/peak calcining temperature, and the atmosphere under which calcining is conducted, among other variables.
  • the calcining step can be conducted in a time period that can be in a range from 45 minutes to 18 hours, such as, for example, from 45 minutes to 15 hours, from 1 hour to 12 hours, from 2 hours to 10 hours, from 3 hours to 10 hours, or from 4 hours to 10 hours.
  • the solid promoter can comprise (or consist essentially of, or consist of) a treated solid oxide.
  • the treated solid oxide can be a calcined solid oxide, a metal-treated solid oxide, a metal-treated chemically-modified solid oxide, or a combination thereof.
  • the solid oxide of the treated solid oxide can be any suitable solid oxide, or any solid oxide disclosed herein, such as alumina, silica-alumina, silica-coated alumina, aluminophosphate, sodium carbonate, or sodium bicarbonate, and the like. Combinations of more than one treated solid oxide, if desired, can be used in the processes of this invention.
  • the solid oxide can comprise alumina, silica-alumina, silica-coated alumina, or a mixture thereof.
  • the treated solid oxide can be characterized as a Lewis acid. Additionally or alternatively, the treated solid oxide can be characterized as a Br ⁇ nsted base. Accordingly, in some aspects, the treated solid oxide can be characterized as both a Br ⁇ nsted base and a Lewis acid.
  • the treated solid oxide can be a calcined solid oxide.
  • the treated solid oxide can be formed by calcining at any suitable temperature, or at a temperature in any range disclosed herein. Calcining temperatures in a range from 150 °C to 1000 °C, from 200 °C to 750 °C, or from 200 °C to 600 °C, often can be used.
  • Illustrative and non-limiting examples of treated solid oxides in this aspect of the invention can include calcined sodium carbonate, calcined sodium bicarbonate, calcined potassium carbonate, calcined cesium carbonate, calcined alumina, calcined zirconia, calcined magnesia, and the like, as well as combinations thereof.
  • the treated solid oxide can be a metal-treated solid oxide.
  • the term“metal-treated” solid oxide is meant to encompass solid oxides that may be described alternatively as one or more of metal-containing solid oxides, metal-impregnated solid oxides, metal-modified solid oxides, and/or metal-enriched solid oxides.
  • the metal-treated solid oxide can be produced by a process comprising contacting any suitable solid oxide and any suitable metal- containing compound and calcining. The calcining can be performed concurrently with this contacting step and/or subsequent to this contacting step, and can be performed at any suitable conditions or at any calcining conditions disclosed herein.
  • the metal-treated solid oxide can comprise an alkali metal, an alkaline earth metal, a transition metal, or any combination thereof (e.g., a transition metal and an alkali metal).
  • the metal-treated solid oxide comprises an alkali metal
  • the treated solid oxide can be referred to as an alkali metal-treated solid oxide
  • the alkali metal often comprises sodium, potassium, or cesium, either singly or in combination.
  • alkali-metal treated solid oxides can include sodium-treated alumina, potassium-treated alumina, cesium-treated alumina, sodium-treated aluminophosphate, and the like, as well as combinations thereof.
  • the treated solid oxide can be referred to as an alkaline earth metal-treated solid oxide, and the alkaline earth metal often comprises magnesium, calcium, or barium, either singly or in combination.
  • alkaline earth metal-treated solid oxides can include magnesium-treated alumina, calcium-treated alumina, barium-treated alumina, and the like, as well as combinations thereof.
  • the metal-treated solid oxide comprises a transition metal
  • the treated solid oxide can be referred to as a transition metal- treated solid oxide, and the transition metal can comprise any transition metal disclosed herein, such as titanium, zirconium, hafnium, tungsten, or zinc, and either singly or in combination.
  • transition metal-treated solid oxides can include zinc-treated alumina, zirconium-treated alumina, sodium-tungsten-treated alumina, and the like, as well as combinations thereof.
  • the treated solid oxide can be a metal-treated chemically- modified solid oxide.
  • the metal-treated chemically-modified solid oxide can be produced by a process comprising contacting any suitable solid oxide and any electron-withdrawing anion and calcining (concurrently and/or subsequently) to form the chemically-modified solid oxide, and then contacting the chemically-modified solid oxide with any suitable metal-containing compound.
  • a further calcining step can be used.
  • the metal-treated chemically-modified solid oxide can comprise an alkali metal, an alkaline earth metal, a transition metal, or any combination thereof (e.g., a transition metal and an alkali metal).
  • the metal-treated chemically-modified solid oxide comprises an alkali metal
  • the treated solid oxide can be referred to as an alkali metal-treated chemically- modified solid oxide, and the alkali metal often comprises sodium, potassium, or cesium, either singly or in combination.
  • the metal-treated chemically-modified solid oxide comprises an alkaline earth metal
  • the treated solid oxide can be referred to as an alkaline earth metal-treated chemically-modified solid oxide
  • the alkaline earth metal often comprises magnesium, calcium, or barium, either singly or in combination.
  • the metal- treated chemically-modified solid oxide comprises a transition metal
  • the treated solid oxide can be referred to as a transition metal-treated chemically-modified solid oxide
  • the transition metal can comprise any transition metal disclosed herein, such as titanium, zirconium, hafnium, tungsten, or zinc, and either singly or in combination.
  • metal-treated chemically-modified solid oxides can include sodium-treated chlorided alumina, sodium-treated sulfated alumina, sodium-treated sulfated silica-coated alumina, sodium-treated fluorided silica-coated alumina, sodium-treated fluorided silica-alumina, sodium-treated fluorided-chlorided silica-coated alumina, and the like, as well as combinations thereof.
  • any metal in a metal-treated solid oxide or a metal-treated chemically- modified solid oxide often is present in an amount of at least 0.5 wt. %, or at least 1 wt. %.
  • the metal-treated solid oxide (or metal-treated chemically-modified solid oxide) generally can contain from 1 to 30 wt. % of the metal, based on the weight of the metal- treated solid oxide (or metal-treated chemically-modified solid oxide).
  • the metal-treated solid oxide (or metal-treated chemically-modified solid oxide) can contain from 1 to 25 wt. %, from 2 to 30 wt. %, from 2 to 25 wt. %, from 5 to 30 wt.
  • metal-treated solid oxide from 5 to 25 wt. %, from 3 to 15 wt. %, from 5 to 12 wt. %, or from 6 to 18 wt. %, of the metal, based on the total weight of the metal-treated solid oxide (or metal-treated chemically-modified solid oxide).
  • any suitable chemically-modified solid oxide can be employed in this invention, whether one chemically-modified solid oxide or a mixture or combination of two or more different chemically-modified solid oxides.
  • the chemically- modified solid oxide can comprise a solid oxide contacted with an electron-withdrawing anion, for instance, any solid oxide and any electron-withdrawing anion disclosed herein.
  • the chemically-modified solid oxide can comprise a solid oxide contacted with an electron-withdrawing anion, the solid oxide containing a Lewis-acidic metal ion.
  • suitable chemically-modified solid oxides are disclosed in, for instance, U.S. Patent Nos. 7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, 8,703,886, and 9,023,959, incorporated herein by reference in their entirety.
  • the electron-withdrawing component used to treat or modify the solid oxide can be any component that can increase the Lewis or Br ⁇ nsted acidity of the solid oxide upon treatment (as compared to the solid oxide that is not treated with at least one electron- withdrawing anion).
  • the electron-withdrawing component can be an electron-withdrawing anion derived from a salt, an acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for that anion.
  • electron-withdrawing anions can include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, tungstate, and molybdate, including mixtures and combinations thereof.
  • ionic or non- ionic compounds that serve as sources for these electron-withdrawing anions also can be employed.
  • the electron-withdrawing anion can be, or can comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, or any combination thereof, in some aspects provided herein.
  • the electron-withdrawing anion can comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or combinations thereof.
  • the electron-withdrawing anion can comprise sulfate, fluoride, chloride, or combinations thereof; alternatively, sulfate; alternatively, fluoride and chloride; or alternatively, fluoride.
  • the chemically-modified solid oxide generally can contain from 1 to 30 wt. % of the electron-withdrawing anion, based on the weight of the chemically-modified solid oxide.
  • the chemically-modified solid oxide can contain from 1 to 20 wt. %, from 2 to 20 wt. %, from 3 to 20 wt. %, from 2 to 15 wt. %, from 3 to 15 wt. %, from 3 to 12 wt. %, from 4 to 10 wt. %, or from 5 to 9 wt. %, of the electron-withdrawing anion, based on the total weight of the chemically-modified solid oxide.
  • the chemically-modified solid oxide can comprise fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica- titania, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated silica-coated alumina, or phosphated silica-coated alumina, as well as any mixture or combination thereof.
  • the chemically-modified solid oxide employed in the processes described herein can be, or can comprise, a fluorided solid oxide and/or a sulfated solid oxide, non-limiting examples of which can include fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, fluorided silica- coated alumina, fluorided-chlorided silica-coated alumina, or sulfated silica-coated alumina, as well as combinations thereof.
  • a fluorided solid oxide and/or a sulfated solid oxide non-limiting examples of which can include fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, fluorided silica- coated alumina,
  • the chemically-modified solid oxide can comprise fluorided alumina; alternatively, chlorided alumina; alternatively, sulfated alumina; alternatively, fluorided silica-alumina; alternatively, sulfated silica-alumina; alternatively, fluorided silica-zirconia; alternatively, chlorided silica-zirconia; alternatively, sulfated silica-coated alumina; alternatively, fluorided-chlorided silica-coated alumina; or alternatively, fluorided silica-coated alumina.
  • the chemically-modified solid oxide can comprise a fluorided solid oxide
  • the chemically-modified solid oxide can comprise a sulfated solid oxide.
  • calcination procedures and conditions e.g., calcining temperatures in a range from 150 qC to 1000 qC, from 200 qC to 750 qC, or from 400 qC to 700 qC
  • calcination times e.g., calcination times in a range from 1 minute to 24 hours, from 5 minutes to 10 hours, or from 20 minutes to 6 hours
  • calcination equipment e.g., calcination equipment such as a rotary kiln, muffle furnace, or fluidized bed, among other methods of conveying heat
  • the processes disclosed herein typically are conducted in the presence of a diluent. Mixtures and/or combinations of diluents can be utilized in these processes.
  • the diluent can comprise, consist essentially of, or consist of, any suitable solvent or any solvent disclosed herein, unless otherwise specified.
  • the diluent can comprise a non-protic solvent.
  • non-protic solvents can include tetrahydrofuran (THF), 2,5-Me 2 THF, acetone, toluene, chlorobenzene, pyridine, carbon dioxide, and the like, as well as combinations thereof.
  • the diluent can comprise a weakly coordinating or non-coordinating solvent.
  • weakly coordinating or non-coordinating solvents can include toluene, chlorobenzene, paraffins, halogenated paraffins, and the like, as well as combinations thereof.
  • the diluent can comprise a carbonyl-containing solvent, for instance, ketones, esters, amides, and the like, as well as combinations thereof.
  • carbonyl-containing solvents can include acetone, ethyl methyl ketone, ethyl acetate, propyl acetate, butyl acetate, isobutyl isobutyrate, methyl lactate, ethyl lactate, N,N- dimethylformamide, and the like, as well as combinations thereof.
  • the diluent can comprise THF, 2,5-Me 2 THF, methanol, acetone, toluene, chlorobenzene, pyridine, or a combination thereof; alternatively, THF; alternatively, 2,5-Me 2 THF; alternatively, methanol; alternatively, acetone; alternatively, toluene; alternatively, chlorobenzene; or alternatively, pyridine.
  • the diluent can comprise (or consist essentially of, or consist of) an aromatic hydrocarbon solvent.
  • suitable aromatic hydrocarbon solvents that can be utilized singly or in any combination include benzene, toluene, xylene (inclusive of ortho-xylene, meta-xylene, para-xylene, or mixtures thereof), and ethylbenzene, or combinations thereof; alternatively, benzene; alternatively, toluene; alternatively, xylene; or alternatively, ethylbenzene.
  • the diluent can comprise (or consist essentially of, or consist of) a halogenated aromatic hydrocarbon solvent.
  • suitable halogenated aromatic hydrocarbon solvents that can be utilized singly or in any combination include chlorobenzene, dichlorobenzene, and combinations thereof; alternatively, chlorobenzene; or alternatively, dichlorobenzene.
  • the diluent can comprise (or consist essentially of, or consist of) an ether solvent.
  • suitable ether solvents that can be utilized singly or in any combination include dimethyl ether, diethyl ether, diisopropyl ether, di-n-propyl ether, di-n- butyl ether, diphenyl ether, methyl ethyl ether, methyl t-butyl ether, dihydrofuran, tetrahydrofuran (THF), 2,5-Me 2 THF, 1,2-dimethoxyethane, 1,4-dioxane, and combinations thereof; alternatively, diethyl ether, dibutyl ether, THF, 2,5-Me 2 THF, 1,2-dimethoxyethane, 1,4-dioxane, and combinations thereof; alternatively, THF; or alternatively, diethyl ether.
  • the processes disclosed herein employ a metallalactone or a transition metal-ligand complex.
  • the transition metal of the metallalactone, or of the transition metal- ligand complex can be a Group 3 to Group 8 transition metal or, alternatively, a Group 8 to Group 11 transition metal.
  • the transition metal can be Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au, while in another aspect, the transition metal can be Fe, Ni, or Rh.
  • the transition metal can be Fe; alternatively, the transition metal can be Co; alternatively, the transition metal can be Ni; alternatively, the transition metal can be Cu; alternatively, the transition metal can be Ru; alternatively, the transition metal can be Rh; alternatively, the transition metal can be Pd; alternatively, the transition metal can be Ag; alternatively, the transition metal can be Ir; alternatively, the transition metal can be Pt; or alternatively, the transition metal can Au.
  • the transition metal can be Ni.
  • the metallalactone can be a nickelalactone and the transition metal-ligand complex can be a Ni- ligand complex in these aspects.
  • the ligand of the metallalactone, or of the transition metal-ligand complex can be any suitable neutral electron donor group and/or Lewis base.
  • the suitable neutral ligands can include sigma-donor solvents that contain a coordinating atom (or atoms) that can coordinate to the transition metal of the metallalactone (or of the transition metal- ligand complex).
  • suitable coordinating atoms in the ligands can include, but are not limited to, O, N, S, and P, or combinations of these atoms.
  • the ligand can be a bidentate ligand.
  • the ligand used to form the metallalactone or the transition metal-ligand complex can be an ether, an organic carbonyl, a thioether, an amine, a nitrile, or a phosphine.
  • the ligand used to form the metallalactone or the transition metal-ligand complex can be an acyclic ether, a cyclic ether, an acyclic organic carbonyl, a cyclic organic carbonyl, an acyclic thioether, a cyclic thioether, a nitrile, an acyclic amine, a cyclic amine, an acyclic phosphine, or a cyclic phosphine.
  • Suitable ethers can include, but are not limited to, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, diphenyl ether, ditolyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5- dimethyltetrahydrofuran, 2,3-dihydrofuran, 2,5-dihydrofuran, furan, benzofuran, isobenzofuran, dibenzofuran, tetrahydropyran, 3,4-dihydro-2H-pyran, 3,6-dihydro-2H-pyran, 2H-pyran, 4H-pyran, 1,3-dioxane, 1,4-dioxane, morpholine, and the like, including substituted derivatives thereof.
  • Suitable organic carbonyls can include ketones, aldehydes, esters, and amides, either alone or in combination, and illustrative examples can include, but are not limited to, acetone, acetophonone, benzophenone, N,N-dimethylformamide, N,N-dimethylacetamide, methyl acetate, ethyl acetate, and the like, including substituted derivatives thereof.
  • Suitable thioethers can include, but are not limited to, dimethyl thioether, diethyl thioether, dipropyl thioether, dibutyl thioether, methyl ethyl thioether, methyl propyl thioether, methyl butyl thioether, diphenyl thioether, ditolyl thioether, thiophene, benzothiophene, tetrahydrothiophene, thiane, and the like, including substituted derivatives thereof.
  • Suitable nitriles can include, but are not limited to, acetonitrile, propionitrile, butyronitrile, benzonitrile, 4-methylbenzonitrile, and the like, including substituted derivatives thereof.
  • Suitable amines can include, but are not limited to, methyl amine, ethyl amine, propyl amine, butyl amine, dimethyl amine, diethyl amine, dipropyl amine, dibutyl amine, trimethyl amine, triethyl amine, tripropyl amine, tributyl amine, aniline, diphenylamine, triphenylamine, tolylamine, xylylamine, ditolylamine, pyridine, quinoline, pyrrole, indole, 2- methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,5-dipropylpyrrole, 2,5-dibutylpyrrole, 2,4-dimethylpyrrole, 2,4-diethylpyrrole, 2,4- dipropylpyrrole, 2,4-dibutylpyrrole, 3,4-di
  • Suitable phosphines and other phosphorus compounds can include, but are not limited to, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, phenylphosphine, tolylphosphine, diphenylphosphine, ditolylphosphine, triphenylphosphine, tritolylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diethylphenylphosphine, tricyclohexylphosphine, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite and tricyclohexyl phosphite, 2-(di-t-butylphos
  • the ligand used to form the metallalactone or the transition metal- ligand complex can be a carbene, for example, a N-heterocyclic carbene (NHC) compound.
  • a N-heterocyclic carbene (NHC) compound for example, a N-heterocyclic carbene (NHC) compound.
  • suitable N-heterocyclic carbene (NHC) materials include the following:
  • metallalactone complexes representedative nickelalactones
  • metallalactone complexes representedative nickelalactones
  • transition metal-ligand complexes corresponding to these illustrative metallalactones are shown below:
  • Metallalactones can be synthesized according to the following general reaction scheme (illustrated with nickel as the transition metal; Ni(COD) 2 is bis(1,5- cyclooctadiene)nickel(0)): ,
  • Suitable ligands, transition metal-ligand complexes, and metallalactones are not limited solely to those ligands, transition metal-ligand complexes, and metallalactones disclosed herein.
  • Other suitable ligands, transition metal-ligand complexes, and/or metallalactones are described, for example, in U.S. Patent Nos. 7,250,510, 8,642,803, and 8,697,909; WO 2015/173276; WO 2015/173277; Journal of Organometallic Chemistry, 1983, 251, C51-C53; Z. Anorg. Allg.
  • the features of the processes disclosed herein e.g., the metallalactone, the diluent, the solid promoter (e.g., the treated solid oxide), the ⁇ , ⁇ -unsaturated carboxylic acid or salt thereof, the transition metal-ligand complex, the olefin, and the conditions under which the ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof, is formed, among others
  • these features may be combined in any combination to further describe the disclosed processes.
  • a process for performing a metallalactone elimination reaction is disclosed.
  • This process can comprise (or consist essentially of, or consist of):
  • a solid promoter e.g., a treated solid oxide
  • Suitable metallalactones, diluents, and solid promoters are disclosed hereinabove.
  • the diluent can comprise the ⁇ , ⁇ -unsaturated carboxylic acid, or the salt thereof, that is formed in step (2) of this process.
  • a process for producing an ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof is disclosed.
  • This process can comprise (or consist essentially of, or consist of):
  • a solid promoter e.g., a treated solid oxide
  • step (3) treating the adduct adsorbed onto the solid promoter to produce the ⁇ , ⁇ - unsaturated carboxylic acid, or the salt thereof.
  • this process for producing an ⁇ , ⁇ -unsaturated carboxylic acid or a salt thereof for instance, at least a portion of the diluent comprising a transition metal of the metallalactone can be removed after step (2), and before step (3), of this process.
  • Suitable metallalactones, diluents, and solid promoters are disclosed hereinabove.
  • the contacting step– step (1)– of these processes can include contacting, in any order, the metallalactone, the diluent, and the solid promoter (e.g., the treated solid oxide), and additional unrecited materials.
  • the contacting step can consist essentially of, or consist of, the metallalactone, the diluent, and the solid promoter (e.g., the treated solid oxide) components.
  • additional materials or features can be employed in the forming step– step (2)– of these processes, and/or in the treating step– step (3)– of the process for producing the ⁇ , ⁇ -unsaturated carboxylic acid, or the salt thereof.
  • these processes for performing a metallalactone elimination reaction and for producing an ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof can employ more than one metallalactone and/or more than one solid promoter (e.g., a mixture of two treated solid oxides). Additionally, a mixture or combination of two or more diluents can be employed, if desired.
  • any suitable reactor, vessel, or container can be used to contact the metallalactone, diluent, and solid promoter (e.g., treated solid oxide), non-limiting examples of which can include a flow reactor, a continuous reactor, a fixed bed reactor, and a stirred tank reactor, including more than one reactor in series or in parallel, and including any combination of reactor types and arrangements.
  • the metallalactone and the diluent contact a fixed bed of the solid promoter (e.g., the treated solid oxide), for instance, in a suitable vessel, such as in a continuous fixed bed reactor.
  • combinations of more than one solid promoter can be used, such as a mixed bed of a first treated solid oxide and a second treated solid oxide, or sequential beds of a first treated solid oxide and a second treated solid oxide.
  • the feed stream can flow upward or downward through the fixed bed.
  • the metallalactone and the diluent can contact the first treated solid oxide and then the second treated solid oxide in a downward flow orientation, and the reverse in an upward flow orientation.
  • the metallalactone and the solid promoter e.g., the treated solid oxide
  • Step (2) of the process for producing an ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof recites forming an adduct of the ⁇ , ⁇ -unsaturated carboxylic acid adsorbed onto the solid promoter (e.g., the treated solid oxide).
  • This adduct can contain all or a portion of the ⁇ , ⁇ -unsaturated carboxylic acid, and is inclusive of salts of the ⁇ , ⁇ -unsaturated carboxylic acid.
  • step (3) of the process for producing an ⁇ , ⁇ -unsaturated carboxylic acid or a salt thereof the adduct adsorbed onto the solid promoter (e.g., the treated solid oxide) is treated to produce the ⁇ , ⁇ -unsaturated carboxylic acid, or the salt thereof.
  • the treating step can comprise contacting the adduct adsorbed onto the solid promoter (e.g., the treated solid oxide) with an acid.
  • the treating step can comprise contacting the adduct adsorbed onto the solid promoter (e.g., the treated solid oxide) with a base.
  • the solid promoter e.g., the treated solid oxide
  • the treating step can comprise contacting the adduct adsorbed onto the solid promoter (e.g., the treated solid oxide) with a suitable solvent.
  • suitable solvents can include carbonyl-containing solvents such as ketones, esters, or amides (e.g., acetone, ethyl acetate, or N,N-dimethylformamide, as described herein above), alcohol solvents, water, and the like, as well as combinations thereof.
  • the treating step can comprise heating the adduct adsorbed onto the solid promoter (e.g., the treated solid oxide) to any suitable temperature.
  • This temperature can be in a range, for example, from 50 °C to 1000 °C, from 100 °C to 800 °C, from 150 °C to 600 °C, from 250 °C to 1000 °C, from 250 °C to 550 °C, or from 150 °C to 500 °C.
  • the duration of this heating step is not limited to any particular period of time, as long of the period of time is sufficient to liberate the ⁇ , ⁇ -unsaturated carboxylic acid from the solid promoter (e.g., the treated solid oxide).
  • the appropriate treating step depends upon several factors, such as the particular diluent used in the process, and the particular solid promoter (e.g., treated solid oxide) used in the process, amongst other considerations.
  • steps can be conducted before, during, and/or after any of the steps described herein.
  • these processes can further comprise a step (e.g., prior to step (1)) of contacting a transition metal-ligand complex with an olefin and carbon dioxide (CO 2 ) to form the metallalactone.
  • Transition metal-ligand complexes are described hereinabove.
  • Suitable olefins can include ethylene, propylene, butene (e.g., 1-butene), pentene, hexene (e.g., 1-hexene), heptene, octene (e.g., 1-octene), styrene, and the like, as well as combinations thereof.
  • a process for producing an ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof is disclosed.
  • This process can comprise (or consist essentially of, or consist of):
  • a solid promoter e.g., a treated solid oxide
  • Suitable transition metal-ligands, olefins, diluents, and solid promoters are disclosed hereinabove.
  • the contacting step– step (I)– of this process can include contacting, in any order, the transition metal-ligand, the olefin, the diluent, the solid promoter (e.g., the treated solid oxide), and carbon dioxide, and additional unrecited materials.
  • the contacting step can consist essentially of, or consist of, contacting, in any order, the transition metal-ligand, the olefin, the diluent, the solid promoter (e.g., the treated solid oxide), and carbon dioxide.
  • this process for producing an ⁇ , ⁇ -unsaturated carboxylic acid, or a salt thereof can employ more than one transition metal-ligand complex, and/or more than one solid promoter (e.g., a mixture of two treated solid oxides), and/or more than one olefin. Additionally, a mixture or combination of two or more diluents can be employed.
  • any suitable reactor, vessel, or container can be used to contact the transition metal-ligand, olefin, diluent, solid promoter (e.g., treated solid oxide), and carbon dioxide, whether using a fixed bed of the solid promoter (e.g., the treated solid oxide), a stirred tank for contacting (or mixing), or some other reactor configuration and process.
  • solid promoter e.g., treated solid oxide
  • carbon dioxide e.g., carbon dioxide
  • the contacting and forming steps of any of the processes disclosed herein can be conducted at a variety of temperatures, pressures, and time periods.
  • the temperature at which the components in step (1) or step (I) are initially contacted can be the same as, or different from, the temperature at which the forming step is performed.
  • the components in the contacting step, can be contacted initially at temperature T1 and, after this initial combining, the temperature can be increased to a temperature T2 for the forming step (e.g., to form the ⁇ , ⁇ - unsaturated carboxylic acid, or the salt thereof).
  • the pressure can be different in the contacting step and the forming step.
  • the time period in the contacting step can be referred to as the contact time, while the time period in forming step can be referred to as the reaction time.
  • the contact time and the reaction time can be, and often are, different.
  • the contacting step and/or the forming step of the processes disclosed herein can be conducted at a temperature in a range from 0 °C to 250 °C; alternatively, from 20 °C to 200 °C; alternatively, from 0 °C to 95 °C; alternatively, from 10 °C to 75 °C; alternatively, from 10 °C to 50 °C; or alternatively, from 15 °C to 70 °C.
  • the temperature can be changed, if desired, to another temperature for the forming step.
  • These temperature ranges also are meant to encompass circumstances where the contacting step and/or the forming step can be conducted at a series of different temperatures, instead of at a single fixed temperature, falling within the respective ranges.
  • the contacting step and/or the forming step of the processes disclosed herein can be conducted at a pressure in a range from 5 to 10,000 psig, such as, for example, from 5 to 2500 psig.
  • the pressure can be in a range from 5 to 500 psig; alternatively, from 25 to 3000 psig; alternatively, from 45 to 1000 psig; or alternatively, from 50 to 250 psig.
  • the contacting step of the processes is not limited to any particular duration of time. That is, the respective components can be initially contacted rapidly, or over a longer period of time, before commencing the forming step. Hence, the contacting step can be conducted, for example, in a time period ranging from as little as 1-30 seconds to as long as 1-12 hours, or more. In non-continuous or batch operations, the appropriate reaction time for the forming step can depend upon, for example, the reaction temperature, the reaction pressure, and the ratios of the respective components in the contacting step, among other variables.
  • the forming step can occur over a time period that can be in a range from 1 minute to 96 hours, such as, for example, from 2 minutes to 96 hours, from 5 minutes to 72 hours, from 10 minutes to 72 hours, or from 15 minutes to 48 hours.
  • the metallalactone/solid promoter catalyst contact/reaction time (or the transition metal-ligand/solid promoter catalyst contact/reaction time) can be expressed in terms of weight hourly space velocity (WHSV)—the ratio of the weight of the metallalactone (or transition metal-ligand complex) which comes in contact with a given weight of solid promoter (e.g., treated solid oxide) per unit time.
  • WHSV weight hourly space velocity
  • the WHSV employed, based on the amount of the solid promoter (e.g., the treated solid oxide) can be in a range from 0.05 to 100, from 0.05 to 50, from 0.075 to 50, from 0.1 to 25, from 0.5 to 10, from 1 to 25, or from 1 to 5.
  • the molar yield of the ⁇ , ⁇ -unsaturated carboxylic acid, or the salt thereof), based on the metallalactone (or based on the transition metal of the transition metal-ligand complex) is at least 2%, and more often can be at least 5%, at least 10%, or at least 15%.
  • the molar yield can be at least 25%, at least 50%, at least 75%, at least 100%, at least 125%, at least 150%, at least 200%, or at least 350%, and often can range up to 10,000%, or 100,000%, or 1,000,000%, as catalytic efficiencies are realized.
  • the specific ⁇ , ⁇ -unsaturated carboxylic acid (or salt thereof) that can be formed or produced using the processes of this invention is not particularly limited.
  • Illustrative and non-limiting examples of the ⁇ , ⁇ -unsaturated carboxylic acid can include acrylic acid, methacrylic acid, 2-ethylacrylic acid, cinnamic acid and the like, as well as combinations thereof.
  • Illustrative and non-limiting examples of the salt of the ⁇ , ⁇ -unsaturated carboxylic acid can include sodium acrylate, magnesium acrylate, sodium methacrylate, and the like, as well as combinations thereof.
  • the ⁇ , ⁇ -unsaturated carboxylic acid (or salt thereof) can be purified and/or isolated and/or separated using suitable techniques which can include, but are not limited to, evaporation, distillation, chromatography, crystallization, extraction, washing, decanting, filtering, drying, and the like, including combinations of more than one of these techniques.
  • the process for performing a metallalactone elimination reaction can further comprise a step of separating or isolating the ⁇ , ⁇ -unsaturated carboxylic acid (or salt thereof) from other components, such as the diluent and/or the solid promoter (e.g., the treated solid oxide).
  • a solid-liquid separations technique can be used.
  • nickelalactone complexes which can be derived from CO 2 –ethylene coupling, were used to evaluate various homogeneous and heterogeneous (solid) promoters in certain examples that follow.
  • the general nickelalactone elimination reaction was performed as follows. A flask was charged with 10 mg of nickelalactone (A, B, or C), promoter, and approximately 10 mL of diluent. The reaction mixture was heated with vigorous stirring on an oil bath under conditions described in the examples below. The reaction mixture was allowed to cool to ambient temperature, then acidified. The yield of acrylic acid was determined by 1 H NMR in D 6 -acetone versus an internal standard sorbic acid stock solution.
  • Example 1 The results of the evaluation of the homogeneous activators/promoters are summarized in Table I.
  • the diluents employed in Example 1 and Examples 2-7 were 5:1 tetrahydrofuran/acetone and tetrahydrofuran, respectively.
  • Example 8 was investigated in tetrahydrofuran, methanol, and acetone.
  • the homogeneous promoter of Example 5 was a solution of methylaluminoxane in toluene, while the homogeneous promoter of Example 6 was a mixture of Mg( n Bu) 2 and methanol, which results in an alkoxide.
  • the homogeneous activators/promoters of Examples 1-8 failed to yield any acrylic acid with any of the nickelalactones investigated.
  • Table I Molar Yields of Examples 1-8.
  • Examples 9-12 were performed in a manner similar to that of Examples 2-7, as reflected in the following reaction scheme (25 equivalents per Ni were based on site concentration (mmol/g) of the solid activator/promoter; HCl was used to liberate the acrylic acid for analysis):
  • Examples 13-24 were performed in a manner similar to that of Examples 9-12, with only nickelalactone A, as reflected in the following reaction scheme (25 equivalents per Ni were based on site concentration (mmol/g) of the solid activator/promoter; HCl was used to liberate the acrylic acid for analysis): .
  • the results of the evaluation of the solid/heterogeneous activators/promoters (calcined at 400 °C) in different diluents/solvents are summarized in Table III.
  • alumina, zirconia, magnesia, magnesium aluminate, and sepiolite produced significant amounts of acrylic acid using different diluents, with generally from 5% to 90% molar yield.
  • Examples 25-33 were performed by mixing 18 ⁇ mol of the nickel compound, 18 ⁇ mol of the diphosphine ligand, 5 mL of diluent (THF or toluene), and the treated solid oxide (200 mg for Examples 25-30, 50 mg for Examples 31-33) at 60 °C for 30 to 60 minutes, as reflected in the following reaction scheme:
  • Aqueous sodium bisulfate was used to liberate the acrylic acid for analysis, followed by extraction into D 2 O/acetone-d 6 to quantify the amount of acrylic acid by 1 H NMR spectroscopy relative to an internal sorbic acid standard.
  • the alumina was calcined at 500 °C in dry air for 3 hours.
  • the zinc-treated alumina of Example 25 was prepared by mixing 10 g of alumina with 30 mL of an aqueous solution containing 2.5 g of zinc chloride. After removing the water in a vacuum oven at 90 °C overnight, the dried powder was calcined at 500 °C in dry air for three hours.
  • the calcium-treated aluminas of Examples 27 and 29 were prepared similarly, except that calcining was performed at 600 °C in dry air for 3 hours.
  • the chlorided alumina of Example 26 was prepared by injecting 3 mL of CCl 4 liquid (and vaporizing the CCl 4 ) over a period of less than 1 minute into a nitrogen gas stream used to calcine the alumina at 500 °C for three hours, resulting in chlorided alumina.
  • the sodium-treated alumina of Example 28 was prepared by mixing 22.8 g of alumina with 60 mL of an aqueous solution containing 4.6 g of sodium bicarbonate. After removing the water in a vacuum oven at 90 °C overnight, the dried powder was calcined at 200 °C in dry air for three hours.
  • Example 31 and Example 32 sodium bicarbonate and cesium carbonate, respectively, were calcined at 200 °C in dry air for 6 hours, while in Example 33, sodium carbonate was not calcined (untreated).
  • reaction product was extracted into D 2 O/acetone-d 6 for acrylate yield determination by 1 H NMR spectroscopy relative to an internal sorbic acid standard.
  • the sodium-treated sulfated alumina of Example 34 was prepared by mixing alumina with a solution of sulfuric acid in methanol, to result in approximately 15 wt. % sulfate based on the weight of the sulfated alumina. After drying under vacuum at 110 °C overnight, the dried powder was calcined at 600 °C in dry air for three hours. After cooling, 4.2 g of the sulfated alumina and 2 g of sodium tert-butoxide were combined in 60 mL of toluene, forming a yellow suspension. The mixture was stirred at ambient temperature for 18 hours, filtered, and washed with 10 mL of toluene, forming the colorless solid (sodium-treated sulfated alumina) of Example 34.
  • Example 36 The sodium-treated chlorided alumina of Example 36 was prepared using the chlorided alumina of Example 26, and following the same sodium treatment procedure used in Example 34.
  • the fluorided silica-coated alumina of Example 41 was prepared by first contacting alumina with tetraethylorthosilicate in isopropanol to equal 25 wt. % SiO 2 . After drying, the silica-coated alumina was calcined at 600 °C for 3 hours. Next, the fluorided silica-coated alumina (7 wt. % F) was prepared by impregnating the calcined silica-coated alumina with an ammonium bifluoride solution in methanol, drying, and then calcining at 600 °C for 3 hours.
  • the sodium-treated fluorided silica-coated alumina of Example 35 was prepared using the fluorided silica-coated alumina of Example 41, and following the same sodium treatment procedure used in Example 34.
  • Example 37 The sodium-treated sulfated silica-coated alumina (8 wt. % sulfate) of Example 37 was prepared using silica-coated alumina prepared as described in Example 41, and then sulfating and sodium treating in the manner described in Example 34.
  • the sodium-treated fluorided silica-alumina of Example 38 used a silica-alumina having 13% alumina by weight, a surface area of 400 m 2 /g, and a pore volume of 1.2 mL/g, as a base material. This material was mixed with an aqueous solution containing ammonium hydrogen fluoride, dried under vacuum at 110 °C overnight, and calcined at 450 °C in dry air for three hours. The fluorided silica-alumina was then sodium treated in the same manner as described in Example 34.
  • the sodium-treated tungsten alumina of Example 39 was prepared by first saturating 12.91 g of alumina (surface area of 300 m 2 , pore volume of 1.2 mL/g, average particle size of 100 microns) with an aqueous solution of 6.341 g of ammonium metatungstate hydrate in 50 mL of deionized water to give a wet sand consistency. After isolating and drying the solid, the solid was calcined at 600 °C for 3 hours. The sodium treatment was performed in the same manner as described in Example 34.
  • the sodium-treated aluminophosphate of Example 40 was prepared by first adding 100 mL of deionized water to 1 mole of aluminum nitrate nonahydrate, and heating the mixture to 60 °C, which resulted in a uniform clear liquid. Then, 0.9 mol of ammonium phosphate dibasic was added and dissolved into the solution. After 1 hour of stirring at 60 °C, concentrated ammonium hydroxide was added until gelation occurred, forming a hard solid. The solid was broken up into smaller pieces, and washed three times in 4 L of warm deionized water. A final wash was accomplished in 4 L of n-propanol, followed by filtration, and then drying in a vacuum oven at 110 °C. The dried powder was then calcined at 600 °C for 3 hours, and subsequently sodium treated in the manner described in Example 34.
  • Example 34-41 The results of the evaluation of the treated solid oxides of Examples 34-41 are summarized in Table V. Unexpectedly, in contrast with the fluorided silica-coated alumina of Example 41 (which produced no acrylic acid), the treated solid oxides of Examples 34-40 produced significant amounts of acrylic acid, with from 38% to 181% molar yield.
  • the metal-treated chemically-modified solid oxides of Examples 34-35 and 37-38 were particularly successful in catalytically producing acrylic acid directly from CO 2 and ethylene, with molar yields in excess of 100% (based on the transition metal of the transition metal- ligand complex).
  • a process for performing a metallalactone elimination reaction comprising:
  • Aspect 2 The process defined in aspect 1, wherein at least a portion of the diluent comprises the ⁇ , ⁇ -unsaturated carboxylic acid, or the salt thereof, formed in step (2).
  • Aspect 4 The process defined in aspect 3, wherein at least a portion of the diluent comprising a transition metal of the metallalactone is removed after step (2).
  • Aspect 5 The process defined in any one of aspects 1-4, wherein in step (1), the metallalactone and the diluent contact a fixed bed of the treated solid oxide.
  • Aspect 6 The process defined in any one of aspects 1-4, wherein in step (1), the metallalactone and the treated solid oxide are contacted by mixing/stirring in the diluent.
  • Aspect 7 The process defined in any one of aspects 3-6, wherein the treating step comprises contacting the adduct adsorbed onto the treated solid oxide with any suitable acid, or any acid disclosed herein, e.g., HCl, sodium bisulfate, or acetic acid.
  • any suitable acid e.g., HCl, sodium bisulfate, or acetic acid.
  • the treating step comprises contacting the adduct adsorbed onto the treated solid oxide with any suitable base, or any base disclosed herein, e.g., carbonates (e.g., Na 2 CO 3 , Cs 2 CO 3 , MgCO 3 ), hydroxides (e.g., Mg(OH) 2 , NaOH), or alkoxides (e.g., Al(O i Pr) 3 , Na(O t Bu), Mg(OEt) 2 ).
  • any suitable base e.g., carbonates (e.g., Na 2 CO 3 , Cs 2 CO 3 , MgCO 3 ), hydroxides (e.g., Mg(OH) 2 , NaOH), or alkoxides (e.g., Al(O i Pr) 3 , Na(O t Bu), Mg(OEt) 2 ).
  • Aspect 9 The process defined in any one of aspects 3-6, wherein the treating step comprises contacting the adduct adsorbed onto the treated solid oxide with any suitable solvent, or any solvent disclosed herein, e.g., carbonyl-containing solvents such as ketones, esters, or amides (e.g., acetone, ethyl acetate, N,N-dimethylformamide), alcohol solvents, or water.
  • any suitable solvent e.g., carbonyl-containing solvents such as ketones, esters, or amides (e.g., acetone, ethyl acetate, N,N-dimethylformamide), alcohol solvents, or water.
  • Aspect 10 The process defined in any one of aspects 3-6, wherein the treating step comprises heating the adduct adsorbed onto the treated solid oxide to any suitable temperature, or a temperature in any range disclosed herein, e.g., from 50 °C to 1000 °C, from 100 °C to 800 °C, from 150 °C to 600 °C, or from 250 °C to 550 °C.
  • Aspect 11 The process defined in any one of the preceding aspects, further comprising a step of contacting a transition metal-ligand complex with an olefin and carbon dioxide (CO 2 ) to form the metallalactone.
  • Aspect 13 The process defined in aspect 11 or 12, wherein the olefin comprises any suitable olefin or any olefin disclosed herein, e.g., ethylene, propylene, or 1-butene.
  • Aspect 14 The process defined in any one of aspects 1-13, wherein the ⁇ , ⁇ - unsaturated carboxylic acid, or a salt thereof, comprises any suitable ⁇ , ⁇ -unsaturated carboxylic acid, or any ⁇ , ⁇ -unsaturated carboxylic acid disclosed herein, or a salt thereof, e.g., acrylic acid, methacrylic acid, 2-ethylacrylic acid, cinnamic acid, sodium acrylate, magnesium acrylate, or sodium methacrylate.
  • acrylic acid, methacrylic acid, 2-ethylacrylic acid, cinnamic acid e.g., acrylic acid, methacrylic acid, 2-ethylacrylic acid, cinnamic acid, sodium acrylate, magnesium acrylate, or sodium methacrylate.
  • Aspect 15 The process defined in any one of aspects 1-14, wherein the molar yield of the ⁇ , ⁇ -unsaturated carboxylic acid, or the salt thereof, based on the metallalactone (or based on the transition metal of the transition metal-ligand complex) is in any range disclosed herein, e.g., at least 5%, at least 10%, at least 15%, at least 25%, at least 50%, at least 100%, at least 150%, or at least 200%.
  • Aspect 16 The process defined in any one of aspects 1-15, wherein the process further comprises a step of isolating the ⁇ , ⁇ -unsaturated carboxylic acid, or the salt thereof, e.g., using any suitable separation / purification procedure or any separation / purification procedure disclosed herein, e.g., evaporation, distillation, or chromatography.
  • Aspect 17 The process defined in any one of aspects 1-16, wherein the contacting step and/or the forming step is/are conducted at any suitable pressure or at any pressure disclosed herein, e.g., from 5 psig to 10,000 psig, or from 45 psig to 1000 psig.
  • Aspect 18 The process defined in any one of aspects 1-17, wherein the contacting step and/or the forming step is/are conducted at any suitable temperature or at any temperature disclosed herein, e.g., from 0 °C to 250 °C, from 0 °C to 95 °C, or from 15 °C to 70 °C.
  • Aspect 19 The process defined in any one of aspects 1-18, wherein the contacting step is conducted at any suitable weight hourly space velocity (WHSV) or any WHSV disclosed herein, e.g., from 0.05 to 50, from 1 to 25, or from 1 to 5, based on the amount of the treated solid oxide.
  • WHSV weight hourly space velocity
  • Aspect 20 The process defined in any one of aspects 1-19, wherein the treated solid oxide is a Lewis acid.
  • Aspect 21 The process defined in any one of aspects 1-19, wherein the treated solid oxide is a Br ⁇ nsted base.
  • Aspect 22 The process defined in any one of aspects 1-19, wherein the treated solid oxide is a Br ⁇ nsted base and a Lewis acid.
  • Aspect 23 The process defined in any one of aspects 1-22, wherein the treated solid oxide comprises any suitable solid oxide, or any solid oxide disclosed herein.
  • Aspect 24 The process defined in aspect 23, wherein the solid oxide comprises Al 2 O 3 , B 2 O 3 , BeO, Bi 2 O 3 , CdO, Co 3 O 4 , Cr 2 O 3 , CuO, Fe 2 O 3 , Ga 2 O 3 , La 2 O 3 , Mn 2 O 3 , MoO 3 , Na 2 O, NiO, P 2 O 5 , Sb 2 O 5 , SiO 2 , SnO 2 , SrO, ThO 2 , TiO 2, V 2 O 5 , WO 3 , Y 2 O 3 , ZnO, ZrO 2 , K 2 O, CaO, La 2 O 3 , or Ce 2 O 3 , including mixed oxides thereof, and combinations thereof.
  • Aspect 25 The process defined in aspect 23, wherein the solid oxide comprises silica, alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, or a combination thereof.
  • Aspect 26 The process defined in aspect 23, wherein the solid oxide comprises magnesium aluminate, calcium aluminate, zinc aluminate, zirconium aluminate, sodium aluminate, magnesium zirconium oxide, sodium zirconium oxide, calcium zirconium oxide, lanthanum chromium oxide, barium titanium oxide, or a combination thereof.
  • Aspect 27 The process defined in aspect 23, wherein the solid oxide comprises sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, or a combination thereof.
  • Aspect 28 The process defined in any one of aspects 1-27, wherein the treated solid oxide is a calcined solid oxide.
  • Aspect 29 The process defined in any one of aspects 1-28, wherein prior to step (1) or step (I), the treated solid oxide is formed by calcining at any suitable temperature, or at a temperature in any range disclosed herein, e.g. from 150 °C to 1000 °C, from 200 °C to 750 °C, or from 200 °C to 600 °C.
  • Aspect 30 The process defined in any one of aspects 1-27, wherein the treated solid oxide is a metal-treated solid oxide.
  • Aspect 31 The process defined in aspect 30, wherein prior to step (1) or step (I), the metal-treated solid oxide is produced by a process comprising contacting any suitable solid oxide and any suitable metal-containing compound and calcining (concurrently and/or subsequently).
  • Aspect 32 The process defined in aspect 30 or 31, wherein the metal-treated solid oxide comprises an alkali metal, an alkaline earth metal, a transition metal, or any combination thereof, and generally at an amount in a range from 1 to 30 wt. %, from 5 to 25 wt. %, or from 6 to 18 wt. %, based on the total weight of the metal-treated solid oxide.
  • Aspect 33 The process defined in any one of aspects 30-32, wherein the metal-treated solid oxide comprises an alkali metal (an alkali metal-treated solid oxide), e.g., sodium, potassium, or cesium, as well as combinations thereof.
  • an alkali metal an alkali metal-treated solid oxide
  • Aspect 34 The process defined in any one of aspects 30-32, wherein the metal-treated solid oxide comprises an alkaline earth metal (an alkaline earth metal-treated solid oxide), e.g., magnesium, calcium, or barium, as well as combinations thereof.
  • an alkaline earth metal an alkaline earth metal-treated solid oxide
  • Aspect 35 The process defined in any one of aspects 30-32, wherein the metal-treated solid oxide comprises a transition metal (a transition metal-treated solid oxide), e.g., titanium, zirconium, hafnium, tungsten, or zinc, as well as combinations thereof.
  • Aspect 36 The process defined in any one of aspects 1-27, wherein the treated solid oxide is a metal-treated chemically-modified solid oxide.
  • Aspect 37 The process defined in aspect 36, wherein prior to step (1) or step (I), the metal-treated chemically-modified solid oxide is produced by a process comprising contacting any suitable solid oxide and any suitable electron-withdrawing anion and calcining (concurrently and/or subsequently) to form the chemically-modified solid oxide, and contacting the chemically-modified solid oxide with any suitable metal-containing compound.
  • Aspect 38 The process defined in aspect 36 or 37, wherein the metal-treated chemically-modified solid oxide comprises an alkali metal, an alkaline earth metal, a transition metal, or any combination thereof, and generally at an amount in a range from 1 to 30 wt. %, from 5 to 25 wt. %, or from 6 to 18 wt. %, based on the total weight of the metal- treated chemically-modified solid oxide.
  • Aspect 39 The process defined in any one of aspects 36-38, wherein the metal-treated chemically-modified solid oxide comprises an alkali metal (an alkali metal-treated chemically-modified solid oxide), e.g., sodium, potassium, or cesium, as well as combinations thereof.
  • an alkali metal an alkali metal-treated chemically-modified solid oxide
  • Aspect 40 The process defined in any one of aspects 36-38, wherein the metal-treated chemically-modified solid oxide comprises an alkaline earth metal (an alkaline earth metal- treated chemically-modified solid oxide), e.g., magnesium, calcium, or barium, as well as combinations thereof.
  • an alkaline earth metal an alkaline earth metal- treated chemically-modified solid oxide
  • Aspect 41 The process defined in any one of aspects 36-38, wherein the metal-treated chemically-modified solid oxide comprises a transition metal (a transition metal-treated chemically-modified solid oxide), e.g., titanium, zirconium, hafnium, tungsten, or zinc, as well as combinations thereof.
  • a transition metal e.g., titanium, zirconium, hafnium, tungsten, or zinc, as well as combinations thereof.
  • Aspect 42 The process defined in any one of aspects 36-41, wherein the chemically- modified solid oxide comprises a solid oxide contacted with an electron-withdrawing anion, e.g., any solid oxide and any electron-withdrawing anion disclosed herein.
  • an electron-withdrawing anion e.g., any solid oxide and any electron-withdrawing anion disclosed herein.
  • Aspect 43 The process defined in aspect 42, wherein (a) the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof, and (b) the electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, tungstate, or any combination thereof.
  • Aspect 44 The process defined in any one of aspects 36-43, wherein the solid oxide comprises alumina, silica-alumina, silica-coated alumina, or a mixture thereof.
  • Aspect 45 The process defined in any one of aspects 36-44, wherein the electron- withdrawing anion comprises sulfate, fluoride, chloride, or any combination thereof.
  • Aspect 46 The process defined in any one of aspects 36-44, wherein the electron- withdrawing anion comprises sulfate.
  • Aspect 47 The process defined in any one of aspects 36-44, wherein the electron- withdrawing anion comprises fluoride, chloride, or both.
  • Aspect 48 The process defined in any one of aspects 36-43, wherein the chemically- modified solid oxide comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, tungstated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica- zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.
  • Aspect 49 The process defined in any one of aspects 36-43, wherein the chemically- modified solid oxide comprises chlorided alumina, fluorided silica-alumina, fluorided silica- coated alumina, fluorided-chlorided silica-coated alumina, sulfated alumina, sulfated silica- coated alumina, or a combination thereof.
  • Aspect 50 The process defined in any one of aspects 1-29, wherein the treated solid oxide comprises calcined sodium carbonate, calcined sodium bicarbonate, calcined potassium carbonate, calcined cesium carbonate, or a combination thereof.
  • Aspect 51 The process defined in any one of aspects 1-31, wherein the treated solid oxide comprises sodium-treated alumina, potassium-treated alumina, cesium-treated alumina, sodium-treated aluminophosphate, or a combination thereof.
  • Aspect 52 The process defined in any one of aspects 1-31, wherein the treated solid oxide comprises magnesium-treated alumina, calcium-treated alumina, barium-treated alumina, or a combination thereof.
  • Aspect 53 The process defined in any one of aspects 1-31, wherein the treated solid oxide comprises zinc-treated alumina, zirconium-treated alumina, sodium-tungsten-treated alumina, or a combination thereof.
  • Aspect 54 The process defined in any one of aspects 1-31, wherein the treated solid oxide comprises sodium-treated chlorided alumina, sodium-treated sulfated alumina, sodium- treated tungstated alumina, sodium-treated sulfated silica-coated alumina, sodium-treated fluorided silica-coated alumina, sodium-treated fluorided silica-alumina, sodium-treated fluorided-chlorided silica-coated alumina, or a combination thereof.
  • Aspect 55 The process defined in any one of aspects 1-54, wherein the treated solid oxide has any suitable surface area, or a surface area in any range disclosed herein, e.g., from 10 m 2 /g to 750 m 2 /g, from 20 m 2 /g to 500 m 2 /g, or from 30 m 2 /g to 350 m 2 /g.
  • Aspect 56 The process defined in any one of aspects 1-55, wherein the treated solid oxide has any suitable pore volume, or a pore volume in any range disclosed herein, e.g., from 0.1 mL/g to 2.5 mL/g, from 0.1 mL/g to 1.5 mL/g, or from 0.2 mL/g to 1.0 mL/g.
  • Aspect 57 The process defined in any one of aspects 1-56, wherein the diluent comprises any suitable non-protic solvent, or any non-protic solvent disclosed herein.
  • Aspect 58 The process defined in any one of aspects 1-56, wherein the diluent comprises any suitable weakly coordinating or non-coordinating solvent, or any weakly coordinating or non-coordinating solvent disclosed herein.
  • Aspect 59 The process defined in any one of aspects 1-56, wherein the diluent comprises any suitable carbonyl-containing solvent, or any carbonyl-containing solvent disclosed herein, e.g., ketones, esters, or amides (e.g., acetone, ethyl acetate, or N,N- dimethylformamide).
  • suitable carbonyl-containing solvent e.g., ketones, esters, or amides (e.g., acetone, ethyl acetate, or N,N- dimethylformamide).
  • Aspect 60 The process defined in any one of aspects 1-56, wherein the diluent comprises any suitable ether solvent, or any ether solvent disclosed herein, e.g., THF, dimethyl ether, diethyl ether, or dibutyl ether.
  • suitable ether solvent e.g., THF, dimethyl ether, diethyl ether, or dibutyl ether.
  • Aspect 61 The process defined in any one of aspects 1-56, wherein the diluent comprises any suitable aromatic hydrocarbon solvent, or any aromatic hydrocarbon solvent disclosed herein, e.g., benzene, xylene, or toluene.
  • the diluent comprises any suitable aromatic hydrocarbon solvent, or any aromatic hydrocarbon solvent disclosed herein, e.g., benzene, xylene, or toluene.
  • Aspect 62 The process defined in any one of aspects 1-56, wherein the diluent comprises any suitable halogenated aromatic hydrocarbon solvent, or any halogenated aromatic hydrocarbon solvent disclosed herein, e.g., chlorobenzene or dichlorobenzene.
  • Aspect 63 The process defined in any one of aspects 1-56, wherein the diluent comprises THF, 2,5-Me 2 THF, methanol, acetone, toluene, chlorobenzene, pyridine, or a combination thereof.
  • Aspect 64 The process defined in any one of aspects 1-63, wherein the transition metal of the metallalactone (or of the transition metal-ligand complex) is a Group 8-11 transition metal.
  • Aspect 65 The process defined in any one of aspects 1-63, wherein the transition metal of the metallalactone (or of the transition metal-ligand complex) is Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au.
  • Aspect 66 The process defined in any one of aspects 1-63, wherein the transition metal of the metallalactone (or of the transition metal-ligand complex) is Ni, Fe, or Rh.
  • Aspect 67 The process defined in any one of aspects 1-63, wherein the metallalactone is a nickelalactone, e.g., any suitable nickelalactone or any nickelalactone disclosed herein.
  • Aspect 68 The process defined in any one of aspects 1-67, wherein the ligand of the metallalactone (or of the transition metal-ligand complex) is any suitable neutral electron donor group and/or Lewis base, or any neutral electron donor group and/or Lewis base disclosed herein.
  • Aspect 69 The process defined in any one of aspects 1-67, wherein the ligand of the metallalactone (or of the transition metal-ligand complex) is a bidentate ligand.
  • Aspect 70 The process defined in any one of aspects 1-69, wherein the ligand of the metallalactone (or of the transition metal-ligand complex) comprises at least one of a nitrogen, phosphorus, sulfur, or oxygen heteroatom.
  • Aspect 71 The process defined in any one of aspects 1-69, wherein the ligand of the metallalactone (or of the transition metal-ligand complex) is any suitable carbene group or any carbene group disclosed herein.
  • Aspect 72 The process defined in any one of aspects 1-69, wherein the metallalactone, ligand, or transition metal-ligand complex is any suitable metallalactone, ligand, or transition metal-ligand complex, or is any metallalactone, ligand, or transition metal-ligand complex disclosed herein.

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Abstract

L'invention concerne des procédés de production d'un acide carboxylique α,β-insaturé, tel que l'acide acrylique, ou un sel de celui-ci, faisant appel à des oxydes solides traités. Les oxydes solides traités peuvent être des oxydes solides calcinés, des oxydes solides traités par un métal, ou des oxydes solides chimiquement modifiés traités par un métal, pouvant être représentés à titre d'exemples par l'alumine traitée au sodium, l'alumine traitée au calcium, l'alumine traitée au zinc, l'alumine sulfatée traitée au sodium, l'alumine revêtue de silice fluorée traitée au sodium, et autres matériaux similaires.
PCT/US2017/025837 2016-04-06 2017-04-04 Procédés de production d'acides carboxyliques α,β-insaturés et de sels de ceux-ci WO2017176669A1 (fr)

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CN202211087783.2A CN115433075A (zh) 2016-04-06 2017-04-04 产生α,β-不饱和羧酸和其盐的方法
CN201780022267.2A CN109071398B (zh) 2016-04-06 2017-04-04 产生α,β-不饱和羧酸和其盐的方法
EP17718237.5A EP3426627A1 (fr) 2016-04-06 2017-04-04 Procédés de production d'acides carboxyliques , -insaturés et de sels de ceux-ci

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