Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/12—Silica and alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
  • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
  • B01J29/46—Iron group metals or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
  • B01J37/18—Reducing with gases containing free hydrogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
  • C07D307/08—Preparation of tetrahydrofuran
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
  • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties

Definitions

• Embodiments of the present invention generally relate catalysts suitable for tetrahydrofuran synthesis from 1,4-butanediol. Specific embodiments pertain to catalysts suitable for such processes, and processes for synthesizing tetrahydrofuran.
• Tetrahydrofuran is a useful chemical that can be used as a high-purity solvent, or be polymerized to form polytetramethylene oxide. This polymer can be used to make elastomeric polyurethane fibers like Spandex.
• Maleic and/or succinic diesters can be hydrogenated over copper-based catalysts in the gas phase at elevated pressures to give mixtures of THF, gamma-butyrolactone (GBL), and 1,4-butanediol (BDO).
• Byproducts of this hydrogenation/hydrogenolysis process include n-butanol and its derivatives, including dimethyl ether, dibutyl ether, butyraldehyde, and linear ethers of butanol with the esterifying alcohol.
• GBL is used for preparing pyrrolidones such as pyrrolidone itself and N-methylpyrrolidone.
• BDO finds use in the production of polyurethanes and polyesters, and, importantly, is used for preparing THF.
• the complete process for the synthesis of THF is as follows: First, maleic anyhdride undergoes esterification with methanol (or ethanol) to form dimethyl maleate (DMM). Then, DMM is hydrogenated to form BDO and methanol (or ethanol). This step has been carried out using a catalyst comprising copper, manganese and alumina. Finally, the resultant stream containing BDO is converted, to whatever extent required, via dehydration and ring closure, to THF. This step is typically carried out using copper on alumina catalyst.
• THF butanol
• BME butyl methyl ether
• the catalyst composition comprises about 3 to about 50 wt % copper oxide on a gamma-alumina support, wherein the catalyst composition comprises less than about 1.5 wt % silica and the catalyst composition has Lewis acidity and no, or substantially no, Br ⁇ nsted acidity.
• the catalyst composition wherein the catalyst composition has substantially only Lewis acidity determinable from IR absorption spectra of pyridine adsorbed on the catalyst.
• the gamma-alumina contains substantially no stabilizers.
• the amount of silica can be varied.
• the catalyst composition comprises less than about 1 wt % silica.
• the catalyst composition comprises less than about 0.5 wt % silica.
• the catalyst composition comprises substantially no silica.
• the amount of copper oxide can also be varied. Accordingly, in one or more embodiments, the catalyst composition contains from about 3 to about 30 wt % copper oxide. In further embodiments, the catalyst composition contains from about 10 to about 15 wt % copper oxide.
• a second aspect of the invention relates to a method of synthesizing tetrahydrofuran.
• the method comprises contacting a stream comprising 1,4-butanediol with a catalyst composition comprising about 3 to about 50 wt % copper oxide on a gamma-alumina support, wherein the catalyst composition comprises less than about 1.5 wt % silica, and with the proviso that the catalyst composition has Lewis acidity and no or substantially no Br ⁇ nsted acidity, thereby converting at least a portion of the 1,4-butanediol into tetrahydrofuran.
• the catalyst composition wherein the catalyst composition has substantially only Lewis acidity determinable from IR absorption spectra of pyridine adsorbed on the catalyst.
• the gamma-alumina contains substantially no stabilizers.
• the method further comprises reducing the CuO to copper metal prior to contacting the catalyst composition with a stream comprising 1,4-butanediol.
• the amount of silica can be varied.
• the catalyst composition comprises less than about 1 wt % silica.
• the catalyst composition comprises less than about 0.5 wt % silica.
• the catalyst composition comprises substantially no silica.
• the amount of copper oxide can also be varied. Accordingly, in one or more embodiments, the catalyst composition contains from about 3 to about 30 wt % copper oxide. In further embodiments, the catalyst composition contains from about 10 to about 15 wt % copper oxide.
• a third aspect of the invention pertains to a catalyst system for the synthesis of tetrahydrofuran from maleic anhydride.
• the system comprises a first catalyst composition effective to convert dimethyl maleate and dimethyl succinate to1,4-butanediol and methanol, and a second catalyst composition comprising about 3 to about 50 wt % copper oxide on a gamma-alumina support, wherein the catalyst composition comprises less than about 1.5 wt % silica, and the catalyst composition has Lewis acidity and no or substantially no Br ⁇ nsted acidity.
• the copper oxide is reduced to copper metal.
• the catalyst composition wherein the catalyst composition has substantially only Lewis acidity determinable from IR absorption spectra of pyridine adsorbed on the catalyst.
• the gamma-alumina contains substantially no stabilizers.
• the setup of the catalyst system can be varied.
• the first and second catalyst compositions are in pellet form in a fixed bed reactor.
• the fixed bed reactor contains a layer of the first catalyst composition over a layer of the second catalyst composition.
• the system further comprises a protective layer over the layer of the first catalyst composition, which may comprise copper and chromium.
• the first and second catalyst compositions are in pellet form in separate reactors.
• the system further comprises a protective layer over the first catalyst composition, which may comprise copper and chromium.
• aspects of this invention pertain to an acid catalyst suitable for converting BDO to THF.
• catalysts for this process also give ether byproducts from previous steps in THF synthesis to give ethers like BME and DME.
• the solid acid catalyst that converts BDO to THF in the commercial stream is critical in BME formation.
• this acid catalyst contains only Lewis acidity (as opposed to Br ⁇ nsted acidity) in the form of gamma alumina, then the BME and DME formed is minimal compared to catalysts that contain Br ⁇ nsted acidity.
• the amount of BME and/or DME can also be reduced by controlling the amount of silica or stabilizers in the gamma alumina.
• one aspect of the invention relates to a catalyst comprising copper supported on gamma alumina which contains only Lewis acidity. Other embodiments do not contain additives to the alumina, such as silica.
• one aspect of the invention relates to a catalyst composition for the synthesis of tetrahydrofuran, the catalyst composition comprising about 3 to about 50 wt % copper oxide on a gamma-alumina support, wherein the catalyst composition comprises less than about 1.5 wt % silica and the catalyst composition has Lewis acidity and no, or substantially no, Br ⁇ nsted acidity.
• the catalyst composition has substantially only Lewis acidity determinable from IR absorption spectra of pyridine adsorbed on the catalyst.
• the amount of copper can be varied.
• the catalyst composition contains from about 3 to about 30 wt % copper oxide, or more specifically about 5 to about 50. In other embodiments, the catalyst composition contains from about 5 to about 20, or 10 to about 15 wt % copper oxide.
• the amount of silica can be varied.
• the catalyst composition comprises less than about 1 wt %, 0.5 wt %, 0.25 wt %, or 0.1 wt % silica.
• the catalyst composition comprises no silica, or substantially no silica.
• the dehydration catalyst used according to the present invention has no Br ⁇ nsted acidity, but does have Lewis acidity.
• a “Br ⁇ nsted acid” is a chemical species that donates a proton to a Br ⁇ nsted base. Br ⁇ nsted acidity is distinguished from Lewis acidity, in that a “Lewis acid” is a chemical species that accepts an electron pair from another species.
• “no Br ⁇ nsted acidity” means that there is no detectable Br ⁇ nsted acidity using the diffuse reflectance Fourier infrared transform spectroscopy (DRIFTS) procedure described below in the Examples section. This procedure measures the relative amounts of pyridine adsorbed on Br ⁇ nsted and Lewis sites on solids.
• DRIFTS diffuse reflectance Fourier infrared transform spectroscopy
• the gamma-alumina contains substantially no additives, including stabilizers.
• stabilizers include oxides of various metals (i.e., lanthanum, zirconium, etc.)
• Other components which can add Br ⁇ nsted acidity to the catalyst composition include, but are not limited to, aluminosilicate zeolites (i.e., ZSM-5), other microporous materials (i.e., SAPOs, ALPOs etc.), and heteropolyacids.
• aluminosilicate zeolites i.e., ZSM-5
• other microporous materials i.e., SAPOs, ALPOs etc.
• heteropolyacids i.e., aluminosilicate zeolites, other microporous materials
• some stabilizers may increase Lewis acidity.
• the catalyst described herein can be prepared via techniques well known in the art. For example, copper can be put onto gamma-alumina via the incipient wetness technique using an aqueous solution of Cu(NO 3 ) 2 up to about 95% of the pore volume. The catalyst can then be calcined to decompose the nitrate to the oxide form. Suitable calcination temperatures range from about 300 to about 500° C. In one embodiment, the calcination temperature is about 350° C.
• the catalyst composition can then be formed into any suitable shape. In a particular embodiment, the catalyst composition is formed into pellets. In an even more particular embodiment, pellets have a size of about 1 ⁇ 8′′ by 1 ⁇ 8′′.
• the catalyst is usually reduced in H 2 containing gas to obtain metallic copper prior to use.
• embodiments of the catalysts described herein are useful for the synthesis of THF. Accordingly, another aspect of the invention relate to processes for preparing (THF) in a mixture with gamma-butyrolactone and 1,4-butanediol.
• the method comprises contacting a stream comprising 1,4-butanediol with a catalyst composition comprising about 3 to about 50 wt % copper oxide on a gamma-alumina support, wherein the catalyst composition comprises less than about 1.5 wt % silica, and with the proviso that the catalyst composition has Lewis acidity and no Br ⁇ nsted acidity, thereby converting at least a portion of the 1,4-butanediol into tetrahydrofuran.
• the catalyst composition has substantially only Lewis acidity determinable from IR absorption spectra of pyridine adsorbed on the catalyst.
• the gamma-alumina contains substantially no stabilizers.
• THF in high yield and high purity by hydrogenation and hydrogenolysis of maleic and succinic diesters (usually dimethyl maleate (DMM) and succinate (DMS)) and the resultant BDO over Cu-containing catalysts in the gas phase. That is the reaction begins with DMM, which undergoes hydrogenation to DMS. Then, the DMS undergoes hydrogenolysis to GBL, BDO, and then THF.
• the THF fraction may be more than 10 mol % as a proportion of the target products.
• the amount of silica is varied.
• the catalyst composition comprises less than about 1 wt % silica, less than about 0.5 wt % silica, less than about 0.25 wt % silica, less than about 0.1wt % silica.
• the catalyst composition comprises substantially no silica.
• the amount of copper oxide can also be varied.
• the catalyst composition can contain from about 3 to about 30, or about 10 to about 15 wt % copper oxide.
• Typical reaction conditions for this stage of the overall process, as well as for the previous stages are as follows.
• the hydrogenation and hydrogenolysis of dimethyl maleate to 1,4-butandiol is performed in the gas phase.
• the diester stream is vaporized in a hydrogen-containing gas stream under reaction pressure at temperatures of about 150 to about 220° C.
• the vapors are passed over the catalysts.
• the molar ratio of hydrogen in the reactant present in the reactor before the hydrogenation catalyst to diester is in the range from about 50 to about 500:1, specifically from about 60 to about 400:1, and more specifically from about 70 to about 300:1.
• the hydrogenation can be operated with hydrogen recycling (circulation gas).
• the hydrogen consumed in the reaction plus that removed via off-gas and gas removed via effervescence, is replenished continually in the form of fresh hydrogen.
• the molar ratio of fresh hydrogen to diester here is generally from about 3.5 to about 10:1, specifically from about 4 to about 8:1, and more specifically from about 5 to about 7:1.
• the reaction conditions of the dehydration and ring closure of 1,4-butanediol to THF can include pressures in the range from about 10 to about 100 bar, specifically from about 20 to about 80 bar, and more specifically about 30 to about 60 bar.
• the reaction temperatures can be selected to be from about 150 to about 300° C., specifically from about 155 to about 250° C., and more specifically from about 160 to about 230° C. In some embodiments, there is an increase in reaction temperature in the reactor during the reaction.
• the catalysts for the hydrogenation/hydrogenolysis to 1,4-butanediol and dehydration/ring closure to THF there are several arrangements of the catalysts for the hydrogenation/hydrogenolysis to 1,4-butanediol and dehydration/ring closure to THF.
• a common setup for these catalysts is a fixed bed reactor with the catalyst compositions in pelletized form.
• One such protective layer comprises copper and chromium.
• the final configuration features the protective layer over the BDO synthesis catalyst layer, which in turn overlies the THF synthesis catalyst.
• a second catalyst may also have a protective layer.
• the reaction of DMM to BDO can take place over a copper-manganese-alumina catalyst.
• the reaction of BDO to THF is carried out over a copper-alumina catalyst of the type described herein.
• the two reactions may take place sequentially in one reactor, with staged catalyst beds, or in two separate reactors.
• the catalysts may be present in layers all in one reactor or in two or more reactors.
• An example of the latter setup comprises the first catalyst in the first reactor and the second catalyst in a second reactor.
• another aspect of the invention relates to a catalyst system for the synthesis of tetrahydrofuran from maleic anhydride, the system comprising a first catalyst composition effective to convert dimethyl maleate and dimethyl succinate to1,4-butanediol and methanol; and a second catalyst composition comprising about 3 to about 50 wt % copper oxide on a gamma-alumina support, wherein the catalyst composition comprises less than about 1.5 wt % silica, and with the proviso that the catalyst composition has Lewis acidity and no Br ⁇ nsted acidity.
• the catalyst composition can be modified as discussed above.
• the catalyst composition has substantially only Lewis acidity determinable from IR absorption spectra of pyridine adsorbed on the catalyst.
• the gamma-alumina contains substantially no stabilizers.
• the first and second catalyst compositions are in pellet form in a fixed bed reactor.
• the fixed bed reactor contains a layer of the first catalyst composition over a layer of the second catalyst composition.
• the catalyst system further comprises a protective layer over the layer of the first catalyst composition.
• One such protective layer comprises copper and chromium.
• the first and second catalyst compositions are in pellet form in separate reactors.
• the catalyst system further comprises a protective layer over the first catalyst composition.
• the protective layer comprises copper and chromium.
• Catalyst 1 was prepared on gamma-alumina via the incipient wetness technique using an aqueous solution of 16 wt % Cu(NO 3 ) 2 .
• the Cu containing catalyst was dried and then calcined to decompose the nitrate to the oxide.
• the resulting catalyst contained 11% CuO.
• the catalyst was reduced in a stream containing hydrogen to obtain metallic Cu before use.
• Catalyst 2 was prepared the same way as Example 1 but the gamma-alumina was physically mixed with 5 wt % of HZSM-5 (zeolitic crystals). It is considered comparative because the HZSM-5 adds Br ⁇ nsted acidity to the catalyst composition.
• HZSM-5 zeolitic crystals
• Catalyst 3 was prepared the same way as Example 1, but the gamma alumina contained 1.33% SiO 2 .
• the acidity test was done with an FTIR of adsorbed pyridine.
• the sample was ground to ⁇ 10 micron particle size just prior to analysis to limit intake of moisture and contaminants.
• the sample was placed directly on the heated post in the Spectra Tech Controlled Environment Chamber (CEC), and leveled with a spatula, but not packed down. Any spills were cleaned with a pipette or miniature vacuum cleaner, as any loose powder can get into the gas flow lines and/or the o-ring, which could cloud future data.
• the cover was screwed on, making sure the windows were clean and uncracked.
• the cell height (CEC) was aligned to maximize the IR energy throughput.
• a quick scan was carried out to make sure there is a signal between 1800 and 1400 cm ⁇ 1 .
• the gain was set so that the signal was at maximum but all still on scale.
• a gain of one should give an energy of about 4400 cm ⁇ 1 . This is 10% of the beam energy.
• a single beam monitor should give a “valid” throughput from 4000 to 1300 cm ⁇ 1 (regardless of the gain).
• the sample was then heated and dried.
• the sample was occasionally scanned to make sure the IR signal was still present. Note that heating externally may change the results obtained, as it may change the surface OH groups. This must be determined for each sample.
• the sample was cooled to approximately 40° C. so that the background spectrum could be obtained.
• the 1640 cm ⁇ 1 region was checked to ensure all water was gone.
• the background spectrum of the dried sample was collected and saved.
• Equilibration was achieved by removing excess pyridine from the gas lines and the sample. This was accomplished by leaving the sample sitting for 30 minutes with the cell at 40° C. A scan of the sample was taken at 40° C. after equilibration.
• K-Munk correction which converts data such that peak intensity will be linear with concentration, was used. Following the manufacturer's instructions, K-Munk was applied on the final spectrum collected and the resultant units were in K-Munk.
• Peak areas are calculated using a peak-fitting program and with determined extinction coefficients, dependent on sample type, IR peak areas are quantifiable into ⁇ moles/gram of Lewis or Br ⁇ nsted acidity for a given sample.
• extinction coefficients were determined to be 6.09 for Lewis and 9.32 Br ⁇ nsted acid-sites.
• Baseline corrected peak area measurement in absorbance is obtainable at 1546 cm ⁇ 1 for the Br ⁇ nsted peak and 1450/1455 cm ⁇ 1 for Lewis peak. The following calculation is used:
• Examples 1 and 3 did not exhibit Br ⁇ nsted acidity, although all of the examples had Lewis acidity to varying degrees.
• the above catalysts were tested in a flow reactor at 185° C., 195° C., and 205° C.
• the feed mixture was comprised of 31% methanol, either 2% or 4% butanol, 7% gamma butyrolactone, 55% BDO, and 1% water.
• Each of the catalysts was tested for BME and DME production.
• Table 2 below shows the formation of BME, given as GC peak area %.
• Table 3 below shows the formation of DME values, also given as GC peak area %.
• Example 1 Example 2
• Example 3 2 185 0.17 0.95 0.45 2 195 0.55 2.4 0.7 2 205 1.1 2.1 1.5 4 185 0.2 1.1 0.5 4 195 0.3 1.3 0.75
• Example 2 which was the comparative example, produced the greatest amount of both BME and DME.
• Examples 1 and 3 produced less BME and DME, with Example 1 producing the least amount of BME and DME.
• the examples that did not contain Br ⁇ onsted acidity produced less of the usually undesired BME and DME byproducts than did the example that did contain Br ⁇ nsted acidity.

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