WO2015005942A1 - Procédés de production d'acide méthacrylique - Google Patents

Procédés de production d'acide méthacrylique Download PDF

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Publication number
WO2015005942A1
WO2015005942A1 PCT/US2013/067036 US2013067036W WO2015005942A1 WO 2015005942 A1 WO2015005942 A1 WO 2015005942A1 US 2013067036 W US2013067036 W US 2013067036W WO 2015005942 A1 WO2015005942 A1 WO 2015005942A1
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WIPO (PCT)
Prior art keywords
isobutene
percent
catalyst
ethanol
methacrolein
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Application number
PCT/US2013/067036
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English (en)
Inventor
Junming SUN
Changjun Liu
Yong Wang
Colin Smith
Kevin Martin
Padmesh Venkitasubramanian
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Washington State University
Archer Daniels Midland Company
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Application filed by Washington State University, Archer Daniels Midland Company filed Critical Washington State University
Publication of WO2015005942A1 publication Critical patent/WO2015005942A1/fr
Priority to US14/683,257 priority Critical patent/US9403749B2/en
Priority to US15/183,991 priority patent/US9751823B2/en

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    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • 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
    • B01J37/20—Sulfiding

Definitions

  • the present application concerns processes for making methacrylic acid via methacrolein from isobutene.
  • isobutene is widely used for the production of a variety of industrially important products, and has been used to make methacrylic acid via methacrolein in one commercially known route.
  • Isobutene has however been produced commercially to date through the catalytic or steam cracking of fossil feedstocks. As fossil resources are depleted and/or become more costly to use, renewable source-based routes to isobutene are increasingly needed - especially in consideration of increased demand for isobutene.
  • the objectives of the hard template method were to suppress ethanol dehydration and acetone polymerization, while enabling a surface basic site-catalyzed ethanol dehydrogenation to acetaldehyde, an acetaldehyde to acetone conversion via aldol-condensation/dehydrogenation, and a Bronsted and Lewis acidic/basic site-catalyzed acetone-to-isobutene reaction pathway.
  • the present invention in one aspect concerns a process for making methacrylic acid via methacrolein from a biobased isobutene, wherein the biobased isobutene is prepared from ethanol in the presence of a Zn x Zr y O z mixed oxide catalyst, the biobased isobutene is oxidized to methacrolein and the methacrolein is oxidized to methacrylic acid.
  • the Zn x Zr y O z mixed oxide catalyst exhibits improved stability for the conversion, exhibiting less than 10 percent loss, more preferably less than 5 percent loss and still more preferably less than 2 percent loss in isobutene selectivity over a period of 200 hours on stream.
  • the Zn x Zr y O z mixed oxide catalyst is made by a process as described in the '433 application, broadly comprising forming a solution of one or more Zn compounds, combining one or more zirconium-containing solids with the solution of one or more Zn compounds, drying the wetted solids, then calcining the dried solids.
  • the present invention concerns a process for making methacrylic acid via methacrolein from a biobased isobutene, wherein the biobased isobutene is prepared from acetic acid in the presence of a catalyst, the biobased isobutene is oxidized to methacrolein and the methacrolein is oxidized to methacrylic acid.
  • the catalyst is a Zn x Zr y O z mixed oxide catalyst, especially a catalyst made by a process as described in the '433 application, and the process of making the starting biobased isobutene is carried out as described in the '312 application.
  • Figure 1 schematically depicts a process for producing a wholly biobased methacrylic acid from a wholly biobased isobutene made from ethanol in the presence of a Zn x Zr y O z mixed oxide catalyst, especially such a catalyst made by a process as described in the '433 application.
  • FIG. 2 schematically depicts a process for producing a biobased methacrylic acid, particularly a wholly biobased methacrylic acid, from a biobased and especially a wholly biobased isobutene made from acetic acid, according to the second aspect of the present invention as summarized above.
  • a process 10 is schematically illustrated wherein ethanol 12 is converted to isobutene 14 in the presence of a catalyst, particularly, a Zn x Zr y O z mixed oxide catalyst.
  • the isobutene 14 is then combined with oxygen from an oxygen source 16 and oxidized to yield methacrolein, which is then oxidized with oxygen from oxygen source 16 to provide a methacrylic acid product 18.
  • the ethanol 12 is conventionally derived from biological carbon sources, for example, by fermentation of five- and especially six-carbon sugars, so that the isobutene 14 and subsequent methacrylic acid product 18 are desirably wholly-biobased.
  • biobased we mean those materials whose carbon content is shown by ASTM D6866 to be derived from or based in significant part (at least 20 percent or more) upon biological products or renewable agricultural materials (including but not being limited to plant, animal and marine materials) or forestry materials. "Wholly biobased” thus will be understood as referring to materials whose carbon content by ASTM D6866 is entirely or substantially entirely (for example, 95 percent or more) indicated as of biological origin. [0015] In this respect ASTM Method D6866, similar to radiocarbon dating, compares how much of a decaying carbon isotope remains in a sample to how much would be in the same sample if it were made of entirely recently grown materials. The percentage is called the biobased content of the product.
  • Samples are combusted in a quartz sample tube and the gaseous combustion products are transferred to a borosilicate break seal tube.
  • liquid scintillation is used to count the relative amounts of carbon isotopes in the carbon dioxide in the gaseous combustion products.
  • 13C/12C and 14C/12C isotope ratios are counted (14C) and measured (13C/12C) using accelerator mass spectrometry.
  • Zero percent 14C indicates the entire lack of 14C atoms in a material, thus indicating a fossil (for example, petroleum based) carbon source.
  • One hundred percent 14C after correction for the post-1950 bomb injection of 14C into the atmosphere, indicates a modern carbon source.
  • ASTM D6866 effectively distinguishes between biobased materials and petroleum derived materials in part because isotopic fractionation due to physiological processes, such as, for example, carbon dioxide transport within plants during photosynthesis, leads to specific isotopic ratios in natural or biobased compounds.
  • physiological processes such as, for example, carbon dioxide transport within plants during photosynthesis
  • the 13C/12C carbon isotopic ratio of petroleum and petroleum derived products is different from the isotopic ratios in natural or bioderived compounds due to different chemical processes and isotopic fractionation during the generation of petroleum.
  • radioactive decay of the unstable 14C carbon radioisotope leads to different isotope ratios in biobased products compared to petroleum products.
  • the ethanol 12 can in this regard be derived from any known process whereby five and/or six carbon sugars from conventional grain milling operations or from processing of a lignocellulosic biomass more generally may be converted to one or more products inclusive of ethanol, at least in some part by fermentation means. Both aerobic and anaerobic processes are thus contemplated, using any of the variety of yeasts (e.g., kluyveromyces lactis, kluyveromyces lipolytics, saccharomyces cerevisiae, s. uvarum, s. monacensis, s. pastorianus, s. bayanus, s. ellipsoidues, Candida shehata, c.
  • yeasts e.g., kluyveromyces lactis, kluyveromyces lipolytics, saccharomyces cerevisiae, s. uvarum, s. monacensis, s. pastorianus,
  • melibiosica c. intermedia
  • any of the variety of bacteria e.g., Clostridium sporogenes, c. indolis, c. sphenoides, c. sordelli, Candida bracarensis, Candida dubliniensis, zymomonas mobilis, z. pomaceas
  • Clostridium sporogenes, c. indolis, c. sphenoides, c. sordelli, Candida bracarensis, Candida dubliniensis, zymomonas mobilis, z. pomaceas e.g., Clostridium sporogenes, c. indolis, c. sphenoides, c. sordelli, Candida bracarensis, Candida dubliniensis, zymomonas mobilis, z. pomaceas
  • the ethanol 12 is then according to a first aspect of the invention converted to isobutene 14 in the presence preferably of a Zn x Zr y O z mixed oxide catalyst as described in the '433 application, having excellent stability for the conversion of ethanol to isobutene in exhibiting less than 10 percent loss in isobutene selectivity over a period of 200 hours on stream under atmospheric pressure ( ⁇ 5 psig) and at 450 °C, at full conversion of the ethanol 12 to the isobutene 14.
  • the catalyst exhibits less than 5 percent loss in isobutene selectivity over a period of 200 hours on stream, and more preferably less than 2 percent.
  • a Zn/Zr ratio (x:y) of from 1 :100 to 10:1 , preferably from 1 :30 to 1 :1 , especially 1 :20 to 1 :5, and still more preferably 1 :12 to 1 :10.
  • any range of values is given for any aspect or feature of the mixed oxide catalysts or any process described for using the mixed oxide catalysts
  • the given ranges will be understood as disclosing and describing all subranges of values included within the broader range.
  • the range of 1 : 100 to 10:1 will be understood as disclosing and describing not only the specific preferred and more preferred subranges given above, but also every other subrange including a value for x between 1 and 10 and every other subrange including a value for y between 1 and 100.
  • Nanosized white powders were obtained, having a mean particle size of less than 10 nanometers.
  • the catalysts made by the method of the '433 application and used in the method of Figure 1 (for converting ethanol 12 to isobutene 14) likewise comprise aggregates of less than10 nm-sized particles, with a highly crystalline structure.
  • the Zn oxide component is again highly dispersed on the Zr oxide component.
  • a Zn 1 Zr 10 O 2 mixed oxide catalyst prepared according to the method of the '433 application also has a smaller surface area, roughly 49 square meters per gram, as compared to 138 square meters per gram for a Zn-
  • compositional difference was also observed between catalysts prepared by the two methods, in that the Zn x Zr y O z mixed oxide catalysts according to the '433 application preferably are substantially sulfur-free, containing less than 0.14 weight percent of sulfur, as compared to, for example, 3.68 weight percent of sulfur in the same Zn 1 Zr 10 O 2 mixed oxide catalyst prepared according to the former hard template method.
  • the Zn x Zr y O z mixed oxide catalysts of the '433 application and preferred for use herein have improved stability for the conversion of ethanol 12 to isobutene 14; while the contributions if any of the larger crystallite size and smaller surface area to this improved stability are not presently understood, it is nevertheless believed that at least the much reduced sulfur content of the inventive catalysts does contribute materially to this improved stability.
  • the Zn x Zr y O z mixed oxide catalysts preferred for use in the present invention can be characterized in practice as having improved stability for the conversion of ethanol to isobutene, exhibiting less than 10 percent loss in isobutene selectivity over a period of 200 hours on stream, from a different, compositional perspective the preferred more stable Zn x Zr y O z mixed oxide catalysts can be
  • still more stable catalysts are provided, having a sulfur content of less than 0.01 percent by weight, and still more preferably the catalysts will have a sulfur content of less than 0.001 percent by weight.
  • Such catalysts may be made by a process broadly comprising, in certain embodiments, forming a solution of one or more Zn compounds, combining one or more zirconium-containing solids with the solution of one or more Zn compounds so that the solution wets the zirconium-containing solids to a state of incipient wetness, drying the wetted solids, then calcining the dried solids.
  • a solution is formed of one or more Zr compounds, the solution is combined with one or more Zn-containing solids so that the solution wets the Zn-containing solids to a state of incipient wetness, the wetted solids are dried and then the dried solids are calcined.
  • any combination of zinc and zirconium materials and any solvent can be used that will permit the zinc and zirconium components to mix homogeneously whereby, through incipient wetness impregnation, one of the zinc or zirconium components are well dispersed on a solid of the other component for subsequent drying and conversion to the oxide forms through calcining.
  • drying step can be accomplished in a temperature range of from 60 degrees Celsius to 200 degrees Celsius over at least about 3 hours, while the calcining can take place at a temperature of from 300 degrees Celsius to 1500 degrees Celsius, but more preferably a temperature of from 400 to 600 degrees Celsius is used.
  • the calcination time can be from 10 minutes to 48 hours, with from 2 to 10 hours being preferred.
  • suitable Zn x Zr y O z mixed oxide catalysts can also be prepared by a hard template method, except that a suitable very low sulfur content carbon is used for the hard template such that the finished catalyst will contain not more than 2 percent by weight of sulfur, especially not more than 0.5 percent by weight of sulfur and still more preferably will contain not more than 0.1 weight percent (by total weight of the catalyst) of sulfur.
  • a suitable very low sulfur content carbon is used for the hard template such that the finished catalyst will contain not more than 2 percent by weight of sulfur, especially not more than 0.5 percent by weight of sulfur and still more preferably will contain not more than 0.1 weight percent (by total weight of the catalyst) of sulfur.
  • a variety of such very low sulfur carbons are available commercially from various suppliers; in general, the lower the sulfur content, the better for forming the highly active, stable mixed oxide catalysts preferred for use in a process of the present invention (whether based on ethanol as in Figure 1 or acetic acid as in Figure 2).
  • Processes for converting the ethanol 12 to isobutene 14 using these catalysts may be conducted in a manner and under conditions described in the Sun journal article, or in a manner and under conditions described in Mizuno et al or the several other prior publications concerned with the production of products inclusive of isobutene from ethanol.
  • Mizuno et al. is particularly directed to the production of propylene from ethanol, it is nevertheless considered to be well within the capabilities of those skilled in the art to determine what conditions embraced by Mizuno et al. or other similar references will be most appropriate to produce isobutene among the possible products, without undue
  • reaction temperature may be in a range from 350 to 700 degrees Celsius, preferably, in a range from 400 to 500 degrees Celsius
  • the WHSV can be in a range from 0.01 hr "1 to 10 hr "1 , preferably from 0.05 hr "1 to 2 hr "1 .
  • Ethanol/water solution with steam to carbon ratios from 0 to 20, preferably from 2 to 5 can be used.
  • the isobutene 14 is oxidized with oxygen from an oxygen source 16 to yield methacrolein according to any known process and using any known catalyst for this purpose, and the methacrolein is further oxidized to produce a methacrylic acid product 18, again according to any known process and using any known catalyst for the second oxidation step from methacrolein to methacrylic acid.
  • US 8,273,313 to Galloway describes a system and process for separating methacrolein from methacrylic acid and acetic acid in the gas phase product from a partial oxidation of isobutene in two oxidation steps, purportedly maximizing recovery of all three components at minimum capital and energy cost, under conditions minimizing polymerization and plugging by solids deposition in compressors, columns and the like.
  • US 7,732,367 to Stevenson et al. concerns a catalyst for accomplishing the gas-phase methacrolein oxidation to methacrylic acid and methods of making the catalyst, where the catalyst includes at least molybdenum, phosphorus, vanadium, bismuth and a first component selected from potassium, rubidium, cesium, thallium or mixtures or combinations of these, has at least 57% medium pores and a nitric acid to molybdenum ratio of at least 0.5 to 1 or a nitric acid to M012 ratio of at least 6.0:1.
  • US 5,23 ,226 to Hammon et al. also relates particularly to the gas-phase oxidation of methacrolein to methacrylic acid, disclosing a process for the catalytic gas-phase oxidation of methacrolein to methacrylic acid in a fixed-bed reactor at elevated temperature on catalytically-active oxides with a single pass conversion of from 45 to 95 percent. Because of the
  • the reaction temperature is maintained from 280 to 340 degrees Celsius until a methacrolein conversion of from 20 to 40 percent is reached, at which point the reaction temperature is reduced at once, incrementally or continuously by from 5 to 40 degrees Celsius until a conversion of from 45 to 95 percent has been accomplished, with the proviso that the reaction temperature is not less than 260 degrees Celsius.
  • Suitable catalysts are indicated as those described in EP 265733, EP 102688 and DE 3010434.
  • FIG. 2 a process is schematically illustrated according to a second aspect of the present invention, providing biobased and preferably wholly biobased methacrylic acid via methacrolein from a corresponding biobased and preferably wholly biobased isobutene, wherein the isobutene is prepared from acetic acid in the presence of a catalyst, the biobased isobutene is oxidized to methacrolein and the methacrolein is oxidized to methacrylic acid.
  • the catalyst is a
  • Zn x Zr y O z mixed oxide catalyst especially a catalyst made by a process as described in the '433 application, and the process of making the starting biobased isobutene is carried out as described in the incorporated '312 application.
  • acetic acid 22 is converted to isobutene 24, and the isobutene 24 is oxidized (as described above in connection with Figure 1) using oxygen from an oxygen source 26 to provide a methacrylic acid product 28.
  • the acetic acid 22 can be obtained by various methods from a number of starting materials. If desired, at least a portion of the acetic acid that is conventionally produced in the oxidation of isobutene 24 through methacrolein to the methacrylic acid product 28 can be recovered and recycled to form a portion of the acetic acid 22 that is used.
  • the acetic acid 22 can be produced from a source 30 of five and six carbon sugars by fermentation.
  • US 6,509,180 and US 8,252,567 seek to improve upon known processes for making ethanol and butanol/hexanol, respectively, by means including the fermentation of five and six carbon sugars into acetic acid.
  • the acetic acid is esterified to form an acetate ester which may then be hydrogenated (using hydrogen from, e.g., steam reforming of natural gas, electrolysis of water, gasification of biomass or partial oxidation of hydrocarbons generally) to ethanol.
  • the ethanol formed in this manner can be used to make butanol and hexanol, by subjecting the ethanol with acetate, acetic acid or mixtures thereof to an acidogenic fermentation using, for example, species of the bacteria Clostridium ⁇ Clostridium kluyveri s mentioned), to produce butyrate, butyric acid, caproate, caproic acid or mixtures thereof.
  • These materials then in turn are acidified to convert butyrate and caproate to butyric acid and caproic acid, the butyric and caproic acids are esterified and then the butyric and caproic acid esters undergo reduction by hydrogenation, hydrogeno lysis or reduction by carbon monoxide to provide butanol and ethanol.
  • the fermentation of the five and six carbon sugars 30 to form acetic acid 22 can be accomplished by various organisms. More particularly, homoacetogenic microorganisms are able through fermentation to produce acetic acid with 100% carbon yield; these
  • microorganisms internally convert carbon dioxide to acetate, in contrast to a process for producing ethanol from sugars obtained from biomass, wherein carbon dioxide is produced as a byproduct.
  • Any of the known fermentation methods may, in short, be used as described in the '312 application to produce acetic acid 22 for conversion to isobutene 24 in the presence of the Zn x Zr y O z mixed oxide catalysts, but homoacetogenic fermentation methods are considered preferable in that carbon dioxide is not produced as a byproduct - the carbon dioxide represents a yield loss from the overall process to make isobutene and as a greenhouse gas is undesirable particularly in the context of a process to make a needed product more sustainably from renewable resources.
  • the acetic acid feedstock 22 can be made from ethanol 32, according to any of several known methods employing oxidative fermentation with acetic acid bacteria of the genus Acetobacter.
  • the acetic acid feedstock 22 can be made from methanol 34 through combination with carbon monoxide according to the most industrially used route for making acetic acid, for example, in the presence of a catalyst under conditions effective for the carbonylation of methanol.
  • a catalyst under conditions effective for the carbonylation of methanol.
  • a variety of carbonylation catalysts are known in this regard, see, for example, US 5,672,743; US 5,728, 871 ; US 5,773,642; US 5,883,289; US 5,883,295.
  • methanol 34 from carbon dioxide (such as may be produced in the production of ethanol 32 by fermentation or recovered from combustion processes or other industrial emissions) and from carbon dioxide, carbon monoxide and hydrogen derived from the gasification of a biomass, though it will be appreciated that methanol 34 or these "building block" gases can alternately or additionally be obtained from a biomass by anaerobic digestion through methane, from electrolysis of water using energy from geothermal sources, by electrolytic cleavage of carbon dioxide to produce carbon monoxide and water and so forth. As well, it will be appreciated that the methanol 34 could be prepared from methane from natural gas, but preferably a substantial proportion and more preferably all of the methanol 34 used will be wholly biobased.
  • Ethanol to isobutene runs were conducted with the catalysts thus prepared in a fixed-bed stainless steel reactor, having an inside diameter of 5 millimeters. A given amount of catalyst was packed between quartz wool beds. A thermocouple was placed in the middle of the catalyst bed to monitor the reaction temperatures. Before beginning the reaction, the catalyst beds were first pretreated by flowing 50 ml/minute of nitrogen at 450 degrees Celsius through the catalyst over a half hour, then a mixture of ethanol/water at steam to carbon ratios from 1 to 5 was introduced into an evaporator at 180 degrees Celsius by means of a syringe pump and carried into the reactor by the flowing nitrogen carrier gas. Meanwhile, the product line was heated to in excess of 150 degrees Celsius before a cold trap, to avoid condensing the liquid products in the product line.
  • a 25 weight percent solution of acetic acid in water was then introduced into an evaporator at 180 degrees Celsius by means of a syringe pump, and the vaporized steam/acetic acid was carried into the reactor by a flowing nitrogen carrier gas at an acetic acid concentration in the gas phase of 1.36 weight percent and a WHSV of 0.1 grams of acetic acid per gram of catalyst per hour. Meanwhile, the product line was heated to in excess of 150 degrees Celsius before a cold trap, to avoid condensing the liquid products in the product line.
  • a number of additional catalysts were prepared by first drying commercial zirconium hydroxide at 120 degrees Celsius for more than 5 hours. Calculated amounts of Zn(N0 3 ) 2 (from Sigma-Aldrich, more than 99.8 percent purity) were dissolved in water to form a series of clear solutions. The dried zirconium hydroxide (also from Sigma-Aldrich, more than 99.8 percent purity) was then mixed with the solutions in turn by incipient wetness, in order to form wet powders impregnated with Zn in certain proportions to the zirconium in the form of the dried zirconium hydroxide powder.
  • the wetted powders were then dried at 80 degrees Celsius for 4 hours, followed by calcination at the temperature indicated in Table 1 below for 3 hours, to obtain a series of Zn x Zr y O z catalysts by an incipient wetness method.
  • These catalysts were used to convert ethanol to isobutene in the manner of Example 1.
  • Particular reaction conditions whether the reaction temperature, WHSV or steam to carbon ratio, for example, were varied to compare the effect on the selectivities to acetone and isobutene at full conversion of the ethanol.
  • some amount of sulfur was purposely doped into the catalyst to assess the effect of sulfur at those certain levels on the selectivities to acetone and to isobutene.
  • the catalyst for example 28 was doped with 10 ppm of sulfur
  • for example 29 the catalyst was doped with 50 ppm of sulfur and for example 30 with 200 ppm (by weight).
  • additional Zn x Zr y O z mixed oxide catalysts_ were prepared both by the incipient wetness method (IW in Table 2 below) but also by the prior art hard template method (HT), and these were evaluated and the products analyzed using the same apparatus and method described above but under different sets of reaction conditions (as summarized in Table 2 below).

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Abstract

Cette invention concerne des procédés de production d'acide méthacrylique par l'intermédiaire de méthacroléine obtenue à partir d'un bio-iosobutène, le bio-isobutène étant préparé à partir d'éthanol ou d'acide acétique en présence d'un catalyseur à base d'un mélange d'oxydes de type ZnxZryOz, le bio-isobutène étant oxydé en méthacroléine et la méthacroléine étant en outre oxydée en acide méthacrylique.
PCT/US2013/067036 2012-10-31 2013-10-28 Procédés de production d'acide méthacrylique WO2015005942A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105056957A (zh) * 2015-08-17 2015-11-18 上海工程技术大学 生物乙醇制异丁烯的三元复合氧化物催化剂及制备和应用

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