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WO2014204509A1 - Procédé et catalyseur de conversion d'acide acétique en isobutène et propylène - Google Patents

Procédé et catalyseur de conversion d'acide acétique en isobutène et propylène Download PDF

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Publication number
WO2014204509A1
WO2014204509A1 PCT/US2013/063644 US2013063644W WO2014204509A1 WO 2014204509 A1 WO2014204509 A1 WO 2014204509A1 US 2013063644 W US2013063644 W US 2013063644W WO 2014204509 A1 WO2014204509 A1 WO 2014204509A1
Authority
WO
WIPO (PCT)
Prior art keywords
isobutene
propylene
hydrogen
catalyst
acetic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2013/063644
Other languages
English (en)
Inventor
Sun JUNMING
Liu SHANGJUN
Wang Yong
Colin Smith
Kevin Martin
Padmesh Venkitasubramanian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Archer Daniels Midland Co
Washington State University WSU
Original Assignee
Archer Daniels Midland Co
Washington State University WSU
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
Application filed by Archer Daniels Midland Co, Washington State University WSU filed Critical Archer Daniels Midland Co
Publication of WO2014204509A1 publication Critical patent/WO2014204509A1/fr
Priority to US14/683,236 priority Critical patent/US9580365B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2072—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by condensation
    • C07C1/2074—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by condensation of only one compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This application concerns renewable source-derived isobutene and propylene and processes for making isobutene and propylene.
  • isobutene is widely used for the production of a variety of industrially important products, such as butyl rubber for example.
  • Isobutene has been produced commercially to date through the catalytic or steam cracking of fossil feedstocks, and the development of a commercially viable process for the manufacture of Isobutene from a renewable source-based feedstock is increasingly Important as fossil resources are depleted and/or become more costly to use - especially in consideration of increased demand for isobutene.
  • the objectives of the hard template method were to suppress ethanol dehydration end acetone polymerization, while enabling a surface basic site-catalyzed ethanol dehydrogenation to acetaldehyde, an aeetaldehyde to acetone conversion via aidol- condensation/dehydrogenafion, and a Brdnsted and Lewis acidic/basic site- catalyzed acetone-to-isobutene reaction pathway.
  • the present invention concerns the still further discovery that the Zn >: Zr y O;-; mixed oxide catalysts (whether made by the hard template method or by the method of the '433 application) are also able, in the presence of hydrogen, to produce renewable source-based propylene from acetic acid. Additionally, propylene can be produced as the more favored product from the acetic acid, in comparison to the isobutene product.
  • the present invention relates to a process for converting acetic acid to propylene In the presence of a catalyst, and in the farther presence of hydrogen.
  • Propylene is itself an important industrial chemical, and the capacity to selectively produce propylene in a certain proportion alongside isobutene through using the same mixed oxide catalyst (by adjusting the amount of hydrogen used and/or by additional adjustments in reaction conditions as further Illustrated hereafter) adds substantial value for those skilled in the art.
  • the Invention can be understood as relating to a process for converting acetic acid to both of propylene and isobutene as co-products.
  • propylene is produced preferentially compared to isobutene.
  • the relative proportion of propylene and isobutene products is altered by adjusting the amount of hydrogen present.
  • acetic acid can be made by a variety of methods from a number of different starting materials, including through carhonylation of methanol derived from sequestered carbon dioxide, for example, the capability of these mixed oxide catalysts to catalyze the conversion of acetic ac d to such valuable products enables a range of options for utilizing renewable resources more efficiently, ail as described in greater detail hereafter.
  • FIG. 1 schematically depicts particular embodiments of a process according to the second aspect, wherein acetic acid is converted to propylene and Isobutene in the presence of a catalyst and in the further presence of hydrogen, wherein various options for obtaining the acetic acid are suggested.
  • Figure 2 shows the yields of products in a process according to the '312 application over time, carried out as described In Example 1 (Not of the invention) below.
  • FIG. 3 shows the effect of added hydrogen on the product distribution in the conversion of acetic acid to Isobutene in a process otherwise carried out as in the '312 application (and as further described in Examples 2 and 3 below), while employing an improved stability mixed oxide catalyst as described in the '433 application in the presence of the added hydrogen.
  • Figure 4 shows the yields of the various products found in a process of the present invention over time, as described further in Example 5 below.
  • Figure 5 shows how the product distribution Is altered by using different partial pressures of hydrogen in Examples 5 through 8, in converting acetic acid to products including Isobutene and propylene over an improved stability mixed oxide catalyst as described in the '433 application. . Description Of Embodiments
  • FIG. 1 a preferred but purely Illustrative embodiment 10 of a process of the present invention is schematically illustrated, wherein acetic acid 12 is converted to isobutene 14 and propylene 18 in the presence of a catalyst and further in the presence of hydrogen from a source 18 of such hydrogen.
  • a suitable catalyst is a Zn >: Zr y O. 3 ⁇ 4 mixed oxide catalyst.
  • the ZnyZryQ* mixed oxide catalyst can be made by a "bard template” or “confined space synthesis” method generally of the character used by Jacobsen et si., " esoporous Zeolite Single Crystals", Journal of the American Chemical Society, vol. 122, pp. 7116-7117 (2000), wherein nanozeolites were prepared.
  • the same carbon black (BP 2000, Cabot Corp.) may be used as a hard template for the synthesis of nanosized
  • the BP 2000 template Prior to use. the BP 2000 template is dried, for example, at 180 °C overnight.
  • the Zn x Zr y O ⁇ mixed oxide catalysts may be made as described in the '433 application, 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-eontaining 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.
  • the Zn x Zr y 0 2 mixed oxide catalysts are characterized by a 2n/ ⁇ r ratio (xiy) 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 these catalysts or any process described for using these catalysts 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.
  • the catalysts made by the preferred incipient wetness method are consistent In their particle size with the catalysts described in the incorporated journal article, namely, comprising aggregates of less fhanI O nm-sized particles with a highly crystalline structure.
  • the Zn oxide component is again highly dispersed on the Zr oxide component.
  • the Zn x Zr y 0 2 mixed oxide catalysts are characterized as low sulfur catalysts, containing less than 0,14 percent by weight of sulfur
  • the catalysts made by the incipient wetness method were indicated as desirably substantially sulfur-free, preferably including less than 0.01 percent by weight of sulfur and more preferably including less than 0.001 weight percent of sulfur, it was postulated that the reduced sulfur content enabled by the Incipient wetness method as compared to the hard template method contributed significantly to the much improved stability observed for the incipient wetness method catalysts of the prior related application for the ethanol to isobutene process.
  • the zinc and zirconium compounds and solids In these embodiments have a sufficiently low sulfur content in order to produce a low sulfur content when combined according to the preferred incipient wetness method of the '433 application, 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 tor subsequent dtym ' g and conversion to the oxide forms through calcining.
  • low sulfur catalysts can also be made by the incipient wetness method starting with zinc and zirconium compounds that are sulfur-free or substantially sulfur-free, then doping in a desired sulfur content.
  • drying step can be accomplished in a temperature range of from 80 degrees Celsius to 200 degrees Celsius over at least 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.
  • low sulfur catalysts as described herein could be prepared by a hard template method as described in the earlier incorporated publication, except that a suitably very low sulfur content carbon is used for the hard template to realize a low sulfur content in the finished catalyst,
  • the process 10 can be conducted continuously in the gas phase, using a fixed bed reactor or flow bed reactor.
  • the reaction temperature may be in a range from 350 to 700 degrees Celsius, preferably, In a range from 400 to 600 degrees Celsius, and 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 " ⁇
  • Acetic acid/water solutions with steam to carbon ratios from 0 to 20. preferably from 2 to 5 can be used to provide acetic acid to the catalyst.
  • Hydrogen is supplied from a source 18, generally In combination with an inert carrier gas such as nitrogen.
  • an inert carrier gas such as nitrogen.
  • hydrogen would comprise at least 20 percent by volume but not more than 80 percent by volume of a combined hydrogen/nitrogen gas mixture
  • the maximum proportion of propylene that can be achieved by adjusting the partial pressure of hydrogen in a reactor can be expected to vary- somewhat based on differences in reaction temperature, in the use of different Zn x Zr y O z mixed oxide-type catalysts (whether made by the hard template or incipient wetness methods) and other like considerations, but generally it is expected that at least some proportion of isobutene will always be present as a co-product with propylene, even using pure hydrogen - in contrast to the production of isobutene to the exclusion of propylene that is enabled where no hydrogen is present. In any event, it is considered that those skilled in the ad will be well able by routine optimization to determine how much hydrogen is needed to produce the desired propylene and isobutene products in an economically advantageous proportion to one another.
  • the acetic acid 12 can be obtained by various methods from a number of starting materials, which in turn permits a number of integrated processes to be considered for providing improved utilization of renewable resources.
  • acetic acid can be produced from a source of five and six carbon sugars 20 by fermentation
  • US 8,509,180 and US 8,252,567 seek to improve upon known processes for making ethanol and
  • hutanol/hexanol respectively, by means including the fermentation of five and six carbon sugars into acetic acid.
  • the acetic acid is
  • the ethanol formed in this manner can be used to make butan s! and hexanoi, by subjecting the ethanol with acetate, acetic acid or mixtures thereof to an acidogenic fermentation using, for example, species of the bacteria Clostridium (Clostridium kiuyveri is mentioned), to produce butyrate, butyric acid, caproate, caproic acid or mixtures thereof.
  • the fermentation of five and six carbon sugars to form acetic acid 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.
  • bomoacetogens given by US 8,252,567 are microorganisms of the genus Mooreila and Clostridium, especially
  • the acetic acid feedstock 12 can be made from ethane! 22, according to any of several known methods employing oxidative fermentation with acetic acid bacteria of the genus Aceiobacter,
  • the acetic acid feedstock 12 can be made from methanol 24 through combination wi h 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 5,872,743; US 5 1 728 ! 871 ; US 5,773,642; US 5,883,289; US 5,883.295.
  • syngas may be produced by gasification of a biomass, and methanol then produced from the syngas with additional hydrogen provided, for example, through electrolysis of water.
  • the electrical energy required for the electrolysis may in turn be generated from combustion of additional biomass, through steam from heat energy captured from the methanol synthesis or from combustion of a biomass fraction (llgnin, for example), with optional capture and recycle of carbon dioxide from the flue gas to be used in the methanol synthesis.
  • a variety of options for producing methanol from biomass have been presented in the literature, see, for example, US 2007/0254969 A1 by Olah et al; US 8,645,442 and US
  • acetic acid feedstock 12 may be made using renewable resources inclusive fundamentally of foio ass, carbon monoxide and carbon dioxide gases.
  • the required acetic acid may be made at least in some part by anaerobic fermentation using carbon monoxide and carbon dioxide gases themselves for a carbon source.
  • the catalyst thus prepared was then placed in a fixed-bed stainless steel reactor having an inside diameter of 5 millimeters, with 100 mg of the catalyst being packed between quartz wool beds.
  • a thermocouple was placed in the middle of the catalyst bed to monitor the reaction temperature.
  • the catalyst bed was pretreated by flowing 50 ml/minute of nitrogen at 450 degrees Celsius through the catalyst over a half hour.
  • 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 earner gas at an acetic acid concentration in the gas phase of 1 ,38 weight percent and a WHSV of 0.1 grams of acetic acid per gram of catalyst per hour.
  • No hydrogen was input to the reactor, 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 reaction temperature of 415 degrees Celsius was employed.
  • an online micro-GC MicroGC 3000A equipped with molecular sieves 5A, plot U columns and thermal conductivity detectors was used to analyze the product gases specifically, using nitrogen as a reference gas.
  • [0O48J Figure 2 shows the results of a one-pass durability test of the Zn;2r. 3 ⁇ 4 0 £ catalyst prepared by the incipient wetness impregnation method.
  • the catalyst showed very high stability over the full duration of the run, with no signs of observable deactivation after more than 1400 minutes of time-on-stream operation.
  • [OOSOJ Figure 4 shows the results over time in a one-pass durability test of the same ZniZr 8 0 2 catalyst as used in previous examples, at a reaction temperature of 450 degrees Celsius and using the 50/50 H 2 /N 2 mixture. After 15 hours on stream, little to no deactivation was observed, indicating the stability seen in Example 1 (Not of the Invention) in converting acetic acid to isobutene was not compromised in producing propylene from acetic acid with the catalyst and with hydrogen addition.
  • Figure 5 displays the varying product distributions realized using a Zr Zr-toOz mixed oxide catalyst prepared in the same manner as in Example 1 (Not of the Invention) except in relation to the ratio of Zn to Zr, and run in the manner, using the apparatus and reaction conditions of Example 4 hut also varying the amount of hydrogen used in combination with nitrogen. More particularly, mixtures of hydrogen and nitrogen were used that employed 20 volumetric percent, 50 percent, 80 percent and 100 percent of hydrogen, with the balance if any being nitrogen.
  • propylene and isobutene were produced in a roughly 50/50 proportion to one another with the 20/80 mixture of hydrogen and nitrogen, while no greater proportion of propylene was realized relative to isobutene under the conditions tested and with the indicated catalyst above a hydrogen content of about 80 percent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé pour convertir l'acide acétique en propylène et isobutène à titre de principaux produits hydrocarbonés effectué, en présence d'un catalyseur et en présence en outre d'hydrogène. Dans certains modes de réalisation, un catalyseur à base d'un mélange d'oxydes ZnxZryOz est utilisé pour mettre en œuvre un procédé en phase gazeuse, et le propylène est produit de préférence à l'isobutène en utilisant au moins une certain quantité d'hydrogène dans le procédé. Dans d'autres modes de réalisation, un catalyseur à base d'un mélange d'oxydes ZnxZryOz obtenu par un procédé d'imprégnation à humidité naissante est utilisé et recommandé comme étant très stable pour procéder à la conversion.
PCT/US2013/063644 2012-10-31 2013-10-07 Procédé et catalyseur de conversion d'acide acétique en isobutène et propylène Ceased WO2014204509A1 (fr)

Priority Applications (1)

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US14/683,236 US9580365B2 (en) 2012-10-31 2015-04-10 Process and catalyst for conversion of acetic acid to isobutene and propylene

Applications Claiming Priority (2)

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US201361836190P 2013-06-18 2013-06-18
US61/836,190 2013-06-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150210607A1 (en) * 2012-10-31 2015-07-30 Archer Daniels Midland Company Use of byproduct acetic acid from oxidative methods of making acrylic acid and/or methacrylic acid
CN108097300A (zh) * 2017-12-15 2018-06-01 南开大学 用于乙酸转化制备异丁烯的催化剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090124835A1 (en) * 2005-11-01 2009-05-14 Tatsuo Yamaguchi Processes for production of isobutene and tertiary butanol
WO2011112503A1 (fr) * 2010-03-08 2011-09-15 Dow Global Technologies Llc Composition de catalyseur pour la conversion directe d'éthanol en propylène

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090124835A1 (en) * 2005-11-01 2009-05-14 Tatsuo Yamaguchi Processes for production of isobutene and tertiary butanol
WO2011112503A1 (fr) * 2010-03-08 2011-09-15 Dow Global Technologies Llc Composition de catalyseur pour la conversion directe d'éthanol en propylène

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LID, C. ET AL.: "A study of ZnxZryOz mixed oxides for direct conversion of ethanol to isobutene", APPLIED CATALYSIS A: GENERAL, vol. 467, 15 July 2013 (2013-07-15), pages 91 - 97 *
SUN, J. ET AL.: "Direct conversion of bio-ethanol to isobutene on nanosized ZnxZryOz mixed oxides with balanced acid-base sites", JOURNAL OF THE AMERIC- AN CHEMICAL SOCIETY, vol. 133, 2011, pages 11096 - 11099 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150210607A1 (en) * 2012-10-31 2015-07-30 Archer Daniels Midland Company Use of byproduct acetic acid from oxidative methods of making acrylic acid and/or methacrylic acid
US9156746B2 (en) * 2012-10-31 2015-10-13 Washington State University Use of byproduct acetic acid from oxidative methods of making acrylic acid and/or methacrylic acid
CN108097300A (zh) * 2017-12-15 2018-06-01 南开大学 用于乙酸转化制备异丁烯的催化剂及其制备方法

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