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Title: Conversion of 2,3-butanediol to butadiene

Abstract

A composition comprising 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by exposure to a catalyst comprising (a) M.sub.xO.sub.y wherein M is a rare earth metal, a group IIIA metal, Zr, or a combination thereof, and x and y are based upon an oxidation state of M, or (b) M.sup.3.sub.a(PO.sub.4).sub.b where M.sup.3 is a group IA, a group IIA metal, a group IIIA metal, or a combination thereof, and a and b are based upon the oxidation state of M.sup.3. Embodiments of the catalyst comprising M.sub.xO.sub.y may further include M.sup.2, wherein M.sup.2 is a rare earth metal, a group IIA metal, Zr, Al, or a combination thereof. In some embodiments, 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by a catalyst comprising M.sub.xO.sub.y, and the methyl vinyl carbinol is subsequently dehydrated to 1,3-butadiene by exposure to a solid acid catalyst.

Inventors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1322100
Patent Number(s):
9,434,659
Application Number:
14/607,871
Assignee:
Battelle Memorial Institute (Richland, WA) PNNL
DOE Contract Number:
AC05-76RL01830
Resource Type:
Patent
Resource Relation:
Patent File Date: 2015 Jan 28
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lilga, Michael A., Frye, Jr, John G., Lee, Suh-Jane, and Albrecht, Karl O. Conversion of 2,3-butanediol to butadiene. United States: N. p., 2016. Web.
Lilga, Michael A., Frye, Jr, John G., Lee, Suh-Jane, & Albrecht, Karl O. Conversion of 2,3-butanediol to butadiene. United States.
Lilga, Michael A., Frye, Jr, John G., Lee, Suh-Jane, and Albrecht, Karl O. Tue . "Conversion of 2,3-butanediol to butadiene". United States. doi:. https://www.osti.gov/servlets/purl/1322100.
@article{osti_1322100,
title = {Conversion of 2,3-butanediol to butadiene},
author = {Lilga, Michael A. and Frye, Jr, John G. and Lee, Suh-Jane and Albrecht, Karl O.},
abstractNote = {A composition comprising 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by exposure to a catalyst comprising (a) M.sub.xO.sub.y wherein M is a rare earth metal, a group IIIA metal, Zr, or a combination thereof, and x and y are based upon an oxidation state of M, or (b) M.sup.3.sub.a(PO.sub.4).sub.b where M.sup.3 is a group IA, a group IIA metal, a group IIIA metal, or a combination thereof, and a and b are based upon the oxidation state of M.sup.3. Embodiments of the catalyst comprising M.sub.xO.sub.y may further include M.sup.2, wherein M.sup.2 is a rare earth metal, a group IIA metal, Zr, Al, or a combination thereof. In some embodiments, 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by a catalyst comprising M.sub.xO.sub.y, and the methyl vinyl carbinol is subsequently dehydrated to 1,3-butadiene by exposure to a solid acid catalyst.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Sep 06 00:00:00 EDT 2016},
month = {Tue Sep 06 00:00:00 EDT 2016}
}

Patent:

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  • Embodiments of an integrated method for step-wise conversion of 2,3-butanediol to 2-butanol, and optionally to hydrocarbons, are disclosed. The method includes providing an acidic catalyst, exposing a composition comprising aqueous 2,3-butanediol to the acidic catalyst to produce an intermediate composition comprising methyl ethyl ketone, providing a hydrogenation catalyst that is spatially separated from the acidic catalyst, and subsequently exposing the intermediate composition to the hydrogenation catalyst to produce a composition comprising 2-butanol. The method may further include subsequently exposing the composition comprising 2-butanol to a deoxygenation catalyst, and deoxygenating the 2-butanol to form hydrocarbons. In some embodiments, the hydrocarbons comprisemore » olefins, such as butenes, and the method may further include subsequently exposing the hydrocarbons to a hydrogenation catalyst to form saturated hydrocarbons.« less
  • 2,3-Butanediol is a feedstock chemical of potential industrial importance. It can serve as a monomer for many polymers of consumer interest that are currently supplied by the fossil fuel industry. Bacillus polymyxa can grow on inexpensive waste products of the food-processing industry and produce this glycol. This paper describes a mutant strain of B. polymyxa which displays constitutive production of catabolic ..cap alpha..-acetolactate synthase, an enzyme in the 2,3-butanediol pathway which is normally produced only in the late log or stationary phase of growth. The mutant was obtained by treating the wild type with nitrosoguanidine and subjecting it to amore » penicillin counterselection procedure. One of the selected mutant strains produced four times as much of the glycol as the wild type and utilized approximately 25% of the energy source, compared with essentially complete utilization of the energy source by the wild type. Studies are under way to optimize the production of the glycol by the mutant.« less
  • Paired synthesis, an energy-efficient electrochemical process, was applied to two biomass derived feedstocks. Sorbitol and calcium gluconate were produced by pairing electrochemical reduction of glucose with indirect electrogenerated bromine oxidation of glucose. The optimum electrode materials and operating conditions for the paired synthesis are: Raney nickel powder cathode, a packed bed anode of graphite chips, an initial glucose concentration of 1.6 M, a 0.4 M calcium bromide electrolyte, ca. pH 7, 60/sup 0/C, applied current of 25 mA per gram of cathode material, a solution velocity of 0.08 cm/sec, a six-minute residence time outside the reactor and parallel electrolyte solutionmore » and current flow. The 2,3-butanediol paired synthesis consisted of oxidation of acetoin by electrogenerated bromine at the anode followed by the electro-reduction of acetoin to 2-butanone at the cathode. The high boiling 2,3-butanediol is converted to the low boiling 2-butanone via the paired synthesis, which facilitates the recovery process. The optimum electrode materials and operating conditions for the 2,3-butanediol paired synthesis are: an amalgamated zinc cathode, a packed bed anode of graphite chips, 1 M 2,3-butanediol, 0.02 M acetoin, 1 M NaBr, ca. pH 7, 20/sup 0/C, 1.4 mA/cm/sup 2/ cathode current density, 1 mA/cm/sup 2/ anode current density, 0.04 cm/sec solution velocity, 4 minute residence time outside the reactor, and parallel electrolyte solution and current flow.« less
  • The bioconversion of sugars present in wood hemicellulose to 2,3-butanediol by Klebsiella pneumoniae grown on high sugar concentrations was investigated. When K. pneumoniae was grown under finite air conditions in the presence of added acetic acid, 50 g of D-glucose and D-xylose per liter could be converted to 25 and 27 g of butanediol per liter, respectively. The efficiency of bioconversion decreased with increasing sugar substrate concentrations (up to 200 g/liter). Butanediol production at low sugar substrate concentrations was less efficient when the organism was grown under aerobic conditions; however, final butanediol values were higher for cultures grown on anmore » initial sugar concentration of 150 g/liter, particularly when the inoculum was first acclimatized to high sugar levels. When a double fed-batch approach (daily additions of sugars together with yeast extract) was used under aerobic conditions, up to 88 and 113 g of combined butanediol and acetyl methyl carbinol per liter could be obtained from the utilization of 190 g of D-xylose and 226 g of D-glucose per liter, respectively. 22 references.« less
  • The respiratory quotient (RQ) was found to be a suitable control parameter for optimum oxygen supply for the production of 2,3-butanediol + acetoin under microaerobic conditions. In laboratory scale continuous cultures optimum production of 2,3-butanediol + acetoin was obtained at an RQ value between 4.0 to 4.5. This agreed well with the optimum RQ value (4.0) stoichiometrically derived from the bioreactions involved. In fed-batch cultures product concentration as high as 102.9 g/L can be achieved within 32 h cultivation with an RQ control algorithm for oxygen supply. Under similar conditions only 85.7 g/L product was obtained with control of constantmore » oxygen supply rate throughout the cultivation. In pilot scale batch cultures under identical oxygen supply rate the achievable RQ value was found to be strongly influenced by the reactor type and scale. The initial oxygen supply rate influenced the achievable RQ as well. However, in all the reactors studied the specific product formation rate of cells in the exponential growth phase was only a function of RQ. The same optimum RQ value as found in continuous cultures was obtained. It was thus concluded that RQ can be used as a control parameter for optimum production of 2,3-butanediol + acetoin in both laboratory and pilot plant scale reactors.« less