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US-12616963-B2 - Chrome-free copper catalysts for fatty ester hydrogenolysis/hydrogenation

US12616963B2US 12616963 B2US12616963 B2US 12616963B2US-12616963-B2

Abstract

A method of preparing a calcined hydrogenolysis/hydrogenation catalyst includes mixing a copper-containing material, manganese-containing material, sodium aluminate, and water to obtain an aqueous slurry; contacting the aqueous slurry with a caustic material to form a precipitate in a caustic aqueous slurry; removing the precipitate from the caustic aqueous slurry; and removing residual water from the precipitate to form a dried precipitate; calcining the dried precipitate to form the calcined hydrogenolysis/hydrogenation catalyst exhibiting a Brunauer-Emmett-Teller (“BET”) surface area of about 5 m 2 /g to about 75 m 2 /g. The calcined hydrogenolysis/hydrogenation catalyst may include a spinel structure crystallite size of about 15 nm or less. The calcined hydrogenolysis/hydrogenation catalyst may include a tenorite crystallite size of about 20 nm to 30 nm.

Inventors

  • Jian-Ping Chen
  • Arunabha Kundu
  • Joseph C. Dellamorte

Assignees

  • BASF CORPORATION

Dates

Publication Date
20260505
Application Date
20210624

Claims (8)

  1. 1 . A powder form hydrogenolysis/hydrogenation catalyst comprising: copper oxide; manganese oxide; and alumina; wherein the hydrogenolysis/hydrogenation catalyst has a Brunauer-Emmett-Teller (“BET”) surface area of about 5 to about 75 m 2 /g, wherein the catalyst, when calcined, exhibits particle size distribution d 50 from about 4 μm to about 12 μm in diameter, wherein the catalyst, when calcined, exhibits spinel structure at about 55 to about 70 percent by weight of the CuO in the catalyst and exhibits tenorite structure at about 30 to about 45 percent by weight of the CuO in the catalyst, and wherein the hydrogenolysis/hydrogenation catalyst is substantially free of chromium and is not in the presence of a binder.
  2. 2 . The hydrogenolysis/hydrogenation catalyst of claim 1 , wherein the hydrogenolysis/hydrogenation catalyst exhibits a crystal phase of CuAl 2 O 4 , Cu 1.5 Mn 1.5 O 4 , Cu 3 Mn 3 O 8 , Cu 0.451 Mn 0.594 O 2 , Mn 2 O 3 , MnAl 2 O 4 , or a combination of any two or more thereof, and wherein the BET surface area of the hydrogenolysis/hydrogenation catalyst is about 20 m 2 /g to about 70 m 2 /g.
  3. 3 . The hydrogenolysis/hydrogenation catalyst of claim 1 , wherein the hydrogenolysis/hydrogenation catalyst comprise spinel structures having a crystallite size about 15 nm or less or wherein the hydrogenolysis/hydrogenation catalyst comprises tenorite structures having a crystallite size of about 20 nm to about 30 nm.
  4. 4 . The hydrogenolysis/hydrogenation catalyst of claim 1 comprising CuO from about 35 wt % to about 65 wt %, Mn 2 O 3 from about 8 wt % to about 60 wt %, and Al 2 O 3 from about 2 wt % to about 40 wt %.
  5. 5 . The hydrogenolysis/hydrogenation catalyst of claim 1 exhibiting a crystal phase of CuO and one or more phases selected from CuAl 2 O 4 , Cu 1.5 Mn 1.5 O 4 , Cu 3 Mn 3 O 8 , Cu 0.451 Mn 0.594 O 2 , Mn 2 O 3 , MnAl 2 O 4 .
  6. 6 . A method of hydrogenating a carbonyl-containing organic compound, the method comprising contacting the carbonyl-containing organic compound with the hydrogenolysis/hydrogenation catalyst of claim 1 .
  7. 7 . The method of claim 6 , wherein the method is carried out in a slurry phase reactor.
  8. 8 . A catalyst comprising: copper oxide; manganese oxide; and alumina; wherein the catalyst has a Brunauer-Emmett-Teller (“BET”) surface area of about 5 to about 75 m 2 /g, wherein the catalyst, when calcined, exhibits particle size distribution d 50 from about 4 μm to about 12 μm in diameter, wherein the catalyst, when calcined, exhibits spinel structure at about 55 to about 70 percent by weight of the CuO in the catalyst and exhibits tenorite structure at about 30 to about 45 percent by weight of the CuO in the catalyst, and wherein the catalyst is substantially free of chromium and is not in the presence of a binder.

Description

CROSS-REFERENCE TO RELATED APPLICATION(S) This application is a national stage entry under 35 U.S.C. § 371 of International Application No. PCT/US2021/038934, filed on Jun. 24, 2021, which claims the priority to U.S. Provisional Patent Application No. 63/045,967, filed on Jun. 30, 2020. The contents of these applications are hereby incorporated by reference herein in their entirety. TECHNOLOGY The present technology relates generally to the field of catalysts for hydrogenolysis/hydrogenation. More specifically, it is related to copper-manganese-aluminum based catalysts in powder form slurry phase for fatty acid ester hydrogenolysis/hydrogenation. BACKGROUND Commercial slurry processes for producing fatty alcohols typically employ copper-chromium (CuCr) catalysts. As environmental regulation becomes stricter on chromium containing chemicals or catalysts, it is crucial to develop catalysts that do not contain chromium but instead utilize other materials as both chemical and mechanical stability promoters. SUMMARY In one aspect, the present technology provides a method of preparing a calcined hydrogenolysis/hydrogenation catalyst, the method includes: mixing a copper-containing material, a manganese-containing solution, and sodium aluminate solution; adding a caustic material to form an aqueous slurry that includes a precipitate; collecting the precipitate; drying the precipitate to form a dried precipitate; and calcining the dried precipitate to form the calcined hydrogenolysis/hydrogenation catalyst; wherein: the calcined hydrogenolysis/hydrogenation catalyst exhibits a Brunauer-Emmett-Teller (“BET”) surface area of about 5 m2/g to about 75 m2/g; and the calcined hydrogenolysis/hydrogenation catalyst is substantially free of chromium. In some embodiments, the calcined hydrogenolysis/hydrogenation catalyst may have a spinel structure crystallite size of about 15 nm or less. In some embodiments, the calcined hydrogenolysis/hydrogenation catalyst may have a tenorite crystallite size of about 20 nm to 30 nm. In another aspect, the present technology provides a calcined hydrogenolysis/hydrogenation catalyst prepared according to the method described herein in any embodiment. In a related aspect, the present technology provides a hydrogenolysis/hydrogenation catalyst that includes: copper oxide; manganese oxide; and alumina; wherein the hydrogenolysis/hydrogenation catalyst has a Brunauer-Emmett-Teller (“BET”) surface area of about 5 to about 75 m2/g, and wherein the hydrogenolysis/hydrogenation catalyst is substantially free of chromium. In another related aspect, the present technology provides a method of hydrogenating a carbonyl-containing organic compound, the method includes contacting the carbonyl-containing organic compound with a hydrogenolysis/hydrogenation catalyst that includes: copper oxide; manganese oxide; and alumina; wherein: the hydrogenolysis/hydrogenation catalyst exhibits a Brunauer-Emmett-Teller (“BET”) surface area of about 5 to about 75 m2/g. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a three line graph showing particle size formation during precipitation by the size of d10 (d=0.1), d50 (d=0.5), and d90 (d=0.9) for Example 1. FIG. 2 is a graph relating to particle size formation as a function of time based upon “Volume In,” according to Example 1. As described herein, each plot shows the Cumulative Volume % (vol %) distribution of particles detected via laser diffraction within a particle size range. FIG. 3 is a graph relating to particle size formation as a function of time based upon “percent passing,” according to Example 1. As described herein, each plot shows a normal distribution curve in which a majority of the sample volume is occupied by the mid-range sized particles (i.e., Volume %). FIG. 4 is a graph showing the XRD spectra for the catalyst of Example 2, according to the examples. FIG. 5 is a graph showing the XRD spectra for the catalyst of Example 3, according to the examples. FIG. 6 is a graph showing the XRD spectra for the catalyst of Example 4, according to the examples. FIG. 7 is a graph showing the XRD spectra for the catalyst of Example 5, according to the examples. FIG. 8 is a graph showing the XRD spectra for the catalyst of Example 7, according to the examples. FIG. 9 is a graph showing the XRD spectra for the catalyst of Example 8, according to the examples. FIG. 10 is a graph comparing methyl ester conversion as a percentage as a function of time for a standard CuCr catalyst, a CuAl catalyst, and the described Cu—Mn—Al catalyst, according to the examples. FIG. 11 is a graph comparing fatty alcohol selectivity as a percentage as a function of time for a standard CuCr catalyst, a CuAl catalyst, and the described Cu—Mn—Al catalyst, according to the examples. FIG. 12 is a graph comparing fatty alcohol yield as a percentage as a function of time for a standard CuCr catalyst, a CuAl catalyst, and the described Cu—Mn—Al catalyst, according to the examples. FIG. 13 is a gr