阅读说明：本技术 铜挤出物催化剂及用于氢化和氢解的应用 (Copper extrudate catalyst and use for hydrogenation and hydrogenolysis ) 是由 陈建平 A·孔杜 M·安杰尔 于 2020-03-19 设计创作，主要内容包括：一种氢解催化剂,所述氢解催化剂包含催化组分,所述催化组分包含氧化铜、氧化锰和氧化铝；以及粘结剂,所述粘结剂包含锆组分,其中所述催化剂包含至少约30.0重量％的氧化铜,并且所述催化剂基本上不含硅或其氧化物。所述氢解催化剂可有效地将脂肪酸酯转化为脂肪醇。(A hydrogenolysis catalyst comprising a catalytic component comprising copper oxide, manganese oxide, and aluminum oxide; and a binder comprising a zirconium component, wherein the catalyst comprises at least about 30.0 wt% copper oxide, and the catalyst is substantially free of silicon or oxides thereof. The hydrogenolysis catalyst is effective to convert the fatty acid ester to the fatty alcohol.)

1. A hydrogenolysis catalyst comprising:

a catalytic component comprising copper oxide, manganese oxide, and aluminum oxide; and

a binder, the binder comprising a zirconium component,

wherein:

the catalyst comprises at least about 30.0 wt.% copper oxide, and

the catalyst is substantially free of silicon or oxides thereof.

2. The hydrogenolysis catalyst of claim 1 wherein the copper oxide is present in an amount of about 35 wt% to about 75 wt% based on the weight of the hydrogenolysis catalyst.

3. The hydrogenolysis catalyst of claim 1 or 2 wherein the copper oxide is present in an amount of about 45 wt.% to about 55 wt.%.

4. The hydrogenolysis catalyst of any one of claims 1-3 wherein the manganese oxide is present in an amount of about 0 wt% to about 10 wt% by weight of the hydrogenolysis catalyst.

5. The hydrogenolysis catalyst of any one of claims 1-4 wherein the manganese oxide is present in an amount of about 5 wt% to about 12 wt% based on the weight of the hydrogenolysis catalyst.

6. The hydrogenolysis catalyst of any one of claims 1-5 wherein the alumina is present in an amount of about 15 wt% to about 40 wt% by weight of the hydrogenolysis catalyst.

7. The hydrogenolysis catalyst of any one of claims 1-6 wherein the alumina is present in an amount of about 20 wt.% to about 35 wt.% by weight of the hydrogenolysis catalyst.

8. The hydrogenolysis catalyst of any one of claims 1-7 wherein the zirconium component is zirconium oxide.

9. The hydrogenolysis catalyst of any one of claims 1-8 wherein the zirconium component is present in an amount of about 4 wt% to about 15 wt% by weight of the hydrogenolysis catalyst.

10. The hydrogenolysis catalyst of any one of claims 1-9 wherein the zirconium component is present in an amount of about 5 wt% to about 12 wt% based on the weight of the hydrogenolysis catalyst.

11. The hydrogenolysis catalyst of any one of claims 1-10 wherein the binder further comprises alumina.

12. The hydrogenolysis catalyst of any one of claims 1-11 wherein the hydrogenolysis catalyst further comprises an alkali metal component.

13. The hydrogenolysis catalyst of claim 12 wherein the base metal component comprises sodium.

14. The hydrogenolysis catalyst of any one of claims 1-13 wherein the alkali metal is present in an amount of about 0 wt.% to about 1 wt.%.

15. The hydrogenolysis catalyst of any one of claims 1-14 wherein the hydrogenolysis catalyst is in an unreduced form and exhibits an X-ray powder diffraction curve having 2 Θ peaks at 31.1 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 61.7 °, 64.9 °, 68.1 ° and the hydrogenolysis catalyst is in an unreduced form and exhibits an X-ray powder diffraction curve having 2 Θ peaks.

16. The hydrogenolysis catalyst of any one of claims 1-15 wherein the hydrogenolysis catalyst is a calcined and extruded hydrogenolysis catalyst.

17. The hydrogenolysis catalyst of any one of claims 1-16 wherein the hydrogenolysis catalyst exhibits greater than 0.25cm³Pore volume per gram.

18. The hydrogenolysis catalyst of any one of claims 1-17 wherein the hydrogenolysis catalyst exhibits about 0.8g/cm³To about 1.5g/cm³The packing bulk density of (2).

19. The hydrogenolysis catalyst of any one of claims 1-18 wherein the hydrogenolysis catalyst has about 15m²G to about 70m²(ii) a Bruna-Emmett-Teller ("BET") surface area in grams.

20. The hydrogenolysis catalyst of any one of claims 1-19 wherein the hydrogenolysis catalyst is in the form of a solid extrudate or tablet.

21. The hydrogenolysis catalyst of claim 15 wherein the hydrogenolysis catalyst is in unreduced form and exhibits an X-ray powder diffraction curve having 2 Θ peaks at 18.9 °, 31.1 °, 32.5 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 53.6 °, 58.3 °, 59.1 °, 61.7 °, 64.9 °, 66.8 °, 68.1 °, 72.2 °, 75.1 °, and 77.0 °.

22. A method of preparing a calcined hydrogenation catalyst, the method comprising:

mixing a catalytic component with a binder system and water to obtain a material mixture;

shaping the material mixture to obtain a shaped material mixture;

calcining the shaped material mixture at a temperature and for a time sufficient to cure to form the calcined hydrogenolysis catalyst;

wherein:

the catalytic component comprises copper oxide, manganese oxide and aluminum oxide;

the binder system comprises a zirconium component;

the calcined hydrogenolysis catalyst comprises at least 30 wt.% copper oxide; and is

The calcined hydrogenolysis catalyst is substantially free of silicon or its oxide.

23. The method of claim 22, wherein the catalytic component comprises a pre-calcined powder comprising copper oxide, manganese oxide, and aluminum oxide.

24. The method of claim 23, wherein the pre-calcined powder is calcined at a temperature of about 400 ℃ to about 800 ℃.

25. The method of any one of claims 22 to 24, wherein the zirconium component is zirconium acetate.

26. The method of any one of claims 22-25, wherein the binder system further comprises alumina.

27. The method of any one of claims 22 to 26, further comprising mixing an extrusion aid selected from a polymeric polysaccharide, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, or a mixture of two or more thereof.

28. The method of any one of claims 22 to 27, further comprising removing at least some water from the wet material mixture prior to calcining.

29. The method of any one of claims 22 to 28, wherein the calcining is performed at a temperature of about 200 ℃ to about 1000 ℃.

30. The method of claim 29, wherein the temperature is about 450 ℃ to about 550 ℃.

31. A hydrogenolysis catalyst prepared by the method of any one of claims 22-30.

32. A method of performing hydrogenolysis of a fatty acid ester comprising contacting the fatty acid ester with a hydrogenolysis catalyst comprising:

a catalytic component comprising copper oxide, manganese oxide, and aluminum oxide; and

a binder comprising a zirconium component;

wherein:

the hydrogenolysis catalyst comprises at least 30% copper oxide; and is

The hydrogenolysis catalyst is substantially free of silicon or oxides thereof.

33. The method of claim 32, wherein the fatty acid ester is represented by formula I:

R¹-CO-OR²(I)，

wherein

R¹And R²Each independently of the others, is branched or unbranched C₁To C₂₄Alkyl or branched or unbranched C₂To C₂₄An alkenyl group.

34. The method of claim 33, wherein R¹And R²Each independently is C₁₀To C₁₄Branched or unbranched alkyl or C₁₀To C₁₄A branched or unbranched alkenyl group.

35. The method of claim 33, wherein R¹And R²Each independently is C₁₂To C₁₄Branched or unbranched alkyl.

36. The method of claim 33, wherein when R is¹Is C₁₀To C₁₈Branched or unbranched alkyl or C₁₀To C₁₈When there is a branched or unbranched alkenyl radical, R²Is C₁To C₆An alkyl group.

37. The method of claim 36, wherein R²Is methyl.

38. The method of any of claims 33 to 37, wherein the copper oxide is present in an amount from about 35 wt% to about 75 wt% based on the weight of the hydrogenolysis catalyst.

39. The method of any of claims 33 to 38, wherein the manganese oxide is present in an amount of about 1 wt% to about 20 wt%, based on the weight of the hydrogenolysis catalyst.

40. The method of any of claims 33 to 39, wherein the alumina is present in an amount of about 15 wt% to about 40 wt% based on the weight of the hydrogenolysis catalyst.

41. The method of any one of claims 33 to 40, wherein the zirconium component is zirconium oxide.

42. The method of any of claims 33 to 41, wherein the zirconium component is present in an amount of about 1 wt% to about 20 wt%, based on the weight of the hydrogenolysis catalyst.

43. The method of any one of claims 33-42, wherein the binder further comprises alumina.

44. The method of any one of claims 33 to 43, wherein the hydrogenolysis catalyst further comprises an alkali metal component.

45. The method of claim 44, wherein the alkali metal component comprises sodium.

46. The method of any one of claims 44 or 45, wherein the alkali metal is present in an amount of about 0 wt.% to about 1 wt.%.

47. The process of any one of claims 33 to 46, wherein the hydrogenolysis catalyst is in unreduced form and exhibits an X-ray powder diffraction curve having 2 θ peaks of 31.1 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 61.7 °, 64.9 °, 68.1 °.

48. The method of any one of claims 33 to 47, wherein the hydrogenolysis catalyst is a calcined and extruded hydrogenolysis catalyst.

49. The method of any one of claims 33 to 48, wherein the hydrogenolysis catalyst exhibits greater than 0.25cm³Pore volume per gram.

50. Such asThe method of any of claims 33 to 49, wherein the hydrogenolysis catalyst exhibits about 0.8g/cm³To about 1.5g/cm³The packing bulk density of (2).

51. The method of any one of claims 33 to 50, wherein the hydrogenolysis catalyst has about 15m²G to about 70m²(ii) a Bruna-Emmett-Teller ("BET") surface area in grams.

52. The process of claim 47, wherein the hydrogenolysis catalyst is in unreduced form and exhibits an X-ray powder diffraction curve having 2 θ peaks at 18.9 °, 31.1 °, 32.5 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 53.6 °, 58.3 °, 59.1 °, 61.7 °, 64.9 °, 66.8 °, 68.1 °, 72.2 °, 75.1 ° and 77.0 °.

53. The process of any one of claims 33 to 52, wherein said process is carried out at a temperature of at least about 170 ℃.

54. The method of claim 53, wherein the temperature is about 170 ℃ to about 220 ℃.

55. The hydrogenolysis catalyst of any one of claims 1-21 wherein the hydrogenolysis catalyst is free of silicon or an oxide thereof.

56. The method of any one of claims 22 to 30, wherein the calcined hydrogenolysis catalyst is free of silicon or oxides.

57. The method of any one of claims 32 to 54, wherein the hydrogenolysis catalyst is free of silicon or oxides.

58. The method of any one of claims 22-30, wherein forming the material mixture comprises extruding, sheeting, or spheronizing.

Technical Field

The present technology relates to catalysts useful as hydrogenolysis catalysts, and more particularly, to catalysts useful for the hydrogenolysis of fatty acid ester compounds to form fatty alcohols. The present technology also relates to methods of making such catalysts and the use of such catalysts in hydrogenolysis.

Background

Hydrogenolysis is a chemical reaction used to convert esters to alcohols, generally illustrated by the following reaction:

R-CO-OR’+2H₂→RCH₂-OH+R’-OH

copper is a known catalyst for hydrogenolysis reactions. There is a continuing need to provide catalysts that maximize the desired hydrogenolysis products while eliminating the formation of by-products and the leaching of contaminants from the catalyst into the products (e.g., silica). It is also desirable to provide hydrogenolysis catalysts, methods of making and methods of using the same that exhibit higher catalyst activity, have longer useful life, and operate at lower temperatures than existing catalysts.

Disclosure of Invention

In one aspect, the present technology provides a hydrogenolysis catalyst comprising a catalytic component comprising copper oxide, manganese oxide, and aluminum oxide; and a binder comprising a zirconium component, wherein the catalyst comprises at least about 30.0 wt% copper oxide, and the catalyst is substantially free of silicon or oxides thereof.

In one aspect, the present technology provides methods of preparing the catalysts described herein for hydrogenolysis. The method comprises mixing a catalytic component with a binder system and water to obtain a material mixture; shaping the material mixture to obtain a shaped material mixture; calcining the shaped material mixture at a temperature and for a time sufficient to cure to form the calcined hydrogenolysis catalyst; wherein: the catalytic component comprises copper oxide, manganese oxide and aluminum oxide; the binder system comprises a zirconium component; the calcined hydrogenolysis catalyst comprises at least 30 wt.% copper oxide; and the calcined hydrogenolysis catalyst is substantially free of silicon or its oxide.

In another aspect, the present technology provides a catalyst for hydrogenolysis prepared by the method described herein in any of the embodiments.

In one method, the present technology provides a method of performing hydrogenolysis of a fatty acid ester, wherein the method comprises hydrogenolysis of a fatty acid ester by contacting the fatty acid ester with a hydrogenolysis catalyst as described herein in any embodiment.

Drawings

Figure 1 shows a graph showing% conversion of wax ester feed to fatty alcohol using exemplary catalyst 5 and a comparative reference catalyst containing silica according to the procedure in example 2.

FIG. 2 shows a graph showing the cumulative intrusion ("pore volume", cm) of exemplary catalyst 1A³Per g) as pore diameterA graph of the function of (c).

FIG. 3 shows the incremental pore volume as pore diameter for an exemplary catalyst 1AA graph of the function of (c).

Fig. 4 shows a graph showing the X-ray powder diffraction spectrum of exemplary catalyst 5.

Detailed Description

Various embodiments are described below. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation on the broader aspects discussed herein. An aspect described in connection with a particular embodiment is not necessarily limited to that embodiment, and may be practiced with any other embodiment.

As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there is a use of a term that is not clear to one of ordinary skill in the art, then "about" will mean up to plus or minus 10% of the particular term, given the context in which the term is used.

The use of the terms "a" and "an" and "the" and similar referents in the context of describing elements (especially in the context of the following claims) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate embodiments and does not pose a limitation on the scope of the claims unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential.

Generally, "substituted" refers to the replacement of the bond of one or more hydrogen atoms contained in an alkyl, alkenyl, cycloalkyl, or aryl (e.g., alkyl) group as defined below by a bond other than a hydrogen atom or a non-carbon atom. Substituted groups also include groups in which one or more bonds of a carbon atom or a hydrogen atom are replaced with one or more bonds of a heteroatom, including double or triple bonds. Thus, unless otherwise specified, a substituted group will be substituted with one or more substituents. In some embodiments, a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of the substituent include: halogen (i.e., F, Cl, Br, and I); a hydroxyl group; alkoxy, alkenyloxy, alkynyloxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy; carbonyl (oxo); a carboxyl group; an ester; urethane; an oxime; a hydroxylamine; an alkoxyamine; an arylalkoxyamine; a thiol; a sulfide; a sulfoxide; a sulfone; a sulfonyl group; a sulfonamide; an amine; an N-oxide; hydrazine; a hydrazide; hydrazone; an azide; an amide; urea; amidines; guanidine; an enamine; an imide; an isocyanate; an isothiocyanate; a cyanate ester; a thiocyanate; an imine; a nitro group; nitriles (i.e., CN); and the like.

As used herein, "alkyl" includes straight and branched chain alkyl groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons, or in some embodiments, from 1 to 8 carbon atoms. As used herein, "alkyl" includes cycloalkyl as defined below. Alkyl groups may be substituted or unsubstituted. Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, tert-butyl, neopentyl, and isopentyl. Representative substituted alkyl groups can be substituted one or more times with, for example, amino, thio, hydroxy, cyano, alkoxy, and/or halo groups (e.g., F, Cl, Br, and I groups). As used herein, the term haloalkyl is an alkyl having one or more halo groups. In some embodiments, haloalkyl refers to perhaloalkyl.

An alkenyl group is a straight, branched, or cyclic alkyl group having 2 to about 20 carbon atoms and further including at least one double bond. In some embodiments, alkenyl groups have from 2 to 12 carbons, or typically from 2 to 8 carbon atoms. The alkenyl group may be substituted or unsubstituted. Alkenyl groups include, for example, ethenyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, hexadienyl, and the like. Alkenyl groups may be substituted similarly to alkyl groups. Divalent alkenyl groups, i.e., alkenyl groups having two points of attachment include, but are not limited to, CH-CH ═ CH₂、C＝CH₂Or C ═ CHCH₃。

Reference to an "alkali metal component" means a material for delivering an alkali metal, such as a metal oxide, hydroxide or carbonate, which may be in powder form or an aqueous solution.

Reference to "binder" or "binder system" means a material suitable for binding components together to form a shaped catalyst. Typically, the binder component is extrudable and used to form an extruded catalyst and/or the binder component is capable of forming a tableted catalyst. Thus, the binder or binder system may comprise zirconia, alumina, and mixtures thereof.

All references to pore diameter and pore volume in the specification and claims of this application are based on measurements using the mercury porosimetry. A typical process is described by Experimental Methods in Catalytic Research, Academic Press, New York,1968, of Anderson. Pore volume was determined using the catalyst in the form of an oxide. That is, the pore sizes and pore volumes reported herein are obtained after calcination but prior to any reduction of the oxide. Those skilled in the art will generally refer to a catalyst containing a metal oxide as the "oxide" or "oxide precursor" form of the catalyst.

The catalyst of the present technology is based on a calcined co-precipitated mixture of copper oxide-alumina and manganese oxide and zirconium acetate solution. The formation of the catalyst involves mixing and extrusion of the precursor materials, followed by drying and calcination. Other additives may be included in the mixture to form the catalyst.

The copper extrudate catalysts described herein exhibit improved catalytic hydrogenolysis activity and equivalent selectivity to the fatty alcohol process compared to current commercial catalysts that include common binders (e.g., calcium silicate, sodium silicate, silica sol, clay, etc.). These customary binders contain silica which can leach out under the reaction conditions, in particular with regard to fatty alcohols which influence the product quality by the purity of the silica. The catalysts of the present technology as described herein include a zirconium-based binder system (e.g., ZrO)₂Or ZrO₂-Al₂O₃) And does not contain silica that can leach out into the alcohol product during fatty alcohol production. Surprisingly, the inventors have found that the hydrogenolysis catalysts of the present technology are tabulated in comparison to current commercially available catalystsExhibit strong mechanical strength, high activity towards hydrogenation/hydrogenolysis reactions for the production of fatty alcohols and improved selectivity over a wider operating temperature range.

Hydrogenolysis catalysts for producing fatty alcohols from fatty acid esters are provided. Methods of making and using them are also provided. These catalysts are formed from a catalytic component and a binder, which are processed together, for example by extrusion or tableting, to form the catalyst. The catalytic components include copper oxide, manganese oxide and aluminum oxide. The binder includes a zirconium component (e.g., ZrO)₂Or ZrO₂-Al₂O₃)。

Catalyst composition

In one aspect, the hydrogenolysis catalyst comprises a catalytic component comprising copper oxide, manganese oxide, and aluminum oxide; and a binder comprising a zirconium component, wherein the catalyst comprises at least about 30.0 wt% copper oxide, and the catalyst is substantially free of silicon or oxides thereof.

In any of the embodiments herein, the hydrogenolysis catalyst can be substantially free of silicon or an oxide thereof. Additionally, the hydrogenolysis catalyst can be free of silicon or oxides thereof to reduce exposure to such materials. As used herein, a hydrogenolysis catalyst can be free of such materials if they are present in an amount that does not materially affect the physical, chemical and catalytic properties of the catalyst when compared to a catalyst that is completely free of such materials. Preferably, such materials, if present, will be present in trace amounts, but in amounts no greater than about 1.5 wt%, more preferably no greater than 0.5 wt%. For example, the phrase "substantially free of silicon or oxides thereof" refers to less than about 1.5 wt.%, less than about 1 wt.%, less than about 0.5 wt.%, less than about 0.1 wt.%, less than about 0.01 wt.%, or 0 wt.%, based on the total weight of the hydrogenolysis catalyst. In any of the embodiments herein, the hydrogenolysis catalyst can be free of silicon or its oxide.

In any of the embodiments herein, the hydrogenolysis catalyst can comprise at least 30 wt.% copper oxide. For example, in any of the embodiments herein, the copper oxide may be present in an amount from about 35 wt% to about 75 wt% based on the weight of the hydrogenolysis catalyst. Suitable amounts of copper oxide can include, but are not limited to, about 35 wt.% to about 75 wt.%, about 40 wt.% to about 65 wt.%, about 45 wt.% to about 55 wt.%, or any range including and/or between any two of the foregoing values. For example, the amount of copper oxide can include, but is not limited to, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the hydrogenolysis catalyst comprises manganese oxide in an amount of about 0 wt% to about 10 wt% by weight of the hydrogenolysis catalyst. Suitable amounts of manganese oxide include, but are not limited to, about 0 wt% to about 10 wt%, about 3 wt% to about 10 wt%, about 5 wt% to about 10 wt%, about 6 wt% to about 9 wt%, or any range including and/or between any two of the foregoing values. For example, the manganese oxide may be present in an amount of about 1 weight percent, about 2 weight percent, about 3 weight percent, about 4 weight percent, about 5 weight percent, about 6 weight percent, about 7 weight percent, about 8 weight percent, about 9 weight percent, about 10 weight percent, or any range between and/or including any two of the foregoing values.

In any of the embodiments herein, the hydrogenolysis catalyst comprises alumina in an amount of about 15 wt% to about 40 wt% by weight of the hydrogenolysis catalyst. Suitable amounts of alumina can include, but are not limited to, about 15 wt.% to about 40 wt.%, about 20 wt.% to about 35 wt.%, about 25 wt.% to about 35 wt.%, or any range between and/or including any two of the foregoing values. For example, the alumina can be present in an amount of about 15 wt.%, about 20 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, about 40 wt.%, or any range including and/or between any two of the foregoing values.

The hydrogenolysis catalyst can include a binder, wherein the binder includes a zirconium component. In any of the embodiments herein, the zirconium component may be present in the reduced metal or oxide form, or as a precursor to such formAnd in one or more oxidation states as described above. For example, the zirconium component is zirconium oxide (e.g., ZrO)₂) Exist in the form of (1). In any of the embodiments herein, the zirconium component is present in an amount from about 4 wt% to about 15 wt%, by weight of the hydrogenolysis catalyst. Suitable amounts of the zirconium component include, but are not limited to, about 4 wt.% to about 15 wt.%, about 5 wt.% to about 12 wt.%, about 5 wt.% to about 8 wt.%, or any range including and/or between any two of the foregoing values. For example, the zirconium component may be present in an amount of about 4 weight percent, about 5 weight percent, about 6 weight percent, about 7 weight percent, about 8 weight percent, about 9 weight percent, about 10 weight percent, about 11 weight percent, about 12 weight percent, about 13 weight percent, about 14 weight percent, about 15 weight percent, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the catalyst may further comprise silica. For example, the binder may be zirconia-alumina (ZrO)₂-Al₂O₃) A binder system is present.

In any of the embodiments herein, the hydrogenolysis catalyst can comprise about 45% to about 55% by weight copper oxide, about 5% to about 12% by weight manganese oxide, about 20% to about 35% by weight alumina, and about 5% to about 12% by weight zirconia.

The hydrogenolysis catalyst described in any of the embodiments herein can further include an alkali metal component. In any of the embodiments herein, the alkali metal is selected from the group consisting of: sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and combinations thereof. These metals may be present as reduced metals or oxides, or as precursors of such forms, and in one or more oxidation states as described above. For example, the alkali metal component may include sodium in the form of disodium oxide. In any of the embodiments herein, the alkali metal component may be present in an amount of from 0 wt% to about 1 wt%, by weight of the hydrogenation catalyst. For example, the alkali metal component may be present in an amount of about 0.01 wt%, 0.05 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, or any range including and/or between any two of the foregoing values.

The hydrogenolysis catalyst can be provided in the form of tablets or extrudates. One way of handling the mixture of all ingredients is to extrude it through a shaping orifice to form an extruded catalyst body or extrudate. The other catalyst bodies may be shaped as spheres or any other convenient form. Another method is to tablet the catalyst. For example, the hydrogenolysis catalyst can be extruded or pelletized to sizes including, but not limited to, the following: 1/8 inches by 1/8 inches, 3/16 inches by 3/16 inches, 1/4 inches by 1/4 inches, 3/16 inches by 1/4 inches, 1/4 inches by 1/16 inches, or 1/8 inches by 1/16 inches.

In any of the embodiments herein, the hydrogenolysis catalyst can be provided in a tableted or extruded form and can exhibit a crush strength in an amount of about 1.0lbs/mm to about 6.0 lbs/mm. For example, the hydrogenolysis catalyst can exhibit a side pressure strength of about 1.0lbs/mm, about 1.5lbs/mm, about 2.0lbs/mm, about 2.5lbs/mm, about 3.0lbs/mm, about 3.5lbs/mm, about 4.0lbs/mm, about 4.5lbs/mm, about 5.0lbs/mm, about 5.5lbs/mm, about 6.0lbs/mm, or any range including and/or between any two of the foregoing values. In some embodiments, the catalyst may exhibit a side pressure strength of about 3.5lbs/mm to about 5.0 lbs/mm. In any embodiment, the hydrogenolysis catalyst after use in one or more catalytic processes (i.e., spent catalyst) can exhibit a crush strength as described herein.

In any of the embodiments herein, the hydrogenolysis catalyst can be calcined. In any of the embodiments herein, the catalyst is a calcined and extruded catalyst.

In particular, these hydrogenolysis catalysts contain a large amount of mesopores. Reference to "mesoporous" or "mesoporous" means having a porosity in the range of about 50 angstroms to about 1000 angstromsThose of a pore size within the range. For example, the hydrogenolysis catalyst can have a value of aboutTo aboutAboutTo aboutAboutTo aboutAboutTo aboutAboutTo aboutOr a pore size including and/or ranging between any two of the foregoing values.

In any of the embodiments herein, the hydrogenolysis catalyst can have greater than or equal to 0.2cm³Pore volume per gram. For example, the hydrogenolysis catalyst can have about 0.2cm³G, about 0.25cm³G, about 0.3cm³G, about 0.35cm³G, about 0.4cm³G, about 0.45cm³G, about 0.5cm³G, about 0.55cm³G, about 0.6cm³G, about 0.65cm³G, about 0.7cm³G, about 0.75cm³G, about 0.8cm³(iv)/g, or any range of pore volumes including and/or between any two of the foregoing values.

Herein, theIn any embodiment, the hydrogenolysis catalyst can have about 0.8g/cm³To about 1.5g/cm³The packing bulk density of (2). For example, the hydrogenolysis catalyst can have about 0.8g/cm³About 0.9g/cm³About 1.0g/cm³About 1.2g/cm³About 1.3g/cm³About 1.4g/cm³About 1.5g/cm³Or a packed bulk density including and/or in any range between any two of the preceding values. In any of the embodiments herein, the hydrogenolysis catalyst can have about 0.8g/cm³To about 1.5g/cm³About 0.8g/cm to about 1g/cm³About 0.8g/cm³To about 0.95g/cm³Or a packed bulk density including and/or in any range between any two of the preceding values. In any of the embodiments herein, the hydrogenolysis catalyst can be in the form of a sheet and has about 1.0g/cm³About 1.1g/cm³About 1.2g/cm³About 1.3g/cm³About 1.4g/cm³About 1.5g/cm³Or a packed bulk density including and/or in any range between any two of the preceding values.

In any of the embodiments herein, the hydrogenolysis catalyst can have about 15m²G to about 70m²Brunauer-Emmett-Teller ("BET") surface area in grams. For example, the hydrogenation catalyst has a particle size of about 15m²G, about 20m²A,/g, about 25m²G, about 30m²G, about 35m²A,/g, about 40m²G, about 45m²A,/g, about 50m²(g, about 55 m)²G, about 60m²G, about 65m²G, about 70m²(ii)/g, or any range including and/or between any two of the foregoing values. In any of the embodiments herein, the hydrogenation catalyst has about 15m²G to about 70m²A,/g, about 25m²G to about 65m²G, about 45m²G to about 60m²A,/g, about 50m²G to about 60m²(ii)/g, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the hydrogenolysis catalyst is in an unreduced form and exhibits an X-ray powder diffraction curve having 2 Θ peaks at 31.1 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 61.7 °, 64.9 °, 68.1 °. In any of the embodiments herein, the hydrogenolysis catalyst is in an unreduced form and exhibits an X-ray powder diffraction curve having 2 Θ peaks at 18.9 °, 31.1 °, 32.5 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 53.6 °, 58.3 °, 59.1 °, 61.7 °, 64.9 °, 66.8 °, 68.1 °, 72.2 °, 75.1 °, and 77.0 °.

In any of the embodiments herein, the hydrogenolysis catalyst has a value of aboutTo aboutThe size of the copper oxide crystallites. For example, the calcined hydrogenolysis catalyst can have a value of aboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutOr any range including and/or between any two of the preceding valuesThe size of the copper oxide crystallites. In any embodiment, the calcined hydrogenation catalyst may have a composition of aboutTo aboutThe size of the copper oxide crystallites.

Preparation method

In one aspect, a method of preparing a catalyst for hydrogenolysis as described herein is provided. The method comprises mixing a catalytic component with a binder system and water to obtain a material mixture; shaping the material mixture to obtain a shaped material mixture; calcining the shaped material mixture at a temperature and for a time sufficient to cure to form the calcined hydrogenolysis catalyst; wherein: the catalytic component comprises copper oxide, manganese oxide and aluminum oxide; the binder system comprises a zirconium component; the calcined hydrogenolysis catalyst comprises at least 30 wt.% copper oxide; and the calcined hydrogenolysis catalyst is substantially free of silicon or its oxide.

In any of the embodiments herein, the calcined hydrogenolysis catalyst is free of silicon or its oxide.

In any of the embodiments herein, the catalytic component comprises a mixture of copper oxide, manganese oxide, and aluminum oxide provided in the form of a pre-calcined powder. The pre-calcined powder may be calcined at a temperature of from about 300 ℃ to about 750 ℃. Suitable calcination temperatures may include, but are not limited to, about 300 ℃, about 350 ℃, about 400 ℃, about 450 ℃, about 500 ℃, about 550 ℃, about 600 ℃, about 650 ℃, about 700 ℃, about 750 ℃, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the zirconium component may comprise zirconium acetate. In any of the embodiments herein, the binder may further comprise silica.

In any of the embodiments herein, the method may further comprise mixing one or more extrusion aids into the material mixture. Suitable extrusion aids may include, but are not limited to, polymeric polysaccharides, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, or mixtures of two or more thereof. For example, the extrusion aids can be selected from commercially available extrusion aids including, but not limited to, Zusoplast, Methocel, Walocel, or mixtures thereof.

The method includes calcining the material mixture at a temperature and for a time sufficient to cure to form a calcined hydrogenation catalyst. In any of the embodiments herein, the calcining may be performed at a temperature of from about 200 ℃ to about 1000 ℃. For example, the calcining may occur at a temperature of about 200 ℃, about 250 ℃, about 300 ℃, about 350 ℃, about 400 ℃, about 450 ℃, about 500 ℃, about 550 ℃, about 600 ℃, about 650 ℃, about 700 ℃, about 750 ℃, about 800 ℃, about 850 ℃, about 900 ℃, about 950 ℃, about 1000 ℃, or any range including and/or between any two of the foregoing values. In any of the embodiments herein, the calcination temperature may be from 400 ℃ to about 650 ℃, from about 400 ℃ to about 550 ℃, or from about 450 ℃ to about 500 ℃. In any of the embodiments herein, the calcining may occur for a time period of from about 0.5 hours to about 4 hours. In any embodiment, the calcining may occur for about 0.5 hours, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, or any range of time between and/or including any two of the values recited above.

In any of the embodiments herein, the material mixture may be formed by extrusion, tableting, or spheronization. In any of the embodiments herein, shaping may be extruding or tabletting the material mixture to obtain a shaped material mixture. For example, the shaped material mixture may be extruded or sheeted into dimensions including, but not limited to, the following: 1/8 inches by 1/8 inches, 3/16 inches by 3/16 inches, 1/4 inches by 1/4 inches, 3/16 inches by 1/4 inches, 1/4 inches by 1/16 inches, or 1/8 inches by 1/16 inches. In any of the embodiments herein, shaping may include spheroidizing the material mixture to obtain a shaped material mixture.

In any of the embodiments herein, the hydrogenolysis catalyst provided in the form of a pellet or extrusion can exhibit a crush strength in an amount of about 1.0lbs/mm to about 6.0 lbs/mm. For example, the catalyst may exhibit a side crush strength of about 1.0lbs/mm, about 1.5lbs/mm, about 2.0lbs/mm, about 2.5lbs/mm, about 3.0lbs/mm, about 3.5lbs/mm, about 4.0lbs/mm, about 4.5lbs/mm, about 5.0lbs/mm, about 5.5lbs/mm, about 6.0lbs/mm, or any range including and/or between any two of the foregoing values. In some embodiments, the catalyst may exhibit a side pressure strength of about 3.5lbs/mm to about 5.0 lbs/mm.

The method may further comprise removing at least some of the water from the wet material mixture prior to calcining. For example, removing may include drying the wet material mixture. In any of the embodiments herein, the removing can be performed at a temperature including, but not limited to, about 40 ℃ to about 150 ℃. For example, the removal can be performed at a temperature of about 40 ℃, about 50 ℃, about 60 ℃, about 70 ℃, about 80 ℃, about 90 ℃, about 100 ℃, about 110 ℃, about 120 ℃, about 130 ℃, about 140 ℃, about 150 ℃, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the calcined hydrogenolysis catalyst can comprise at least 30 wt.% copper oxide. For example, in any of the embodiments herein, the copper oxide may be present in an amount from about 35 wt% to about 75 wt% based on the weight of the calcined hydrogenolysis catalyst. Suitable amounts of copper oxide can include, but are not limited to, about 35 wt.% to about 75 wt.%, about 40 wt.% to about 65 wt.%, about 45 wt.% to about 55 wt.%, or any range including and/or between any two of the foregoing values. For example, the amount of copper oxide can include, but is not limited to, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the calcined hydrogenolysis catalyst comprises manganese oxide in an amount of about 0 wt% to about 10 wt% based on the weight of the calcined hydrogenolysis catalyst. Suitable amounts of manganese oxide include, but are not limited to, about 0 wt% to about 10 wt%, about 3 wt% to about 10 wt%, about 5 wt% to about 10 wt%, about 6 wt% to about 9 wt%, or any range including and/or between any two of the foregoing values. For example, the manganese oxide may be present in an amount of about 1 weight percent, about 2 weight percent, about 3 weight percent, about 4 weight percent, about 5 weight percent, about 6 weight percent, about 7 weight percent, about 8 weight percent, about 9 weight percent, about 10 weight percent, or any range between and/or including any two of the foregoing values.

In any of the embodiments herein, the calcined hydrogenolysis catalyst comprises alumina in an amount of about 15 wt% to about 40 wt% based on the weight of the calcined hydrogenolysis catalyst. Suitable amounts of alumina can include, but are not limited to, about 15 wt.% to about 40 wt.%, about 20 wt.% to about 35 wt.%, about 25 wt.% to about 35 wt.%, or any range between and/or including any two of the foregoing values. For example, the alumina can be present in an amount of about 15 wt.%, about 20 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, about 40 wt.%, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the zirconium component is present in the calcined hydrogenolysis catalyst in an amount of about 4 wt% to about 15 wt% based on the weight of the calcined hydrogenolysis catalyst. Suitable amounts of the zirconium component include, but are not limited to, about 4 wt.% to about 15 wt.%, about 5 wt.% to about 12 wt.%, about 5 wt.% to about 8 wt.%, or any range including and/or between any two of the foregoing values. For example, the zirconium component may be present in an amount of about 4 weight percent, about 5 weight percent, about 6 weight percent, about 7 weight percent, about 8 weight percent, about 9 weight percent, about 10 weight percent, about 11 weight percent, about 12 weight percent, about 13 weight percent, about 14 weight percent, about 15 weight percent, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the catalyst may further comprise silica. For example, the binder may be zirconia-alumina (ZrO)₂-Al₂O₃) A binder system is present.

In any of the embodiments herein, the calcined hydrogenolysis catalyst can comprise about 45% to about 55% by weight copper oxide, about 5% to about 12% by weight manganese oxide, about 20% to about 35% by weight alumina, and about 5% to about 12% by weight zirconia.

The calcined hydrogenolysis catalyst can have a molecular weight in the range of about 150 to about 1000 angstromsPore size in the range of (1). For example, the calcined hydrogenolysis catalyst can have a value of aboutTo aboutAboutTo aboutAboutTo aboutAboutTo aboutAboutTo aboutOr a pore size including and/or ranging between any two of the foregoing values.

In any of the embodiments herein, the calcined hydrogenolysis catalyst can have greater than or equal to 0.2cm³Pore volume per gram. For example, the calcined hydrogenolysis catalyst can haveAbout 0.2cm³G, about 0.25cm³G, about 0.3cm³G, about 0.35cm³G, about 0.4cm³G, about 0.45cm³G, about 0.5cm³G, about 0.55cm³G, about 0.6cm³G, about 0.65cm³G, about 0.7cm³G, about 0.75cm³G, about 0.8cm³(iv)/g, or any range of pore volumes including and/or between any two of the foregoing values.

In any of the embodiments herein, the calcined hydrogenolysis catalyst can have about 0.8g/cm³To about 1.5g/cm³The packing bulk density of (2). For example, the calcined hydrogenolysis catalyst can have about 0.8g/cm³About 0.9g/cm³About 1.0g/cm³About 1.1g/cm³About 1.2g/cm³About 1.3g/cm³About 1.4g/cm³About 1.5g/cm³Or a packed bulk density including and/or in any range between any two of the preceding values. In any of the embodiments herein, the calcined hydrogenolysis catalyst can have about 0.8g/cm³To about 1.5g/cm³About 0.8g/cm to about 1g/cm³About 0.8g/cm³To about 0.95g/cm³Or a packed bulk density including and/or in any range between any two of the preceding values. In any of the embodiments herein, the calcined hydrogenolysis catalyst can be in the form of a tablet and has about 1.0g/cm³About 1.1g/cm³About 1.2g/cm³About 1.3g/cm³About 1.4g/cm³About 1.5g/cm³Or a packed bulk density including and/or in any range between any two of the preceding values.

In any of the embodiments herein, the calcined hydrogenolysis catalyst can have about 15m²G to about 70m²BET surface area in g. For example, the calcined hydrogenolysis catalyst has about 15m²G, about 20m²A,/g, about 25m²G, about 30m²G, about 35m²A,/g, about 40m²G, about 45m²A,/g, about 50m²(g, about 55 m)²G, about 60m²G, about 65m²G, about 70m²Per g, or bagsAny range of BET surface area between any two of the foregoing values and/or inclusive. In any of the embodiments herein, the calcined hydrogenolysis catalyst has about 15m²G to about 70m²A,/g, about 25m²G to about 65m²G, about 45m²G to about 60m²A,/g, about 50m²G to about 60m²(ii)/g, or any range including and/or between any two of the foregoing values.

In any of the embodiments herein, the hydrogenolysis catalyst is in an unreduced form and exhibits an X-ray powder diffraction curve having 2 Θ peaks at 31.1 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 61.7 °, 64.9 °, 68.1 °. In any of the embodiments herein, the hydrogenolysis catalyst is in an unreduced form and exhibits an X-ray powder diffraction curve having 2 Θ peaks at 18.9 °, 31.1 °, 32.5 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 53.6 °, 58.3 °, 59.1 °, 61.7 °, 64.9 °, 66.8 °, 68.1 °, 72.2 °, 75.1 °, and 77.0 °.

In any of the embodiments herein, the calcined hydrogenolysis catalyst has a value of aboutTo aboutThe size of the copper oxide crystallites. For example, the calcined hydrogenolysis catalyst can have a value of aboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutAboutOr any range of copper oxide crystallite sizes including and/or between any two of the foregoing values. In any embodiment, the calcined hydrogenolysis catalyst can have a value of aboutTo aboutThe size of the copper oxide crystallites.

In another aspect, the present technology provides a catalyst for hydrogenolysis prepared by the method described herein in any of the embodiments.

Application method

In one aspect, a method of performing hydrogenolysis of a fatty acid ester is provided, wherein the method comprises hydrogenolysis of a fatty acid ester by contacting the fatty acid ester with a hydrogenolysis catalyst as described herein in any embodiment.

In any of the embodiments herein, the fatty acid ester can be a compound of formula I:

R¹-CO-OR²(I)

wherein R is¹And R²Each independently of the others, is branched or unbranched C₁To C₂₄Alkyl or branched or unbranched C₂To C₂₄An alkenyl group.

In any embodiment herein, R¹And R²May each independently be C₁₀To C₁₄Branched or unbranched alkyl or C₁₀To C₁₄A branched or unbranched alkenyl group. In any embodiment herein, R¹And R²Can be independent of each otherGround is C₁₂To C₁₄Branched or unbranched alkyl. In some embodiments herein, when R is¹Is C₁₀To C₁₈Branched or unbranched alkyl or C₁₀To C₁₈When there is a branched or unbranched alkenyl radical, R²May be C₁To C₆An alkyl group. For example, R²May be C₁To C₄An alkyl group. In any embodiment herein, R²May be a methyl group.

In any embodiment herein, R¹And R²Together may be composed of C₁To C₂₄Alkyl or C₁To C₂₄Alkenyl groups such that the compounds represented by formula (I) form wax esters having a total of 12 to 36 carbon atoms.

The hydrogenolysis catalysts of the present technology exhibit improved activity and selectivity for fatty alcohol formation at lower temperatures compared to currently commercially available catalysts, such as catalysts containing silicon or its oxides (figure 1). In any of the embodiments herein, the process may be carried out at a temperature of at least about 170 ℃. For example, the temperature may be from about 170 ℃ to about 250 ℃, from about 170 ℃ to about 220 ℃, or from about 170 ℃ to about 180 ℃. Suitable temperatures include, but are not limited to, about 170 ℃, about 175 ℃, about 180 ℃, about 185 ℃, about 190 ℃, about 195 ℃, about 200 ℃, about 205 ℃, about 210 ℃, about 215 ℃, about 220 ℃, about 225 ℃, about 230 ℃, about 235 ℃, about 240 ℃, about 245 ℃, about 250 ℃, or any range including and/or between any two of the foregoing values.

The invention thus generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.

Examples

Examples 1 to 5: a series of copper catalysts with different copper oxide, manganese oxide, alumina and zirconia contents were prepared as follows. The calcined copper manganese aluminum powder, zirconium acetate, alumina, organic binder (i.e., Zusoplast), and water were mixed and kneaded. The mixture was then extruded with an extruder and dried. The extrudates are then calcined at 250 ℃ to 1000 ℃. As shown in the figure2, exemplary catalyst 1A is shown inExhibit a pore size in the range of about 0.1 to 0.35cm³Pore volume per gram. FIG. 3 showsToExemplary catalyst 1A mesoporous in between. The catalyst had the properties outlined in table 1, where "3F" refers to 3 grooves or three lobes.

Catalysts 1E, 3A, 4A, 5 and the reference catalyst containing copper/silica were characterized by temperature programmed reduction and copper metal dispersion. The results are summarized in the following table.

The temperature-programmed reduction peak temperature indicates that the catalyst is easily reduced by hydrogen. A catalyst with a lower peak temperature will be more easily reduced under the same reduction conditions. As shown in the above table, catalysts 1E, 3A, 4A, and 5 exhibited lower peak temperatures than the reference catalyst. In addition, catalysts 1E, 3A, 4A and 5 exhibited higher copper metal dispersion than the reference catalyst. Copper metal dispersion is the ratio of surface copper metal to total copper metal. Higher copper dispersion means smaller copper metal crystallite size, which will generally have higher catalytic activity. These will be further demonstrated in examples 6 and 7 for the hydrogenolysis activity of the esters.

XRD analysis: data for exemplary catalyst 5 was collected using a PANalytical MPD X' Pert Pro diffraction system. Cu K_αThe radiation was used in the analysis with a generator set of 45kV and 40 mA. The optical path consists of a 1-degree dispersion slit, a 2-degree anti-dispersion slit, a sample and an X' Celerator position sensitive detector. Each catalyst sample was first prepared by wrapping the sample around a circular mounting. The using step length is 0.017 DEG 2Step scans of theta and scan speeds of 0.036 deg. 2 theta per second, the data collected from the circular mount covers a range of 10 deg. to 90 deg. 2 theta. The X' Pert Pro HighScore program was used for phase recognition analysis.

Monoclinic and/or cubic copper oxide (CuO/Cu) as shown below₂O) is the major phase of exemplary catalyst 5.

Phase determination

^*A reduced catalyst.

International diffractive data center (ICDD)

The complete list of θ 2 peaks in fig. 4 is 18.9 °, 31.1 °, 32.5 °, 36.0 °, 36.8 °, 38.8 °, 44.6 °, 48.8 °, 53.6 °, 58.3 °, 59.1 °, 61.7 °, 64.9 °, 66.8 °, 68.1 °, 72.2 °, 75.1 °, and 77.0 °.

Example 6: hydrogenolysis of fatty acid wax esters in a liquid phase process. For the liquid phase wax ester hydrogenolysis catalyst test, 100cc of the catalyst extrudates described in example 1 were charged to a 1.25 inch inner diameter stainless steel fixed bed downflow reactor. An equal volume of inert 14 x 28 mesh alpha alumina particles was loaded into the catalyst and used as a gap filler. The reactor was also equipped with an 3/16 inch thermowell equipped with six thermocouples, one at the inlet and five equally spaced across the catalyst bed, which was about 8 inches in length. The reactor was heated by a furnace equipped with a jacket around the reactor tubes.

After loading, the reactor was charged with 2 standard liters per minute (slpm) of N₂Purge for about 1 hour to remove air, then flow N₂The mixture was heated to 190 ℃. By passingIntroducing H in a stepwise manner at atmospheric pressure₂To activate the catalyst. After completion of the reduction, the temperature was lowered to 170 ℃ in 100 standard liters per hour (slph) of hydrogen. The temperature was stabilized at 170 ℃ and the reactor was pressurized from atmospheric pressure to 1015 psig.

The commercially available wax ester was then fed (C)₁₂-C₁₄Wax ester) was pumped into the reactor at a rate of 63g/h, giving about 0.73h^-1Total LHSV. The hydrogen to wax ester molar ratio was 50.

Hydrogenolysis was performed according to the following reaction scheme:

R-COOH+R’CH₂OH→R-CO-O-R’+2H₂→RCH₂OH+R’-OH

product samples were collected continuously every 24 hours at temperatures of 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C and/or 220 deg.C, respectively. These samples were analyzed by an offline Agilent6890GC equipped with a Quadrex Carbowax 20M column (75M × 0.32mm × 0.25 μ M) and a flame ionization detector. C₁₂、C₁₄、C₁₆And C₁₈Fatty alcohols are the desired products, while hydrocarbons (e.g. dodecane, hexadecane) are by-products. No other products were detected in any appreciable amount.

As shown in table 2, exemplary catalysts 1A, 1B, and 5 exhibited overall improved% wax ester conversion over the temperature range of 170 ℃ to 220 ℃ compared to a reference copper catalyst containing silica. The exemplary copper catalysts showed average increases in% wax ester conversion at 170 ℃, about 14%, at 180 ℃, and about 13% at 190 ℃, respectively, compared to the reference copper catalyst. As shown in fig. 1, exemplary catalyst 5 exhibited a 33% increase in wax ester conversion at 170 ℃, 28% at 180 ℃, 9% at 190 ℃, 8% at 200 ℃, and 0.4% at 220 ℃, respectively, as compared to the reference copper catalyst. As shown in table 3, exemplary catalyst 5 also showed lower% conversion of hydrocarbon by-product at 200 ℃ and 220 ℃, respectively. Thus, exemplary catalysts of the present technology exhibit higher% conversion at lower temperatures than comparative commercial reference catalysts.

Table 2.

^*Reference is made to copper and silica catalysts.

Table 3.

^*Reference is made to copper and silica catalysts.

Example 7: hydrogenolysis of fatty acid methyl esters in a gas phase process. For the vapor phase methyl ester hydrogenolysis catalyst test, 15cc of catalyst (extrudate) was charged to a 0.9 inch inner diameter stainless steel fixed bed downflow reactor. An equal volume of inert 28 x 48 mesh alpha alumina particles was loaded into the catalyst and used as a gap filler. The reactor was also equipped with an 3/16 inch thermowell equipped with six thermocouples, one at the inlet and five equally spaced across the catalyst bed, which was about 6 inches in length. The reactor was heated by a furnace equipped with a jacket around the reactor tubes.

After loading, the reactor was run in 15slph N₂Purge for about 1 hour to remove air, then flow N₂The mixture was heated to 190 ℃. By introducing H in a stepwise manner at atmospheric pressure₂To activate the catalyst. After the reduction was complete, the temperature stabilized at 210 ℃ and the reactor was pressurized from atmospheric pressure to 435 psig.

After pressurization, the hydrogen flow rate was adjusted to 800slph with the temperature stabilized at 210 ℃. Commercial methyl was then fed (C) at a rate of 32.5g/h₁₂-C₁₄Methyl ester) was pumped into the reactor to obtain about 2.5h^-1Total LHSV. The molar ratio of hydrogen to methyl ester was 250.

Hydrogenolysis was performed according to the following reaction scheme:

R-CO-O-Me+2H₂→RCH₂OH+MeOH

product samples were collected continuously every 24 hours at temperatures of 210 ℃ and/or 230 ℃ respectively. These samples were analyzed by an off-line Agilent6890GC equipped with a Quadrex Carbowax 20M column (75M x 0.32mm x 0.25 μ M) and a flame ionization detector. C₁₂、C₁₄、C₁₆And C₁₈Fatty alcohols are the desired products, while hydrocarbons (e.g., dodecane, tetradecane, and hexadecane) are by-products. No other products were detected in any appreciable amount.

As shown in table 4, exemplary catalyst 5 exhibited a comparative% gas phase hydrogenolysis conversion of methyl esters to fatty alcohol products at 210 ℃ to 230 ℃ compared to a reference copper catalyst containing silica. Similarly, exemplary catalyst 5 exhibited a low% conversion of methyl esters to hydrocarbon byproducts as compared to the reference copper catalyst containing silica.

^*Reference is made to copper and silica catalysts.

As shown in the above examples, the catalysts of the present technology unexpectedly show improved% liquid phase hydrogenolysis conversion of wax ester feed to fatty alcohol product and lower conversion to hydrocarbon by-products compared to commercial copper catalysts containing silica. Furthermore, the catalysts of the present technology surprisingly show comparative% gas phase hydrogenolysis conversion of methyl ester feed to aliphatic alcohol product and low conversion to hydrocarbon by-products compared to commercial copper catalysts containing silica.

While certain embodiments have been shown and described, it will be appreciated that changes and modifications may be made by those of ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

The embodiments illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," and the like are to be read broadly and not limited. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase "consisting essentially of …" will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of …" excludes any element not specified.

The present disclosure is not limited to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made thereto without departing from the spirit and scope of the invention. Functionally equivalent methods and compositions, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing description, which are within the scope of the present disclosure. Such modifications and variations are intended to fall within the scope of the appended claims. The disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds or compositions, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are described in terms of markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any single member or subgroup of members of the markush group.

As will be understood by those skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be readily identified as being fully descriptive and such that the same range is broken down into at least equal two, three, four, five, ten, etc. parts. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, a middle third, and an upper third, etc. As those skilled in the art will also appreciate, all terms such as "at most," "at least," "greater than," "less than," and the like include the referenced number and refer to a range that may be subsequently broken down into sub-ranges as discussed above. Finally, as will be understood by those of skill in the art, a range includes each individual member.

All publications, patent applications, issued patents, and other documents mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Where a definition contained in a text incorporated by reference contradicts a definition in this disclosure, the definition contained in the text incorporated by reference is excluded.

Other embodiments are set forth in the following claims.