One-step method for preparing BCI

Abstract

The present disclosure relates to a one-step process for preparing BCI. The process involves contacting a starting material comprising MCDDK with hydrogen in a reaction zone in the presence of a catalyst mixture to produce a product mixture comprising BCI wherein the catalyst mixture comprises a solid acid catalyst and a hydrogenation catalyst.

Description

Background Art Technical Field

[0001] The present disclosure relates to a one-step method for preparing BCI by using MCDDK as a starting material. More particularly, the method uses a catalyst mixture comprising a solid acid catalyst and a hydrogenation catalyst.

[0002] Related technical description

[0003] Muskenone is one of the most potent commercially available macrocyclic musks. It is a very good, versatile musk, and its smell and its use in flavors and fragrances are somewhat similar to keto musk and musk ketone. Saturated macrocyclic ketones with 14 to 18 ring members, such as musk ketone (3-methylcyclopentadecanone), are popular spices or fragrances. Since these compounds from natural sources can only be obtained in small quantities, the synthesis of these compounds has always been the subject of comprehensive research. All methods currently developed involve multi-step synthesis with limited overall performance relative to the starting materials.

[0004] An efficient industrial route for preparing muscene ketone starts from MCDDK and includes a 6-step synthesis involving the important intermediate BCI. BCI is formed from MCDDK (obtained from CDDK) via a 3-step synthetic route involving: dehydrogenation cyclization to the corresponding polyunsaturated bicyclic compound, hydrogenation to a monounsaturated bicyclic compound (e.g., BCI and its positional isomers), and isomerization to BCI. The disadvantages of the current process are the limited overall yield of BCI produced from MCDDK (58-63 wt % relative to the starting material), the need to use at least a set of three different operating units (one of which is an autoclave), and the amount of waste generated. Summary of the invention

[0005] The present disclosure provides a one-step process for preparing BCI. The one-step process comprises contacting a starting material comprising MCDDK with hydrogen in a reaction zone in the presence of a catalyst mixture to produce a product mixture comprising BCI, wherein the catalyst mixture comprises a solid acid catalyst and a hydrogenation catalyst. DETAILED DESCRIPTION

[0006] The foregoing general description and the following detailed description are exemplary and explanatory only and do not limit the invention as defined by the appended claims. Other features and benefits of any one or more embodiments will be apparent from the following detailed description and from the claims.

[0007] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. In addition, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0008] Moreover, "a / an" is used to describe the elements and components described herein. This is done only for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one / a or at least one / a, and the singular also includes the plural, unless it is obvious that it is otherwise intended.

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those of ordinary skill in the art to which the present invention belongs. In the event of a conflict, this specification, including definitions, shall prevail. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, materials, methods and examples are illustrative only and are not intended to be limiting.

[0010] When amount, concentration or other values ​​or parameters are given with scope, preferred range or a series of upper preferred values ​​and / or lower preferred values, this should be understood as particularly disclosing all scopes formed by any pairing of any upper range limit or preferred value and any lower range limit or preferred value, and whether these scopes are disclosed separately.When numerical range is enumerated herein, unless otherwise indicated, the scope is intended to include all integers and fractions in its endpoints and the scope.For example, when enumerating the scope of "1 to 10", the enumerated scope should be interpreted as including "1 to 8", "3 to 10", "2 to 7", "1.5 to 6", "3.4 to 7.8", "1 to 2 and 7-10", "2 to 4 and 6 to 9", "1 to 3.6 and 7.2 to 8.9", "1-5 and 10", "2 and 8 to 10", "1.5-4 and 8" and other scopes.

[0011] Although compositions and methods are described herein as "comprising" various components or steps, these compositions and methods can also "consist essentially of" or "consist of" the various components or steps, unless otherwise stated.

[0012] Some olefin molecules can exist as cis or trans stereoisomers. Unless explicitly indicated, an olefin (molecule, structure, formula, or chemical name) as used herein includes both cis and trans stereoisomers, as well as any combination or mixture of cis and trans stereoisomers.

[0013] Before presenting details of the following embodiments, some terms are defined or clarified.

[0014] As used herein, the term "MCDDK" is a compound named 2-(2-methyl-2-propenyl)cyclododecane-1-one, 2-(2-methylprop-2-enyl)cyclododecane-1-one, or 2-(2-methylallyl)cyclododecane-1-one, and is represented by the following formula (I):

[0015]

[0016] As used herein, the term "BCI" is a compound named 14-methylbicyclo[10.3.0]pentadeca-[1,(12)]-ene, or 2,3,4,5,6,7,8,9,10,11,12,13-dodecahydro-2-methyl-1H-cyclopentacyclododecene, and is represented by the following formula (II):

[0017]

[0018] As used herein, the term "MDIENE" is a compound designated as 14-methylbicyclo[10.3.0]pentadeca-[1,(12)]-14-diene and is represented by the following formula (III):

[0019]

[0020] As used herein, the term "solid acid catalyst" refers to a solid catalyst comprising a Bronsted acid (or proton) site and / or a Lewis acid (non-proton) site. A Bronsted acid site is a site with an ionizable hydrogen atom. A Lewis acid site is an electron accepting site.

[0021] As used herein, the term "amorphous" means a solid without a crystalline ordered structure.

[0022] As used herein, the term "fixed bed catalyst" means a catalyst, typically in the form of pellets or granules, packed in a static bed that allows the passage of a gas or liquid.

[0023] As used herein, the term "contact time" or "reaction time" is calculated by dividing the weight (in grams) of the catalyst mixture present in the reaction zone by the MCDDK flow rate through the reaction zone. The MCDDK flow rate is expressed as the weight (in grams) of MCDDK passing through the reaction zone per hour. This calculation is particularly applicable to processes carried out in a continuous mode in a reaction zone with a fixed bed catalyst. The terms "contact time" and "reaction time" can be used interchangeably in this disclosure.

[0024] As used herein, the term "yield of BCI" means the total molar amount of BCI produced in the methods of the present disclosure compared to the total molar amount of MCDDK (the limiting reactant).

[0025] The present disclosure provides a one-step process for preparing BCI. The one-step process comprises contacting a starting material comprising MCDDK with hydrogen in a reaction zone in the presence of a catalyst mixture to produce a product mixture comprising BCI, wherein the catalyst mixture comprises a solid acid catalyst and a hydrogenation catalyst.

[0026] In some embodiments, the starting material comprises at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at least 95 wt%, or at least 98 wt%, or at least 99 wt% MCDDK based on the total weight of the starting material. In some embodiments, the starting material consists essentially of, or consists of, MCDDK.

[0027] In some embodiments, based on the total weight of the starting material, no more than 10wt%, or no more than 5wt%, or no more than 2wt%, or no more than 1wt%, or no more than 0.5wt%, or no more than 0.2wt%, or no more than 0.1wt% of basic compounds, such as amines and / or nitro compounds, are present in the reaction zone. In some embodiments, the reaction zone is substantially free of any basic compounds, or does not contain any basic compounds. In some embodiments, based on the total weight of the starting material, no more than 10wt%, or no more than 5wt%, or no more than 2wt%, or no more than 1wt%, or no more than 0.5wt%, or no more than 0.2wt%, or no more than 0.1wt% of water is fed into the reaction zone. This includes water and hydrogen carried by the starting material. In some embodiments, substantially no water or no water is fed into the reaction zone. In some embodiments, based on the total weight of the starting material, no more than 10wt%, or no more than 5wt%, or no more than 2wt%, or no more than 1wt%, or no more than 0.5wt%, or no more than 0.2wt%, or no more than 0.1wt% of sulfur-containing compounds are present in the reaction zone. In some embodiments, the reaction zone is substantially free of any sulfur-containing compounds, or is free of any sulfur-containing compounds.

[0028] MCDDK and hydrogen can be fed to the reaction zone alone or together. In certain embodiments, MCDDK and hydrogen are mixed and fed to the reaction zone together. In certain embodiments, MCDDK is preheated and vaporized to form MCDDK gas to be fed to the reaction zone. Typically, the molar ratio of hydrogen and MCDDK fed to the reaction zone is about 5: 1 to about 100: 1, or about 10: 1 to about 100: 1, or about 10: 1 to about 60: 1, or about 20: 1 to about 40: 1. In certain embodiments, the upper limit of the molar ratio is 100, 90, 80, 70, 60, 50, 40, 30 or 20. In certain embodiments, the lower limit of the molar ratio is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0029] In some embodiments, the method of the present disclosure is carried out in the absence of substantially or in the absence of solvent. In some embodiments, MCDDK and hydrogen are present in the reaction zone in a gaseous state, that is, MCDDK gas and hydrogen contact in the presence of a catalyst mixture in the reaction zone. The catalyst mixture comprises a solid acid catalyst and a hydrogenation catalyst. In some embodiments, the reaction zone is a fixed bed reactor, and can be a plug flow, tubular or other design (i.e., a packed bed reactor) filled with a solid catalyst, that is, a solid acid catalyst and a hydrogenation catalyst are present in the reaction zone as a fixed bed catalyst. The method of the present disclosure can be carried out in batches or in a continuous mode. In some embodiments, the method is carried out in a continuous mode. For example, MCDDK gas and hydrogen can be continuously fed to the reaction zone, and a fixed bed catalyst and a continuous flow as a product mixture can be present.

[0030] In some embodiments, the solid acid catalyst is selected from the group consisting of: aluminum oxide, silica-alumina, zeolite, silicoaluminophosphate, aluminophosphate, sulfated zirconium oxide, zirconium oxide (zirconium dioxide), zinc oxide, and mixtures thereof. In certain embodiments, the solid acid catalyst is selected from the group consisting of: aluminum oxide, silica-alumina, zeolite, sulfated zirconium oxide, and mixtures thereof. In certain embodiments, the solid acid catalyst is selected from the group consisting of: aluminum oxide, silica-alumina, zeolite, sulfated zirconium oxide, and mixtures thereof. In certain embodiments, the solid acid catalyst is selected from the group consisting of: aluminum oxide, silica-alumina, sulfated zirconium oxide, and mixtures thereof. In certain embodiments, the solid acid catalyst is an amorphous silica-alumina catalyst, which comprises amorphous silica-alumina, is substantially composed of amorphous silica-alumina, or is composed of amorphous silica-alumina. In certain embodiments, the amorphous silica-alumina catalyst is substantially free of, or does not contain any amorphous silica-alumina supported metal or metal compound. In some embodiments, based on the weight of amorphous silica-alumina, the amount of metal or metal compound supported by amorphous silica-alumina is no more than 3%, or no more than 2%, or no more than 1%, or no more than 0.5%, or no more than 0.2%, or no more than 0.1%, or no more than 0.05%, or no more than 0.02%, or no more than 0.01%. In some embodiments, based on the total weight of the solid acid catalyst, the solid acid catalyst comprises at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 98%, or at least 99% amorphous silica-alumina. In some embodiments, silica-alumina (e.g., amorphous silica-alumina) has a Si:Al (silicon: aluminum) molar ratio of no more than 20, or no more than 15, or no more than 10, or no more than 9, or no more than 8, or no more than 7, or no more than 6, or no more than 5, or no more than 4, or no more than 3, or no more than 2, or no more than 1. In some embodiments, the silica-alumina (eg, amorphous silica-alumina) has a Si:Al molar ratio of at least 0.01, or at least 0.05, or at least 0.1, or at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5.

[0031] In certain embodiments, the hydrogenation catalyst is a heterogeneous catalyst. Examples of hydrogenation catalysts include one or more noble metals (e.g., Pt, Pd, Ru) supported by a carrier (i.e., a supported noble metal catalyst), that is, the hydrogenation catalyst comprises one or more noble metals supported by a carrier, is substantially composed of one or more noble metals supported by a carrier, or is composed of one or more noble metals supported by a carrier. Preferred noble metals are Pt and / or Pd. Examples of hydrogenation catalysts also include one or more non-noble metals supported by a carrier. This non-noble metal is selected from the group consisting of: cobalt, nickel, iron, and mixtures thereof. Examples of carriers include activated carbon, silicon dioxide (SiO2), calcium carbonate, barium sulfate, metal oxides, and mixtures thereof. Preferred carriers are selected from the group consisting of: silicon dioxide, metal oxides, and mixtures thereof. In certain embodiments, the carrier includes or is aluminum oxide (Al2O3). Examples of hydrogenation catalysts also include cobalt oxide, nickel oxide, and iron oxide.

[0032] In some embodiments, the hydrogenation catalyst is selected from the group consisting of: Pd / alumina, Pt / alumina, Ru / alumina, Pd / C, Pt / C, Ru / C, Pd / silica, Pt / silica, Ru / silica, and mixtures thereof. In some embodiments, the hydrogenation catalyst is selected from the group consisting of: Pd / alumina, Pt / alumina, and mixtures thereof. In some embodiments, the hydrogenation catalyst comprises Pd / alumina, or is Pd / alumina. In some embodiments, the hydrogenation catalyst comprises Pt / alumina, or is Pt / alumina. The term "X / Y" as used herein with respect to a hydrogenation catalyst means metal X supported by a carrier Y.

[0033] Typically, the content of the precious metal is 0.1 wt% to 15 wt% based on the total weight of the catalyst. In some embodiments, the content of the precious metal is 0.2 wt% to 10 wt%, or 0.5 wt% to 10 wt%, or 1 wt% to 10 wt%, based on the total weight of the catalyst. In some embodiments, the upper limit of the content of the precious metal is 15 wt%, or 14 wt%, or 13 wt%, or 12 wt%, or 11 wt%, or 10 wt%, or 9 wt%, or 8 wt%, or 7 wt%, based on the total weight of the catalyst. In some embodiments, the lower limit of the content of the precious metal is 0.001 wt%, or 0.01 wt%, or 0.1 wt%, or 0.2 wt%, or 0.4 wt%, or 0.5 wt%, or 0.8 wt%, or 1 wt%, or 1.2 wt%, or 1.4 wt%, or 1.6 wt%, or 1.8 wt%, or 2 wt%, based on the total weight of the catalyst.

[0034] In some embodiments, solid acid catalyst and hydrogenation catalyst are both in powder form, which are uniformly mixed to form a catalyst mixture, which is then granulated and sieved to a desired particle size. In some embodiments, a suitable binder can be used together with a catalyst mixture to form particles with appropriate strength. In some embodiments, the catalyst mixture is in the form of particles, and the particle size is from about 50 μm to about 1000 μm, or from about 100 μm to about 800 μm, or from about 150 μm to about 600 μm, or from about 200 μm to about 400 μm. In some embodiments, by the number of particles, at least 50% of the particles, or at least 60% of the particles, or at least 70% of the particles, or at least 75% of the particles, or at least 80% of the particles, or at least 85% of the particles, or at least 90% of the particles, or at least 95% of the particles, or at least 98% of the particles include both solid acid catalyst and hydrogenation catalyst, are substantially composed of both solid acid catalyst and hydrogenation catalyst, or are composed of both solid acid catalyst and hydrogenation catalyst. In some embodiments, substantially each or each particle in the catalyst mixture comprises, consists essentially of, or consists of both a solid acid catalyst and a hydrogenation catalyst.

[0035] In some embodiments, the solid acid catalyst is an amorphous silica-alumina catalyst, and the hydrogenation catalyst is a supported noble metal catalyst (e.g., Pd / alumina). The weight ratio of silica-alumina to the noble metal is from about 1000:1 to about 5000:1, or from about 1600:1 to about 4500:1, or from about 2000:1 to about 4500:1, or from about 2000:1 to about 4000:1. In some embodiments, the upper limit of the weight ratio is 6500, 6000, 5500, 5000, 4800, 4500, 4200, 4000, 3800, 3500, 3200, or 3000. In some embodiments, the lower limit of the weight ratio is 500, 800, 1000, 1200, 1500, 1600, 1800, 2000, 2100, 2200, 2300, or 2400.

[0036] In some embodiments, the methods of the present disclosure are carried out at a temperature (reaction temperature, or temperature in the reaction zone) of about 150°C to about 400°C, or about 200°C to about 300°C, or about 230°C to about 270°C, or about 220°C to about 260°C. In some embodiments, the reaction temperature is at least 120°C, or at least 130°C, or at least 140°C, or at least 150°C, or at least 160°C, or at least 170°C, or at least 180°C, or at least 190°C, or at least 200°C, or at least 210°C, or at least 220°C. In some embodiments, the reaction temperature does not exceed 400°C, or does not exceed 380°C, or does not exceed 360°C, or does not exceed 340°C, or does not exceed 320°C, or does not exceed 300°C, or does not exceed 280°C, or does not exceed 270°C, or does not exceed 260°C.

[0037] The process of the present disclosure can be carried out at a pressure (reaction pressure, or pressure in the reaction zone) of no more than about 25 bar, or no more than about 20 bar, or no more than about 15 bar, or no more than about 10 bar, or no more than about 5 bar, or no more than about 4 bar, or no more than about 3 bar, or no more than about 2 bar, or no more than about 1.5 bar. In some embodiments, the reaction pressure is at least about 0.01 bar.

[0038] The contact time in the method of the present disclosure can be in the range of about 0.25 hour to about 2 hours, or about 0.4 hour to about 1.5 hours, or about 0.5 hour to about 1 hour. In some embodiments, the contact time is at least 0.05 hour, or at least 0.1 hour, or at least 0.15 hour, or at least 0.2 hour, or at least 0.25 hour, or at least 0.3 hour, or at least 0.4 hour, or at least 0.5 hour. In some embodiments, the contact time is no more than 4 hours, or no more than 3 hours, or no more than 2.5 hours, or no more than 2 hours, or no more than 1.5 hours, or no more than 1 hour.

[0039] The method of the present disclosure produces a product mixture comprising BCI. In certain embodiments, the product mixture also comprises hydrogenated MCDDK, MDIENE, positional isomers of BCI, and / or saturated BCI as by-products. The desired product BCI can be separated and recovered by methods known in the art such as distillation. In certain embodiments, the yield of BCI is at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%. The method of the present disclosure is a one-step method. As used herein, the term "one-step" about the method means that the method directly produces BCI without separating or purifying any reaction intermediates produced during the method.

[0040] Many aspects and embodiments have been described above and are exemplary and non-limiting only. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

[0041] Examples

[0042] The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.

[0043] Fixed catalyst bed preparation

[0044] Solid acid catalyst and hydrogenation catalyst are mixed in powder form, and then granulated and sieved to a particle size of 200-400 μm. The particles of the catalyst mixture are then mixed with silicon carbide (SiC, as a diluent) particles in a volume ratio of 1: 1. The resulting mixture is loaded into a vertical tube reactor to form a fixed catalyst bed. An additional amount of SiC is loaded into a fixed bed reactor to form a SiC layer on top of the catalyst bed. The reactor is then heated to 120 ° C for 6 hours under a nitrogen stream to dry and activate the solid acid catalyst.

[0045] General Procedures

[0046] MCDDK and hydrogen are fed to a preheater for mixing and preheating at 200°C to form a gaseous mixture. The MCDDK / hydrogen gas mixture is then fed to the top of a fixed bed reactor and passed through the reactor in a downflow mode. The product mixture effluent from the bottom of the reactor is collected in a gas-liquid trap for cooling, and gas (e.g., hydrogen) is separated from the liquid product mixture. A sample of the liquid product mixture is taken out for GC-MS analysis.

[0047] illustrate

[0048] SiAl is an amorphous silica-alumina catalyst (solid acid catalyst). The amorphous silica-alumina catalyst was obtained from WR Grace & Co. 0702 Catalyst.

[0049] Pd / C is palladium supported on an activated carbon carrier (hydrogenation catalyst). The Pd content is 5 wt % based on the total weight of the catalyst. The catalyst was obtained from Clariant.

[0050] Pd / Al2O3 is palladium supported on an alumina carrier (hydrogenation catalyst). The Pd content is 5 wt % based on the total weight of the catalyst. The catalyst was obtained from Johnson Matthey.

[0051] Ru / Al2O3 is ruthenium supported on an alumina carrier (hydrogenation catalyst). The Ru content is 5 wt% based on the total weight of the catalyst. The catalyst was obtained from Johnson Matthey.

[0052] Pt / Al2O3 is platinum supported on an alumina carrier (hydrogenation catalyst). The Pt content is 5 wt % based on the total weight of the catalyst. The catalyst was obtained from Merck.

[0053] Example 1 (comparison):

[0054] Only amorphous silica-alumina was used as catalyst. No hydrogenation catalyst was used in this example. The reaction conditions and results are shown in Table 1.

[0055] Table 1

[0056]

[0057] Note: In the table, T means reaction temperature in degrees Celsius; CT means contact time in hours; H2 / MCDDK means the molar ratio of hydrogen fed to the reaction zone to MCDDK; Conversion means the conversion of MCDDK; and "BCI+Iso" means BCI and its positional isomers.

[0058] Example 2:

[0059] Various catalyst mixtures were tested for the process of the present disclosure. The reaction temperature was 200° C. The contact time was 0.5 hours. The molar ratio of hydrogen to MCDDK fed to the reaction zone was 40. Other reaction conditions and results are shown in Table 2.

[0060] Table 2

[0061]

[0062] Note: In the table, SiAl / Metal means the weight ratio of silica-alumina to the noble metal.

[0063] Example 3:

[0064] In Example 3, the contact time effect was tested for the method of the present disclosure. The catalyst mixture used in the method was a mixture of amorphous silica-alumina catalyst and Pd / Al2O3 catalyst. The weight ratio of silica-alumina to precious metal (Pd) was 2480. The reaction temperature was 200°C. Other reaction conditions and results are shown in Table 3.

[0065] Table 3

[0066]

[0067] Example 4:

[0068] In Example 4, the reaction temperature effect was tested for the method of the present disclosure. The catalyst mixture used in the method was a mixture of an amorphous silica-alumina catalyst and a Pd / Al2O3 catalyst. The weight ratio of silica-alumina to precious metal (Pd) was 2480. Other reaction conditions and results are shown in Table 4.

[0069] Table 4

[0070]

[0071] Example 5:

[0072] In Example 5, the H2 / MCDDK molar ratio effect was tested for the method of the present disclosure. The catalyst mixture used in the method was a mixture of amorphous silica-alumina catalyst and Pd / Al2O3 catalyst. The weight ratio of silica-alumina to precious metal (Pd) was 3820. The reaction temperature was 250°C. Other reaction conditions and results are shown in Table 5.

[0073] Table 5

[0074]

[0075] Example 6:

[0076] Various solid acid catalysts were tested for the method of the present disclosure. The reaction temperature was 250° C. The contact time was 1 hour. The molar ratio of hydrogen to MCDDK fed to the reaction zone was 20. The weight ratio of the solid acid catalyst to the precious metal (Pd) was 3820. Other reaction conditions and results are shown in Table 6.

[0077] Table 6

[0078]

[0079] Note: γ-Al2O3 is a commercial gamma alumina from Sasol (Puralox Sba-200). CBV-400 is a commercial 12-membered ring USY zeolite from Zeolyst.

[0080] Example 7:

[0081] The catalyst mixture of SiAl and Pd / Al2O3 was compared with a single Pd / SiAl catalyst. Pd / SiAl is palladium supported on a SiAl carrier. The Pd content is 0.025wt% based on the total weight of the catalyst. The reaction temperature is 250°C. The contact time is 1 hour. The molar ratio of hydrogen fed to the reaction zone to MCDDK is 20. In the SiAl and Pd / Al2O3 catalyst mixture, the weight ratio of SiAl to the precious metal (Pd) is 3820. Other reaction conditions and results are shown in Table 7.

[0082] Table 7

[0083]

[0084] It should be noted that not all of the activities described above in the general description or examples are required, a portion of a specific activity may not be required, and one or more additional activities may be performed in addition to those described. Furthermore, the order in which the activities are listed is not necessarily the order in which they are performed.

[0085] In the foregoing description, concepts have been described with reference to specific embodiments. However, it will be appreciated by those skilled in the art that various modifications and changes may be made without departing from the scope of the invention as set forth in the following claims. Therefore, this description should be considered illustrative rather than restrictive, and all such modifications are intended to be included within the scope of the invention.

[0086] Benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, benefits, advantages, solutions to problems, and any one or more features that may cause any benefit, advantage, or solution to occur or make it more obvious are not to be construed as key, necessary, or essential features of any or all claims.

[0087] It is to be understood that, for clarity, certain features described herein in the context of separate embodiments may also be provided in a single embodiment in combination. Conversely, for brevity, the various features described in the context of a single embodiment may also be provided individually or in any sub-combination.

Claims

1. A method for preparing BCI, comprising: A starting material comprising MCDDK is contacted with hydrogen in the presence of a catalyst mixture in a reaction zone to produce a product mixture comprising BCI, wherein the catalyst mixture comprises a solid acid catalyst and a hydrogenation catalyst.

2. The method according to claim 1, wherein: The molar ratio of hydrogen to MCDDK fed to the reaction zone is from about 5:1 to about 100:

1.

3. The method according to claim 1 or 2, wherein: The solid acid catalyst is selected from the group consisting of alumina, silica-alumina, zeolites, silicoaluminophosphates, aluminophosphates, sulfated zirconia, zirconium oxide, zinc oxide, and mixtures thereof.

4. A method according to any one of the preceding claims, wherein: The solid acid catalyst is an amorphous silica-alumina catalyst.

5. A method according to any one of the preceding claims, wherein: The hydrogenation catalyst is a supported noble metal catalyst.

6. The method of claim 5, wherein: The carrier is alumina.

7. A method according to any one of the preceding claims, wherein: The hydrogenation catalyst is Pd / alumina and / or Pt / alumina.

8. A method according to any one of the preceding claims, wherein: The catalyst mixture is in the form of particles, and at least 50% of the particles contain both the solid acid catalyst and the hydrogenation catalyst.

9. The method according to any one of claims 1 to 3 or 8, wherein: The solid acid catalyst is an amorphous silica-alumina catalyst, the hydrogenation catalyst is a supported noble metal catalyst, and the weight ratio of silica-alumina to the noble metal is about 1000:1 to about 4500:

1.

10. A method according to any one of the preceding claims, wherein: The reaction temperature is from about 150°C to about 400°C.

11. A method according to any one of the preceding claims, wherein: The yield of BCI is at least about 75%.

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