Process for preparing one or more monoalcohols, diols and triols each having two or three carbon atoms

Abstract

The present invention relates to a method for preparing one or more monoalcohols, diols, and triols, each having two or three carbon atoms, and more particularly to a method for preparing one or more monoalcohols, diols, and triols using a nickel-containing catalyst, wherein the catalyst comprises zirconium oxide, and 5 to 60% by weight of the catalyst consists of zirconium oxide, calculated as ZrO2.

Description

[Technical Field]

[0001] The present invention relates to a method for preparing one or more monoalcohols, diols, and triols, each having two or three carbon atoms, and more particularly to a method for preparing one or more monoalcohols, diols, and triols using a nickel-containing catalyst, wherein the catalyst comprises zirconium oxide, and 5 to 50% by weight of the catalyst consists of zirconium oxide, calculated as ZrO2. [Background technology]

[0002] The chemical industry recognizes the need to reduce the carbon footprint of its products, i.e., the amount of carbon dioxide equivalent emitted per unit of production. To this end, there is growing interest in utilizing renewable feedstocks derived from biomass. A subclass of these feedstocks is sugars and their common sugar derivatives, such as sugar alcohols.

[0003] It is known that the reaction of sugar alcohols such as sorbitol with hydrogen (hydrogenolysis) can yield diols, triols, polyols, alcohols, and even alkanes. Among these products, 1,2-propanediol (1,2-PDO, PDA, propylene glycol) and ethylene glycol (EG) have attracted the most attention due to their potential applications as formulation additives in the polymer, food, feed, agriculture, personal care, and home care industries. It is also known that specific reaction conditions and additives are required to selectively convert sorbitol to these glycols. In particular, alkali and earth alkali metal hydroxides are added to aqueous and / or alcoholic sorbitol feed mixtures.

[0004] However, the use of dissolved base in addition to the required hydrothermal conditions directly poses a problem for the stability of the catalyst used. Thus, a recent review of heterogeneous catalyst research for sorbitol hydrogenolysis (Journal of Environmental Chemical Engineering 2022, 10, 107229; DOI: 10.1016 / j.jece.2022.107229) cited catalyst stability as a persistent challenge. Wang et al. (ChemCatChem 2019, 11, 4123-4129; DOI: 10.1002 / cctc.201900299) presented a catalyst containing Cu and an activated carbon support. During subsequent batch reactions using aqueous sorbitol feed (5% by mass) and Ca(OH)2 as an additive, the catalytic activity continuously decreased. This indicated that the catalyst was not stable under the tested reaction conditions (240 °C, 50 bar).

[0005] Attempts to operate without base additives have also been discussed in the academic literature. For example, Xin Jin et al. (ACS Catal. 2015, 5, 6545-6558; DOI: 10.1021 / acscatal.5b01324) presented a catalyst containing Cu, CaO, and Al2O3 and discussed its use in the hydrocracking of sorbitol (0.18 mol / L). Even without the addition of a hydroxide base, this catalyst was unstable at 230 °C and 76 bar, and the substrate conversion continuously decreased in successive batch experiments. Chen et al. (Catalysis Communications 2013, 39, 86-89; DOI: 10.1016 / j.catcom.2013.05.012) presented a catalyst containing Ni and MgO and tested it for the conversion of aqueous sorbitol (20 wt%). Under the applied reaction conditions, erosion of the support (MgO) occurred, resulting in a decrease in sorbitol conversion. In the above prior art, it is believed that the basic oxides CaO and MgO in the catalyst formulation replaced hydroxide additives at the expense of their dissolving effect, which limits the stability of the catalyst.

[0006] US 6,900,361 B2 describes a three-step continuous process for converting lactose to glycol. The third step is hydrogenolysis of the alditol-containing intermediate derived from this process to obtain glycol. Nickel-containing catalysts have been proposed as particularly useful hydrogenation catalysts, and US 5,814,112 and US 6,152,975 are cited as references. US 5,814,112 discloses a catalyst containing nickel and ruthenium, where the ruthenium is added to retard or reduce agglomeration or sintering of the nickel-dispersed phase. Each test was conducted using an aqueous phenolic reaction mixture without a basic additive. US 6,152,975 also discloses the addition of a metal other than ruthenium to a nickel-containing catalyst to inhibit or reduce agglomeration or sintering. Again, the tests were conducted on an aqueous phenolic reaction mixture without a basic additive. Finally, the initial concentration of lactose in the aqueous feed in US Pat. No. 6,900,361 B2 is specified to be 5-20% by weight, which is low and significantly reduces the economic viability of the process.

[0007] EP 2 403 818 A1 discloses a process for obtaining glycols (e.g., 1,2-PDO, EG, GLY) from sorbitol. The claimed catalyst comprises a polyacid-promoted zirconium oxide support impregnated with at least one catalytically active metal, such as nickel. The polyacid promoter is specified to contain at least one of chromium, molybdenum, tungsten, phosphorus, sulfur, or an organic polyacid. No examples of catalyst stability are provided. The average sorbitol conversion reached 71%, significantly limiting the overall glycol yield. Thus, the art lacks a catalyst that is sufficiently stable under the required operating conditions for producing glycols in high yields from sugar alcohols.

[0008] Despite the development of numerous catalysts for preparing diols and triols having two or three carbon atoms from sugars and sugar alcohols, respectively, there remains a need for more effective catalysts that overcome stability limitations and can be used on an industrial scale, particularly for catalysts that are stable in water at high temperatures, e.g., above 100°C, especially in the presence of acid or base, and that enable highly efficient processes for preparing diols and triols having two or three carbon atoms from sugars and sugar alcohols. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] US 6,900,361 B2 [Patent Document 2] US 5,814,112 [Patent Document 3] US 6,152,975 [Patent Document 4] EP 2 403 818 A1 [Non-patent literature]

[0010] [Non-Patent Document 1] Journal of Environmental Chemical Engineering 2022,10,107229;DOI:10.1016 / j.jece.2022.107229 [Non-patent document 2] Wang et al.,ChemCatChem 2019,11,4123-4129;DOI:10.1002 / cctc.201900299 [Non-patent document 3] Xin Jin et al.,ACS Catal.2015,5,6545-6558;DOI:10.1021 / acscatal.5b01324 [Non-patent document 4] Chen et al.,Catalysis Communications 2013,39,86-89;DOI:10.1016 / j.catcom.2013.05.012 Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, a further object of the present invention was to provide a method for preparing one or more diols and triols having two or three carbon atoms, respectively, that is not limited by a lack of catalyst stability. This involves selecting a catalyst that is mechanically and chemically stable in aqueous solutions of sugars and sugar alcohols at high temperatures, e.g., temperatures above 100°C. Preferably, the catalyst's stability should remain high even in the presence of acid or base additives during the hydrogenolysis reaction. Furthermore, the selected catalyst contains a hydrogenation metal, such as nickel or nickel and copper, to achieve high activity in the hydrogenolysis of sugars and sugar alcohols. This is necessary to achieve high levels of feedstock conversion and product yield. Furthermore, it has surprisingly been found that selected catalyst compositions containing high concentrations of hydrogenation metals, e.g., nickel and copper, particularly those in which 40 to 90% by weight of the catalyst is nickel and / or nickel and copper, achieve high activity in the hydrogenolysis of sugars and sugar alcohols. [Means for solving the problem]

[0012] Accordingly, the present invention relates to a method for preparing one or more monoalcohols, diols and triols having 2 or 3 carbon atoms, respectively, comprising the steps of: (i) providing a liquid aqueous feed stream comprising one or more sugars and sugar alcohols each having 3, 5, or 6 carbon atoms; (ii) feeding the liquid aqueous feed stream provided in accordance with step (i) to a reaction zone containing a catalyst comprising nickel and subjecting the feed stream to reaction conditions in the reaction zone to obtain a reaction mixture comprising one or more of a monoalcohol, a diol, and a triol; (iii) removing a liquid aqueous effluent stream from the reaction zone comprising one or more of a monoalcohol, a diol, and a triol; Including, Here, the catalyst contains zirconium oxide, and 5 to 60 mass % of the catalyst is made of zirconium oxide calculated as ZrO2.

[0013] Preferably, the catalyst further comprises a metal oxide, the metal of the metal oxide is preferably selected from the group consisting of Na, Mg, Al, Si, K, Ca, Ti, Mn, Co, Cu, Zn, Nb, Mo, La, Hf, W, and combinations of two or more thereof, more preferably from the group consisting of Na, Mg, Al, Si, Ca, Ti, Mn, Co, Cu, La, Hf, and combinations of two or more thereof, more preferably from the group consisting of Al, Si, Mn, Co, Cu, and combinations of two or more thereof, more preferably from the group consisting of Cu, Co, and combinations of two or more thereof, more preferably the metal of the metal oxide is Cu, more preferably the catalyst further comprises a metal oxide selected from the group consisting of CuO, CoO, Co2O3, Co3O4, and mixtures thereof, more preferably the catalyst further comprises CuO.

[0014] The catalyst preferably has a crystallinity in the range of 60-100%, preferably 80-100%, more preferably 90-100%, based on the total catalyst, as determined from the powder X-ray diffraction pattern of the catalyst, preferably as determined from the powder X-ray diffraction pattern of the catalyst according to the following formula, more preferably as determined from the powder X-ray diffraction pattern of the catalyst according to Example 4-1:

number

[0015] The powder X-ray diffraction pattern of the catalyst preferably shows signal peaks in the 2θ angle ranges of 28° to 29° and 31° to 32°.

[0016] Signal peaks in the 2θ angle ranges of 28° to 29° and 31° to 32° indicate crystalline ZrO2 in the monoclinic crystal phase. The difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle ranges of 28° to 29° and 31° to 32° is preferably greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°. The difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 28° to 29° is preferably at least three times greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°. The difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 28° to 29° is preferably at least six times greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°.

[0017] It is preferred that the catalyst comprises a monoclinic crystalline phase containing zirconium oxide and a tetragonal crystalline phase optionally containing zirconium oxide, wherein the monoclinic crystalline phase comprises zirconium oxide in an amount of 5 to 100 mass % and the tetragonal crystalline phase comprises zirconium oxide in an amount of 0 to 20 mass %, based on 100 mass % of all crystalline phases in the catalyst, as determined from a powder X-ray diffraction pattern of the catalyst, preferably as determined from a powder X-ray diffraction pattern of the catalyst according to Example 4-1.

[0018] As determined from the powder X-ray diffraction pattern of the catalyst, preferably as determined from the powder X-ray diffraction pattern of the catalyst according to Example 4-1, it is preferred that the monoclinic crystalline phase contains zirconium oxide in an amount of 10 to 80 mass % and the tetragonal crystalline phase contains zirconium oxide in an amount of 0 to 10 mass % based on 100 mass % of all crystalline phases in the catalyst. As determined from the powder X-ray diffraction pattern of the catalyst, preferably as determined from the powder X-ray diffraction pattern of the catalyst according to Example 4-1, it is preferred that the monoclinic crystalline phase contains zirconium oxide in an amount of 25 to 70 mass % and the tetragonal crystalline phase contains zirconium oxide in an amount of 0 to 5 mass % based on 100 mass % of all crystalline phases in the catalyst. As determined from the powder X-ray diffraction pattern of the catalyst, preferably as determined from the powder X-ray diffraction pattern of the catalyst according to Example 4-1, it is preferred that the monoclinic crystalline phase contains zirconium oxide in an amount of 30 to 60 mass % and the tetragonal crystalline phase contains zirconium oxide in an amount of 0 to 5 mass %, based on 100 mass % of all crystalline phases in the catalyst.

[0019] The catalyst preferably comprises 40 to 90 mass %, preferably 45 to 85 mass %, and more preferably 50 to 80 mass % of nickel (calculated as NiO).

[0020] It is preferable that 40 to 90 mass %, and preferably 60 to 85 mass % of the catalyst is made of nickel and copper (calculated as NiO and CuO).

[0021] The catalyst is preferably substantially free of aluminum oxide, preferably substantially free of Al2O3.

[0022] Preferably, 40 to 60 mass % of the catalyst consists of nickel (calculated as NiO), 10 to 30 mass % of the catalyst consists of copper (calculated as CuO), and 20 to 40 mass % of the catalyst consists of zirconium oxide (calculated as ZrO2).

[0023] Preferably, the catalyst is substantially free of CrO3 and / or Cr2O3, more preferably substantially free of CrO3 and Cr2O3.

[0024] The catalyst is preferably in the form of extrusions and / or in the form of a powder, preferably in the form of extrusions, more preferably in the form of extrudates and / or in the form of tablets, more preferably in the form of cylindrical tablets.

[0025] When the catalyst is in the form of a cylindrical tablet, the cylindrical tablet preferably has a diameter x height in the range of 1 x 1 to 10 x 10 mm, preferably 1.5 x 1.5 to 7 x 7 mm, more preferably 2.0 x 2.0 to 6 x 6 mm.

[0026] Preferably, the sugar having three carbon atoms is glyceraldehyde.

[0027] Preferably, one or more of the sugars having five carbon atoms is selected from the group consisting of ribose, arabinose, xylose, lyxose, and combinations of two or more thereof.

[0028] Preferably, one or more of the sugars having six carbon atoms are selected from the group consisting of glucose, galactose, maltose, lactose, sucrose, allose, altrose, mannose, gulose, idose, talose, and combinations of two or more thereof.

[0029] Preferably, the sugar alcohol having 3 carbon atoms is glycerol.

[0030] Preferably, one or more of the sugar alcohols having five carbon atoms are selected from the group consisting of arabitol, ribitol, xylitol, and combinations of two or more thereof, and more preferably, the sugar alcohols having six carbon atoms include xylitol.

[0031] Preferably, one or more of the sugar alcohols having six carbon atoms are selected from the group consisting of mannitol, iditol, galactitol, sorbitol, and combinations of two or more thereof, and more preferably, the sugar alcohol having six carbon atoms comprises sorbitol.

[0032] Preferably, one or more of the monoalcohols, diols and triols, each having two or three carbon atoms, are selected from the group consisting of 1,2-propanediol, ethylene glycol, 1,3-propanediol, glycerol, 1-propanol, 2-propanol, ethanol, and combinations of two or more thereof.

[0033] Preferably, one or more of the diols and triols having 2 or 3 carbon atoms, respectively, are selected from the group consisting of 1,2-propanediol, ethylene glycol, glycerol, and combinations of two or more thereof.

[0034] Preferably, the diol having two carbon atoms comprises ethylene glycol.

[0035] Preferably, the diol having 3 carbon atoms comprises 1,2-propanediol.

[0036] Preferably, the triol having three carbon atoms comprises glycerol.

[0037] The liquid aqueous feed stream of step (ii) preferably contains 20 to 99% by weight, preferably 25 to 60% by weight, more preferably 25 to 40% by weight of sugars or sugar alcohols having 3, 5 or 6 carbon atoms, respectively. It is preferred that the liquid aqueous feed stream provided in step (i) further comprises a solvent, preferably a solvent comprising a monoalcohol, preferably the monoalcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol and 1-butanol, more preferably the monoalcohol is selected from the group consisting of methanol, ethanol and 1-butanol, more preferably the monoalcohol is ethanol.

[0038] Preferably, the method involves the preparation of one or more diols and triols having 2 or 3 carbon atoms, respectively.

[0039] Preferably, the liquid aqueous feed stream provided in step (i) comprises one or more sugars and sugar alcohols each having 5 or 6 carbon atoms.

[0040] It is preferred that the liquid aqueous feed stream provided in step (i) further comprises a compound selected from the group consisting of a base, a Lewis acid and combinations thereof, and preferably the liquid aqueous feed stream provided in step (i) further comprises a base.

[0041] When the liquid aqueous feed stream provided in step (i) further comprises a base, it is preferred that in step (i) the base is selected from the group consisting of metal hydroxides and metal carbonates, wherein the metals of the metal hydroxides and metal carbonates are preferably selected from the group consisting of Li, Na, K, Ca, Mg, and combinations of two or more thereof, more preferably the base comprises one or more metal hydroxides and carbonates selected from the group consisting of LiOH, NaOH, Na2CO3, KOH, K2CO3, Ca(OH)2, Mg(OH)2, and mixtures of two or more thereof, preferably NaOH, Na2CO3, KOH, K2CO3, Ca(OH)2, Mg(OH)2, and mixtures of two or more thereof, more preferably the base comprises one or more metal hydroxides and metal carbonates selected from the group consisting of NaOH, Na2CO3, KOH, K2CO3, and mixtures of two or more thereof, more preferably the base comprises NaOH, preferably NaOH.

[0042] When the liquid aqueous feed stream provided in step (i) further comprises a base, it is preferred that the liquid aqueous feed stream provided in step (i) comprises 0.1 to 8 wt. % of the base, preferably 0.3 to 7 wt. %, more preferably 4 to 6 wt. %.

[0043] When the liquid aqueous feed stream provided in step (i) further comprises a Lewis acid, it is preferred that in step (i) the Lewis acid is selected from the group consisting of metal polyacids, wherein the metal of the metal polyacid is preferably selected from the group consisting of Mo, W, and combinations of two or more thereof, and more preferably the Lewis acid comprises one or more metal polyacids selected from the group consisting of H2WO4, (NH4)2MoO2, and combinations thereof.

[0044] The reaction conditions according to step (ii) preferably include a reaction pressure in the range of 40 to 250 bar, preferably 60 to 200 bar, more preferably 80 to 120 bar.

[0045] The reaction conditions according to step (ii) preferably include a temperature in the range of 140 to 220°C, preferably 170 to 200°C.

[0046] The reaction conditions for step (ii) are 0.1 to 5 h -1 , preferably 0.2 to 5 hours -1 It is preferred that the liquid hourly space velocity is in the range of

[0047] Preferably, the liquid aqueous feed stream provided in step (i) and fed to the reaction zone in step (ii) further comprises H2.

[0048] When the liquid aqueous feed stream provided in step (i) and fed to the reaction zone in step (ii) further comprises H2, it is preferred that the liquid aqueous feed stream exhibits an H2:sugar or sugar alcohol molar ratio of H2 to sugar or sugar alcohol in the range of 1 to 8, preferably 1.5 to 7, more preferably 1.8 to 7.

[0049] Preferably, the liquid aqueous effluent stream removed in step (iii) comprises 10 to 95 mol % C, preferably 30 to 95 mol % C, more preferably 40 to 95 mol % C, more preferably 50 to 90 mol % C, based on 100 mol % C of one or more sugars and sugar alcohols, each having 5 or 6 carbon atoms, where mol % C is defined according to formula (I):

number

[0050] Preferably, the liquid aqueous effluent stream removed in step (iii) comprises 10 to 95 mol % C, preferably 30 to 95 mol % C, more preferably 40 to 95 mol % C, even more preferably 50 to 90 mol % C, based on 100 mol % C, of ​​one or more of sugars and sugar alcohols having 5 or 6 carbon atoms, respectively, 1,2-propanediol, glycerol and ethylene glycol, where mol % C is defined according to formula (II):

number

[0051] Preferably, the liquid aqueous effluent stream removed in step (iii) comprises 10 to 95 mol % C, preferably 20 to 95 mol % C, more preferably 30 to 95 mol % C, even more preferably 40 to 90 mol % C, of ​​1,2-propanediol, based on 100 mol % C of one or more sugars and sugar alcohols, each having 5 or 6 carbon atoms, where mol % C is defined according to formula (III):

number

[0052] Preferably the process is a continuous process.

[0053] The process is preferably operated in a trickle bed reactor.

[0054] The present invention further relates to a method for preparing a catalyst, preferably a catalyst for the process according to the invention, said method comprising the following steps: (a) preparing a first mixture comprising zirconium oxide and water; (b) preparing a second mixture comprising a nickel precursor selected from the group consisting of nickel nitrate, nickel halide, nickel acetate, nickel sulfate, and optionally a copper precursor selected from the group consisting of copper nitrate, copper halide, copper acetate, copper sulfate, copper amine complexes, and combinations of two or more thereof, and water; (c) mixing the first mixture obtained in step (a), the second mixture obtained in step (b), and a precipitant to obtain a slurry containing solids and water; (d) removing water from the slurry obtained in step (c) to obtain a solid; (e) optionally drying the solid obtained in step (d) at a temperature in the range of 80 to 150°C to obtain a dry solid; (f) calcining the solid obtained in step (d), preferably the dried solid obtained in step (e), at a temperature in the range of 300 to 700 °C to obtain a catalyst comprising nickel oxide and zirconium oxide, preferably a catalyst for the process according to any one of embodiments 1 to 41, wherein 5 to 60 wt. % of the catalyst consists of zirconium oxide, calculated as ZrO. Includes.

[0055] When the present invention relates to a method for preparing a catalyst, preferably, step (a) comprises the following steps: (a.1) preparing a solution comprising a zirconium precursor selected from the group consisting of zirconium nitrate, zirconium halide, zirconyl halide, zirconium acetate, zirconium sulfate, and combinations of two or more thereof, and water; (a.2) mixing the solution prepared in step (a.1) with a precipitant to obtain a suspension; (a.3) removing water from the suspension obtained in step (a.3) to obtain a solid; (a.4) optionally drying the solid obtained in step (a.4) at a temperature in the range of 80 to 150°C to obtain a dry solid; (a.5) calcining the solid obtained in step (a.3), preferably the dried solid obtained in step (a.4), at a temperature in the range of 400-800°C to obtain zirconium oxide; Includes.

[0056] The zirconium oxide preferably has a crystallinity in the range of 60 to 100%, preferably 80 to 100%, more preferably 90 to 100%, based on the total zirconium oxide, as determined from the powder X-ray diffraction pattern of the zirconium oxide, preferably as determined from the powder X-ray diffraction pattern of the zirconium oxide according to the following formula, more preferably as determined from the powder X-ray diffraction pattern of the zirconium oxide according to Example 1-1:

number

[0057] The powder X-ray diffraction pattern of zirconium oxide preferably exhibits signal peaks in the 2θ angle ranges of 28° to 29° and 31° to 32°, and preferably the signal peaks indicate crystalline zirconium oxide of a monoclinic crystal phase.

[0058] The difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle ranges of 28° to 29° and 31° to 32° is preferably greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°. The difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 28° to 29° is preferably at least two times greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°. The difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 28° to 29° is preferably at least four times greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°.

[0059] It is preferred that the zirconium oxide comprises a monoclinic crystalline phase and, optionally, a tetragonal crystalline phase, wherein the zirconium oxide comprises 50 to 100% by mass of monoclinic crystals and 0 to 50% by mass of tetragonal crystalline phase, based on 100% by mass of all crystalline phases in the zirconium oxide, as determined from the powder X-ray diffraction pattern of the zirconium oxide, preferably as determined from the powder X-ray diffraction pattern of the zirconium oxide according to Example 1-1. It is preferred that the zirconium oxide comprises 70 to 100% by mass of monoclinic crystals and 0 to 30% by mass of tetragonal crystalline phase, based on 100% by mass of all crystalline phases in the zirconium oxide, as determined from the powder X-ray diffraction pattern of the zirconium oxide, preferably as determined from the powder X-ray diffraction pattern of the zirconium oxide according to Example 1-1. As determined from the powder X-ray diffraction pattern of zirconium oxide, preferably as determined from the powder X-ray diffraction pattern of zirconium oxide according to Example 1-1, it is preferred that the zirconium oxide contains 80 to 100 mass% monoclinic crystals and 0 to 20 mass% tetragonal crystalline phase, based on 100 mass% of all crystalline phases in the zirconium oxide.As determined from the powder X-ray diffraction pattern of zirconium oxide, preferably as determined from the powder X-ray diffraction pattern of zirconium oxide according to Example 1-1, it is preferred that the zirconium oxide contains 90 to 100 mass% monoclinic crystals and 0 to 10 mass% tetragonal crystalline phase, based on 100 mass% of all crystalline phases in the zirconium oxide.

[0060] In step (c) and / or step (a.3), it is preferred that the precipitating agent is selected from the group consisting of sodium carbonate, sodium hydroxide, ammonia, ammonium hydroxide, and combinations of two or more thereof.

[0061] In one embodiment, the catalyst is obtained through a series of steps: precipitation, washing, drying, and annealing. After the annealing step, the catalyst is in an oxidized state. The oxidized state is characterized by the presence of metals in the form of metal oxides or mixed metal oxides. Preferably, Ni is present as NiO, Zr is present as ZrO2, and Cu is present as CuO. The composition of the catalyst is determined by analyzing the elemental content of the material in the oxidized state. The obtained value is converted to oxide content using the molecular weights of the metals and oxides.

[0062] In one embodiment, the catalyst is reduced prior to use or reduced during use. Thus, the active catalyst comprises nickel in a reduced state, preferably as nickel metal. In this case, the catalyst comprises nickel including an oxidation state of 0.

[0063] In one embodiment, the reduction of the catalyst is incomplete. Thus, the active catalyst comprises nickel in an oxidation state, preferably as nickel oxide, more preferably NiO. In this case, the catalyst comprises nickel comprising an oxidation state selected from the group consisting of +I, +II, +III, +IV, and combinations of two or more thereof, more preferably the catalyst comprises nickel comprising the +II oxidation state.

[0064] In one embodiment, when Cu is present in the catalyst, the catalyst is reduced before use or during use. Thus, the active catalyst contains copper in a reduced state, preferably as copper metal. In this case, the catalyst contains copper in the zero oxidation state.

[0065] A further object of the present invention was to provide a method for preparing one or more diols and triols having two or three carbon atoms, respectively, that is not limited by a lack of catalyst stability. This involves selecting a catalyst that is mechanically and chemically stable in aqueous solutions of sugars and sugar alcohols at high temperatures. Preferably, the catalyst's stability must remain high in the presence of a base additive during the hydrogenolysis reaction. Furthermore, the selected catalyst contains a hydrogenation metal, such as nickel or nickel-copper, to achieve high activity in the hydrogenolysis of sugars and sugar alcohols. This is necessary to achieve high levels of feedstock conversion and product yield. Furthermore, it has been surprisingly discovered that selected catalyst compositions containing high concentrations of hydrogenation metals, such as nickel and copper, particularly those in which 40 to 90% by weight of the catalyst is nickel and / or nickel and copper, achieve high activity in the hydrogenolysis of sugars and sugar alcohols.

[0066] Accordingly, the present invention further relates to a method for preparing one or more diols and triols having 2 or 3 carbon atoms, respectively, comprising the steps of: (i) providing a liquid aqueous feed stream comprising one or more sugars and sugar alcohols each having 5 or 6 carbon atoms; (ii) feeding the liquid aqueous feed stream provided in accordance with step (i) to a reaction zone containing a catalyst comprising nickel and subjecting the feed stream to reaction conditions in the reaction zone to obtain a reaction mixture comprising one or more of a diol and a triol; (iii) removing a liquid aqueous effluent stream from the reaction zone comprising one or more of the diol and triol; Including, Here, the catalyst contains zirconium oxide, with 5 to 50 mass% of the catalyst being zirconium oxide calculated as ZrO2, and 0 to 15 mass% of the catalyst being aluminum oxide calculated as Al2O3.

[0067] In one embodiment, the catalyst is obtained through a series of steps: precipitation, washing, drying, and annealing. After the annealing step, the catalyst is in an oxidized state. The oxidized state is characterized by the presence of metals in the form of metal oxides or mixed metal oxides. Preferably, Ni is present as NiO, Zr is present as ZrO2, and Al is present as Al2O3. The composition of the catalyst is determined by analyzing the elemental content of the material in the oxidized state. The obtained value is converted to oxide content using the molecular weights of the metals and oxides.

[0068] In one embodiment, the catalyst is reduced prior to use or reduced during use. Thus, the active catalyst comprises nickel in a reduced state, preferably as nickel metal. In this case, the catalyst comprises nickel including an oxidation state of 0.

[0069] In one embodiment, the reduction of the catalyst is incomplete. Thus, the active catalyst comprises nickel in an oxidation state, preferably as nickel oxide, more preferably NiO. In this case, the catalyst comprises nickel comprising an oxidation state selected from the group consisting of +I, +II, +III, +IV, and combinations of two or more thereof, more preferably the catalyst comprises nickel comprising the +II oxidation state.

[0070] In one embodiment, the catalyst is substantially free of aluminum oxide, preferably substantially free of Al2O3. When the catalyst is substantially free of aluminum oxide, preferably substantially free of Al2O3, 0% by weight of the catalyst consists of aluminum oxide calculated as Al2O3. In a further embodiment, the catalyst comprises aluminum oxide, wherein 0.01-15% by weight of the catalyst consists of aluminum oxide calculated as Al2O3.

[0071] Preferably, the catalyst further comprises a metal oxide, wherein the metal of the metal oxide is preferably selected from the group consisting of Na, Mg, Si, K, Ca, Ti, Mn, Co, Cu, Zn, Nb, Mo, La, Hf, W, and combinations of two or more thereof, more preferably from the group consisting of Na, Mg, Si, Ca, Ti, Mn, Cu, Mo, La, Hf, W, and combinations of two or more thereof, more preferably from the group consisting of Si, Ca, Cu, Mn, Mo, and combinations of two or more thereof, more preferably from the group consisting of Si, Mo, and combinations thereof, and more preferably the catalyst is selected from the group consisting of SiO2, CuO, MoO x wherein x is 1 to 3, and mixtures thereof.

[0072] It is preferred that 0 to 10 mass %, preferably 0 to 5.5 mass % of the catalyst consists of aluminum oxide calculated as Al2O3.

[0073] It is preferred that 40 to 90 mass %, preferably 60 to 85 mass % of the catalyst is made of nickel calculated as NiO.

[0074] It is preferred that 0.1 to 5.5 mass %, preferably 2 to 5.5 mass %, more preferably 3 to 5 mass % of the catalyst consists of aluminum oxide calculated as Al2O3.

[0075] Preferably, 65 to 75 mass% of the catalyst is composed of nickel calculated as NiO, 5 to 7 mass% of the catalyst is composed of zirconium oxide calculated as ZrO2, and 3 to 5 mass% of the catalyst is composed of aluminum oxide calculated as Al2O3.

[0076] Preferably, 65 to 75 mass% of the catalyst is composed of nickel calculated as NiO, 5 to 7 mass% of the catalyst is composed of zirconium oxide calculated as ZrO2, 3 to 5 mass% of the catalyst is composed of aluminum oxide calculated as Al2O3, and 15 to 25 mass% of the catalyst is composed of silicon oxide calculated as SiO2.

[0077] In one embodiment, the catalyst comprises nickel and copper. When the catalyst comprises nickel and copper, it is preferred that 40 to 90 wt. %, preferably 60 to 85 wt. % of the catalyst consists of nickel and copper, calculated as NiO and CuO.

[0078] In one embodiment, the catalyst is obtained through a series of steps: precipitation, washing, drying, and annealing. After the annealing step, the catalyst is in an oxidized state. The oxidized state is characterized by the presence of metals in the form of metal oxides or mixed metal oxides. Preferably, Ni is present as NiO, Cu is present as CuO, Zr is present as ZrO2, and Mo is present as MoO3. The composition of the catalyst is determined by analyzing the elemental content of the material in the oxidized state. The obtained value is converted to oxide content using the molecular weights of the metals and oxides.

[0079] In one embodiment, the catalyst is reduced prior to use or during use. Thus, the active catalyst comprises reduced nickel and copper, preferably as nickel metal and copper metal. In this case, the catalyst comprises nickel and copper including the zero oxidation state.

[0080] In one embodiment, the reduction of the catalyst is incomplete. Thus, the active catalyst comprises nickel and copper in oxidation states, preferably as nickel oxide and copper oxide, more preferably NiO and CuO. In this case, the catalyst comprises nickel and copper in oxidation states selected from the group consisting of +I, +II, +III, +IV, and combinations of two or more thereof, more preferably the catalyst comprises nickel and copper in the +II oxidation state.

[0081] When the catalyst comprises nickel and copper, it is preferred that the catalyst be substantially free of aluminum oxide, preferably substantially free of Al2O3.

[0082] When the catalyst contains nickel and copper, it is preferred that 40 to 60 mass% of the catalyst be nickel calculated as NiO, 10 to 30 mass% of the catalyst be copper calculated as CuO, and 20 to 40 mass% of the catalyst be zirconium oxide calculated as ZrO2.

[0083] When the catalyst contains nickel and copper, it is preferable that 40 to 60 mass% of the catalyst consists of nickel calculated as NiO, 10 to 30 mass% of the catalyst consists of copper calculated as CuO, 20 to 40 mass% of the catalyst consists of zirconium oxide calculated as ZrO2, and 0.1 to 5 mass% of the catalyst consists of molybdenum oxide calculated as MoO3.

[0084] It is preferred that the zirconium oxide comprises one or more crystalline phases and / or is amorphous, wherein the one or more crystalline phases of the zirconium oxide are selected from the group consisting of the monoclinic, tetragonal, and cubic phases of zirconium oxide, and mixtures of two or three thereof.

[0085] The catalyst is preferably substantially free of CrO3 and / or Cr2O3, preferably substantially free of CrO3 and Cr2O3.

[0086] The catalyst is preferably in the form of extrusions and / or in the form of a powder, preferably in the form of extrusions, more preferably in the form of extrudates and / or in the form of tablets, more preferably in the form of cylindrical tablets.

[0087] When the catalyst is in the form of a cylindrical tablet, the cylindrical tablet preferably has a diameter x height in the range of 1 x 1 to 10 x 10 mm, preferably 2 x 2 to 7 x 7 mm, more preferably 2.5 x 2.5 to 6 x 6 mm.

[0088] Preferably, one or more of the sugars having five carbon atoms is selected from the group consisting of ribose, arabinose, xylose, lyxose, and combinations of two or more thereof.

[0089] Preferably, one or more of the sugars having six carbon atoms are selected from the group consisting of glucose, galactose, maltose, lactose, sucrose, allose, altrose, mannose, gulose, idose, talose, and combinations of two or more thereof.

[0090] Preferably, one or more of the sugar alcohols having five carbon atoms are selected from the group consisting of arabitol, ribitol, xylitol, and combinations of two or more thereof, and more preferably, the sugar alcohols having six carbon atoms include xylitol.

[0091] Preferably, one or more of the sugar alcohols having six carbon atoms are selected from the group consisting of mannitol, iditol, galactitol, sorbitol, and combinations of two or more thereof, and more preferably, the sugar alcohol having six carbon atoms comprises sorbitol.

[0092] It is preferred that one or more of the diols and triols each having 2 or 3 carbon atoms are selected from the group consisting of 1,2-propanediol, ethylene glycol, 1,3-propanediol, glycerol, and combinations of two or more thereof, and preferably one or more of the diols and triols each having 2 or 3 carbon atoms are selected from the group consisting of 1,2-propanediol, ethylene glycol, glycerol, and combinations of two or more thereof.

[0093] Preferably, the diol having two carbon atoms comprises ethylene glycol.

[0094] Preferably, the diol having 3 carbon atoms comprises 1,2-propanediol.

[0095] Preferably, the triol having three carbon atoms comprises glycerol.

[0096] The liquid aqueous feed stream prepared in step (ii) preferably contains 20 to 60% by weight, preferably 25 to 50% by weight, more preferably 25 to 40% by weight of sugars or sugar alcohols having 5 or 6 carbon atoms, respectively.

[0097] It is preferred that the liquid aqueous feed stream provided in step (i) further comprises a solvent, preferably a solvent comprising a monohydric alcohol, preferably the solvent comprising a monohydric alcohol, more preferably the monohydric alcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol and 1-butanol.

[0098] It is preferred that the liquid aqueous feed stream provided in step (i) further comprises a compound selected from the group consisting of a base, a Lewis acid and combinations thereof, preferably a base.

[0099] When the liquid aqueous feed stream provided in step (i) further comprises a base, it is preferred that the base is selected from the group consisting of metal hydroxides, wherein the metal of the metal hydroxide is preferably selected from the group consisting of Li, Na, K, Ca, Mg, and combinations of two or more thereof, more preferably the base comprises one or more metal hydroxides selected from the group consisting of LiOH, NaOH, KOH, Ca(OH), Mg(OH), and mixtures of two or more thereof, preferably from the group consisting of NaOH, KOH, Ca(OH), Mg(OH), and mixtures of two or more thereof, more preferably the base comprises one or more metal hydroxides selected from the group consisting of NaOH, KOH, and mixtures of two or more thereof, more preferably the base comprises NaOH.

[0100] When the liquid aqueous feed stream provided in step (i) further comprises a base, it is preferred that the liquid aqueous feed stream provided in step (i) comprises 0.1 to 8 wt. % of the base, preferably 0.3 to 7 wt. %, more preferably 4 to 6 wt. %.

[0101] When the liquid aqueous feed stream provided in step (i) further comprises an acid, the acid is preferably selected from the group consisting of phosphoric acid, sulfuric acid, and combinations thereof.

[0102] When the liquid aqueous feed stream provided in step (i) further comprises a Lewis acid, it is preferred that the Lewis acid is selected from the group consisting of metal polyacids, wherein the metal of the metal polyacid is preferably selected from the group consisting of Mo, W, and combinations of two or more thereof, and more preferably the Lewis acid comprises one or more metal polyacids selected from the group consisting of H2WO4, (NH4)2MoO2, and combinations thereof.

[0103] The reaction conditions according to step (ii) preferably include a reaction pressure in the range of 40 to 170 bar, preferably 60 to 150 bar, more preferably 80 to 120 bar.

[0104] The reaction conditions according to step (ii) preferably include a temperature in the range of 140 to 210°C, preferably 170 to 200°C.

[0105] The reaction conditions for step (ii) are 0.1 to 5 h -1 , preferably 0.2 to 5 hours -1 It is preferred that the liquid hourly space velocity is in the range of

[0106] Preferably, the liquid aqueous feed stream provided in step (i) and fed to the reaction zone in step (ii) further comprises H2.

[0107] When the liquid aqueous feed stream provided in step (i) and fed to the reaction zone in step (ii) further comprises H2, it is preferred that the liquid aqueous feed stream exhibits an H2:sugar or sugar alcohol molar ratio of H2 to sugar or sugar alcohol in the range of 1 to 8, preferably 1.5 to 7, more preferably 1.8 to 7.

[0108] Preferably, the liquid aqueous effluent stream removed in step (iii) comprises, based on 100 mol % C of one or more sugars and sugar alcohols having 5 or 6 carbon atoms, respectively, 10 to 95 mol % C, preferably 15 to 95 mol % C, more preferably 20 to 85 mol % C, more preferably 25 to 80 mol % C of one or more diols and triols having 2 or 3 carbon atoms, respectively, where mol % C is defined according to formula (I):

number

[0109] Preferably, the liquid aqueous effluent stream removed in step (iii) comprises 10 to 95 mol % C, preferably 15 to 90 mol % C, more preferably 20 to 85 mol % C, even more preferably 25 to 80 mol % C, based on 100 mol % C, of ​​one or more of sugars and sugar alcohols having 5 or 6 carbon atoms, respectively, 1,2-propanediol, glycerol and ethylene glycol, where mol % C is defined according to formula (II):

number

[0110] Preferably, the liquid aqueous effluent stream removed in step (iii) comprises 10 to 80 mol % C, preferably 15 to 75 mol % C, more preferably 20 to 70 mol % C, even more preferably 25 to 65 mol % C, of ​​1,2-propanediol, based on 100 mol % C of one or more sugars and sugar alcohols, each having 5 or 6 carbon atoms, where mol % C is defined according to formula (III):

number

[0111] Preferably the process is a continuous process.

[0112] The process is preferably operated in a trickle bed reactor. [Brief explanation of the drawings]

[0113] [Figure 1] FIG. 1 shows the X-ray diffraction pattern of the ZrO powder synthesized in Example 1-1. Markers in the graph indicate the positions of diffraction signals shown in database references for specific zirconium dioxide crystalline phases. The references were obtained from the Powder Diffraction File database and are identified in the legend by PDF numbers (XX-XXX-XXXX). Matching the recorded signal positions with the reference signal positions reveals the qualitative phase composition of the zirconium dioxide powder of Example 1-1. [Figure 2] Figure 2 shows the X-ray diffraction patterns of catalyst A-1 before use synthesized in Example 2-1 and catalyst A-1 after use according to Example 3-1. Qualitative evaluation by matching the reference pattern was performed in the same manner as in Figure 1 / Example 1-1. [Figure 3] Figure 3 shows the X-ray diffraction patterns of Catalyst B synthesized in Comparative Example 1-1 before use and Catalyst B after use in Comparative Example 2-1. Qualitative evaluation by matching the reference pattern was performed in the same manner as in Figure 1 / Example 1-1. DETAILED DESCRIPTION OF THE INVENTION

[0114] The present invention is further described by the following series of embodiments and combinations of embodiments resulting from the indicated dependencies and backward references. In particular, in each instance where a range of embodiments is mentioned, it should be noted that in the context of terms such as "described in any one of embodiments 1 to 4...", all embodiments within this range are meant to be expressly disclosed to those skilled in the art, i.e., this expression means that those skilled in the art will understand this as being synonymous with "described in any one of embodiments 1, 2, 3, and 4...". Furthermore, it should be expressly noted that the following set of embodiments represents a suitably structured part of the description directed to general and preferred aspects of the present invention, rather than a set of claims determining the scope of protection.

[0115] 1. A process for preparing one or more monoalcohols, diols and triols each having 2 or 3 carbon atoms, comprising: (i) providing a liquid aqueous feed stream comprising one or more sugars and sugar alcohols each having 3, 5, or 6 carbon atoms; (ii) feeding the liquid aqueous feed stream provided in accordance with step (i) to a reaction zone containing a catalyst comprising nickel and subjecting the feed stream to reaction conditions in the reaction zone to obtain a reaction mixture comprising one or more of a monoalcohol, a diol, and a triol; (iii) removing a liquid aqueous effluent stream from the reaction zone comprising one or more of a monoalcohol, a diol, and a triol; Including, The method wherein the catalyst comprises zirconium oxide, and wherein 5 to 60 wt. % of the catalyst consists of zirconium oxide calculated as ZrO2.

[0116] 2. The method of embodiment 1, wherein the catalyst further comprises a metal oxide, and the metal of the metal oxide is preferably selected from the group consisting of Na, Mg, Al, Si, K, Ca, Ti, Mn, Co, Cu, Zn, Nb, Mo, La, Hf, W, and combinations of two or more thereof, more preferably from the group consisting of Na, Mg, Al, Si, Ca, Ti, Mn, Co, Cu, La, Hf, and combinations of two or more thereof, more preferably from the group consisting of Al, Si, Mn, Co, Cu, and combinations of two or more thereof, more preferably from the group consisting of Cu, Co, and combinations thereof; more preferably, the metal of the metal oxide is Cu; more preferably, the catalyst further comprises a metal oxide selected from the group consisting of CuO, CoO, Co2O3, Co3O4, and mixtures thereof; more preferably, the catalyst further comprises CuO.

[0117] 3. The catalyst has a crystallinity in the range of 60-100%, preferably 80-100%, more preferably 90-100%, based on the total catalyst, as determined from the powder X-ray diffraction pattern of the catalyst, preferably as determined from the powder X-ray diffraction pattern of the catalyst according to the following formula, more preferably as determined from the powder X-ray diffraction pattern of the catalyst according to Example 4-1:

number

[0118] 4. The method of any one of embodiments 1 to 3, wherein the powder X-ray diffraction pattern of the catalyst exhibits signal peaks in the 2θ angle ranges of 28° to 29° and 31° to 32°, and wherein the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle ranges of 28° to 29° and 31° to 32° is greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°, more preferably, the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 28° to 29° is at least three times greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°, and more preferably, the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 28° to 29° is at least six times greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°.

[0119] 5. The catalyst comprises a monoclinic crystalline phase containing zirconium oxide and a tetragonal crystalline phase optionally containing zirconium oxide, preferably, as determined from a powder X-ray diffraction pattern of the catalyst, preferably according to Example 4-1, based on 100% by mass of all crystalline phases in the catalyst, the monoclinic crystalline phase comprises zirconium oxide in an amount of 5 to 100% by mass and the tetragonal crystalline phase comprises zirconium oxide in an amount of 0 to 20% by mass, preferably, as determined from a powder X-ray diffraction pattern of the catalyst, preferably according to Example 4-1, based on 100% by mass of all crystalline phases in the catalyst, 5. The method of any one of embodiments 1 to 4, wherein the monoclinic crystalline phase comprises zirconium oxide in an amount of 25 to 70% by weight and the tetragonal crystalline phase comprises zirconium oxide in an amount of 0 to 5% by weight, based on 100% by weight of all crystalline phases in the catalyst, as determined from the powder X-ray diffraction pattern of the catalyst, preferably as determined from the powder X-ray diffraction pattern of the catalyst according to Example 4-1; more preferably, the monoclinic crystalline phase comprises zirconium oxide in an amount of 30 to 60% by weight and the tetragonal crystalline phase comprises zirconium oxide in an amount of 0 to 5% by weight, based on 100% by weight of all crystalline phases in the catalyst, as determined from the powder X-ray diffraction pattern of the catalyst, preferably as determined from the powder X-ray diffraction pattern of the catalyst according to Example 4-1.

[0120] 6. The method according to any one of the preceding embodiments, wherein 40 to 90% by weight, preferably 45 to 85% by weight, more preferably 50 to 80% by weight of the catalyst consists of nickel calculated as NiO.

[0121] 7. The method according to any one of the preceding embodiments, wherein 40 to 90% by weight, preferably 60 to 85% by weight, of the catalyst consists of nickel and copper, calculated as NiO and CuO.

[0122] 8. The method of any one of the preceding embodiments, wherein the catalyst is substantially free of aluminum oxide, preferably substantially free of Al2O3.

[0123] 9. The method of any one of the preceding claims, wherein 40-60 wt.% of the catalyst consists of nickel, calculated as NiO, 10-30 wt.% of the catalyst consists of copper, calculated as CuO, and 20-40 wt.% of the catalyst consists of zirconium oxide, calculated as ZrO.

[0124] 10. The method of any one of embodiments 1 to 9, wherein the catalyst is substantially free of CrO3 and / or Cr2O3, preferably substantially free of CrO3 and Cr2O3.

[0125] 11. The method according to any one of the preceding embodiments, wherein the catalyst is in the form of extrusions and / or in the form of a powder, preferably in the form of extrudates and / or in the form of tablets, more preferably in the form of cylindrical tablets.

[0126] 12. The method according to any one of the preceding embodiments, wherein the cylindrical tablet has a diameter x height in the range of 1 x 1 to 10 x 10 mm, preferably 1.5 x 1.5 to 7 x 7 mm, more preferably 2.0 x 2.0 to 6 x 6 mm.

[0127] 13. The method of any one of embodiments 1 to 12, wherein the sugar having 3 carbon atoms is glyceraldehyde.

[0128] 14. The method of any one of the preceding claims, wherein one or more of the sugars having 14.5 carbon atoms are selected from the group consisting of ribose, arabinose, xylose, lyxose, and combinations of two or more thereof.

[0129] 15. The method of any one of the preceding claims, wherein one or more of the sugars having 6 carbon atoms are selected from the group consisting of glucose, galactose, maltose, lactose, sucrose, allose, altrose, mannose, gulose, idose, talose, and combinations of two or more thereof.

[0130] 16. The method of any one of embodiments 1 to 15, wherein the sugar alcohol having 3 carbon atoms is glycerol.

[0131] 17. The method of any one of the preceding claims, wherein one or more of the sugar alcohols having 17.5 carbon atoms are selected from the group consisting of arabitol, ribitol, xylitol, and combinations of two or more thereof, and more preferably, the sugar alcohol having 6 carbon atoms comprises xylitol.

[0132] 18. The method of any one of the preceding claims, wherein one or more of the sugar alcohols having 6 carbon atoms are selected from the group consisting of mannitol, iditol, galactitol, sorbitol, and combinations of two or more thereof, more preferably, the sugar alcohol having 6 carbon atoms comprises sorbitol.

[0133] 19. The method of any one of embodiments 1 to 18, wherein one or more of the monoalcohols, diols, and triols, each having 2 or 3 carbon atoms, are selected from the group consisting of 1,2-propanediol, ethylene glycol, 1,3-propanediol, glycerol, 1-propanol, 2-propanol, ethanol, and combinations of two or more thereof.

[0134] 20. The method of any one of embodiments 1 to 19, wherein one or more of the diols and triols, each having 2 or 3 carbon atoms, are selected from the group consisting of 1,2-propanediol, ethylene glycol, glycerol, and combinations of two or more thereof.

[0135] 21. The method of any one of embodiments 1 to 20, wherein the diol having 2 carbon atoms comprises ethylene glycol.

[0136] 22. The method of any one of the preceding embodiments, wherein the diol having 3 carbon atoms comprises 1,2-propanediol.

[0137] 23. The method of any one of embodiments 1 to 22, wherein the triol having 3 carbon atoms comprises glycerol.

[0138] 24. The method of any one of the preceding embodiments, wherein the liquid aqueous feed stream of step (ii) comprises 20 to 99% by weight, preferably 25 to 60% by weight, more preferably 25 to 40% by weight, of sugars or sugar alcohols having 3, 5 or 6 carbon atoms, respectively.

[0139] 25. The method of any one of embodiments 1 to 24, wherein the liquid aqueous feed stream provided in step (i) further comprises a solvent, preferably a solvent comprising a monoalcohol, preferably the monoalcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol and 1-butanol, more preferably the monoalcohol is selected from the group consisting of methanol, ethanol and 1-butanol, more preferably the monoalcohol is ethanol.

[0140] 26. The method of any one of embodiments 1 to 25, wherein the method relates to the preparation of one or more diols and triols having 2 or 3 carbon atoms, respectively.

[0141] 27. The method of any one of embodiments 1 to 26, wherein the liquid aqueous feed stream provided in step (i) comprises one or more sugars and sugar alcohols, each having 5 or 6 carbon atoms.

[0142] 28. The method of any one of embodiments 1 to 27, wherein the liquid aqueous feed stream provided in step (i) further comprises a compound selected from the group consisting of a base, a Lewis acid, and combinations thereof, preferably wherein the liquid aqueous feed stream provided in step (i) further comprises a base.

[0143] 29. The method of embodiment 28, wherein in step (i), the base is selected from the group consisting of metal hydroxides and metal carbonates, and the metals of the metal hydroxides and metal carbonates are preferably selected from the group consisting of Li, Na, K, Ca, Mg, and combinations of two or more thereof; more preferably, the base comprises one or more metal hydroxides and carbonates selected from the group consisting of LiOH, NaOH, Na2CO3, KOH, K2CO3, Ca(OH)2, Mg(OH)2, and mixtures of two or more thereof, preferably NaOH, Na2CO3, KOH, K2CO3, Ca(OH)2, Mg(OH)2, and mixtures of two or more thereof; more preferably, the base comprises one or more metal hydroxides and metal carbonates selected from the group consisting of NaOH, Na2CO3, KOH, K2CO3, and mixtures of two or more thereof; more preferably, the base comprises NaOH, preferably NaOH.

[0144] 30. The method of embodiment 28 or 29, wherein the liquid aqueous feed stream provided in step (i) comprises 0.1 to 8 wt. %, preferably 0.3 to 7 wt. %, more preferably 4 to 6 wt. % of a base.

[0145] 31. The method of embodiment 28, wherein in step (i), the Lewis acid is selected from the group consisting of metal polyacids, and the metal of the metal polyacid is preferably selected from the group consisting of Mo, W, and combinations of two or more thereof, and more preferably the Lewis acid comprises one or more metal polyacids selected from the group consisting of H2WO4, (NH4)2MoO2, and combinations thereof.

[0146] 32. The process of any one of the preceding embodiments, wherein the reaction conditions according to step (ii) comprise a reaction pressure in the range of 40 to 250 bar, preferably 60 to 200 bar, more preferably 80 to 120 bar.

[0147] 33. The method of any one of embodiments 1 to 32, wherein the reaction conditions according to step (ii) comprise a temperature in the range of 140 to 220°C, preferably 170 to 200°C.

[0148] 34. The reaction conditions for step (ii) are 0.1 to 5 h -1 , preferably 0.2 to 5 hours -1 34. The method of any one of the preceding claims, comprising a liquid hourly space velocity in the range of

[0149] 35. The method of any one of the preceding embodiments, wherein the liquid aqueous feed stream provided in step (i) and fed to the reaction zone in step (ii) further comprises H2.

[0150] 36. The method of embodiment 35, wherein the liquid aqueous feed stream exhibits a H2:sugar or sugar alcohol molar ratio of H2 to sugar or sugar alcohol in the range of 1 to 8, preferably 1.5 to 7, more preferably 1.8 to 7.

[0151] 37. The liquid aqueous effluent stream removed in step (iii) comprises 10 to 95 mol % C, preferably 30 to 95 mol % C, more preferably 40 to 95 mol % C, more preferably 50 to 90 mol % C, based on 100 mol % C of one or more sugars and sugar alcohols, each having 5 or 6 carbon atoms, and one or more monoalcohols, diols and triols, each having 2 or 3 carbon atoms, where mol % C is defined according to formula (I):

number

[0152] 38. The liquid aqueous effluent stream removed in step (iii) comprises 10 to 95 mol % C, preferably 30 to 95 mol % C, more preferably 40 to 95 mol % C, more preferably 50 to 90 mol % C, of ​​one or more of sugars and sugar alcohols, each having 5 or 6 carbon atoms, 1,2-propanediol, glycerol, and ethylene glycol, based on 100 mol % C, where mol % C is defined according to formula (II):

number

[0153] 39. The liquid aqueous effluent stream removed in step (iii) comprises 1,2-propanediol at 10 to 95 mol % C, preferably 20 to 95 mol % C, more preferably 30 to 95 mol % C, even more preferably 40 to 90 mol % C, based on 100 mol % C of one or more sugars and sugar alcohols, each having 5 or 6 carbon atoms, where mol % C is defined according to formula (III):

number

[0154] 40. The method of any one of embodiments 1 to 39, which is a continuous method.

[0155] 41. The method of any one of embodiments 1 to 40, operated in a trickle-bed reactor.

[0156] 42. A method for preparing a catalyst, preferably a catalyst for the method according to any one of embodiments 1 to 41, comprising the following steps: (a) preparing a first mixture comprising zirconium oxide and water; (b) preparing a second mixture comprising a nickel precursor selected from the group consisting of nickel nitrate, nickel halide, nickel acetate, nickel sulfate, and optionally a copper precursor selected from the group consisting of copper nitrate, copper halide, copper acetate, copper sulfate, copper amine complexes, and combinations of two or more thereof, and water; (c) mixing the first mixture obtained in step (a), the second mixture obtained in step (b), and a precipitant to obtain a slurry containing solids and water; (d) removing water from the slurry obtained in step (c) to obtain a solid; (e) optionally drying the solid obtained in step (d) at a temperature in the range of 80 to 150°C to obtain a dry solid; (f) calcining the solid obtained in step (d), preferably the dried solid obtained in step (e), at a temperature in the range of 300 to 700 °C to obtain a catalyst comprising nickel oxide and zirconium oxide, preferably a catalyst for the process according to any one of embodiments 1 to 41, wherein 5 to 60 wt. % of the catalyst consists of zirconium oxide, calculated as ZrO. A method comprising:

[0157] 43. Step (a) comprises the steps of: (a.1) preparing a solution comprising a zirconium precursor selected from the group consisting of zirconium nitrate, zirconium halide, zirconyl halide, zirconium acetate, zirconium sulfate, and combinations of two or more thereof, and water; (a.2) mixing the solution prepared in step (a.1) with a precipitant to obtain a suspension; (a.3) removing water from the suspension obtained in step (a.3) to obtain a solid; (a.4) optionally drying the solid obtained in step (a.4) at a temperature in the range of 80 to 150°C to obtain a dry solid; (a.5) calcining the solid obtained in step (a.3), preferably the dried solid obtained in step (a.4), at a temperature in the range of 400-800°C to obtain zirconium oxide; 43. The method of embodiment 42, comprising:

[0158] 44. The zirconium oxide has a crystallinity in the range of 60 to 100%, preferably 80 to 100%, more preferably 90 to 100%, based on the total zirconium oxide, as determined from a powder X-ray diffraction pattern of the zirconium oxide, preferably as determined from a powder X-ray diffraction pattern of the zirconium oxide according to the following formula, more preferably as determined from a powder X-ray diffraction pattern of the zirconium oxide according to Example 1-1:

number

[0159] 45. The powder X-ray diffraction pattern of the zirconium oxide exhibits signal peaks in the 2θ angle ranges of 28° to 29° and 31° to 32°, preferably the signal peaks indicate crystalline zirconium oxide of a monoclinic crystal phase, more preferably the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle ranges of 28° to 29° and 31° to 32° is greater than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°, more preferably the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range .... 45. The method of any one of embodiments 42 to 44, wherein the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29° is at least two times higher than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°, and more preferably, the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 28° to 29° is at least four times higher than the difference between the maximum signal intensity and the baseline signal intensity in the 2θ angle range of 29.5° to 31°.

[0160] 46. ​​Zirconium oxide comprises a monoclinic crystalline phase and, optionally, a tetragonal crystalline phase, preferably, as determined from a powder X-ray diffraction pattern of zirconium oxide, preferably, as determined from a powder X-ray diffraction pattern of zirconium oxide according to Example 1-1, the zirconium oxide comprises monoclinic crystals in an amount of 50 to 100 mass%, and tetragonal crystalline phase in an amount of 0 to 50 mass%, based on 100 mass% of all crystalline phases in the zirconium oxide, preferably, as determined from a powder X-ray diffraction pattern of zirconium oxide, preferably, as determined from a powder X-ray diffraction pattern of zirconium oxide according to Example 1-1, the zirconium oxide comprises monoclinic crystals in an amount of 70 to 100 mass%, and tetragonal crystalline phase in an amount of 0 to 30 mass%, based on 100 mass% of all crystalline phases in the zirconium oxide. 46. ​​The method according to any one of embodiments 42 to 45, wherein the zirconium oxide comprises monoclinic crystals in an amount of 80 to 100% by mass and tetragonal crystal phase in an amount of 0 to 20% by mass, based on 100% by mass of all crystalline phases in the zirconium oxide, as determined from an X-ray powder diffraction pattern of the zirconium oxide, preferably as determined from an X-ray powder diffraction pattern of the zirconium oxide according to Example 1-1; more preferably, the zirconium oxide comprises monoclinic crystals in an amount of 90 to 100% by mass and tetragonal crystal phase in an amount of 0 to 10% by mass, based on 100% by mass of all crystalline phases in the zirconium oxide, as determined from an X-ray powder diffraction pattern of the zirconium oxide, preferably as determined from an X-ray powder diffraction pattern of the zirconium oxide according to Example 1-1.

[0161] 47. The method of any one of embodiments 42 to 46, wherein in step (c) and / or step (a.3), the precipitating agent is selected from the group consisting of sodium carbonate, sodium hydroxide, ammonia, ammonium hydroxide, and combinations of two or more thereof.

[0162] The present invention is further described by the following second set of embodiments and combinations of embodiments resulting from the indicated dependencies and backward references. The second set of embodiments can be combined with any one of the above first set of embodiments and the below third set of embodiments. In particular, in each instance where a range of embodiments is mentioned, for example, in the context of terms such as "... as described in any one of embodiments 1' to 4'," it is to be noted that all embodiments within this range are expressly disclosed to those skilled in the art, i.e., this expression is to be understood by those skilled in the art as being synonymous with "... as described in any one of embodiments 1', 2', 3', and 4'." Furthermore, it is to be expressly noted that the following set of embodiments represents a suitably structured part of the description directed to general and preferred aspects of the present invention, rather than a set of claims determining the scope of protection.

[0163] 1'. A method for preparing one or more diols and triols having 2 or 3 carbon atoms, respectively, comprising the steps of: (i) providing a liquid aqueous feed stream comprising one or more sugars and sugar alcohols each having 5 or 6 carbon atoms; (ii) feeding the liquid aqueous feed stream provided in accordance with step (i) to a reaction zone containing a catalyst comprising nickel and subjecting the feed stream to reaction conditions in the reaction zone to obtain a reaction mixture comprising one or more of a diol and a triol; (iii) removing a liquid aqueous effluent stream from the reaction zone comprising one or more of the diol and triol; Including, A process wherein the catalyst comprises zirconium oxide, wherein 5 to 50 wt. % of the catalyst consists of zirconium oxide calculated as ZrO2, and 0 to 15 wt. % of the catalyst consists of aluminum oxide calculated as Al2O3.

[0164] 2'. The catalyst further comprises a metal oxide, and the metal of the metal oxide is preferably selected from the group consisting of Na, Mg, Si, K, Ca, Ti, Mn, Co, Cu, Zn, Nb, Mo, La, Hf, W, and combinations of two or more thereof, more preferably from the group consisting of Na, Mg, Si, Ca, Ti, Mn, Cu, Mo, La, Hf, W, and combinations of two or more thereof, more preferably from the group consisting of Si, Ca, Cu, Mn, Mo, and combinations of two or more thereof, more preferably from the group consisting of Si, Cu, Mo, and combinations thereof, and more preferably the catalyst is selected from the group consisting of SiO2, CuO, MoO x The method of embodiment 1', further comprising a metal oxide selected from the group consisting of: wherein x is 1 to 3, and mixtures thereof.

[0165] 3'. The method of embodiment 1' or 2', wherein 0 to 10 wt. % of the catalyst consists of aluminum oxide, calculated as Al2O3, preferably 0 to 5.5 wt. %.

[0166] 4'. The method of any one of embodiments 1' to 3', wherein 40 to 90 wt. % of the catalyst consists of nickel, calculated as NiO, preferably 60 to 85 wt. %.

[0167] 5'. The method of any one of embodiments 1' to 4', wherein 0.1 to 5.5 wt.%, preferably 2 to 5.5 wt.%, more preferably 3 to 5 wt.% of the catalyst consists of aluminum oxide calculated as Al2O3.

[0168] 6'. The method of any one of embodiments 1' to 5', wherein 65 to 75 weight percent of the catalyst consists of nickel, calculated as NiO; 5 to 7 weight percent of the catalyst consists of zirconium oxide, calculated as ZrO2; and 3 to 5 weight percent of the catalyst consists of aluminum oxide, calculated as Al2O3.

[0169] 7'. The method of any one of embodiments 1' to 6', wherein 65 to 75 weight percent of the catalyst consists of nickel, calculated as NiO; 5 to 7 weight percent of the catalyst consists of zirconium oxide, calculated as ZrO2; 3 to 5 weight percent of the catalyst consists of aluminum oxide, calculated as Al2O3; and 15 to 25 weight percent of the catalyst consists of silicon oxide, calculated as SiO2.

[0170] 8'. The method of any one of embodiments 1' to 4', wherein 40 to 90 wt. % of the catalyst consists of nickel and copper, calculated as NiO and CuO, preferably 60 to 85 wt. %.

[0171] 9'. The method of any one of embodiments 1' to 4' or 8', wherein the catalyst is substantially free of aluminum oxide, preferably substantially free of Al2O3.

[0172] 10'. The method of any one of embodiments 1' to 4', 8', or 9', wherein 40 to 60 weight percent of the catalyst consists of nickel, calculated as NiO, 10 to 30 weight percent of the catalyst consists of copper, calculated as CuO, and 20 to 40 weight percent of the catalyst consists of zirconium oxide, calculated as ZrO2.

[0173] 11'. The method of any one of embodiments 1' to 4', 8', 9', or 10', wherein 40 to 60 weight percent of the catalyst consists of nickel calculated as NiO, 10 to 30 weight percent of the catalyst consists of copper calculated as CuO, 20 to 40 weight percent of the catalyst consists of zirconium oxide calculated as ZrO2, and 0.1 to 5 weight percent of the catalyst consists of molybdenum oxide calculated as MoO3.

[0174] 12'. The method of any one of embodiments 1' to 11', wherein the zirconium oxide comprises one or more crystalline phases and / or is amorphous, and the one or more crystalline phases of the zirconium oxide are selected from the group consisting of a monoclinic phase, a tetragonal phase, a cubic phase of zirconium oxide, and mixtures of two or three thereof.

[0175] 13'. The method of any one of embodiments 1' to 12', wherein the catalyst is substantially free of CrO3 and / or Cr2O3, preferably substantially free of CrO3 and Cr2O3.

[0176] 14'. The method of any one of embodiments 1' to 13', wherein the catalyst is in the form of a molding and / or a powder, preferably in the form of a molding, more preferably in the form of an extrudate and / or in the form of a tablet, more preferably in the form of a cylindrical tablet.

[0177] 15'. The method of embodiment 14', wherein the cylindrical tablet has a diameter x height in the range of 1 x 1 to 10 x 10 mm, preferably 2 x 2 to 7 x 7 mm, more preferably 2.5 x 2.5 to 6 x 6 mm.

[0178] The method of any one of embodiments 1' to 15', wherein one or more of the sugars having 16'.5 carbon atoms are selected from the group consisting of ribose, arabinose, xylose, lyxose, and combinations of two or more thereof.

[0179] 17'. The method of any one of embodiments 1' to 16', wherein one or more of the sugars having 6 carbon atoms are selected from the group consisting of glucose, galactose, maltose, lactose, sucrose, allose, altrose, mannose, gulose, idose, talose, and combinations of two or more thereof.

[0180] 18'. The method of any one of embodiments 1' to 17', wherein one or more of the sugar alcohols having 5 carbon atoms are selected from the group consisting of arabitol, ribitol, xylitol, and combinations of two or more thereof, and more preferably, the sugar alcohol having 6 carbon atoms comprises xylitol.

[0181] 19'. The method of any one of embodiments 1' to 18', wherein one or more of the sugar alcohols having 6 carbon atoms are selected from the group consisting of mannitol, iditol, galactitol, sorbitol, and combinations of two or more thereof, more preferably the sugar alcohol having 6 carbon atoms comprises sorbitol.

[0182] 20'. The method of any one of embodiments 1' to 19', wherein one or more of the diols and triols each having 2 or 3 carbon atoms are selected from the group consisting of 1,2-propanediol, ethylene glycol, 1,3-propanediol, glycerol, and combinations of two or more thereof, preferably one or more of the diols and triols each having 2 or 3 carbon atoms are selected from the group consisting of 1,2-propanediol, ethylene glycol, glycerol, and combinations of two or more thereof.

[0183] 21'. The method of any one of embodiments 1' to 20', wherein the diol having 2 carbon atoms comprises ethylene glycol.

[0184] 22'. The method of any one of embodiments 1' to 21', wherein the diol having 3 carbon atoms comprises 1,2-propanediol.

[0185] 23'. The method of any one of embodiments 1' to 22', wherein the triol having 3 carbon atoms comprises glycerol.

[0186] 24'. The method of any one of embodiments 1' to 23', wherein the liquid aqueous feed stream prepared in step (ii) comprises 20 to 60% by weight, preferably 25 to 50% by weight, more preferably 25 to 40% by weight, of sugars or sugar alcohols having 5 or 6 carbon atoms, respectively.

[0187] 25'. The method of any one of embodiments 1' to 24', wherein the liquid aqueous feed stream provided in step (i) further comprises a solvent, preferably a solvent comprising a monohydric alcohol, preferably a solvent comprising a monohydric alcohol, more preferably said monohydric alcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol and 1-butanol.

[0188] 26'. The method of any one of embodiments 1' to 25', wherein the liquid aqueous feed stream provided in step (i) further comprises a compound selected from the group consisting of a base, a Lewis acid, and combinations thereof, preferably a base.

[0189] 27'. The method of embodiment 26', wherein in step (i), the base is selected from the group consisting of metal hydroxides, and the metal of the metal hydroxide is preferably selected from the group consisting of Li, Na, K, Ca, Mg, and a combination of two or more thereof; more preferably, the base comprises one or more metal hydroxides selected from the group consisting of LiOH, NaOH, KOH, Ca(OH)2, Mg(OH)2, and a mixture of two or more thereof, preferably from the group consisting of NaOH, KOH, Ca(OH)2, Mg(OH)2, and a combination of two or more thereof; more preferably, the base comprises one or more metal hydroxides selected from the group consisting of NaOH, KOH, and a combination of two or more thereof; more preferably, the base comprises NaOH.

[0190] 28'. The process of embodiment 26' or 27', wherein the liquid aqueous feed stream provided in step (i) comprises 0.1 to 8 wt. % of a base, preferably 0.3 to 7 wt. %, more preferably 4 to 6 wt. %.

[0191] 29'. The method of embodiment 26', wherein in step (i), the acid is selected from the group consisting of phosphoric acid, sulfuric acid, and combinations thereof.

[0192] 30'. The method of embodiment 26', wherein in step (i), the Lewis acid is selected from the group consisting of metal polyacids, and the metal of the metal polyacid is preferably selected from the group consisting of Mo, W, and combinations of two or more thereof, and more preferably the Lewis acid comprises one or more metal polyacids selected from the group consisting of H2WO4, (NH4)2MoO2, and combinations thereof.

[0193] 31'. The process of any one of embodiments 1' to 30', wherein the reaction conditions according to step (ii) comprise a reaction pressure in the range of 40 to 170 bar, preferably 60 to 150 bar, more preferably 80 to 120 bar.

[0194] 32'. The method of any one of embodiments 1' to 31', wherein the reaction conditions according to step (ii) comprise a temperature in the range of 140 to 210°C, preferably 170 to 200°C.

[0195] 33'. The reaction conditions for step (ii) are 0.1 to 5 h -1 , preferably 0.2 to 5 hours -1 The method of any one of embodiments 1' to 32', comprising a liquid hourly space velocity in the range of

[0196] 34'. The method of any one of embodiments 1' to 33', wherein the liquid aqueous feed stream provided in step (i) and fed to the reaction zone in step (ii) further comprises H2.

[0197] 35'. The method of embodiment 34', wherein the liquid aqueous feed stream exhibits a H2:sugar or sugar alcohol molar ratio of H2 to sugar or sugar alcohol in the range of 1 to 8, preferably 1.5 to 7, more preferably 1.8 to 7.

[0198] 36'. The liquid aqueous effluent stream removed in step (iii) comprises, based on 100 mol % C of one or more sugars and sugar alcohols having 5 or 6 carbon atoms, respectively, 10 to 95 mol % C, preferably 15 to 90 mol % C, more preferably 20 to 85 mol % C, more preferably 25 to 80 mol % C of one or more diols and triols having 2 or 3 carbon atoms, respectively, where mol % C is defined according to formula (I):

number

[0199] 37'. The liquid aqueous effluent stream removed in step (iii) comprises one or more of sugars and sugar alcohols, each having 5 or 6 carbon atoms, of 1,2-propanediol, glycerol and ethylene glycol, at 10 to 95 mol % C, preferably 15 to 90 mol % C, more preferably 20 to 85 mol % C, and even more preferably 25 to 80 mol % C, based on 100 mol % C, where mol % C is defined according to formula (II):

number

[0200] 38'. The liquid aqueous effluent stream removed in step (iii) comprises 10 to 80 mol % C, preferably 15 to 75 mol % C, more preferably 20 to 70 mol % C, and even more preferably 25 to 65 mol % C, of ​​1,2-propanediol, based on 100 mol % C of one or more sugars and sugar alcohols, each having 5 or 6 carbon atoms, where mol % C is defined according to formula (III):

number

[0201] 39'. The method according to any one of embodiments 1' to 38', which is a continuous method.

[0202] 40'. The method of any one of embodiments 1' to 39', operated in a trickle bed reactor.

[0203] The term "bar" as used in the context of the present invention refers to "bar (abs)", also called "bara", i.e. bar (absolute value). [Example]

[0204] The present invention is further illustrated by the following examples and comparative examples.

[0205] Example 1-1: Synthesis of the support material for catalyst A-1 Zirconium oxide (ZrO2) powder was prepared through a series of steps: precipitation, washing, drying, and calcination. Zr(NO3)4 solution (10.7 wt% Zr) was used as the starting material. 25 wt% NH3 solution was used as the precipitant.

[0206] A mixing vessel was charged with 1 part by weight of deionized water and 1 part by weight of a 25% by weight NH3 solution. No heating was applied, and the temperature of the mixture was below 40°C. 2 parts by weight of Zr(NO3)4 solution were then added continuously to the stirring vessel over a period of 25 minutes. After the addition of the nitrate, the pH of the mixture was measured with a glass electrode. This value was adjusted to 7.5 with nitric acid, if necessary. The contents of the mixing vessel were heated to 85°C and stirred for an additional 6 hours.

[0207] The resulting suspension was filtered, and the filter cake was washed with deionized water until the electrical conductivity of the filtrate, measured with a WTW Cond 330i instrument equipped with a TetraCon 325 probe, was less than 200 μS / cm. The cake was then dried in a drying cabinet at 120°C. The precursor thus obtained was calcined in flowing air at 520°C for 1 hour to obtain the final zirconium oxide powder.

[0208] The zirconium oxide powder obtained as described above was subjected to powder X-ray diffraction (PXRD) for characterization. Data were collected using a diffractometer (D8 Advance Series II, Bruker AXS GmbH) equipped with a LYNXEYE detector operated with a copper anode X-ray tube at 40 kV and 40 mA. The Bragg-Brentano geometry was used, and an air scattering shield was used to reduce air scattering. Prior to measurement, the sample was ground using an IKA TubeMill at 20,000 rpm for 2 minutes with 30-second intervals. The sample was homogenized in a mortar and then pressed into a standard flat sample holder provided by Bruker AXS GmbH for Bragg-Brentano geometry data collection. A glass plate was used to compress and flatten the sample powder, achieving a flat sample surface. Data were collected from an angular range of 10 to 70° 2θ with a 2θ step size of 0.02°, while the variable divergence slit was set at a fixed angle of 0.3°.

[0209] The recorded diffraction pattern is shown in Figure 1. Comparison of the signal positions with database references and consideration of the relative signal intensities revealed a dominant contribution of the monoclinic phase to the overall diffraction pattern.

[0210] The crystallinity and crystalline phase composition of the sample (w 結晶 The chromaticity (σ) and crystallite size (CS) were calculated from the recorded diffraction patterns using the modeling software DIFFRAC.TOPAS V7 provided by Bruker AXS GmbH, Karlsruhe. The regression of the recorded PXRD patterns took into account the background intensity, the crystalline structure of the identified phases, and the instrumental parameters. First-order Chebychev coefficients were used to simulate the background. The crystallinity was defined as the fraction of the signal area occupied by the crystalline phase after background subtraction:

number

[0211] The crystallinity of the as-synthesized ZrO2 powder was evaluated to be 100%. No amorphous phase was required to describe the experimental PXRD pattern. 91% by mass of the crystalline ZrO2 in the sample was crystallized in the monoclinic phase, while the tetragonal phase was 9% by mass. Therefore, the sample is primarily composed of crystalline ZrO2 in the monoclinic phase.

[0212] Example 2-1: Synthesis of catalyst A-1 A catalyst powder containing nominally 52 wt% NiO, 17 wt% CuO, and 31 wt% ZrO2 was prepared through a series of steps: precipitation, washing, drying, and calcination. Nickel nitrate (Ni(NO3)2), copper nitrate (Cu(NO3)2), and zirconium oxide (ZrO2) powder from Example 1-1 were used as starting materials. Sodium carbonate (Na2CO3) was used as a precipitant. The nitrates and carbonates were used as aqueous solutions with predetermined concentrations. The consumption amount was based on the above catalyst composition and the amount of ZrO2.

[0213] A nickel nitrate (14.2 wt% Ni) solution and a copper nitrate (15.6 wt% Cu) solution were mixed to form a metal precursor solution. 1.5 L of deionized water was placed in a mixing vessel, and 156 g of the zirconium oxide powder from Example 1-1 was added. The vessel was heated to 65°C. The metal precursor solution was then continuously added to the mixing vessel over 1 hour. A 20 wt% sodium carbonate solution was added simultaneously to maintain a pH of 6.2 as measured by a glass electrode. After the metal precursor solution was completely added, the pH was adjusted to 7.7 using the sodium carbonate solution. The contents of the vessel were stirred at constant temperature for an additional 1.5 hours.

[0214] The resulting suspension was filtered, and the filter cake was washed with deionized water until the electrical conductivity of the filtrate, measured with a WTW Cond 330i instrument equipped with a TetraCon 325 probe, was less than 200 μS / cm. The cake was then dried in a drying cabinet at 120° C. The precursor thus obtained was calcined in flowing air at 520° C. for 1 hour to obtain the above oxide composition.

[0215] The catalyst powder was mixed with 3% by weight of graphite and compressed to form cylindrical tablets measuring 3 x 3 mm (diameter x height). The tablets were calcined in flowing air at 500 °C for 1 hour. Prior to use, the catalyst tablets were reduced in a gas mixture containing 50% by volume of H2 and 50% by volume of N2 at 280 °C for 2 hours.

[0216] Example 3-1: Hydrogenolysis of sorbitol using catalyst A-1 The conversion using catalyst A was carried out in a fixed-bed reactor (10 mL). After loading the catalyst, a standard reduction procedure was employed. For this purpose, the reactor containing the catalyst was heated to 120 °C under a N2 atmosphere (120 nL / h). After reaching the temperature, the N2 feed was stopped and H2 (50 nL / h) was added for 1 h. The temperature was then increased to 200 °C and the reaction was continued for another 4 h. Afterwards, the reactor was cooled to room temperature under a N2 atmosphere.

[0217] After reduction of the catalyst, a feed consisting of 40 wt. % sorbitol and 5 wt. % NaOH was added at 110 bar, 200 °C, LHSV = 2.9 h. -1 The details are shown in Table 1-1.

[0218] Glycol yields are expressed as mole % C, which represents the molar conversion of C atoms of the starting material (e.g., sorbitol) to the desired glycols 1,2-propanediol (1,2-PDO), ethylene glycol (EG), and glycerol (GLY). The yields were calculated according to the general formula (IV):

number

[0219]

number

[0220] [Table 1]

[0221] Example 4-1: Analysis of Catalyst A-1 before use and after use Catalyst A-1 was analyzed before use (synthesized according to Example 2-1) and after use (sorbitol hydrogenolysis according to Example 3-1).

[0222] The radial lateral crushing strength (SCS) of a single tablet was used as a descriptor of mechanical stability. The analysis was performed on a commercially available Sotax ST50 system operating in "Constant Speed" mode. For each measurement, a cylindrical catalyst tablet was placed between a fixed bracket and a moving piston approaching at 0.35 mm / s. The force required to push the piston was monitored until the catalyst tablet broke, and the maximum force (in Newtons) was recorded as the tablet's SCS value. This measurement was repeated for 20 tablets of each catalyst type, and the arithmetic mean of the obtained values ​​was calculated.

[0223]

number

[0224] Chemical stability was tested by elemental analysis. Aliquots of the crushed catalyst were subjected to metal content determination by ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy). A mixture of H2SO4, HNO3, and HClO4 was applied to digest the samples. After evaporating the digested solution to dryness, the solid residue was redissolved in dilute HCl (10% by volume). The resulting solution was analyzed on an Agilent 5100 spectrometer. Results were quantified using external calibration after subtracting blank values. Results are expressed as elemental ratios to exclude the influence of absolute mass changes resulting from catalyst reduction and organic adsorption.

[0225] [Table 2]

[0226] In summary, no significant changes in the mechanical properties of the catalyst tablets were observed, indicating the high mechanical stability of the catalyst material described in this invention. Furthermore, the results of chemical analysis indicate that there is no or very limited dissolution of the catalyst components, which would shift the determined metal ratio. Therefore, the catalyst material of this invention has high chemical stability and is suitable for use under hydrothermal operating conditions and with basic additives in the feed mixture.

[0227] [Table 3]

[0228] * A NiCu alloy was used for the representative fit of the recorded diffraction patterns, but the contributions of metallic Ni and Cu are also suitable for describing the sample.

[0229] PXRD characterization of catalyst A-1 as synthesized and catalyst A-1 after use in Example 3-1 was performed according to the method described in Example 1-1. The respective powder X-ray diffraction patterns are shown in Figure 2. Qualitative analysis of the signal positions and intensities compared with a reference revealed that both samples were dominated by the monoclinic crystalline phase of zirconium oxide. Contributions from amorphous material and tetragonal ZrO2 were negligible. Quantitative evaluation of the diffraction patterns revealed that the crystalline phase composition (w 結晶 No significant changes were observed in the saturation temperature (Tc) or crystallite size (CS), highlighting the good stability properties of catalyst A-1 (Table 3-1).

[0230] Comparative Example 1-1: Synthesis of Catalyst B-1 A catalyst powder containing 51 wt% NiO, 17 wt% CuO, 1.5 wt% MoO, and 30.5 wt% ZrO was prepared through a series of precipitation, washing, drying, and calcination steps. Nickel nitrate (Ni(NO)), ammonium heptamolybdate ((NH)MoO) 24 ), copper nitrate (Cu(NO3)2), and zirconium acetate (Zr(C2H3O2)4) were used as starting materials. Sodium carbonate (Na2CO3) was used as a precipitant. The amounts of each used were in accordance with the above catalyst composition and the prescribed concentration levels.

[0231] Nickel nitrate, copper nitrate, and zirconium acetate solutions were mixed with deionized water to obtain a solution with the following metal content: 7.0 wt% Ni, 2.4 wt% Cu, and 4.1 wt% Zr. This mixed solution was continuously added to a mixing vessel over a period of 2 hours. A 20 wt% sodium carbonate solution was added simultaneously to maintain a pH of 6.2, as measured by a glass electrode. The vessel was temperature-controlled at 65°C. After complete addition of the metal precursor solution, the pH was adjusted to 7.7 using the sodium carbonate solution. The contents of the vessel were stirred at constant temperature for an additional 1.5 hours.

[0232] The resulting suspension was filtered, and the filter cake was washed with deionized water until the electrical conductivity of the filtrate, measured with a WTW Cond 330i instrument equipped with a TetraCon 325 probe, was less than 200 μS / cm. The still-wet filter cake was mixed with solid ammonium heptamolybdate. The cake was then dried in a drying cabinet at 120°C. The hydroxide-carbonate mixture thus obtained was calcined in flowing air at 520°C for 1 hour to obtain the oxide composition described.

[0233] The catalyst powder was mixed with 3% by mass of graphite and compressed into cylindrical tablets measuring 3 x 3 mm (diameter x height). The tablets were calcined in flowing air at 500 °C for 1 hour. Before use, the catalyst tablets were reduced in a gas mixture containing 50% by volume of H2 and 50% by volume of N2 at 280 °C for 2 hours.

[0234] Comparative Example 2-1: Hydrogenolysis of sorbitol using catalyst B-1 The conversion using catalyst B-1 was carried out in a fixed-bed reactor (10 mL). After loading the catalyst, a standard reduction procedure was employed. For this purpose, the reactor containing the catalyst was heated to 120 °C under a N2 atmosphere (120 nL / h). After reaching the temperature, the N2 supply was stopped and H2 (50 nL / h) was added for 1 h. The temperature was then increased to 200 °C and the reaction was continued for another 4 h. Afterwards, the reactor was cooled to room temperature under a N2 atmosphere.

[0235] After reduction of the catalyst, a feed consisting of 40 wt. % sorbitol and 5 wt. % NaOH was added at 110 bar, 200 °C, LHSV = 2.9 h. -1 The details are shown in Table 3-1.

[0236] Glycol yields are expressed as mole % C, which represents the molar conversion of C atoms of the starting material (e.g., sorbitol) to the desired glycols 1,2-propanediol (1,2-PDO), ethylene glycol (EG), and glycerol (GLY). The yields were calculated according to the general formula (IV): The following formula shows an example of the mole % C of 1,2-PDO in Experiment 4 of Table 3-1.

[0237]

number

[0238]

number

[0239] [Table 4]

[0240] Comparative Example 3-1: Analysis of Catalyst B-1 before and after use Catalyst B-1 was analyzed before use (synthesized according to Comparative Example 1-1) and after use (sorbitol hydrogenolysis according to Comparative Example 2-1). The method was the same as in Example 4-1. The only exception was that the contribution from tetragonal ZrO2 to the diffraction pattern of catalyst B-1 could not be modeled by a defined crystalline phase. Therefore, the regression instead considered the contribution from amorphous ZrO2. The inability to model ZrO2 in catalyst B-1 as a crystalline phase is believed to be due to the presence of small crystallites with poor long-range order.

[0241] [Table 5]

[0242] Compared with Example 4-1, Catalyst B was found to lack mechanical and chemical catalytic stability. The mechanical stability of the catalyst tablets after the test was significantly reduced, which may lead to the formation of fines, increased pressure loss, or reactor blockage in commercial operation. Elemental analysis revealed a clear decrease in the Zr / Ni mass ratio of the spent catalyst. This suggests chemical instability and leaching of the zirconium oxide support contained in Catalyst B-1. This material is not suitable for use under the tested reaction conditions.

[0243] [Table 6]

[0244] X-ray diffraction patterns of as-synthesized Catalyst B-1 and Catalyst B-1 after use in Comparative Example 2-1 are shown in Figure 3. As can be inferred from the absence of corresponding signal peaks in the recorded PXRD patterns, no crystalline monoclinic ZrO2 was observed in these experiments. Instead, the zirconium oxide support was amorphous before use. After use, a distinct tetragonal zirconium oxide phase formed, indicating a significant change in the material, which is believed to underlie the unfavorable stability characteristics of Catalyst B-1.

[0245] The PXRD pattern of Catalyst B-1 after use in Comparative Example 2-1 also shows the presence of SiC inert material, which could not be completely separated from the catalyst due to the destruction of most of the tablets in the catalyst bed. Therefore, quantitative evaluation was performed only on the as-synthesized Catalyst B-1. The crystallinity of the samples was generally lower for the as-synthesized Catalyst B-1 than for Catalyst A-1, highlighting the presence of X-ray amorphous material in Catalyst B-1. Furthermore, the contribution of ZrO2 to the crystalline phase composition of Catalyst B-1 was minor. The measured crystallite size of Catalyst B-1 was smaller than that of Catalyst A-1.

[0246] Overall, the low crystallinity and absence of crystalline ZrO2 in the monoclinic crystal phase indicate the lack of stability of catalyst B-1.

[0247] Example 1: Synthesis of Catalyst A A catalyst powder containing 71.0 wt% NiO, 6.0 wt% ZrO2, 4.3 wt% Al2O3, and 18.7 wt% SiO2 was prepared through a series of processes: precipitation, washing, drying, and annealing. Nickel nitrate (Ni(NO3)2), zirconium nitrate (Zr(NO3)4), sodium aluminate (NaAlO2), and diatomaceous earth (amorphous SiO2) were used as starting materials. Sodium carbonate (Na2CO3) was used as a precipitant. The amounts of each component were determined according to the catalyst composition and the specified concentration levels.

[0248] First, a 1.8% by mass aqueous solution of sodium aluminate was prepared in a mixing vessel. Next, 1 mass equivalent of a 20% by mass sodium carbonate solution was added. The mixture was heated to 95°C, followed by the addition of diatomaceous earth. A second addition of a 20% by mass aqueous solution of sodium carbonate, the same amount as the first addition, was then added to the mixing vessel. Then, a zirconium nitrate solution (Zr content: 10.8% by mass) was added over 0.5 hours. The pH measured with a glass electrode was 9.7. A nickel nitrate solution (Ni content: 13.5% by mass) was continuously added over 1.5 hours to lower the pH and terminate the precipitation. After the addition was completed, the pH measured with a glass electrode was 8.3.

[0249] The resulting suspension was filtered, and the filter cake was washed with deionized water until the electrical conductivity of the filtrate was less than 200 μS / cm, as measured with a WTW Cond 330i instrument equipped with a TetraCon 325 probe. The cake was then dried at 100°C in a drying cabinet or spray dryer. The hydroxide-carbonate mixture thus obtained was annealed in flowing air at 500°C for 4 hours to obtain the oxide composition described.

[0250] The catalyst powder was mixed with 4% by mass of graphite and compressed into cylindrical tablets measuring 3 × 3 mm (diameter × height). Prior to use, the catalyst tablets were dried in a nitrogen stream at 350 °C for 2 h and reduced in a gas mixture containing 50% by volume of H2 and 50% by volume of N2 at 450 °C for 12 h.

[0251] Example 2: Synthesis of Catalyst B A catalyst powder containing 51 wt% NiO, 17 wt% CuO, 1.5 wt% MoO, and 30.5 wt% ZrO was prepared by a series of steps: precipitation, washing, drying, and annealing. Nickel nitrate (Ni(NO), ammonium heptamolybdate ((NH)MoO). 24 ), copper nitrate (Cu(NO3)2), and zirconium acetate (Zr(C2H3O2)4) were used as starting materials. Sodium carbonate (Na2CO3) was used as a precipitant. The amounts of each used were in accordance with the above catalyst composition and the prescribed concentration levels.

[0252] Nickel nitrate, copper nitrate, and zirconium acetate solutions were mixed with deionized water to obtain a solution with the following metal content: 7.0% by weight Ni, 2.4% by weight Cu, and 4.1% by weight Zr. This mixed solution was continuously added to a mixing vessel over a period of 2 hours. A 20% by weight sodium carbonate solution was added simultaneously to maintain a pH of 6.2 as measured by a glass electrode. The vessel was temperature-controlled at 65°C.

[0253] The resulting suspension was filtered, and the filter cake was washed with deionized water until the electrical conductivity of the filtrate, measured with a WTW Cond 330i instrument equipped with a TetraCon 325 probe, was less than 200 μS / cm. The still-wet filter cake was mixed with solid ammonium heptamolybdate. The cake was then dried at 100°C in a drying cabinet or spray dryer. The hydroxide-carbonate mixture thus obtained was annealed in flowing air at 500°C for 4 hours to obtain the oxide composition described.

[0254] The catalyst powder was mixed with 3% by weight of graphite and compressed into cylindrical tablets measuring 6 x 3 mm (diameter x height). The tablets were annealed in flowing air at 500 °C for 4 hours. Before use, the catalyst tablets were reduced in a gas mixture containing 50% by volume of H2 and 50% by volume of N2 at 240 °C for 2 hours, then cooled and passivated in air at room temperature.

[0255] Examples 3 and 4: Mechanical and chemical testing of the catalysts of Examples 1 and 2 The catalysts of Examples 1 and 2 were subjected to a catalyst stability test. For this purpose, 15 g of the reduced and air-stabilized catalyst was loaded onto the concentric collector mesh of a 300 mL stainless steel autoclave. The autoclave was filled with 180 g of an aqueous feed solution containing 25% by weight of sorbitol and 2% by weight of sodium hydroxide (NaOH). The sealed autoclave was heated to 200 °C, and H gas was introduced under continuous stirring up to a pressure of 110 bar. After 12 hours, the reaction was stopped, and the reactor was cooled and depressurized. The spent catalyst sample was collected and dried.

[0256] The radial lateral crushing strength (SCS) of a single tablet was used as a descriptor of mechanical stability. The analysis was performed on a commercially available Sotax ST50 system operating in "Constant Speed" mode. For each measurement, a catalyst cylindrical tablet was placed between a fixed bracket and a moving piston approaching at 0.35 mm / s. The force required to push the piston was monitored until the catalyst tablet broke, and the maximum force (in Newtons) was recorded as the tablet's SCS value.

[0257] This measurement was repeated for 20 tablets of each type of catalyst, and the arithmetic mean of the obtained values ​​was calculated.

[0258]

number

[0259] The designation "spent catalyst" refers to tablets that have been used under reaction conditions, recovered and dried. i indicates a counter of 20 consecutive measurements of tablets.

[0260] The same procedure and evaluation was carried out on 20 tablets of catalyst prior to use.

[0261]

number

[0262] Here, "fresh catalyst" refers to the reduced and air-stabilized tablet prior to being subjected to reaction conditions.

[0263] The remaining mechanical stability of the catalyst after subjecting it to reaction conditions was expressed as a percentage of the value for the fresh catalyst according to the following formula:

[0264]

number

[0265] The solid-free reaction solution obtained in the above test was subjected to the determination of metal content by ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy). A mixture of H2SO4, HNO3 and HClO4 was applied to digest the sample. After evaporating the digested solution to dryness, the solid residue was redissolved in dilute HCl (10% by volume). The resulting solution was analyzed on an Agilent 5100 spectrometer. The results were quantified by subtracting the blank value and using external calibration. All measurement results for Examples 3 and 4 are shown in Table 1.

[0266] [Table 7]

[0267] The test results for dissolved nickel in the reaction solution indicate low chemical corrosion for the catalysts described in Examples 1 and 2. Furthermore, the catalysts of Examples 1 and 2 retain their tablet shape after being subjected to the test conditions. The relative decrease in SCS observed for the catalyst of Example 1 is compensated for by the high absolute SCS value of the spent catalyst. For the catalyst of Example 2, the SCS is almost completely retained after the test. Thus, the catalysts of Examples 1 and 2 have high stability in terms of corrosion and mechanical degradation under the conditions relevant to the present invention.

[0268] Comparative Example 1: Synthesis of Catalyst C A catalyst powder containing 72.3 wt% NiO, 8 wt% ZrO2, 19.5 wt% Al2O3, and 0.2 wt% Na2O was prepared through a series of steps: precipitation, washing, drying, and annealing. Nickel nitrate (Ni(NO3)2), zirconium oxide (ZrO2), and aluminum nitrate (Al(NO3)3) were used as starting materials. Sodium carbonate (Na2CO3) was used as a precipitant. The amounts of each were determined according to the catalyst composition and the specified concentration levels.

[0269] First, deionized water and zirconium oxide powder were added to a mixing vessel to form a slurry with a solids content of 1.8% by weight. In a separate vessel, nickel nitrate solution and aluminum nitrate solution were mixed with deionized water to obtain a solution with the following concentrations, calculated based on the metals: 7.0% by weight Ni and 1.3% by weight Al. This mixed solution was continuously added to the mixing vessel containing the zirconium oxide suspension over a period of 0.25 hours. A 20% by weight sodium carbonate solution was added simultaneously to maintain a pH of 8.1, as measured by a glass electrode. The vessel was temperature-controlled at 50°C.

[0270] The resulting suspension was filtered, and the filter cake was washed with deionized water until the electrical conductivity of the filtrate was less than 200 μS / cm, as measured with a WTW Cond 330i instrument equipped with a TetraCon 325 probe. The cake was then dried at 100°C in a drying cabinet or spray dryer. The hydroxide-carbonate mixture thus obtained was annealed in flowing air at 500°C for 4 hours to obtain the oxide composition described.

[0271] The catalyst powder was mixed with 3% by weight of graphite and compressed into cylindrical tablets measuring 5 x 3 mm (diameter x height). Prior to use, the catalyst tablets were annealed in an air stream at 460 °C for 4 hours. They were then reduced in a gas mixture containing 50% by volume of H2 and 50% by volume of N2 at 400 °C for 5 hours, cooled, and passivated in air at room temperature.

[0272] Comparative Example 2: Synthesis of Catalyst D A catalyst powder containing 58% by mass CuO, 30% by mass Al2O3, and 12% by mass MnO2 was prepared through a series of processes: precipitation, washing, drying, and annealing. Copper nitrate (Cu(NO3)2), sodium aluminate (NaAlO2), and manganese nitrate (Mn(NO3)2) were used as starting materials. Sodium carbonate (Na2CO3) was used as a precipitant. The amounts of each used were in accordance with the above catalyst composition and the prescribed concentration levels.

[0273] Copper nitrate (Cu content 15.5% by mass), manganese nitrate (Mn content 15% by mass), and sodium aluminate solution (Al content 12.5% ​​by mass) were prepared according to the target catalyst composition. These solutions were continuously added to a mixing vessel containing deionized water in an amount equivalent to 1 / 4 of the copper nitrate solution. A 20% by mass sodium carbonate solution was added simultaneously to maintain the pH at 7.0 as measured with a glass electrode. The vessel was temperature-controlled at 25°C.

[0274] The resulting suspension was filtered, and the filter cake was washed with deionized water until the electrical conductivity of the filtrate was less than 200 μS / cm, as measured with a WTW Cond 330i instrument equipped with a TetraCon 325 probe. The cake was then dried at 100°C in a drying cabinet or spray dryer. The hydroxide-carbonate mixture thus obtained was annealed in flowing air at 600°C for 4 hours to obtain the oxide composition described.

[0275] The catalyst powder was mixed with 3% graphite by mass and compressed into granules to obtain a specific bulk density equal to 40-50% of that of the corresponding tablet product. The granules were then compressed into cylindrical tablets measuring 3.2 x 3.2 mm (diameter x height). The catalyst tablets were annealed in flowing air at 750 °C for 4 hours to obtain a specific bulk density of 1.1 g / mL. They were then reduced in a gas mixture containing 50% H2 by volume and 50% N2 by volume at 220 °C for 2 hours, then cooled and passivated in air at room temperature.

[0276] Comparative Example 3: Synthesis of Catalyst E The catalyst extrudates were prepared according to the procedure disclosed in Example 1 of WO 2020 / 117532 A1. The calcination temperature was 600°C. The resulting material contained 76.2% by weight CuO, 13.6% by weight SiO2, 5.9% by weight CaO, 0.9% by weight MnO2, and 3.4% by weight Na2O. Prior to use, the catalyst tablets were reduced in a gas mixture containing 50% by volume H2 and 50% by volume N2 at 220°C for 2 hours, then cooled and passivated in air at ambient temperature.

[0277] Comparative Examples 4-6: Mechanical and Chemical Testing of the Catalysts of Comparative Examples 1-3 The catalysts of Comparative Examples 1-3 were subjected to the catalyst stability test described for Examples 3 and 4. For the catalysts of Comparative Examples 1 and 2, the radial lateral crush strength (SCS) of a single tablet was used as a descriptor of mechanical stability. The measurement was carried out as described in Examples 3 and 4.

[0278] The cutting hardness (CH) of a single extruded strand was used as a descriptor of the mechanical stability of the catalyst of Comparative Example 3. Analysis was performed on a Zwick BZ2.5 / TS1S system. For each single strand measurement, the catalyst extrusion was placed between a fixed bracket and a 0.3 mm wide moving blade approaching at a constant speed of 0.027 mm / s. The force required to push the blade was monitored until the strand broke, and the maximum force in Newtons was recorded as the SH value of the strand. Breakage was detected when the measured force was 30% lower than the maximum force for this test.

[0279] Measurements were repeated for 20 strands for each catalyst type, and the arithmetic mean of the values ​​obtained was calculated.

[0280]

number

[0281] Herein, the designation "spent catalyst" refers to extruded strands that have been used under reaction conditions, recovered and dried.

[0282] The same procedure and evaluation was carried out on 20 catalyst strands prior to use.

[0283]

number

[0284] Here, "fresh catalyst" refers to the reduced and air-stabilized tablet prior to being subjected to reaction conditions.

[0285] The remaining mechanical stability of the catalyst after subjecting it to reaction conditions was expressed as a percentage of the value for the fresh catalyst according to the following formula:

[0286]

number

[0287] The solid-free reaction solution obtained in the above test was subjected to measurement of the metal content by ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy). The measurement details were the same as in Examples 3 and 4. All measurement results for Comparative Examples 5 and 6 are shown in Table 2.

[0288] [Table 8]

[0289] Test results for dissolved metals in the reaction solution indicated that the catalyst described in Comparative Example 2 was subject to chemical corrosion, but the catalysts of Comparative Examples 1 and 3 were not. However, the tablet integrity of the catalyst of Comparative Example 1 was compromised under the test conditions. The catalysts of Comparative Examples 2 and 3 retained their shape after being subjected to the test conditions. However, the relative reduction in SCS or SH of the catalysts of Comparative Examples 2 and 3 was higher than that of the catalysts of Examples 1 and 2. Furthermore, the absolute residual values ​​of SCS or SH of the used catalysts of Comparative Examples 2 and 3 were also lower. Thus, Comparative Examples 3 to 6 demonstrate that the catalysts of Comparative Examples 1 to 3 are less stable in terms of corrosion and mechanical degradation under the conditions relevant to the method of the present invention.

[0290] Example 5: Sorbitol conversion test using the catalyst of Example 1 The conversion using the catalyst of Example 1 was carried out in a fixed-bed reactor (200 mL). After loading the catalyst, no additional reduction procedure was employed. A feed consisting of 10-40 wt. % sorbitol and 0.0-0.45 wt. % NaOH was added at 110 bar, 200 °C, and LHSV = 0.3 h. -1 The details are shown in Table 3.

[0291] Glycol yields are given in mole % C, which represents the molar conversion of C atoms of the starting material (e.g., sorbitol) to the desired glycols 1,2-propanediol (1,2-PDO), ethylene glycol (EG), and glycerol (GLY). The yields were calculated according to the general formula (IV):

[0292]

number

[0293] The following formula shows an example of the mole % C of 1,2-PDO in Experiment 4 of Table 3.

[0294]

number

[0295] [Table 9]

[0296] Table 5 shows complete conversion of sorbitol under all applied reaction conditions. Selectivities up to 40.5 mol % C for 1,2-propanediol (1,2-PDO), 22.5 mol % C for glycerin (GLY), and 16.0 mol % C for ethylene glycol (EG) were achieved. Yields of 1,2-PDO, GLY, and EG are shown in mol % C calculated according to equation (I).

[0297] Example 6: Sorbitol conversion test using the catalyst of Example 1 The conversion using the catalyst of Example 1 was carried out in a fixed-bed reactor (200 mL). After loading the catalyst, no additional reduction procedure was employed. A feed consisting of 40 wt. % sorbitol and 0.45 wt. % NaOH was used at 110-150 bar, 200 °C, and LHSV = 0.15-1.2 h. -1 The liquid was sent to the reactor under the following conditions. Details are shown in Table 4.

[0298] [Table 10]

[0299] Table 4 shows complete conversion of sorbitol under all applied reaction conditions. Selectivities of 30.7 mol % C for 1,2-propanediol (1,2-PDO), 23.5 mol % C for glycerol (GLY), and up to 15.4 mol % C for sorbitol were achieved. Yields of 1,2-PDO, GLY, and EG are shown in mol % C calculated according to equation (I).

[0300] Examples 7 and 8 and Comparative Example 7: High-throughput screening The catalysts of Examples 1 and 2 and Comparative Example 1 were tested in a high-throughput reactor system containing up to 16 parallel fixed-bed reactors. The reactors were filled with either 0.6 mL or 2.4 mL of catalyst and configured with different LHSVs for particle size fractions ranging from 250 to 315 μm. All reactors were connected to the same liquid feed and the same educt gas and could be individually heated to reaction temperature. The products were condensed in a liquid condenser, and the gas was routed to a multiport valve and analyzed by an online gas chromatograph. The condensed liquid samples were analyzed offline by offline gas chromatography and HPLC. The throughput reactor system is shown in Figure 1.

[0301] Example 7: High-throughput screening of sorbitol using the catalyst from Example 1 The reactions were carried out in a fixed-bed reactor (0.6 mL) for 48 h per experiment. No additional reduction procedure was performed after catalyst loading. The feed consisted of 40 wt. % sorbitol and 0.72–4.88 wt. % NaOH. The reactor was pumped under 110 bar. The temperature and space velocity were adjusted throughout the experiment. Details are shown in Table 5.

[0302] [Table 11]

[0303] Table 5 shows that under all applied reaction conditions, conversions of sorbitol up to 100 mol% C were achieved. Selectivities of up to 43.83 mol% C for 1,2-propanediol (1,2-PDO), 26.4 mol% C for glycerin (GLY), and 15.00 mol% C for ethylene glycol (EG) were achieved. The yields of 1,2-PDO, GLY, and EG are shown in mol% C calculated according to equation (I).

[0304] Example 8: High-throughput screening of sorbitol using the catalyst from Example 2 Conversions using the catalyst of Example 2 were carried out in a fixed-bed reactor (0.6 mL) for 48 hours per run. No additional reduction procedure was employed after catalyst loading. A feed consisting of 40 wt. % sorbitol and 0.72-4.88 wt. % NaOH was pumped to the reactor at 110 bar. Temperature and space velocity were adjusted throughout the run. Details are given in Table 6.

[0305] [Table 12]

[0306] Table 6 shows that under all applied reaction conditions, conversions of sorbitol up to 100 mol% C were achieved. Selectivities of up to 45.31 mol% C for 1,2-propanediol (1,2-PDO), 23.99 mol% C for glycerin (GLY), and 16.13 mol% C for ethylene glycol (EG) were achieved. The yields of 1,2-PDO, GLY, and EG are shown in mol% C calculated according to equation (I).

[0307] Comparative Example 7: High-throughput screening of sorbitol using the catalyst of Comparative Example 1 Reactions using the catalyst of Comparative Example 1 were carried out in a fixed-bed reactor (0.6 mL) for 48 hours per experiment. No additional reduction procedure was employed after catalyst loading. A feed consisting of 40 wt. % sorbitol and 0.72-4.88 wt. % NaOH was pumped into the reactor under 110 bar. The temperature and space velocity were adjusted throughout the experiment. Details are shown in Table 7.

[0308] [Table 13]

[0309] Table 7 shows sorbitol conversions of up to 100 mol% C under all applied reaction conditions. Selectivities of up to 44.89 mol% C for 1,2-propanediol (1,2-PDO), 22.7 mol% C for glycerin (GLY), and 15.29 mol% C for ethylene glycol (EG) were achieved. The yields of 1,2-PDO, GLY, and EG are shown in terms of mol% C calculated according to Equation (I). However, Comparative Example 4 revealed that the mechanical stability of the catalyst of Comparative Example 1 was insufficient. Therefore, the conversion and selectivity results shown in Table 7 cannot be sustainably achieved in an industrial process using the catalyst of Comparative Example 1.

[0310] Comparative Example 8: High-throughput screening of sorbitol using the catalyst of Comparative Example 2 Reactions using the catalyst of Comparative Example 2 were carried out in a fixed-bed reactor (0.6 mL) for 48 hours per experiment. No additional reduction procedure was employed after catalyst loading. A feed consisting of 40 wt. % sorbitol and 0.72-4.88 wt. % NaOH was pumped into the reactor under 110 bar. The temperature and space velocity were adjusted throughout the experiment. Details are shown in Table 8.

[0311] [Table 14]

[0312] Table 8 shows sorbitol conversions of up to 100 mol% C under all applied reaction conditions. Selectivities of up to 42.71 mol% C for 1,2-propanediol (1,2-PDO), 7.15 mol% C for glycerol (GLY), and 9.76 mol% C for ethylene glycol (EG) were achieved. The yields of 1,2-PDO, GLY, and EG are shown in mol% C calculated according to Equation (I). The test had to be stopped after Run 4 due to an increase in pressure drop over the reactor caused by loss of catalyst stability. Therefore, the conversion and selectivity results shown in Table 8 cannot be sustainably achieved in an industrial process using the catalyst of Comparative Example 2.

[0313] Comparative Example 9: High-throughput screening of sorbitol using the catalyst of Comparative Example 3 Reactions using the catalyst of Comparative Example 3 were carried out in a fixed-bed reactor (0.6 mL) for 48 hours per experiment. No additional reduction procedure was employed after catalyst loading. A feed consisting of 40 wt. % sorbitol and 0.72-4.88 wt. % NaOH was pumped into the reactor under 110 bar. The temperature and space velocity were adjusted throughout the experiment. Details are shown in Table 9.

[0314] [Table 15]

[0315] Table 9 shows sorbitol conversions of up to 100 mol% C under all reaction conditions applied. Selectivities of 41.98 mol% C for 1,2-propanediol (1,2-PDO), 11.51 mol% C for glycerin (GLY), and 10.37 mol% C for ethylene glycol (EG) were achieved. The yields of 1,2-PDO, GLY, and EG are shown in terms of mol% C calculated according to Equation (I). Table 9 shows the results of Run 1 and Run 7, obtained under identical operating conditions at the beginning and end of the catalytic test. In Run 7, the sorbitol conversion was significantly lower than that of Run 1, indicating a decrease in catalytic activity and therefore a lack of catalyst stability. Therefore, the conversion and selectivity results shown in Table 9 cannot be sustainably achieved in an industrial process using the catalyst of Comparative Example 3.

[0316] Cited prior art: - US 6,900,361 B2 - EP 2 403 818 A1 - US 5,814,112 A - US 6,152,975 A - Journal of Environmental Chemical Engineering 2022,10,107229 - Wang et al., ChemCatChem 2019,11,4123-4129 - Xin Jin et al.,ACS Catal.2015,5,6545-6558 - Chen et al.,Catalysis Communications 2013,39,86-89

Claims

1. 1. A process for preparing one or more monoalcohols, diols and triols each having 2 or 3 carbon atoms, comprising: (i) providing a liquid aqueous feed stream comprising one or more sugars and sugar alcohols each having 3, 5, or 6 carbon atoms; (ii) feeding the liquid aqueous feed stream provided in accordance with step (i) to a reaction zone containing a catalyst comprising nickel and subjecting the feed stream to reaction conditions in the reaction zone to obtain a reaction mixture comprising one or more of a monoalcohol, a diol, and a triol; (iii) removing a liquid aqueous effluent stream from said reaction zone comprising one or more of a monoalcohol, a diol, and a triol; Including, The catalyst contains zirconium oxide, and 5 to 60 mass % of the catalyst is ZrO ２ zirconium oxide calculated as

2. The catalyst further comprises a metal oxide, and the metal of the metal oxide is preferably selected from the group consisting of Na, Mg, Al, Si, K, Ca, Ti, Mn, Co, Cu, Zn, Nb, Mo, La, Hf, W, and combinations of two or more thereof, more preferably from the group consisting of Na, Mg, Al, Si, Ca, Ti, Mn, Co, Cu, La, Hf, and combinations of two or more thereof, more preferably from the group consisting of Al, Si, Mn, Co, Cu, and combinations of two or more thereof, more preferably from the group consisting of Cu, Co, and combinations thereof, more preferably the metal of the metal oxide is Cu, and more preferably the catalyst is selected from the group consisting of CuO, CoO, Co ２ O ３ , Co ３ O ４ 10. The method of claim 1, further comprising a metal oxide selected from the group consisting of: and mixtures thereof, more preferably wherein the catalyst further comprises CuO.

3. 3. The method of claim 1 or 2, wherein the catalyst has a crystallinity in the range of 60 to 100%, based on the total catalyst, as determined from a powder X-ray diffraction pattern of the catalyst.

4. 4. The method according to claim 1, wherein the powder X-ray diffraction pattern of the catalyst exhibits signal peaks in the 2θ angle ranges of 28° to 29° and 31° to 32°.

5. 5. The method of any one of claims 1 to 4, wherein the catalyst comprises a monoclinic crystalline phase comprising zirconium oxide and a tetragonal crystalline phase optionally comprising zirconium oxide, and preferably the monoclinic crystalline phase comprises zirconium oxide in an amount of 5 to 100% by weight and the tetragonal crystalline phase comprises zirconium oxide in an amount of 0 to 20% by weight, based on 100% by weight of all crystalline phases in the catalyst, as determined from a powder X-ray diffraction pattern of the catalyst.

6. 6. The process according to any one of claims 1 to 5, wherein 40 to 90% by weight of the catalyst consists of nickel, calculated as NiO, preferably 45 to 85% by weight, more preferably 50 to 80% by weight.

7. 7. The process according to any one of claims 1 to 6, wherein 40 to 90% by weight, preferably 60 to 85% by weight, of the catalyst consists of nickel and copper, calculated as NiO and CuO.

8. 8. The method of any one of claims 1 to 7, wherein one or more of the sugars having six carbon atoms is preferably selected from the group consisting of glucose, galactose, maltose, lactose, sucrose, allose, altrose, mannose, gulose, idose, talose, and combinations of two or more thereof.

9. 9. The method of any one of claims 1 to 8, wherein the one or more of the monoalcohols, diols, and triols, each having 2 or 3 carbon atoms, are selected from the group consisting of 1,2-propanediol, ethylene glycol, 1,3-propanediol, glycerol, 1-propanol, 2-propanol, ethanol, and combinations of two or more thereof.

10. 10. The method of claim 9, wherein the one or more of the diols and triols having 2 or 3 carbon atoms, respectively, are selected from the group consisting of 1,2-propanediol, ethylene glycol, glycerol, and combinations of two or more thereof.

11. 11. The method of any one of claims 1 to 10, wherein the liquid aqueous feed stream of step (ii) comprises 20 to 99%, preferably 25 to 60%, more preferably 25 to 40% by weight of sugars or sugar alcohols having 3, 5 or 6 carbon atoms, respectively.

12. The liquid aqueous feed stream provided in step (i) further comprises a compound selected from the group consisting of a base, a Lewis acid and combinations thereof, preferably the liquid aqueous feed stream provided in step (i) further comprises a base, preferably the base is selected from the group consisting of a metal hydroxide and a metal carbonate, the metal of the metal hydroxide and the metal carbonate is preferably selected from the group consisting of Li, Na, K, Ca, Mg and combinations of two or more thereof, more preferably the base is LiOH, NaOH, Na ２ CO ３ , KOH, K. ２ CO ３ , Ca(OH) ２ , Mg(OH) ２ and mixtures of two or more thereof, preferably NaOH, Na ２ CO ３ , KOH, K. ２ CO ３ , Ca(OH) ２ , Mg(OH) ２ and combinations of two or more thereof, and more preferably, the base is selected from the group consisting of NaOH, Na ２ CO ３ , KOH, K. ２ CO ３ 12. The method of any one of claims 1 to 11, wherein the base comprises one or more metal hydroxides and metal carbonates selected from the group consisting of:

13. 13. The process according to any one of claims 1 to 12, wherein the reaction conditions according to step (ii) comprise a reaction pressure in the range of from 40 to 250 bar, preferably from 60 to 200 bar, more preferably from 80 to 120 bar.

14. 14. The process according to any one of claims 1 to 13, wherein the reaction conditions according to step (ii) comprise a temperature in the range of from 140 to 220°C, preferably from 170 to 200°C.

15. The liquid aqueous feed stream provided in step (i) and fed to the reaction zone in step (ii) is ２ 15. The method of any one of claims 1 to 14, further comprising:

16. 16. A method for preparing a catalyst, preferably a catalyst for the method according to any one of claims 1 to 15, comprising the following steps: (a) preparing a first mixture comprising zirconium oxide and water; (b) preparing a second mixture comprising a nickel precursor selected from the group consisting of nickel nitrate, nickel halide, nickel acetate, nickel sulfate, and optionally a copper precursor selected from the group consisting of copper nitrate, copper halide, copper acetate, copper sulfate, copper amine complexes, and combinations of two or more thereof, and water; (c) mixing the first mixture obtained in step (a), the second mixture obtained in step (b), and a precipitant to obtain a slurry containing solids and water; (d) removing water from the slurry obtained in step (c) to obtain a solid; (e) optionally drying the solid obtained in step (d) at a temperature in the range of 80 to 150°C to obtain a dry solid; (f) calcining the solid obtained in step (d), preferably the dried solid obtained in step (e), at a temperature in the range of 300 to 700°C to obtain a catalyst comprising nickel oxide and zirconium oxide, preferably a catalyst for the process according to any one of claims 1 to 15, wherein 5 to 60% by weight of the catalyst is ZrO ２ and zirconium oxide, calculated as A method comprising:

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