Alcohol conversion process

Abstract

The present invention relates to a process for the conversion of alcohols, wherein a homogeneous transition metal catalyst is used. In this process, an alcohol mixture is used as starting material to produce medium chain length bioalcohols, in particular propanol and isobutanol, at increased productivity.

Description

[0001] This invention relates to a method for alcohol conversion.

[0002] The common industrial production of alcohols is mainly based on the carbonyl synthesis process. This process involves reacting an olefin with a carbonyl synthesis gas, which is a mixture of hydrogen and carbon monoxide in a 1:1 molar ratio. This reaction is followed by the hydrogenation of an aldehyde to the desired alcohol.

[0003] Alternative methods for synthesizing alcohols are based on the Guerbet reaction, known for decades (M. Guerbet, CR Hebd. Séances Acad. Sci. [French Academy of Sciences Weekly] 1899, 128, pp. 511-513). The generally accepted mechanism for producing Guerbet alcohols involves three steps: (i) dehydrogenation of a primary alcohol to the corresponding aldehyde; (ii) condensation of two aldehyde molecules into an α,β-unsaturated aldehyde in the absence of water; and (iii) hydrogenation of the unsaturated aldehyde to a dimer alcohol. The Guerbet reaction requires a basic catalyst, such as sodium hydroxide, potassium hydroxide, sodium alkoxide, or potassium alkoxide. Homogeneous or heterogeneous metal catalysts are often added to accelerate the dehydrogenation and hydrogenation steps. However, the Guerbet reaction is generally limited by harsh conditions, poor selectivity, separation problems, and low yields.

[0004] In the chemical industry, 1-butanol is an important intermediate product and solvent used in a wide variety of products, including paints and various plastics. To date, 1-butanol has been produced from petroleum-based feedstocks, resulting in a significant carbon footprint for both 1-butanol and the resulting products. Therefore, it is important for the chemical industry to find and develop an economical and sustainable route for producing butanol with a lower carbon footprint.

[0005] Ethanol can be a sustainable feedstock for the production of chemicals. Using ethanol in the Guerbert reaction could be a profitable and sustainable route to the production of 1-butanol. Although the Guerbert reaction has been used to produce higher alcohols from alcohols with higher boiling points than ethanol to date, there is currently no industrial application of the Guerbert reaction using ethanol as a feedstock for the production of 1-butanol. While the Guerbert reaction itself may appear to be a simple chemical reaction, using ethanol as a feedstock introduces inherent problems, particularly regarding selectivity. Because the product 1-butanol itself may also undergo dehydrogenation, higher alcohols are often produced as byproducts in this process, making the reaction unprofitable on an industrial scale to date.

[0006] The efficient production of medium-sized bioethanol (particularly propanol and isobutanol) has been extremely challenging to date. Fermentation has been proposed for industrial use; however, this fermentation is disadvantageous due to its very low space / time yields and often suffers from low selectivity. This leads to very energy-intensive purification.

[0007] WO 2013 / 156399 A1 relates to the use of at least one having formula R in the presence of at least one base in a homogeneous phase. 1 Alcohols with -CH2-CH2-OH groups (R group) 1 A method for producing branched alcohols (which may be different or the same and selected from straight-chain or branched C2-C3 alkyl groups), characterized by using at least one complex compound containing Ru(II), wherein Ru(II) has at least one ligand L. 1 At least one ligand is at least bidentate, L 1 At least one coordination site is a nitrogen atom.

[0008] A. Kaithal et al., “Ruthenium(II)-Catalyzed β-Methylation of Alcohols using Methanol as C1 Source”, CHEMCATCHEM, Vol. 11, No. 21, 2019-05-16, pp. 5287-5291, describes the selective introduction of methyl branches into the carbon chain of alcohols using a low-load ruthenium precatalyst [RuH(CO)(BH4)(HN(C2H4PPh2)2)] (Ru-MACHO-BH) with methanol as both the methylating agent and the reaction medium.

[0009] US 2015 / 246863 A1 relates to the synthesis of long-chain Guerbert alcohols, and more particularly to the synthesis of mixtures of Guerbert alcohols containing long-chain, multi-branched Guerbert alcohols.

[0010] N. Biswas et al., “Acridine-Based SNS-Ruthenium Pincer Complex-Catalyzed Borrowing Hydrogen-Mediated CC Alkylation Reaction: Application to the Guerbet Reaction”, SYNLETT, Vol. 34, No. 6, 2022-07-08, pp. 622-628, discusses the study of SNS-based ruthenium pincer catalysts and their application in the Guerbet condensation of primary alcohols to obtain β-alkylated dimers.

[0011] Y. Xie et al., “Highly efficient process for Production of Biofuel from Ethanol Catalyzed by Ruthenium Pincer Complexes”, Journal of the American Society, Vol. 138, No. 29, 2016-07-18, pp. 9077-9080, relates to a Guerbert-type process using ruthenium pincer catalysis for the production of biofuel from ethanol.

[0012] WO 2012 / 119928 A1 relates to a method for producing an alkanolamine containing a primary amino group and a hydroxyl group by amination of a diol containing two hydroxyl groups with ammonia and removal of water.

[0013] US 2010 / 298613 A1 discloses a method for producing alcohols, which includes dimerizing a starting material alcohol having four or fewer carbon atoms in an environment with a hydrogen partial pressure of 0.1 MPa or higher.

[0014] To date, catalytic routes for the production of medium-chain bioethanol have been academic in nature only, and therefore these methods are not industrially feasible, for example due to unresolved problems such as low catalyst stability, low space / time yields and / or cumbersome purification.

[0015] Therefore, the object of the present invention is to provide an alcohol conversion method that allows for a profitable and sustainable route to produce medium-chain bioethanol with increased productivity.

[0016] Therefore, this invention relates to an alcohol conversion method based on the Guerbert reaction, wherein a homogeneous transition metal catalyst is used. This method employs a mixture of alcohols as starting materials, thereby allowing a profitable and sustainable route to produce medium-chain alcohols such as isobutanol, 1-propanol, and 1-butanol with increased productivity. The ratio of the obtained alcohols can be effectively controlled using the ratio of the starting alcohols. Ideally, biobutanol can be obtained with increased productivity.

[0017] This invention particularly relates to an alcohol conversion method, which includes...

[0018] (i) Provide component C, which is at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, and a reduced form of the precursor;

[0019] (ii) Preparation of liquid mixture M E The liquid mixture contains at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c Alcohols and bases of the group consisting of -CH2-OH, and components C and R provided according to (i). a R b and R c Each is independently selected from the group consisting of: H and C1-C4-alkyl; wherein R a -CH2-CH2-OH, R b -CH2-CH2-OH and R c -CH2-OH are different from each other;

[0020] (iii) Make the liquid mixture M prepared according to (ii) E In the reaction space S G Under conditions of alcohol conversion, and in S G Obtain reaction mixture M G The reaction mixture contains at least one alcohol selected from the group consisting of: R b -CH2-CH2-(CHR a -CH2) x -OH,R a -CH2-CH2-(CHR b -CH2) x -OH and R c -CH2-(CHR a -CH2) x -OH, x is an integer in the range of 1 to 4, wherein the alcohol conversion conditions include the reaction mixture M in the range of 100°C to 250°C. G Temperature and at 1 × 10 5Up to 4 × 10 6 The reaction space S within the Pa range G The pressure in the middle;

[0021] (iv) From the reaction mixture M obtained according to (iii) G Separate at least one alcohol selected from the group consisting of: R b -CH2-CH2-(CHR a -CH2) x -OH,R a -CH2-CH2-(CHR b -CH2) x -OH and R c -CH2-(CHR a -CH2) x -OH, to obtain mixture M CS ;

[0022] in

[0023] (a) The base is selected from the group consisting of: ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide, ammonium carbonate, ammonium bicarbonate, alkali metal carbonate, alkali metal bicarbonate, alkaline earth metal carbonate, alkaline earth metal bicarbonate, alkali metal alkoxide, alkaline earth metal alkoxide, alkali metal amide, alkaline earth metal amide, alkali metal 2,2,6,6-tetramethylpiperidine, alkaline earth metal 2,2,6,6-tetramethylpiperidine, secondary amino acids, and mixtures of two or more thereof.

[0024] (b) The catalyst comprises a compound having formula (A).

[0025] (A),

[0026] in

[0027] M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0028] L 1 and L 2 PR is independent of each other d R e NR d R e SR d , SH, S(=O)R g C5-C containing at least one heteroatom selected from nitrogen and sulfur 10 - heteroaryl, AsR d R e SbR d R e And N-heterocyclic carbene represented by the following structure:

[0029] or ;

[0030] L 3 Choose from the following groups: CO, PR d R e R f AsR d R e R f SbR d R e R f SR d R e R g CN, R g NC, N2, PF3, pyridine, and thiophene;

[0031] R 1 R 2 R 3 and R 4 It is hydrogen, or it forms an acridine unit together with the pyridyl unit of the catalyst having formula (A), or R 1 and R 2 Or R 3 and R 4 Together with the pyridyl unit of a compound having formula (A), a quinolinyl unit is formed;

[0032] n is 0 or 1;

[0033] Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, OH, OR, NR g 2. NH3, NR g 3 and R g 2NSO2R g ;

[0034] R d R e R f R g R 5 R 6 and R 7 Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10-Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C5-C 10 -aryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and unsubstituted or substituted C5-C atoms containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heteroaryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and

[0035] X is optional and selected from the group consisting of: one, two, three, four, five, six, or seven substituents at any carbon atom on the acridine unit, or one, two, three, four, or five substituents at any carbon atom on the quinolinyl unit, or one substituent at a carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C. 10 -alkyl; and

[0036] (c) The precursor of a catalyst comprising a compound having formula (A) comprises a mixture of: 1) a compound containing metal M; 2) at least one component selected from the group consisting of: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, organic carbonyl compounds, C1-C 10 -alkyl, C3-C 12 -Cycloalkyl, C2-C 12 -Alkenyl, C3-C 15 -cycloalkenyl, C5-C 20 - aryl, CN, CO, OH, OC(=O)CF3, OSO2CF3, hydrides, pyridine, halides, hydroxides, and thiophenes; and 3) compounds having the formula (H).

[0037] (H),

[0038] M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0039] L 1 and L 2 PR is independent of each other d R e NR d R e SR d , SH, S(=O)R g C5-C containing at least one heteroatom selected from nitrogen and sulfur 10 - heteroaryl, AsR d R e SbR d R e And N-heterocyclic carbene represented by the following structure:

[0040] or ;

[0041] R 1 R 2 R 3 and R 4 It is hydrogen, or it forms an acridine unit together with the pyridyl unit of the catalyst having formula (A), or R 1 and R 2 Or R 3 and R 4 Together with the pyridyl unit of the catalyst having formula (A), a quinolinyl unit is formed;

[0042] n is 0 or 1;

[0043] R d R e R f R g R 5 R 6 and R 7 Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10- Heterocyclic group, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C5-C 10 -aryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and unsubstituted or substituted C5-C atoms containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heteroaryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and

[0044] X is optional and selected from the group consisting of: one, two, three, four, five, six, or seven substituents at any carbon atom on the acridine unit, or one, two, three, four, or five substituents at any carbon atom on the quinolinyl unit, or one substituent at a carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C. 10 -alkyl.

[0045] The method according to the invention is preferably a continuous method. Alternatively, the method is preferably a semi-batch method or a batch method.

[0046] Preferably, the liquid mixture M prepared according to (ii) E 90 to 100 wt%, more preferably 95 to 100 wt%, more preferably 98 to 100 wt%, more preferably 99 to 100 wt%, comprising at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c Alcohols, bases, and component C of the group consisting of -CH2-OH.

[0047] Preferably, according to the reaction space S of (iii) G Contains reaction mixture M G The gas phase comprises at least one inert gas, more preferably selected from the group consisting of nitrogen, argon and mixtures thereof.

[0048] In the method according to the invention, the alcohol conversion conditions according to (iii) preferably include 1 × 10⁻⁶. 5 Up to 3.5 × 10 6 Within the Pa range, more preferably within 1 × 10 Pa. 5 Up to 3.1 × 106 Within the Pa range, more preferably within 1 × 10 Pa. 5 Up to 2 × 10 6 Within the Pa range, more preferably within 1 × 10 Pa. 5 Up to 1.5 × 10 6 The reaction space S within the Pa range G The pressure in the mixture. Furthermore, the alcohol conversion conditions according to (iii) preferably include a reaction mixture M in the range of 100°C to 200°C, more preferably in the range of 120°C to 180°C, and even more preferably in the range of 130°C to 160°C. G The temperature.

[0049] Preferably, the alcohol conversion conditions according to (iii) include those based on reaction mixture M. G The total weight of the reaction mixture M is in the range of 0.1 to 10 wt%, more preferably in the range of 0.5 to 8 wt%, and even more preferably in the range of 1 to 5 wt%. G The amount of alkali in the solution.

[0050] Preferably, the alcohol conversion conditions according to (iii) include those based on reaction mixture M. G The total weight of the reaction mixture M is in the range of 0.001 to 2 wt%, more preferably in the range of 0.001 to 1 wt%, and even more preferably in the range of 0.001 to 0.5 wt%. G The amount of component C in the middle.

[0051] In another preferred embodiment, according to the reaction space S of (iii) G Contains reaction mixture M G The gas phase contains H2, and the alcohol conversion conditions according to (iii) include maintaining the partial pressure of H2 in the gas phase at 2 × 10⁻⁶. 4 Up to 3.1 × 10 6 Within the range of Pa, more preferably within 2 × 10 Pa. 4 Up to 1.1 × 10 6 Within the range of Pa, more preferably within 2 × 10 Pa. 4 Up to 6 × 10 5 Within the range of Pa.

[0052] The partial pressure of H2 in the gas phase is preferably maintained by introducing H2 into the gas phase. Alternatively, the partial pressure of H2 in the gas phase is preferably maintained by relaxation of the gas phase, and more preferably by removing at least a portion of H2 from the gas phase.

[0053] In the context of this invention, "maintaining" the partial pressure of H2 in the gas phase includes ensuring that the partial pressure of H2 remains within a desired range during the reaction. While an active step is not mandatory when the partial pressure of H2 is within the desired range, the pressure can still be adjusted to different portions of that range if desired. However, to ensure that the partial pressure of H2 is neither too high nor too low, it is preferable to regulate the partial pressure of H2, or it must be regulated to ensure that the partial pressure of H2 is maintained within the desired range. This regulation can be achieved, for example, through relaxation of the gas phase (which in this case reduces the partial pressure of H2), or alternatively, by introducing H2 into the gas phase (which in this case increases the partial pressure of H2). Depending on the partial pressure of H2 during the reaction, one or even both of these alternatives can be performed, if desired, to regulate the partial pressure of H2 and maintain it within the desired pressure range throughout the reaction.

[0054] The pressure during the reaction can be monitored, for example, by determining the total pressure and comparing it with the initial pressure. Since hydrogen tends to accumulate during the reaction, changes in the H2 partial pressure, such as an increase, cause the pressure to increase over time. For example, by actively measuring and controlling the total pressure during the reaction, it is possible to ensure that the H2 partial pressure remains within the required protection range. If the accumulated total pressure is too high, this is often at least partly a result of the increase in H2 partial pressure. Hydrogen can be removed from the gas phase by relaxation of the gas phase, and the H2 partial pressure can be maintained within the desired range. Therefore, in a preferred embodiment, the H2 partial pressure in the gas phase is preferably maintained within the appropriate range by monitoring the total pressure of the reaction and adjusting the total pressure (if necessary), preferably by relaxation of the gas phase (in which case the H2 partial pressure can be reduced), or alternatively by introducing H2 into the gas phase (in which case the H2 partial pressure can be increased).

[0055] Alternatively, the partial pressure of hydrogen can be determined by other means, such as collecting and analyzing a sample of the gas phase during the reaction. As another alternative, the pressure can be monitored via online measurement and adjusted accordingly as outlined above.

[0056] Preferably, component C comprises a mixture, wherein the mixture comprises: 1) a compound containing metal M; 2) at least one component selected from the group consisting of: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, organic carbonyl compounds, C1-C 10 -alkyl, C3-C 12 -Cycloalkyl, C2-C 12-Alkenyl, C3-C 15 -cycloalkenyl, C5-C 20 -Aryl, hydride, pyridine, halide, hydroxide and thiophene; and 3) compounds having the formula (H').

[0057] (H'),

[0058] M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0059] L 1 and L 2 PR is independent of each other d R e NR d R e SR d SH and S(=O)R g ;

[0060] L 3 Choose from the following groups: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, pyridine, and thiophene;

[0061] R 1 R 2 R 3 and R 4 It is hydrogen, or it forms an acridine unit together with the pyridyl unit of the catalyst, which includes a compound having formula (A);

[0062] n is 0 or 1, and if R 1 R 2 R 3 and R 4 If it is hydrogen, then n is 0;

[0063] R d R e R f and R g Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C.10 -alkyl; C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic; C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O and S. 10 - heteroaryl; and

[0064] Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, and OH.

[0065] Preferably, component C comprises a compound containing metal M selected from the group consisting of: IrCl3 x H2O, [Ir(COD)Cl]2, [Ir(COE)2Cl]2, [Ir(C2H4)2Cl]2, [Ir(COD)OH]2, [Ir(COD)MeO]2, [IrCp]2, etc. Cl2], [IrCpCl2], Ir4(CO) 12 [Ir(PPh3)2(CO)Cl], [Ir(acetylacetone)3], and [Ir(acetylacetone)(COD)], where Cp is a cyclopentadienyl group. It is pentamethylcyclopentadienyl, COD is 1,5-cyclooctadienyl, COE is cyclooctenyl, and methylallyl is 2-methylallyl. Alternatively, component C preferably comprises a compound containing metal M selected from the group consisting of: [Ru(p-cymene)Cl2]2, [Ru(benzene)Cl2] y [Ru(CO)2Cl2] y —where y is in the range of 1 to 1000 in each case, [Ru(CO)3Cl2]2, [Ru(COD)(allyl)], RuCl3 x H2O, [Ru(acetylacetone)3], [Ru(DMSO)4Cl2], [Ru(cyclopentadienyl)(CO)2Cl], [Ru(cyclopentadienyl)(CO)2H], [Ru(cyclopentadienyl)(CO)2]2, [Ru(Cp)(CO)2Cl], [Ru(Cp (CO)₂H]、[Ru(Cp) [Ru(indyl)(CO)2Cl], [Ru(indyl)(CO)2H], [Ru(indyl)(CO)2]2, Ruthenium dicrenecrolein, [Ru(COD)Cl2]2, [Ru(Cp)2]2 (COD)Cl]、[Ru3(CO) 12 [Ru(PPh3)4(H)2] 、[Ru(PPh3)3(Cl)2], [Ru(PPh3)3(CO)(CI)2], [Ru(PPh3)3(CO)(CI)(H)], [Ru(PPh3)3(CO)(H)2], and [Ru(cyclooctadienyl)(methylallyl)2], where Cp is cyclopentadienyl, Cp It is pentamethylcyclopentadienyl, COD is 1,5-cyclooctadienyl, and methylallyl is 2-methylallyl.

[0066] Preferably, the reduced form of the precursor comprises a compound having the formula (PI) or (P-II):

[0067] (PI)

[0068] Where R 1 R 2 R 3 and R 4 It is hydrogen, or forms a tetrahydroquinoline unit, decahydroquinoline unit, tetrahydroacrylidine unit, or tetradecahydroacrylidine unit together with an N-containing ring; and

[0069] Where L 1 and L 2 They are independent of each other as defined above;

[0070] (P-II)

[0071] Where R 1 R 2 R 3 and R 4 It is hydrogen; and

[0072] Where L 1 and L 2 They are independent of each other as defined above.

[0073] More preferably, the reduced form of the precursor includes compounds having the formula (PI):

[0074] (PI)

[0075] Where R 1 R 2 R 3 and R 4 It is hydrogen, or it forms a tetrahydroacrylidine unit or a tetradecahydroacrylidine unit together with an N-containing ring.

[0076] In another preferred embodiment, the reduced form of the precursor comprises a compound having the formula (P-II):

[0077] (P-II)

[0078] Where R 1 R 2 R 3 and R 4 It is hydrogen; and

[0079] Where L 1 and L 2 They are independent of each other as defined above.

[0080] Preferably, component C comprises a compound having formula (A').

[0081] (A'),

[0082] Among them, M and R 1 R 2 R 3 and R 4 L 1 L 2 L 3 Y and n are as defined above.

[0083] In another preferred embodiment, component C comprises a compound having formula (B).

[0084] (B),

[0085] in

[0086] M can be freely selected from the following groups: Ir, Ru, and Mn;

[0087] L 1 and L 2 PR is independent of each other d R e NR d R e SR d SH and S(=O)R g ;

[0088] L 3 Choose from the following groups: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, pyridine, and thiophene;

[0089] R d R e R f and R gChoose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group; C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O and S. 10 - Heteroaryl; and Y is selected from the group consisting of: H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO and OH.

[0090] Preferably, component C comprises a compound having formula (C).

[0091] (C),

[0092] in

[0093] M can be freely selected from the following groups: Ir, Ru, and Mn;

[0094] L 1 and L 2 PR is independent of each other d R e NR d R e SR d SH and S(=O)R g ;

[0095] L 3 Choose from the following groups: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, pyridine, and thiophene;

[0096] R d R e R f and R g Choose independently from the following groups: H; unsubstituted or substituted C1-C 10-alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group; C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O and S. 10 - heteroaryl; and

[0097] Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, and OH.

[0098] M is preferably selected from the group consisting of Ir and Ru, and more preferably M is Ru.

[0099] L 3 CO is preferred.

[0100] Preferably, L 1 and L 2 Each is (PR) d R e ), and where R d and R e It is C1-C 10 -alkyl, more preferably wherein R d and R e Each is either isopropyl or tert-butyl. Alternatively, L 1 and L 2 Preferably, each is (PR) d R e ), and where R d and R e It is C3-C 10 -cycloalkyl, more preferably wherein R d and R e Each is a cyclohexyl group. Alternatively, L... 1 and L 2 Each is (PR) d R e ), and where R d and R e It is C5-C 10 -Aryl.

[0101] Y is preferably selected from the group consisting of F, Cl, Br and I, more preferably selected from the group consisting of Cl or Br, and even more preferably Y is Cl. It is also preferred that Y is CO.

[0102] Preferably, component C comprises a compound having formula (D).

[0103] (D),

[0104] Cy stands for cyclohexyl.

[0105] Preferably, component C comprises a reducing form of a catalyst having formula (D').

[0106] (D'),

[0107] Cy stands for cyclohexyl.

[0108] Furthermore, preferably, component C comprises a compound having formula (E).

[0109] (E),

[0110] Where iPr is isopropyl.

[0111] Preferably, component C comprises a reducing form of a catalyst having formula (E').

[0112] (E'),

[0113] Where iPr is isopropyl.

[0114] Furthermore, it is preferred that component C comprises a compound having formula (F).

[0115] (F),

[0116] Where tBu is tert-butyl.

[0117] Preferably, component C comprises a reduced form of a catalyst having formula (F').

[0118] (F'),

[0119] Where tBu is tert-butyl.

[0120] The integer x is preferably 1 or 2, and more preferably 1.

[0121] Preferably, R a R b and R cThe following are selected independently: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; preferably, they are selected from the group consisting of H, methyl, ethyl, propyl, and isopropyl; more preferably, they are selected from the group consisting of H, ethyl, and propyl; and even more preferably, R. a R b and R c At least one of them is H, more preferably R. a and R c It is H.

[0122] In a preferred embodiment, the liquid mixture M prepared according to (ii) E It further includes a compound having formula (G) or its reduced form.

[0123] (G),

[0124] Where R 1 R 2 R 3 and R 4 L 1 L 2 And n are as defined above. In a more preferred embodiment, R is a compound having formula (G) or its reduced form. 1 R 2 R 3 and R 4 L 1 L 2 R and n with at least one of the catalyst, its precursor, the reduced form of the catalyst, and the reduced form of the precursor of component C. 1 R 2 R 3 and R 4 L 1 L 2 Same as n. In the liquid mixture M prepared according to (ii) and subjected to the alcohol conversion conditions according to (iii) E In this process, the molar ratio of the compound having formula (G) or its reduced form relative to component C is more preferably in the range of 1:1 to 10:1, more preferably in the range of 1.02:1 to 8:1, and more preferably in the range of 1.05:1 to 5:1.

[0125] Preferably, the compound having formula (G) or its reduced form is selected from the group consisting of: dicyclohexyl-[[5-(dicyclohexylphosphonylmethyl)acridin-4-yl]methyl]phosphine, diisopropyl-[[5-(diisopropylphosphonylmethyl)acridin-4-yl]methyl]phosphine, dicyclohexyl-[[5-(dicyclohexylphosphonylmethyl)pyridin-4-yl]methyl]phosphine and diisopropyl-[[5-(diisopropylphosphonylmethyl)pyridin-4-yl]methyl]phosphine, more preferably wherein the compound having formula (G) or its reduced form is cyclohexyl-[[5-(dicyclohexylphosphonylmethyl)acridin-4-yl]methyl]phosphine or diisopropyl-[[5-(diisopropylphosphonylmethyl)acridin-4-yl]methyl]phosphine.

[0126] Preferably, the alkali is selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides, and mixtures of two or more thereof. The alkali metal hydroxide is preferably selected from the group consisting of NaOH, KOH, and mixtures thereof, more preferably wherein the alkali metal hydroxide is KOH. The alkali metal alkoxide is preferably selected from the group consisting of sodium alkoxide, potassium alkoxide, and mixtures of two or more thereof, more preferably selected from the group consisting of sodium ethoxide, potassium ethoxide, and mixtures thereof.

[0127] At least one alcohol R a -CH2-CH2-OH and at least one selected from R b -CH2-CH2-OH and R c At least one of the alcohols in the group consisting of -CH2-OH is preferably a bio-based alcohol, more preferably available from sugar-containing crops, and even more preferably from one or more of sugarcane and corn.

[0128] According to (ii) the liquid mixture M E Further preferably, it includes a solvent component comprising one or more solvents. More preferably, one or more solvents of the solvent component have a boiling point of 140°C or higher at 1 atm (101325 Pa), more preferably 160°C or higher, more preferably 180°C or higher, and more preferably 190°C or higher.

[0129] In another preferred embodiment, based on 100 wt% water, the solvent component has a water solubility at 25°C in the range of 0 to 0.5 wt%, more preferably in the range of 0 to 0.1 wt%, more preferably in the range of 0 to 0.05 wt%, and more preferably in the range of 0 to 0.01 wt%. It is also preferred that, based on 1 kg of catalyst, the distribution coefficient of the catalyst in the solvent component and water system is 0 to 0.01, more preferably 0 to 0.005, and more preferably 0 to 0.005.

[0130] In a more preferred embodiment, the solvent component comprises at least two solvents with a boiling point of 180°C or higher at 1 atm (101325 Pa).

[0131] In a preferred embodiment, the solvent component comprises at least one solvent selected from the group consisting of: biphenyl, diphenyl ether, 1-tert-butyl-3,5-dimethylbenzene, xylene, mesitylene, toluene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decahydronaphthalene, n-butyl butyrate, n-hexyl hexanoate, n-octyl octanoate, texanole, di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, and mixtures of two or more thereof, more preferably. The solvent is selected from the group consisting of biphenyl, diphenyl ether, 1-tert-butyl-3,5-dimethylbenzene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decahydronaphthalene, n-butyl butyrate, n-hexyl hexanoate, n-octyl octanoate, texanole, di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, and mixtures of two or more thereof, more preferably from the group consisting of biphenyl, diphenyl ether, and mixtures thereof, wherein more preferably, the solvent is a mixture of biphenyl and diphenyl ether.

[0132] In another preferred embodiment, the solvent is a mixture of at least two aromatic hydrocarbons with a boiling point of 180°C or higher. The solvent is preferably selected from the group consisting of: biphenyl, diphenyl ether, 1-tert-butyl-3,5-dimethylbenzene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decahydronaphthalene, n-butyl butyrate, n-hexyl hexanoate, n-octyl octanoate, texanole, di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, and mixtures of two or more thereof, preferably selected from the group consisting of: biphenyl, diphenyl ether, and mixtures thereof, wherein more preferably, the solvent is a mixture of biphenyl and diphenyl ether.

[0133] In a preferred embodiment, the solvent does not include any of benzene, toluene, xylene, or mesitylene.

[0134] Preferably, the solvent does not form an azeotropic mixture with water. An azeotropic mixture, or a mixture with a constant heating point, is a mixture of two or more components in a fluid state whose proportions cannot be altered or changed by simple distillation. This is because when an azeotropic mixture is boiled, the vapor has the same proportions of components as the unboiled mixture. Each azeotropic mixture has a characteristic boiling point. It is not possible to separate the components by fractional distillation.

[0135] In a more preferred embodiment, the solvent component comprises a mixture of biphenyl and diphenyl ether, wherein the molar ratio of biphenyl to diphenyl ether is in the range of 1:2 to 1:6, preferably in the range of 1:2.5 to 1:4.

[0136] Preferably, the liquid mixture M prepared according to (ii) E 90 to 100 wt%, more preferably 95 to 100 wt%, more preferably 98 to 100 wt%, more preferably 99 to 100 wt%, comprising at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c Alcohols, bases, solvent components, and catalysts consisting of the group -CH2-OH.

[0137] The alcohol conversion conditions according to (iii) preferably include those based on reaction mixture M. G The total weight of the reaction mixture M is in the range of 5 to 50 wt%, more preferably in the range of 5 to 30 wt%, and even more preferably in the range of 5 to 10 wt%. G The amount of solvent in the solution.

[0138] According to (iv), the mixture M obtained CS Preferably, it contains component C and further contains a solvent component.

[0139] Preferably, the liquid reaction mixture M obtained according to (iii) G Further comprising at least one unreacted alcohol selected from the group consisting of: R a -CH2-CH2-OH, R b -CH2-CH2-OH and R c -CH2-OH, the method further includes obtaining -CH2-OH from the liquid reaction mixture M G At least a portion of the unreacted alcohol is separated from M. More preferably, from M G At least a portion of the unreacted alcohol is separated by one or more of distillation, extraction, flash evaporation, and membrane separation. More preferably, the unreacted alcohol is separated from M... G At least a portion of the unreacted alcohol separated in (ii) or (iii) is recycled.

[0140] The method according to the invention preferably further includes

[0141] (v) Make the mixture M obtained according to (iv) CS At least a portion of the mixture M is recycled to (ii) or (iii); even more preferably, the mixture M recycled in (v) is recycled to (ii) or (iii). CS At least a portion of it comprises at least a portion of component C. More preferably, the mixture M recycled in (v) CS At least a portion of it comprises at least a portion of component C and at least a portion of solvent component.

[0142] The method according to the invention preferably further includes

[0143] (v) By separating the solvent components and treating the separated solvent components as a liquid mixture M E or reaction mixture M G A portion is recycled to (ii) or (iii) to obtain the mixture M according to (iv). CS At least a portion of it is recycled back into (ii) or (iii).

[0144] In a preferred embodiment, the reaction space S R Contained in a reactor vessel, wherein the reactor vessel is more preferably a fully mixed reactor vessel. Even more preferably, the reactor vessel is selected from the group consisting of: stirred tank reactors, fixed bed reactors, moving bed reactors, and fluidized bed reactors.

[0145] The invention is further illustrated by the following set of embodiments and combinations of embodiments derived from the dependent relationships and reverse references shown. In particular, it should be noted that in each instance of reference to a series of embodiments, such as in the context of the term "method as described in any one of Embodiments 1 to 4," each embodiment in this series is intended to clearly disclose to those skilled in the art that the wording of this term should be understood by those skilled in the art to be synonymous with "method as described in any one of Embodiments 1, 2, 3, and 4." Furthermore, it should be clearly noted that the following set of embodiments represents appropriate structural portions of the general description of preferred aspects of the invention and therefore appropriately supports, but does not represent, the claims of the invention.

[0146] 1. A method for alcohol conversion, comprising:

[0147] (i) Provide component C, which is at least one of a catalyst, a precursor thereof, a reduced form of the catalyst and a reduced form of the precursor;

[0148] (ii) Preparation of liquid mixture M E The liquid mixture contains at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c Alcohols and bases of the group consisting of -CH2-OH, and the components C and R provided according to (i). a R b and R c Each is independently selected from the group consisting of: H and C1-C4-alkyl; wherein R a -CH2-CH2-OH, R b -CH2-CH2-OH and R c-CH2-OH are different from each other;

[0149] (iii) Make the liquid mixture M prepared according to (ii) E In the reaction space S G Under conditions of alcohol conversion, and in S G Obtain reaction mixture M G The reaction mixture contains at least one alcohol selected from the group consisting of: R b -CH2-CH2-(CHR a -CH2) x -OH,R a -CH2-CH2-(CHR b -CH2) x -OH and R c -CH2-(CHR a -CH2) x -OH, x is an integer in the range of 1 to 4, wherein these alcohol conversion conditions include the reaction mixture M in the range of 100°C to 250°C. G Temperature and at 1 × 10 5 Up to 4 × 10 6 The reaction space S within the Pa range G The pressure in the middle;

[0150] (iv) From the reaction mixture M obtained according to (iii) G Separate at least one alcohol selected from the group consisting of: R b -CH2-CH2-(CHR a -CH2) x -OH,R a -CH2-CH2-(CHR b -CH2) x -OH and R c -CH2-(CHR a -CH2) x -OH, to obtain mixture M CS ;

[0151] in

[0152] (a) The base is selected from the group consisting of: ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide, ammonium carbonate, ammonium bicarbonate, alkali metal carbonate, alkali metal bicarbonate, alkaline earth metal carbonate, alkaline earth metal bicarbonate, alkali metal alkoxide, alkaline earth metal alkoxide, alkali metal amide, alkaline earth metal amide, alkali metal 2,2,6,6-tetramethylpiperidine, alkaline earth metal 2,2,6,6-tetramethylpiperidine, secondary amino acids, and mixtures of two or more thereof.

[0153] (b) The catalyst comprises a compound having formula (A).

[0154] (A),

[0155] in

[0156] M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0157] L 1 and L 2 PR is independent of each other d R e NR d R e SR d , SH, S(=O)R g C5-C containing at least one heteroatom selected from nitrogen and sulfur 10 - heteroaryl, AsR d R e SbR d R e And N-heterocyclic carbene represented by the following structure:

[0158] or ;

[0159] L 3 Choose from the following groups: CO, PR d R e R f AsR d R e R f SbR d R e R f SR d R e R g CN, R g NC, N2, PF3, pyridine, and thiophene;

[0160] R 1 R 2 R 3 and R 4 It is hydrogen, or forms an acridine unit together with the pyridyl unit of the catalyst having formula (A), or R 1 and R 2 Or R 3 and R 4 Together with the pyridyl unit of the compound having formula (A), a quinolinyl unit is formed;

[0161] n is 0 or 1;

[0162] Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, OH, OR, NR g 2. NH3, NR g 3 and R g 2NSO2R g ;

[0163] R d R e R f R g R 5 R 6 and R 7 Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C5-C 10 -aryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and unsubstituted or substituted C5-C atoms containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heteroaryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and

[0164] X is optional and selected from the group consisting of: one, two, three, four, five, six, or seven substituents located at any carbon atom on the acridine unit, or one, two, three, four, or five substituents located at any carbon atom on the quinolinyl unit, or one substituent located at a carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C. 10 -alkyl; and

[0165] (c) The precursor of the catalyst comprising a compound having formula (A) comprises a mixture containing: 1) a compound containing metal M; 2) at least one component selected from the group consisting of: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, organic carbonyl compounds, C1-C 10 -alkyl, C3-C 12 -Cycloalkyl, C2-C 12 -Alkenyl, C3-C 15 -cycloalkenyl, C5-C 20 - aryl, CN, CO, OH, OC(=O)CF3, OSO2CF3, hydrides, pyridine, halides, hydroxides, and thiophenes; and 3) compounds having the formula (H).

[0166] (H),

[0167] M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0168] L 1 and L 2 PR is independent of each other d R e NR d R e SR d , SH, S(=O)R g C5-C containing at least one heteroatom selected from nitrogen and sulfur 10 - heteroaryl, AsR d R e SbR d R e And N-heterocyclic carbene represented by the following structure:

[0169] or ;

[0170] R 1 R 2 R 3 and R 4 It is hydrogen, or forms an acridine unit together with the pyridyl unit of the catalyst having formula (A), or R 1 and R 2 Or R 3 and R 4Together with the pyridyl unit of the catalyst having formula (A), a quinolinyl unit is formed;

[0171] n is 0 or 1;

[0172] R d R e R f R g R 5 R 6 and R 7 Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C5-C 10 -aryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and unsubstituted or substituted C5-C atoms containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heteroaryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and

[0173] X is optional and selected from the group consisting of: one, two, three, four, five, six, or seven substituents located at any carbon atom of the acridine unit, or one, two, three, four, or five substituents located at any carbon atom of the quinolinyl unit, or one substituent located at a carbon atom of the pyridyl unit, wherein these substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C. 10 -alkyl.

[0174] 2. The method described in Example 1 is a continuous method.

[0175] 3. The method described in Example 1 is a semi-batch method or a batch method.

[0176] 4. The method as described in any one of Examples 1 to 3, wherein the liquid mixture M prepared according to (ii) E 90 to 100 wt%, preferably 95 to 100 wt%, more preferably 98 to 100 wt%, and even more preferably 99 to 100 wt%, comprise the following: at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c The alcohol, the base, and component C of the group consisting of -CH2-OH.

[0177] 5. The method as described in any one of Examples 1 to 4, wherein the reaction space S according to (iii) G The reaction mixture M contains G The gas phase contains at least one inert gas, preferably selected from the group consisting of nitrogen, argon, and mixtures thereof.

[0178] 6. The method as described in any one of Examples 1 to 5, wherein the alcohol conversion conditions according to (iii) include 1 × 10 5 Up to 3.5 × 10 6 Within the Pa range, preferably within 1 × 10 Pa. 5 Up to 3.1 × 10 6 Within the Pa range, more preferably within 1 × 10 Pa. 5 Up to 2 × 10 6 Within the Pa range, more preferably within 1 × 10 Pa. 5 Up to 1.5 × 10 6 The reaction space S within the Pa range G The pressure within.

[0179] 7. The method as described in any one of Examples 1 to 6, wherein the alcohol conversion conditions according to (iii) include the reaction mixture M in the range of 100°C to 200°C, preferably in the range of 120°C to 180°C, more preferably in the range of 130°C to 160°C. G The temperature.

[0180] 8. The method as described in any one of Examples 1 to 7, wherein the alcohol conversion conditions according to (iii) include the reaction mixture M G The total weight of the reaction mixture M is in the range of 0.1 to 10 wt%, preferably in the range of 0.5 to 8 wt%, and more preferably in the range of 1 to 5 wt%. G The amount of alkali in the solution.

[0181] 9. The method as described in any one of Examples 1 to 8, wherein the alcohol conversion conditions according to (iii) include the reaction mixture M G The total weight of the reaction mixture M is in the range of 0.001 to 2 wt%, preferably in the range of 0.001 to 1 wt%, and more preferably in the range of 0.001 to 0.5 wt%. G The amount of component C in the middle.

[0182] 10. The method as described in any one of Examples 1 to 9, wherein the reaction space S according to (iii) G The reaction mixture M contains G And a gas phase, wherein the gas phase contains H2, and wherein the alcohol conversion conditions according to (iii) include maintaining the H2 partial pressure of the gas phase at 2 × 10⁻⁶. 4 Up to 3.1 × 10 6 Within the range of Pa, preferably within 2 × 10 Pa. 4 Up to 1.1 × 10 6 Within the range of Pa, more preferably within 2 × 10 Pa. 4 Up to 6 × 10 5 Within the range of Pa.

[0183] 11. The method as described in Example 10, wherein the H2 partial pressure of the gas phase is maintained by introducing H2 into the gas phase.

[0184] 12. The method as described in Example 10 or 11, wherein the H2 partial pressure of the gas phase is maintained by relaxation of the gas phase, preferably by removing at least a portion of H2 from the gas phase.

[0185] 13. The method of any one of Examples 10 to 12, wherein the partial pressure of H2 in the gas phase is maintained by monitoring the total pressure during the reaction, preferably by monitoring and, if necessary, by adjusting the total pressure of the gas phase, more preferably by relaxing the gas phase and / or by introducing H2 into the gas phase.

[0186] 14. The method of any one of Examples 10 to 12, wherein the partial pressure of H2 in the gas phase is maintained by: taking a sample of the gas phase and analyzing it during the reaction, and, if necessary, preferably adjusting the total pressure of the gas phase, more preferably by relaxing the gas phase and / or by introducing H2 into the gas phase.

[0187] 15. The method of any one of Examples 1 to 14, wherein component C comprises a mixture, wherein the mixture comprises: 1) a compound containing metal M; 2) at least one component selected from the group consisting of: CO, PRd R e R f SR d R e R d CN, R d NC, N2, PF3, organic carbonyl compounds, C1-C 10 -alkyl, C3-C 12 -Cycloalkyl, C2-C 12 -Alkenyl, C3-C 15 -cycloalkenyl, C5-C 20 -Aryl, hydride, pyridine, halide, hydroxide and thiophene; and 3) compounds having the formula (H').

[0188] (H'),

[0189] M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0190] L 1 and L 2 PR is independent of each other d R e NR d R e SR d SH and S(=O)R g ;

[0191] L 3 Choose from the following groups: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, pyridine, and thiophene;

[0192] R 1 R 2 R 3 and R 4 It is hydrogen, or it forms an acridine unit together with the pyridyl unit of the catalyst, which includes a compound having formula (A);

[0193] n is 0 or 1, and if R 1 R 2 R 3 and R 4 If it is hydrogen, then n is 0;

[0194] R d R e R f and Rg Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic; C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O and S. 10 - heteroaryl; and

[0195] Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, and OH.

[0196] 16. The method as described in any one of Examples 1 to 14, wherein the component C comprises a compound containing metal M selected from the group consisting of: IrCl3 x H2O, [Ir(COD)Cl]2, [Ir(COE)2Cl]2, [Ir(C2H4)2Cl]2, [Ir(COD)OH]2, [Ir(COD)MeO]2, [IrCp]2, etc. Cl2], [IrCpCl2], Ir4(CO) 12 [Ir(PPh3)2(CO)Cl], [Ir(acetylacetone)3], and [Ir(acetylacetone)(COD)], where Cp is a cyclopentadienyl group. It is pentamethylcyclopentadienyl, COD is 1,5-cyclooctadienyl, COE is cyclooctenyl, and methylallyl is 2-methylallyl.

[0197] 17. The method as described in any one of Examples 1 to 14, wherein component C comprises a compound containing metal M selected from the group consisting of: [Ru(p-cymene)Cl2]2, [Ru(benzene)Cl2] y [Ru(CO)2Cl2] y—where y is in the range of 1 to 1000 in each case, [Ru(CO)3Cl2]2, [Ru(COD)(allyl)], RuCl3 x H2O, [Ru(acetylacetone)3], [Ru(DMSO)4Cl2], [Ru(cyclopentadienyl)(CO)2Cl], [Ru(cyclopentadienyl)(CO)2H], [Ru(cyclopentadienyl)(CO)2]2, [Ru(Cp)(CO)2Cl], [Ru(Cp (CO)₂H]、[Ru(Cp) [Ru(indyl)(CO)2Cl], [Ru(indyl)(CO)2H], [Ru(indyl)(CO)2]2, Ruthenium dicrenecrolein, [Ru(COD)Cl2]2, [Ru(Cp)2]2 (COD)Cl]、[Ru3(CO) 12 [Ru(PPh3)4(H)2] 、 [Ru(PPh3)3(Cl)2], [Ru(PPh3)3(CO)(CI)2], [Ru(PPh3)3(CO)(CI)(H)], [Ru(PPh3)3(CO)(H)2], and [Ru(cyclooctadienyl)(methylallyl)2], where Cp is cyclopentadienyl, Cp It is pentamethylcyclopentadienyl, COD is 1,5-cyclooctadienyl, and methylallyl is 2-methylallyl.

[0198] 18. The method as described in any one of Examples 1 to 14, wherein component C comprises a compound having formula (B).

[0199] (B),

[0200] in

[0201] M can be freely selected from the following groups: Ir, Ru, and Mn;

[0202] L 1 and L 2 PR is independent of each other d R e NR d R e SR d SH and S(=O)R g ;

[0203] L 3 Choose from the following groups: CO, PR d R e R f SR d R eR d CN, R d NC, N2, PF3, pyridine, and thiophene;

[0204] R d R e R f and R g Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group; C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O and S. 10 - heteroaryl; and

[0205] Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, and OH.

[0206] 19. The method as described in any one of Examples 1 to 14, wherein component C comprises a compound having formula (C).

[0207] (C),

[0208] in

[0209] M can be freely selected from the following groups: Ir, Ru, and Mn;

[0210] L 1 and L 2 PR is independent of each other d R e NR d R e SR d SH and S(=O)R g ;

[0211] L 3 Choose from the following groups: CO, PR d R e R f SR d R e R d CN, Rd NC, N2, PF3, pyridine, and thiophene;

[0212] R d R e R f and R g Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group; C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O and S. 10 - heteroaryl; and

[0213] Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, and OH.

[0214] 20. The method as described in any one of Examples 1 to 14, 18 and 19, wherein M is selected from the group consisting of Ir and Ru, wherein M is preferably Ru.

[0215] 21. The method as described in any one of Examples 1 to 14, 18 and 19, wherein L 3 It is CO.

[0216] 22. The method as described in any one of Examples 1 to 14 and 18 to 21, wherein L 1 and L 2 Each is (PR) d R e ), and where R d and R e It is C1-C 10 -alkyl, preferably wherein R d and R e Each is either isopropyl or tert-butyl.

[0217] 23. The method as described in any one of Examples 1 to 14 and 17 to 21, wherein L 1 and L 2 Each is (PR) d R e ), and where R dand R e It is C3-C 10 -cycloalkyl, preferably wherein R d and R e Each is a cyclohexyl group.

[0218] 24. The method as described in any one of Examples 1 to 14 and 18 to 21, wherein L 1 and L 2 Each is (PR) d R e ), and where R d and R e It is C5-C 10 -Aryl.

[0219] 25. The method as described in any one of Examples 1 to 14 and 18 to 24, wherein Y is selected from the group consisting of F, Cl, Br and I, preferably from the group consisting of Cl or Br, and more preferably wherein Y is Cl.

[0220] 26. The method as described in any one of Examples 1 to 14 and 18 to 24, wherein Y is CO.

[0221] 27. The method as described in any one of Examples 1 to 14, wherein component C comprises a compound having formula (D).

[0222] (D),

[0223] Cy stands for cyclohexyl.

[0224] 28. The method as described in any one of Examples 1 to 14 and 27, wherein component C comprises a reduced form of a catalyst having formula (D').

[0225] (D'),

[0226] Cy stands for cyclohexyl.

[0227] 29. The method as described in any one of Examples 1 to 14, wherein component C comprises a compound having formula (E).

[0228] (E),

[0229] Where iPr is isopropyl.

[0230] 30. The method as described in any one of Examples 1 to 14 and 29, wherein component C comprises a reduced form of a catalyst having formula (E').

[0231] (E'),

[0232] Where iPr is isopropyl.

[0233] 31. The method as described in any one of Examples 1 to 14, wherein component C comprises a compound having formula (F).

[0234] (F),

[0235] Where tBu is tert-butyl.

[0236] 32. The method as described in any one of Examples 1 to 14 and 31, wherein component C comprises a reduced form of a catalyst having formula (F').

[0237] (F'),

[0238] Where tBu is tert-butyl.

[0239] 33. The method as described in any one of Examples 1 to 32, wherein the reduced form of the precursor comprises a compound having the formula (PI) or (P-II):

[0240] (PI)

[0241] Where R 1 R 2 R 3 and R 4 It is hydrogen, or forms a tetrahydroquinoline unit, decahydroquinoline unit, tetrahydroacrylidine unit, or tetradecahydroacrylidine unit together with an N-containing ring; and

[0242] Where L 1 and L 2 They are independent of each other as defined above;

[0243] (P-II)

[0244] Where R 1 R 2 R 3 and R 4 It is hydrogen; and

[0245] Where L 1 and L 2 They are independent of each other as defined above.

[0246] 34. The method as described in any one of Examples 1 to 32, wherein the reduced form of the precursor comprises a compound having the formula (PI):

[0247] (PI)

[0248] Where R 1 R 2 R 3 and R 4 It is hydrogen, or it forms a tetrahydroacrylidine unit or a tetradecahydroacrylidine unit together with an N-containing ring.

[0249] 35. The method as described in any one of Examples 1 to 32, wherein the reduced form of the precursor comprises a compound having the formula (P-II):

[0250] (P-II)

[0251] Where R 1 R 2 R 3 and R 4 It is hydrogen; and

[0252] Where L 1 and L 2 They are independent of each other as defined above.

[0253] 36. The method as described in any one of Examples 1 to 35, wherein the integer x is 1 or 2, preferably wherein the integer x is 1.

[0254] 37. The method as described in any one of Examples 1 to 36, wherein R a R b and R c The following are selected independently: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; preferably, they are selected from the group consisting of H, methyl, ethyl, propyl, and isopropyl; more preferably, they are selected from the group consisting of H, ethyl, and propyl; and even more preferably, R. a R b and R c At least one of them is H, more preferably R. a and R c It is H.

[0255] 38. The method as described in any one of Examples 1 to 37, wherein the liquid mixture M prepared according to (ii) E It further includes a compound having formula (G) or its reduced form.

[0256] (G),

[0257] Where R 1 R 2 R 3 and R 4 L 1 L 2And n is as defined above.

[0258] 39. The method as described in Example 38, wherein the compound having formula (G) or its reduced form R 1 R 2 R 3 and R 4 L 1 L 2 R and n with at least one of the catalyst, its precursor, the reduced form of the catalyst, and the reduced form of the precursor of component C. 1 R 2 R 3 and R 4 L 1 L 2 Same as n.

[0259] 40. The method as described in Example 38 or 39, wherein the liquid mixture M prepared according to (ii) and subjected to the alcohol conversion conditions according to (iii) E In this process, the molar ratio of the compound having formula (G) or its reduced form relative to the component C is in the range of 1:1 to 10:1, preferably in the range of 1.02:1 to 8:1, and more preferably in the range of 1.05:1 to 5:1.

[0260] 41. The method of any one of Examples 38 to 40, wherein the compound having formula (G) or its reduced form is selected from the group consisting of: dicyclohexyl-[[5-(dicyclohexylphosphonylmethyl)acridin-4-yl]methyl]phosphine, diisopropyl-[[5-(diisopropylphosphonylmethyl)acridin-4-yl]methyl]phosphine, dicyclohexyl-[[5-(dicyclohexylphosphonylmethyl)pyridin-4-yl]methyl]phosphine and diisopropyl-[[5-(diisopropylphosphonylmethyl)pyridin-4-yl]methyl]phosphine, preferably wherein the compound having formula (G) or its reduced form is cyclohexyl-[[5-(dicyclohexylphosphonylmethyl)acridin-4-yl]methyl]phosphine or diisopropyl-[[5-(diisopropylphosphonylmethyl)acridin-4-yl]methyl]phosphine.

[0261] 42. The method of any one of Examples 1 to 41, wherein the base is selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides and mixtures thereof.

[0262] 43. The method as described in Example 42, wherein the alkali metal hydroxide is selected from the group consisting of NaOH, KOH and mixtures thereof, preferably wherein the alkali metal hydroxide is KOH.

[0263] 44. The method as described in Example 42, wherein the alkali metal alkoxide is selected from the group consisting of sodium alkoxide, potassium alkoxide, and mixtures of two or more thereof, preferably selected from the group consisting of sodium ethoxide, potassium ethoxide, and mixtures thereof.

[0264] 45. The method as described in any one of Examples 1 to 44, wherein the at least one alcohol R a -CH2-CH2-OH and at least one of the following selected from R b -CH2-CH2-OH and R c At least one of the alcohols in the group consisting of -CH2-OH is a bio-based alcohol, preferably available or obtained from sugar-containing crops, more preferably from one or more of sugarcane and corn.

[0265] 46. ​​The method as described in any one of Examples 1 to 3 and 5 to 45, wherein the liquid mixture M according to (ii) E It further includes a solvent component, which contains one or more solvents.

[0266] 47. The method as described in Example 46, wherein the solvent component has a boiling point of 140°C or higher at 1 atm (101325 Pa), preferably 160°C or higher, more preferably 180°C or higher, and even more preferably 190°C or higher.

[0267] 48. The method as described in Examples 46 or 47, wherein, based on 100 wt% water, the solvent component has a water solubility at 25°C in the range of 0 to 0.5 wt%, preferably in the range of 0 to 0.1 wt%, more preferably in the range of 0 to 0.05 wt%, and even more preferably in the range of 0 to 0.01 wt%.

[0268] 49. The method as described in any one of Examples 46 to 48, wherein, based on 1 kg of catalyst, the distribution coefficient of the catalyst in the system of solvent component and water is 0 to 0.01, preferably 0 to 0.005, more preferably 0 to 0.005.

[0269] 50. The method of any one of Examples 46 to 49, wherein the solvent component comprises at least two solvents having a boiling point of 180°C or higher at 1 atm (101325 Pa).

[0270] 51. The method of any one of Examples 46 to 50, wherein the solvent does not form an azeotropic mixture with water.

[0271] 52. The method of any one of Examples 46 to 51, wherein the solvent component comprises at least one solvent selected from the group consisting of: biphenyl, diphenyl ether, 1-tert-butyl-3,5-dimethylbenzene, xylene, mesitylene, toluene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decahydronaphthalene, n-butyl butyrate, n-hexyl hexanoate, n-octyl octanoate, texanole, di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, and two or more thereof. The mixture is preferably selected from the group consisting of biphenyl, diphenyl ether, 1-tert-butyl-3,5-dimethylbenzene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decahydronaphthalene, n-butyl butyrate, n-hexyl hexanoate, n-octyl octanoate, texanole, di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, and mixtures of two or more thereof, more preferably selected from the group consisting of biphenyl, diphenyl ether and mixtures thereof, wherein more preferably, the solvent is a mixture of biphenyl and diphenyl ether.

[0272] 53. The method as described in any one of Examples 46 to 51, wherein the solvent does not include any one of benzene, toluene, xylene, or mesitylene.

[0273] 54. The method of any one of Examples 46 to 53, wherein the solvent component comprises a mixture of biphenyl and diphenyl ether, wherein the molar ratio of biphenyl to diphenyl ether is in the range of 1:2 to 1:6, preferably in the range of 1:2.5 to 1:4.

[0274] 55. The method as described in any one of Examples 46 to 54, wherein the liquid mixture M prepared according to (ii) E 90 to 100 wt%, preferably 95 to 100 wt%, more preferably 98 to 100 wt%, and even more preferably 99 to 100 wt%, comprise the following: at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c The alcohol, the base, the solvent component, and the catalyst of the group consisting of -CH2-OH.

[0275] 56. The method as described in any one of Examples 46 to 55, wherein the alcohol conversion conditions according to (iii) include the reaction mixture M G The total weight of the reaction mixture M is in the range of 5 to 50 wt%, preferably in the range of 5 to 30 wt%, and more preferably in the range of 5 to 10 wt%. G The amount of the solvent in the solution.

[0276] 57. The method as described in any one of Examples 46 to 56, wherein the mixture M obtained according to (iv) CS It contains component C and further contains the solvent component.

[0277] 58. The method as described in any one of Examples 1 to 57, wherein the liquid reaction mixture M obtained according to (iii) G Further comprising at least one unreacted alcohol selected from the group consisting of: R a -CH2-CH2-OH, R b -CH2-CH2-OH and R c -CH2-OH, the method further includes obtaining -CH2-OH from the liquid reaction mixture M G At least a portion of the unreacted alcohol is separated from the alcohol.

[0278] 59. The method as described in Example 58, wherein, from M G At least a portion of the unreacted alcohol is separated by one or more of distillation, extraction, flash evaporation and membrane separation.

[0279] 60. The method as described in Example 58 or 59, wherein the material from M... G At least a portion of the at least one unreacted alcohol separated in (ii) or (iii) is recycled.

[0280] 61. The method as described in any one of Examples 1 to 60, further comprising:

[0281] (v) Make the mixture M obtained according to (iv) CS At least a portion of it is recycled back into (ii) or (iii).

[0282] 62. The method as described in Example 61, wherein the mixture M is recycled in (v). CS The at least portion of it contains at least a portion of component C.

[0283] 63. The method as described in any one of Examples 61 or 62, wherein the mixture M is recycled in (v). CS The at least portion comprises at least a portion of component C and at least a portion of solvent component.

[0284] 64. The method as described in any one of Examples 1 to 60, further comprising:

[0285] (v) By separating the solvent component and using the separated solvent component as the liquid mixture M E Or the reaction mixture M GA portion is recycled to (ii) or (iii) to obtain the mixture M according to (iv). CS At least a portion of it is recycled back into (ii) or (iii).

[0286] 65. The method as described in any one of Examples 1 to 64, wherein the reaction space S R Contained in a reactor vessel, wherein the reactor vessel is preferably a fully mixed reactor vessel.

[0287] 66. The method of Example 65, wherein the reactor vessel is selected from the group consisting of: stirred tank reactor, fixed bed reactor, moving bed reactor and fluidized bed reactor.

[0288] The invention is further illustrated by the following examples, which are provided to illustrate certain aspects of the invention and are not to be construed as limiting the invention. Example

[0289] The determination of the distribution coefficient of the solvent component in water includes the following steps:

[0290] 1. Combine two components (e.g., feed and solvent components) at a predetermined solvent ratio;

[0291] 2. Under a defined extraction temperature, the combined components are subjected to turbulent mixing over a relatively long period of time (> 10 min);

[0292] 3. Phase separation is permitted;

[0293] 4. Collect samples of each phase at the extraction temperature;

[0294] 5. Centrifuge the sample at the extraction temperature and remove the clear sample;

[0295] 6. Analyze the sample; and

[0296] 7. Compare the results of the extract and raffinate – calculate the partition balance / partition coefficient at the selected temperature.

[0297] Example 1

[0298] 42.52 g ethanol, 7.74 g methanol, 4.52 g KOH solution (50 wt% in water), 243.8 mg Cy-Acr-PNP, and 82.6 mg Ru(acac)3 were transferred to a screw-cap flask and stirred overnight at room temperature under an argon atmosphere. This solution was then transferred via syringe to a 300 mL HC autoclave, and the flask was rinsed with 19.96 g ethanol. Then, 7.99 g of solvent (biphenyl and diphenyl ether in a molar ratio of 1:3) was added, and the autoclave was heated to T.i = 150°C with stirring at 750 rpm. Periodically remove samples, filter them using a 2 μm syringe filter, combine them with the internal standard 1,4-dioxane (0.8 g sample, 0.2 g standard), and finally analyze them by GC.

[0299] The resulting catalyst has the following structure:

[0300]

[0301] GC analysis revealed the formation of 1-propanol, isobutanol, 2-methyl-but-1-ol, and 1-pentanol. The area percentages of each alcohol formed were 1.4 at.-%, 0.1 at.-%, 0.2 at.-%, and < 0.1 at.-%, respectively.

[0302] References cited:

[0303] -M. Guerbet, CR Hebd. Séances Acad. Sci. 1899, 128, p. 511-513

[0304] -WO 2013 / 156399 A1

[0305] -A.Kaithal et al., "Ruthenium(II)-Catalyzed β-Methylation of Alcoholsusing Methanol as C1 Source", CHEMCATCHEM, vol. 11, no. 21, 2019-05-16, pages5287 to 5291

[0306] -US 2015 / 246863 A1

[0307] -N.Biswas et al., "Acridine-Based SNS-Ruthenium Pincer Complex-Catalyzed Borrowing Hydrogen-Mediated CC Alkylation Reaction: Application to the Guerbet Reaction", SYNLETT, vol. 34, no. 06, 2022-07-08, pages 622 to 628

[0308] -Y.Xie et al., “Highly efficient Process for Production of Biofuelfrom Ethanol Catalyzed by Ruthenium Pincer Complexes”, Journal of theAmerican Society, vol. 138, no. 29, 2016-07-18, pages 9077 to 9080

[0309] -WO 2012 / 119928 A1

[0310] -US 2010 / 298613 A1。

Claims

1. A method for alcohol conversion, comprising: (i) Provide component C, which is at least one of a catalyst, a precursor thereof, a reduced form of the catalyst and a reduced form of the precursor; (ii) Preparation of liquid mixture M E The liquid mixture contains at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c Alcohols and bases of the group consisting of -CH2-OH, and the components C and R provided according to (i). a R b and R c Each is independently selected from the group consisting of: H and C1-C4-alkyl; wherein R a -CH2-CH2-OH, R b -CH2-CH2-OH and R c -CH2-OH are different from each other; (iii) Make the liquid mixture M prepared according to (ii) E In the reaction space S G Under conditions of alcohol conversion, and in S G Obtain reaction mixture M G The reaction mixture contains at least one alcohol selected from the group consisting of: R b -CH2-CH2-(CHR a -CH2) x -OH,R a -CH2-CH2-(CHR b -CH2) x -OH and R c -CH2-(CHR a -CH2) x -OH, x is an integer in the range of 1 to 4, wherein these alcohol conversion conditions include the reaction mixture M in the range of 100°C to 250°C. G Temperature and at 1 × 10 5 Up to 4 × 10 6 The reaction space S within the Pa range G The pressure in the middle; (iv) From the reaction mixture M obtained according to (iii) G Separate at least one alcohol selected from the group consisting of: R b -CH2-CH2-(CHR a -CH2) x -OH,R a -CH2-CH2-(CHR b -CH2) x -OH and R c -CH2-(CHR a -CH2) x -OH, to obtain mixture M CS ; in (a) The base is selected from the group consisting of: ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide, ammonium carbonate, ammonium bicarbonate, alkali metal carbonate, alkali metal bicarbonate, alkaline earth metal carbonate, alkaline earth metal bicarbonate, alkali metal alkoxide, alkaline earth metal alkoxide, alkali metal amide, alkaline earth metal amide, alkali metal 2,2,6,6-tetramethylpiperidine, alkaline earth metal 2,2,6,6-tetramethylpiperidine, secondary amino acids, and mixtures of two or more thereof. (b) The catalyst comprises a compound having formula (A). (A)， in M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru; L 1 and L 2 PR is independent of each other d R e NR d R e SR d , SH, S(=O)R g C5-C containing at least one heteroatom selected from nitrogen and sulfur 10 - heteroaryl, AsR d R e SbR d R e And N-heterocyclic carbene represented by the following structure: or ; L 3 Choose from the following groups: CO, PR d R e R f AsR d R e R f SbR d R e R f SR d R e R g CN, R g NC, N2, PF3, pyridine, and thiophene; R 1 R 2 R 3 and R 4 It is hydrogen, or forms an acridine unit together with the pyridyl unit of the catalyst having formula (A), or R 1 and R 2 Or R 3 and R 4 Together with the pyridyl unit of the compound having formula (A), a quinolinyl unit is formed; n is 0 or 1; Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, OH, OR, NR g 2. NH3, NR g 3 and R g 2NSO2R g ; R d R e R f R g R 5 R 6 and R 7 Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C5-C 10 -aryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and unsubstituted or substituted C5-C atoms containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heteroaryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and X is optional and selected from the group consisting of: one, two, three, four, five, six, or seven substituents located at any carbon atom on the acridine unit, or one, two, three, four, or five substituents located at any carbon atom on the quinolinyl unit, or one substituent located at a carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C. 10 -alkyl; and (c) The precursor of the catalyst comprising a compound having formula (A) comprises a mixture containing: 1) a compound containing metal M; 2) at least one component selected from the group consisting of: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, organic carbonyl compounds, C1-C 10 -alkyl, C3-C 12 -Cycloalkyl, C2-C 12 -Alkenyl, C3-C 15 -cycloalkenyl, C5-C 20 - aryl, CN, CO, OH, OC(=O)CF3, OSO2CF3, hydrides, pyridine, halides, hydroxides, and thiophenes; and 3) compounds having the formula (H). (H)， M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru; L 1 and L 2 PR is independent of each other d R e NR d R e SR d , SH, S(=O)R g C5-C containing at least one heteroatom selected from nitrogen and sulfur 10 - heteroaryl, AsR d R e SbR d R e And N-heterocyclic carbene represented by the following structure: or ; R 1 R 2 R 3 and R 4 It is hydrogen, or forms an acridine unit together with the pyridyl unit of the catalyst having formula (A), or R 1 and R 2 Or R 3 and R 4 Together with the pyridyl unit of the catalyst having formula (A), a quinolinyl unit is formed; n is 0 or 1; R d R e R f R g R 5 R 6 and R 7 Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic group, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C5-C 10 -aryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and unsubstituted or substituted C5-C atoms containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heteroaryl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; and X is optional and selected from the group consisting of: one, two, three, four, five, six, or seven substituents located at any carbon atom of the acridine unit, or one, two, three, four, or five substituents located at any carbon atom of the quinolinyl unit, or one substituent located at a carbon atom of the pyridyl unit, wherein these substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C. 10 -alkyl.

2. The method as described in claim 1, wherein, The liquid mixture M prepared according to (ii) E 90 to 100 wt%, preferably 95 to 100 wt%, more preferably 98 to 100 wt%, and even more preferably 99 to 100 wt%, comprise the following: at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c The alcohol, the base, and component C of the group consisting of -CH2-OH.

3. The method as described in claim 1 or 2, wherein, According to (iii), the reaction space S G The reaction mixture M contains G And a gas phase, wherein the gas phase contains H2, and wherein the alcohol conversion conditions according to (iii) include maintaining the H2 partial pressure of the gas phase at 2 × 10⁻⁶. 4 Up to 3.1 × 10 6 Within the range of Pa, preferably within 2 × 10 Pa. 4 Up to 1.1 × 10 6 Within the range of Pa, more preferably within 2 × 10 Pa. 4 Up to 6 × 10 5 Within the range of Pa.

4. The method of claim 3, wherein, The partial pressure of H2 in this gas phase is maintained by introducing H2 into the gas phase; or The partial pressure of H2 in the gas phase is maintained by relaxation of the gas phase, preferably by removing at least a portion of H2 from the gas phase.

5. The method according to any one of claims 1 to 4, wherein, Component C comprises a mixture, wherein the mixture contains: 1) a compound containing metal M; 2) at least one component selected from the group consisting of: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, organic carbonyl compounds, C1-C 10 -alkyl, C3-C 12 -Cycloalkyl, C2-C 12 -Alkenyl, C3-C 15 -cycloalkenyl, C5-C 20 -Aryl, hydride, pyridine, halide, hydroxide and thiophene; and 3) compounds having the formula (H'). (H’)， M is selected from the following groups: Ir, Mn, Os, Pd, Pt, Rh, and Ru; L 1 and L 2 PR is independent of each other d R e NR d R e SR d SH and S(=O)R g ; L 3 Choose from the following groups: CO, PR d R e R f SR d R e R d CN, R d NC, N2, PF3, pyridine, and thiophene; R 1 R 2 R 3 and R 4 It is hydrogen, or it forms an acridine unit together with the pyridyl unit of the catalyst, which includes a compound having formula (A); n is 0 or 1, and if R 1 R 2 R 3 and R 4 If it is hydrogen, then n is 0; R d R e R f and R g Choose independently from the following groups: H; unsubstituted or substituted C1-C 10 -alkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; unsubstituted or substituted C3-C 10 -Cycloalkyl, wherein the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C. 10 -alkyl; C3-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heterocyclic; C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O and S. 10 - heteroaryl; and Y is selected from the following groups: H, F, Cl, Br, I, OC (=O)CF3, OSO2CF3, CN, CO, and OH.

6. The method according to any one of claims 1 to 5, wherein, Component C includes compounds having formula (D). (D)， Where Cy is cyclohexyl; or Component C includes compounds having formula (E). (E)， Where iPr is isopropyl; or Component C includes compounds having formula (F). (F)， Where tBu is tert-butyl.

7. The method according to any one of claims 1 to 6, wherein, R a It is H or methyl.

8. The method according to any one of claims 1 to 7, wherein, R b and R c They are independently selected from the following groups: H and methyl.

9. The method according to any one of claims 1 to 8, wherein, The liquid mixture M prepared according to (ii) E It further includes a compound having formula (G) or its reduced form. (G)， Where R 1 R 2 R 3 and R 4 L 1 L 2 And n is as defined above.

10. The method of claim 9, wherein, The liquid mixture M prepared according to (ii) and subjected to the alcohol conversion conditions according to (iii) E In this context, the molar ratio of the compound having formula (G) or its reduced form relative to component C is in the range of 1:1 to 10:

1.

11. The method as claimed in any one of claims 1 and 3 to 10, wherein, According to (ii), the liquid mixture M E It further includes a solvent component, which contains one or more solvents.

12. The method of claim 11, wherein, The solvent component has one or more solvents having a boiling point of 140°C or higher at 1 atm (101325 Pa).

13. The method of claim 11 or 12, wherein, The solvent component contains at least two solvents with a boiling point of 180°C or higher at 1 atm (101325 Pa).

14. The method according to any one of claims 11 to 13, wherein, The liquid mixture M prepared according to (ii) E 90 to 100 wt%, preferably 95 to 100 wt%, consists of the following: at least one alcohol R a -CH2-CH2-OH, at least one of which is selected from R b -CH2-CH2-OH and R c The alcohol, the base, the solvent component, and the catalyst of the group consisting of -CH2-OH.

15. The method according to any one of claims 1 to 14, wherein, The liquid reaction mixture M obtained according to (iii) G Further comprising at least one unreacted alcohol selected from the group consisting of: R a -CH2-CH2-OH, R b -CH2-CH2-OH and R c -CH2-OH, the method further includes obtaining -CH2-OH from the liquid reaction mixture M G At least a portion of the unreacted alcohol is separated from M, wherein preferably it is from M. G At least a portion of the at least one unreacted alcohol separated in (ii) or (iii) is recycled.

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