A saturated alcohol and a method for preparing a saturated alcohol from unsaturated aldehydes and ketones

Abstract

The present invention relates to the field of chemical technology, and discloses a saturated alcohol and a method for preparing a saturated alcohol from unsaturated aldehydes and ketones. The method comprises: (1) in the presence of a first catalyst, unsaturated aldehydes and ketones are subjected to a first contact reaction with hydrogen to obtain a first product; the first product contains at least 99wt% of saturated aldehydes and ketones; (2) in the presence of a second catalyst, hydrogen is subjected to a second contact reaction with the first product to obtain a saturated alcohol; based on the total mass of the first catalyst, the first catalyst contains 0.1-0.2wt% of Pd element, 0.2-2.8wt% of Ni element, 0.1-1% of auxiliary element and 96-99.6wt% of carrier; based on the total mass of the second catalyst, the second catalyst contains 35-50wt% of Cu element, 10-40wt% of Co element and 20-35wt% of Ti element in terms of oxide.

Description

Technical Field

[0001] The invention relates to the technical field of chemical industry, and in particular to a saturated alcohol and a method for preparing the saturated alcohol from unsaturated aldehydes and ketones. Background Art

[0002] The hydrogenation of C=C double bonds and C=O double bonds in unsaturated aldehydes and ketones to prepare corresponding saturated aldehydes and ketones or saturated alcohols is an important fine chemical reaction. Alcohol compounds and aldehyde and ketone compounds are important chemicals and have a wide range of uses in industry and daily life.

[0003] For example, hydrogenated cinnamaldehyde, the hydrogenation product of the C=C double bond in cinnamaldehyde, has a strong balsamic aroma and hyacinth fragrance, and can be used to prepare fragrances such as hyacinth, clove and rose, while cinnamyl alcohol, the hydrogenation product of the C=C double bond and C=O double bond in cinnamaldehyde, also has similar hyacinth and cream fragrances, and is mainly used to prepare apricot, peach, raspberry, plum and other flavor essences, cosmetic essences and soap essences; another example is methyl isobutyl ketone, the hydrogenation product of the C=C double bond in mesityl oxide, which is a medium-boiling point solvent with a very wide range of uses, and is mainly used as nitrocellulose and polyvinyl chloride. It is also the main raw material for rubber antioxidants and some organic syntheses, while methyl isobutyl alcohol, the hydrogenation product of the C=C double bond and C=O double bond in mesityl oxide, is mainly used in the fields of mineral flotation, coatings, pesticides, medicines, synthetic resins, cellulose and adhesives.

[0004] The traditional hydrogenation of unsaturated aldehydes and ketones is often accompanied by side reactions such as condensation of ketones, condensation of ketones and alcohols, polymerization of unsaturated carbon-carbon bonds, dehydration of alcohols, and etherification of alcohols. Some by-products, especially water, are difficult to separate from the products, resulting in a complex separation process downstream. In addition, the process of hydrogenating unsaturated aldehydes and ketones to produce saturated alcohols is uncontrollable because the selectivity of the catalyst for saturated aldehydes and ketones is determined, resulting in uncontrollable intermediate products. Generally, only the final product saturated alcohol can be obtained directly, and it is difficult to obtain high-purity intermediate products. The intermediate products can only be treated as hazardous waste or sold at a low price.

[0005] Therefore, many companies currently organize the production of saturated aldehydes and ketones and saturated alcohols according to their own independent production processes. First, they fail to take into account the characteristics and correlation of the two product production processes to achieve overall process optimization. Second, because the two products have independent production processes, their production process flows are separated from each other, and each company invests in and builds its own equipment, resulting in a long process flow, increased investment, and high energy consumption.

[0006] The key to solving the above problems lies in the selection of highly active and highly selective catalysts; there are many types of reaction catalysts for the hydrogenation of unsaturated aldehydes and ketones to prepare the corresponding saturated aldehydes and ketones or saturated alcohols, and their active components include copper, nickel, cobalt, molybdenum, palladium, platinum, ruthenium, etc.

[0007] CN105727992A discloses a palladium-nickel supported hydrogenation catalyst, which contains palladium, nickel, Al 2 O 3 The catalyst is a carrier characterized in that, based on 100% of the mass of the catalyst, the Pd content is 0.02-0.6%; and the Ni content is 0.04-3%.

[0008] CN116212893A discloses a single-atom nickel-modified alumina-supported palladium catalyst, wherein the nickel loading is 0.5-2wt% and the palladium loading is 0.5-2wt%.

[0009] CN103880787A discloses a method for preparing γ-butyrolactone and acetone by coupling reaction, characterized in that the components of the catalyst, calculated by mass percentage, are: CuO: 5%-20%, ZnO: 20%-40%; MgO: 40%-75%.

[0010] CN113019378A discloses a catalyst for hydrogenation of olefinic aldehydes, characterized in that the catalyst comprises, by mass percentage, 5-50% NiO, 5-25% CuO, 0.1-10% MgO, and the remainder γAl 2 O 3 ; Among them, the carrier is MgO-γAl 2 O 3 , the active components are Ni and Cu.

[0011] Currently, the selectivity of the disclosed hydrogenation catalysts is generally lower than 98.0%, resulting in low product yield and increased separation costs. Summary of the invention

[0012] The purpose of the present invention is to solve the problems of low conversion rate and selectivity and uncontrollable intermediate products in the method for preparing saturated alcohols from unsaturated aldehydes and ketones in the prior art.

[0013] In order to achieve the above object, a first aspect of the present invention provides a method for preparing a saturated alcohol from an unsaturated aldehyde or ketone, the method comprising:

[0014] (1) in the presence of a first catalyst, subjecting an unsaturated aldehyde or ketone to a first contact reaction with hydrogen to obtain a first product; the first product contains at least 99 wt % of saturated aldehyde or ketone; based on the hydrogen consumption of the unsaturated bonds in the unsaturated aldehyde or ketone, the amount of hydrogen used is at least 10% in excess;

[0015] (2) in the presence of a second catalyst, subjecting hydrogen to a second contact reaction with the first product to obtain a saturated alcohol; the amount of hydrogen used is at least 10% in excess of the amount of hydrogen consumed by the unsaturated bonds in the first product;

[0016] Based on the total mass of the first catalyst, the first catalyst contains 0.1-0.2wt% of Pd element, 0.2-2.8wt% of Ni element, 0.1-1% of auxiliary element and 96-99.6wt% of carrier; the auxiliary element is selected from at least one of Sn, Mg and Zn; the carrier is selected from at least one of silicon dioxide, aluminum oxide and activated carbon;

[0017] Based on the total mass of the second catalyst, the second catalyst contains 35-50 wt% of Cu element, 10-40 wt% of Co element and 20-35 wt% of Ti element in terms of oxides.

[0018] The second aspect of the present invention provides a saturated alcohol prepared by the method described in the first aspect.

[0019] The method for preparing saturated alcohols from unsaturated aldehydes and ketones provided by the present invention has at least the following advantages:

[0020] (1) The method of the present invention hydrogenates unsaturated aldehydes and ketones through two consecutive hydrogenation stages to prepare saturated alcohols, which effectively solves the problem of increased by-products and poor catalyst activity caused by excessive temperature rise of the catalyst bed;

[0021] (2) The raw material components in the first catalyst provided by the present invention can form a mosaic structure, thereby improving the catalytic activity, the conversion rate of the raw materials and the selectivity of the target product.

[0022] In addition, the specific type of promoter element in the first catalyst provided by the present invention can improve the surface properties of the catalyst, and prevent carbon-carbon double bonds and carbon-oxygen double bonds from forming colloids or other byproducts on the catalyst surface to block the pores or cover the catalyst hydrogenation active sites;

[0023] The synergistic effect between the specific types and specific ratios of active ingredients of the second catalyst provided by the present invention improves the activity of the catalyst; at the same time, it also weakens the side reactions of dehydration and bond breaking of hydroxyl groups on the catalyst surface, thereby greatly improving the selectivity of the catalyst.

[0024] In particular, when the method provided by the present invention is used to prepare saturated alcohol, the raw material conversion rate is greater than 99.7%, and the product selectivity is greater than 99.5%.

[0025] (3) The intermediate product of the method provided by the present invention is controllable and can be used to directly produce saturated alcohols, and can also be used to produce intermediate products such as saturated aldehydes and ketones, which can flexibly respond to market changes.

[0026] (4) The method provided by the present invention is suitable for industrial scale-up production of saturated alcohols. The method is suitable for continuous large-scale production of saturated alcohols, has stable product quality, is easy to operate, has a safe and controllable industrial process, has mild process conditions, has low energy and material consumption, and is green and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Picture 1 It is a process flow diagram of a method for preparing saturated alcohol under a preferred specific embodiment of the present invention.

[0028] Description of Reference Numerals

[0029] 1, 2, 5, 6, 8, 10 and 11 are logistics pipelines

[0030] 3. Circulator 4. First hydrogenation reactor 7. Second hydrogenation reactor

[0031] 9. Gas-liquid separation tank 12. Separation tower 13. Heat exchanger DETAILED DESCRIPTION

[0032] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0033] As mentioned above, the first aspect of the present invention provides a method for preparing a saturated alcohol from an unsaturated aldehyde or ketone, the method comprising:

[0034] (1) in the presence of a first catalyst, subjecting an unsaturated aldehyde or ketone to a first contact reaction with hydrogen to obtain a first product; the first product contains at least 99 wt % of saturated aldehyde or ketone; based on the hydrogen consumption of the unsaturated bonds in the unsaturated aldehyde or ketone, the amount of hydrogen used is at least 10% in excess;

[0035] (2) in the presence of a second catalyst, subjecting hydrogen to a second contact reaction with the first product to obtain a saturated alcohol; the amount of hydrogen used is at least 10% in excess of the amount of hydrogen consumed by the unsaturated bonds in the first product;

[0036] Based on the total mass of the first catalyst, the first catalyst contains 0.1-0.2wt% of Pd element, 0.2-2.8wt% of Ni element, 0.1-1% of auxiliary element and 96-99.6wt% of carrier; the auxiliary element is selected from at least one of Sn, Mg and Zn; the carrier is selected from at least one of silicon dioxide, aluminum oxide and activated carbon;

[0037] Based on the total mass of the second catalyst, the second catalyst contains 35-50 wt% of Cu element, 10-40 wt% of Co element and 20-35 wt% of Ti element in terms of oxides.

[0038] In the present invention, in the first contact reaction and the second contact reaction, the hydrogen consumption of the unsaturated bond refers to the amount of hydrogen required for hydrogenating the unsaturated bond to a saturated bond; illustratively, when the unsaturated aldehyde or ketone is CH2=CH-CHO, the amount of hydrogen used is at least 10% in excess of the hydrogen consumption of the unsaturated bond, which means that when the hydrogen consumption of the unsaturated bond is 2 mol, the amount of hydrogen used is at least 2.2 mol. The present invention will not be described in detail here, and those skilled in the art should not be construed as limiting the present invention.

[0039] Preferably, in the first catalyst, the auxiliary element is Sn. The inventors have found that under this preferred embodiment, the method provided by the present invention is used to prepare saturated alcohols, and the raw material conversion rate, product selectivity and product yield are higher.

[0040] Preferably, in the first catalyst, the carrier is alumina. The inventors have found that under this preferred embodiment, the method provided by the present invention is used to prepare saturated alcohols, and the raw material conversion rate, product selectivity and product yield are higher.

[0041] Preferably, the unsaturated aldehydes and ketones are selected from at least one of aliphatic aldehydes and / or ketones, aromatic aldehydes and / or ketones, and alicyclic aldehydes and / or ketones containing at least one olefin.

[0042] More preferably, the unsaturated aldehyde or ketone is selected from at least one of mesityl oxide, cinnamaldehyde, phorone and 2,6-dimethyl-2-heptene-4-one.

[0043] More preferably, the concentration of the unsaturated aldehydes and ketones is 10-100 wt %.

[0044] Preferably, in step (1), the conditions of the first contact reaction are: temperature of 60-150°C, pressure of 1-10 MPa, and weight space velocity of 0.2-3.0 h -1 .

[0045] Preferably, in step (2), the conditions of the second contact reaction are: temperature of 70-200°C, pressure of 1-10 MPa, and weight space velocity of 0.5-2.0 h -1 .

[0046] In the present invention, the pressure is hydrogen pressure.

[0047] Preferably, the method further comprises preparing the first catalyst by a method comprising the following steps:

[0048] I-1. In the presence of a solvent, a Pd source, a Ni source and an auxiliary agent source are mixed to obtain a mixed solution;

[0049] I-2, impregnating the carrier material source with the mixed solution to obtain an impregnated material; the pH value of the mixed solution in the initial system for the impregnation treatment is 2-3;

[0050] I-3, sequentially subjecting the impregnated material to drying treatment I and roasting treatment I;

[0051] The amounts of the Pd source, the Ni source, the auxiliary agent source and the carrier material source are such that, based on the total mass of the first catalyst, the first catalyst contains 0.1-0.2wt% of Pd element, 0.2-2.8wt% of Ni element, 0.1-1% of auxiliary agent element and 96-99.6wt% of carrier. The inventors have found that under this preferred embodiment, the method provided by the present invention is used to prepare saturated alcohols, and the raw material conversion rate, product selectivity and product yield are higher.

[0052] Preferably, in step I-1, the solvent is selected from at least one of water and ethanol.

[0053] It should be noted that when the pH value of the mixed solution in the initial system for immersion treatment is not within the range of 2-3, the pH value can be adjusted using conventional reagents in the art. For example, the reagents can be hydrochloric acid and / or citric acid.

[0054] Preferably, the conditions of the calcination treatment I include: a temperature of 440-460° C. and a time of 3-4 hours.

[0055] Preferably, the conditions of the drying treatment I include: a temperature of 110-130° C. and a time of 3-6 hours.

[0056] Preferably, the Pd source is selected from soluble salts containing Pd.

[0057] More preferably, the Pd source is selected from at least one of palladium nitrate, palladium chloride and palladium acetate.

[0058] Preferably, the Ni source is selected from soluble salts containing Ni.

[0059] More preferably, the Ni source is selected from at least one of nickel nitrate, nickel chloride and nickel oxalate.

[0060] Preferably, the carrier material source is selected from SiO 2 ,γ-Al 2 O 3 At least one of C

[0061] Preferably, the auxiliary agent source is selected from at least one of magnesium nitrate, magnesium chloride, zinc nitrate, zinc chloride, stannous sulfate and stannous chloride.

[0062] Preferably, the method further comprises preparing the second catalyst by a method comprising the following steps:

[0063] II-1, mixing a solution containing a Cu source, a Co source and a Ti source with urea under stirring to obtain an intermediate I;

[0064] II-2, after the intermediate I is allowed to stand for 5-10 hours, the obtained material is subjected to drying treatment II and roasting treatment II in sequence;

[0065] The amounts of the Cu source, the Co source and the Ti source are such that the second catalyst prepared contains 35-50wt% of Cu, 10-40wt% of Co and 20-35wt% of Ti, based on the total mass of the second catalyst, in terms of oxide. The inventors have found that under this preferred embodiment, the method provided by the present invention is used to prepare saturated alcohols, and the raw material conversion rate and product selectivity are high.

[0066] Preferably, in step II-1, the stirring conditions include: a stirring speed of 200-400 rpm, a temperature of 70-100° C., and a time of 6-10 h.

[0067] Preferably, in step II-1, the solvent of the solution containing the Cu source, the Co source and the Ti source is selected from water.

[0068] Preferably, the total molar amount of the Cu element, the Co element and the Ti element is calculated as A, and the molar ratio of the urea to the A is 1:0.5-1.

[0069] Preferably, the concentration of urea is 20-30 wt%.

[0070] Preferably, the conditions of the calcination treatment II include: a temperature of 450-550° C. and a time of 2-5 hours.

[0071] Preferably, the conditions of the drying treatment II include: a temperature of 110-130° C. and a time of 3-6 hours.

[0072] More preferably, the method for preparing the second catalyst further comprises: after the calcination treatment II, a molding treatment is further performed, and the conditions of the molding treatment include: a pressure of 80-100 KN.

[0073] Preferably, the Cu source is selected from soluble salts containing Cu.

[0074] More preferably, the Cu source is selected from at least one of ketone nitrate, ketone chloride and basic copper carbonate.

[0075] Preferably, the Co source is selected from soluble salts containing Co.

[0076] More preferably, the Co source is selected from at least one of cobalt nitrate, cobalt chloride and cobalt acetate.

[0077] Preferably, the Ti source is selected from soluble salts containing Ti.

[0078] More preferably, the Ti source is selected from at least one of titanium chloride and titanium oxalate.

[0079] In the present invention, in the method for preparing the second hydrogenation reaction, a conventional washing step in the art is also included. For example, in step II-2, the obtained material is washed with water 3-5 times before drying. The present invention will not be described in detail here, and those skilled in the art should not be construed as limiting the present invention.

[0080] In the present invention, in order to improve the activity and selectivity of the first catalyst and the second catalyst, the catalyst can also be pretreated conventionally by methods known in the art. For example, the pretreatment method can be: before the first contact reaction and / or the second contact reaction, the first catalyst and / or the second catalyst are subjected to reduction treatment, wherein the reduction treatment of the first catalyst is carried out at 400-450° C. H 2 The reduction treatment of the second catalyst is carried out in a H atmosphere at 200-250°C. 2 The present invention will not be described in detail here, and those skilled in the art should not be construed as limiting the present invention.

[0081] The following combination Picture 1 Preferred embodiments of the present invention are described in detail, but the present invention is not limited thereby.

[0082] exist Picture 1 In the method of the present invention, the method comprises:

[0083] (1) In the presence of a first catalyst, an unsaturated aldehyde or ketone raw material is subjected to a first contact reaction in a first hydrogenation reactor 4 via a logistics pipeline 1 with a first hydrogen in a logistics pipeline 2 and a second hydrogen in a circulation machine 3 to obtain a first product;

[0084] (2) In the presence of a second catalyst, the first product obtained by the first contact reaction enters the second hydrogenation reactor 7 through the logistics pipeline 5 and the heat exchanger 13 to continue the second contact reaction, the logistics after the reaction enters the gas-liquid separation tank 9 through the logistics pipeline 8, the hydrogen enters the circulation machine 3 through the logistics pipeline 11 for recycling, and the logistics containing saturated alcohol enters the separation tower 12 through the logistics pipeline 10 to obtain saturated alcohol.

[0085] In the present invention, the method provided by the present invention can be directly used to prepare saturated aldehydes and ketones. Picture 1 To explain:

[0086] (1) In the presence of a first catalyst, unsaturated aldehydes and ketones are reacted in a first hydrogenation reactor 4 with the first hydrogen in a logistics pipeline 2 and the second hydrogen in a circulation machine 3 via a logistics pipeline 1. The logistics after the reaction enters a gas-liquid separation tank 9 via a logistics pipeline 6, and the hydrogen enters the circulation machine 3 via a pipeline 11 for recycling. The first product containing saturated aldehydes and ketones enters a separation tower 12 via a logistics pipeline 10 to obtain saturated aldehydes and ketones.

[0087] As mentioned above, the second aspect of the present invention provides a saturated alcohol prepared by the method described in the first aspect.

[0088] The present invention will be described in detail below by way of examples.

[0089] In the following examples, unless otherwise specified, the experimental reagents and raw materials involved are commercially available, and the reagents are all analytically pure products.

[0090] Preparation Example 1

[0091] Preparation of a First Catalyst IA.

[0092] The method for preparing the first catalyst comprises the following steps:

[0093] I-1. In the presence of 80 ml of water, 0.17 g of PdCl 2 , 1.0g Ni(NO 3 ) 2 6H 2 O and 0.96 g SnCl 2 ·2H 2 O for mixing (stirring speed of 100 rpm for 0.2 h), and adding water to 100 ml to obtain a mixed solution;

[0094] I-2, 99.2g of γ-Al 2 O 3 The mixed solution is impregnated with the mixed solution to obtain an impregnated material; the pH value of the mixed solution in the initial system for the impregnation treatment is 2;

[0095] I-3. The impregnated material is subjected to drying treatment I and calcination treatment I in sequence; the temperature of the drying treatment I is 110°C and the time is 4 hours; the conditions of the calcination treatment I are: temperature is 440°C and the time is 4 hours; the first catalyst is obtained, named IA, and the specific results are shown in Table 1.

[0096] Preparation Example 2

[0097] Preparation of First Catalyst IB.

[0098] I-1. In the presence of 80 ml of 20 vol% ethanol aqueous solution, 0.43 g of Pd(CH 3 COO 2 , 7.10 g of Ni(HCOO) 2 and 1.92 g of SnCl 2 ·2H 2 O was mixed (stirring speed was 100 rpm, time was 0.2 h), and 20 volume % ethanol aqueous solution was added to 100 ml to obtain a mixed solution;

[0099] I-2, 96.0g of γ-Al 2 O 3 The mixed solution is impregnated with the mixed solution to obtain an impregnated material; the pH value of the mixed solution in the initial system for the impregnation treatment is 3;

[0100] I-3. The impregnated material is subjected to drying treatment I and calcination treatment I in sequence; the temperature of the drying treatment I is 130°C and the time is 4 hours; the conditions of the calcination treatment I are: temperature is 460°C and the time is 4 hours; the first catalyst is obtained, named IB, and the specific results are shown in Table 1.

[0101] Preparation Example 3

[0102] Preparation of a first catalyst IC.

[0103] This preparation example was carried out in a similar process to that of Preparation Example 1, except that 5.28 g of Mg(NO 3 ) 2 6H 2 O replaces SnCl in Preparation Example 1 2 ·2H 2 O.

[0104] The rest is the same as Preparation Example 1.

[0105] The first catalyst was prepared and named IC. The specific results are shown in Table 1.

[0106] Preparation Example 4

[0107] A first catalyst ID was prepared.

[0108] This preparation example was carried out in a similar process to that of Preparation Example 1, except that 2.28 g of Zn(NO 3 ) 2 6H 2O replaces SnCl in Preparation Example 1 2 ·2H 2 O.

[0109] The rest is the same as Preparation Example 1.

[0110] The first catalyst was prepared and named ID. The specific results are shown in Table 1.

[0111] Preparation Example 5

[0112] Preparation of a First Catalyst IE.

[0113] This preparation example was carried out in a similar process to that of Preparation Example 1, except that 99.2 g of SiO 2 Substituting γ-Al in Preparation Example 1 2 O 3 .

[0114] The rest is the same as Preparation Example 1.

[0115] The first catalyst was prepared and named IE. The specific results are shown in Table 1.

[0116] Preparation Example 6

[0117] A first catalyst IF was prepared.

[0118] This preparation example was carried out in a similar process to that of Preparation Example 1, except that 0.42 g of PdCl 2 , 99.05 g of γ-Al 2 O 3 .

[0119] The rest is the same as Preparation Example 1.

[0120] The first catalyst was prepared and named IF. The specific results are shown in Table 1.

[0121] Preparation Example 7

[0122] A first catalyst IG was prepared.

[0123] This preparation example was carried out in a similar process to that of Preparation Example 1, except that 15.0 g of Ni(NO 3 ) 2 6H 2 O, 96.4 g of γ-Al 2 O 3 .

[0124] The rest is the same as Preparation Example 1.

[0125] The first catalyst was prepared and named IG. The specific results are shown in Table 1.

[0126] Table 1

[0127] IA <![CDATA[0.1wt%Pd-0.2wt%Ni-0.5wt%Sn / Al 2 THE 3 ]]> IB <![CDATA[0.2wt%Pd-2.8wt%Ni-1.0wt%Sn / Al 2 THE 3 ]]> I C <![CDATA[0.1wt%Pd-0.2wt%Ni-0.5wt%Mg / Al 2 THE 3 ]]> ID <![CDATA[0.1wt%Pd-0.2wt%Ni-0.5wt%Zn / Al 2 THE 3 ]]> IE <![CDATA[0.1wt%Pd-0.2wt%Ni-0.5wt%Sn / SiO 2 ]]> IF <![CDATA[0.25wt%Pd-0.2wt%Ni-0.5wt%Sn / Al 2 THE 3 ]]> IG <![CDATA[0.1wt%Pd-3.0wt%Ni-0.5wt%Sn / Al 2 THE 3 ]]>

[0128] Preparation Example 8

[0129] Preparation of Second Catalyst II-A.

[0130] II-1, under stirring, 139.1gCu 2 (OH) 2 CO 3 、70.9gCo(CH 3 COO 2 and 205.0gTi(C 2 O 4 ) 2 300 mL of the aqueous solution was mixed with urea (concentration of 30 wt%) (stirring speed of 300 rpm, temperature of 80° C., time of 8 h) to obtain intermediate I;

[0131] II-2. The intermediate I was allowed to stand for 10 hours, washed with deionized water three times, and the obtained material was subjected to drying treatment II and calcination treatment II in turn; the temperature of the drying treatment II was 110°C and the time was 4 hours; the conditions of the calcination treatment II were: temperature was 480°C and the time was 4 hours; the first catalyst was obtained, named II-A, and the specific results are shown in Table 2.

[0132] The total molar amount of Cu element, Co element and Ti element is calculated as A, and the molar ratio of the urea to the A is 1:0.5.

[0133] Preparation Example 9

[0134] Preparation of Second Catalyst II-B.

[0135] II-1, under stirring, 212.8gCu(NO 3 ) 2 ·3H 2 O, 310.9gCo(NO 3 ) 2 6H 2 O and 118.8 g TiCl 4 400 mL of the aqueous solution was mixed with urea (concentration of 20 wt%) (stirring speed of 300 rpm, temperature of 80° C., time of 8 h) to obtain intermediate I;

[0136] II-2. The intermediate I was allowed to stand for 5 hours, washed with deionized water three times, and the obtained material was subjected to drying treatment II and calcination treatment II in turn; the temperature of the drying treatment II was 110°C and the time was 4 hours; the conditions of the calcination treatment II were: temperature 480°C and time 4 hours; the first catalyst was obtained, named II-B, and the specific results are shown in Table 2.

[0137] The total molar amount of the Cu element, the Co element and the Ti element is calculated as A, and the molar ratio of the urea to the A is 1:1.

[0138] Preparation Example 10

[0139] Preparation of Second Catalyst II-C.

[0140] This preparation example was carried out in a similar process to that of Preparation Example 8, except that 109.7 g of Zn(NO 3 ) 2 6H 2 O replaces Co(CH 3 COO 2 .

[0141] The rest is the same as Preparation Example 8.

[0142] The second catalyst was prepared and named II-C. The specific results are shown in Table 2.

[0143] Preparation Example 11

[0144] Preparation of Second Catalyst II-D.

[0145] This preparation example was carried out using a process similar to that of Preparation Example 8, except that 445.4 g of Mg(NO 3 ) 2 6H 2 O replaces the Ti(C 2 O 4 ) 2 .

[0146] The rest is the same as Preparation Example 8.

[0147] The second catalyst was prepared and named II-D. The specific results are shown in Table 2.

[0148] Preparation Example 12

[0149] Preparation of Second Catalyst II-E.

[0150] This preparation example was carried out using a process similar to that of Preparation Example 8, except that 380.6 g Ti (C 2 O 4) 2 and 55.7gCu 2 (OH) 2 CO 3 .

[0151] The rest is the same as Preparation Example 8.

[0152] The second catalyst was prepared and named II-E. The specific results are shown in Table 2.

[0153] Table 2

[0154]

[0155] Example 1

[0156] This example is used to illustrate the present invention, using Preparation Example 1 as the first catalyst, Preparation Example 8 as the second catalyst, according to the process parameters in Table 3, and the method described below to prepare saturated alcohol.

[0157] The method for preparing saturated alcohol comprises the following steps:

[0158] Catalyst pretreatment:

[0159] The first catalyst was heated at 420 °C in H 2 atmosphere for reduction treatment; and

[0160] The second catalyst was heated at 250 °C in H 2 Perform reduction treatment in the atmosphere;

[0161] (1) in the presence of a first catalyst, subjecting an unsaturated aldehyde or ketone to a first contact reaction with hydrogen to obtain a first product;

[0162] (2) In the presence of a second catalyst, subjecting hydrogen to a second contact reaction with the first product to obtain a saturated alcohol.

[0163] Unless otherwise specified, the remaining examples were carried out using a process similar to that of Example 1, except that the first catalyst and the second catalyst in each example were different, see Table 3 for details (Note: the parameters not listed in Table 3 are the same as the corresponding parameters in Example 1).

[0164] Table 3

[0165]

[0166] Table 3 (Continued)

[0167]

[0168] Test Example 1

[0169] The conversion rate and selectivity of the first product and saturated alcohol prepared in each example and comparative example were measured. The specific results are shown in Table 4.

[0170] Test method: Conversion and selectivity were measured by gas chromatography.

[0171] Unless otherwise specified, MIBK in Table 4 is methyl isobutyl ketone; MIBC is methyl isobutyl alcohol; DIBK is diisobutyl ketone; and DIBC is diisobutyl alcohol.

[0172] Table 4

[0173]

[0174] It can be seen from the results in Table 4 that the method of the present invention has a higher raw material conversion rate and better product selectivity for preparing saturated alcohols; and can controllably produce saturated aldehydes and ketones as intermediate products with high conversion rate and high selectivity.

[0175] Test Example 2

[0176] In the present invention, the conversion rate and selectivity results of the first product and saturated alcohol prepared in Examples 1-2 in industrial scale-up production are provided as examples, wherein the scale-up is at the ton level, and the specific results are shown in Table 5.

[0177] Unless otherwise specified, MIBK in Table 4 is methyl isobutyl ketone; MIBC is methyl isobutyl alcohol; DIBK is diisobutyl ketone; and DIBC is diisobutyl alcohol.

[0178] Table 5

[0179]

[0180]

[0181] It can be seen from the results in Table 5 that the method provided by the present invention is suitable for industrial scale-up production of saturated alcohols, and the product quality is stable.

[0182] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing saturated alcohols from unsaturated aldehydes and ketones, characterized in that: The method includes: (1) in the presence of a first catalyst, subjecting an unsaturated aldehyde or ketone to a first contact reaction with hydrogen to obtain a first product; the first product contains at least 99 wt % of saturated aldehyde or ketone; based on the hydrogen consumption of the unsaturated bonds in the unsaturated aldehyde or ketone, the amount of hydrogen used is at least 10% in excess; (2) in the presence of a second catalyst, subjecting hydrogen to a second contact reaction with the first product to obtain a saturated alcohol; the amount of hydrogen used is at least 10% in excess of the amount of hydrogen consumed by the unsaturated bonds in the first product; Based on the total mass of the first catalyst, the first catalyst contains 0.1-0.2wt% of Pd element, 0.2-2.8wt% of Ni element, 0.1-1% of auxiliary element and 96-99.6wt% of carrier; the auxiliary element is selected from at least one of Sn, Mg and Zn; the carrier is selected from at least one of silicon dioxide, aluminum oxide and activated carbon; Based on the total mass of the second catalyst, the second catalyst contains 35-50 wt% of Cu element, 10-40 wt% of Co element and 20-35 wt% of Ti element in terms of oxides.

2. The method according to claim 1, characterized in that: In the first catalyst, the promoter element is Sn; And / or, in the first catalyst, the carrier is alumina.

3. The method according to claim 1 or 2, characterized in that: The unsaturated aldehydes and ketones are selected from at least one of aliphatic aldehydes and / or ketones, aromatic aldehydes and / or ketones, and alicyclic aldehydes and / or ketones containing at least one olefin; preferably at least one of mesityl oxide, cinnamaldehyde, phorone, and 2,6-dimethyl-2-heptene-4-one.

4. The method according to any one of claims 1 to 3, characterized in that: In step (1), the conditions of the first contact reaction are: temperature of 60-150°C, pressure of 1-10 MPa, and weight space velocity of 0.2-3.0 h -1 .

5. The method according to any one of claims 1 to 4, characterized in that: In step (2), the conditions of the second contact reaction are: temperature of 70-200°C, pressure of 1-10 MPa, and weight space velocity of 0.5-2.0 h -1 .

6. The method according to any one of claims 1 to 5, characterized in that: The method further comprises preparing the first catalyst by a method comprising the following steps: I-1. In the presence of a solvent, a Pd source, a Ni source and an auxiliary agent source are mixed to obtain a mixed solution; I-2, impregnating the carrier material source with the mixed solution to obtain an impregnated material; the pH value of the mixed solution in the initial system for the impregnation treatment is 2-3; I-3, sequentially subjecting the impregnated material to drying treatment I and roasting treatment I; The amounts of the Pd source, the Ni source, the additive source and the carrier material source are such that, based on the total mass of the first catalyst, the first catalyst contains 0.1-0.2wt% of Pd element, 0.2-2.8wt% of Ni element, 0.1-1% of additive element and 96-99.6wt% of carrier.

7. The method according to claim 6, characterized in that The conditions of the calcination treatment I include: a temperature of 440-460° C. and a time of 3-4 hours.

8. The method according to claim 6 or 7, characterized in that: The Pd source is selected from a soluble salt containing Pd; preferably at least one of palladium nitrate, palladium chloride and palladium acetate; And / or, the Ni source is selected from soluble salts containing Ni; preferably at least one of nickel nitrate, nickel chloride and nickel oxalate.

9. The method according to any one of claims 1 to 8, characterized in that: The method further comprises preparing the second catalyst by a method comprising the following steps: II-1, mixing a solution containing a Cu source, a Co source and a Ti source with urea under stirring to obtain an intermediate I; II-2, after the intermediate I is allowed to stand for 5-10 hours, the obtained material is subjected to drying treatment II and roasting treatment II in sequence; The amounts of the Cu source, the Co source and the Ti source are such that the prepared second catalyst contains 35-50wt% of Cu element, 10-40wt% of Co element and 20-35wt% of Ti element in terms of oxide, based on the total mass of the second catalyst.

10. The method according to claim 9, characterized in that The total molar amount of Cu element, Co element and Ti element is calculated as A, and the molar ratio of the urea to the A is 1:0.5-1.

11. The method according to claim 9 or 10, characterized in that: The concentration of the urea is 20-30 wt%.

12. The method according to claims 9-11, characterized in that: The conditions of the calcination treatment II include: a temperature of 450-550° C. and a time of 2-5 hours.

13. The method according to any one of claims 6 to 12, characterized in that: The Cu source is selected from soluble salts containing Cu; And or, the Co source is selected from soluble salts containing Co; And or, the Ti source is selected from soluble salts containing Ti.

14. A saturated alcohol prepared by the method according to any one of claims 1 to 13.

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