Method for preparing alkynol through ethynylation reaction of ketone

Abstract

The invention relates to the technical field of organic synthesis, in particular to a method for preparing alkynol through a ketone ethynylation reaction, which comprises the following steps: reacting an acetylene-containing raw material with ketone in the presence of liquid ammonia and alkali to generate alkynol; the acetylene-containing raw material is prepared from the following components in percentage by mole: 97 mol% to 99.9 mol% of acetylene, 0.002 mol% to 0.51 mol% of carbon dioxide, 0.001 mol% to 0.5 mol% of C3-C4 unsaturated hydrocarbon and 0.005 mol% to 2 mol% of non-reactive gas; the non-reactive gas comprises at least one of oxygen, argon and nitrogen. According to the method, the acetylene-containing raw material with the specific composition and the ketone react in the presence of the liquid ammonia and the alkali, the conversion rate and the reaction selectivity of the ketone can be effectively improved at the same time by controlling the content of carbon dioxide and C3-C4 unsaturated hydrocarbon in the acetylene-containing raw material, and the method is simple in process and suitable for industrial production.

Description

Technical Field

[0001] This application relates to the field of organic synthesis technology, and in particular to a method for preparing alkynols by ketethynylation reaction. Background Technology

[0002] The acetylation of ketones to prepare alkynyl alcohols is a very useful reaction, particularly suitable for the synthesis of intermediates for vitamin E and fragrances. For example, the acetylation of acetone and 6-methyl-5-hepten-2-one yields methylbutynol and dehydrolinalool, which are intermediates in the synthesis of the fragrance linalool; the alkynyl alcohol product obtained from the acetylation of 2-butanone is an intermediate in the synthesis of the fragrance ethyllinalool; and the alkynyl alcohol products obtained from the acetylation of geranylacetone, hexahydropseudoionone, and phytone are intermediates in the synthesis of vitamin E.

[0003] Currently, the industrial production of acetylenols by ketethynylation mostly uses acetylene-containing gas prepared by the calcium carbide method as the acetylene source, alkali (such as KOH) as the catalyst, and liquid ammonia as the solvent. The conversion rate of this method is between 50% and 96%, and the selectivity is less than 96%, which means that the reaction efficiency is low. Summary of the Invention

[0004] Based on this, the main objective of this application is to provide a method for preparing alkynols by ketone acetylation reaction with high reaction efficiency that can meet the requirements of industrial production. By controlling the composition of acetylene-containing raw materials, the conversion rate and reaction selectivity of ketones can be improved.

[0005] In a first aspect, this application provides a method for preparing alkynols by ketethynylation reaction, comprising the following steps:

[0006] The reaction of acetylene-containing raw material and ketone in the presence of liquid ammonia and alkali produces alkynol;

[0007] The acetylene-containing raw material comprises, by mole percentage: 97 mol%-99.9 mol% acetylene, 0.002 mol%-0.51 mol% carbon dioxide, 0.001 mol%-0.5 mol% C3-C4 unsaturated hydrocarbons, and 0.005 mol%-2 mol% non-reactive gases; the non-reactive gases include at least one of oxygen, argon, and nitrogen.

[0008] In some embodiments, the C3-C4 unsaturated hydrocarbons include at least one of propadiene, methylacetylene, vinylacetylene, butadiene, and butadiene.

[0009] In some embodiments, the acetylene-containing feedstock is prepared via a partial oxidation process of natural gas. It is understood that even after purification, it is difficult to achieve a purity of 100 mol% when preparing acetylene-containing feedstock via the partial oxidation process of natural gas. This application utilizes the aforementioned acetylene-containing feedstock and, by controlling the content of its impurity components, carbon dioxide and C3-C4 unsaturated hydrocarbons, achieves high conversion rate and high selectivity without the need for complex purification processes to control the acetylene content close to 100 mol%.

[0010] In some embodiments, the total content of oxygen and argon in the acetylene-containing raw material is ≤0.5 mol%;

[0011] And / or, in the acetylene-containing raw material, the nitrogen content is ≤1.5 mol.

[0012] In some embodiments, the acetylene-containing raw material comprises, by mole percentage: 99 mol%-99.9 mol% acetylene, 0.002 mol%-0.01 mol% carbon dioxide, 0.001 mol%-0.5 mol% C3-C4 unsaturated hydrocarbons, and 0.005 mol%-2 mol% non-reactive gases.

[0013] In some embodiments, the ketone has the structural formula shown in Formula I:

[0014] Formula I;

[0015] Among them, R 1 and R 2 Each is independently selected from C1-C16 alkyl, C2-C16 alkenyl, C4-C16 dienyl, C3-C16 cycloalkyl, or C3-C16 cycloalkenyl;

[0016] Optional, R 1 Selected from C1-C16 alkyl, C2-C16 alkenyl, C4-C16 dienyl, or C3-C16 cycloalkenyl; R 2 It is a C1-C16 alkyl group;

[0017] Optionally, the ketone has 3-18 carbon atoms;

[0018] Optionally, the ketone includes at least one of acetone, 2-butanone, 6-methyl-5-hepten-2-one, 6-methyl-5-octen-2-one, geranylacetone, hexahydro-pseudo-ionone, phytone, and dihydro-β-ionone.

[0019] In some embodiments, the structural formula of the alkynol is shown in Formula II:

[0020] Formula II;

[0021] Optionally, the alkynol includes at least one selected from 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, dehydrolinalool, dehydroethyllinalool, dehydronerol, 3,7,11-trimethyldodecyn-3-ol, dehydroisophytol, and 3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)pent-1-yn-3-ol.

[0022] In some embodiments, the alkali includes at least one of potassium hydroxide, sodium hydroxide, and cesium hydroxide;

[0023] Optionally, the base includes potassium hydroxide;

[0024] Optionally, the alkali is an aqueous solution of alkali;

[0025] Optionally, the mass concentration of the aqueous solution of the alkali is 45wt%-50wt%.

[0026] In some embodiments, one or more of the following features are satisfied:

[0027] (1) The molar ratio of the ketone to the base is 1:(0.01-0.12), or optionally 1:(0.02-0.09).

[0028] (2) The molar ratio of the ketone to the acetylene in the acetylene-containing raw material is 1:(2.1-7), or optionally 1:(2.5-5);

[0029] (3) The molar ratio of the ketone to the liquid ammonia is 1:(10-60), or optionally 1:(18-40).

[0030] In some embodiments, the reaction temperature is 0°C-30°C, and optionally 5°C-15°C;

[0031] And / or, the reaction time is 2h-10h, optionally 4h-6h.

[0032] Studies have found that when using acetylene-containing gas prepared by the calcium carbide method as the acetylene source, KOH as the catalyst, and liquid ammonia as the solvent to prepare alkynols, the conversion rate is between 50% and 96%, and the selectivity is less than 96%, indicating a problem of low reaction efficiency.

[0033] One method claims that the yield of saturated ketone acetylation reaction can reach 98% in the presence of 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical (PGMA / SiO2-TEMPO) supported on polyglycidyl methacrylate / silicone. However, the preparation process of PGMA / SiO2-TEMPO is extremely complex and expensive, and it can only be recycled 7 times, with an unknown long-term service life. Furthermore, PGMA / SiO2-TEMPO has strong oxidizing properties, posing a significant safety risk when in contact with acetylene, and thus cannot meet the requirements for industrial production.

[0034] The inventors discovered that the composition of acetylene-containing feedstock has a significant impact on reaction efficiency. Specifically, the content of C3-C4 unsaturated hydrocarbons affects the conversion rate and selectivity of the ketony acetylation reaction; excessive carbon dioxide content affects the activity of the alkaline catalyst, leading to a deterioration in reaction efficiency; although oxygen, argon, and nitrogen do not participate in the acetylation reaction, these impurities accumulate during industrial production due to the recycling of feedstock, and excessive content can also cause significant fluctuations in production operation.

[0035] This application uses a specific composition of acetylene-containing feedstock to react with ketones in the presence of liquid ammonia and alkali. By controlling the content of carbon dioxide and C3-C4 unsaturated hydrocarbons in the acetylene-containing feedstock, and keeping the content of oxygen, argon and nitrogen within certain limits, the conversion rate and reaction selectivity of ketones can be effectively improved simultaneously. Moreover, the process is simple and suitable for industrial production. Detailed Implementation

[0036] The method for preparing alkynyl alcohols by ketethynylation of this application is further described in detail below with reference to specific embodiments. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in this application and in its specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0038] In this application, "one or more" means any one, two or more of the listed items.

[0039] In this application, terms such as "first aspect," "second aspect," "third aspect," and "fourth aspect" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, terms such as "first," "second," "third," and "fourth" serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0040] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0041] In this application, numerical ranges are involved. Unless otherwise specified, the numerical ranges mentioned above are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. In addition, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed in this application should be understood to include any and all subranges to which they are included.

[0042] In this application, the term "alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C1-16 alkyl," refer to alkyl groups containing 1-16 carbon atoms, and each occurrence can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, or C16 alkyl. These alkyl groups can be branched or have a branched structure. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butyl(-CH2CH(CH3)CH2CH3), 1-hexyl(-CH2CH2CH2CH2CH2CH3), 2-hexyl(-CH(CH3)CH2CH2CH2CH3), 3-hexyl(-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl(-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl(-CH(CH3)CH( CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3 and octyl (-(CH2)7CH3).

[0043] In this application, the term "alkenyl" refers to a monovalent residue formed by the loss of a hydrogen atom from an unsaturated hydrocarbon containing a C=C, comprising a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C2-16 alkenyl," refer to alkenyl groups containing 2-16 carbon atoms, which, each time appearing independently, can be C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, C6 alkenyl, C7 alkenyl, C8 alkenyl, C9 alkenyl, C10 alkenyl, C11 alkenyl, C12 alkenyl, C13 alkenyl, C14 alkenyl, C15 alkenyl, or C16 alkenyl. These alkenyl groups can be branched or have a branched structure.

[0044] In this application, the term "dienyl" differs from "alkenyl" in that it contains two C=C atoms. Phrases containing this term, such as "C4-16 dienyl," refer to dienyl groups containing 4-16 carbon atoms. Each occurrence can be independently of C4 dienyl, C5 dienyl, C6 dienyl, C7 dienyl, C8 dienyl, C9 dienyl, C10 dienyl, C11 dienyl, C12 dienyl, C13 dienyl, C14 dienyl, C15 dienyl, and C16 dienyl. These dienyl groups can be branched or have a branched structure.

[0045] In this application, "cycloalkyl" and "cycloalkenyl" differ from "alkyl" and "alkenyl" in that they contain a cyclic structure formed by at least 3 carbon atoms. The C3-C16 in "C3-C16 cycloalkyl" and "C3-C16 cycloalkenyl" refers to the total number of carbon atoms, including both cyclic and non-cyclic carbon atoms, and each occurrence is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16.

[0046] In this application, "reaction selectivity" refers to the ability of a reaction system to preferentially select a particular pathway from multiple possible reaction pathways in a chemical reaction. It determines which reaction pathways are preferentially selected, thus affecting the type and purity of the final product, the tendency to form the target product, and the degree of byproduct formation. Specifically, "reaction selectivity" refers to the ability of a ketone to react and generate the corresponding alkynol. Reaction selectivity = alkynol yield / ketone conversion rate × 100%. Wherein, ketone conversion rate = (initial ketone mass - ketone mass after reaction) / initial ketone mass × 100%. The ketone mass after reaction is calculated by gas chromatography to determine the concentration of ketone in the ketone acetylation reaction product. The alkynol yield is calculated by gas chromatography to determine the concentration of alkynol in the ketone acetylation reaction product, then divided by the theoretical mass of the alkynol, and then multiplied by 100%.

[0047] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and liquid-liquid mixtures, and volume (molar) percentage for gas-gas mixtures.

[0048] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0049] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0050] In this application, room temperature generally refers to 4℃-30℃, and preferably 20±5℃.

[0051] In a first aspect, this application provides a method for preparing alkynols by ketethynylation reaction, comprising the following steps:

[0052] The reaction of acetylene-containing raw material and ketone in the presence of liquid ammonia and alkali produces alkynol;

[0053] The acetylene-containing raw material comprises, by mole percentage: 97 mol%-99.9 mol% acetylene, 0.002 mol%-0.51 mol% carbon dioxide, 0.001 mol%-0.5 mol% C3-C4 unsaturated hydrocarbons, and 0.005 mol%-2 mol% non-reactive gases; the non-reactive gases include at least one of oxygen, argon, and nitrogen.

[0054] The composition of acetylene-containing feedstock has a significant impact on reaction efficiency. The content of C3-C4 unsaturated hydrocarbons affects the conversion rate and selectivity of the ketone acetylation reaction. Excessive carbon dioxide content can negatively affect the activity of the alkaline catalyst, leading to decreased reaction efficiency. Although oxygen, argon, and nitrogen do not participate in the acetylation reaction, these impurities accumulate during industrial production due to feedstock recycling, and excessive levels can cause significant fluctuations in production. This application utilizes a specific composition of acetylene-containing feedstock to react with ketones in the presence of liquid ammonia and an alkaline environment. By controlling the content of carbon dioxide and C3-C4 unsaturated hydrocarbons in the acetylene-containing feedstock and maintaining the contents of oxygen, argon, and nitrogen within certain limits, the conversion rate and reaction selectivity of the ketone can be effectively improved simultaneously. Furthermore, the process is simple and suitable for industrial production.

[0055] In some specific examples, the acetylene content can be 97 mol%, 97.5 mol%, 98 mol%, 98.5 mol%, 99 mol%, 99.5 mol%, 99.9 mol%, etc.; the carbon dioxide content can be 0.002 mol%, 0.1 mol%, 0.2 mol%, 0.3 mol%, 0.4 mol%, 0.503 mol%, 0.51 mol%, etc.; and the C3-C4 unsaturated hydrocarbon content can be 0.001 mol%, 0.1 mol%, 0.2 mol%, 0.3 mol%, 0.4 mol%, 0.487 mol%, 0.5 mol%, etc.

[0056] In some embodiments, the C3-C4 unsaturated hydrocarbons include at least one of propadiene, methylacetylene, vinylacetylene, butadiene, and butadiene.

[0057] In some embodiments, the acetylene-containing feedstock is prepared via a natural gas partial oxidation process. Understandably, the calcium carbide method for acetylene production generates large quantities of difficult-to-treat calcium carbide waste and toxic gases (phosphine, hydrogen sulfide, etc.), resulting in significant waste. Furthermore, the violent reaction of calcium carbide with water releases a large amount of heat and generates acetylene, posing high safety risks during use, transportation, and storage, and easily leading to accidents. The natural gas partial oxidation process for acetylene production solves the problems of excessive waste and high safety risks associated with the calcium carbide method. Additionally, the main impurities in acetylene produced by the natural gas partial oxidation process include carbon dioxide, oxygen, argon, C3-C4 unsaturated hydrocarbons (propadiene, methylacetylene, vinylacetylene, butadiene, and butadiene), and nitrogen. By controlling the content of these impurities, the conversion rate and reaction selectivity of the ketone can be effectively improved simultaneously.

[0058] In some embodiments, the total content of oxygen and argon in the acetylene-containing raw material is ≤0.5mol%, optionally 0.001mol%-0.5mol%, for example 0.001mol%, 0.1mol%, 0.2mol%, 0.3mol%, 0.4mol%, 0.5mol%, etc.; further optionally, the oxygen content is ≤0.45mol.

[0059] In some embodiments, the nitrogen content in the acetylene-containing raw material is ≤1.5 mol%, which can be selected from 0.05 mol% to 1.5 mol%, for example 0.05 mol%, 0.1 mol%, 0.2 mol%, 0.3 mol%, 0.4 mol%, 0.487 mol%, 0.5 mol%, 1 mol%, 1.1 mol%, 1.2 mol%, 1.3 mol%, 1.4 mol%, 1.5 mol%, etc.

[0060] In some embodiments, the acetylene-containing feedstock contains ≤0.13 mol of propadiene.

[0061] In some embodiments, the acetylene-containing raw material contains ≤0.23 mol of methylacetylene.

[0062] In some embodiments, the acetylene-containing raw material contains ≤0.1 mol% vinylacetylene, optionally ≤0.06 mol%.

[0063] In some embodiments, the butyrylene content in the acetylene-containing feedstock is ≤0.05 mol%, optionally ≤0.04 mol%.

[0064] In some embodiments, the butadiene content in the acetylene-containing feedstock is ≤0.1 mol%, optionally ≤0.06 mol%.

[0065] In some embodiments, the acetylene-containing raw material, by molar percentage, comprises: 99 mol%-99.9 mol% acetylene, 0.002 mol%-0.01 mol% carbon dioxide, 0.001 mol%-0.5 mol% C3-C4 unsaturated hydrocarbons, and 0.005 mol%-2 mol% non-reactive gases. Understandably, the acetylene-containing raw material can be purified through processes such as acid washing and alkali washing to obtain a high-purity acetylene-containing raw material with a purity ≥99%.

[0066] In some embodiments, the ketone has the structural formula shown in Formula I:

[0067] Formula I;

[0068] Among them, R 1 and R 2 Each is independently selected from C1-C16 alkyl, C2-C16 alkenyl, C4-C16 dienyl, C3-C16 cycloalkyl, or C3-C16 cycloalkenyl;

[0069] Optional, R 1 Selected from C1-C16 alkyl, C2-C16 alkenyl, C4-C16 dienyl, or C3-C16 cycloalkenyl; R 2 It is a C1-C16 alkyl group.

[0070] In some embodiments, the C3-C16 cycloalkenyl group is Understandable, "Refers to the connection site."

[0071] In some embodiments, the ketone has 3-18 carbon atoms, such as 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18.

[0072] In some embodiments, the ketone includes at least one selected from acetone, 2-butanone, 6-methyl-5-hepten-2-one, 6-methyl-5-octen-2-one, geranylacetone (CAS No.: 3796-70-1), hexahydro-β-ionone (CAS No.: 1604-34-8), phytone (CAS No.: 502-69-2), and dihydro-β-ionone (CAS No.: 502-69-2).

[0073] In some embodiments, the structural formula of the alkynol is shown in Formula II:

[0074] Formula II;

[0075] Optionally, the alkynol includes at least one selected from 2-methyl-3-butynin-2-ol, 3-methyl-1-pentyn-3-ol, dehydrolinalool (CAS No.: 29171-20-8), dehydroethyllinalool (CAS No.: 24173-47-5), dehydronerol (CAS No.: 2387-68-0), 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604-35-9), dehydroisophytol (CAS No.: 29171-23-1), and 3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)pent-1-yn-3-ol (CAS No.: 57291-29-9).

[0076] Furthermore, the reaction of acetylene-containing raw material and ketone in the presence of liquid ammonia and alkali to produce alkynol is shown in the following reaction formula:

[0077] .

[0078] In some embodiments, the alkali includes at least one of potassium hydroxide, sodium hydroxide, and cesium hydroxide;

[0079] Optionally, the alkali includes potassium hydroxide;

[0080] Optionally, the alkali is an aqueous solution of alkali.

[0081] Understandably, using an aqueous solution of alkali as feed is more convenient, and there is no limit to the concentration of the aqueous solution. However, considering solubility and minimizing the introduction of water, the mass concentration of the aqueous solution of alkali is 45wt%-50wt%, such as 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, etc.

[0082] In some embodiments, one or more of the following features are satisfied:

[0083] (1) The molar ratio of the ketone to the base is 1:(0.01-0.12), which can be selected as 1:(0.02-0.09), such as 1:0.01, 1:0.03, 1:0.05, 1:0.07, 1:0.09, 1:0.1, 0.12, etc.;

[0084] (2) The molar ratio of the ketone to the acetylene in the acetylene-containing raw material is 1:(2.1-7), which can be selected as 1:(2.5-5), such as 1:2.1, 1:2.5, 1:3, 1:4, 1:5, 1:6, 1:7, etc.;

[0085] (3) The molar ratio of the ketone to the liquid ammonia is 1:(10-60), which can be selected as 1:(18-40), such as 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, etc.

[0086] In some embodiments, the reaction temperature is 0℃-30℃, and can be selected as 5℃-15℃, such as 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, etc.

[0087] And / or, the reaction time is 2h-10h, optionally 4h-6h, such as 2h, 4h, 6h, 8h, 10h, etc.

[0088] For experimental parameters not specified in the following specific embodiments, please refer to the guidelines given in this application document first, or refer to experimental manuals or other experimental methods known in the art, or refer to the experimental conditions recommended by the manufacturer.

[0089] The main reagent sources for each embodiment and comparative example are as follows:

[0090] The acetylene-containing feedstock is prepared by the natural gas partial oxidation process of Wanhua Chemical Sichuan's acetylene unit. The low-purity acetylene-containing feedstock (acetylene purity 97-99%) comes from the concentration process of Wanhua Chemical Sichuan's acetylene unit, while the high-purity acetylene-containing feedstock (acetylene purity ≥99%) comes from the purification process of Wanhua Chemical Sichuan's acetylene unit.

[0091] Liquid ammonia, 99.9% pure, sourced from liquid ammonia cylinders, purchased from liquid air gas.

[0092] Potassium hydroxide, 95% purity, purchased from Beijing Innochem, brand name innochem.

[0093] Sodium hydroxide, 99% purity, purchased from Beijing Innochem, brand name innochem.

[0094] Cesium hydroxide, 50% aqueous solution, purchased from Beijing Innocare, brand name Adamas.

[0095] Acetone and 2-butanone, 99.5% purity, purchased from Beijing Inokai, brand name Adamas.

[0096] 6-Methyl-5-hepten-2-one, 98% purity, purchased from Beijing Inokai, brand name Leyan.

[0097] 6-Methyl-5-octen-2-one, with a purity of 98%, was prepared using the industry-renowned Saucy-Marbet reaction. The specific steps were as follows: 3-methyl-1-pentyn-3-ol (brand: Anaiji, purity 98%), 2-methoxypropene (purity 98%, brand: Acmec), and naphthol phosphate (CAS No.: 35193-63-6, purity 99%, brand: Alfa) were added to an autoclave at a molar ratio of 1:3:0.1%. The autoclave was sealed and pressurized with 1 MPaG of nitrogen for 20 min. The nitrogen was then vented, and the temperature was raised to 150°C and maintained for 4 h. The reaction solution was cooled to room temperature and distilled at atmospheric pressure and 120°C to remove light components such as 2-methoxypropene and 2,2-dimethoxypropane. Then, the solution was distilled under reduced pressure, and the fraction distilled at 85-86°C was collected at 2.5 kPa to obtain 6-methyl-5-octen-2-one with a purity >98%.

[0098] Geraniol acetone (CAS No.: 3796-70-1), 98% pure, purchased from Beijing Innocare, brand name Adamas.

[0099] Hexahydro-pseudo-ionone (CAS No.: 1604-34-8), with a purity of 98%, was prepared by hydrogenation of geranylacetone (CAS No.: 3796-70-1). The specific steps were as follows: 200 g of ethanol and 1 g of palladium on carbon (Innochem brand, 10% palladium on carbon, containing approximately 50-65% water) were added to a 1 L autoclave. The autoclave was sealed and pressurized with 2.5 MPaG of nitrogen for 20 min. The nitrogen was then purged, and the autoclave was purged three times with 1 MPaG of hydrogen. The temperature was raised to 100 °C, and 2 MPaG of hydrogen was introduced into the autoclave. 200 g of geranylacetone was then added dropwise to the autoclave using a horizontal pump (dropping time 1 h). Hydrogen gas was continuously introduced to maintain the pressure inside the reactor at 2 MPaG. The reaction was terminated after 6 h of heat treatment. The mixture was then cooled to room temperature, filtered through diatomaceous earth, and ethanol was removed by vacuum distillation to obtain 191 g of hexahydropyronone with a purity >98%.

[0100] Phytoketone (CAS No.: 502-69-2), with a purity >98%, was prepared by hydrogenation of farnesylacetone (CAS No.: 1117-52-8, purity 98%, brand: Innochem). The specific steps were as follows: 200g of ethanol and 1g of palladium on carbon (brand: Innochem, 10% palladium on carbon, water content approximately 50-65%) were added to a 1L autoclave. The autoclave was sealed and pressurized with 2.5MPaG nitrogen for 20 minutes. The nitrogen was then purged, and the autoclave was purged three times with 1MPaG hydrogen. The temperature was raised to 120℃, and 2MPaG hydrogen was introduced into the autoclave. 200g of farnesylacetone was added dropwise to the autoclave using a horizontal pump (dropping time 1 hour). Hydrogen was continuously introduced to maintain the pressure inside the autoclave at 2MPaG. The reaction was stopped after 8 hours of incubation. The mixture was cooled to room temperature, filtered through diatomaceous earth, and the ethanol was removed by vacuum distillation to obtain phytoketone with a purity >98%.

[0101] Dihydro-β-ionone (CAS No.: 502-69-2), 97% pure, purchased from Beijing Inokai, brand name Anaiji.

[0102] The gas chromatography conditions for testing the purity of acetylene-containing raw materials and the reaction products of ketone acetylation are as follows:

[0103] Three-channel analysis, with pre- and post-FID analysis of organic components. A six-way injection valve carries the sample into the injection port, into the PLOT-Q column for separation to pre-FID detection. Components that cannot be separated are cut by a DEANSWITCH and separated onto an Al2O3 column for post-FID detection. An auxiliary TCD analysis of H2 / O2 / N2 / CO / CO2 / CH4 is performed; components are separated by HayeSep A+ and MolSieve 13X before TCD detection.

[0104] Chromatography model: Agilent 8890;

[0105] Inlet: Temperature 250℃, split ratio 40:1;

[0106] Column 1: 2Ft 1 / 16 1mm HayeSep A 80 / 100 UM 41mm;

[0107] Column 2: 1.7m 1 / 16 1mm HayeSep A 80 / 100 UM 41mm;

[0108] Column 3: 4m 1 / 16 1mm MolSieve 13X 80 / 100 UM 41mm;

[0109] Column 4: HP-PLOT Q 30m×530μm×40μm, flow rate 4mL / min;

[0110] Column 5: HP-PLOT Al2O3 30m×530μm×15μm, flow rate 8mL / min;

[0111] Column 6: Damping column 0.76m×200μm×0μm, flow rate 8mL / min;

[0112] Front FID detector: temperature 300℃, air 300mL / min, hydrogen 40mL / min, tail gas (N2) 25mL / min;

[0113] Post-FID detector: temperature 300℃, air 300mL / min, hydrogen 40mL / min, tail gas (N2) 25mL / min;

[0114] Assisted TCD: Temperature 250℃, reference gas (He) 25mL / min, make-up gas (He) 10mL / min;

[0115] Programmed temperature rise: Hold at 60℃ for 3 min, then increase to 180℃ at 10℃ / min and hold for 12 min.

[0116] PCM A: N2, PCM B: He, AUX PCMB: He.

[0117] Valve box: 70℃.

[0118] event:

[0119]

[0120] The gas chromatographic conditions used in this application to test the reaction products of ketone acetylation are as follows:

[0121] Instrument model: Agilent 8890 B;

[0122] Injection volume: 0.5 μL;

[0123] Inlet temperature: 300℃;

[0124] Flow split ratio: 30 / 1;

[0125] Column: Agilent HP-5, 30 m × 250 μm × 0.25 μm;

[0126] Column flow rate: 1.5 mL / min;

[0127] Temperature program: Start at 40℃, hold for 5 min, then increase to 300℃ at 10℃ / min, hold for 5 min;

[0128] Detector temperature: 300℃; air flow rate: 400mL / min; hydrogen flow rate: 40mL / min; nitrogen flow rate: 25mL / min.

[0129] Example 1

[0130] 2 MPaG of nitrogen was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia, cooled to -30℃, and liquid ammonia (600.2 g, 35.24 mol) was added. Stirring was started. Once the internal temperature dropped to -30℃, low-purity acetylene feedstock (118.1 g, 4.41 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the low-purity acetylene feedstock was: acetylene 97.128%, oxygen 0.411%, argon 0.063%, carbon dioxide 0.503%, nitrogen 1.408%, and C3-C4 unsaturated hydrocarbons 0.487% (including 0.125% propadiene, 0.221% methylacetylene, 0.053% vinylacetylene, 0.033% butadiene, and 0.055% butadiene).

[0131] The temperature inside the reactor was raised to 15°C, and 45% KOH (3.66 g, 0.029 mol) and acetone (85.72 g, 1.47 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 4 hours. A sample of the reaction solution was taken, and gas chromatography showed that the acetone conversion rate was 99.247%, and the selectivity of the product 2-methyl-3-butyn-2-ol was 98.204%.

[0132] Example 2

[0133] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (400.1 g, 23.49 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, low-purity acetylene-containing feedstock (130.7 g, 4.93 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the low-purity acetylene-containing feedstock was: acetylene 98.331%, oxygen 0.142%, argon 0.008%, carbon dioxide 0.231%, nitrogen 1.061%, and C3-C4 unsaturated hydrocarbons 0.227% (including 0.068% propadiene, 0.088% methylacetylene, 0.022% vinylacetylene, 0.018% butadiene, and 0.031% butadiene).

[0134] The temperature inside the reactor was raised to 30°C. Using a horizontal pump, 45% NaOH (2.506 g, 0.028 mol) and acetone (137.14 g, 2.35 mol) were added sequentially. After the addition was complete, the reaction mixture was kept at this temperature for 2 hours. A sample of the reaction solution was taken, and gas chromatography showed that the acetone conversion rate was 99.435%, and the selectivity of the product 2-methyl-3-butyn-2-ol was 98.213%.

[0135] Example 3

[0136] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (600.1 g, 35.24 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, high-purity acetylene-containing raw material (115.8 g, 4.40 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the high-purity acetylene-containing raw material was: acetylene 99.035%, oxygen 0.095%, argon 0.005%, carbon dioxide 0.009%, nitrogen 0.851%, and C3-C4 unsaturated hydrocarbons 0.005% (including 0.0011% propadiene, 0.0018% methylacetylene, 0.0009% vinylacetylene, 0.0007% butadiene, and 0.0005% butadiene).

[0137] The temperature inside the reactor was raised to 10°C, and 45% KOH (4.39 g, 0.035 mol) and acetone (102.84 g, 1.76 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 3 hours. A sample of the reaction solution was taken, and gas chromatography showed that the acetone conversion rate was 99.565%, and the selectivity of the product 2-methyl-3-butyn-2-ol was 98.635%.

[0138] Example 4

[0139] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (600.3 g, 35.25 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, high-purity acetylene-containing raw material (115.6 g, 4.41 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the high-purity acetylene-containing raw material was: acetylene 99.277%, oxygen 0.087%, argon 0.004%, carbon dioxide 0.008%, nitrogen 0.621%, and C3-C4 unsaturated hydrocarbons 0.003% (including 0.0005% propadiene, 0.0009% methylacetylene, 0.0005% vinylacetylene, 0.0006% butadiene, and 0.0005% butadiene).

[0140] The temperature inside the reactor was raised to 0℃, and 50% CsOH (5.28 g, 0.018 mol) and 2-butanone (127.73 g, 1.76 mol) were added sequentially to the reactor using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 10 h. A sample of the reaction solution was taken, and gas chromatography showed that the conversion rate of 2-butanone was 99.633%, and the selectivity of the product 3-methyl-1-pentyn-3-ol was 98.533%.

[0141] Example 5

[0142] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (600.2 g, 35.24 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, high-purity acetylene-containing raw material (115.6 g, 4.41 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the high-purity acetylene-containing raw material was: acetylene 99.261%, oxygen 0.095%, argon 0.004%, carbon dioxide 0.008%, nitrogen 0.627%, and C3-C4 unsaturated hydrocarbons 0.005% (including 0.0014% propadiene, 0.0016% methylacetylene, 0.0007% vinylacetylene, 0.0007% butadiene, and 0.0006% butadiene).

[0143] The temperature inside the reactor was raised to 5°C, and 45% KOH (4.39 g, 0.035 mol) and 6-methyl-5-hepten-2-one (226.93 g, 1.76 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 6 hours. A sample of the reaction solution was taken, and gas chromatography showed that the conversion rate of 6-methyl-5-hepten-2-one was 99.215%, and the selectivity of the product dehydrolinalool was 98.457%.

[0144] Example 6

[0145] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas, cooled to -30℃, and liquid ammonia (400.1 g, 23.49 mol) was added. Stirring was started. Once the internal temperature dropped to -30℃, high-purity acetylene-containing raw material (77.1 g, 2.94 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the high-purity acetylene-containing raw material was: acetylene 99.178%, oxygen 0.081%, argon 0.005%, carbon dioxide 0.009%, nitrogen 0.723%, and C3-C4 unsaturated hydrocarbons 0.004% (including 0.0011% propadiene, 0.0012% methylacetylene, 0.0005% vinylacetylene, 0.0007% butadiene, and 0.0005% butadiene).

[0146] The temperature inside the reactor was raised to 10°C, and 45% KOH (4.39 g, 0.035 mol) and 6-methyl-5-octen-2-one (168.09 g, 1.17 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 4 hours. A sample of the reaction solution was taken, and gas chromatography showed that the conversion rate of 6-methyl-5-octen-2-one was 99.107%, and the selectivity of the product dehydroethyl linalool was 98.589%.

[0147] Example 7

[0148] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (600.2 g, 35.24 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, high-purity acetylene-containing raw material (107.9 g, 4.11 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the high-purity acetylene-containing raw material was: acetylene 99.214%, oxygen 0.089%, argon 0.004%, carbon dioxide 0.008%, nitrogen 0.681%, and C3-C4 unsaturated hydrocarbons 0.004% (including 0.0009% propadiene, 0.0012% methylacetylene, 0.0006% vinylacetylene, 0.0008% butadiene, and 0.0005% butadiene).

[0149] The temperature inside the reactor was raised to 5°C, and 45% KOH (3.66 g, 0.029 mol) and geranylacetone (116.47 g, 0.59 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 3 hours. A sample of the reaction solution was taken, and gas chromatography showed that the conversion rate of geranylacetone was 99.012%, and the selectivity of the product dehydroneryl alcohol was 99.127%.

[0150] Example 8

[0151] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (400.1 g, 23.49 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, high-purity acetylene-containing raw material (77.1 g, 2.94 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the high-purity acetylene-containing raw material was: acetylene 99.233%, oxygen 0.075%, argon 0.005%, carbon dioxide 0.009%, nitrogen 0.673%, and C3-C4 unsaturated hydrocarbons 0.005% (including 0.0017% propadiene, 0.0015% methylacetylene, 0.0006% vinylacetylene, 0.0007% butadiene, and 0.0005% butadiene).

[0152] The temperature inside the reactor was raised to 10°C, and 45% KOH (7.32 g, 0.059 mol) and hexahydropseudoionone (198.12 g, 0.98 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 4 hours. A sample of the reaction solution was taken, and gas chromatography showed that the conversion rate of hexahydropseudoionone was 98.583%, and the selectivity of the product 3,7,11-trimethyldodecyn-3-ol was 98.982%.

[0153] Example 9

[0154] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (400.1 g, 23.49 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, high-purity acetylene-containing raw material (76.6 g, 2.94 mol) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the high-purity acetylene-containing raw material was: acetylene 99.812%, oxygen 0.032%, argon 0.002%, carbon dioxide 0.004%, nitrogen 0.147%, and C3-C4 unsaturated hydrocarbons 0.003% (including 0.0008% propadiene, 0.0009% methylacetylene, 0.0005% vinylacetylene, 0.0005% butadiene, and 0.0003% butadiene).

[0155] The temperature inside the reactor was raised to 12°C, and 45% KOH (6.59 g, 0.053 mol) and phytone (160.91 g, 0.59 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 4 hours. A sample of the reaction solution was taken, and gas chromatography showed that the phytone conversion rate was 98.551%, and the selectivity of the product dehydroisophytol was 98.996%.

[0156] Example 10

[0157] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (600.2 g, 35.24 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, high-purity acetylene-containing raw material (107.3 g, 4.11 mol) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the high-purity acetylene-containing raw material was: acetylene 99.765%, oxygen 0.036%, argon 0.003%, carbon dioxide 0.007%, nitrogen 0.184%, and C3-C4 unsaturated hydrocarbons 0.005% (including 0.0015% propadiene, 0.0016% methylacetylene, 0.0008% vinylacetylene, 0.0006% butadiene, and 0.0005% butadiene).

[0158] The temperature inside the reactor was raised to 10℃, and 45% KOH (3.66 g, 0.029 mol) and dihydro-β-ionone (117.67 g, 0.59 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 3 hours. A sample of the reaction solution was taken, and gas chromatography showed that the conversion rate of dihydro-β-ionone was 99.112%, and the selectivity of the product 3-methyl-5-(2,6,6-trimethylcyclohexyl-1-enyl)pent-1-yn-3-ol was 99.031%.

[0159] Comparative Example 1

[0160] 2 MPaG of nitrogen gas was added to a 2L high-pressure reactor and maintained at pressure for 20 min. Then, the reactor was purged three times with 0.5 MPaG of ammonia gas. The temperature was lowered to -30℃, and liquid ammonia (600.2 g, 35.24 mol) was added, followed by stirring. Once the internal temperature dropped to -30℃, low-purity acetylene-containing feedstock (118.1 g, 4.41 mol acetylene) was added to the reactor and dissolved in the liquid ammonia under continuous stirring. The molar composition of the low-purity acetylene-containing feedstock was: acetylene 97.355%, oxygen 0.321%, argon 0.055%, carbon dioxide 0.531%, nitrogen 1.211%, and C3-C4 unsaturated hydrocarbons 0.527% (of which, propadiene 0.137%, methylacetylene 0.251%, vinylacetylene 0.061%, butadiene 0.029%, and butadiene 0.049%).

[0161] The temperature inside the reactor was raised to 15°C, and 45% KOH (3.66 g, 0.029 mol) and acetone (85.72 g, 1.47 mol) were added sequentially using a horizontal pump. After the addition was complete, the reaction was maintained at this temperature for 4 hours. A sample of the reaction solution was taken, and gas chromatography showed that the acetone conversion rate was 98.311%, and the selectivity of the product 2-methyl-3-butyn-2-ol was 97.053%.

[0162] The composition and performance of the examples and comparative examples are summarized in Table 1.

[0163] Table 1 Summary of composition and performance of the examples and comparative examples

[0164]

[0165] As shown in Table 1, Examples 1-9, using acetylene-containing feedstocks with defined compositions and reacting with different ketones, all achieved high ketone conversion rates (≥98.5%) and high alkynol selectivity (≥98%). Meanwhile, as shown in Example 1 and Comparative Example 1, when the carbon dioxide content and the content of C3-C4 unsaturated hydrocarbons exceed the defined ranges, even with higher acetylene purity, a significant deterioration in ketone conversion rate and alkynol selectivity occurs.

[0166] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0167] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A method for preparing alkynols via ketethynylation, characterized in that, Includes the following steps: The reaction of acetylene-containing raw material and ketone in the presence of liquid ammonia and alkali produces alkynol; The acetylene-containing raw material comprises, by mole percentage: 97 mol%-99.9 mol% acetylene, 0.002 mol%-0.51 mol% carbon dioxide, 0.001 mol%-0.5 mol% C3-C4 unsaturated hydrocarbons, and 0.005 mol%-2 mol% non-reactive gases; the non-reactive gases include at least one of oxygen, argon, and nitrogen.

2. The method for preparing alkynols by ketethynylation reaction as described in claim 1, characterized in that, The C3-C4 unsaturated hydrocarbons include at least one of propadiene, methylacetylene, vinylacetylene, butadiene, and butadiene.

3. The method for preparing alkynols by ketethynylation reaction as described in claim 1 or 2, characterized in that, The acetylene-containing feedstock is prepared by a partial oxidation process of natural gas.

4. The method for preparing alkynols by ketethynylation reaction as described in claim 1 or 2, characterized in that, In the acetylene-containing raw material, the total content of oxygen and argon is ≤0.5 mol%; And / or, in the acetylene-containing raw material, the nitrogen content is ≤1.5 mol.

5. The method for preparing alkynols by ketethynylation reaction as described in claim 1 or 2, characterized in that, The acetylene-containing raw material comprises, by molar percentage: 99 mol%-99.9 mol% acetylene, 0.002 mol%-0.01 mol% carbon dioxide, 0.001 mol%-0.5 mol% C3-C4 unsaturated hydrocarbons, and 0.005 mol%-2 mol% non-reactive gases.

6. The method for preparing alkynols by ketethynylation reaction as described in claim 1 or 2, characterized in that, The structural formula of the ketone is shown in Formula I: Formula I; Among them, R 1 and R 2 Each is independently selected from C1-C16 alkyl, C2-C16 alkenyl, C4-C16 dienyl, C3-C16 cycloalkyl, or C3-C16 cycloalkenyl; Optional, R 1 Selected from C1-C16 alkyl, C2-C16 alkenyl, C4-C16 dienyl, or C3-C16 cycloalkenyl; R 2 It is a C1-C16 alkyl group; Optionally, the ketone has 3-18 carbon atoms; Optionally, the ketone includes at least one of acetone, 2-butanone, 6-methyl-5-hepten-2-one, 6-methyl-5-octen-2-one, geranylacetone, hexahydro-pseudo-ionone, phytone, and dihydro-β-ionone.

7. The method for preparing alkynols by ketethynylation reaction as described in claim 6, characterized in that, The structural formula of the alkynol is shown in Formula II: Formula II; Optionally, the alkynol includes at least one selected from 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, dehydrolinalool, dehydroethyllinalool, dehydronerol, 3,7,11-trimethyldodecyn-3-ol, dehydroisophytol, and 3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)pent-1-yn-3-ol.

8. The method for preparing alkynols by ketethynylation reaction as described in claim 1 or 2, characterized in that, The alkali includes at least one of potassium hydroxide, sodium hydroxide, and cesium hydroxide; Optionally, the base includes potassium hydroxide; Optionally, the alkali is an aqueous solution of alkali; Optionally, the mass concentration of the aqueous solution of the alkali is 45wt%-50wt%.

9. The method for preparing alkynols by ketethynylation reaction as described in claim 1 or 2, characterized in that, It meets one or more of the following characteristics: (1) The molar ratio of the ketone to the base is 1:(0.01-0.12), or optionally 1:(0.02-0.09). (2) The molar ratio of the ketone to the acetylene in the acetylene-containing raw material is 1:(2.1-7), or optionally 1:(2.5-5); (3) The molar ratio of the ketone to the liquid ammonia is 1:(10-60), or optionally 1:(18-40).

10. The method for preparing alkynols by ketethynylation reaction as described in claim 1 or 2, characterized in that, The reaction temperature is 0℃-30℃, and can be selected as 5℃-15℃; And / or, the reaction time is 2h-10h, optionally 4h-6h.

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