Preparation method of higher carbon alcohol

Abstract

The present invention provides a method for preparing higher alcohols. The method includes hydrogenating a higher aldehyde raw material under the action of a Ni / Al2O3 catalyst to obtain a higher alcohol; wherein, by weight percentage, the higher aldehyde raw material includes the following components of C6~C14: 0.3~10% of α-olefins, 3~8% of β-olefins, 0~60% of alkanes, 20~60% of normal aldehydes, 10~25% of isomeric aldehydes, and the rest are enols. The method of the present invention has high catalyst activity, low cost, good selectivity, mild catalyst reaction conditions, no other by-products, environmentally friendly reaction process, and high product yield; compared with a multi-stage hydrogenation process, the one-stage hydrogenation process of the present invention does not require other organic solvents during the reaction process, has the advantages of simple operation, low catalyst cost, and high reaction yield; the method has high economic value and broad industrial application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemicals, and in particular to a method for preparing higher carbon alcohols. Background Art

[0002] Higher-carbon alcohols refer to mixtures of monohydric alcohols containing more than 6 carbon atoms. They are the main basic raw materials for the synthesis of surfactants, detergents, plasticizers and many other fine chemicals. Their processed products are widely used in the fields of textiles, papermaking, food, medicine, leather, etc. At present, the global consumption of higher-carbon alcohols is about 15 million tons. With the rapid development of my country's fine chemical industry, the annual average demand for higher-carbon alcohols in the domestic market exceeds one million tons, and is increasing at an average annual rate of 10%. For a long time, the mainstream higher-carbon alcohol production method, namely the process technology of higher-carbon olefin hydroformylation, has been monopolized by foreign countries. The raw materials used in the oil hydrogenation method are expensive and the source is unstable, which has restricted the production of higher-carbon alcohols and its downstream industries.

[0003] Chinese patent CN113717029A discloses a method for preparing higher alcohols from butene oligomers, wherein butene dimers are hydroformylated to obtain higher aldehydes, which are then hydrogenated to produce higher alcohols. The active component of the hydrogenation catalyst is one or more of Ni, Cu, Mg, and Na, the selective additive is one or more of Co, Ca, Sr, or Ba, and the carrier is one or more of ammonia-treated alumina, silica, or diatomaceous earth. The hydrogenation catalyst is prepared by a precipitation deposition method. The hydrogenation reaction temperature is 80-250°C, the reaction pressure is 0.1-10 MPa, and the hydrogen space velocity is 100-20,000 h-1. -1 , aldehyde conversion rate is 96-99%, and alcohol selectivity is 96-99%. In addition, Chinese patent CN110964563A discloses a method for preparing crude mixed alcohol products by refining synthesis gas with multi-stage hydrogenation technology, in which high carbon alcohols are obtained by multi-stage hydrogenation refining of crude Fischer-Tropsch synthesis fractions.

[0004] However, the catalyst composition and preparation process of the above scheme are complex; the hydrogenation reaction temperature and pressure are high, the energy consumption is high, and there are great safety hazards; and the hydrogenation process generally adopts a multi-stage hydrogenation process, which is difficult to operate. Summary of the Invention

[0005] The main purpose of the present invention is to provide a method for preparing higher carbon alcohols to solve the problems in the prior art of complex preparation process of higher carbon alcohols, low aldehyde conversion rate and low selectivity when using higher carbon aldehydes as raw materials.

[0006] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a method for preparing higher carbon alcohols is provided, wherein a high carbon aldehyde raw material is subjected to hydrogenation catalysis under the action of a Ni / Al2O3 catalyst to obtain a higher carbon alcohol; wherein, the high carbon aldehyde raw material includes the following components of C6 to C14, calculated by weight percentage: 0.3 to 10% of α-olefins, 3 to 8% of β-olefins, 0 to 60% of alkanes, 20 to 60% of normal aldehydes, 10 to 25% of isomeric aldehydes, and the rest are enols.

[0007] Furthermore, the high-carbon aldehyde raw material is a product obtained by hydroformylating C5-C13 olefins, or a product obtained by oxidizing C6-C14 alkanes, or a product obtained by hydrogenating fatty acid methyl esters of natural alcohols.

[0008] Furthermore, the reaction temperature of the hydrogenation catalysis is 120-150° C., and the reaction pressure is 2.0-5.0 MPa.

[0009] Furthermore, the feed rate of high carbon aldehyde raw material is 20-50 g / h, and the volume space velocity is 1.25-2.00 h -1 .

[0010] Furthermore, the hydrogen-to-oil ratio of the hydrogenation catalyst is 1:(1-2); preferably, the volume space velocity of hydrogen is 1.50-2.00h -1 .

[0011] Furthermore, the mass ratio of the catalyst to the high-carbon aldehyde raw material is (0.8-2):1; preferably, the catalyst has a four-leaf clover structure, a bulk density of 0.7-0.8 g / mL, a lateral pressure strength of >100 N / cm, and a wear loss of <0.2 wt%.

[0012] Furthermore, the catalyst is synthesized using the following method: nickel nitrate, sodium hydroxide, water glass and ammonia water are mixed for co-precipitation, and then the co-precipitated product is dried at 120-160° C. for 3-6 hours to obtain a synthetic product of the catalyst.

[0013] Furthermore, the catalyst is formed using the following method: step S1: performing a first calcination on the synthetic product of the catalyst to obtain a first calcined product; step S2: mixing pseudo-boehmite and water and stirring for 10 to 30 minutes, then adding concentrated nitric acid and mixing and stirring for 20 to 60 minutes, and standing for 2 to 3 hours to obtain a binder; step S3: kneading the first calcined product, the binder and the sesbania powder for 30 to 60 minutes to form a catalyst precursor; step S4: performing a second calcination on the catalyst precursor to obtain a catalyst.

[0014] Furthermore, the first roasting temperature is 500-600°C and the time is 3-6 hours; and / or the second roasting is a three-stage roasting, including a first-stage roasting, a second-stage roasting and a third-stage roasting performed in sequence; the first-stage roasting temperature is 100-140°C and the time is 5-20 hours; the second-stage roasting temperature is 200-300°C and the time is 3-6 hours; the third-stage roasting temperature is 500-600°C and the time is 3-6 hours.

[0015] Furthermore, before carrying out hydrogenation catalysis, the step of performing a two-stage activation of the catalyst in the catalytic bed is included: the fixed bed temperature of the catalytic bed is raised from 45-55°C to 115-125°C and maintained for 1.5-2.5 hours to perform the first-stage activation; then the temperature is raised to 195-205°C and maintained for 5.5-6.5 hours to perform the second-stage activation; finally, the temperature is lowered to the reaction temperature of hydrogenation catalysis; preferably, the hydrogen flow rate of the two-stage activation is 8-12 L / h, and the hydrogen pressure is 2-4 MPa.

[0016] The technical solution of the present invention uses a C6-C14 high-carbon aldehyde mixture as raw material, uses a specific catalyst, and adopts a one-stage hydrogenation process to achieve high conversion and high selectivity of high-carbon aldehyde hydrogenation to higher-carbon alcohols. The method of the present invention has high catalyst activity, low cost, good selectivity, mild catalyst reaction conditions, no other by-products, an environmentally friendly reaction process, and high product yield. Compared with multi-stage hydrogenation processes, the one-stage hydrogenation process of the present invention does not require additional organic solvents during the reaction process, has the advantages of simple operation, low catalyst cost, and high reaction yield. This method has high economic value and broad prospects for industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0018] Figure 1 Shows the XRD patterns of the catalyst before and after forming and calcining according to Example 1 of the present invention;

[0019] Figure 2 shows a photo of the catalyst after forming and calcining according to Example 1 of the present invention; and

[0020] Figure 3 A flow chart of a hydrogenation catalytic process according to an embodiment of the present invention is shown.

[0021] The above drawings include the following reference numerals:

[0022] 1. Raw material tank; 2. Metering pump; 3. Flow meter; 4. Continuous flow fixed-bed reactor; 5. High-pressure separation tank; 6. Product tank; 7. Back-pressure valve; A. New hydrogen; B. Higher alcohol product; C. Vent; a. Uncalcined catalyst 1; b. Uncalcined catalyst 2; c. Calcined catalyst 1; d. Calcined catalyst 2. DETAILED DESCRIPTION

[0023] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0024] Explanation of terms:

[0025] Hydrogen-to-oil ratio: the ratio of hydrogen feed rate (L / h) to raw material feed rate (g / h).

[0026] As described in the background of the present invention, the prior art has the problems of complex preparation process of higher carbon alcohols, low aldehyde conversion rate and low selectivity when using higher carbon aldehydes as raw materials. In order to solve the above problems, in a typical embodiment of the present invention, a method for preparing higher carbon alcohols is provided, wherein the higher carbon aldehyde raw material is subjected to hydrogenation catalysis under the action of Ni / Al2O3 catalyst to obtain higher carbon alcohols; wherein, the higher carbon aldehyde raw material comprises the following components of C6 to C14, calculated by weight percentage: 0.3 to 10% of α-olefins, 3 to 8% of β-olefins, 0 to 60% of alkanes, 20 to 60% of normal aldehydes, 10 to 25% of isomeric aldehydes, and the rest are enols.

[0027] The present invention uses a C6-C14 mixture containing higher-carbon aldehydes as a raw material, feeds it into a fixed-bed reactor, and conducts a hydrogenation reaction with a hydrogenation catalyst loaded therein. The hydrogenation reaction materials undergo gas-liquid separation to produce higher-carbon alcohol products. The method of the present invention features high catalyst activity, low cost, good selectivity, mild catalytic reaction conditions, the absence of other byproducts, an environmentally friendly reaction process, and high product yield. Compared with multi-stage hydrogenation processes, the one-stage hydrogenation process of the present invention does not require additional organic solvents during the reaction, offering the advantages of simple operation, low catalyst cost, and high reaction yield. This method has high economic value and broad prospects for industrial application. Preferably, the higher-carbon aldehyde raw material comprises the following C11-C14 components, by weight: 0.3-10% α-olefins, 3-8% β-olefins, 0-60% alkanes, 20-60% normal aldehydes, 10-25% isomeric aldehydes, and the remainder enols.

[0028] In a preferred embodiment, the high-carbon aldehyde raw material is a product obtained by hydroformylation of C5-C13 olefins, or a product obtained by oxidation of C6-C14 alkanes, or a product obtained by hydrogenation of fatty acid methyl esters of natural alcohols, preferably a product obtained by hydroformylation of C5-C13 olefins, and more preferably a product obtained by hydroformylation of C10-C13 olefins. The high-carbon aldehyde raw material prepared from the above materials is more suitable for the preparation of high-carbon alcohols using the method of the present invention. The hydroformylation method refers to the process in which carbon monoxide and hydrogen react with C5-C13 olefins in the presence of a catalyst and under pressure to generate a fatty aldehyde having one more carbon atom than the original olefin used. Accordingly, both the alkane oxidation method and the natural alcohol fatty acid methyl ester hydrogenation method use conventional definitions in the art, which are understandable to those skilled in the art and will not be repeated here.

[0029] Preferably, the high carbon aldehyde raw material comprises the following components of C11 to C14 by weight percentage: 0.3 to 6% of α-olefins, 5 to 8% of β-olefins, 27 to 53% of alkanes, 27 to 45% of normal structural aldehydes, and 11 to 23% of isomeric aldehydes. Most preferably, the high carbon aldehyde raw material is a mixture containing high carbon aldehydes synthesized by the hydroformylation method of C10 to C13 olefins, which comprises, by weight percentage, 2.3% of C11 α-olefins, 2.1% of C11 β-olefins, 3.1% of C12 α-olefins, 3.5% of C12 β-olefins, 24.2% of C11 alkanes, 26.4% of C12 alkanes, 12.8% of C12 normal structural aldehydes, 5 0.1% of C12 iso-olefins, 14.3% of C13 normal-olefins, 5.9% of C13 iso-olefins, and 0.3% of C14 normal-olefins; or the high-carbon aldehyde raw material is a mixture containing high-carbon aldehydes synthesized by the hydroformylation of C10-C13 olefins, which includes, by weight percentage, 0.1% of C11α-olefins, 2.6% of C11β-olefins, 0.2% of C12α-olefins, 3.2% of C1 2β-olefins, 12.4% of C11 alkanes, 14.7% of C12 alkanes, 21.2% of C12 normal aldehydes, 10.1% of C12 isoaldehydes, 23.4% of C13 normal aldehydes, 12.0% of C13 isoaldehydes, and 0.1% of C14 normal aldehydes; or a mixture containing high-carbon aldehydes synthesized by hydroformylation of C10-C13 olefins, calculated by weight percentage, comprising Including 0.1% C11α-olefins, 3.7% C11β-olefins, 0.2% C12α-olefins, 4.3% C12β-olefins, 26.8% C11 alkanes, 26.0% C12 alkanes, 13.6% C12 normal aldehydes, 5.8% C12 isoaldehydes, 13.8% C13 normal aldehydes, 5.6% C13 isoaldehydes, and 0.1% C14 normal aldehydes.

[0030] In order to further improve the feedstock conversion rate and catalyst selectivity of the hydrogenation catalytic reaction, in a preferred embodiment, the reaction temperature of the hydrogenation catalytic reaction is 120-150° C., and the reaction pressure is 2.0-5.0 MPa.

[0031] Based on similar reasons, in a preferred embodiment, the feed rate of the high carbon aldehyde raw material is 20-50 g / h, and the volume space velocity is 1.25-2.00 h -1 .

[0032] In order to further reduce the amount of hydrogen used while fully hydrogenating the high-carbon aldehyde raw material, thereby better reducing costs, in a preferred embodiment, the hydrogen-to-oil ratio of the hydrogenation catalyst is 1:(1-2); preferably, the volume space velocity of hydrogen is 1.50-2.00h -1 .

[0033] Based on similar reasons, in a preferred embodiment, the mass ratio of the catalyst to the high-carbon aldehyde raw material is (0.8~2):1, which can further reduce the cost of catalyst use; preferably, the catalyst has a four-leaf clover structure, a bulk density of 0.7~0.8g / mL, a lateral pressure strength of >100N / cm, and an abrasion of <0.2wt%. Under the above conditions, the catalyst has higher activity and is more suitable for the high-carbon aldehyde hydrogenation catalytic reaction of the present invention.

[0034] In a preferred embodiment, the catalyst is synthesized using the following method: nickel nitrate, sodium hydroxide, water glass and ammonia water are mixed for co-precipitation, and then the co-precipitated product is dried at 120-160° C. for 3-6 hours to obtain a synthetic product of the catalyst. Under the above conditions, the distribution of each component can be more uniform, and the dispersion and uniformity of nickel are more ideal.

[0035] In a preferred embodiment, the catalyst is formed using the following method: Step S1: performing a first calcination on the synthesized product of the catalyst to obtain a first calcined product; Step S2: mixing pseudo-boehmite and water and stirring for 10 to 30 minutes, then adding concentrated nitric acid and stirring for 20 to 60 minutes, and allowing to stand for 2 to 3 hours to obtain a binder; Step S3: kneading the first calcined product, the binder, and sesbania powder for 30 to 60 minutes to obtain a catalyst precursor; Step S4: performing a second calcination on the catalyst precursor to obtain the catalyst. These conditions can better disperse the components and promote better catalyst formation.

[0036] In order to further eliminate impurities such as moisture, organic matter, oxides, etc. in the catalyst, increase its pore structure, improve the thermal stability and pressure resistance of the catalyst, improve the impregnation and dispersion of the active substance, increase the specific surface area of the catalyst, and improve the reaction activity of the catalyst, in a preferred embodiment, the temperature of the first calcination is 500-600°C and the time is 3-6 hours; and / or the second calcination is a three-stage calcination, including a first-stage calcination, a second-stage calcination and a third-stage calcination performed in sequence; the temperature of the first stage calcination is 100-140°C and the time is 5-20 hours; the temperature of the second stage calcination is 200-300°C and the time is 3-6 hours; the temperature of the third stage calcination is 500-600°C and the time is 3-6 hours.

[0037] In a preferred embodiment, prior to the hydrogenation catalytic reaction, the catalyst is subjected to a two-stage activation step in the catalyst bed: the fixed bed temperature of the catalyst bed is raised from 45-55°C to 115-125°C and maintained for 1.5-2.5 hours for the first stage of activation; the temperature is then raised to 195-205°C and maintained for 5.5-6.5 hours for the second stage of activation; and the temperature is finally lowered to the reaction temperature for the hydrogenation catalytic reaction. Preferably, the hydrogen flow rate for the two-stage activation is 8-12 L / h and the hydrogen pressure is 2-4 MPa. Under these conditions, the catalytic activity of the catalyst can be further improved, thereby improving the conversion rate and selectivity of the reaction.

[0038] Typically, but not limitatively, the reaction temperature of the hydrogenation catalysis is 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C or a range consisting of any two of them, and the reaction pressure is 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa, 4.5 MPa, 5.0 MPa or a range consisting of any two of them.

[0039] Typically, but not limited to, the feed rate of the high carbon aldehyde raw material is 20 g / h, 25 g / h, 30 g / h, 35 g / h, 40 g / h, 45 g / h, 50 g / h or a range consisting of any two of them, and the volume space velocity is 1.25 h -1 , 1.3h -1 , 1.4h -1 , 1.5h -1 , 1.6h -1 , 1.7h -1 , 1.8h -1 , 1.9h -1 , 2.00h -1 Or a range of values consisting of any two of them.

[0040] Typically, but not limited to, the hydrogen-to-oil ratio of the hydrogenation catalyst is 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, or a range consisting of any two of them; the volumetric space velocity of hydrogen is 1.50h -1 , 1.6h -1 , 1.7h -1 , 1.8h -1 , 1.9h -1 , 2.00h -1 Or a range of values consisting of any two of them.

[0041] Typically, but not limitatively, the mass ratio of the catalyst to the high-carbon aldehyde raw material is 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1 or a range consisting of any two of these values.

[0042] Typically but not limitatively, during the catalyst forming process, the temperature of the first calcination is 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C or a range consisting of any two of them, and the time is 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h or a range consisting of any two of them.

[0043] Typically, but not limiting, the second calcination is a three-stage calcination, the temperature of the first stage calcination is 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C or a range of values consisting of any two of them, and the time is 5h, 8h, 10h, 12h, 15h, 18h, 20h or a range of values consisting of any two of them; the temperature of the second stage calcination is 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, The temperature of the three-stage roasting is 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃ or the range consisting of any two of them, and the time is 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h or the range consisting of any two of them.

[0044] The present application is further described in detail below with reference to specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0045] Unless otherwise specified, the liquid-phase hydrogenation of higher carbon aldehydes to higher carbon alcohols in the following examples was carried out on a 20-30 mL continuous flow fixed bed, and no other organic solvent was required during the reaction. The raw materials and products of the reaction in this application were qualitatively and quantitatively analyzed using a GCAgilent 7890B gas chromatograph.

[0046] Example 1

[0047] High carbon aldehyde raw materials: The mixture containing high-carbon aldehydes synthesized by the hydroformylation method of C10-C13 olefins includes, by weight percentage, 2.3% of C11α-olefins, 2.1% of C11β-olefins, 3.1% of C12α-olefins, 3.5% of C12β-olefins, 24.2% of C11 alkanes, 26.4% of C12 alkanes, 12.8% of C12 normal aldehydes, 5.1% of C12 isoaldehydes, 14.3% of C13 normal aldehydes, 5.9% of C13 isoaldehydes, and 0.3% of C14 normal aldehydes.

[0048] Catalyst synthesis: Nickel nitrate, sodium hydroxide, water glass and ammonia water are mixed for co-precipitation, and then the co-precipitated product is dried at 140° C. for 5 hours to obtain a synthetic product of the catalyst.

[0049] Catalyst molding:

[0050] Step S1, heating the synthesized product of the catalyst to 550° C. and calcining for 5 hours to obtain a first calcined product;

[0051] Step S2: Pseudo-boehmite and water were mixed and stirred for 20 minutes, and then concentrated nitric acid was added and mixed and stirred for 40 minutes, and allowed to stand for 2.5 hours to obtain an adhesive;

[0052] Step S3: kneading the first calcined product, the binder and the sesbania powder for 50 minutes to form a catalyst precursor;

[0053] Step S4: The catalyst precursor was calcined in three stages: first at 120°C for 12 hours, then at 250°C for 5 hours, and finally at 550°C for 5 hours, to obtain a shaped Ni / Al2O3 catalyst. The catalyst had a diameter of 1.8 × 1.6 mm, a four-leaf clover structure, a bulk density of 0.75 g / mL, a lateral compressive strength of 118 N / cm3, and an abrasion loss of <0.2 wt%.

[0054] Catalyst activation: 20 mL of the formed Ni / Al2O3 catalyst was filled into a 20 mL continuous flow fixed bed with a hydrogen flow rate of 10 L / h and a hydrogen pressure of 3 MPa. The fixed bed temperature was raised from 50°C to 120°C and maintained for 2 h; then raised to 200°C and maintained for 5 h; and finally cooled to 140°C.

[0055] Hydrogenation catalysis: The high-carbon aldehyde feedstock is fed into a continuous flow fixed bed and hydrogenated over an activated Ni / Al2O3 catalyst to produce high-carbon alcohols. The hydrogenation reaction temperature is 140°C, the reaction pressure is 3 MPa, the feed rate is 20 g / h, the hydrogen-to-oil ratio is 1:1, and the mass ratio of catalyst to high-carbon aldehyde feedstock is 1:1.

[0056] Examples 2 to 5

[0057] The difference from Example 1 is that the reaction temperature of the hydrogenation catalysis is different, see Tables 1 and 2 for details.

[0058] Examples 6 to 9

[0059] The difference from Example 1 is that the reaction pressure of the hydrogenation catalysis is different, see Tables 1 and 2 for details.

[0060] Examples 10 to 11

[0061] The difference from Example 1 is that the feed amount of raw materials for hydrogenation catalysis is different, see Tables 1 and 2 for details.

[0062] Examples 12 to 16

[0063] The difference from Example 1 is that 30 mL of the molded Ni / Al2O3 catalyst was filled into a 30 mL continuous flow fixed bed for activation and hydrogenation catalysis; the feed amount of raw materials for hydrogenation catalysis was different; see Tables 1 and 2 for details.

[0064] Example 17

[0065] High carbon aldehyde raw materials: The invention relates to a mixture containing high-carbon aldehydes synthesized by the hydroformylation method of C10-C13 olefins, which comprises, by weight percentage, 0.1% of C11α-olefins, 2.6% of C11β-olefins, 0.2% of C12α-olefins, 3.2% of C12β-olefins, 12.4% of C11 alkanes, 14.7% of C12 alkanes, 21.2% of C12 normal aldehydes, 10.1% of C12 isoaldehydes, 23.4% of C13 normal aldehydes, 12.0% of C13 isoaldehydes, and 0.1% of C14 normal aldehydes.

[0066] Catalyst synthesis: Nickel nitrate, sodium hydroxide, water glass and ammonia water are mixed for co-precipitation, and then the co-precipitated product is dried at 120° C. for 6 hours to obtain a synthetic product of the catalyst.

[0067] Catalyst molding:

[0068] Step S1, heating the synthesized product of the catalyst to 500° C. and calcining for 6 hours to obtain a first calcined product;

[0069] Step S2: Pseudo-boehmite and water were mixed and stirred for 10 minutes, and then concentrated nitric acid was added and mixed and stirred for 20 minutes, and the mixture was allowed to stand for 2.5 hours to obtain an adhesive;

[0070] Step S3: kneading the first calcined product, the binder and the sesbania powder for 30 minutes to form a catalyst precursor;

[0071] Step S4: The catalyst precursor was calcined in three stages: first at 100°C for 20 hours, then at 200°C for 6 hours, and finally at 500°C for 6 hours, to obtain a shaped Ni / Al2O3 catalyst. The catalyst had a diameter of 1.8 × 1.6 mm, a four-leaf clover structure, a bulk density of 0.8 g / mL, a lateral compressive strength of 109 N / cm3, and an abrasion loss of <0.2 wt%.

[0072] Catalyst activation: 20 mL of the formed Ni / Al2O3 catalyst was filled into a 20 mL continuous flow fixed bed with a hydrogen flow rate of 8 L / h and a hydrogen pressure of 2 MPa. The fixed bed temperature was raised from 45°C to 115°C and maintained for 2.5 h; then raised to 195°C and maintained for 6.5 h; and finally cooled to 140°C.

[0073] Hydrogenation catalysis: The high-carbon aldehyde feedstock is fed into a continuous flow fixed bed and hydrogenated over an activated Ni / Al2O3 catalyst to produce high-carbon alcohols. The hydrogenation reaction temperature is 140°C, the reaction pressure is 3 MPa, the feed rate is 20 g / h, the hydrogen-to-oil ratio is 1:1, and the mass ratio of catalyst to high-carbon aldehyde feedstock is 0.8:1.

[0074] Example 18

[0075] High carbon aldehyde raw materials: The mixture containing high-carbon aldehydes synthesized by the hydroformylation method of C10-C13 olefins includes, by weight percentage, 0.1% of C11α-olefins, 3.7% of C11β-olefins, 0.2% of C12α-olefins, 4.3% of C12β-olefins, 26.8% of C11 alkanes, 26.0% of C12 alkanes, 13.6% of C12 normal aldehydes, 5.8% of C12 isoaldehydes, 13.8% of C13 normal aldehydes, 5.6% of C13 isoaldehydes, and 0.1% of C14 normal aldehydes.

[0076] Catalyst synthesis: Nickel nitrate, sodium hydroxide, water glass and ammonia water are mixed for co-precipitation, and then the co-precipitated product is dried at 160° C. for 3 hours to obtain a synthetic product of the catalyst.

[0077] Catalyst molding:

[0078] Step S1, heating the synthesized product of the catalyst to 600° C. and calcining for 3 hours to obtain a first calcined product;

[0079] Step S2: Pseudo-boehmite and water were mixed and stirred for 30 minutes, and then concentrated nitric acid was added and mixed and stirred for 60 minutes, and allowed to stand for 2.5 hours to obtain an adhesive;

[0080] Step S3: kneading the first calcined product, the binder and the sesbania powder for 60 minutes to form a catalyst precursor;

[0081] Step S4: The catalyst precursor was calcined in three stages: first at 140°C for 5 hours, then at 300°C for 3 hours, and finally at 600°C for 3 hours, to obtain a shaped Ni / Al2O3 catalyst. The catalyst had a diameter of 1.8 × 1.6 mm, a four-leaf clover structure, a bulk density of 0.73 g / mL, a lateral compressive strength of 136 N / cm3, and an attrition loss of <0.2 wt%.

[0082] Catalyst activation: 20 mL of the formed Ni / Al2O3 catalyst was filled into a 20 mL continuous flow fixed bed with a hydrogen flow rate of 12 L / h and a hydrogen pressure of 4 MPa. The fixed bed temperature was raised from 55°C to 125°C and maintained for 1.5 h; then raised to 205°C and maintained for 5.5 h; and finally cooled to 140°C.

[0083] Hydrogenation catalysis: The high-carbon aldehyde feedstock is fed into a continuous flow fixed bed and hydrogenated over an activated Ni / Al2O3 catalyst to produce high-carbon alcohols. The hydrogenation reaction temperature is 140°C, the reaction pressure is 3 MPa, the feed rate is 20 g / h, the hydrogen-to-oil ratio is 1:2, and the mass ratio of catalyst to high-carbon aldehyde feedstock is 2:1.

[0084] The results of the raw material conversion rate of the above examples are shown in Table 1, the product selectivity results are shown in Table 2, and the properties of higher alcohols are shown in Table 3; among them, alkanes do not react and the content of C14 normal structural aldehyde is too low and is not listed. The XRD patterns of the catalyst before and after forming and calcining of Example 1 are shown in Figure 1 In Example 1, two catalysts were prepared in parallel, namely Catalyst 1 and Catalyst 2. The data in Tables 1 to 3 are all for Catalyst 1. Figure 1 a is uncalcined catalyst 1, b is uncalcined catalyst 2, c is calcined catalyst 1, d is calcined catalyst 2; the photo of the shaped calcined catalyst 1 (1.8×1.6 mm) of Example 1 is shown in Figure 2 ; The hydrogenation catalytic process flow chart of the above embodiment is as follows Figure 3As shown, the feed amount of high-carbon aldehyde raw material in the raw material tank 1 is controlled by the metering pump 2, and the intake amount of new hydrogen A is controlled by the flow meter 3. The high-carbon aldehyde raw material and new hydrogen A are sent to the continuous flow fixed bed reactor 4 containing the catalyst for hydrogenation catalytic reaction. The hydrogenation product first enters the high-pressure separation tank 5 for gas-liquid separation, and the liquid product enters the product tank 6 to obtain the high-carbon alcohol product B, and the gas is discharged through the back pressure valve 7.

[0085] Table 1

[0086]

[0087]

[0088] Table 2

[0089]

[0090]

[0091] Table 3

[0092] project Superior product standard (GBT 26463-2011) Example 1 Color ≤10 8.5 Moisture ug / g ＜800 794.425 Carbonyl value ug / g ＜60 54 Acid value mg / g ＜0.03 0.022 Saponification value mg / g ＜0.5 0.32 Iodine value g / 100g ＜0.3 0.25 Hydroxyl value mg / g 290±5 288.19 hydrocarbon% ＜0.4 0.2 Average relative molecular mass 193±3 194.07 Normal structure rate% ＞71 76

[0093] As can be seen from the above, each embodiment of the present invention uses a C6~C14 high carbon aldehyde mixture as a raw material, uses a specific catalyst, and adopts a one-stage hydrogenation process to achieve high conversion and high selectivity of high carbon aldehyde hydrogenation to high carbon alcohols. The method of the present invention has high catalyst activity, low cost, good selectivity, mild catalyst reaction conditions, no other by-products, environmentally friendly reaction process, and high product yield. Compared with the multi-stage hydrogenation process, the one-stage hydrogenation process of the present invention does not require other organic solvents during the reaction process, has the advantages of simple operation, low catalyst cost, and high reaction yield. The method has high economic value and broad prospects for industrial application. In addition, it can be seen that when each process parameter is within the preferred range of the present invention, the preparation effect is better.

[0094] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for preparing higher alcohols, characterized in that: The high carbon aldehyde raw material is subjected to hydrogenation catalysis under the action of Ni / Al2O3 catalyst to obtain the high carbon alcohol; Wherein, the high carbon aldehyde raw material comprises the following components of C6~C14 by weight percentage: 0.3~10% of α-olefins, 3~8% of β-olefins, 0~60% of alkanes, 20~60% of normal aldehydes, 10~25% of isomeric aldehydes, and the rest are enols; The catalyst is synthesized by the following method: nickel nitrate, sodium hydroxide, water glass and ammonia water are mixed for co-precipitation, and then the co-precipitated product is dried at 120-160° C. for 3-6 hours to obtain a synthetic product of the catalyst; The catalyst is formed using the following method: Step S1: performing a first calcination on the synthesized product of the catalyst to obtain a first calcined product; Step S2: Pseudo-boehmite and water are mixed and stirred for 10-30 minutes, and then concentrated nitric acid is added and mixed and stirred for 20-60 minutes, and allowed to stand for 2-3 hours to obtain an adhesive; Step S3: kneading the first calcined product, the binder and the sesbania powder for 30 to 60 minutes to form a catalyst precursor; Step S4: performing a second calcination on the catalyst precursor to obtain the catalyst; Before carrying out the hydrogenation catalysis, the method further comprises the step of performing a double-stage activation of the catalyst in a catalytic bed.

2. The preparation method according to claim 1, characterized in that The high-carbon aldehyde raw material is a product obtained by hydroformylating C5-C13 olefins, or a product obtained by oxidizing C6-C14 alkanes, or a product obtained by hydrogenating natural alcohols using fatty acid methyl esters.

3. The preparation method according to claim 1 or 2, characterized in that The reaction temperature of the hydrogenation catalysis is 120-150° C., and the reaction pressure is 2.0-5.0 MPa.

4. The preparation method according to claim 1 or 2, characterized in that The feed rate of the high carbon aldehyde raw material is 20~50g / h, and the volume space velocity is 1.25~2.00h -1 .

5. The preparation method according to claim 1 or 2, characterized in that The hydrogen-to-oil ratio of the hydrogenation catalyst is 1:(1~2).

6. The preparation method according to claim 5, characterized in that The volume space velocity of hydrogen in the hydrogenation catalysis is 1.50~2.00h -1 .

7. The preparation method according to claim 1 or 2, characterized in that The mass ratio of the catalyst to the high-carbon aldehyde raw material is (0.8~2):

1.

8. The preparation method according to claim 7, characterized in that The catalyst has a four-leaf clover structure, a bulk density of 0.7-0.8 g / mL, a lateral pressure strength of more than 100 N / cm, and an abrasion loss of less than 0.2 wt%.

9. The preparation method according to claim 1, characterized in that The first calcination temperature is 500-600° C. and the time is 3-6 hours; and / or The second roasting is a three-stage roasting, including a first-stage roasting, a second-stage roasting and a third-stage roasting performed in sequence; the temperature of the first-stage roasting is 100-140°C and the time is 5-20 hours; the temperature of the second-stage roasting is 200-300°C and the time is 3-6 hours; the temperature of the third-stage roasting is 500-600°C and the time is 3-6 hours.

10. The preparation method according to claim 1 or 2, characterized in that: The two-stage activation step includes: raising the fixed bed temperature of the catalytic bed from 45-55°C to 115-125°C and maintaining it for 1.5-2.5 hours to perform the first-stage activation; then raising the temperature to 195-205°C and maintaining it for 5.5-6.5 hours to perform the second-stage activation; and finally cooling it to the reaction temperature of the hydrogenation catalysis.

11. The preparation method according to claim 10, characterized in that: The hydrogen flow rate of the double-stage activation is 8-12 L / h, and the hydrogen pressure is 2-4 MPa.

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