A catalyst for catalytically recombining and cracking butanol and octanol residual liquid and a preparation method thereof

Abstract

The present invention relates to a catalyst for catalytically cracking and splitting the residual liquid of butanol and octanol and a preparation method thereof. The catalyst comprises a catalyst carrier, a catalyst active center and a promoter. The catalyst active center is titanium oxide, and the promoter is one or more of iron, cobalt, nickel, manganese, copper, molybdenum, tungsten, tin and their oxides. The catalyst carrier is one or more of alumina, silica, magnesium-aluminum hydrotalcite, hydroxyapatite, Y-type molecular sieve, A-type molecular sieve, ZSM-5, Beta-molecular sieve, coconut shell charcoal, XC-72R, XC-72. The catalyst of the present invention has good catalytic effect on the cracking and splitting of the residual liquid of butanol and octanol and a long service life, and can be used for the continuous flow catalytic cracking reaction of the heavy components of the residual liquid of butanol and octanol, realizing the large-scale continuous cracking treatment of the heavy components of the residual liquid of butanol and octanol, which will significantly reduce the cracking cost of the heavy components of the residual liquid of butanol and octanol and improve the economic benefits of the heavy components of the residual liquid of butanol and octanol.

Description

Technical Field

[0001] The invention belongs to the technical field of cracking catalysts, and in particular relates to a catalyst for catalyzing the recombination and cracking decomposition of butanol residue and a preparation method thereof. Background Art

[0002] Butyl octanol is an important organic chemical raw material, mainly including butanol and octanol. Butyl octanol is widely used in industry. It can be used as a solvent for fatty acids, resins, paints, cosmetics, etc. Butyl octanol is also an important raw material for the synthesis of fine chemical products, mainly used in the production of plasticizers. Butyl octanol can also be used to produce other chemicals such as butyl acetate and butyl methacrylate.

[0003] The main production process of butyl octanol is carbonyl synthesis. During the production, a part of waste liquid will be discharged, which is called butyl octanol residue, accounting for about 6% to 10% of the total output of butyl octanol products. The components of butyl octanol residue are complex, and contain a large number of valuable components. If it is discharged directly, it will not only cause waste of resources but also pollute the environment. In the past, it was mostly used as fuel. However, with the development of industrialization and the increasing market demand for butyl octanol year by year, the output of butyl octanol residue has also increased accordingly, and the economic efficiency of using it directly as fuel is poor. At present, various production enterprises use the different boiling points of the components in the butyl octanol residue to choose to use the multi-tower distillation method to separate the C4~C8 light components in the residue, such as butyraldehyde, butanol, C5~C7 components, octanol, octenal, etc., for recycling. The remaining heavy components account for about 40% of the total amount of butyl octanol residue, containing more aldehyde condensation products (including acetal, cyclic acetal, etc.) and long carbon chain esters, which are difficult to handle.

[0004] The heavy components of the butanol residue can be cracked to obtain light components such as C4 and C8 with utilization value, and then returned to the fractionation unit for recovery and separation, thereby further improving the economic benefits of the butanol residue. The existing cracking of the heavy components of the butanol residue mainly includes thermal cracking reaction and catalyst catalytic reaction. The former has high energy consumption and produces a large amount of wastewater, while the latter is more popular because it is easy to separate, renewable and basically does not produce wastewater. At present, the catalysts that are considered to be able to catalyze the recombination and splitting of the butanol residue include molecular sieve catalysts, such as HZSM-5, HY, MCM-41, and metal oxide catalysts, such as active metal oxides such as alumina. The existing TiO2 catalyst prepared by the Sol-gel method has a good effect on catalyzing the recombination and splitting of the butanol residue. In the initial use, it can make the sum of the C4 and C8 substance contents in the catalytic cracking reaction liquid reach about 40% of the total mass of the reaction liquid, but the activity of the TiO2 catalyst decreases significantly after repeated use, and the service life is short. Summary of the invention

[0005] The object of the present invention is to provide a solid catalyst with good catalytic effect, good stability and long service life for catalytic recombination and cracking of butanol and octanol residual liquid, and a preparation method thereof.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] A catalyst for catalytic recombination and cracking of butanol and octanol residual liquid, which comprises a catalyst carrier, a catalyst active center loaded on the catalyst carrier and a promoter.

[0008] Specifically, the catalyst active center is titanium oxide.

[0009] Specifically, the promoter is one or more of iron, cobalt, nickel, manganese, copper, molybdenum, tungsten, tin and their oxides.

[0010] Specifically, the catalyst carrier is one or more of alumina, silica, magnesium aluminum hydrotalcite, hydroxyapatite, Y-type molecular sieve, A-type molecular sieve, ZSM-5, Beta-molecular sieve, coconut shell charcoal, XC-72R, XC-72.

[0011] Specifically, the mass of the titanium oxide is 1% - 45% of the total mass of the catalyst, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%.

[0012] Specifically, the mass of the promoter is 0.01% - 8% of the total mass of the catalyst, such as 0.01%, 0.05%, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%.

[0013] Specifically, the specific surface area of the catalyst is 95 - 120m 2 / g, further preferably 95 - 110m 2 / g, and still further preferably 95 - 105m 2 / g.

[0014] Furthermore, the mass of the titanium oxide is 8% - 25% of the total mass of the catalyst.

[0015] Furthermore, the mass of the titanium oxide is 10% - 20% of the total mass of the catalyst.

[0016] Further, the mass of the promoter is 0.5% - 5% of the total mass of the catalyst.

[0017] Furthermore, the mass of the promoter is 2% - 5% of the total mass of the catalyst.

[0018] Further, the catalyst carrier is activated alumina pellets and / or activated silica pellets.

[0019] Further, the particle size of the catalyst carrier is 0.3 - 3 mm.

[0020] According to some specific embodiments of the present invention, the catalyst carrier is activated alumina pellets with a particle size of 0.3 - 3 mm or activated silica pellets with a particle size of 0.3 - 3 mm.

[0021] Further, the promoter is one or more of iron oxide, nickel oxide, or copper oxide.

[0022] According to some specific embodiments of the present invention, the promoter is iron oxide or the promoter is nickel oxide and copper oxide.

[0023] The present invention also provides a method for preparing the above catalyst for catalytic recombination and cracking of butanol and octanol residues, and the preparation method includes the following steps:

[0024] (1) Impregnate the catalyst carrier with a promoter precursor solution, dry it, and calcine it at 400 - 500 °C to obtain a carrier material loaded with the promoter;

[0025] (2) Mix the catalyst active center precursor with a first solvent and then impregnate the carrier material loaded with the promoter, and dry to obtain a catalyst precursor;

[0026] (3) Heat-treat the catalyst precursor in a second solvent at 80 - 250 °C, wash it with water, and dry to obtain a catalyst intermediate;

[0027] (4) Calcinate the catalyst intermediate at 150 - 500 °C to obtain the catalyst,

[0028] wherein the catalyst active center precursor is one or more of isopropyl titanate, tetrabutyl titanate, or titanium tetrachloride,

[0029] The promoter precursor is one or more of iron nitrate, iron acetate, iron sulfate, iron chloride, iron acetylacetonate complex, cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt chloride, cobalt acetylacetonate complex, nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, nickel acetylacetonate complex, manganese nitrate, manganese acetate, manganese sulfate, manganese chloride, manganese acetylacetonate complex, copper nitrate, copper acetate, copper sulfate, copper chloride, copper acetylacetonate complex, molybdenum nitrate, molybdenum acetate, molybdenum sulfate, molybdenum chloride, molybdenum acetylacetonate complex, tungsten nitrate, tungsten acetate, tungsten sulfate, tungsten chloride, tungsten acetylacetonate complex, tin nitrate, tin acetate, tin sulfate, tin chloride, tin acetylacetonate complex.

[0030] In the embodiment of the present invention, the feeding mass of the catalyst support is 0.8 to 2 times the sum of the feeding masses of the promoter precursor and the catalyst active center precursor.

[0031] In the embodiment of the present invention, the feeding molar ratio of the catalyst active center precursor to the promoter precursor is (3 to 15):1.

[0032] Further, the feeding molar ratio of the catalyst active center precursor to the promoter precursor is (8 to 15):1.

[0033] Still further, the feeding molar ratio of the catalyst active center precursor to the promoter precursor is (10 to 15):1.

[0034] In the embodiment of the present invention, the first solvent is ethanol and / or toluene.

[0035] In the embodiment of the present invention, the solvent of the promoter precursor solution is water.

[0036] Specifically, the second solvent is one or more of water, ethanol, methanol, butanol, isopropanol, toluene, N,N-dimethylformamide.

[0037] In the embodiment of the present invention, the second solvent is a mixed solvent of one or more of ethanol, methanol, butanol, isopropanol and water.

[0038] In the embodiment of the present invention, the drying temperatures in the step (1), step (2) and step (3) are independently 100 to 150 °C, such as 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C.

[0039] In the embodiment of the present invention, the impregnation in the step (1) and step (2) respectively adopts equal-volume impregnation. Preferably, the number of impregnation times in the step (2) is 2 times.

[0040] In the embodiments of the present invention, the temperature of the heat treatment in step (3) is 160-220°C, such as 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C.

[0041] Specifically, the time of the heat treatment in step (3) is 1-48 h, further preferably 15-40 h, still further preferably 15-30 h, and even more preferably 20-28 h.

[0042] In the embodiments of the present invention, the time of the heat treatment in step (3) is 20-25 h.

[0043] In the embodiments of the present invention, the temperature of the roasting in step (4) is 150-250°C.

[0044] Specifically, the time of the roasting in step (4) is 1-24 h.

[0045] In the embodiments of the present invention, the time of the roasting in step (4) is 3-6 h.

[0046] Specifically, the roasting in step (4) is carried out in one or more atmospheres of air, nitrogen or hydrogen.

[0047] In the embodiments of the present invention, the roasting in step (4) is carried out in an air atmosphere.

[0048] Due to the application of the above technical solutions, the present invention has the following advantages compared with the prior art:

[0049] Through the optimization of the components of the catalyst for catalytic recombination and cracking of butanol-octanol residue and the adjustment of the preparation method, the present invention obtains a supported heterogeneous catalyst with titanium oxide as the active center, which has good catalytic effect on the recombination and cracking of butanol-octanol residue and a long service life. It can be used for the continuous flow catalytic cracking reaction of butanol-octanol residue heavy components, realizing the large-scale continuous cracking treatment of butanol-octanol residue heavy components, significantly reducing the cracking cost of butanol-octanol residue heavy components, and improving the economic benefits of butanol-octanol residue heavy components. Description of the Drawings

[0050] Figure 1 XRD pattern of catalyst A prepared in Example 1;

[0051] Figure 2 Nitrogen adsorption-desorption isotherm diagram of catalyst A prepared in Example 1;

[0052] Figure 3 XRD pattern of catalyst E prepared in Comparative Example 3;

[0053] Figure 4Nitrogen desorption isotherm diagram of catalyst E prepared in Comparative Example 3;

[0054] Figure 5 It is a diagram of the catalytic stability test results of catalyst A in Example 1 running continuously for 205 h. Detailed implementation manners

[0055] The above scheme is further described below in conjunction with specific embodiments; it should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited by the scope of the following embodiments; the implementation conditions adopted in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are usually the conditions in conventional experiments.

[0056] For those without specific experimental steps or conditions indicated in the embodiments, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. Unless otherwise specified in the following embodiments, all raw materials are obtained through commercial purchase or prepared by conventional methods in this field.

[0057] In the present invention, unless otherwise specified, “%” refers to mass percentage. Example 1

[0058] This example provides a preparation method of a catalyst for catalytic recombination and cracking of butanol and octanol residues and the prepared catalyst, which are specifically as follows:

[0059] (1) Dissolve 20 g of ferric nitrate nonahydrate in 30 mL of deionized water to obtain a ferric nitrate solution. Take 200 g of activated alumina balls with a particle size of 0.5 - 1 mm and add them to the ferric nitrate solution. After isovolumetric impregnation for 5 hours, first dry them to constant weight in a blast drying oven at 120 °C, and then calcine them in a flowing air atmosphere at 450 °C for 5 h to obtain a support material, that is, alumina balls loaded with iron oxide.

[0060] (2) Mix 200 g of tetrabutyl titanate, 50 g of absolute ethanol and 30 g of toluene evenly to obtain a mixed solution. Divide the mixed solution into two equal volumes and impregnate the support material in step (1). Specifically, take half of the volume of the mixed solution, add the support material in step (1), impregnate for 5 hours, dry in a blast drying oven at 120 °C for 12 hours, add the obtained material to the other half of the volume of the mixed solution, impregnate again for 5 hours, and then dry to constant weight in a blast drying oven at 120 °C.

[0061] (3) Add 50 g of the material obtained in step (2) to 140 g of deionized water, hydrothermal react at 200 °C in a hydrothermal autoclave for 24 hours, filter after cooling to room temperature, wash with deionized water, and dry to constant weight in a blast drying oven at 120 °C.

[0062] (4) The material obtained in step (3) is calcined in a flowing air atmosphere at 180 °C for 3 hours, cooled to 30 °C in a flowing air atmosphere and then taken out to obtain catalyst A. From the XRD pattern of catalyst A ( Figure 1 ), it can be seen that titanium oxide is anatase and is well dispersed on the catalyst support. According to the nitrogen adsorption and desorption isotherm of catalyst A ( Figure 2 ), the specific surface area of catalyst A calculated by using the BET formula is 100.3 m 2 / g. The pores in catalyst A are mainly macropores formed by particle accumulation. Example 2

[0063] This example provides another preparation method of a catalyst for catalytic recombination and cracking of butanol and octanol residue and the prepared catalyst, which is as follows:

[0064] (1) 7 g of nickel acetate and 8 g of copper chloride are dissolved in 50 mL of deionized water to obtain a mixed solution of nickel acetate and copper chloride. 200 g of activated silica spheres with a particle size of 0.5 - 1 mm are added to the mixed solution of nickel acetate and copper chloride. After isovolumetric impregnation for 5 hours, it is first dried to constant weight in a forced air drying oven at 120 °C, and then calcined at 450 °C for 5 h in a flowing air atmosphere to obtain a carrier material, that is, silica supported with nickel oxide and copper oxide.

[0065] (2) 100 g of isopropyl titanate, 20 g of absolute ethanol and 20 g of toluene are mixed evenly to obtain a mixed solution. The carrier material obtained in step (1) is added to this mixed solution. After isovolumetric impregnation for 12 hours, it is dried to constant weight in a forced air drying oven at 120 °C.

[0066] (3) 50 g of the material obtained in step (2) is added to 140 g of deionized water, hydrothermally treated at 180 °C in a hydrothermal autoclave for 24 hours, filtered after cooling to room temperature, washed with water, and dried to constant weight in a forced air drying oven at 120 °C.

[0067] (4) The material obtained in step (3) is calcined in a flowing air atmosphere at 250 °C for 6 hours, cooled to 30 °C in a flowing air atmosphere and then taken out to obtain catalyst B.

[0068] Comparative Example 1

[0069] This comparative example provides another preparation method of a catalyst for catalytic recombination and cracking of butanol and octanol residue and the prepared catalyst, which is as follows:

[0070] (1) 100 g of tetrabutyl titanate, 25 g of absolute ethanol and 15 g of toluene are mixed evenly to obtain a mixed solution. 200 g of activated alumina spheres with a particle size of 0.5 - 1 mm are added thereto. After isovolumetric impregnation for 5 hours, it is dried in a forced air drying oven at 120 °C for 12 hours.

[0071] (2) The material obtained in step (1) is calcined in a flowing air atmosphere at 550 °C for 3 hours, cooled to 30 °C in a flowing air atmosphere and then taken out to obtain catalyst C.

[0072] Comparative Example 2

[0073] This comparative example provides another method for preparing a catalyst for catalytically cracking the residue of butanol and octanol and the prepared catalyst, which is as follows:

[0074] (1) Dissolve 20 g of ferric nitrate nonahydrate in 30 mL of deionized water to obtain a ferric nitrate solution. Take 200 g of activated alumina spheres with a particle size of 0.5 - 1 mm and add them to the ferric nitrate solution. After isovolumetric impregnation for 5 hours, first dry them to constant weight in a forced-air drying oven at 120 °C, and then calcine them in a flowing air atmosphere at 450 °C for 5 h to obtain a support material, that is, alumina spheres loaded with iron oxide.

[0075] (2) Mix 200 g of tetrabutyl titanate, 50 g of absolute ethanol and 30 g of toluene evenly to obtain a mixed solution. Divide the mixed solution into two equal volumes and impregnate the support material obtained in step (1). Specifically, take half of the volume of the mixed solution, add the support material obtained in step (1), impregnate for 5 hours, dry in a forced-air drying oven at 120 °C for 12 hours, add the obtained material to the other half of the volume of the mixed solution, impregnate again for 5 hours, and then dry to constant weight in a forced-air drying oven at 120 °C.

[0076] (3) The material obtained in step (2) is calcined in a flowing air atmosphere at 180 °C for 3 hours, cooled to 30 °C in a flowing air atmosphere and then taken out to obtain catalyst D.

[0077] Comparative Example 3

[0078] This example provides another method for preparing a catalyst for catalytically cracking the residue of butanol and octanol and the prepared catalyst, which is as follows:

[0079] (1) Dissolve 20.0 g of ferric nitrate nonahydrate in 30 mL of deionized water to obtain a ferric nitrate solution. Take 200 g of activated alumina spheres with a particle size of 0.5 - 1 mm and add them to the ferric nitrate solution. After isovolumetric impregnation for 5 hours, first dry them to constant weight in a forced-air drying oven at 120 °C, and then calcine them in a flowing air atmosphere at 450 °C for 5 h to obtain a support material, that is, alumina spheres loaded with iron oxide.

[0080] (2) Mix 100 g of isopropyl titanate, 20 g of absolute ethanol and 20 g of toluene evenly to obtain a mixed solution. Add the support material obtained in step (1) to the mixed solution, impregnate for 12 hours isovolumetrically, and then dry to constant weight in a forced-air drying oven at 120 °C.

[0081] (3) Add 50 g of the material obtained in step (2) to 140 g of deionized water, hydrothermal react at 200 °C for 24 hours in a hydrothermal autoclave, filter after cooling to room temperature, wash with deionized water, and dry in a forced-air drying oven at 120 °C until constant weight.

[0082] (4) Calcinate the material obtained in step (3) in a flowing air atmosphere at 550 °C for 3 hours, cool to 30 °C in a flowing air atmosphere and take out to obtain catalyst E. From the XRD pattern of catalyst E ( Figure 3 ), it can be seen that after increasing the calcination temperature, the crystallinity of titanium oxide has increased, the particles have also grown significantly, and agglomeration has occurred. From the nitrogen adsorption-desorption isotherm of catalyst E ( Figure 4 ), catalyst E has an obvious mesoporous structure. The specific surface area of catalyst C calculated by the BET formula is 150.8 m 2 / g. Compared with catalyst A, the loading amount of the active component of catalyst E is reduced.

[0083] Catalytic performance test

[0084] Use the catalysts prepared in the above examples and comparative examples to catalyze the heavy components of butanol-octanol residue respectively. The specific operation is as follows: Add 5 g of catalyst and 20 g of heavy components of butanol-octanol residue to a high-pressure reactor. After purging with nitrogen 3 times, fill with nitrogen to 5 bar, react at 250 °C under stirring conditions of 600 rpm for 6 h. After cooling to 30 °C, first discharge the nitrogen in the high-pressure reactor, and take the reaction solution for gas chromatography detection and analysis.

[0085] The heavy components of butanol-octanol residue used in the catalytic performance test are from the bottom material of the distillation column after the C4 (butyraldehyde, butanol, butyric acid) and C8 (2-ethylhexanal, 2-ethyl-2-hexenal, 2-ethylhexanol, 2-ethylhexanoic acid) components are recovered from the butanol-octanol residue by a distillation column. After gas chromatography detection and analysis, the sum of the contents of C4 and C8 substances in the heavy components of butanol-octanol residue is 7% of the total mass of the heavy components of butanol-octanol residue.

[0086] The sum of the contents of C4 and C8 substances in the reaction solution after catalytic cracking with catalyst A of Example 1 is 45.3% of the total mass of the reaction solution.

[0087] The sum of the contents of C4 and C8 substances in the reaction solution after catalytic cracking with catalyst B of Example 2 is 43.4% of the total mass of the reaction solution.

[0088] The sum of the contents of C4 and C8 substances in the reaction solution after catalytic cracking with catalyst C of Comparative Example 1 is 13.5% of the total mass of the reaction solution.

[0089] The sum of the contents of C4 and C8 substances in the reaction solution after catalytic cracking with catalyst D of Comparative Example 2 is 29.53% of the total mass of the reaction solution.

[0090] The sum of the contents of C4 and C8 substances in the reaction liquid after catalytic cracking with the catalyst E of Comparative Example 3 is 30.1% of the total mass of the reaction liquid.

[0091] Catalyst stability test

[0092] The catalysts prepared in the above-mentioned examples and comparative examples were respectively used to continuously flow-catalyze the heavy components of butanol-octanol residue. The specific operation was as follows: A 25 mL fixed bed was formed by loading the catalyst in a 316L stainless steel circular tube reactor with an inner diameter of 10 mm, an outer diameter of 12 mm, and a length of 320 mm. After purging with nitrogen for 10 min, the nitrogen was back-pressured to 15 bar, the reactor was heated to 250 °C, and the heavy components of butanol-octanol residue were pumped in at a flow rate of 1 mL / min. The reaction liquid flowing out of the reactor was sampled instantaneously at different time points during continuous operation, and the sum of the contents of C4 (butyraldehyde, butanol, butyric acid) and C8 (2-ethylhexanal, 2-ethyl-2-hexenal, 2-ethylhexanol, 2-ethylhexanoic acid) was detected and analyzed by gas chromatography.

[0093] The catalytic effect of the catalyst A of Example 1 is stable. The change curves of the contents of C4 and C8 substances at different time points during continuous operation for 205 h are shown in Figure 5 , when running to 205 h, the sum of the contents of C4 and C8 substances in the instantaneous sample of the reaction liquid is 48.52%. When continuously running to 205 h, the sum of the contents of C4 and C8 substances in the instantaneous sample of the reaction liquid still remains above 40%.

[0094] The catalytic effect of the catalyst B of Example 2 is relatively stable. When continuously running to 200 h, the sum of the contents of C4 and C8 substances in the instantaneous sample of the reaction liquid is 40.79%.

[0095] When using the catalyst C of Comparative Example 1 and continuously running to 3 h, the sum of the contents of C4 and C8 substances in the instantaneous reaction sample is 15.2%. Since the initial activity of the catalyst C is significantly lower than that of the catalyst A and the catalyst B, the continuous operation is terminated after 3 h.

[0096] When using the catalyst D of Comparative Example 2 and continuously running to 3 h, the sum of the contents of C4 and C8 substances in the instantaneous reaction sample is 33.4%. Since the initial activity of the catalyst D is significantly lower than that of the catalyst A and the catalyst B, the continuous operation is terminated after 3 h.

[0097] When using the catalyst E of Comparative Example 3 and continuously running to 3 h, the sum of the contents of C4 and C8 substances in the instantaneous sample of the reaction liquid is 31.1%. Since the initial activity of the catalyst E is significantly lower than that of the catalyst A and the catalyst B, the continuous operation is terminated after 3 h.

[0098] The above test results of catalytic performance and stability show that the catalysts of Examples 1-2 have significantly better catalytic effects on the heavy components of butanol-octanol residue and long-term catalytic stability than the catalysts of Comparative Examples 1-3. The catalysts of Example 1 and Example 2 have better performance and long service life, and can be used for the continuous-flow catalytic cracking reaction of the heavy components of butanol-octanol residue, realizing the large-scale continuous cracking treatment of the heavy components of butanol-octanol residue, which will significantly reduce the cracking cost of the heavy components of butanol-octanol residue and improve the economic benefits of the heavy components of butanol-octanol residue. In addition, the catalyst of Example 1 has the best performance and the lowest energy consumption and cost during preparation, and is the most preferred catalyst.

[0099] The above embodiments are only used to illustrate the technical concept and characteristics of the present invention, and their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and should not be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A catalyst for catalytically recombining and cracking butanol and octanol residual liquid, characterized in that, The catalyst includes a catalyst carrier, a catalyst active center supported on the catalyst carrier, and a promoter. The catalyst active center is titanium oxide, and the promoter is one or more of iron oxide, nickel oxide, or copper oxide. The catalyst carrier is activated alumina pellets and / or activated silica pellets. The mass of the titanium oxide is 10% - 20% of the total mass of the catalyst, and the mass of the promoter is 2% - 5% of the total mass of the catalyst. The specific surface area of the catalyst is 95 - 120 m 2 / g. The preparation method of the catalyst comprises the following steps: (1) Impregnate the catalyst support with a promoter precursor solution, dry it, and calcine it at 400-500 °C to obtain a support material loaded with the promoter; (2) Mix the catalyst active center precursor with a first solvent and then impregnate the support material loaded with the promoter, and dry to obtain a catalyst precursor; (3) Heat-treat the catalyst precursor in a second solvent at 80-250 °C, wash it with water, and dry to obtain a catalyst intermediate; (4) Calcinate the catalyst intermediate at 150-250 °C to obtain the catalyst, wherein the catalyst active center precursor is one or more of isopropyl titanate, tetrabutyl titanate, and titanium tetrachloride, and the promoter precursor is one or more of iron nitrate, iron acetate, iron sulfate, iron chloride, iron acetylacetonate complex, nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, nickel acetylacetonate complex, copper nitrate, copper acetate, copper sulfate, copper chloride, and copper acetylacetonate complex.

2. The catalyst for catalytically recombining and cracking butanol and octanol residual liquid according to claim 1, characterized in that, The particle size of the catalyst support is 0.3-3 mm.

3. The catalyst for catalytically reorganizing and cracking butanol and octanol residual liquid according to claim 1, wherein The feeding mass of the catalyst support is 0.8-2 times the sum of the feeding masses of the promoter precursor and the catalyst active center precursor.

4. The catalyst for catalytically recombining and cracking the butanol and octanol residual liquid according to claim 1, wherein, The feeding molar ratio of the catalyst active center precursor to the promoter precursor is (10-15):

1.

5. The catalyst for catalytically reforming and cracking butanol and octanol residual liquid according to claim 1, wherein The first solvent is ethanol and / or toluene; and / or, the solvent of the promoter precursor solution is water.

6. The catalyst for catalytically reorganizing and cracking the butanol and octanol residual liquid according to claim 1, characterized in that, The second solvent is one or more of water, ethanol, methanol, butanol, isopropanol, toluene, and N,N-dimethylformamide.

7. The catalyst for catalytic recombination and cracking of butanol and octanol residue according to claim 6, characterized in that, The second solvent is water.

8. The catalyst for catalytically reforming and cracking butanol and octanol residual liquid according to claim 1, characterized in that, The drying temperatures in steps (1), (2), and (3) are independently 100-150 °C.

9. The catalyst for catalytically recombining and cracking butanol and octanol residual liquid according to claim 1, characterized in that, The impregnations in steps (1) and (2) are respectively carried out by isovolumetric impregnation.

10. The catalyst for catalytically recombining and cracking butanol and octanol residues according to claim 1, characterized in that, The heat-treatment temperature in step (3) is 160-220 °C; and / or, the heat-treatment time in step (3) is 1-48 h.

11. The catalyst for catalytically cracking and splitting the residue of butanol and octanol according to claim 1, characterized in that, The calcination time in step (4) is 1-24 h.

12. The catalyst for catalytically reforming and cracking butanol and octanol residual liquid according to claim 10, characterized in that, The calcination in step (4) is carried out in an air atmosphere.

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