Catalyst for catalyzing recombination decomposition of butanol and octanol residual liquid and preparation method of catalyst

Abstract

The invention relates to a catalyst for catalyzing recombination and splitting of butanol and octanol raffinate and a preparation method thereof, the catalyst comprises a catalyst carrier, a catalyst active center and a cocatalyst, the catalyst active center is titanium oxide, the cocatalyst is one or more of iron, cobalt, nickel, manganese, copper, molybdenum, tungsten, tin and oxides thereof, and the catalyst carrier is titanium oxide. The catalyst carrier is one or more of aluminum oxide, silicon oxide, magnesium-aluminum hydrotalcite, hydroxyapatite, a Y-type molecular sieve, an A-type molecular sieve, ZSM-5, a Beta-molecular sieve, coconut shell charcoal, XC-72R and XC-72. The catalyst disclosed by the invention is good in effect of catalyzing the recombination decomposition of the butanol and octanol residual liquid and long in service life, can be used for continuous flow catalytic cracking reaction of the butanol and octanol residual liquid heavy components, realizes large-scale continuous cracking treatment of the butanol and octanol residual liquid heavy components, remarkably reduces the recombination decomposition cost of the butanol and octanol residual liquid, and has a wide application prospect. The economic benefits of the heavy components in the butanol and octanol residual liquid are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of cracking catalysts, and particularly 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 invention aims to provide a solid catalyst having good catalytic effect, good stability and long service life for catalyzing the recombination and splitting decomposition of butanol residue and a preparation method thereof.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is: A catalyst for catalyzing the recombination and splitting of butanol residue comprises a catalyst carrier, a catalyst active center loaded on the catalyst carrier and a co-catalyst.

[0007] Specifically, the catalyst active center is titanium oxide.

[0008] Specifically, the promoter is one or more of iron, cobalt, nickel, manganese, copper, molybdenum, tungsten, tin and oxides thereof.

[0009] 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, and XC-72.

[0010] Specifically, the mass of the titanium oxide is 1% to 45% of the total mass of the catalyst, for example 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%, and 45%.

[0011] Specifically, the mass of the promoter is 0.01% to 8% of the total mass of the catalyst, for example, 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%, and 8%.

[0012] Specifically, the specific surface area of ​​the catalyst is 95-120 m 2 / g, more preferably 95 to 110 m 2 / g, and further preferably 95~105m 2 / g.

[0013] Furthermore, the mass of the titanium oxide is 8% to 25% of the total mass of the catalyst.

[0014] Furthermore, the mass of the titanium oxide is 10% to 20% of the total mass of the catalyst.

[0015] Furthermore, the mass of the promoter is 0.5% to 5% of the total mass of the catalyst.

[0016] Furthermore, the mass of the co-catalyst is 2% to 5% of the total mass of the catalyst.

[0017] Furthermore, the catalyst carrier is activated alumina beads and / or activated silicon oxide beads.

[0018] Furthermore, the particle size of the catalyst carrier is 0.3~3mm.

[0019] According to some specific embodiments of the present invention, the catalyst carrier is an activated alumina ball with a particle size of 0.3-3 mm or an activated silicon oxide ball with a particle size of 0.3-3 mm.

[0020] Furthermore, the promoter is one or more of iron oxide, nickel oxide or copper oxide.

[0021] According to some specific embodiments of the present invention, the co-catalyst is iron oxide or the co-catalyst is nickel oxide and copper oxide.

[0022] The present invention also provides a method for preparing the catalyst for catalyzing the recombination and splitting of the butanol residue, the preparation method comprising the following steps: (1) impregnating a catalyst carrier with a promoter precursor solution, drying, and calcining at 400-500° C. to obtain a promoter-loaded carrier material; (2) mixing a catalyst active center precursor with a first solvent, impregnating the carrier material loaded with the co-catalyst, and drying to obtain a catalyst precursor; (3) heat treating the catalyst precursor in a second solvent at 80-250° C., washing with water, and drying to obtain a catalyst intermediate; (4) calcining the catalyst intermediate at 150-500° C. to obtain the catalyst, Wherein, the catalyst active center precursor is one or more of isopropyl titanate, tetrabutyl titanate, and titanium tetrachloride. The co-catalyst precursor is one or more of ferric nitrate, ferric acetate, ferric sulfate, ferric chloride, ferric acetylacetonate complex, cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt chloride, acetylacetonate cobalt complex, nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, acetylacetonate nickel complex, manganese nitrate, manganese acetate, manganese sulfate, manganese chloride, acetylacetonate manganese complex, copper nitrate, copper acetate, copper sulfate, copper chloride, acetylacetonate copper complex, molybdenum nitrate, molybdenum acetate, molybdenum sulfate, molybdenum chloride, acetylacetonate molybdenum complex, tungsten nitrate, tungsten acetate, tungsten sulfate, tungsten chloride, tungsten acetylacetonate complex, tin nitrate, tin acetate, tin sulfate, tin chloride, and tin acetylacetonate complex.

[0023] In an embodiment of the present invention, the feed mass of the catalyst carrier is 0.8 to 2 times the sum of the feed masses of the co-catalyst precursor and the catalyst active center precursor.

[0024] In an embodiment of the present invention, the molar ratio of the catalyst active center precursor to the co-catalyst precursor is (3-15):1.

[0025] Furthermore, the feed molar ratio of the catalyst active center precursor to the co-catalyst precursor is (8-15):1.

[0026] Furthermore, the feed molar ratio of the catalyst active center precursor to the co-catalyst precursor is (10-15):1.

[0027] In an embodiment of the present invention, the first solvent is ethanol and / or toluene.

[0028] In an embodiment of the present invention, the solvent of the co-catalyst precursor solution is water.

[0029] Specifically, the second solvent is one or more of water, ethanol, methanol, butanol, isopropanol, toluene, and N,N-dimethylformamide.

[0030] In an embodiment of the present invention, the second solvent is a mixed solvent of one or more of ethanol, methanol, butanol, isopropanol and water.

[0031] In an embodiment of the present invention, the drying temperatures in step (1), step (2) and step (3) are independently 100-150°C, for example, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C.

[0032] In the embodiment of the present invention, the impregnation in step (1) and step (2) is performed by impregnation of equal volumes. Preferably, the number of impregnations in step (2) is 2 times.

[0033] In an embodiment of the present invention, the temperature of the heat treatment in step (3) is 160-220°C, for example, 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.

[0034] Specifically, the heat treatment time in step (3) is 1 to 48 hours, more preferably 15 to 40 hours, further preferably 15 to 30 hours, and further preferably 20 to 28 hours.

[0035] In an embodiment of the present invention, the heat treatment time in step (3) is 20 to 25 hours.

[0036] In an embodiment of the present invention, the calcination temperature in step (4) is 150-250°C.

[0037] Specifically, the calcination time in step (4) is 1 to 24 hours.

[0038] In an embodiment of the present invention, the calcination time in step (4) is 3 to 6 hours.

[0039] Specifically, the calcination in step (4) is carried out in one or more atmospheres of air, nitrogen or hydrogen.

[0040] In an embodiment of the present invention, the calcination in step (4) is carried out in an air atmosphere.

[0041] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art: The invention obtains a supported multiphase catalyst with titanium oxide as an active center by optimizing the components of a catalyst for catalyzing the recombination and cracking decomposition of butanol residue and adjusting the preparation method. The catalyst has good effect of catalyzing the recombination and cracking decomposition of butanol residue and has a long service life, can be used for continuous flow catalytic cracking reaction of heavy components of butanol residue, realizes large-scale continuous cracking treatment of heavy components of butanol residue, significantly reduces the cost of recombination and cracking decomposition of butanol residue, and improves the economic benefit of heavy components of butanol residue. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 XRD spectrum of catalyst A prepared in Example 1; Figure 2 The nitrogen adsorption-desorption isotherm diagram of the catalyst A prepared in Example 1; Figure 3 XRD spectrum of catalyst E prepared in Comparative Example 3; Figure 4 The nitrogen elution isotherm diagram of the catalyst E prepared in Comparative Example 3; Figure 5This is a graph showing the catalytic stability test results of the catalyst A of Example 1 after continuous operation for 205 hours. DETAILED DESCRIPTION

[0043] 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 to 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.

[0044] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the art can be used. Unless otherwise specified in the following examples, all raw materials are commercially available or prepared by conventional methods in the art.

[0045] In the present invention, unless otherwise specified, "%" refers to mass percentage. Example 1

[0046] This embodiment provides a method for preparing a catalyst for catalyzing the recombination and splitting of butanol residue and the prepared catalyst, which are specifically as follows: (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 beads with a particle size of 0.5-1 mm and add them to the ferric nitrate solution. After equal volumes are immersed for 5 hours, they are first dried in a 120°C forced air drying oven to constant weight, and then calcined at 450°C in a flowing air atmosphere for 5 hours to obtain a carrier material, i.e., alumina beads loaded with iron oxide.

[0047] (2) 200 g of tetrabutyl titanate, 50 g of anhydrous ethanol and 30 g of toluene are mixed to obtain a mixed solution, and the mixed solution is used to impregnate the support material of step (1) twice in equal volumes. Specifically, half the volume of the mixed solution is added to the support material of step (1), and after impregnation for 5 hours, it is dried in a 120° C. forced air drying oven for 12 hours. The obtained material is added to the other half volume of the mixed solution, and after impregnation for another 5 hours, it is dried in a 120° C. forced air drying oven to constant weight.

[0048] (3) 50 g of the material obtained in step (2) was added to 140 g of deionized water, and the mixture was hydrothermally heated at 200° C. for 24 hours in a hydrothermal kettle. After cooling to room temperature, the mixture was filtered, washed with deionized water, and dried in a 120° C. forced air drying oven to constant weight.

[0049] (4) The material obtained in step (3) was calcined at 180°C for 3 hours in a flowing air atmosphere, and then cooled to 30°C in a flowing air atmosphere to obtain catalyst A. From the XRD spectrum of catalyst A ( Figure 1) shows that titanium oxide is anatase and is well dispersed on the catalyst support. According to the nitrogen adsorption and desorption isotherms of catalyst A ( Figure 2 ), the specific surface area of ​​catalyst A was calculated using the BET formula to be 100.3 m 2 / g, the pores in catalyst A are mainly macropores formed by particle accumulation. Example 2

[0050] This embodiment provides another method for preparing a catalyst for catalyzing the recombination and splitting of butanol residue and the prepared catalyst, which are as follows: (1) 7 g of nickel acetate and 8 g of cupric chloride were dissolved in 50 mL of deionized water to obtain a mixed solution of nickel acetate and cupric chloride. 200 g of activated silica beads with a particle size of 0.5-1 mm were added to the mixed solution of nickel acetate and cupric chloride. After equal volumes were immersed for 5 hours, the mixture was first dried in a 120°C forced air drying oven to constant weight, and then calcined at 450°C in a flowing air atmosphere for 5 hours to obtain a carrier material, i.e., silica loaded with nickel oxide and copper oxide.

[0051] (2) 100 g of isopropyl titanate, 20 g of anhydrous ethanol and 20 g of toluene were mixed evenly to obtain a mixed solution, the support material of step (1) was added to the mixed solution, and after equal volumes were immersed for 12 hours, the solution was dried in a 120° C. forced air drying oven to constant weight.

[0052] (3) 50 g of the material obtained in step (2) was added to 140 g of deionized water, and the mixture was heated in a hydrothermal kettle at 180° C. for 24 hours. After cooling to room temperature, the mixture was filtered, washed with water, and dried in a 120° C. forced air drying oven to constant weight.

[0053] (4) The material obtained in step (3) was calcined at 250°C in a flowing air atmosphere for 6 hours, cooled to 30°C in a flowing air atmosphere, and taken out to obtain catalyst B.

[0054] Comparative Example 1 This comparative example provides another method for preparing a catalyst for catalyzing the recombinant splitting of butanol residue and the prepared catalyst, which are as follows: (1) 100 g of tetrabutyl titanate, 25 g of anhydrous ethanol and 15 g of toluene were mixed evenly to obtain a mixed solution, to which 200 g of activated alumina beads with a particle size of 0.5-1 mm were added. After equal volumes were immersed for 5 hours, the mixture was dried in a 120°C forced air drying oven for 12 hours.

[0055] (2) The material obtained in step (1) was calcined at 550°C for 3 hours in a flowing air atmosphere, cooled to 30°C in a flowing air atmosphere, and taken out to obtain catalyst C.

[0056] Comparative Example 2 This comparative example provides another method for preparing a catalyst for catalyzing the recombinant splitting of butanol residue and the prepared catalyst, which are as follows: (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 beads with a particle size of 0.5-1 mm and add them to the ferric nitrate solution. After equal volumes are immersed for 5 hours, they are first dried in a 120°C forced air drying oven to constant weight, and then calcined at 450°C in a flowing air atmosphere for 5 hours to obtain a carrier material, i.e., alumina beads loaded with iron oxide.

[0057] (2) 200 g of tetrabutyl titanate, 50 g of anhydrous ethanol and 30 g of toluene are mixed to obtain a mixed solution, and the mixed solution is used to impregnate the support material of step (1) twice in equal volumes. Specifically, half the volume of the mixed solution is added to the support material of step (1), and after impregnation for 5 hours, it is dried in a 120° C. forced air drying oven for 12 hours. The obtained material is added to the other half volume of the mixed solution, and after impregnation for another 5 hours, it is dried in a 120° C. forced air drying oven to constant weight.

[0058] (3) The material obtained in step (2) was calcined at 180°C for 3 hours in a flowing air atmosphere, cooled to 30°C in a flowing air atmosphere, and taken out to obtain catalyst D.

[0059] Comparative Example 3 This embodiment provides another method for preparing a catalyst for catalyzing the recombination and splitting of butanol residue and the catalyst prepared therefrom, which are specifically as follows: (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 beads with a particle size of 0.5-1 mm and add them into the ferric nitrate solution. After equal volumes are immersed for 5 hours, they are first dried in a 120°C forced air drying oven to constant weight, and then calcined at 450°C in a flowing air atmosphere for 5 hours to obtain a carrier material, i.e., alumina beads loaded with iron oxide.

[0060] (2) 100 g of isopropyl titanate, 20 g of anhydrous ethanol and 20 g of toluene were mixed evenly to obtain a mixed solution, the support material of step (1) was added to the mixed solution, and after equal volumes were immersed for 12 hours, the solution was dried in a 120° C. forced air drying oven to constant weight.

[0061] (3) 50 g of the material obtained in step (2) was added to 140 g of deionized water, and the mixture was hydrothermally heated at 200° C. for 24 hours in a hydrothermal kettle. After cooling to room temperature, the mixture was filtered, washed with deionized water, and dried in a 120° C. forced air drying oven to constant weight.

[0062] (4) The material obtained in step (3) was calcined at 550°C for 3 hours in a flowing air atmosphere, cooled to 30°C in a flowing air atmosphere, and then taken out to obtain catalyst E. From the XRD spectrum of catalyst E ( Figure 3 ) It can be seen that after increasing the calcination temperature, the crystallinity of titanium oxide is improved, the particles grow significantly, and agglomeration occurs. From the nitrogen adsorption and desorption isotherms of catalyst E ( Figure 4 ), catalyst E has an obvious mesoporous structure. The specific surface area of ​​catalyst C calculated by BET formula is 150.8 m 2 / g. Compared with Catalyst A, the active component loading of Catalyst E is reduced.

[0063] Catalytic performance test The catalysts prepared in the above embodiments and comparative examples were respectively used to catalyze the heavy components of the butanol residual liquid. The specific operation was as follows: 5 g of catalyst and 20 g of the butanol residual liquid heavy components were added to a high-pressure reactor, and nitrogen was introduced for replacement 3 times, and then nitrogen was filled to 5 bar. The reaction was carried out at 250 ° C and 600 rpm under stirring conditions for 6 h. After cooling to 30 ° C, the nitrogen in the high-pressure reactor was first removed, and the reaction liquid was taken for gas chromatography analysis.

[0064] The heavy component of the butanol residue used in the catalytic performance test comes from the bottom material of the distillation tower after the butanol residue is distilled through a distillation tower to recover C4 (butyraldehyde, butanol, butyric acid) and C8 (2-ethylhexanal, 2-ethyl-2-hexenal, 2-ethylhexanol, 2-ethylhexanoic acid) components. After gas chromatography analysis, the sum of the contents of C4 and C8 substances in the heavy component of the butanol residue is 7% of the total mass of the heavy component of the butanol residue.

[0065] The sum of the contents of C4 and C8 substances in the reaction liquid after the catalytic cracking reaction using the catalyst A of Example 1 is 45.3% of the total mass of the reaction liquid.

[0066] The sum of the contents of C4 and C8 substances in the reaction liquid after the catalytic cracking reaction using the catalyst B of Example 2 is 43.4% of the total mass of the reaction liquid.

[0067] The sum of the contents of C4 and C8 substances in the reaction liquid after the catalytic cracking reaction using the catalyst C of Comparative Example 1 is 13.5% of the total mass of the reaction liquid.

[0068] The sum of the contents of C4 and C8 substances in the reaction liquid after the catalytic cracking reaction using the catalyst D of Comparative Example 2 was 29.53% of the total mass of the reaction liquid.

[0069] The sum of the contents of C4 and C8 substances in the reaction liquid after the catalytic cracking reaction using the catalyst E of Comparative Example 3 was 30.1% of the total mass of the reaction liquid.

[0070] Catalyst stability test The catalysts prepared in the above embodiments and comparative examples were respectively used to continuously flow catalyze the heavy components of the butanol residue. The specific operation was as follows: a 316L stainless steel round tube reactor with an inner diameter of 10 mm, an outer diameter of 12 mm, and a length of 320 mm was filled with the catalyst to form a 25 mL fixed bed. After nitrogen was purged for 10 minutes, nitrogen was introduced to a back pressure of 15 bar. The reactor was heated to 250° C., and the heavy components of the butanol residue were pumped in at a flow rate of 1 mL / min. The reaction mixture was continuously run and instantaneous samples of the reaction liquid flowing out of the reactor were taken at different time points. 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 analyzed by gas chromatography.

[0071] The catalytic effect of catalyst A in Example 1 was stable. The content variation curves of C4 and C8 substances at different time points during the continuous operation of 205 h were shown in FIG. Figure 5 When the operation reached 205h, the sum of the contents of C4 and C8 substances in the instantaneous sample of the reaction liquid was 48.52%. After continuous operation until 205h, the sum of the contents of C4 and C8 substances in the instantaneous sample of the reaction liquid remained above 40%.

[0072] The catalytic effect of the catalyst B of Example 2 was relatively stable. When the continuous operation lasted for 200 hours, the sum of the contents of C4 and C8 substances in the instantaneous sample of the reaction liquid was 40.79%.

[0073] When the catalyst C of comparative example 1 was continuously operated for 3 hours, the sum of the contents of C4 and C8 substances in the instantaneous reaction sample was 15.2%. Since the initial activity of catalyst C was significantly lower than that of catalyst A and catalyst B, the continuous operation was terminated after 3 hours.

[0074] When the catalyst D of Comparative Example 2 was continuously operated for 3 hours, the sum of the contents of C4 and C8 substances in the instantaneous reaction sample was 33.4%. Since the initial activity of catalyst D was significantly lower than that of catalyst A and catalyst B, the continuous operation was terminated after 3 hours.

[0075] When the catalyst E of Comparative Example 3 was continuously operated for 3 hours, the sum of the contents of C4 and C8 substances in the instantaneous sample of the reaction liquid was 31.1%. Since the initial activity of catalyst E was significantly lower than that of catalyst A and catalyst B, the continuous operation was terminated after 3 hours.

[0076] The above catalytic performance and stability test results show that the catalysts of Examples 1 to 2 have a significant catalytic effect on the heavy component of the butanol residue and a long-term catalytic stability that are superior to the catalysts of Comparative Examples 1 to 3. The catalysts of Examples 1 and 2 have better performance and longer service life, and can be used for the continuous flow catalytic cracking reaction of the heavy component of the butanol residue, realizing large-scale continuous cracking treatment of the heavy component of the butanol residue, which will significantly reduce the cost of the recombination and cracking of the butanol residue, and improve the economic benefits of the heavy component of the butanol 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.

[0077] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A catalyst for catalyzing the recombination and splitting of butanol residue, characterized in that: The catalyst comprises a catalyst carrier, a catalyst active center and a co-catalyst supported on the catalyst carrier, wherein the catalyst active center is titanium oxide, the co-catalyst is one or more of iron, cobalt, nickel, manganese, copper, molybdenum, tungsten, tin and oxides thereof, the catalyst carrier is one or more of aluminum oxide, silicon oxide, magnesium aluminum hydrotalcite, hydroxyapatite, Y-type molecular sieve, A-type molecular sieve, ZSM-5, Beta-molecular sieve, coconut shell charcoal, XC-72R and XC-72, the mass of the titanium oxide is 1% to 45% of the total mass of the catalyst, the mass of the co-catalyst is 0.01% to 8% of the total mass of the catalyst, and the specific surface area of ​​the catalyst is 95 to 120 m 2 / g.

2. The catalyst for catalyzing the recombination and splitting of butanol residue according to claim 1, characterized in that: The mass of the titanium oxide is 8% to 25% of the total mass of the catalyst, and the mass of the co-catalyst is 0.5% to 5% of the total mass of the catalyst.

3. The catalyst for catalyzing the recombination and splitting of butanol residue according to claim 1, characterized in that: The catalyst carrier is an activated alumina ball and / or an activated silicon oxide ball, and / or the particle size of the catalyst carrier is 0.3-3 mm; and / or the promoter is one or more of iron oxide, nickel oxide or copper oxide.

4. The method for preparing a catalyst for catalyzing the recombination and splitting of butanol raffinate according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: (1) impregnating a catalyst carrier with a promoter precursor solution, drying, and calcining at 400-500° C. to obtain a promoter-loaded carrier material; (2) mixing a catalyst active center precursor with a first solvent, impregnating the carrier material loaded with the co-catalyst, and drying to obtain a catalyst precursor; (3) heat treating the catalyst precursor in a second solvent at 80-250° C., washing with water, and drying to obtain a catalyst intermediate; (4) calcining the catalyst intermediate at 150-500° C. to obtain the catalyst, Wherein, the catalyst active center precursor is one or more of isopropyl titanate, tetrabutyl titanate, and titanium tetrachloride. The co-catalyst precursor is one or more of ferric nitrate, ferric acetate, ferric sulfate, ferric chloride, ferric acetylacetonate complex, cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt chloride, acetylacetonate cobalt complex, nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, acetylacetonate nickel complex, manganese nitrate, manganese acetate, manganese sulfate, manganese chloride, acetylacetonate manganese complex, copper nitrate, copper acetate, copper sulfate, copper chloride, acetylacetonate copper complex, molybdenum nitrate, molybdenum acetate, molybdenum sulfate, molybdenum chloride, acetylacetonate molybdenum complex, tungsten nitrate, tungsten acetate, tungsten sulfate, tungsten chloride, tungsten acetylacetonate complex, tin nitrate, tin acetate, tin sulfate, tin chloride, and tin acetylacetonate complex.

5. The preparation method according to claim 4, characterized in that: The feed mass of the catalyst carrier is 0.8 to 2 times the sum of the feed masses of the co-catalyst precursor and the catalyst active center precursor.

6. The preparation method according to claim 4, characterized in that: The feed molar ratio of the catalyst active center precursor to the co-catalyst precursor is (3-15):

1.

7. The preparation method according to claim 4, characterized in that: The first solvent is ethanol and / or toluene; And / or, the solvent of the co-catalyst precursor solution is water.

8. The preparation method according to claim 4, characterized in that: The second solvent is one or more of water, ethanol, methanol, butanol, isopropanol, toluene, and N,N-dimethylformamide.

9. The preparation method according to claim 8, characterized in that: The second solvent is water.

10. The preparation method according to claim 4, characterized in that: The drying temperatures in step (1), step (2) and step (3) are independently 100-150°C.

11. The preparation method according to claim 4, characterized in that: The impregnation in step (1) and step (2) is performed by impregnation with equal volumes.

12. The preparation method according to claim 4, characterized in that: The temperature of the heat treatment in step (3) is 160-220° C.; and / or the time of the heat treatment in step (3) is 1-48 hours.

13. The preparation method according to claim 4, characterized in that: The calcination temperature in step (4) is 150-250° C.; and / or the calcination time in step (4) is 1-24 hours.

14. The preparation method according to claim 4, characterized in that: The calcination in step (4) is carried out in one or more atmospheres of air, nitrogen or hydrogen.

15. The preparation method according to claim 14, characterized in that: The calcination in step (4) is carried out in an air atmosphere.

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