A bifunctional catalyst for hydroformylation product hydrogenation to higher alcohols and a method for preparing the same

Abstract

The present application belongs to the technical field of chemical catalysts, and particularly relates to a bifunctional catalyst for hydrogenation of Fischer-Tropsch-hydroformylation products to produce high carbon alcohol and a preparation method thereof. The catalyst mainly comprises an active component Ni, an active component Pd and a pretreated carrier material, and the carrier material is selected from one of pretreated coconut shell activated carbon, walnut shell activated carbon and apricot shell activated carbon. The bifunctional hydrogenation catalyst is mainly used for hydrogenation of Fischer-Tropsch-hydroformylation products to produce high carbon alcohol, and can efficiently convert aldehyde, acid and olefin in the Fischer-Tropsch-hydroformylation products into high carbon alcohol and alkane in one step. The bifunctional hydrogenation catalyst shows excellent stability in a fixed bed continuous long period reaction evaluation.

Description

Technical Field

[0001] This invention belongs to the field of chemical catalyst technology, specifically relating to a bifunctional catalyst for the hydrogenation of Fischer-Tropsch hydroformylation products to higher alcohols and its preparation method. Background Technology

[0002] Catalytic hydrogenation to produce higher alcohols is one of the most important catalytic reactions in organic chemical synthesis, both in the laboratory and industrial production. It uses gaseous hydrogen and a heterogeneous catalyst to convert raw materials into higher alcohol products. my country has made some breakthroughs in catalytic hydrogenation technology, which plays a crucial role not only in the further processing of petroleum but also in the increasingly widespread application of fine chemicals. However, many catalytic hydrogenation processes still utilize outdated technologies from the 1950s and 60s, lagging significantly behind those of developed countries. The core of improving catalytic hydrogenation technology lies in improving the catalyst. The quality of the catalyst directly affects the overall reaction efficiency; a good catalyst can achieve the reaction process under conditions of lower energy consumption, less pollution, safety, and reliability.

[0003] Currently, my country's indirect coal liquefaction (Fischer-Tropsch synthesis) capacity is approximately 8.5 million tons per year. If the olefins byproducts of indirect coal liquefaction could be converted into high-value oxygen-containing chemicals such as aldehydes and alcohols through hydroformylation and subsequent hydrogenation, the economics of indirect coal liquefaction could be significantly improved. After hydroformylation, the olefins byproducts of indirect coal liquefaction contain high-carbon aldehydes, acids, and alkanes. Further hydrogenation can produce high-carbon alcohols and saturated alkanes. Due to the complex composition of the hydrogenation feedstock (aldehydes, acids, alkanes) and the presence of acidic substances, stringent requirements are placed on the efficiency of the hydrogenation catalyst and the stability of the continuous reaction.

[0004] Nickel-based catalysts have been widely used in the field of hydrogenation due to their high hydrogenation activity, low temperature, and low operating energy consumption. In the early high-pressure process for preparing butanol and octanol, Ni-based catalysts were mostly used for liquid-phase hydrogenation, which had a relatively high operating pressure. With the development of the chemical industry, a series of medium-pressure hydrogenation catalysts with Ni as the main active component were developed around 1990.

[0005] Many universities, research institutes, and companies have conducted research on hydrogenation catalysts. The Ni-ZrO / SiO2 hydrogenation catalyst described in patent EP421196 of the German company Hoechst, and another Ni-based hydrogenation catalyst described in patent CN1045548C of the same company, uses alkaline earth metal Mg as a promoter and can be used in the hydrogenation of propionaldehyde to n-propanol. Its hydrogenation product contains 0.7% unconverted aldehyde and a small amount of byproducts. The Ni-based hydrogenation catalyst described in patent DE43100538 of the German company BASF, in addition to the second component Cu, also includes a third component Zr and a fourth component Mo. The Ni-based hydrogenation catalyst mentioned in patent EP394842 of the German company Huels, in addition to Cu as the first promoter, also includes Cr as the second promoter. The Russian company GurevichGs' patent EP326674 describes a two-step process for producing butanol and octanol, and its Ni-based liquid-phase hydrogenation refining catalyst includes Cr as a promoter. The propionaldehyde hydrogenation described in CN100590108C is a gas-phase hydrogenation process carried out on a Cu-Zn catalyst, wherein the main mass composition of the Cu-Zn catalyst is CuO content of 29.4%-50% and ZnO content of 49.4%-70%.

[0006] To achieve the hydrogenation of higher alcohols from the hydroformylation products of Fischer-Tropsch by-product olefins, the hydrogenation catalyst needs to possess the hydrogenation catalytic performance of both aldehydes and acids, while also maintaining stability for long-term continuous reactions in the presence of acidic feedstocks.

[0007] Therefore, this invention develops a bifunctional hydrogenation catalyst with high efficiency in hydrogenating both aldehydes and acids, and stable performance in continuous long-cycle reactions. This bifunctional hydrogenation catalyst enables the one-step, efficient conversion of aldehydes, acids, and olefins contained in Fischer-Tropsch hydroformylation products into higher alcohols and alkanes, and exhibits excellent stability in fixed-bed continuous long-cycle reaction evaluations. The above method utilizes a bifunctional hydrogenation catalyst with high catalytic activity and ultra-high stability, effectively improving the economics of the hydrogenation process from Fischer-Tropsch hydroformylation products to higher alcohols. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide a bifunctional hydrogenation catalyst and its preparation method, which is mainly used for the hydrogenation of Fischer-Tropsch hydroformylation products to produce higher alcohols. This bifunctional catalyst has excellent catalytic activity, enabling the efficient one-step conversion of aldehydes, acids, and olefins contained in Fischer-Tropsch hydroformylation products into higher alcohols and alkanes, and exhibits excellent stability in fixed-bed continuous long-cycle reaction evaluation.

[0009] The bifunctional catalyst for the hydrogenation of Fischer-Tropsch hydroformylation products to higher alcohols of the present invention mainly consists of active component Ni, active component Pd, and pretreated support material; the support material is selected from one of pretreated coconut shell activated carbon, walnut shell activated carbon, and apricot shell activated carbon; the pretreatment of the support material refers to pretreating the support material with trimethylchlorosilane reagent at a temperature of 50-200℃, a silane reagent concentration of 20%-50%, and a treatment time of 4-20h.

[0010] In a preferred embodiment, the bifunctional hydrogenation catalyst contains 10%-40% Ni and 0.05%-2.0% Pd by mass, with the remainder being the mass of a pretreated support.

[0011] In a preferred embodiment, the bifunctional hydrogenation catalyst preferably contains 15%-30% Ni and 0.1%-0.8% Pd by mass, with the remainder being the mass of a pretreated support.

[0012] In a preferred embodiment, the catalyst is preferably supported by either coconut shell activated carbon or apricot shell activated carbon; the pretreatment of the support material refers to pretreating the support material with trimethylchlorosilane reagent at a preferred temperature of 80-120°C, a preferred silane reagent concentration of 30%-40%, and a preferred treatment time of 6-10 hours.

[0013] In a preferred embodiment, the catalyst has a specific surface area of ​​400-1200 m². 2 / g, pore volume 0.4-1.5cm³ 3 / g, bulk density is 0.4-1.5g / cm³ 3 .

[0014] In a preferred embodiment, the bifunctional hydrogenation catalyst is prepared by a stepwise impregnation method, including the following preparation steps: (1) At 25-60°C, the nickel salt is completely dissolved in an ethanol solvent. After complete dissolution, the pretreated support material is added. The catalyst is air-dried at room temperature for 6-24 hours and calcined at 300-500°C for 8-12 hours. (2) After the catalyst in step (1) is cooled to 25-60°C, the palladium salt is completely dissolved in an ethanol solvent. After complete dissolution, the catalyst prepared in step (1) is added. The catalyst is air-dried at room temperature for 6-24 hours and calcined at 150-250°C for 2-6 hours to obtain the bifunctional hydrogenation catalyst.

[0015] In a preferred embodiment, the nickel salt of the bifunctional hydrogenation catalyst is selected from Ni(NO3)2, Ni(CH3COO)2, NiCl2, and NiCO3; and the palladium salt is selected from Pd(NO3)2, PdCl2, and PdSO4.

[0016] In a preferred embodiment, the bifunctional hydrogenation catalyst is used in the hydrogenation reaction of Fischer-Tropsch hydroformylation products to higher alcohols. In the presence of the bifunctional hydrogenation catalyst, the Fischer-Tropsch hydroformylation products react with hydrogen in a reactor, enabling the efficient one-step conversion of aldehydes, acids, and olefins contained in the Fischer-Tropsch hydroformylation products into higher alcohols and alkanes. Furthermore, the catalyst exhibits extremely high stability. The Fischer-Tropsch hydroformylation product feedstock is delivered into the reaction system using a high-pressure pump, with a liquid hourly space velocity (LHSV) of 0.5-2.0 h⁻¹. -1 Hydrogen feedstock is fed in gaseous form with a gas space velocity of 1000-8000 h⁻¹. -1 The molar ratio of raw materials to hydrogen is 1:1 to 1:100.

[0017] The beneficial effects of this invention include, but are not limited to, the following: This bifunctional hydrogenation catalyst enables the efficient one-step conversion of aldehydes, acids, and olefins contained in the Fischer-Tropsch hydroformylation product into higher alcohols and alkanes, and exhibits excellent stability in fixed-bed continuous long-cycle reaction evaluations. The above method utilizes a bifunctional hydrogenation catalyst with high catalytic activity and ultra-high stability, effectively improving the economics of the hydrogenation process from Fischer-Tropsch hydroformylation products to higher alcohols. Detailed Implementation

[0018] The catalyst of the present invention is implemented according to the above steps. The following is a detailed description through examples. Unless otherwise specified, the content and percentage in this application are calculated by "mass".

[0019] Example 1

[0020] 9.68g of Ni(NO3)2·6H2O was dissolved in 12g of anhydrous ethanol. After the raw material was completely dissolved, 10g of pretreated apricot shell activated carbon was added. After uniform impregnation, the carbon was air-dried at room temperature for 12 hours, and then calcined in a muffle furnace at 400℃ for 8 hours with a heating rate of 2℃ / min. After cooling, the active component Pd was impregnated and loaded. 24.4mg of Pd(NO3)2·nH2O (Pd content 41.0%) was dissolved in 9.5g of anhydrous ethanol. After complete dissolution, 10g of the above-prepared supported Ni catalyst was added. After uniform impregnation, the carbon was air-dried at room temperature for 12 hours, and then calcined in a muffle furnace at 200℃ for 4 hours to obtain a bifunctional hydrogenation catalyst. The apricot shell activated carbon pretreatment mentioned above refers to treating the apricot shell activated carbon with 25% trimethylchlorosilane reagent at 60℃ for 4 hours to obtain the pretreated apricot shell activated carbon support.

[0021] The bifunctional hydrogenation catalyst prepared above was loaded into a fixed-bed reactor with a catalyst loading of 4 ml. Hydrogen gas was introduced, and the catalyst reduction temperature was 623 K, the reduction time was 4 h, the reduction pressure was 0.1 MPa, and the reducing gas space velocity was 1000 h⁻¹.-1 After the catalyst is reduced by hydrogen, the Fischer-Tropsch hydroformylation product is pumped into the reactor via a high-pressure metering pump to begin the reaction. The hydrogenation reaction temperature is 453 K, the reaction pressure is 5 MPa, and the liquid hourly space velocity (LISH) is 1.5 h⁻¹. -1 The hydrogen / liquid feed molar ratio was 10. Liquid products were collected in a high-pressure absorption vessel and analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector. Reaction tail gas was analyzed online using an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 1.

[0022] Example 2

[0023] Except for replacing 9.68g of Ni(NO3)2·6H2O with 17.28g of Ni(NO3)2·6H2O in the catalyst preparation, the other processes were the same as in Example 1. The reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0024] Example 3

[0025] Except for replacing 9.68 g of Ni(NO3)2·6H2O with 24.19 g of Ni(NO3)2·6H2O in the catalyst preparation, the other processes were the same as in Example 1. The results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0026] Example 4

[0027] Except for replacing 24.4 mg Pd(NO3)2·nH2O (Pd content 41.0%) with 61.0 mg Pd(NO3)2·nH2O (Pd content 41.0%) in the catalyst preparation, the other processes were the same as in Example 1. The reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0028] Example 5

[0029] Except for replacing 24.4 mg Pd(NO3)2·nH2O (Pd content 41.0%) with 195.2 mg Pd(NO3)2·nH2O (Pd content 41.0%) in the catalyst preparation, the other processes were the same as in Example 1. The reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0030] Example 6

[0031] Except for the use of 35% trimethylchlorosilane reagent instead of 25% trimethylchlorosilane reagent in catalyst preparation, the process was the same as in Example 1. The results of the bifunctional hydrogenation catalyst reaction are listed in Table 1.

[0032] Example 7

[0033] Except for the use of 45% trimethylchlorosilane reagent instead of 25% trimethylchlorosilane reagent in catalyst preparation, the process was the same as in Example 1. The results of the bifunctional hydrogenation catalyst reaction are listed in Table 1.

[0034] Example 8

[0035] Except for the use of apricot shell activated carbon support treated at 100°C instead of 60°C in catalyst preparation, the other processes were the same as in Example 1. The reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0036] Example 9

[0037] Except for the use of apricot shell activated carbon support treated at 150°C instead of 60°C in catalyst preparation, the other processes were the same as in Example 1. The reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0038] Example 10

[0039] Except for replacing the 4-hour treatment with apricot shell activated carbon support with 8 hours of treatment in the catalyst preparation process, the other processes were the same as in Example 1. The reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0040] Example 11

[0041] Except for replacing the 4-hour treatment of the apricot shell activated carbon support with a 15-hour treatment of apricot shell activated carbon in the catalyst preparation, the other processes were the same as in Example 1. The reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0042] Example 12

[0043] The optimized catalyst preparation method involved dissolving 17.28 g of Ni(NO3)2·6H2O in 12 g of anhydrous ethanol. After complete dissolution, 10 g of pretreated apricot shell activated carbon was added, and the mixture was thoroughly impregnated. The carbon was then air-dried at room temperature for 12 hours, followed by calcination in a muffle furnace at 400°C for 8 hours (heating rate 2°C / min). After cooling, the active component Pd was impregnated and loaded. 61 mg of Pd(NO3)2·nH2O (Pd content 41.0%) was dissolved in 9.5 g of anhydrous ethanol. After complete dissolution, 10 g of the prepared supported Ni catalyst was added, and the mixture was thoroughly impregnated. The carbon was then air-dried at room temperature for 12 hours, followed by calcination in a muffle furnace at 200°C for 4 hours to obtain the bifunctional hydrogenation catalyst. The aforementioned apricot shell activated carbon pretreatment refers to treating the apricot shell activated carbon with 35% trimethylchlorosilane reagent at 100°C for 8 hours to obtain the pretreated apricot shell activated carbon support.

[0044] The catalyst small-scale evaluation process was the same as in Example 1, and the reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0045] Comparative Example 1

[0046] 17.28 g of Ni(NO3)2·6H2O and 61 mg of Pd(NO3)2·nH2O (Pd content 41.0%) were dissolved in 12 g of anhydrous ethanol. After all the raw materials were dissolved, 10 g of pretreated apricot shell activated carbon was added, and the mixture was impregnated evenly. The carbon was then air-dried at room temperature for 12 hours, and then calcined in a muffle furnace at 400℃ for 8 hours at a muffle furnace heating rate of 2℃ / min to obtain a bifunctional hydrogenation catalyst. The aforementioned pretreatment of the apricot shell activated carbon refers to treating the apricot shell activated carbon with 35% trimethylchlorosilane reagent at 100℃ for 8 hours to obtain the pretreated apricot shell activated carbon carrier.

[0047] The catalyst small-scale evaluation process was the same as in Example 1, and the reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0048] Comparative Example 2

[0049] 61 mg of Pd(NO3)2·nH2O (Pd content 41.0%) was dissolved in 9.5 g of anhydrous ethanol. After complete dissolution, 10 g of pretreated apricot shell activated carbon was added, and the mixture was thoroughly impregnated. The carbon was then air-dried at room temperature for 12 hours, followed by calcination in a muffle furnace at 200 °C for 4 hours (heating rate 2 °C / min). After cooling, the active component Ni was impregnated and loaded. 17.28 g of Ni(NO3)2·6H2O was dissolved in 12 g of anhydrous ethanol. After complete dissolution, 10 g of the prepared supported Pd catalyst was added, and the mixture was thoroughly impregnated. The carbon was then air-dried at room temperature for 12 hours, followed by calcination in a muffle furnace at 400 °C for 8 hours to obtain a bifunctional hydrogenation catalyst. The aforementioned pretreatment of the apricot shell activated carbon refers to treating the activated carbon with 35% trimethylchlorosilane reagent at 100 °C for 8 hours to obtain the pretreated apricot shell activated carbon support.

[0050] The catalyst small-scale evaluation process was the same as in Example 1, and the reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0051] Comparative Example 3

[0052] The catalyst preparation process is the same as in Example 12, except that untreated apricot shell activated carbon support is used instead of pretreated apricot shell activated carbon support in the catalyst preparation process. The other processes are the same as in Example 12.

[0053] The catalyst small-scale evaluation process was the same as in Example 1, and the reaction results of the bifunctional hydrogenation catalyst are listed in Table 1.

[0054] Table 1. Hydrogenation performance of bifunctional catalysts for by-product hydroformylation of olefins

[0055]

[0056] Note: [1] Higher alcohols and oxygen-containing compounds such as aldehydes and acids have a carbon number range of 5-16, while alkanes have a carbon number range of 4-15.

[0057] The results above demonstrate that the bifunctional hydrogenation catalyst provided by this invention is applicable to the method of hydrogenating Fischer-Tropsch by-product olefin hydroformylation products to higher alcohols. In the presence of the bifunctional hydrogenation catalyst, the Fischer-Tropsch hydroformylation products are hydrogenated with hydrogen in a reactor, enabling the efficient one-step conversion of aldehydes, acids, and olefins contained in the Fischer-Tropsch hydroformylation products into higher alcohols and alkanes. Furthermore, this bifunctional hydrogenation catalyst exhibits excellent stability in a fixed-bed continuous long-cycle reaction evaluation. The method utilizes a bifunctional hydrogenation catalyst with high catalytic activity and ultra-high stability, effectively improving the economics of the hydrogenation process of Fischer-Tropsch hydroformylation products to produce higher alcohols, and has significant industrial production implications.

[0058] The present invention has been described in detail above, but it is not limited to the specific embodiments described herein. Those skilled in the art will understand that other modifications and variations can be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims

1. The application of a bifunctional catalyst in the hydrogenation of Fischer-Tropsch hydroformylation products to higher alcohols, characterized in that: The catalyst mainly consists of active components Ni and Pd, and a pretreated support material. The support material is selected from one of the following: pretreated coconut shell activated carbon, walnut shell activated carbon, or apricot shell activated carbon. The support material pretreatment involves using trimethylchlorosilane reagent at a temperature of 50-200℃, a silane reagent concentration of 20%-50%, and a treatment time of 4-20 h. In the presence of the bifunctional hydrogenation catalyst, the Fischer-Tropsch hydroformylation product undergoes a hydrogenation reaction with hydrogen in a reactor. This allows for the efficient one-step conversion of the aldehydes, acids, and olefins contained in the Fischer-Tropsch hydroformylation product into higher alcohols and alkanes. The Fischer-Tropsch hydroformylation product feedstock is pumped into the reaction system using a high-pressure pump, with a liquid hourly space velocity (LISH) of 0.5-2.0 h⁻¹. -1 Hydrogen feedstock is fed in gaseous form with a gas space velocity of 1000-8000 h⁻¹. -1 The molar ratio of raw materials to hydrogen is 1:1 to 1:100; the mass content of Ni and Pd in ​​the catalyst is 10%-40% and 0.05%-1.0%, respectively, and the remainder is the mass of the pretreated support.

2. The application as described in claim 1, characterized in that: The preferred mass contents of Ni and Pd in ​​the catalyst are 15%-30% and 0.2%-0.4%, respectively, with the remainder being the mass of the pretreated support.

3. The application as described in claim 1 or 2, characterized in that: The carrier material is either coconut shell activated carbon or apricot shell activated carbon; the carrier material pretreatment refers to the pretreatment of the carrier material with trimethylchlorosilane reagent at a temperature of 80-120℃, a silane reagent concentration of 30%-40%, and a treatment time of 6-10h.

4. The application as described in claim 1, characterized in that: The catalyst has a specific surface area of ​​400-1200 m². 2 / g, pore volume 0.4-1.5 cm³ 3 / g, bulk density is 0.4-1.5 g / cm³ 3 .

5. The use of a catalyst according to any one of claims 1-4, characterized in that: The catalyst was prepared by a stepwise impregnation method, including the following preparation steps: (1) At 25-60℃, the nickel salt was completely dissolved in ethanol solvent. After complete dissolution, the pretreated support material was added, and the catalyst was air-dried at room temperature for 6-24 hours and calcined at 300-500℃ for 8-12 hours. (2) When the catalyst in step (1) was cooled to 25-60℃, the palladium salt was completely dissolved in ethanol solvent. After complete dissolution, the catalyst prepared in step (1) was added, and the catalyst was air-dried at room temperature for 6-24 hours and calcined at 150-250℃ for 2-6 hours to obtain a bifunctional hydrogenation catalyst.

6. The application as described in claim 5, characterized in that: The nickel salt is selected from Ni(NO3)2, Ni(CH3COO)2, NiCl2, and NiCO3; the palladium salt is selected from Pd(NO3)2, PdCl2, and PdSO4.

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