Pd-MOF catalyst, preparation method, application and method for preparing butyl acrylate through acetylene carbonylation

Abstract

The invention belongs to the technical field of metal organic framework materials and acetylene carbonylation, and particularly relates to a Pd-MOF catalyst, a preparation method, application and a method for preparing butyl acrylate through acetylene carbonylation, the preparation method comprises the following steps: S1, dissolving a compound containing Ni < 2 + > and an organic ligand in a solvent, and mixing to obtain a clear solution; the organic ligands are 4, 4 '-dipyridyl and 1, 3, 5-benzene tricarbonic acid; s2, transferring the settled solution into a hydrothermal reaction kettle, sealing, cooling after reaction, and washing and drying to obtain Ni-MOF; s3, soaking the Ni-MOF in a deuterated solvent containing a Pd < 2 + > compound, cooling after reaction, and washing and drying a reaction product to obtain the Pd-MOF catalyst. The prepared material has a topological structure capable of enhancing stability, has high catalytic activity, is easy to recover and recycle, and can be well used for preparing butyl acrylate through acetylene carbonylation.

Description

Technical Field

[0001] The invention belongs to the technical field of metal organic framework materials and acetylene carbonylation, and specifically relates to a Pd-MOF catalyst, a preparation method, an application and a method for preparing butyl acrylate by acetylene carbonylation. Background Art

[0002] Butyl acrylate is an important organic compound, mainly used for the production of monomers for homopolymers and copolymers, and is mainly used in the production of PVC, PVB, PMMA protective films, plastic packaging materials, optical fiber coatings, UV light-curing coatings, inks, adhesives and other fields. At present, most industrial production of butyl acrylate adopts the propylene oxidation method, in which propylene and butanol are esterified under the action of a catalyst to produce butyl acrylate; however, with the rise in oil prices, the cost of propylene and butanol has also increased, causing the cost of this process to increase accordingly. On the other hand, the process of converting coal into acetylene through calcium carbide in the traditional coal chemical industry has a serious problem of tail gas emissions. If the main component of the tail gas, CO, is recovered and reacted with acetylene through carbonylation to synthesize butyl acrylate with higher added value, the resource utilization rate can be greatly improved, and the technological and economic progress of the downstream coal chemical industry can be promoted, which is in line with my country's national conditions of energy structure and is green and environmentally friendly.

[0003] Acetylene carbonylation refers to the synthesis of acrylic acid (ester) using acetylene, CO and compounds with replaceable hydrogen atoms (such as water, alcohol, thiol or alkyne, etc.) as raw materials. The reaction was first proposed by Reppe in 1939, so it is also called the Reppe synthesis method. In the reaction of preparing butyl acrylate by acetylene carbonylation, most homogeneous catalysts are used, mainly including nickel-based catalytic systems (such as Ni(CO)4, NiBr2), palladium-based catalytic systems (such as Pd(OAc)2), iron-based catalytic systems (such as Fe(CO)5) and cobalt-based catalytic systems (such as Co2(CO)8). Although these catalysts are highly active, their further development is limited by problems such as high toxicity, high price and difficulty in recovery. Therefore, inexpensive, efficient and easy-to-separate heterogeneous catalysts have become a research hotspot for acetylene carbonylation reactions.

[0004] Referring to the Chinese patent application document with application number 201910401439.8, a catalyst for preparing methyl acrylate by carbonylation of acetylene and its application method are disclosed, and a heterogeneous nickel-based catalyst with a hydrogen-type molecular sieve as a carrier is reported, which can be used to catalyze the carbonylation reaction of acetylene, CO and methanol, but the reaction temperature is 160°C to 260°C, and the initial pressure is 2MPa to 5MPa. The acetylene conversion rate and methyl acrylate selectivity can reach up to 60% and 80% respectively. However, the carbonylation reaction temperature and pressure of the nickel-based catalyst are relatively high, the acetylene conversion rate and product selectivity are relatively low, and there are more by-products. Referring to the Chinese patent application document with application number 201710842449.6, a method for synthesizing acrylic acid or acrylic ester is disclosed, and a bidentate ligand chelate catalyst of palladium supported on an inorganic carrier is prepared, which can be used in the preparation of butyl acrylate by acetylene carbonylation. However, the catalytic system and the preparation process are relatively complicated. In addition, there are problems such as poor stability of the active components in the main catalyst, and difficulty in separation and recovery of the catalyst additive and the ligand, which leads to an increase in the amount of catalyst used and causes excessively high use costs.

[0005] In summary, how to provide a catalyst for acetylene carbonylation to butyl acrylate that has good stability, is easy to recycle and has good catalytic activity is a current challenge. Summary of the invention

[0006] In view of the technical problems existing in the prior art, the present invention provides a Pd-MOF catalyst, a preparation method, an application thereof and a method for preparing butyl acrylate by carbonylation of acetylene.

[0007] The present invention adopts transition metal palladium ions and organic ligands to self-assemble into a Pd-MOF catalyst, which has a topological structure that can enhance stability, has high catalytic activity, is easy to recover and recycle, and can be well used in the preparation of butyl acrylate by carbonylation of acetylene.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

[0009] A method for preparing a Pd-MOF catalyst comprises the following steps:

[0010] S1, first contain Ni 2+ The compound and the organic ligand are dissolved in a solvent in a molar ratio of 5:(1-20), and mixed to obtain a clear solution; the organic ligand is a mixture of 4,4'-bipyridine and 1,3,5-benzenetricarboxylic acid in equimolar proportions;

[0011] S2. The clarified solution of step S1 is transferred to a hydrothermal reactor and sealed, and maintained at 50°C to 200°C for 6h to 30h. After the reaction is completed, the temperature is cooled to room temperature, and the reaction product is washed and dried to obtain Ni-MOF.

[0012] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ The compound is reacted in a deuterated solvent at 60°C to 100°C for 24 to 120 hours. During the reaction, the Pd 2+ The deuterated solvent of the compound was added every 12 hours. Each time it was added, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1g:100ml, and the Pd-containing 2+ Pd in ​​deuterated solvents 2+ The concentration is 0.05 mol / L; after the reaction is completed, the temperature is cooled to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0013] It is further defined that in step S1, Ni 2+ The compound contains Ni 2+ Nitrate, containing Ni 2+ Acetate, containing Ni 2+ Halogenated salts containing Ni 2+ Carbonate or containing Pd 2+ of perchlorate.

[0014] It is further defined that in step S1, the solvent is water and / or an organic solvent; the organic solvent is any one or any combination of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-diethylacetamide, acetonitrile, methanol, ethanol, tetrahydrofuran and dichloromethane.

[0015] It is further defined that in step S2, the drying temperature is 40°C to 140°C.

[0016] Further defined, in step S3, the Pd 2+ The compound contains Pd 2+ Nitrates containing Pd 2+ acetate, containing Pd 2+ Halogenated salts containing Pd 2+ Carbonate or containing Pd 2+ of perchlorate.

[0017] In step S3, the deuterated solvent is any one or any combination of deuterated chloroform, deuterated dimethyl sulfoxide, deuterated tetrachloroethane and deuterated ethylene glycol.

[0018] A Pd-MOF catalyst prepared by using a preparation method of a Pd-MOF catalyst.

[0019] Application of the Pd-MOF catalyst in acetylene carbonylation reaction.

[0020] A method for preparing butyl acrylate by carbonylation of acetylene comprises the following steps:

[0021] Adding a catalyst, n-butanol and a solvent into a reactor, replacing the air in the reactor with nitrogen; the catalyst is the Pd-MOF catalyst; the mass of the catalyst is 0.1% to 5% of the mass of the solvent; the mass of the n-butanol is 5% to 45% of the mass of the solvent;

[0022] Under stirring, acetylene is continuously introduced until the solvent is saturated, the acetylene partial pressure is 0.1MPa-0.6MPa, CO is then introduced to the initial reaction pressure of 0.8MPa-6MPa, the molar ratio of acetylene to CO = 1:1-1:10, the molar ratio of C2H2 to n-butanol = 1:1-1:20, and then heated to 20°C-160°C, and reacted for 0.1h-3h;

[0023] After the reaction is completed, the reactor is cooled to room temperature, and the reaction product is taken for solid-liquid separation. The liquid product is purified by distillation to obtain butyl acrylate; the solid is recovered and directly reused.

[0024] It is further defined that the solvent is one or more of tetrahydrofuran, acetone, acetonitrile, toluene, methanol or n-hexane.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The Pd-MOF catalyst of the present invention has strong structural stability. This is because the metal ions and organic ligands in the porous material are connected by coordination bonds to form a MOFs-type crystal structure, and the bond energy of the coordination bond is 60 to 350 KJmol -1 , the bond energy is stronger than weak bonds such as van der Waals force and ammonia bond. Therefore, the Pd-MOF porous material system composed of coordination bonds has better stability than other materials composed of weak bonds.

[0027] 2. The Pd-MOF catalyst of the present invention has porosity and pore type diversity. Due to the directionality of the coordination bond and the spatial size of the organic ligand itself, the material has porous characteristics and permanent porosity; in addition, the material also has a porous structure, which is a typical feature of the H3 type hysteresis loop isotherm, and is a typical porous material. The synergistic effect of different pore structures improves the catalytic activity of the catalyst.

[0028] 3. The Pd-MOF catalyst of the present invention has an adsorption effect. Since the material has a very high specific surface area and the pores are mainly mesopores, it has good adsorption properties; in this way, in the catalytic reaction, the raw gas can be adsorbed on the catalyst surface or pores and more reaction surfaces are provided, which is more conducive to the catalytic reaction, thereby improving the catalytic effect.

[0029] 4. The Pd-MOF catalyst of the present invention has a large specific surface area, which provides more exposure possibilities for active sites. By adjusting the reaction time and reaction temperature when preparing Ni-MOF, the pore size and specific surface area of ​​the obtained material can be adjusted. Increasing the reaction temperature and increasing the reaction time are helpful to increase the specific surface area of ​​the material and increase the pore size of the material. The pore size range is between 4.35 and 18.42 nm, and the specific surface area can be controlled between 449.58 and 1928.24 m 2 .g -1 The prepared Pd-MOF porous synergistic effect helps to optimize the catalytic performance. These advantages greatly improve the catalytic efficiency, and the catalyst is easy to recycle and can be recycled many times, which improves the economic feasibility.

[0030] 5. The present invention uses Pd-MOF catalyst as the catalyst for acetylene carbonylation reaction, which has a simple preparation method, high catalytic activity, good product selectivity, simple catalyst recovery method and good repeated service life.

[0031] 6. The present invention uses Pd-MOF catalyst for the carbonylation of acetylene to prepare butyl acrylate. The reaction process conditions are mild, the conversion rate of raw material n-butanol is ≥99%, and the selectivity of butyl acrylate is ≥99%. The reaction of the raw material n-butanol is reduced to complete, and the incomplete reaction that causes n-butanol to easily form an azeotrope with butyl acrylate is avoided, the separation difficulty in the product distillation separation process is reduced, and the energy consumption cost in the product separation process is reduced.

[0032] 7. The present invention adopts a one-step method of acetylene carbonylation to prepare butyl acrylate, which makes good use of carbide acetylene, avoids the problem of large carbide acetylene production and overcapacity, not only conforms to the development trend of energy structure, has raw material cost advantages, but also can promote the technological and economic progress of coal chemical downstream. Therefore, the Pd-MOF catalyst provided by the present invention has good industrial development and application prospects in the method of preparing butyl acrylate by acetylene carbonylation. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 N2 adsorption-desorption isotherms and pore size distribution of Pd-MOF. DETAILED DESCRIPTION

[0034] The technical solution protected by the present invention is now described in detail in conjunction with the embodiments. However, it is obvious that the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the described embodiments of the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0035] All features disclosed in this specification, except mutually exclusive features and / or steps, can be combined in any manner.

[0036] The present invention provides a method for preparing a Pd-MOF catalyst, comprising the following steps:

[0037] S1, containing Ni 2+ The compound and the organic ligand are dissolved in a solvent in a molar ratio of 5:(1-20), and mixed to obtain a clear solution.

[0038] In the present invention, Ni 2+ The molar ratio of the compound to the organic ligand is 5:1, 5:5, 5:10, 5:15 or 5:20.

[0039] In the present invention, the organic ligand comprises 4,4'-bipyridine and 1,3,5-benzenetricarboxylic acid mixed in equal moles.

[0040] In step S1 of the present invention, Ni 2+ The compound contains Ni 2+ Nitrate, containing Ni 2+ Acetate, containing Ni 2+ Halogenated salts containing Ni 2+ Carbonate or containing Ni 2+ of perchlorate.

[0041] In step S1 of the present invention, the solvent is water and / or an organic solvent; the organic solvent is any one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-diethylacetamide, acetonitrile, methanol, ethanol, tetrahydrofuran and dichloromethane, or a mixture of any two of them.

[0042] In the present invention, when the organic solvent is a mixture of multiple solvents, the mixing volume ratio of each solvent is not specifically limited, and the solvents can be mixed in any ratio.

[0043] In this step, the mixing is carried out by fully stirring at room temperature or by using microwave ultrasound.

[0044] S2. The clarified solution of step S1 is transferred to a hydrothermal reactor and sealed, and maintained at 50°C to 200°C for 6h to 30h. After the reaction is completed, the temperature is cooled to room temperature, and the reaction product is washed and dried to obtain Ni-MOF.

[0045] In step S2 of the present invention, the drying temperature is 40°C to 140°C.

[0046] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ The reaction is carried out in a deuterated solvent containing the compound at 60°C to 100°C for 24 to 120 hours. 2+The deuterated solvent of the compound was added every 12 hours. Each time it was added, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1g:100ml, containing Pd 2+ Pd in ​​deuterated solvents 2+ The concentration is 0.05 mol / L; after the reaction is completed, the temperature is cooled to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0047] In the present invention, Pd 2+ The compound contains Pd 2+ Nitrates containing Pd 2+ acetate, containing Pd 2+ Halogenated salts containing Pd 2+ Carbonate or containing Pd 2+ of perchlorate.

[0048] In the present invention, the deuterated solvent is any one or any combination of deuterated chloroform, deuterated dimethyl sulfoxide, deuterated tetrachloroethane and deuterated ethylene glycol.

[0049] When the deuterated solvent is a mixture of a plurality of solvents, the volume ratio of each solvent is not limited and the solvents can be mixed in any ratio.

[0050] Preferably, the deuterated solvent is deuterated chloroform.

[0051] In the present invention, Pd 2+ The deuterated solvent of the compound is added every 12 hours, so the holding time is generally selected to be an integer multiple of 12.

[0052] In the present invention, the Pd-MOF catalyst prepared by the preparation method of the Pd-MOF catalyst has strong stability, porosity, diversity of pore types, adsorption effect, and large specific surface area, is more conducive to the catalytic reaction, greatly improves the catalytic efficiency, is easy to recover, can be recycled for multiple times, can be used in the acetylene carbonylation reaction, has mild reaction conditions, and the raw material n-butanol conversion rate and butyl acrylate selectivity are both greater than 99%.

[0053] The present invention also provides a method for preparing butyl acrylate by carbonylation of acetylene, comprising the following steps:

[0054] A catalyst, n-butanol and a solvent are added into a reactor, and the air in the reactor is replaced by nitrogen. The catalyst is a Pd-MOF catalyst. The mass of the catalyst is 0.1% to 5% of the mass of the solvent. The mass of n-butanol is 5% to 45% of the mass of the solvent. Acetylene is continuously introduced under stirring until the solvent is saturated with absorption, and the acetylene partial pressure is 0.1MPa to 0.6MPa. CO is then introduced until the initial reaction pressure is 0.8MPa to 6MPa, the molar ratio of acetylene to CO is 1:1 to 1:10, and the molar ratio of C2H2 to n-butanol is 1:1 to 1:20. The reaction is then heated to 20°C to 160°C and reacted for 0.1h to 3h. After the reaction is completed, the reactor is cooled to room temperature, and the reaction product is taken for solid-liquid separation. The liquid product is purified by distillation to obtain butyl acrylate. The solid is recovered and directly reused.

[0055] In the present invention, the solvent is one or more of tetrahydrofuran, acetone, acetonitrile, toluene, methanol or n-hexane.

[0056] The following is a detailed description of the preparation method of the Pd-MOF catalyst provided by the present invention and its advantages as a catalyst in the preparation of butyl acrylate by carbonylation of acetylene using several groups of specific examples.

[0057] It should be noted that, unless otherwise specified, the chemicals, reagents, etc. used in the following examples are all conventional commercial products in the art.

[0058] It should be noted that, unless otherwise specified, the operating steps used in the following embodiments are routine operations in the art.

[0059] Example 1

[0060] In this embodiment, the preparation method of the Pd-MOF catalyst includes the following steps:

[0061] S1. Dissolve Ni(NO3)2 (1 mmol), 1,3,5-benzenetricarboxylic acid (1 mmol), and 4,4'-bipyridine (1 mmol) in 40 ml of N,N-dimethylformamide (hereinafter referred to as DMF), and stir thoroughly at room temperature until the solution becomes clear.

[0062] S2. The clarified solution was transferred to a hydrothermal reactor and sealed, and maintained at 80°C for 30 hours. After the reaction was completed, the reactor temperature dropped to room temperature, the supernatant was poured out, and the product was washed with DMF, ethanol and deionized water in turn, and dried in vacuum at 40°C to obtain Ni-MOF.

[0063] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ Deuterated chloroform of the compound (where Pd 2+ The concentration of Pd was 0.05 mol / L) and kept at 60 °C for 24 h.2+ Deuterated chloroform (containing Pd 2+ The deuterated solvent of the compound was added every 12 hours. Each time, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1 g: 100 ml; after the reaction is completed, the temperature is lowered to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0064] In this embodiment, the Pd-MOF catalyst prepared above is used as an acetylene carbonylation catalyst to prepare butyl acrylate by a one-step acetylene carbonylation process.

[0065] In this embodiment, the method for preparing butyl acrylate by carbonylation of acetylene comprises the following steps:

[0066] Add 100 ml acetone, 32 ml n-butanol, and 0.5 g Pd-MOF catalyst to a 250 ml autoclave. Seal the reactor, introduce 0.5 MPa high-purity nitrogen to replace the air in the reactor, replace 3 times, introduce 0.15 MPa acetylene at a stirring speed of 500 r / min for 30 min. Then introduce carbon monoxide until the reaction pressure (total system pressure) is 3.5 MPa. Rapidly heat to 40°C and react at a speed of 500 r / min for 20 min.

[0067] In this embodiment, the tail gas is tested online after the reaction is completed, the liquid phase product and the catalyst are separated by centrifugation, and the liquid phase product is analyzed. The catalytic reaction performance is calculated based on the analysis results of the tail gas and the liquid phase product, and the conversion rate of n-butanol is 85%, and the selectivity of butyl acrylate is 99%.

[0068] Example 2

[0069] In this embodiment, the preparation method of the Pd-MOF catalyst includes the following steps:

[0070] S1. Dissolve Ni(NO3)2 (1 mmol), 1,3,5-benzenetricarboxylic acid (1 mmol), and 4,4'-bipyridine (1 mmol) in 40 ml of DMF and stir thoroughly at room temperature until the solution becomes clear.

[0071] S2. The clarified solution was transferred to a hydrothermal reactor, sealed, and maintained at 100°C for 30 hours. After the reaction was completed, the reactor temperature dropped to room temperature, the supernatant was poured out, and the product was washed with DMF, ethanol and deionized water in turn, and dried in vacuum at 40°C to obtain a Ni-MOF catalyst.

[0072] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ Deuterated chloroform of the compound (where Pd 2+The concentration of Pd was 0.05 mol / L) and kept at 60 °C for 48 h. 2+ Deuterated chloroform (containing Pd 2+ The deuterated solvent of the compound was added every 12 hours. Each time, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1 g: 100 ml; after the reaction is completed, the temperature is lowered to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0073] In this embodiment, the Pd-MOF catalyst prepared above is used as an acetylene carbonylation catalyst to prepare butyl acrylate by a one-step acetylene carbonylation process.

[0074] In this embodiment, the method for preparing butyl acrylate by carbonylation of acetylene comprises the following steps:

[0075] Add 100ml acetone, 32ml n-butanol, and 0.5g Pd-MOF catalyst to a 250ml autoclave. Seal the reactor, introduce 0.5MPa high-purity nitrogen to replace the air in the reactor, replace 3 times, introduce 0.15MPa acetylene at a stirring speed of 500r / min for 30min. Then introduce carbon monoxide until the reaction pressure (total system pressure) is 3.5MPa. Rapidly heat to 40℃ and react at a speed of 500r / min for 20min.

[0076] In this embodiment, the tail gas is tested online after the reaction is completed, the liquid phase product and the catalyst are separated by centrifugation, and the liquid phase product is analyzed. The catalytic reaction performance is calculated based on the analysis results of the tail gas and the liquid phase product, and the conversion rate of n-butanol is 92%, and the selectivity of butyl acrylate is 99%.

[0077] Example 3

[0078] In this embodiment, the preparation method of the Pd-MOF catalyst includes the following steps:

[0079] S1. Dissolve Ni(NO3)2 (1 mmol), 1,3,5-benzenetricarboxylic acid (1 mmol), and 4,4'-bipyridine (1 mmol) in 40 ml of DMF and stir thoroughly at room temperature until the solution becomes clear.

[0080] S2. The clarified solution was transferred to a hydrothermal reactor and sealed, and maintained at 120°C for 30 hours. After the reaction was completed, the reactor temperature dropped to room temperature, the supernatant was poured out, and the product was washed with DMF, ethanol and deionized water in turn, and dried in vacuo at 40°C to obtain a Pd-MOF catalyst.

[0081] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+Deuterated chloroform of the compound (where Pd 2+ The concentration of Pd was 0.05 mol / L) and kept at 60 °C for 72 h. 2+ Deuterated chloroform (containing Pd 2+ The deuterated solvent of the compound was added every 12 hours. Each time, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1 g: 100 ml; after the reaction is completed, the temperature is lowered to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0082] In this embodiment, the Pd-MOF catalyst prepared above is used as an acetylene carbonylation catalyst to prepare butyl acrylate by a one-step acetylene carbonylation process.

[0083] In this embodiment, the method for preparing butyl acrylate by carbonylation of acetylene comprises the following steps:

[0084] Add 100 ml acetone, 32 ml n-butanol, and 0.5 g Pd-MOF catalyst to a 250 ml autoclave. Seal the reactor, introduce 0.5 MPa high-purity nitrogen to replace the air in the reactor, replace 3 times, introduce 0.15 MPa acetylene at a stirring speed of 500 r / min for 30 min. Then introduce carbon monoxide until the reaction pressure (total system pressure) is 3.5 MPa. Rapidly heat to 40°C and react at a speed of 500 r / min for 20 min.

[0085] In this embodiment, the tail gas is tested online after the reaction is completed, the liquid phase product and the catalyst are separated by centrifugation, and the liquid phase product is analyzed. The catalytic reaction performance is calculated based on the analysis results of the tail gas and the liquid phase product, and the conversion rate of n-butanol is 87%, and the selectivity of butyl acrylate is 96%.

[0086] Example 4

[0087] In this embodiment, the preparation method of the Pd-MOF catalyst includes the following steps:

[0088] S1. Dissolve Ni(NO3)2 (1 mmol), 1,3,5-benzenetricarboxylic acid (1 mmol), and 4,4'-bipyridine (1 mmol) in 40 ml of DMF and stir thoroughly at room temperature until the solution becomes clear.

[0089] S2. The clarified solution was transferred to a hydrothermal reactor and sealed, and maintained at 80°C for 30 hours. After the reaction was completed, the reactor temperature dropped to room temperature, the supernatant was poured out, and the product was washed with DMF, ethanol and deionized water in turn, and dried in vacuo at 40°C to obtain a Pd-MOF catalyst.

[0090] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ Deuterated chloroform of the compound (where Pd 2+ The concentration of Pd was 0.05 mol / L) and kept at 60 °C for 96 h. 2+ Deuterated chloroform (containing Pd 2+ The deuterated solvent of the compound was added every 12 hours. Each time, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1 g: 100 ml; after the reaction is completed, the temperature is lowered to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0091] In this embodiment, the Pd-MOF catalyst prepared above is used as an acetylene carbonylation catalyst to prepare butyl acrylate by a one-step acetylene carbonylation process.

[0092] In this embodiment, the method for preparing butyl acrylate by carbonylation of acetylene comprises the following steps:

[0093] Add 100ml acetone, 20ml n-butanol, and 0.5g Pd-MOF catalyst to a 250ml autoclave. Seal the reactor, introduce 0.5MPa high-purity nitrogen to replace the air in the reactor, replace 3 times, introduce 0.15MPa acetylene at a stirring speed of 500r / min for 30min. Then introduce carbon monoxide until the reaction pressure (total system pressure) is 3.5MPa. Rapidly heat to 40℃ and react at a speed of 500r / min for 20min.

[0094] In this embodiment, the tail gas is tested online after the reaction is completed, the liquid phase product and the catalyst are separated by centrifugation, and the liquid phase product is analyzed. The catalytic reaction performance is calculated based on the analysis results of the tail gas and the liquid phase product, and the conversion rate of n-butanol is 96%, and the selectivity of butyl acrylate is 99%.

[0095] Example 5

[0096] In this embodiment, the preparation method of the Pd-MOF catalyst includes the following steps:

[0097] S1. Dissolve Ni(NO3)2 (1 mmol), 1,3,5-benzenetricarboxylic acid (1 mmol), and 4,4'-bipyridine (1 mmol) in 40 ml of DMF and stir thoroughly at room temperature until the solution becomes clear.

[0098] S2. The clarified solution was transferred to a hydrothermal reactor and sealed, and maintained at 80°C for 30 hours. After the reaction was completed, the reactor temperature dropped to room temperature, the supernatant was poured out, and the product was washed with DMF, ethanol and deionized water in turn, and dried in vacuo at 40°C to obtain a Pd-MOF catalyst.

[0099] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ Deuterated chloroform of the compound (where Pd 2+ The concentration of Pd was 0.05 mol / L) and kept at 60 °C for 120 h. 2+ Deuterated chloroform (containing Pd 2+ The deuterated solvent of the compound was added every 12 hours. Each time, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1 g: 100 ml; after the reaction is completed, the temperature is lowered to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0100] In this embodiment, the Pd-MOF catalyst prepared above is used as an acetylene carbonylation catalyst to prepare butyl acrylate by a one-step acetylene carbonylation process.

[0101] In this embodiment, the method for preparing butyl acrylate by carbonylation of acetylene comprises the following steps:

[0102] Add 100 ml acetone, 16 ml n-butanol, and 0.5 g Pd-MOF catalyst to a 250 ml autoclave. Seal the reactor, introduce 0.5 MPa high-purity nitrogen to replace the air in the reactor, replace 3 times, introduce 0.15 MPa acetylene at a stirring speed of 500 r / min for 30 min. Then introduce carbon monoxide until the reaction pressure (total system pressure) is 3.5 MPa. Rapidly heat to 40 ° C, and react at a speed of 500 r / min for 20 min.

[0103] In this embodiment, the tail gas is tested online after the reaction is completed, the liquid phase product and the catalyst are separated by centrifugation, and the liquid phase product is analyzed. The catalytic reaction performance is calculated based on the analysis results of the tail gas and the liquid phase product, and the conversion rate of n-butanol is 99%, and the selectivity of butyl acrylate is 99%.

[0104] Example 6

[0105] In this embodiment, the preparation method of the Pd-MOF catalyst includes the following steps:

[0106] S1. Dissolve Ni(NO3)2 (1 mmol), 1,3,5-benzenetricarboxylic acid (1 mmol), and 4,4'-bipyridine (1 mmol) in 40 ml of DMF and stir thoroughly at room temperature until the solution becomes clear.

[0107] S2. The clarified solution was transferred to a hydrothermal reactor and sealed, and maintained at 80°C for 30 hours. After the reaction was completed, the reactor temperature dropped to room temperature, the supernatant was poured out, and the product was washed with DMF, ethanol and deionized water in turn, and dried in vacuo at 40°C to obtain a Pd-MOF catalyst.

[0108] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ Deuterated chloroform of the compound (where Pd 2+ The concentration of Pd was 0.05 mol / L) and kept at 60 °C for 120 h. 2+ Deuterated chloroform (containing Pd 2+ The deuterated solvent of the compound was added every 12 hours. Each time, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1 g: 100 ml; after the reaction is completed, the temperature is lowered to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0109] In this embodiment, the Pd-MOF catalyst prepared above is used as an acetylene carbonylation catalyst to prepare butyl acrylate by a one-step acetylene carbonylation process.

[0110] In this embodiment, the method for preparing butyl acrylate by carbonylation of acetylene comprises the following steps:

[0111] Add 100ml acetone, 32ml n-butanol, and 0.5g Pd-MOF catalyst to a 250ml autoclave. Seal the reactor, introduce 0.5MPa high-purity nitrogen to replace the air in the reactor, replace 3 times, introduce 0.15MPa acetylene at a stirring speed of 500r / min for 30min. Then introduce carbon monoxide until the reaction pressure (total system pressure) is 3.5MPa. Rapidly heat to 80℃ and react at a speed of 500r / min for 20min.

[0112] In this embodiment, the tail gas is tested online after the reaction is completed, the liquid phase product and the catalyst are separated by centrifugation, and the liquid phase product is analyzed. The catalytic reaction performance is calculated based on the analysis results of the tail gas and the liquid phase product, and the conversion rate of n-butanol is 96%, and the selectivity of butyl acrylate is 92%.

[0113] Example 7

[0114] In this embodiment, the preparation method of the Pd-MOF catalyst includes the following steps:

[0115] S1. Dissolve Ni(NO3)2 (1 mmol), 1,3,5-benzenetricarboxylic acid (1 mmol), and 4,4'-bipyridine (1 mmol) in 40 ml of DMF and stir thoroughly at room temperature until the solution becomes clear.

[0116] S2. The clarified solution was transferred to a hydrothermal reactor and sealed, and maintained at 80°C for 30 hours. After the reaction was completed, the reactor temperature dropped to room temperature, the supernatant was poured out, and the product was washed with DMF, ethanol and deionized water in turn, and dried in vacuo at 40°C to obtain a Pd-MOF catalyst.

[0117] S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ Deuterated chloroform of the compound (where Pd 2+ The concentration of Pd was 0.05 mol / L) and kept at 60 °C for 120 h. 2+ Deuterated chloroform (containing Pd 2+ The deuterated solvent of the compound was added every 12 hours. Each time, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1 g: 100 ml; after the reaction is completed, the temperature is lowered to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

[0118] In this embodiment, the Pd-MOF catalyst prepared above is used as an acetylene carbonylation catalyst to prepare butyl acrylate by a one-step acetylene carbonylation process.

[0119] In this embodiment, the method for preparing butyl acrylate by carbonylation of acetylene comprises the following steps:

[0120] Add 100ml tetrahydrofuran, 16ml n-butanol, and 0.5g Pd-MOF catalyst to a 250ml autoclave. Seal the reactor, introduce 0.5MPa high-purity nitrogen to replace the air in the reactor, replace 3 times, introduce 0.15MPa acetylene at a stirring speed of 500r / min for 30min. Then introduce carbon monoxide until the reaction pressure (total system pressure) is 3.5MPa. Rapidly heat to 40℃ and react at a speed of 500r / min for 20min.

[0121] In this embodiment, the tail gas is tested online after the reaction is completed, the liquid phase product and the catalyst are separated by centrifugation, and the liquid phase product is analyzed. The catalytic reaction performance is calculated based on the analysis results of the tail gas and the liquid phase product, and the conversion rate of n-butanol is 99%, and the selectivity of butyl acrylate is 89%.

[0122] Example 8

[0123] The reaction liquid in Example 5 was directly centrifuged to obtain butyl acrylate, and the solid was recovered; it was then directly recycled as a catalyst. The other reaction conditions were the same as in Example 5. The n-butanol conversion rate and butyl acrylate selectivity were measured at different recycling times, as shown in Table 1.

[0124] Table 1 Conversion rate and selectivity of catalysts under different cycle numbers

[0125] Catalyst application times n-Butanol conversion rate / % Butyl acrylate selectivity / % 1 99 99 2 99 99 3 99 99 4 99 99 5 99 99 6 99 99 7 99 99 8 99 99 9 99 99 10 99 99

[0126] It can be seen from Table 1 that after 10 cycles, the catalyst still has a high conversion rate and selectivity, indicating that the porous catalytic material prepared by the present invention is easy to recycle, can be recycled for many times, and has great catalytic performance.

[0127] Furthermore, the performance of the Pd-MOF catalyst prepared in Example 5 was tested.

[0128] Specifically, the specific surface area, pore volume and average pore size of the Pd-MOF catalyst were tested using conventional methods. The results are shown in Table 1. The N2 adsorption-desorption isotherm and pore size distribution of the Pd-MOF catalyst are shown in Figure 1 .

[0129] Table 1 Structural parameters of Pd-MOF catalysts

[0130] catalyst <![CDATA[Specific surface area / m 2 .g -1 > <![CDATA[Pore volume / cm 3 .g -1 > Average pore size / nm Pd-MOF 1021.09 0.88 10.44

[0131] From Table 1 and Figure 1 It can be concluded that the material also has a porous structure, which is a typical feature of the H3 hysteresis loop isotherm. It is a typical porous material. The synergistic effect of different pore structures improves the catalytic activity of the catalyst. The Pd-MOF catalyst has a very high specific surface area, and the pores are mainly mesopores, which makes the Pd-MOF catalyst have good adsorption and is more conducive to the catalytic reaction.

[0132] In addition, the present invention measured the pore size and specific surface area of ​​the remaining several groups of Pd-MOF catalysts and found that by adjusting the reaction time and reaction temperature when preparing Ni-MOF, the pore size and specific surface area of ​​the obtained material can be adjusted; specifically, when the reaction temperature and reaction time are increased, it is helpful to increase the specific surface area of ​​the material and increase the pore size of the material. The pore size range is between 4.35nm and 18.42nm, and the specific surface area can be controlled at 449.58m 2 .g -1 ~1928.24m 2 .g -1 between, thus helping to optimize the catalytic performance and improve the catalytic efficiency.

[0133] The deuterated solvent in the above embodiments 1 to 5 of the present invention can also be replaced by deuterated dimethyl sulfoxide, deuterated tetrachloroethane or deuterated ethylene glycol, or a mixture of any of deuterated chloroform, deuterated dimethyl sulfoxide, deuterated tetrachloroethane and deuterated ethylene glycol; 2+ The compounds can be 2+Nitrates containing Pd 2+ acetate, containing Pd 2+ Halogenated salts containing Pd 2+ Carbonate or containing Pd 2+ The Pd-MOF catalyst finally prepared was tested and found to have the same catalytic performance as the catalyst in Example 5.

[0134] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a Pd-MOF catalyst, characterized in that: The following steps are involved: S1, first contain Ni 2+ The compound and the organic ligand are dissolved in a solvent in a molar ratio of 5:(1-20), and mixed to obtain a clear solution; the organic ligand is prepared by mixing equimolar amounts of 4,4'-bipyridine and 1,3,5-benzenetricarboxylic acid; S2, transferring the clarified solution of step S1 to a hydrothermal reactor, sealing it, and maintaining it at 50°C to 200°C for 6h to 30h; after the reaction is completed, cooling it to room temperature, taking the reaction product, washing it, and drying it to obtain Ni-MOF; S3, immersing the Ni-MOF obtained in step S2 in a solution containing Pd 2+ The reaction is carried out in a deuterated solvent containing the compound at 60°C to 100°C for 24 to 120 hours. 2+ The deuterated solvent of the compound was added every 12 hours. Each time it was added, Ni-MOF and Pd 2+ The mass volume ratio of the deuterated solvent of the compound is 1g:100ml, and the Pd-containing 2+ Pd in ​​deuterated solvents 2+ The concentration is 0.05 mol / L; after the reaction is completed, the temperature is cooled to room temperature, and the reaction product is washed and dried to obtain a Pd-MOF catalyst.

2. The method for preparing the Pd-MOF catalyst according to claim 1, characterized in that: In the step S1, Ni 2+ The compound contains Ni 2+ Nitrates, containing Ni 2+ Acetate, containing Ni 2+ Halogenated salts containing Ni 2+ Carbonate or containing Ni 2+ of perchlorate.

3. The method for preparing the Pd-MOF catalyst according to claim 1, characterized in that: In step S1, the solvent is water and / or an organic solvent; the organic solvent is any one or any combination of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-diethylacetamide, acetonitrile, methanol, ethanol, tetrahydrofuran and dichloromethane.

4. The method for preparing the Pd-MOF catalyst according to claim 1, characterized in that: In the step S2, the drying temperature is 40°C to 140°C.

5. The method for preparing the Pd-MOF catalyst according to claim 1, characterized in that: In step S3, Pd 2+ The compound contains Pd 2+ Nitrates containing Pd 2+ acetate, containing Pd 2+ Halogenated salts containing Pd 2+ Carbonate or containing Pd 2+ of perchlorate.

6. The method for preparing the Pd-MOF catalyst according to claim 1, characterized in that: In step S3, the deuterated solvent is any one or any combination of deuterated chloroform, deuterated dimethyl sulfoxide, deuterated tetrachloroethane and deuterated ethylene glycol.

7. A Pd-MOF catalyst prepared by the method for preparing the Pd-MOF catalyst according to claim 1.

8. Use of the Pd-MOF catalyst as claimed in claim 7 in acetylene carbonylation reaction.

9. A method for preparing butyl acrylate by carbonylation of acetylene, characterized in that: The following steps are involved: Adding a catalyst, n-butanol and a solvent into a reactor, replacing the air in the reactor with nitrogen; the catalyst is the Pd-MOF catalyst according to claim 5; the mass of the catalyst is 0.1% to 5% of the mass of the solvent; the mass of the n-butanol is 5% to 45% of the mass of the solvent; Under stirring, acetylene is continuously introduced until the solvent is saturated, the acetylene partial pressure is 0.1MPa-0.6MPa, CO is then introduced to the initial reaction pressure of 0.8MPa-6MPa, the molar ratio of acetylene to CO = 1:1-1:10, the molar ratio of C2H2 to n-butanol = 1:1-1:20, and then heated to 20°C-160°C, and reacted for 0.1h-3h; After the reaction is completed, the reactor is cooled to room temperature, and the reaction product is taken for solid-liquid separation. The liquid product is purified by distillation to obtain butyl acrylate; the solid is recovered and directly reused.

10. The method for preparing butyl acrylate by carbonylation of acetylene according to claim 9, characterized in that: The solvent is one or more of tetrahydrofuran, acetone, acetonitrile, toluene, methanol or n-hexane.

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