WO2022012004A1 - 一种用膦配体修饰的催化剂、制备方法与应用 - Google Patents

一种用膦配体修饰的催化剂、制备方法与应用 Download PDF

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WO2022012004A1
WO2022012004A1 PCT/CN2021/071074 CN2021071074W WO2022012004A1 WO 2022012004 A1 WO2022012004 A1 WO 2022012004A1 CN 2021071074 W CN2021071074 W CN 2021071074W WO 2022012004 A1 WO2022012004 A1 WO 2022012004A1
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catalyst
phosphine ligand
reaction
hydrogenation
semi
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郑南峰
荆文彤
李志恺
刘圣杰
陈洁
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Xiamen University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/02—Reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium

Definitions

  • the present invention relates to a catalyst, especially a catalyst modified with a phosphine ligand and a preparation method and application thereof.
  • the catalysts used for selective hydrogenation are: one is to use base metals, such as copper, nickel, etc.; the other is to use precious metals, such as palladium, platinum, etc.; or composite materials of precious metals and base metals, such as palladium-copper, palladium- Bimetallic or metallic materials such as zinc, and palladium-based materials are widely used in catalytic hydrogenation and selective hydrogenation of alkynes due to their excellent hydrogen dissociation ability.
  • base metals such as copper, nickel, etc.
  • precious metals such as palladium, platinum, etc.
  • composite materials of precious metals and base metals such as palladium-copper, palladium- Bimetallic or metallic materials such as zinc, and palladium-based materials are widely used in catalytic hydrogenation and selective hydrogenation of alkynes due to their excellent hydrogen dissociation ability.
  • patent CN101428228A discloses a selective hydrogenation catalyst, wherein the active components of the catalyst are palladium and auxiliary copper, and alumina is used as a carrier.
  • the catalyst is suitable for alkyne-rich residues.
  • the carrier treatment and preparation require high temperatures above 900 °C.
  • the site of the poisoning part is often required to have good selectivity to alkynes, which leads to the low utilization rate of palladium, and increases the use of precious metals, thereby increasing the cost.
  • the method for preparing the selective semi-hydrogenation catalyst especially the method for preparing the selective semi-hydrogenation catalyst only for terminal alkynes, is relatively complicated, and it is difficult to be applied in industrial-scale production. Therefore, the preparation of excellent catalysts with terminal alkyne selective semi-hydrogenation activity can make full use of the active center of the catalyst to improve the activity of the reaction, and at the same time, the operation is simple and convenient, and the preparation cost of the catalyst is reduced, which is of great significance for industrial application and value.
  • An object of the present invention is to solve the existing problems and provide a catalyst.
  • Another object of the present invention is to provide a method for preparing a catalyst.
  • Another object of the present invention is to provide a catalyst application.
  • the present invention adopts following technical scheme:
  • the first aspect of the present invention provides a catalyst modified with a phosphine ligand, the general formula of the catalyst is M-Pd 4 S or M-Pd 4 S/X, the M is a phosphine ligand, and is used for modifying Pd 4 S; the X is a carrier.
  • the carrier is selected from at least one of C, CaCO 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , cerium oxide, molecular sieve, silicon oxide, titanium oxide and diatomaceous earth.
  • the phosphine ligand is an aromatic substituent-containing phosphine ligand.
  • the aromatic substituent-containing phosphine ligand is selected from at least one of bisdiphenylphosphine methane, triphenylphosphine and triphenylphosphine complexes.
  • the triphenylphosphine complex is selected from at least one of triphenylphosphine borane and triphenylphosphine silane.
  • a second aspect of the present invention provides a method for preparing a catalyst modified with a phosphine ligand, comprising:
  • the X is a carrier
  • the phosphine ligand M is a phosphine ligand containing an aromatic substituent.
  • the alcoholic solvent is selected from at least one of ethanol, methanol, propylene glycol, ethylene glycol, n-butanol and isobutanol.
  • the aromatic substituent-containing phosphine ligand is selected from at least one of bisdiphenylphosphine methane, triphenylphosphine, and triphenylphosphine complexes.
  • the triphenylphosphine complex is selected from at least one of triphenylphosphine borane and triphenylphosphine silane.
  • the molar ratio of M:Pd is (5-20):1.
  • the molar ratio of the phosphine ligand M:Pd is (7-15):1.
  • the stirring time is 5-120 min.
  • the stirring time is 10-60min.
  • the stirring temperature is 5-85°C.
  • the temperature of the stirring is 15-55°C.
  • Another aspect of the present invention also provides an application of the catalyst obtained by the above catalyst or the above preparation method, in the semi-hydrogenation of terminal alkyne compounds.
  • a catalyst is applied to a method for semi-hydrogenation of terminal alkyne compounds, comprising the following steps:
  • the terminal alkyne compound is selected from acetylene, propyne, 3-aminophenylacetylene, 3-methylphenylacetylene, 4-tert-butylphenylacetylene, 1-octyne, 2-ethynylpyridine, 4-acetylene at least one of pyridine, phenylacetylene and phenylpropyne.
  • the hydrogenation of alkynes is generally divided into two steps of hydrogenation, the first step of hydrogenation of alkynes to generate alkenes, and then the further hydrogenation of alkenes to generate alkanes, the semi-hydrogenation of alkynes in the present invention refers to the first step of alkynes
  • the process of hydrogenating hydrocarbons to olefins is called semi-hydrogenation of alkynes.
  • Terminal alkynes refer to alkynes whose carbon-carbon triple bonds are located on the terminal carbon, including short-chain alkynes such as acetylene and propyne.
  • Chemical modification refers to attaching active groups or catalytic substances to the surface of the modified object by methods such as adsorption, coating, polymerization, and chemical reaction.
  • Pd 4 S can be selected from nanoscale materials, and its morphology includes but is not limited to particle, flake, and rod.
  • a large sterically hindered ligand is used to modify Pd 4 S or Pd 4 S/X to realize the adsorption of alkynes and the desorption of alkenes to achieve high selectivity of alkenes
  • the phosphine ligand M is used to modify Pd 4 S or Pd 4 S/X to prepare M-Pd 4 S catalyst or M-Pd 4 S/X catalyst with a carrier
  • the catalyst of the present invention realizes high selectivity to terminal alkyne compounds in alkyne semi-hydrogenation reaction sex.
  • the catalyst of the present invention has high selectivity for the semi-hydrogenation of terminal alkyne compounds, and the selectivity exceeds 95% and can be as high as 99% or more.
  • the catalyst of the present invention has a relatively high conversion rate for the semi-hydrogenation catalytic reaction of the terminal alkyne compound, and the conversion rate can reach more than 99%.
  • the catalyst of the present invention has high stability, and is not significantly deactivated after repeated application, and the selectivity is still above 99% after 5 times of application; and the selectivity is still above 98% after 8 times of application.
  • the catalyst prepared by the method does not need to sacrifice a large amount of catalytic activity, and does not need to add toxic substances such as Pb, quinoline, etc., the preparation process is environmentally friendly, and the obtained catalyst is also environmentally friendly.
  • the preparation method of the catalyst of the present invention is simple, universal and good in stability.
  • Fig. 1 is the chromatogram that PPh3-Pd4S Ns catalyst carries out the semi-hydrogenation experiment to phenylacetylene in embodiment 1 by sampling regularly and carries out the chromatogram of product detection by gas chromatography.
  • FIG. 2 is a graph showing the results of the 5-cycle stability experiment of the PPh 3 -Pd 4 S/C catalyst for semi-hydrogenation of phenylacetylene in Example 2.
  • FIG. 2 is a graph showing the results of the 5-cycle stability experiment of the PPh 3 -Pd 4 S/C catalyst for semi-hydrogenation of phenylacetylene in Example 2.
  • FIG. 3 is a graph showing the results of the 8-cycle stability experiment of the semi-hydrogenation experiment of phenylacetylene by the PPh 3 -Pd 4 S/C catalyst in Example 2.
  • FIG. 3 is a graph showing the results of the 8-cycle stability experiment of the semi-hydrogenation experiment of phenylacetylene by the PPh 3 -Pd 4 S/C catalyst in Example 2.
  • Pd Ns Select two-dimensional palladium nanosheets (Pd Ns), add them into an aqueous solution of Na 2 S to make the molar ratio of Pd:S 4:1, raise the temperature to 150° C., keep the hydrogen pressure of 1 MPa, and react for 3 h, Cooling, suction filtration and drying to obtain Pd 4 S Ns.
  • Table 1 shows the experimental results of the semi-hydrogenation of phenylacetylene with PdNs, Pd 4 S Ns and PPh 3 -Pd 4 S Ns catalysts, respectively.
  • Figure 1 shows the semi-hydrogenation of phenyl acetylene with PPh 3 -Pd 4 S Ns catalysts Chromatograms for detection of the product were performed by gas chromatography with timed sampling. It can be seen that the obtained PPh 3 -Pd 4 S Ns catalyst prepared by the present invention performs the hydrogenation reaction of phenylacetylene to obtain an olefin, which is not deeply hydrogenated to alkanes, and is compared with the semi-hydrogenation of PdNs and Pd 4 S Ns. The selectivity of the reaction is greatly improved without significantly reducing the reactivity.
  • reaction steps are: take 20ml of ethanol and transfer it to a 48ml reaction flask, take 2mmol of phenylacetylene as the bottom Put the substance into the reaction bottle and ultrasonically disperse it for 1min, the reaction temperature is 30 °C, add the corresponding amount of catalyst, the molar ratio of substrate to pd is 2000:1, after replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction bottle, set the rotation speed to 1000 rpm and turn on stirring.
  • PPh 3 -Pd 4 S/C catalyst is used for 8 times of semi-hydrogenation reaction with phenylacetylene as a substrate.
  • the reaction conditions are that hydrogen is used as hydrogen source, ethanol is used as solvent, the temperature is 30°C, the pressure of 6 hydrogen atmospheres, and the molar ratio of substrate to Pd is 4000:1.
  • Fig. 3 is a graph showing the results of 8 cycles of stability experiments for the semi-hydrogenation of phenylacetylene with the PPh 3 -Pd 4 S/C catalyst of the present invention.
  • the selectivity of ethylene is kept above 98% in 8 cycles, and the selectivity is kept well, which proves that the catalyst of the present invention has high stability.
  • reaction S3 use the prepared PPh 3 -Pd 4 S/C catalyst to carry out a semi-hydrogenation reaction with different terminal alkyne compounds as substrates.
  • the reaction steps are: take 20ml of ethanol and transfer it to a 48ml reaction flask, take 2mmol of the substrate Put it into the reaction bottle and disperse it ultrasonically for 1min, the reaction temperature is 30 ° C, add the corresponding amount of catalyst, the molar ratio of substrate to pd is 2000:1, after replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction bottle, and set the rotation speed to 1000rpm and turn on stirring.
  • Table 3 is the experimental result data of semi-hydrogenation reaction with different terminal alkyne compounds as substrates. It can be seen that the catalyst of the present invention has very excellent catalytic activity and selectivity for terminal alkyne compounds, and the selectivity of the corresponding alkene is maintained above 98% for a long time.
  • the carrier can also be molecular sieve, silicon oxide, titanium oxide and diatomaceous earth.
  • Table 6 is the different experimental conditions and the result data of the catalyst of the present invention to carry out the semi-hydrogenation reaction. It can be seen that the catalyst of the present invention performs the semi-hydrogenation reaction under different conditions, and when the conversion of phenylacetylene is more than 99%, the selectivity of olefins all reach more than 98%.
  • reaction step is: get the ethanol of 20ml and be transferred in the reaction flask of 48ml, get 2mmol phenylacetylene as substrate and put into reaction In the bottle and ultrasonically dispersed for 1min, the reaction temperature is 30 ° C, the corresponding amount of catalyst is added, the molar ratio of substrate to pd is 2000:1, after replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction bottle, set the rotation speed to 1000rpm and turn it on Stir.
  • Table 8 is the experimental data results of preparing the catalyst of the present invention with different ligands for semi-hydrogenation.
  • the PPh 3 -Pd/C catalyst and the PPh 3 -Pd 4 S/C catalyst with the same Pd molar mass are respectively used for the semi-hydrogenation reaction with phenylacetylene as the substrate.
  • the reaction step is: take 20ml of ethanol and transfer it to 48ml of ethanol In the reaction flask, take 2 mmol of phenylacetylene as the substrate and put it into the reaction flask and ultrasonically disperse it for 1 min.
  • the reaction temperature is 30 ° C.
  • a corresponding amount of catalyst is added, and the molar ratio of substrate to pd is 2000:1.
  • There was 1 bar of hydrogen in the reaction flask the speed was set to 1000 rpm and the stirring was turned on.
  • Figure 4 shows the semi-hydrogenation of phenylacetylene by PPh 3 -Pd/C catalyst and PPh 3 -Pd 4 S/C catalyst, respectively Comparative graph of conversion and selectivity of the reaction.
  • the prepared PPh 3 -Pd 4 S/C catalyst is subjected to a semi-hydrogenation reaction with different reaction substrates 1-phenyl-1 propyne and diphenylacetylene respectively.
  • the reaction step is: take 20ml of ethanol and transfer it to 48ml Put 2 mmol of substrate into the reaction flask and ultrasonically disperse it for 1 min, the reaction temperature is 30 °C, add a corresponding amount of catalyst, the molar ratio of substrate to pd is 2000:1, and keep the reaction flask after replacing the hydrogen for 3 times. With 1 bar of hydrogen, set the speed to 1000 rpm and turn on agitation.
  • Table 9 shows the experimental data of the PPh 3 -Pd 4 S/C catalyst used in the semi-hydrogenation reaction of intermediate alkyne compounds. The results show that the selectivity of the catalyst of the present invention for intermediate alkynes is only 67% and 71%. As the time prolongs, the olefins will be further hydrogenated to alkanes, so the catalyst of the present invention cannot be used as a selective semi-hydrogenation catalyst for intermediate alkyne compounds.
  • the prepared catalyst A, catalyst B, and catalyst C are respectively used as substrates to carry out a semi-hydrogenation reaction
  • the reaction step is: take 20ml of ethanol and transfer it to a 48ml reaction flask, and take 2mmol of phenylacetylene as a substrate Put it into the reaction bottle and disperse it ultrasonically for 1min, the reaction temperature is 30 ° C, add the corresponding amount of catalyst, the molar ratio of substrate to pd is 2000:1, after replacing the hydrogen for 3 times, keep 1 bar of hydrogen in the reaction bottle, and set the rotation speed to 1000rpm and turn on stirring.
  • Table 10 is the experimental data of the semi-hydrogenation reaction of the catalyst of the present invention prepared by different crystal forms of PdxSy. From the experimental data, it can be obtained that Pd 4 S is the PdS phase with the lowest sulfur content, and the prepared catalyst has the highest activity, and Pd 4 S has the highest activity. 4 S is more receptive to phosphine ligands, and the catalysts prepared from it have the highest selectivity to olefins.
  • Comparative Example 4 Compared with Example 6, the difference is that the solvent in S1 is n-hexane, and other conditions are the same as those of Example 6. Experiments show that when the conversion of phenylacetylene is >99%, the time taken is 65 min, and when the conversion is >99%, the olefin selectivity is 67.8%. Comparative Example 6 shows that the catalyst of the present invention is semi-hydrogenated with the catalyst prepared by modifying the alcoholic solvent. The selective effect of the reaction is much higher than that of n-hexane as a solvent.
  • Catalyst 1 Disperse Pd 4 S/C in ethanol solvent, add different ligands respectively, so that the molar ratio of ligand:Pd is 7:1, the stirring time is 60min, the stirring temperature is 20°C, and the catalyst is filtered out by suction.
  • Catalyst 1, Catalyst 2, Catalyst 3, and Catalyst 4 were prepared after washing and drying with ultrapure water for 12 hours.
  • reaction step is: get the ethanol of 20ml and be transferred in the reaction flask of 48ml, get 2mmol phenylacetylene
  • reaction temperature is 30 °C
  • the molar ratio of substrate to pd is 2000:1
  • Table 11 shows the experimental data results of preparing the catalyst of the present invention with different sulfur-containing ligands for semi-hydrogenation. It can be seen that only using sulfur-containing ligands to prepare the catalyst of the present invention cannot achieve high selectivity for the semi-hydrogenation reaction of terminal alkyne compounds.
  • S1 General Treatment of Palladium with Sulfur-Containing Compounds: Treatment of Pd with sulfur-containing compounds results in a reactant of Pd and sulfur-containing compounds.
  • S3 second treatment of palladium with sulfur-containing compound: adding the palladium catalyst obtained by reduction to 100 mL of a solution of n-hexane and sulfur-containing compound, wherein the molar ratio of sulfur-containing compound and Pd measured by bulk Pd metal content The ratio was 2.5:1, and after stirring for 30 min, the solvent was evaporated on a rotary evaporator to prepare a catalyst for later use.
  • S4 Test effect: The prepared catalyst is subjected to a semi-hydrogenation reaction with phenylacetylene as the substrate.
  • the reaction steps are: take 20ml of ethanol and transfer it to a 48ml reaction bottle, take 2mmol of phenylacetylene as the substrate and put it in the reaction bottle And ultrasonically dispersed for 1 min, the reaction temperature was 30 ° C, a corresponding amount of catalyst was added, the molar ratio of substrate to pd was 2000:1, after 3 hydrogen replacements, 1 bar of hydrogen was maintained in the reaction flask, the rotational speed was set to 1000 rpm and the stirring was turned on.
  • Table 12 shows the experimental data of the semi-hydrogenation of catalysts prepared by treating palladium with different sulfur-containing compounds.
  • the catalysts prepared by this method are used for semi-hydrogenation, and the alkene selectivity is low when the conversion of alkynes is >99%, which cannot be achieved. 75%, which is far from the effect achieved by the catalyst of the present invention, and cannot be used as a catalyst for the selective semi-hydrogenation reaction of terminal alkyne compounds.
  • reaction steps are: take 20ml of alcohol solvent and transfer it to a 48ml reaction bottle, take 2mmol of phenylacetylene as a substrate and put it in the reaction bottle and ultrasonically Disperse for 1min, the reaction temperature is 20-80°C, add a corresponding amount of catalyst, the molar ratio of substrate to pd is (1000-4000): 1, after replacing the hydrogen for 3 times, keep 1-3bar of hydrogen in the reaction bottle, set the rotating speed to 1000 rpm and turn on stirring.
  • Table 13 is the experimental result data of triphenylphosphine oxide as the ligand to prepare the catalyst of the present invention and carry out the semi-hydrogenation reaction. It can be seen that the catalyst prepared by triphenylphosphine oxide as the ligand is used for the semi-hydrogenation reaction of terminal alkyne compounds
  • the selectivity result is unsatisfactory, because the catalyst of the present invention requires S and P to coordinate with Pd together, and the coordination ability of O in triphenylphosphine oxide is weaker than that of S, so it cannot coordinate to play a good steric hindrance effect. Thus, the corresponding selectivity cannot be improved.

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Abstract

本发明提供一种用膦配体修饰的催化剂及其制备方法与应用，本发明制备方法采用膦配体M对Pd 4S或Pd 4S/X进行修饰，制备得到M-Pd 4S催化剂或带有载体的M-Pd 4S/X催化剂。本发明制备催化剂在炔烃半加氢反应中，对端炔化合物具有高选择性，并且使用条件温和，稳定性好，利于工业应用。

Description

一种用膦配体修饰的催化剂、制备方法与应用
技术领域：本发明涉及一种催化剂，特别是一种用膦配体修饰的催化剂及其制备方法与应用。
背景技术：
裂解制烯烃在石化工业中具有非常广泛的用途，占据着非常重要的地位。但是，在生产相应烯烃的同时会有微量的炔烃和二烯烃，这些炔烃和二烯烃的含量虽少，但会影响烯烃的聚合效果，降低产品的品质，因此需要将这些痕量的杂质除去。工业上常用的方法有溶剂吸收法、低温精馏法、选择性加氢法等除去相应的炔烃。用催化加氢的方法使相应的炔烃催化加氢生成烯烃是比较简单、方便的方法，然而烯烃又很容易继续深度加氢到烷烃，因此需要制备高效的催化剂只对炔烃有加氢活性，使反应只停留在烯烃而不会深度加氢到烷烃。
用于选择性加氢的催化剂有：一是用贱金属，如铜、镍等；二是用贵金属，如钯、铂等；或者用贵金属与贱金属的复合材料，如钯-铜、钯-锌等双金属或者金属材料，钯基材料由于优异的氢解离能力，被广泛应用于催化加氢以及炔烃选择性加氢中。美国专利NO.128595公开了一种方法，将含炔烃的气体蒸气和惰性烃类溶剂加入到反应容器中与钯、镍等VIII族金属-氧化铝催化剂进行催化加氢，但是含炔烃气体在烃类溶剂中的溶解度较差；专利CN101428228A公开了一种选择性加氢催化剂，其中催化剂的活性组分钯、助剂铜，以氧化铝为载体，催化剂适用于富含炔烃残余物的选择性加氢除炔，其载体处理和制备需要900℃以上的高温来处理。
由于钯的活性高，往往需要毒化部分的位点，才能对炔烃有好的选择性，这就导致了钯的利用率不高，增加了贵金属的使用，从而增加了成本。另一方面，选择性半加氢催化剂制备的方法，特别是只针对端炔选择性半加氢催化剂制备的方法较为复杂，较难进行工业规模的应用生产。因此，制备优异的具有端炔选择性半加氢活性的催化剂，又能充分利用催化剂的活性中心提高反应的活性，同时操作简单便捷，降低催化剂的制备成本，对工业的应用有重要的意义和价值。
发明内容：
本发明的一个目的在于解决现有问题，提供一种催化剂。
本发明的另一个目的在于提供一种催化剂的制备方法。
本发明还有一个目的在于提供一种催化剂应用。
本发明采用以下的技术方案：
本发明第一方面提供一种用膦配体修饰的催化剂，所述催化剂的通式为M-Pd 4S或M-Pd 4S/X，所述M为膦配体，用于修饰Pd 4S；所述X为载体。
优选的，所述载体选自C、CaCO 3、α-Al 2O 3、γ-Al 2O 3、氧化铈、分子筛、氧化硅、氧化钛和硅藻土中的至少一种。
优选的，所述膦配体为含芳香取代基的膦配体。
优选的，所述含芳香取代基的膦配体选自双二苯基膦甲烷、三苯基膦和三苯基膦络合物中的至少一种。
进一步优选的，所述三苯基膦络合物选自三苯基膦硼烷和三苯基膦硅烷中的至少一种。
本发明第二方面提供一种用膦配体修饰的催化剂的制备方法，包括：
将所述Pd 4S或Pd 4S/X分散于醇类溶剂中，加入膦配体M，搅拌，抽滤、干燥，得到M-Pd 4S催化剂或M-Pd 4S/X催化剂，所述X为载体，所述膦配体M为含芳香取代基的膦配体。
优选的，所述醇类溶剂选自乙醇、甲醇、丙二醇、乙二醇、正丁醇和异丁醇中的至少一种。
优选的，所述含芳香取代基的膦配体选自双二苯基膦甲烷、三苯基膦、三苯基膦络合物中的至少一种。
进一步优选的，所述三苯基膦络合物选自三苯基膦硼烷和三苯基膦硅烷中的至少一种。
优选的，所述M:Pd的摩尔比为(5-20):1。
进一步优选的，所述膦配体M:Pd的摩尔比为(7-15):1。
优选的，所述搅拌的时间为5-120min。
进一步优选的，所述搅拌的时间为10-60min。
优选的，所述搅拌的温度为5-85℃。
进一步优选的，所述搅拌的温度为15-55℃。
本发明另一方面还提供一种由上述催化剂或上述制备方法得到的催化剂的应用，应用于端炔化合物半加氢。
一种催化剂应用于端炔化合物半加氢的方法，包括以下步骤：
将醇类溶剂转移至反应瓶中，选取端炔化合物为底物放至反应瓶中分散，反应温度为20-80℃，加入催化剂，底物与Pd的摩尔比为(1000-4000):1，置换氢气，保持1-3个大气压的氢气压力，进行搅拌。
优选的，所述端炔化合物选自乙炔、丙炔、3-氨基苯乙炔、3-甲基苯乙炔、4-叔丁基苯乙炔、1-辛炔、2-乙炔基吡啶、4-乙炔基吡啶、苯乙炔和苯丙炔中的至少一种。
炔烃加氢一般分为两步加氢，第一步炔烃加氢反应生成烯烃，再进一步由烯烃深度加氢反应生成烷烃，本发明所述的炔烃半加氢是指第一步炔烃加氢生成烯烃的过程，故称之为炔烃半加氢。
端炔是指碳碳三键位于末端的碳上的炔烃，包括乙炔，丙炔等短链炔烃。
化学修饰(chemical modification)是指用吸附、涂敷、聚合、化学反应等方法把活性基团或催化物质等附着在被修饰物表面。
对于本发明催化剂的制备Pd 4S可以选用纳米级材料，其形貌包括但不限于颗粒状、片状、棒状。
本发明采用的是对Pd 4S或Pd 4S/X进行修饰大位阻的配体，来实现炔烃的吸附与烯烃的脱附达到烯烃的高选择性，通过膦配体M修饰Pd 4S或Pd 4S/X，制备得到M-Pd 4S催化剂或带有载体的M-Pd 4S/X催化剂，利用本发明催化剂实现在炔烃半加氢反应中对端炔化合物具有高选择性。
有益效果：
(1)本发明的催化剂对端炔化合物半加氢具有较高的选择性，选择性超过95％，可高达至99％以上。
(2)本发明的催化剂对端炔化合物半加氢催化反应的转化率较高，转化率可达到99％以上。
(3)本发明的催化剂稳定性高，多次套用未明显失活，套用5次后选择性 仍然在99％以上；套用8次后选择性也仍然在98％以上。
(4)利用相对廉价的膦配体修饰Pd 4S或Pd 4S/X制备本发明催化剂，可降低制备成本。
(5)该方法制备的催化剂不需要牺牲大量的催化活性，而且无需加入如Pb、喹啉等有毒物质，制备过程对环境友好，获得的催化剂也是绿色环境友好型。
(6)本发明催化剂的制备方法简便，具有普适性，稳定性良好。
附图说明：
图1为实施例1中PPh3-Pd4S Ns催化剂对苯乙炔进行半加氢实验定时取样通过气相色谱进行产物的检测的色谱图。
图2为实施例2中PPh 3-Pd 4S/C催化剂对苯乙炔进行半加氢实验的5次循环稳定性实验结果图。
图3为实施例2中PPh 3-Pd 4S/C催化剂对苯乙炔进行半加氢实验的8次循环稳定性实验结果图。
图4为对比例1中PPh 3-Pd/C催化剂和PPh 3-Pd 4S/C催化剂对苯乙炔进行半加氢实验的转化率和选择性的比较曲线图。
具体实施方式：
下面将结合本发明实施例中的附图，对本发明的技术方案进行描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
实施例1
S1：选取二维的钯纳米片(Pd Ns)，加入Na 2S的水溶液中，使得Pd:S的摩尔比为4:1，升温至150℃，保持氢气1MPa的压力氛围下，反应3h，冷却、抽滤、干燥得到Pd 4S Ns。
S2：将制备得到的Pd 4S Ns分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为10:1，搅拌的时间为10min，搅拌的温度为20℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到PPh 3-Pd 4S Ns催化剂。
S3：将Pd摩尔质量相同的Pd Ns、Pd 4S Ns和PPh 3-Pd 4S Ns催化剂，分别以苯乙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌，定时取样通过气相色谱进行产物的检测。
表1.PdNs、Pd4S Ns和PPh3-Pd4S Ns催化剂分别对苯乙炔进行半加氢反应的实验结果数据
Figure PCTCN2021071074-appb-000001
表1为PdNs、Pd 4S Ns和PPh 3-Pd 4S Ns催化剂分别对苯乙炔进行半加氢反应实验结果数据，图1为PPh 3-Pd 4S Ns催化剂对苯乙炔进行半加氢实验定时取样通过气相色谱进行产物的检测的色谱图。可以看出本发明制备的得到的PPh 3-Pd 4S Ns催化剂对苯乙炔进行加氢反应得到的产物为烯烃，没有深度加氢到烷烃，并且相对于PdNs、Pd 4S Ns的半加氢反应，在不明显降低反应活性的情况下，选择性大大提高。
实施例2：测试本发明催化剂的稳定性
S1：将Pd 4S/C分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为15:1，搅拌的时间为60min，搅拌的温度为30℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得PPh 3-Pd 4S/C催化剂备用。
S2：用制备得到的PPh 3-Pd 4S/C催化剂进行以苯乙炔为底物的半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转 速为1000rpm并打开搅拌。
S3：将制备得到的PPh 3-Pd 4S/C催化剂进行5次套用，图2为PPh 3-Pd 4S/C催化剂对苯乙炔进行半加氢实验的5次循环稳定性实验结果图。从图2中可以看出5次套用后其转化率和选择性都没有下降，苯乙烯的选择性仍能达到99％以上，表明催化剂稳定性良好。
S4：将制备得到的PPh 3-Pd 4S/C催化剂进行以苯乙炔为底物进行半加氢反应8次套用。反应条件为氢气为氢源，乙醇为溶剂，温度30℃、6个氢气大气压的压力、底物与Pd的摩尔比为4000:1。图3为本发明PPh 3-Pd 4S/C催化剂对苯乙炔进行半加氢实验的8次循环稳定性实验结果图，可以看出8次套用后转化率和选择性都没有明显下降，苯乙烯的选择性在8次循环中都保持98％以上，选择性保持良好，证明本发明催化剂稳定性高。
实施例3
S1：将Pd 4S/γ-Al 2O 3分散于乙醇溶剂中，加入不同膦配体M，使得膦配体M:Pd的摩尔比为(5-20):1，搅拌的时间为5-120min，搅拌的温度为30℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到M-Pd 4S/γ-Al 2O 3催化剂备用。不同实验制备条件如表2所示。
S2：将制得的M-Pd 4S/γ-Al 2O 3催化剂进行以苯乙炔为底物的半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。其中由不同条件制备得到催化剂对苯乙炔进行半加氢实验的转化时间和选择性如下表2所示。
从表2中可以看出，当膦配体M:Pd的摩尔比为(5-20):1时，苯乙烯的选择性均超过95％，且当膦配体M选自三苯基膦或双二苯基膦甲烷，膦配体M:Pd的摩尔比低于7:1时，选择性稍有所下降，膦配体M:Pd的摩尔比高于15:1时选择性保持良好，反应活性稍有所下降，因此膦配体M:Pd的摩尔比的最佳比例范围可选在(7-15):1之间。当搅拌的时间为5-120min时，苯乙烯的选择性超过95％；其中当膦配体M:Pd的摩尔比为15:1时，可以看出搅拌的时间为 10-60min时的活性下降不明显且苯乙烯的选择性可高达99％以上，因此，10-60min可为最佳搅拌的时间。另外，从表2可以看出，当膦配体M为三苯基膦和双二苯基膦甲烷时，苯乙炔转化>99％时苯乙烯的选择性达到98％以上，为最佳膦配体的选择。
表2.不同膦配体用量、不同膦配体的种类和不同搅拌时间制备本发明催化剂对苯乙炔进行半加氢反应的结果数据表
Figure PCTCN2021071074-appb-000002
Figure PCTCN2021071074-appb-000003
实施例4
S1：选取Pd质量分数为5％的商业Pd/C，加入Na 2S的水溶液中，使得Pd:S的摩尔比为4:1，升温至150℃，保持氢气1Mpa的压力氛围下，反应3h，冷却、抽滤、干燥，得到Pd 4S/C。
S2：将制备好的Pd 4S/C分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为7:1，搅拌的时间为60min，搅拌的温度为20℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到PPh 3-Pd 4S/C催化剂备用。
S3：用制备得到的PPh 3-Pd 4S/C催化剂分别以不同端炔化合物为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
表3为以不同端炔化合物为底物进行半加氢反应的实验结果数据。可见本发明催化剂对端炔化合物有着非常优异的催化活性及选择性，相应烯烃的选择性能长时间维持在98％以上。
表3.以不同端炔化合物为底物进行半加氢反应的实验结果数据
Figure PCTCN2021071074-appb-000004
Figure PCTCN2021071074-appb-000005
实施例5
S1：选取相同质量的Pd/X，加入K 2S的水溶液中，使得Pd:S的摩尔比为4:1，升温至150℃，保持氢气1Mpa的压力氛围下，反应3h，冷却、抽滤、干燥，得到Pd 4S/X。
S2：将制备好Pd摩尔质量相同的Pd 4S/X分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为7:1，搅拌的时间为60min，搅拌的温度为30℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到PPh 3-Pd 4S/X催化剂备用。
S3：用制备得到的PPh 3-Pd 4S/X催化剂分别以苯乙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表4为本发明催化剂对不同载体制备本发明催化剂进行半加氢实验的结果数据，可见不同载体下制备本发明催化剂对苯乙炔均有优异的催化活性及选择性，相应烯烃的选择性能长时间维持在98％以上。
表4.不同载体制备催化剂进行半加氢实验的结果数据
Figure PCTCN2021071074-appb-000006
Figure PCTCN2021071074-appb-000007
本实施例中，载体还可以是分子筛、氧化硅、氧化钛和硅藻土。
实施例6
S1：将质量相同的Pd 4S/C分散于不同溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为10:1，搅拌的时间为60min，搅拌的温度为25℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得PPh 3-Pd 4S/C催化剂备用。
S2：用制备得到的PPh 3-Pd 4S/C催化剂分别以苯乙炔为底物进行半加氢反应，反应步骤为：用取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表5为不同溶剂用于修饰膦配体制备催化剂用于半加氢反应的实验结果数据，可以看出，不同醇类溶剂均可作为修饰膦配体的溶剂制备本发明催化剂，且进行半加氢反应时苯乙炔转化>99％时烯烃的选择性均达到98％以上，其中乙醇作为溶剂的修饰效果最好，达到99.5％以上。
表5.不同溶剂用于修饰膦配体制备催化剂用于半加氢反应的实验结果数据
溶剂 苯乙炔转化>99％时 苯乙炔转化>99％时
所用时间 烯烃的选择性
乙醇 35min 99.7％
甲醇 35min 99.5％
丙二醇 40min 98.9％
乙二醇 30min 99.0％
正丁醇 45min 98.7％
异丁醇 50min 98.4％
实施例7
S1：将Pd 4S/C分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为10:1，搅拌的时间为60min，搅拌的温度为25℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得PPh 3-Pd 4S/C催化剂备用。
S2：用制备得到的PPh 3-Pd 4S/C催化剂分别以苯乙炔为底物进行半加氢反应，反应步骤为：取20ml醇类溶剂转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为20-80℃，加入相应量催化剂，底物与pd的摩尔比为(1000-4000):1，置换3次氢气后保持反应瓶中有1-3bar的氢气，设置转速为1000rpm并打开搅拌。表6为本发明催化剂进行半加氢反应的不同实验条件及结果数据。可以看出，本发明催化剂在不同条件下进行半加氢反应，苯乙炔转化>99％时，烯烃的选择性均达到98％以上。
表6.本发明催化剂进行半加氢反应的不同实验条件及结果数据
Figure PCTCN2021071074-appb-000008
Figure PCTCN2021071074-appb-000009
实施例8
S1：将Pd 4S/γ-Al 2O 3分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为7:1，搅拌的时间为60min，搅拌的温度为25℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得PPh 3-Pd 4S/γ-Al 2O 3催化剂备用。
S2：用制备得到的PPh 3-Pd 4S/γ-Al 2O 3催化剂分别以不同烯烃和炔烃的混合物为底物进行半加氢反应，反应条件为：在气相流化床中，在60℃温度、10bar的压力下，用氮气作载气，在30％氢气中还原，表7为本发明催化剂对烯烃和炔烃的混合物作为底物进行半加氢反应的实验结果数据，可见本发明催化剂对不同烯烃和炔烃的混合物有着优异的催化活性及选择性，相应烯烃的选择性能长时间维持在99％以上。
表7.本发明催化剂对烯烃和炔烃的混合物作为底物进行半加氢反应的实验结果数据
Figure PCTCN2021071074-appb-000010
实施例9
S1：将Pd 4S/C分散于乙醇溶剂中，加入不同配体，使得配体:Pd的摩尔比为15:1，搅拌的时间为60min，搅拌的温度为20℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到催化剂1、催化剂2备用。
S2:用制备得到的催化剂1、催化剂2分别以苯乙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物 放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表8为不同配体制备本发明催化剂用于半加氢的实验数据结果。
表8.不同配体制备本发明催化剂用于半加氢的实验数据结果
Figure PCTCN2021071074-appb-000011
对比例1
S1：将相同量的Pd/C和的Pd 4S/C分别分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为7:1，搅拌的时间为10min，搅拌的温度为30℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得PPh 3-Pd/C催化剂和PPh 3-Pd 4S/C催化剂备用。
S2：将Pd摩尔质量相同的PPh 3-Pd/C催化剂和PPh 3-Pd 4S/C催化剂分别以苯乙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。对比PPh 3直接修饰Pd/C能否起到和Pd 4S/C相同的作用，图4为PPh 3-Pd/C催化剂和PPh 3-Pd 4S/C催化剂分别对苯乙炔进行半加氢反应的转化率和选择性的比较曲线图。
从图4可以看出PPh 3-Pd/C催化剂的活性和选择性都比PPh 3-Pd 4S/C催化剂来得低，其原因在于PPh 3-Pd 4S/C催化剂中Pd 4S相中的S的引入使得其表面的电子结构更易接受配体且不会影响到Pd的催化活性位点，利用电子效应与位阻效应的协同作用实现了高活性高选择性的效果。
对比例2
S1：将Pd 4S/C分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M， 使得膦配体M:Pd的摩尔比为10:1，搅拌的时间为30min，搅拌的温度为30℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得PPh 3-Pd 4S/C催化剂备用。
S2：将制备得到的PPh 3-Pd 4S/C催化剂分别以不同反应底物1-苯基-1丙炔、二苯乙炔进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
表9为PPh 3-Pd 4S/C催化剂用于中间炔化合物的半加氢反应的实验结果数据，结果显示本发明催化剂对于中间炔的选择性不高仅仅只有67％和71％，且随着时间延长，烯烃会进一步深度加氢为烷烃，因此本发明催化剂无法作为中间炔化合物的选择性半加氢催化剂。
表9.PPh 3-Pd 4S/C催化剂用于中间炔化合物的半加氢反应的实验结果数据
Figure PCTCN2021071074-appb-000012
对比例3
S1：将Pd/γ-Al 2O 3分散于不同量的Na 2S水溶液中，升温至150℃的温度下，保持氢气1MPa的压力下，反应拌3h，冷却、抽滤、干燥得到的PdxSy/γ-Al 2O 3。
S2：将制备得到的PdxSy/γ-Al 2O 3分散于乙醇溶剂中，加入三苯基膦(PPh 3)作为膦配体M，使得膦配体M:Pd的摩尔比为7:1，搅拌的时间为30min，搅拌的温度为30℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到催化剂A、催化剂B、催化剂C备用。
S3：将制备得到的催化剂A、催化剂B、催化剂C分别以苯乙炔作为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催 化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
表10为不同PdxSy的晶型制备本发明催化剂进行半加氢反应的实验结果数据，从实验数据能得到Pd 4S作为含硫量最低的PdS相其制备得到的催化剂活性是最高的，并且Pd 4S更容易接受膦配体，其制备的催化剂对烯烃的选择性最高。
表10.不同PdxSy的晶型制备本发明催化剂进行半加氢反应的实验结果数据
Figure PCTCN2021071074-appb-000013
对比例4：与实施例6相比，不同的是S1中的溶剂为正己烷，其他条件与实施例6相同。实验得到，苯乙炔转化>99％时所用时间为65min，转化>99％时烯烃选择性为67.8％，对比实施例6可知，本发明催化剂使用醇类溶剂进行修饰制备得到的催化剂进行半加氢反应的选择性效果比正己烷作为溶剂高的多。
对比例5
S1：将Pd 4S/C分散于乙醇溶剂中，分别加入不同配体，使得配体:Pd的摩尔比为7:1，搅拌的时间为60min，搅拌的温度为20℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得到催化剂1、催化剂2、催化剂3、催化剂4备用。
S2:用制备得到的催化剂1、催化剂2、催化剂3、催化剂4分别以苯乙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相 应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。
表11为不同含硫配体制备本发明催化剂用于半加氢的实验数据结果，可以看出仅利用含硫配体制备本发明催化无法实现对端炔化合物半加氢反应的高选择性。
表11.不同含硫配体制备本发明催化剂用于半加氢的实验数据结果
Figure PCTCN2021071074-appb-000014
对比例6
S1：用含硫化合物一般处理钯：将含硫化合物处理Pd得到Pd和含硫化合物的反应物。
S2：还原反应：升温温度至150℃，将制备得到的反应物在1:1的H 2:N 2流(100mL/min)中还原1小时，随后在N 2流中冷却，制备得到还原后的钯催化剂。
S3：用含硫化合物对钯进行第二次处理：将还原得到的钯催化剂加入100mL的正己烷和含硫化合物的溶液中，其中，通过本体Pd金属含量测量的含硫化合物与Pd的摩尔比为2.5:1，搅拌30min后，在旋转蒸发器上蒸发溶剂，制备得到催化剂备用。
S4：测试效果：将制备得到的催化剂以苯乙炔为底物进行半加氢反应，反应步骤为：取20ml的乙醇转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为30℃，加入相应量催化剂，底物与pd的摩尔比为2000:1，置换3次氢气后保持反应瓶中有1bar的氢气，设置转速为1000rpm并打开搅拌。表12为不同含硫化合物处理钯制备催化剂进行半加氢的实验结果数据，可以看出该方法制备催化剂用于半加氢反应，炔烃转化>99％时 烯烃选择性低，均达不到75％，远不如本发明催化剂达到的效果，无法作为端炔化合物选择性半加氢反应的催化剂。
表12.不同含硫化合物处理钯制备催化剂进行半加氢的实验结果数据
Figure PCTCN2021071074-appb-000015
对比例7
S1：将Pd 4S/C分散于乙醇溶剂中，加入三苯基氧膦作为配体，使得三苯基氧膦:Pd的摩尔比为7:1，搅拌的时间为60min，搅拌的温度为25℃，抽滤出催化剂，超纯水洗涤干燥12h后制备得催化剂备用。
S2：用制备得到的催化剂以苯乙炔为底物进行半加氢反应，反应步骤为：取20ml醇类溶剂转移至48ml的反应瓶中，取2mmol苯乙炔为底物放至反应瓶中并超声分散1min，反应温度为20-80℃，加入相应量催化剂，底物与pd的摩尔比为(1000-4000):1，置换3次氢气后保持反应瓶中有1-3bar的氢气，设置转速为1000rpm并打开搅拌。
表13为三苯基氧膦作为配体制备本发明催化剂进行半加氢反应的实验结果数据，可以看出三苯基氧膦作为配体制备得到的催化剂用于端炔化合物半加氢反应的选择性结果不理想，由于本发明催化剂需要S和P共同与Pd配位，而三苯基氧膦中O的配位能力比S来的弱，不能配位起到很好的位阻效应，进而无法提高相应的选择性。
表13.三苯基氧膦作为配体制备本发明催化剂进行半加氢反应的实验加果数据
Figure PCTCN2021071074-appb-000016
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (10)

  1. 一种用膦配体修饰的催化剂，其特征在于，所述催化剂的通式为M-Pd 4S或M-Pd 4S/X；所述M为膦配体，用于修饰Pd 4S；所述X为载体。
  2. 根据权利要求1所述的催化剂，其特征在于，所述载体选自C、CaCO 3、α-Al 2O 3、γ-Al 2O 3、氧化铈、分子筛、氧化硅、氧化钛和硅藻土中的至少一种。
  3. 根据权利要求1所述的催化剂，其特征在于，所述膦配体为含芳香取代基的膦配体。
  4. 根据权利要求3所述的催化剂，其特征在于，所述含芳香取代基的膦配体选自双二苯基膦甲烷、三苯基膦和三苯基膦络合物中的至少一种。
  5. 根据权利要求4所述的催化剂，其特征在于，所述三苯基膦络合物选自三苯基膦硼烷和三苯基膦硅烷中的至少一种。
  6. 一种用膦配体修饰的催化剂的制备方法，其特征在于，包括以下步骤：
    将Pd 4S或Pd 4S/X分散于醇类溶剂中，加入膦配体M，搅拌，抽滤、干燥，得到M-Pd 4S催化剂或M-Pd 4S/X催化剂；所述X为载体，所述膦配体M为含芳香取代基的膦配体。
  7. 根据权利要求6所述的制备方法，其特征在于，所述M:Pd的摩尔比为(5-20):1。
  8. 根据权利要求6所述的制备方法，其特征在于，所述含芳香取代基的膦配体选自双二苯基膦甲烷、三苯基膦、三苯基膦络合物中的至少一种。
  9. 根据权利要求6所述的制备方法，其特征在于，所述搅拌的时间为5-120min；所述搅拌的温度为5-85℃。
  10. 一种由权利要求1-5任一项所述的催化剂或由权利要求6-9任一项所述的制备方法所制得的用膦配体修饰的催化剂的应用，其特征在于，所述用膦配体修饰的催化剂应用于端炔化合物半加氢。
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