WO2022257025A1 - 一种单原子分散的钯基催化剂及其制备方法、应用 - Google Patents

一种单原子分散的钯基催化剂及其制备方法、应用 Download PDF

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WO2022257025A1
WO2022257025A1 PCT/CN2021/099012 CN2021099012W WO2022257025A1 WO 2022257025 A1 WO2022257025 A1 WO 2022257025A1 CN 2021099012 W CN2021099012 W CN 2021099012W WO 2022257025 A1 WO2022257025 A1 WO 2022257025A1
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palladium
dispersed
based catalyst
preparation
monoatomically
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PCT/CN2021/099012
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French (fr)
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丁云杰
冯四全
宋宪根
李星局
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中国科学院大连化学物理研究所
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/60—Maleic acid esters; Fumaric acid esters

Definitions

  • the application relates to a monoatomically dispersed palladium-based catalyst and its preparation method and application, belonging to the technical field of catalytic chemical industry.
  • supported metal catalysts account for more than 70%, especially supported noble metal catalysts, which are widely used in various catalyst reactions.
  • supported metal catalysts are usually nano-metal catalysts, and often only the atoms exposed on the surface have catalytic activity, resulting in low utilization efficiency of metal atoms and waste of precious metal resources.
  • single-atom catalysts Compared with nano-metal catalysts, single-atom catalysts have become an emerging hotspot in contemporary research due to their nearly 100% atom utilization and single isolated catalytic active sites.
  • dual-site catalysts with catalytically active metals are more attractive because they not only have the essential characteristics of single-site catalysis, but also have dual catalytic active sites, often showing more The excellent catalytic activity can realize the tandem catalysis or synergistic catalysis of different reactions on adjacent sites.
  • the existence of some catalytic promoter metal atoms has a prominent role and significance in maintaining the reactivity of the catalyst, inhibiting the transition reduction of the catalyst, improving the stability and activity of the catalyst, and adjusting the selectivity of the product.
  • the supported nano-metal particles were heat-treated to perform in-situ atomic-level monodispersion to prepare Pd-based single-atom catalysts.
  • Acetylene molecular formula C 2 H 2 , commonly known as calcium carbide gas, is an important raw material for organic synthesis, known as "the mother of organic synthesis industry". Calcium carbide can be easily prepared by adding water. The Xinjiang region of our country is rich in calcium carbide, which can produce a large amount of acetylene. At the same time, acetylene can be produced by thermal cracking of abundant natural gas at a very low cost, and it can also expand the utilization of natural high added value.
  • acetylene can be polymerized to produce aromatics such as benzene, toluene, xylene, naphthalene, anthracene, styrene, and indene.
  • aromatics such as benzene, toluene, xylene, naphthalene, anthracene, styrene, and indene.
  • Acrylic acid and its derivatives can be prepared by reacting acetylene with carbon monoxide and other compounds (such as water, alcohol, mercaptan).
  • Acetylene fine chemicals are a direction for the development of acetylene chemical industry. It can not only greatly increase the value of acetylene downstream products, but also promote the in-depth development of modern acetylene chemical industry. Using acetylene and CO as raw materials, acetylene carbonylation can occur under the attack of nucleophiles.
  • the existing acetylene double carbonylation to prepare but(enedioic) acid diesters mainly has the following problems: (1) most of them are homogeneous catalytic systems, and there is a problem that the catalyst is easy to lose and the product is difficult to separate; (2) most of the reactions are For the monocarbonylation reaction, acrylic acid and acrylate are generated, so that the selectivity of the target product is low; (3) in the reaction process, the metal catalyst is used in a large amount, and the efficiency is low, and it is necessary to use sulfonic acid and its derivatives as a cocatalyst; (4) the metal catalyst It is basically nanometer metal particles, and the utilization rate of atoms is low; (5) the stability of the supported Pd metal catalyst is not ideal, and it will become palladium black agglomeration during the reaction, resulting in waste and loss of the metal catalyst.
  • the application provides a monoatomically dispersed palladium-based catalyst, including a main catalytic active component and a carrier; the main catalytic active component includes palladium element; the carrier is a surface Activated carbon connected with a sulfur-containing functional group; the palladium element is dispersed in the palladium-based catalyst in the form of a mononuclear complex.
  • the metal Pd in the catalyst is dispersed at the single-atom level, and the metal atom utilization rate is greatly improved and improved.
  • a single-atom dispersed palladium-based catalyst including a main catalytically active component and a carrier;
  • Palladium element is included in the main catalytic active component
  • the carrier is activated carbon with sulfur-containing functional groups attached to the surface;
  • the palladium element is monoatomically dispersed in the palladium-based catalyst in the form of a mononuclear complex, as shown in formula I:
  • X is selected from halogen;
  • the halogen is selected from at least one of Br and I;
  • the mononuclear complex is anchored on the surface of activated carbon through the sulfur-containing functional group.
  • a catalytically active component is also included; the catalytically active component is dispersed on the surface of the carrier;
  • the catalyst-promoting active component includes at least one of an alkali metal element and a transition metal element
  • the alkali metal element is selected from potassium element;
  • the transition metal element is selected from at least one of copper and iron.
  • the halogen is selected from I.
  • the catalyst-promoting active component is dispersed on the surface of the support in the form of halides of alkali metal elements and/or halides of transition metal elements.
  • component A is also included; the component A is dispersed on the surface of the carrier;
  • the component A includes flame retardant metal elements
  • the flame retardant metal element is selected from at least one of bismuth and antimony.
  • the component A is dispersed on the surface of the carrier in the form of simple substance or compound Q;
  • the compound Q is at least one selected from oxides of bismuth, halides of bismuth, oxides of antimony and halides of antimony.
  • the compound Q is selected from at least one of Sb 2 O 3 , SbX' m , Bi 2 O 3 , BiX" n ;
  • X' and X" are independently selected from at least one of Br and I.
  • the mass content of the main catalytically active component is 0.1-3%; wherein, the mass of the main catalytically active component is based on the mass of palladium element.
  • the upper limit of the mass content of the main catalytic active component is independently selected from 3%, 2%, 1%, 0.5%, and the lower limit is independently selected from 0.1% , 2%, 1%, 0.5%.
  • the ratio of the number of moles of the main catalytic active component to the number of moles of the catalytically active component is 1:(0.01 ⁇ 10);
  • the number of moles of the main catalytic active component is calculated by the number of moles of palladium element, and the number of moles of the catalytically active component is calculated by the number of moles of metal elements therein.
  • component A in this application is to prevent the explosion of acetylene.
  • the surface of the activated carbon support contains sulfur functional groups as anchor sites for metals such as active metal Pd, and at the same time electronically interacts with Pd to modulate the catalytic activity of Pd.
  • the molar ratio of palladium in the main catalytic active component to the component A is 1:0.01 ⁇ 10;
  • the mole number of the component A is calculated by the mole number of the flame-retardant metal element.
  • a method for preparing the above-mentioned monoatomically dispersed palladium-based catalyst comprising:
  • the halogenated alkanes are selected from at least one of C 1 -C 6 brominated alkanes and C 1 -C 6 iodoalkanes.
  • the volume-mass ratio of the sulfur source to the activated carbon is (5-100) mL:20 g.
  • step (1) 20-50 ml of deionized water needs to be added for the hydrothermal treatment.
  • the step (4) includes: putting the sample prepared in the step (3) into a quartz tube reactor, and heat-treating it with CO and halogenated alkanes, and the halogenated alkanes are brought in by bubbling with CO, and the CO
  • the flow rate is 30-100ml/min
  • the heat treatment temperature is 150-240° C.
  • the heat treatment time is 1-4 hours, so that the single-atom-level dispersed Pd-based catalyst can be obtained.
  • a drying step is also included after the hydrothermal treatment; the drying temperature is 100-120°C.
  • the sulfur source is selected from thiourea, tetramethylthiourea, 4-acetylthiosemicarbazide, 3,4-dichlorophenylthiourea, o-tolylthiourea, N,N'-di Phenylthiourea, 5 ⁇ vinyloxazolidine ⁇ 2 ⁇ thione, tetrahydropyrrole ⁇ 2 ⁇ thione, sodium 1 ⁇ hydroxypyridinethione, piperidine ⁇ 2 ⁇ thione, 4,5 ⁇ bis(benzene At least one of formylthio)-1,3-dithiolane-2-thione and ethylene trithiocarbonate;
  • the activated carbon is selected from at least one of coconut shell activated carbon and apricot shell activated carbon;
  • the palladium salt is at least one selected from soluble palladium salts.
  • the solution containing palladium salt also includes at least one of potassium salt, copper salt and iron salt.
  • a drying step is also included; the temperature of the drying is 100-120°C.
  • the haloalkane is selected from at least one of CH 3 I and CH 3 Br.
  • the halogenated alkanes are brought in by bubbling with CO.
  • the conditions of the hydrothermal treatment are: the temperature is 100-180°C; the time is 1-24h;
  • the conditions of the roasting I are: the temperature is 300-800°C; the time is 1-6h;
  • the conditions of the calcination II are: the temperature is 300-400°C; the time is 1-4h;
  • the temperature of said equal-volume impregnation is 20-30°C;
  • the conditions of the reaction I are: the temperature is 150-240°C; the time is 1-4h.
  • the upper limit of the reaction I temperature is independently selected from 240°C, 200°C, and 180°C
  • the lower limit is independently selected from 150°C, 200°C, and 180°C.
  • the upper limit of the reaction I is independently selected from 4h, 3h, and 2h, and the lower limit is independently selected from 1h, 3h, and 2h.
  • the palladium salt is selected from palladium chloride.
  • the halogenated alkanes are selected from at least one of C 1 -C 6 bromoalkanes and C 1 -C 6 iodoalkanes.
  • the molar ratio of the halogenated alkanes to carbon monoxide is (0.1-10):1.
  • the flow rate of the mixed gas containing halogenated alkanes and carbon monoxide is 30-100ml/min.
  • the upper limit of the flow rate of the mixed gas containing halogenated alkanes and carbon monoxide is independently selected from 100ml/min, 90ml/min, 70ml/min, 60ml/min, 40ml/min, and the lower limit is independently selected from 30ml/min, 90ml/min, 70ml/min, 60ml/min, 40ml/min.
  • the potassium salt is selected from at least one of soluble potassium salts
  • the copper salt is selected from at least one of soluble copper salts
  • the iron salt is at least one selected from soluble iron salts.
  • the potassium salt is selected from potassium chloride; the copper salt is selected from copper chloride; and the iron salt is selected from ferric chloride.
  • At least one of bismuth salt and antimony salt is also included in the solution containing palladium salt.
  • the bismuth salt is selected from at least one of soluble bismuth salts
  • the antimony salt is at least one selected from soluble antimony salts.
  • the activated carbon is treated at 800-1000° C. for 2-12 hours to remove the oxygen functional groups on the surface of the activated carbon.
  • a kind of preparation method of butenedioic acid diester is provided, and described method comprises:
  • the mixture containing acetylene, carbon monoxide, alcohol compounds, and oxygen is contacted with a monoatomically dispersed palladium-based catalyst to react II to obtain butenedioic acid diester;
  • the single-atom dispersed palladium-based catalyst is selected from at least one of the above-mentioned single-atom dispersed palladium-based catalyst and the single-atom dispersed palladium-based catalyst prepared according to the above method.
  • the butenedioic acid diester includes but(enedioic acid dimethyl ester, but(enedioic acid) diethyl ester, but(enedioic acid) dipropyl ester, but(enedioic acid diethyl) Butyl ester, dipentyl but(ene)dioate, dioctyl but(ene)dioate, or at least one of ethyl methyl but(ene)dioate and methylpropyl but(ene)dioate.
  • the conditions of the reaction II are: the temperature is 60-120°C; the time is 1-24h.
  • the alcohol compound is selected from at least one of methanol, ethanol, propanol, butanol, pentanol, and octanol.
  • the molar ratio of the carbon monoxide to the acetylene is (1-10):1.
  • liquid hourly space velocity of the alcohol compound is 0.1-6h -1 ;
  • the gas hourly space velocities of the carbon monoxide and acetylene are independently selected from 10 to 2000h -1 .
  • the pressure of the carbon monoxide is independently selected from 1.0-6.0Mpa;
  • the pressure of the acetylene is independently selected from 0.01-0.5Mpa;
  • the oxygen comes from oxygen in the air; the pressure of the air is 0.1-3.0Mpa; the hourly space velocity of the air is 50-2000h -1 .
  • halogens are also included;
  • the halogen is from a halogen source
  • the halogen source is selected from at least one of bromine simple substance, iodine simple substance, C 1 -C 6 brominated alkanes, and halogenated alkanes.
  • the mass content of the halogen source in the mixture A is 0.1-5%;
  • Said mixture A includes alcohol compound and halogen source.
  • the halogen source can be fed in a mixture with alcohol compounds.
  • the role of the halogen source in this application is to maintain the stability and sustainability of the catalyst during the reaction.
  • the patent of the present invention has the following innovative points: (1) metal Pd in the catalyst is dispersed at the single-atom level, and the utilization rate of metal atoms is greatly improved and improved; (2) there is no need to use sulfur in the catalytic system The acid additive avoids the reactor corrosion problem caused by the sulfonic acid additive in the homogeneous system; (3) The reaction is carried out continuously in a fixed bed reactor, the process is novel and simple, the conditions are mild, the reaction activity is good, and the product selectivity is high. The conversion rate of acetylene and the selectivity of butenedioic acid diester can reach more than 90%, and the catalyst is easy to separate, which has a higher technical competitive advantage.
  • the catalyst used in the method of the present invention not only improves the C 2 H 2 double carbonylation reaction activity, but also greatly reduces and suppresses the active metal Pd 2+ species into the Pd 0 of the inactive metal state, thereby enhancing the catalytic activity of the catalyst. reactivity.
  • Fig. 1 is the HAADF-STEM figure of the Pd-based catalyst dispersed at the monoatomic level prepared in Example 1;
  • Fig. 2 is the XPS figure of the Pd-based catalyst dispersed at the monoatomic level prepared in Example 1;
  • FIG. 3 is an XAFS diagram of the single-atom-level dispersed Pd-based catalyst prepared in Example 1.
  • the instrument model of the spherical aberration electron microscope (HAADF-STEM) used is JEOL JEM-ARM200F, the test condition is 200kV, and the point resolution is 0.08nm.
  • the product selectivity was calculated according to the composition of each product.
  • the conversion rate of acetylene and the selectivity of products are calculated based on the number of carbon moles of converted acetylene.
  • the coconut shell activated carbon used has an average pore diameter of 1-2 nm; a specific surface area of 800-3000 m 2 /g.
  • the activated carbon support containing sulfur functional groups can be prepared by calcination at 500°C under nitrogen protection for 2 hours overnight.
  • coconut shell activated carbon washed with ordinary water and treat it with H2 at a high temperature of 1000°C for 6h to remove the surface oxygen functional groups, then use 30ml of tetramethylthiourea and 20ml of deionized water to treat it at 180°C for 12h, 120 °C drying overnight, followed by calcination at 500 °C for 2 hours in a nitrogen atmosphere to prepare the activated carbon carrier containing sulfur functional groups.
  • coconut shell activated carbon washed with ordinary water and treat it with H2 at a high temperature of 1000°C for 6h to remove the surface oxygen functional groups, then use 30ml of 3,4-dichlorophenylthiourea and 20ml of deionized water at 150°C After hydrothermal treatment for 6 hours, drying at 120°C overnight, and calcination at 400°C in a nitrogen atmosphere for 3 hours, the activated carbon carrier containing sulfur functional groups can be prepared.
  • the heat treatment temperature is 200° C., and the heat treatment time is 2.0 h, so that the single-atom-level dispersed Pd 1 -K-Bi/AC-S-1 catalyst can be obtained.
  • the mass fraction of Pd is 1wt%
  • the molar ratio of Pd and K is 7.80
  • the molar ratio of Pd and Bi is 1.82.
  • coconut shell activated carbon washed with ordinary water and treat it with H 2 at a high temperature of 1000°C for 6h to remove the surface oxygen functional groups, then use 30ml N,N' ⁇ diphenylthiourea, 20ml of deionized water, and heat at 170°C After hydrothermal treatment for 6 hours, drying at 120°C overnight, and calcination at 400°C in a nitrogen atmosphere for 4 hours, the activated carbon carrier containing sulfur functional groups can be prepared.
  • the heat treatment temperature is 200° C., and the heat treatment time is 2.0 h to obtain the single-atom-level dispersed Pd 1 -Cu-Sb/AC-S catalyst.
  • the mass fraction of Pd is 1wt%
  • the molar ratio of Pd and Cu is 0.19
  • the molar ratio of Pd and Sb is 1.14.
  • the heat treatment temperature is 200° C., and the heat treatment time is 2.0 h to obtain the single-atom-level dispersed Pd 1 -K-Sb/AC-S catalyst.
  • the mass fraction of Pd is 1wt%
  • the molar ratio of Pd and K is 0.16
  • the molar ratio of Pd and Sb is 1.14.
  • the heat treatment temperature is 200° C., and the heat treatment time is 2.0 h, so that the single-atom-level dispersed Pd 1 -K/AC-S catalyst can be obtained.
  • the mass fraction of Pd is 1wt%, and the molar ratio of Pd and K is 0.16.
  • X-ray diffraction XRD X-ray diffraction XRD
  • X-ray absorption fine structure spectrum XAFS X-ray absorption fine structure spectrum
  • HAADF-STEM spherical aberration electron microscope
  • test results of the samples in other examples are similar to the above, and single-atom dispersed catalysts are obtained.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 ).
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 70°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • Adopt the catalyzer that prepares monoatomic Pd-Cu-Bi/S C among the embodiment 3, weigh 0.3g and place the middle part of the fixed-bed reactor of Hastelloy, fill with quartz sand in the upper and lower parts, add 200g ethanol in the feeding tank , the liquid hourly space velocity is 2.0h, the pump flow rate is 50ul/min, and 0.5wt% elemental iodine is dissolved in ethanol.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 70°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • Adopt the catalyzer that prepares monoatomic Pd-Cu-Bi/S C in the embodiment 3, take by weighing 0.3g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g propane in the feeding tank Alcohol, liquid hourly space velocity 2.0h, pump flow rate 50ul/min, 0.5wt% elemental iodine dissolved in propanol.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 70°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • Adopt the catalyzer that prepares monoatomic Pd-Cu-Bi/S C in the embodiment 3, take by weighing 0.3g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g butane in the feed tank Alcohol, liquid hourly space velocity 2.0h, pump flow rate 50ul/min, 0.5wt% elemental iodine dissolved in butanol.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 70°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • Adopt the catalyst of monoatomic Pd-Cu-Bi/S C prepared in embodiment 3, take by weighing 0.3g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g pentamethylene in the feed tank Alcohol, liquid hourly space velocity 2.0h, pump flow rate 50ul/min, 0.5wt% elemental iodine dissolved in amyl alcohol.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 70°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • Adopt the catalyzer that prepares monoatomic Pd-Cu-Bi/S C in the embodiment 3, take by weighing 0.3g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g acetonitrile in the feed tank Alcohol, liquid hourly space velocity 2.0h, pump flow rate 50ul/min, 0.5wt% elemental iodine dissolved in hexanol.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure is 2.0MPa, and the temperature is raised to 70°C for reaction, and the reaction data after 48h of reaction are taken.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 60°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 90°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 50°C for reaction, and the reaction data after 48h of reaction was taken.
  • Adopt the catalyst of preparing monoatomic Pd-Cu-Bi/S C in the embodiment 3, take by weighing 1.0g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g methyl alcohol in the feeding tank , the liquid hourly space velocity is 2.0h ⁇ 1 , the pump flow rate is 50ul/min, and 0.5wt% elemental iodine is dissolved in methanol.
  • the flow rate of air is 30ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 80°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • the flow rate of air is 20ml/min
  • the hourly space velocity of air is 720h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio)
  • the total flow rate of CO/C 2 H 2 is 30ml/min
  • the total system pressure is 1.67MPa
  • the CO partial pressure is 0.9MPa
  • the C 2 H 2 partial pressure is 0.1MPa
  • the air partial pressure was 0.67MPa
  • the temperature was raised to 80°C for reaction, and the reaction data after 48 hours of reaction were taken.
  • Adopt the catalyst of preparing monoatomic Pd-Cu-Bi/S C in the embodiment 3, take by weighing 1.0g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g methyl alcohol in the feeding tank , the liquid hourly space velocity is 2.0h ⁇ 1 , the pump flow rate is 50ul/min, and 0.5wt% elemental iodine is dissolved in methanol.
  • the flow rate of air is 10ml/min
  • the hourly space velocity of air is 360h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio)
  • the total flow rate of CO/C 2 H 2 is 30ml/min
  • the total system pressure is 1.33MPa
  • the CO partial pressure is 0.9MPa
  • the C 2 H 2 partial pressure is 0.1MPa
  • the air partial pressure was 0.33MPa
  • the temperature was raised to 80°C for reaction, and the reaction data after 48 hours of reaction were taken.
  • Adopt the catalyst of preparing monoatomic Pd-Cu-Bi/S C in the embodiment 3, take by weighing 1.0g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g methyl alcohol in the feeding tank , the liquid hourly space velocity is 2.0h ⁇ 1 , the pump flow rate is 50ul/min, and 0.5wt% elemental iodine is dissolved in methanol.
  • the flow rate of air is 5ml/min
  • the hourly space velocity of air is 180h -1
  • the hourly space velocity of carbon monoxide is 972h -1
  • the hourly space velocity of acetylene is 108h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 30ml/min, the total system pressure is 1.2MPa, the CO partial pressure is 0.9MPa, and the C 2 H 2 partial pressure is 0.1MPa , the air partial pressure was 0.16MPa, the temperature was raised to 80°C for reaction, and the data of 48h of reaction was taken.
  • the flow rate of air is 20ml/min
  • the hourly space velocity of air is 720h -1
  • the hourly space velocity of carbon monoxide gas is 648h -1
  • the hourly space velocity of acetylene gas is 72h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 20ml/min, the total system pressure is 2.0MPa, the CO partial pressure is 0.9MPa, and the C 2 H 2 partial pressure is 0.1MPa , the air partial pressure was 1.0MPa, the temperature was raised to 80°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • Adopt the catalyst of preparing monoatomic Pd-Cu-Bi/S C in the embodiment 3, take by weighing 1.0g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g methyl alcohol in the feeding tank , the liquid hourly space velocity is 2.0h ⁇ 1 , the pump flow rate is 50ul/min, and 0.5wt% elemental iodine is dissolved in methanol.
  • the flow rate of air is 10ml/min
  • the hourly space velocity of air is 720h -1
  • the hourly space velocity of carbon monoxide gas is 1296h -1
  • the hourly space velocity of acetylene gas is 144h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 20ml/min, the total system pressure is 3.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 1.0MPa, the temperature was raised to 80°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • the flow rate of air is 20ml/min
  • the hourly space velocity of air is 720h -1
  • the hourly space velocity of carbon monoxide gas is 648h -1
  • the hourly space velocity of acetylene gas is 72h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 20ml/min, the total system pressure is 4.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 2.0MPa, the temperature was raised to 80°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • Adopt the catalyst of preparing monoatomic Pd-Cu-Bi/S C in the embodiment 3, take by weighing 1.0g and place the middle part of the fixed-bed reactor of Hastelloy alloy, the upper and lower parts are filled with quartz sand, add 200g methyl alcohol in the feeding tank , the liquid hourly space velocity is 2.0h ⁇ 1 , the pump flow rate is 50ul/min, and 0.5wt% elemental iodine is dissolved in methanol.
  • the flow rate of air is 40ml/min
  • the hourly space velocity of air is 1080h -1
  • the hourly space velocity of carbon monoxide is 324h -1
  • the hourly space velocity of acetylene is 36h -1 .
  • CO/C 2 H 2 9 (molar ratio), the total flow rate of CO/C 2 H 2 is 20ml/min, the total system pressure is 6.0MPa, the CO partial pressure is 1.8MPa, and the C 2 H 2 partial pressure is 0.2MPa , the air partial pressure was 4.0MPa, the temperature was raised to 80°C for reaction, and the reaction data after 48 hours of reaction were collected.
  • Table 2 shows the reactivity of the catalysts prepared in Examples and Comparative Examples for the carbonylation of acetylene, the conversion rate of acetylene and the selectivity results of each product.

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Abstract

本申请公开了一种单原子分散的钯基催化剂及其制备方法、应用，包括主催化活性组分和载体；所述主催化活性组分为钯元素；所述载体为表面连接有含硫官能团的活性炭；所述钯元素以单核络合物的形式单原子分散在所述钯基催化剂中，所述单核络合物通过所述含硫官能团锚定在活性炭表面。本发明提供的催化剂中贵金属Pd为单原子级分散，所制备的催化剂金属原子利用非常高，其可用于制备丁(烯)二酸二酯，具有良好的催化活性和稳定性。

Description

一种单原子分散的钯基催化剂及其制备方法、应用 技术领域
本申请涉及一种单原子分散的钯基催化剂及其制备方法、应用，属于催化化工技术领域。
背景技术
在工业催化剂中，负载型金属催化剂占比70％以上，尤其负载型贵金属催化剂，广泛用于各种催化剂反应。由于工业生产中，负载型金属催化剂通常为纳米金属催化剂，往往只有表面暴露的原子才具有催化剂活性，造成金属原子利用效率低，贵金属资源浪费。
与纳米金属催化剂相比，单原子催化剂由于其近100％的原子利用率，以及单一孤立的催化活性位点，使得其成为当代研究的新兴热点。
然而，相较于单金属活性位点催化剂，具有助催化活性金属的双活性位点催化剂更具吸引力，它不仅具有单点催化的本质特性，还具有双催化活性位点，往往表现出更佳的催化活性，可以实现不同反应的在相邻位点上的串联催化或协同催化。同时，某些助催化金属原子的存在，对于维持催化剂的反应活性，抑制催化剂的过渡还原，以及提高催化剂的稳定性和活性，调变产物的选择性等方面具有突出的作用和意义。
利用纳米金属颗粒的原位原子级单分散策略，对负载型的纳米金属颗粒进行热处理，将其进行原位原子级单分散，制备出Pd基单原子催化剂。
乙炔，分子式C 2H 2，俗称电石气，是重要的有机合成原料，被称为“有机合成的工业之母”。利用电石加水便可轻易制取，我国新疆地区电石丰富，能够大量富产乙炔。同时，乙炔可由丰富的天然气热裂解制得，成本很低，还能拓展天然的高附加值利用。
此外，从产业链来看，一定条件下乙炔可以聚合生成苯，甲苯，二甲苯，萘，蒽，苯乙烯，茚等芳烃。通过取代反应和加成反应，可生成一系列极有价值的产品。乙炔和一氧化碳及其他化合物(如水，醇，硫醇)等反应制取丙烯酸及其衍生物。
乙炔类精细化学品是乙炔化工发展的一个方向，它不仅可使乙炔下游产品大幅度增值，还可以推动现代乙炔化工向纵深方向发展。利用乙炔和CO作为原料，在亲核试剂进攻下可发生乙炔羰基化反应。
目前，乙炔羰基化制丙烯酸及酯类研究大多为均相催化，发展了[Ni(CO) 4]，[Co(CO) 4] 2，Fe(CO) 5和Pd基催化体系。其中，Pd基催化体系，在引入氮氧配体、和浓硫酸、磺酸等前体下可调变产物选择性，生产丁(烯)二酸，丁(烯)二酸酯、以及马来酸酐等产物。
综上，现有乙炔双羰基化制备丁(烯)二酸二酯主要存在以下几个问题：(1)大多为均相催化体系，存在催化剂易流失，产物分离困难问题；(2)反应大多为单羰基化反应，生成丙烯酸和丙烯酸酯，使得目标产物选择性低；(3)反应过程中金属催化剂用量大，效率低，需要使用磺酸及其衍生物做助催化剂；(4)金属催化剂基本是纳米金属颗粒，原子利用率低；(5)负载Pd金属催化剂稳定性不够理想，反应中会变成钯黑团聚，造成金属催化剂的浪费和流失。
发明内容
基于上述现有技术中存在的问题，本申请提供了一种单原子分散的钯基催化剂，包括主催化活性组分和载体；所述主催化活性组分中包括钯元素；所述载体为表面连接有含硫官能团的活性炭；所述钯元素以单核络合物的形式单原子分散在所述钯基催化剂中。催化剂中金属Pd为单原子级分散，金属原子利用率得到极大提高和改进。
根据本申请的第一方面，提供了一种单原子分散的钯基催化剂，包括主催化活性组分和载体；
所述主催化活性组分中包括钯元素；
所述载体为表面连接有含硫官能团的活性炭；
所述钯元素以单核络合物的形式单原子分散在所述钯基催化剂中，如式I中所示：
Pd(CO) xX y         式I
其中，X选自卤素；所述卤素选自Br、I中的至少一种；
1≤x≤2；1≤y≤4；
所述单核络合物通过所述含硫官能团锚定在活性炭表面。
可选地，在所述单原子分散的钯基催化剂中，还包括助催化活性组分；所述助催化活性组分分散在所述载体表面；
所述助催化活性组分中包括碱金属元素、过渡金属元素中的至少一种；
所述碱金属元素选自钾元素；
所述过渡金属元素选自铜元素、铁元素中的至少一种。
优选地，所述卤素选自I。
可选地，所述助催化活性组分以碱金属元素的卤化物和/或过渡金属元素的卤化物形式分散在所述载体表面。
可选地，在所述单原子分散的钯基催化剂中，还包括组分A；所述组分A分散在所述载体表面；
所述组分A包括阻燃金属元素；
所述阻燃金属元素选自铋元素、锑元素中的至少一种。
可选地，所述组分A以单质或化合物Q的形式分散在所述载体表面；
所述化合物Q选自铋元素的氧化物、铋元素的卤化物、锑元素的氧化物、锑元素的卤化物中的至少一种。
可选地，所述化合物Q选自Sb 2O 3、SbX' m、Bi 2O 3、BiX” n中的至少一种；
其中，0＜m≤6；0＜n≤6；
X'、X”均独立地选自Br、I中的至少一种。
可选地，在所述单原子分散的钯基催化剂中，所述主催化活性组分的质量含量为0.1～3％；其中，所述主催化活性组分的质量以钯元素的质量计。
可选地，在所述单原子分散的钯基催化剂中，所述主催化活性组分的质量含量上限独立地选自3％、2％、1％、0.5％，下限独立地选自0.1％、2％、1％、0.5％。
可选地，在所述单原子分散的钯基催化剂中，所述主催化活性组分的摩尔数与所述助催化活性组分的摩尔数之比为1:(0.01～10)；
其中，所述主催化活性组分的摩尔数以钯元素的摩尔数计，所述助催化活性组分的摩尔数以其中金属元素的摩尔数计。
具体地，本申请中组分A的作用是防止乙炔爆炸。
具体地，本申请中活性碳载体表面含有硫官能团作为活性金属Pd等金属的锚定位点，同时与Pd发生电子相互作用，调变Pd的催化活性。
可选地，所述主催化活性组分中钯与所述组分A的摩尔比为1:0.01～10；
其中，所述组分A的摩尔数以阻燃金属元素的摩尔数计。
根据本申请的第二方面，提供了一种上述单原子分散的钯基催化剂的制备方法，所述制备方法包括：
(1)将含有硫源、活性炭和水的物料，水热处理，得到前驱体i；
(2)在非活性气氛下，将所述前驱体i焙烧I，得到所述载体；
(3)将含有钯盐的溶液等体积浸渍到所述载体中，焙烧II，得到前驱体ii；
(4)将所述前驱体ii与含有卤代烷烃和一氧化碳的混合气接触反应I，即可得到所述单原子分散的钯基催化剂；
所述卤代烷烃选自C 1‐C 6的溴代烷烃、C 1‐C 6的碘代烷烃中的至少一种。
可选地，在所述步骤(1)中，所述硫源和活性炭的体积质量比为(5～100)mL:20g。
可选地，在所述步骤(1)中，水热处理需加入20～50ml的去离子水。
可选地，所述步骤(4)包括：将步骤(3)制备得到的样品放入石英管反应器中，利用CO和卤代烷烃对其进行热处理，卤代烷烃用CO进行鼓泡带入，CO流速30～100ml/min，热处理温度为150～240℃，热处理时间为1～4h，即可得到所述的单原子级分散的Pd基催化剂。
可选地，在所述步骤(1)中，水热处理后还包括烘干步骤；烘干的温度为100～120℃。
可选地，所述硫源选自硫脲、四甲基硫脲、4‐乙酰基氨基硫脲、3,4‐二氯苯基硫脲、邻甲苯基硫脲、N,N’‐二苯基硫脲、5‐乙烯基恶唑烷‐2‐硫酮、四氢吡咯‐2‐硫酮、1‐羟基吡啶硫酮钠、哌啶‐2‐硫酮、4,5‐双(苯甲酰硫基)‐1,3‐二硫杂环戊二烯‐2‐硫酮、三硫代碳酸乙烯酯中的至少一种；
所述活性炭选自椰壳活性炭、杏壳活性炭中的至少一种；
所述钯盐选自可溶性钯盐中的至少一种。
可选地，在所述步骤(3)中，所述含有钯盐的溶液中还包括钾盐、铜盐、铁盐中的至少一种。
可选地，所述焙烧II之前，还包括烘干步骤；所述烘干的温度为100～120℃。
可选地，所述卤代烷烃选自CH 3I、CH 3Br中的至少一种。
可选地，所述卤代烷烃由CO进行鼓泡带入。
可选地，所述水热处理的条件为：温度为100～180℃；时间为1～24h；
所述焙烧I的条件为：温度为300～800℃；时间为1～6h；
所述焙烧II的条件为：温度为300～400℃；时间为1～4h；
所述等体积浸渍的温度为20～30℃；
所述反应I的条件为：温度为150～240℃；时间为1～4h。
可选地，所述反应I的温度上限独立地选自240℃、200℃、180℃，下限独立地选自150℃、200℃、180℃。
可选地，所述反应I的时间上限独立地选自4h、3h、2h，下限独立地选自1h、3h、2h。
可选地，所述钯盐选自氯化钯。
可选地，在所述步骤(4)中，所述卤代烷烃选自C 1‐C 6溴代烷烃、C 1‐C 6的碘代烷烃中至少一种。
所述卤代烷烃和一氧化碳的摩尔比为(0.1～10):1。
可选地，所述含有卤代烷烃和一氧化碳的混合气的流速为30～100ml/min。
可选地，所述含有卤代烷烃和一氧化碳的混合气的流速上限独立地选自100ml/min、90ml/min、70ml/min、60ml/min、40ml/min，下限独立地选自30ml/min、90ml/min、70ml/min、60ml/min、40ml/min。
可选地，所述钾盐选自可溶性钾盐中的至少一种；
所述铜盐选自可溶性铜盐中的至少一种；
所述铁盐选自可溶性铁盐中的至少一种。
可选地，所述钾盐选自氯化钾；所述铜盐选自氯化铜；所述铁盐选自氯化铁。
可选地，在所述含有钯盐的溶液中，还包括铋盐、锑盐中的至少一种。
可选地，所述铋盐选自可溶性铋盐中的至少一种；
所述锑盐选自可溶性锑盐中的至少一种。
可选地，在所述步骤(1)之前，还包括如下步骤：
在含氢气氛下，将活性碳在800～1000℃下处理2～12h，去除活性炭表面的氧官能团。
根据本申请的第三方面，提供了一种丁烯二酸二酯的制备方法，所述方法包括：
将含有乙炔、一氧化碳、醇类化合物、氧气的混合物，与单原子分散的钯基催化剂接触反应II，即可得到丁烯二酸二酯；
所述单原子分散的钯基催化剂选自上述单原子分散的钯基催化剂、根据上述方法制备得到的单原子分散的钯基催化剂中的至少一种。
可选地，所述丁烯二酸二酯包括丁(烯)二酸二甲酯、丁(烯)二酸二乙酯、丁(烯)二酸二丙酯、丁(烯)二酸二丁酯、丁(烯)二酸二戊酯、丁(烯)二酸二辛酯，或者丁(烯)二酸甲乙酯、丁(烯)二酸甲丙酯中的至少一种。
可选地，所述反应II的条件为：温度为60～120℃；时间为1～24h。
可选地，所述醇类化合物选自甲醇、乙醇、丙醇、丁醇、戊醇、辛醇中的至少一种。
可选地，所述一氧化碳和所述乙炔的摩尔比为(1～10):1。
可选地，所述醇类化合物的液时空速为0.1～6h ‐1；
所述一氧化碳和乙炔的气时空速均独立地选自10～2000h ‐1。
可选地，所述一氧化碳的压力独立地选自1.0～6.0Mpa；
可选地，所述乙炔的压力独立地选自0.01～0.5Mpa；
所述氧气来自空气中的氧气；所述空气的压力为0.1～3.0Mpa；所述空气气时空速为50～2000h ‐1。
可选地，在所述混合物中，还包括卤素；
所述卤素来自卤素源；
所述卤素源选自溴单质、碘单质、C 1‐C 6的溴代烷烃、卤代烷烃中的至少一种。
可选地，所述卤素源在混合物A中的质量含量为0.1～5％；
所述混合物A包括醇类化合物和卤素源。
可选地，所述卤素源可以和醇类化合物混合进料。
具体地，本申请中卤素源的作用是维持催化剂在反应过程中的稳定性和可持续性。
本申请的有益效果包括但不限于：
与现有技术相比，本发明专利具有以下几个创新点：(1)催化剂中金属Pd为单原子级分散，金属原子利用率得到极大提高和改进；(2)催化体系中无需使用磺酸助剂，避免了均相体系中磺酸助剂造成的反应器腐蚀问题；(3)反应在固定床反应器中连续进行，工艺新颖简单，条件温和，反应活性好，产物选择性高，乙炔转化率和丁烯二酸二酯选择性可达90％以上，催化剂易分离，具有更高的技术竞争优势。总之，本发明方法中使用的催化剂不仅提高了C 2H 2双羰基化反应活性，极大地减小和抑制了活性金属Pd 2+物种转成非活性金属态的Pd 0，从而增强了催化剂的反应活性。
附图说明
图1为实施例1制备的单原子级分散的Pd基催化剂的HAADF‐STEM图；
图2为实施例1制备的单原子级分散的Pd基催化剂的XPS图；
图3为实施例1制备的单原子级分散的Pd基催化剂的XAFS图。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特殊说明，本申请所用原料和试剂均来自商业购买，未经处理直接使用，所用仪器设备采用厂家推荐的方案和参数。
实施例中，所有催化剂评价结果均采用安捷伦公司(Agilent)7890B型液相色谱仪，FID检测器，毛细管柱，内标法分析液相组成，苯甲酸甲酯为内标物。
实施例中，所使用的球差电镜(HAADF‐STEM)的仪器型号为JEOL JEM‐ARM200F，测试条件为200kV,点分辨率0.08nm。
根据各产物组成计算得到产品选择性。
本申请的实施例中，乙炔的转化率、产物的选择性都基于已转化的乙炔的碳摩尔数进行计算。
实施例中，使用的椰壳活性炭的平均孔径为1～2nm；比表面积为800～3000m 2/g。
实施例1
称取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml的硫脲，20ml的去离子水，在180℃水热处理6h，120℃烘干过夜，500℃氮气保护焙烧处理2h，即可制得含硫官能团的活性炭载体。量取5mL37wt％(质量)的浓HCl加入10ml去离子水，称取0.17g PdCl 2、0.08g CuO、0.12g Bi 2O 3溶解于上述15ml的盐酸溶液中，然后25℃下浸渍10.0g上述制备得到的含硫官能团的活性炭载体2h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应器中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO于常温25℃下进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即可得到所述的单原子级分散的Pd 1‐Cu‐Bi/AC‐S‐1催化剂。其中，Pd的质量分数为1wt％，Pd和Cu的摩尔比为0.93,Pd和Bi的摩尔比为1.82。
实施例2
取20g普通水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml的四甲基硫脲，20ml的去离子水，在180℃水热处理12h，120℃烘干过夜，氮气气氛500℃焙烧处理2h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10ml去离子水，称取0.17g PdCl 2、0.24g CuO、0.12g Bi 2O 3溶解于上述15ml的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体 2.0h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应器中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即可得到所述的单原子级分散的Pd 1‐Cu‐Bi/AC‐S‐2催化剂。其中，Pd的质量分数为1wt％，Pd和Cu的摩尔比为0.31,Pd和Bi的摩尔比为1.82。
实施例3
取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml的4‐乙酰基氨基硫脲，20ml的去离子水，在160℃水热处理12h，120℃烘干过夜，氮气气氛700℃焙烧处理2h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10ml去离子水，称取0.17g PdCl 2、0.40g CuO、0.12g Bi 2O 3溶解于上述15ml的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即得到所述单原子级分散的Pd 1‐Cu‐Bi/AC‐S‐3催化剂。其中，Pd的质量分数为1wt％，Pd和Cu的摩尔比为0.19,Pd和Bi的摩尔比为1.82。
实施例4
称取20g普通水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml 3,4‐二氯苯基硫脲，20ml的去离子水，在150℃水热处理6h，120℃烘干过夜，氮气气氛400℃焙烧处理3h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10ml去离子水，称取0.17g PdCl 2、0.02g KI、0.12g Bi 2O 3溶解于上述15ml的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应器中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即可得到所述的单原子级分散的Pd 1‐K‐Bi/AC‐S‐1催化剂。其中，Pd的质量分数为1wt％，Pd和K的摩尔比为7.80,Pd和Bi的摩尔比为1.82。
实施例5
称取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml N,N’‐二苯基硫脲，20ml的去离子水，在170℃水热处理3h，120℃烘干过夜，氮气气氛300℃焙烧处理3h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10ml去离子水，称取0.17g PdCl 2、0.06g KI、0.12g Bi 2O 3溶解于上述15ml的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即得所述单原子级分散的Pd 1‐K‐Bi/AC‐S‐2催化剂。其中，Pd的质量分数为1wt％，Pd和K的摩尔比为2.60,Pd和Bi的摩尔比为1.82。
实施例6
称取20g普通水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml N,N’‐二苯基硫脲，20ml的去离子水，在170℃水热处理6h，120℃烘干过夜，氮气气氛400℃焙烧处理4h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10ml去离子水，称取0.17g PdCl 2、0.10g KI、0.12g Bi 2O 3溶解于上述15ml的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即可得到所述的单原子级分散的Pd 1‐K‐Bi/AC‐S‐3催化剂。其中，Pd的质量分数为1wt％，Pd和K的摩尔比为1.56,Pd和Bi的摩尔比为1.82。
实施例7
取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml四氢吡咯‐2‐硫酮，20ml的去离子水，在170℃水热处理8h，120℃烘干过夜，氮气气氛400℃焙烧处理4h，即可得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10ml去离子水，称取0.17g PdCl 2、0.4g CuO、0.12g Sb 2O 3溶解于上述15ml的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2h，120℃ 烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应器中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即得到所述单原子级分散的Pd 1‐Cu‐Sb/AC‐S催化剂。其中，Pd的质量分数为1wt％，Pd和Cu的摩尔比为0.19,Pd和Sb的摩尔比为1.14。
实施例8
取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml哌啶‐2‐硫酮，20ml的去离子水，在170℃水热处理12h，120℃烘干过夜，氮气气氛400℃焙烧处理4h，即可得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10ml去离子水，称取0.17g PdCl 2、1.0g KI、0.12g Sb 2O 3溶解于上述15ml的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应器中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即得所述单原子级分散的Pd 1‐K‐Sb/AC‐S催化剂。其中，Pd的质量分数为1wt％，Pd和K的摩尔比为0.16,Pd和Sb的摩尔比为1.14。
对比例1
取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，取5ml 37wt％的浓HCl加入10mL去离子水，称取0.17g PdCl 2溶解于上述15mL的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的活性炭载体2h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应器中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即可得到所述的单原子级分散的Pd 1/AC催化剂。其中，Pd的质量分数为1wt％。
实施例9
称取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml的硫脲，20ml的去离子水，在170℃水热处理12h，120℃烘干过夜， 氮气气氛400℃焙烧处理4h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10mL去离子水，称取0.17g PdCl 2溶解于上述15mL的盐酸溶液中，然后25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应器中，用CO和CH 3I(摩尔比为1：1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即可得到所述的单原子级分散的Pd 1/AC‐S催化剂。其中，Pd的质量分数为1wt％。
对比例2
称取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用30ml的硫脲，20ml的去离子水，在170℃水热处理24h，120℃烘干过夜，氮气气氛400℃焙烧处理4h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10mL去离子水，称取0.17g PdCl 2溶解于上述15mL的盐酸溶液中，然后于25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2.0h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h，再在氢气气氛下300℃还原2h后，再降到常温，用1％O 2/Ar进行表面钝化，即可得到负载型纳米颗粒对比的Pd/AC‐S催化剂。其中，Pd的质量分数为1wt％。
实施例10
称取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用等体积的硫脲，20ml的去离子水，在170℃水热处理12h，120℃烘干过夜，氮气气氛400℃焙烧处理4h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10mL去离子水，称取0.17g PdCl 2、0.40g CuO溶解于上述15mL的盐酸溶液中，然后于25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2.0h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即可得到所述的单原子级分散的Pd 1‐Cu/AC‐S催化剂。其中，Pd的质量分数为1wt％，Pd和Cu的摩尔比为0.19。
实施例11
称取20g水洗后的椰壳活性炭用H 2在1000℃的高温下处理6h，去除表面氧官能团，再用等体积的硫脲，20ml的去离子水，在170℃水热处理12h，120℃烘干过夜，氮气气氛400℃焙烧处理4h，即可制得含硫官能团的活性炭载体。量取5mL37wt％的浓HCl加入10mL去离子水，称取0.17g PdCl 2、1.0g KI溶解于上述15mL的盐酸溶液中，然后于25℃浸渍10.0g上述制备得到的含硫官能团的活性炭载体2.0h，120℃烘干过夜，300℃氮气气氛下焙烧2.0h。将上述制备得到的样品放入石英管反应器中，用CO和CH 3I(摩尔比为1:1)对其进行热处理，CH 3I用CO进行鼓泡带入，CO流速60ml/min，热处理温度为200℃，热处理时间为2.0h，即可得到所述的单原子级分散的Pd 1‐K/AC‐S催化剂。其中，Pd的质量分数为1wt％，Pd和K的摩尔比为0.16。
实施例12
采用X射线衍射XRD、X射线吸收精细结构谱XAFS、球差电镜HAADF‐STEM对实施例所得样品进行表征，结果显示：制得的催化剂为单原子分散的催化剂。
其中，以实施例1中的样品为典型代表，其透射电镜照片如图1所示，由图可以看出本方法制备的催化剂中，钯确实是以单原子分布在载体中。其XPS结果如图2所示，显示Pd为二价Pd 2+，异于Pd纳米颗粒Pd 0。其XAFS如图3所示，其拟合结果如表1所示，显示单原子Pd 1催化剂中，Pd第一配位壳层为Pd(CO)I 4结构，结合XPS，判定最终结构为[Pd(CO)I 4] 2‐。
表1
Figure PCTCN2021099012-appb-000001
其他实施例样品的测试结果与上类似，均获得了单原子分散的催化剂。
实施例13
采用实施例1‐11及对比例1、2中制备的催化剂进行以下实验：称取0.3g催化剂放入哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1)。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到70℃反应，取反应48h后的反应数据。
实施例14
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取0.3g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g乙醇，液时空速2.0h，泵流速为50ul/min，乙醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到70℃反应，取反应48h后的反应数据。
实施例15
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取0.3g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g丙醇，液时空速2.0h，泵流速为50ul/min，丙醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到70℃反应，取反应48h后的反应数据。
实施例16
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取0.3g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g丁醇，液时空速2.0h，泵 流速为50ul/min，丁醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到70℃反应，取反应48h后的反应数据。
实施例17
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取0.3g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g戊醇，液时空速2.0h，泵流速为50ul/min，戊醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到70℃反应，取反应48h后的反应数据。
实施例18
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取0.3g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g己醇，液时空速2.0h，泵流速为50ul/min，己醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，，升温到70℃反应，取反应48h后的反应数据。
实施例19
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取0.3g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到60℃反应，取反应48h后的反应数据。
实施例20
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取0.3g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到90℃反应，取反应48h后的反应数据。
实施例21
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取0.3g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到50℃反应，取反应48h后的反应数据。
实施例22
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取1.0g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为30ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到80℃反应，取反应48h后的反应数据。
实施例23
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取1.0g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为20ml/min，空气气时空速为720h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为1.67MPa，CO分压为0.9MPa，C 2H 2分压为0.1MPa，空气分压为0.67MPa，升温到80℃反应，取反应48h后的反应数据。
实施例24
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取1.0g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为10ml/min，空气气时空速为360h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为1.33MPa，CO分压为0.9MPa，C 2H 2分压为0.1MPa，空气分压为0.33MPa，升温到80℃反应，取反应48h后的反应数据。
实施例25
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取1.0g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为5ml/min，空气气时空速为180h ‐1，一氧化碳气时空速为972h ‐1,乙炔气时空速为108h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为30ml/min，系统总压为1.2MPa，CO分压为0.9MPa，C 2H 2分压为0.1MPa，空气分压为0.16MPa，升温到80℃反应，取反应48h数据。
实施例26
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取1.0g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为20ml/min，空气气时空速为720h ‐1，一氧化碳气时空速为648h ‐1,乙炔气时空速为72h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为20ml/min，系统总压为2.0MPa，CO分压为0.9MPa，C 2H 2分压为0.1MPa，空气分压为1.0MPa，升温到80℃反应，取反应48h后的反应数据。
实施例27
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取1.0g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为10ml/min，空气气时空速为720h ‐1，一氧化碳气时空速为1296h ‐1,乙炔气时空速为144h ‐1。CO/C 2H 2＝9(摩 尔比)，CO/C 2H 2的总流速为20ml/min，系统总压为3.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为1.0MPa，升温到80℃反应，取反应48h后的反应数据。
实施例28
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取1.0g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为20ml/min，空气气时空速为720h ‐1，一氧化碳气时空速为648h ‐1,乙炔气时空速为72h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为20ml/min，系统总压为4.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为2.0MPa，升温到80℃反应，取反应48h后的反应数据。
实施例29
采用实施例3中制备单原子Pd‐Cu‐Bi/S＝C的催化剂，称取1.0g置于哈氏合金的固定床反应器中部，上下部用石英砂充填，进料罐中加入200g甲醇，液时空速2.0h ‐1，泵流速为50ul/min，甲醇中溶解有0.5wt％的单质碘。空气的流速为40ml/min，空气气时空速为1080h ‐1，一氧化碳气时空速为324h ‐1,乙炔气时空速为36h ‐1。CO/C 2H 2＝9(摩尔比)，CO/C 2H 2的总流速为20ml/min，系统总压为6.0MPa，CO分压为1.8MPa，C 2H 2分压为0.2MPa，空气分压为4.0MPa，升温到80℃反应，取反应48h后的反应数据。
表2为使用实施例及对比例中制备得到的催化剂用于乙炔羰基化的反应性能乙炔的转化率和各产物的选择性结果。
表2
Figure PCTCN2021099012-appb-000002
Figure PCTCN2021099012-appb-000003
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (26)

  1. 一种单原子分散的钯基催化剂，其特征在于，包括主催化活性组分和载体；
    所述主催化活性组分中包括钯元素；
    所述载体为表面连接有含硫官能团的活性炭；
    所述钯元素以单核络合物的形式单原子分散在所述钯基催化剂中，如式I中所示：
    Pd(CO) xX y  式I
    其中，X选自卤素；所述卤素选自Br、I中的至少一种；
    1≤x≤2；1≤y≤4；
    所述单核络合物通过所述含硫官能团锚定在活性炭表面。
  2. 根据权利要求1所述的单原子分散的钯基催化剂，其特征在于，在所述单原子分散的钯基催化剂中，还包括助催化活性组分；所述助催化活性组分分散在所述载体表面；
    所述助催化活性组分中包括碱金属元素、过渡金属元素中的至少一种；
    所述碱金属元素选自钾元素；
    所述过渡金属元素选自铜元素、铁元素中的至少一种。
  3. 根据权利要求2所述的单原子分散的钯基催化剂，其特征在于，所述助催化活性组分以碱金属元素的卤化物和/或过渡金属元素的卤化物形式分散在所述载体表面。
  4. 根据权利要求2所述的单原子分散的钯基催化剂，其特征在于，在所述单原子分散的钯基催化剂中，还包括组分A；所述组分A分散在所述载体表面；
    所述组分A包括阻燃金属元素；
    所述阻燃金属元素选自铋元素、锑元素中的至少一种。
  5. 根据权利要求4所述的单原子分散的钯基催化剂，其特征在于，所述组分A以单质或化合物Q的形式分散在所述载体表面；
    所述化合物Q选自铋元素的氧化物、铋元素的卤化物、锑元素的氧化物、锑元素的卤化物中的至少一种。
  6. 根据权利要求5所述的单原子分散的钯基催化剂，其特征在于，所述化合物Q选自Sb 2O 3、SbX' m、Bi 2O 3、BiX” n中的至少一种；
    其中，0＜m≤6；0＜n≤6；
    X'、X”均独立地选自Br、I中的至少一种。
  7. 根据权利要求4所述的单原子分散的钯基催化剂，其特征在于，在所述单原子分散的钯基催化剂中，所述主催化活性组分的质量含量为0.1～3％；其中，所述主催化活性组分的质量以钯元素的质量计。
  8. 根据权利要求2所述的单原子分散的钯基催化剂，其特征在于，在所述单原子分散的钯基催化剂中，所述主催化活性组分的摩尔数与所述助催化活性组分的摩尔数之比为1:(0.01～10)；
    其中，所述主催化活性组分的摩尔数以钯元素的摩尔数计，所述助催化活性组分的摩尔数以其中金属元素的摩尔数计。
  9. 根据权利要求4所述的单原子分散的钯基催化剂，其特征在于，所述主催化活性组分中钯与所述组分A的摩尔比为1:(0.01～10)；
    其中，所述组分A的摩尔数以阻燃金属元素的摩尔数计。
  10. 权利要求1至9任一项所述的单原子分散的钯基催化剂的制备方法，其特征在于，所述制备方法包括：
    (1)将含有硫源、活性炭和水的物料，水热处理，得到前驱体i；
    (2)在非活性气氛下，将所述前驱体i焙烧I，得到所述载体；
    (3)将含有钯盐的溶液等体积浸渍到所述载体中，焙烧II，得到前驱体ii；
    (4)将所述前驱体ii与含有卤代烷烃和一氧化碳的混合气接触反应I，即可得到所述单原子分散的钯基催化剂；
    所述卤代烷烃选自C 1‐C 6的溴代烷烃、C 1‐C 6的碘代烷烃中的至少一种。
  11. 根据权利要求10所述的制备方法，其特征在于，所述硫源选自硫脲、四甲基 硫脲、4‐乙酰基氨基硫脲、3,4‐二氯苯基硫脲、邻甲苯基硫脲、N,N’‐二苯基硫脲、5‐乙烯基恶唑烷‐2‐硫酮、四氢吡咯‐2‐硫酮、1‐羟基吡啶硫酮钠、哌啶‐2‐硫酮、4,5‐双(苯甲酰硫基)‐1,3‐二硫杂环戊二烯‐2‐硫酮、三硫代碳酸乙烯酯中的至少一种；
    所述活性炭选自椰壳活性炭、杏壳活性炭中的至少一种；
    所述钯盐选自可溶性钯盐中的至少一种。
  12. 根据权利要求10所述的制备方法，其特征在于，在所述步骤(3)中，所述含有钯盐的溶液中还包括钾盐、铜盐、铁盐中的至少一种。
  13. 根据权利要求12所述的制备方法，其特征在于，所述钾盐选自可溶性钾盐中的至少一种；
    所述铜盐选自可溶性铜盐中的至少一种；
    所述铁盐选自可溶性铁盐中的至少一种。
  14. 根据权利要求10所述的制备方法，其特征在于，所述水热处理的条件为：温度为100～180℃；时间为2～24h；
    所述焙烧I的条件为：温度为300～800℃；时间为1～6h；
    所述焙烧II的条件为：温度为300～400℃；时间为1～4h；
    所述等体积浸渍的温度为20～30℃；
    所述反应I的条件为：温度为150～240℃；时间为1～4h。
  15. 根据权利要求10所述的制备方法，其特征在于，在所述步骤(4)中，所述含有卤代烷烃和一氧化碳的混合气的流速为30～100ml/min。
  16. 根据权利要求10所述的制备方法，其特征在于，在所述步骤(3)中，所述含有钯盐的溶液中还包括铋盐、锑盐中的至少一种。
  17. 根据权利要求16所述的制备方法，其特征在于，所述铋盐选自可溶性铋盐中的至少一种；
    所述锑盐选自可溶性锑盐中的至少一种。
  18. 根据权利要求10所述的制备方法，其特征在于，在所述步骤(1)之前，还包括如下步骤：
    在含氢气氛下，将活性碳在800～1000℃下处理2～12h，去除活性炭表面的氧官能团。
  19. 一种丁烯二酸二酯的制备方法，其特征在于，所述方法包括：
    将含有乙炔、一氧化碳、醇类化合物、氧气的混合物，与单原子分散的钯基催化剂接触反应II，即可得到丁(烯)二酸二酯；
    所述单原子分散的钯基催化剂选自权利要求1至9任一项所述的单原子分散的钯基催化剂、根据权利要求10至18任一项所述方法制备得到的单原子分散的钯基催化剂中的至少一种。
  20. 根据权利要求19所述的制备方法，其特征在于，所述反应II的条件为：温度为60～120℃；时间为1～24h。
  21. 根据权利要求19所述的制备方法，其特征在于，所述醇类化合物选自甲醇、乙醇、丙醇、丁醇、戊醇、辛醇中的至少一种。
  22. 根据权利要求19所述的制备方法，其特征在于，所述一氧化碳和所述乙炔的摩尔比为(1～10):1。
  23. 根据权利要求19所述的制备方法，其特征在于，所述醇类化合物的液时空速为0.1～6h ‐1；
    所述一氧化碳和乙炔的气时空速均独立地选自10～2000h ‐1。
  24. 根据权利要求19所述的制备方法，其特征在于，所述一氧化碳的压力为1.0～6.0Mpa；所述乙炔的压力为0.01～0.5MPa；
    所述氧气来自空气中的氧气；所述空气的压力为0.1～3.0Mpa；所述空气气时空速为50～2000h ‐1。
  25. 根据权利要求19所述的制备方法，其特征在于，在所述混合物中，还包括卤素；
    所述卤素来自卤素源；
    所述卤素源选自溴单质、碘单质、C 1‐C 6的溴代烷烃、卤代烷烃中的至少一种。
  26. 根据权利要求25所述的制备方法，其特征在于，所述卤素源在混合物A中的质量含量为0.1～5％；
    所述混合物A包括醇类化合物和卤素源。
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