CN116351476A - Ligand-copper-based catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof - Google Patents

Ligand-copper-based catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof Download PDF

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CN116351476A
CN116351476A CN202211663119.8A CN202211663119A CN116351476A CN 116351476 A CN116351476 A CN 116351476A CN 202211663119 A CN202211663119 A CN 202211663119A CN 116351476 A CN116351476 A CN 116351476A
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catalyst
acetylene
ligand
copper
reaction
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张海洋
亓继
黄明慧
杨李洁
张前刚
李林峰
郭子瀚
康华强
谢东阳
张金利
代斌
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Shihezi 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/20—Measuring; Control or regulation
    • B01F35/22—Control or regulation
    • B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
    • B01F35/2215—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/20—Measuring; Control or regulation
    • B01F35/22—Control or regulation
    • B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
    • B01F35/2216—Time, i.e. duration, of at least one parameter during the operation
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes
    • C07C21/06—Vinyl chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/2204—Mixing chemical components in generals in order to improve chemical treatment or reactions, independently from the specific application
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to the technical field of catalyst preparation, in particular to a ligand-copper-based catalyst for catalyzing acetylene hydrochlorination, and a preparation method and application thereof. The catalyst of the invention takes coconut shell activated carbon as a carrier and CuCl 2 Is a metallic copper precursor, and a phosphorus ligand compound containing triphenyl assist is used as a ligand. The metal copper atom is embedded into the ligand, the ligand has strong electron supply capability and electron delocalization transfer capability, and the coordination with the metal copper precursor modulates the electronic property of the central metal atom, thus being beneficial to electrophilic addition of acetylene and hydrogen chlorideThe microenvironment of the reaction further improves the adsorption and activation capability of the catalyst on reactants of hydrogen chloride and acetylene; coke deposition and agglomeration of copper active species are inhibited. Has the characteristics of high activity, good stability and the like, and has good economical efficiency and industrial application value when being applied to acetylene hydrochlorination.

Description

Ligand-copper-based catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a ligand-copper-based catalyst for catalyzing acetylene hydrochlorination, and a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is synthesized by polymerization reaction of Vinyl Chloride (VCM) monomer, and the global usage amount thereof occupies the third position of the high polymer material, and is widely applied to the fields of industry, building, agriculture, daily life and the like. Vinyl chloride monomer is mainly synthesized by ethylene method, ethane method and calcium carbide method. Based on the energy characteristics of rich coal, lean oil and less gas in China, the coal-based calcium carbide acetylene method process for preparing the chloroethylene is a main process for producing the polyvinyl chloride in China. However, in the calcium carbide acetylene method, carbon-supported mercury chloride is used as an industrial catalyst to catalyze the hydrochlorination of acetylene. Mercury is extremely volatile and highly toxic at the reaction temperature, and the concentration of the generated toxicity is only 0.01-0.1 mg/L, but the mercury has easy migration and lasting detention, so that the mercury is serious harm and pollution to human health and the global ecological environment. In order to realize the green sustainable development of the PVC industry of the acetylene method in China, the development of the high-efficiency mercury-free catalyst is unprecedented.
The mercury-free noble metal catalyst which is more studied in the hydrochlorination of acetylene comprises Au, pt, pd, cu and the like, and the transition metal ions are easy to form a hybridization orbit with stronger bonding capability so as to accept lone pair electrons provided by hetero atoms. Furthermore, due to the unsaturated d orbitals, covalent bonding with heteroatoms is favored, forming highly dispersed and even monoatomic catalysts. Thus, hutchings and numerous researchers in the country all consider gold-based catalysts as the best candidates for these catalysts in this reaction. However, since gold is mainly used in the money and decoration fields and is expensive, the reserves are low, and the industrial mass application thereof is limited. Cu is relatively low in price, high in abundance, and has good initial conversion performance, so Cu-based catalysts are considered as one of the potential candidates for replacing mercury catalysts. At present, the preparation of the copper-based catalyst is mainly improved in the aspects of addition of auxiliary agents, modification of carriers and the like. Although researchers at home and abroad improve copper-based catalysts to a certain extent, the problems that the interaction force between an active component and a carrier is weak, the active species Cu in the copper-based catalysts is unevenly dispersed, easy to agglomerate and inactivate and the like still exist.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a phosphorus ligand-copper-based catalyst, and a preparation method and application thereof. The catalyst takes a ligand containing a triphenyl-assisted phosphorus compound, coconut shell activated carbon as a carrier and CuCl 2 Is prepared from metallic copper precursor.
In order to achieve the aim of the invention, the technical scheme of the invention is as follows:
the invention provides a ligand-copper-based catalyst for catalyzing hydrochlorination of acetylene, which takes coconut shell activated carbon as a carrier and CuCl 2 The metal copper precursor is the ligand which is a phosphorus ligand compound containing triphenyl assist.
Preferably, the phosphorus ligand compound is one of tris (2-tolyl) phosphine, tris (3-methylphenyl) phosphine or tris (4-methylphenyl) phosphine; a more preferred phosphorus ligand compound is tris (3-tolyl) phosphine.
Preferably, the loading of Cu atoms in the catalyst is from 5 to 15wt%, more preferably from 7.5 to 15wt%, based on the total weight of the catalyst.
Preferably, the molar ratio of the metal copper precursor to the phosphorus ligand compound is 3-11:1, more preferably, the molar ratio of the metal copper precursor to the ligand compound is 5-9:1; most preferably, the molar ratio of the metallic copper precursor to the ligand compound is 7:1.
In the molar ratio range of the metal copper precursor and the phosphorus ligand compound, the copper precursor and the ligand can have stronger interaction. Too low a content of Cl of the ligand compound - And P-containing + Partial interaction is weak, which affects the formation of the complex, and further affects the catalytic activity of the copper-based catalyst; the content of the ligand compound is too high, cl - And P + The stronger the interaction of the anions, the weaker the alkalinity affecting Cl - Proton acceptance leads to reduced catalyst activity.
The invention also provides a preparation method of the ligand-copper-based catalyst for catalyzing acetylene hydrochlorination. The preparation method comprises the following steps: firstly, uniformly mixing a metal precursor and a phosphorus ligand compound in isopropanol; and adding coconut shell activated carbon, stirring uniformly, and performing heat activation and drying treatment to obtain the ligand-copper-based catalyst.
Preferably, the metal precursor and the phosphorus ligand compound are uniformly mixed in isopropanol by adopting a magnetic stirring method, wherein the magnetic stirring time is 12 hours. The purpose of the magnetic stirring is to allow the ligand compound to be uniformly dispersed in isopropanol.
Preferably, the stirring temperature is room temperature, and the stirring time is 12-36h; more preferably, the temperature of stirring is 25℃and the stirring time is 12 hours.
Preferably, the thermal activation is: sealing and keeping the constant temperature for 3 hours in a water bath kettle at 70 ℃, and then opening the constant temperature water bath for 3 hours at the same temperature.
The invention also provides a method for preparing vinyl chloride by hydrochlorination of acetylene, which comprises the step of mixing acetylene with hydrogen chloride to obtain vinyl chloride, wherein the reaction is performed under the catalysis of the ligand-copper-based catalyst.
The reactions mainly involved in the hydrochlorination of acetylene include:
the main reaction: c (C) 2 H 2 +HCl→CH 2 ＝CHCl
Non-polymerization side reactions:
CH 2 ＝CHCl+HCl→CH 3 CHCl 2
CH 2 ＝CHCl+HCl→CH 2 ClCH 2 Cl
polymerization side reaction:
2CH 2 ＝CHCl→CH 2 ClCH＝CCl-CH 3
2C 2 H 2 →CH 2 ＝CH-C≡CH
the prior thermodynamic research shows that the main reaction is greatly influenced by polymerization side reaction, the influence of non-polymerization side reaction on the main reaction is small, the main reaction and the side reaction are both exothermic reactions, but the thermal effect of the polymerization side reaction is larger than that of the main reaction, and the higher temperature is more favorable for inhibiting the polymerization side reaction (the reaction temperature is overhigh, polymerization products can be deposited on the surface of a catalyst to form carbon deposit, so that the catalyst is deactivated), the selectivity of the main reaction is improved, the carbon deposit is reduced, and the metal catalyst has the problem of valence change and deactivation at high temperature. The reaction temperature is controlled at 180 ℃ after comprehensively considering the influence of the temperature on the polymerization side reaction and the reduction deactivation of the catalyst.
The volume ratio of acetylene to hydrogen chloride is 1:1.15, which is the volume ratio commonly used in the art.
The gas phase reaction is carried out in a fixed bed reactor in which a copper-based catalyst containing a phosphorus ligand is packed. The control range of the acetylene airspeed adopts the control range commonly used in the field, and is specifically 90-540h -1 Preferably 180-360h -1 . The reaction time is 12h-300h.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, coconut shell activated carbon is used as a carrier, cuCl2 is used as a metallic copper precursor, and a phosphorus ligand compound containing triphenyl assist is used as a ligand to obtain the phosphorus ligand-copper-based catalyst containing triphenyl assist. The metal copper atoms in the catalyst are embedded in the ligand, and the interaction force between the metal copper atoms and the ligand provides guarantee for anchoring and high dispersion of the active species copper on the coconut shell activated carbon. In addition, the ligand has strong electron supply capability and electron delocalization transfer capability, coordinates with the metal copper precursor to modulate the electronic property of the central metal atom, constructs a microenvironment favorable for electrophilic addition reaction of acetylene and hydrogen chloride, further improves the adsorption activation capability of the catalyst to reactants of hydrogen chloride and acetylene, and inhibits coke deposition and agglomeration of copper active species, thereby remarkably improving the activity and stability of the catalyst. The catalyst provided by the invention has the characteristics of high activity, good stability and the like, and has good economical efficiency and industrial application value when being applied to acetylene hydrochlorination.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a comparison of the performance of examples 1-4 and comparative example 1 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram;
FIG. 2 is a comparison of the performance of examples 2, 5-7 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram;
FIG. 3 is a comparison of the performance of examples 6, 8-11 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram;
FIG. 4 is a comparison of the performance of examples 9, 12-15 and comparative example 1 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram;
FIG. 5 is a comparison of the performance of example 13 and comparative examples 1, 2, 3 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram;
FIG. 6 is a comparison of the performance of example 13 and comparative example 1 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram;
FIG. 7 is a TEM image of a copper-based catalyst before and after use; wherein, (a) is before the catalyst of comparative example 3 is used and (b) is after the catalyst of comparative example 3 is used; (c) Before the catalyst of comparative example 1 was used, and (d) after the catalyst of comparative example 1 was used; (e) Before the catalyst of example 13 was used, and (f) after the catalyst of example 13 was used;
FIG. 8 is a TPD graph of ligand-copper based catalyst (example 13) and comparative catalyst (comparative examples 1, 2, 3) versus reactants hydrogen chloride and acetylene; in the figure, (a) hydrogen chloride and (b) acetylene.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. In the present invention, "wt.%" means weight percent.
The invention provides a ligand-copper-based catalyst for catalyzing hydrochlorination of acetylene, which takes coconut shell activated carbon as a carrier and CuCl 2 The metal copper precursor is the ligand which is a phosphorus ligand compound containing triphenyl assist.
Wherein the phosphorus ligand compound is selected from tris (2-tolyl) phosphine (C) 21 H 21 P,304.37 g/moL), tris (3-tolyl) phosphine (C 21 H 21 P,304.37 g/moL), tris (4-tolyl) phosphine (C 21 H 21 P,304.37 g/moL); a preferred phosphorus ligand compound is tris (3-tolyl) phosphine.
Wherein the molar ratio of the metal copper precursor to the ligand compound is 3-11:1, and preferably the molar ratio of the metal copper precursor to the ligand compound is 5-9:1; most preferably the molar ratio of the metallic copper precursor to the ligand compound is 7:1.
The loading of Cu atoms is 5 to 15wt%, preferably 7.5 to 15wt%, based on the total weight of the copper-based catalyst.
Wherein, the total weight of the catalyst is calculated by the following steps: m is m Total (S) ＝m Carrier body +m Steady state metal precursors +m Ligand 。
The steady state metal precursor is CuCl 2 。
The loading of the copper-based catalyst is 5-15wt%, because when the loading of copper is higher than 15wt%, the activity of the catalyst is not obviously improved, but is easy to agglomerate; when the copper loading is lower than 3wt%, the cost is greatly reduced, but the catalytic performance of the catalyst is also obviously reduced; the invention selects the load amount of 5-15wt percent, and can give consideration to the catalytic performance and the economical efficiency of the catalyst.
For example: in embodiment 13, the load amount is calculated by: m is m Cu /(m Total (S) ＝m Carrier body +m Steady state metal precursors +m Ligand )＝0.625g/(2.681g+1.321g+0.998g)＝12.5wt％。
The preparation method of the ligand-copper-based catalyst for catalyzing acetylene hydrochlorination reaction comprises the following steps:
firstly, uniformly mixing a metallic copper precursor and a ligand compound in an isopropanol solution, then adding coconut shell Activated Carbon (AC), continuously stirring, and then performing heat activation and drying treatment to obtain the ligand-copper-based catalyst.
When the metallic copper precursor and the ligand compound are uniformly mixed in the isopropanol solution, a method commonly used in the prior art, such as magnetic stirring, can be used, the magnetic stirring time is 12 hours, and the stirring temperature is room temperature. The stirring time is 12-36h, preferably 25 ℃, and the stirring time is 12h.
The purpose of the agitation is to thoroughly mix the copper precursor, ligand compound, and coconut shell activated carbon. The appropriate temperature and stirring time are chosen to allow adequate interaction of the copper precursor with the ligand.
The heat activation is that the mixture is stirred and then put into a water bath kettle with the temperature of 70 ℃ to be closed and kept constant for 3 hours, then the mixture is opened and kept constant for 3 hours under the same temperature, and then the mixture is dried.
Firstly, the purpose of sealing the constant temperature and then opening the constant temperature is to: firstly, the sealing is used for preventing the volatilization of the isopropanol solvent and promoting the better dispersion of the copper precursor in the solvent; and after the catalyst is immersed for 3 hours at a constant temperature in a closed manner, the catalyst is opened to prevent the catalyst from aging, and meanwhile, the solvent isopropanol volatilizes more quickly, so that the catalyst is more favorable for drying.
The temperature and time constraints for thermal activation are due to: the boiling point of the solvent isopropanol is about 82.45 ℃. Too high a temperature can cause the isopropyl alcohol to boil and splash, and too low a temperature is unfavorable for the volatilization of the isopropyl alcohol; meanwhile, the pore canal of the active carbon is smoother at 70 ℃, which is more beneficial for the impregnation of the active components into the carrier.
The drying treatment can be specifically drying at 70 ℃ for 12 hours and 120 ℃ for 12 hours.
The hydrochlorination reaction of acetylene of the invention is:
the ligand-copper-based catalyst prepared by the invention is filled in a fixed bed reactor, acetylene and hydrogen chloride reaction gas are introduced, and the space velocity (GHSV) of the acetylene is 180h at 180 DEG C -1 And reacting for 12-300 h under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.15.
Example 1
0.422817g of CuCl were each placed in a 50mL beaker 2 (0.0031700 moL) and 30mL of isopropanol were stirred for 12 hours, 3.57718g of AC was slowly added to the mixture and stirring was continued for 4 hours, then placed in a 70 ℃ water bath kettle and closed at constant temperature for 3 hours, then open constant temperature water bath was continued at the same temperature for 3 hours, finally dried in a forced air drying oven at 70 ℃ for 12 hours and 100 ℃ for 12 hours to give a catalyst with copper loading of 5wt%, designated as 5Cu/AC.
Examples 2 to 4
Using the same preparation procedure as in example 1, varying only the copper loading, a series of xCu/AC catalysts (x=7.5, 10, 15) were obtained, named 7.5Cu/AC, 10Cu/AC, 15Cu/AC in sequence.
Example 5
In this example, the copper loading was 7.5wt% and the molar ratio between copper precursor and ligand was 3:1 to screen different ligands to prepare Cu-yL with Cu loading of 7.5wt% 3/1 An AC catalyst. Cu-yL 3/1 "yL" in/A indicates the kind of ligand, and the subscript "3/1" indicates that the molar amount of ligand is 1 when the molar amount of Cu is 3.
0.79278g of CuCl was placed in a 50mL beaker 2 (0.0059008 moL) and 0.599g of tris (2-tolyl) phosphine (0.0019680 moL) were dissolved in 30mL of isopropanol, magnetically stirred for 12 hours, then 3.609g of AC was slowly added to the mixture, stirring was continued for 4 hours, then placed in a 70℃water bath for closed constant temperature for 3 hours, then continued in an open constant temperature water bath at the same temperature for 3 hours, finally dried in a forced air drying oven at 70℃for 12 hours and 100℃for 12 hours, and the resulting product was designated 7.5Cu-1L 3/1 AC (y=1, tris (2-tolyl) phosphine).
Examples 6 to 7
By using the same preparation procedure as in example 5, only the ligand species was changed to give a series of 7.5Cu-yL 3/1 AC catalyst (y=2, 3, respectively tris (3-tolyl) phosphine and tris (4-tolyl) phosphine), designated 7.5Cu-2L in sequence 3/1 /AC、7.5Cu-3L 3/1 /AC。
Example 8
In this example, the immobilized ligand was 2L (tris (3-tolyl) phosphine), the molar ratio of the immobilized copper precursor to the ligand was 3:1, and 10Cu-2L having a Cu loading of 10wt% was prepared 3/1 An AC catalyst.
1.06g of CuCl was placed in a 50mL beaker 2 (0.0078678 mmoL) and 0.798g of tris (3-tolyl) phosphine (0.0026218 mole) were dissolved in 30mL of isopropanol, magnetically stirred for 12 hours, then 3.145g of AC was slowly added to the mixture and stirred for 4 hours, then placed in a 70℃water bath for 3 hours at closed constant temperature, then placed in an open constant temperature water bath at the same temperature for 3 hours, finally dried in a forced air drying oven at 70℃for 12 hours and 100℃for 12 hours, and the resulting product was designated 10Cu-2L 3/1 /AC。
Examples 9 to 11
By using the same preparation procedure as in example 8, and changing only the copper loading, a series of zCu-2L were obtained 3/1 AC catalyst (z=12.5, 15, 17.5), named 12.5Cu-2L in sequence 3/1 /AC、15Cu-2L 3/1 /AC、17.5Cu-2L 3/1 /AC。
Examples 12 to 15
By using the same preparation procedure as in example 8, and changing only the molar ratio of copper precursor to ligand, a series of 12.5Cu-2L were obtained w the/AC catalyst (w=5/1, 7/1, 9/1, 11/1), named 12.5Cu-2L in sequence 5/1 /AC、12.5Cu-2L 7/1 /AC、12.5Cu-2L 9/1 /AC、12.5Cu-2L 11/1 /AC。
Comparative example 1 (without ligand)
The impregnation process was used in this example to prepare a 12.5Cu/AC catalyst for comparison. The method comprises the following specific steps: 1.321g of CuCl was placed in a 50mL beaker 2 (0.0098325 moL) was dissolved in 30mL of isopropanol, magnetically stirred for 12h, 3.679g of AC was slowly added to the mixture and stirring was continued for 4h, then placed in a 70℃water bath for a closed constant temperature of 3h, then continued in an open constant temperature water bath at the same temperature for 3h, finally dried in a forced air drying oven at 70℃for 12h and 100℃for 12h to give a catalyst with a copper loading of 12.5wt%, designated 12.5Cu/AC.
Comparative example 2 (copper free)
The catalyst without copper was prepared for comparison in this example. The method comprises the following specific steps: 0.428g of tris (3-tolyl) phosphine (0.0014062 moL) was dissolved in 30mL of isopropanol in a 50mL beaker, magnetically stirred for 12h, 4.572g of AC was added at room temperature and stirred for 4h, then placed in a 70℃water bath and closed at constant temperature for 3h, then continued to be left open at the same temperature for 3h in a constant temperature water bath, finally dried at 70℃for 12h in a forced air drying oven and at 100℃for 12h, the product was recorded as 2L/AC.
Comparative example 3 (pure activated carbon AC)
150g of commercial activated carbon was weighed into a three-necked flask, added into a 1moL/L hydrochloric acid solution, mechanically stirred at 70 ℃ for 7 hours, cooled to room temperature, washed with deionized water to neutrality, and finally dried in a forced air drying oven at 120 ℃ for 24 hours to obtain pure activated carbon AC.
Example 16
The gas mixture entering the gas chromatograph is mainly acetylene and vinyl chloride, and sometimes generates trace 1, 1-dichloroethane impurity gas, which is calculated by a peak area normalization method. Since hydrogen chloride after the reaction is completely absorbed, the reaction volume in the system can be regarded as a constant value, the acetylene conversion (X A ) Vinyl chloride selectivity (S) VC ) The calculation method comprises the following steps:
the method for calculating the acetylene conversion rate comprises the following steps: x is X A ＝(Ψ A0 -Ψ A )/Ψ A0 *100%, taking the average of 3 determinations.
VCM selectivity calculation method: s is S VC ＝Ψ VC /(I-Ψ A ) 100%, taking the average of 3 determinations.
Wherein ψ is A0 、Ψ A And psi is VC Representing in sequence the volume fraction of acetylene in the feed gas, the volume fraction of acetylene remaining in the product, and the volume fraction of vinyl chloride in the product.
Filling 5mL of the catalyst prepared in each example and comparative example into a fixed bed reactor, introducing mixed reaction gas of acetylene and hydrogen chloride, and reacting at 180 ℃ for 180h at a space velocity of acetylene (GHSV) -1 And (3) under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.15, reacting for 12 hours, and detecting the conversion rate of acetylene and the selectivity of vinyl chloride. The test results of the hydrochlorination of acetylene catalyzed by each catalyst are shown in Table 1 and FIGS. 1-5. FIG. 1 is a schematic diagram of a conventional gas turbine
TABLE 1 Performance of different catalysts to catalyze hydrochlorination of acetylene
Figure BDA0004004904160000081
Figure BDA0004004904160000091
FIG. 1 is a comparison of the performance of examples 1-4 and comparative example 1 in catalyzing the hydrochlorination of acetylene; wherein (a) is the conversion of acetylene in the reactionA relationship diagram, (b) a relationship diagram of vinyl chloride selectivity versus reaction time; (in the figure, the acetylene airspeed is (GVSH) =180h -1 )。
FIG. 2 is a comparison of the performance of examples 2, 5-7 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram.
FIG. 3 is a comparison of the performance of examples 6, 8-11 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram.
FIG. 4 is a comparison of the performance of examples 9, 12-15 and comparative example 1 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram.
FIG. 5 is a comparison of the performance of example 13 and comparative examples 1, 2, 3 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram.
As can be seen from Table 1 and FIGS. 1-5, the catalytic effect of the copper-based catalyst containing the triphenyl-based phosphorus ligand is significantly improved as compared to the Cu/AC catalyst (FIG. 5). This is probably due to the intercalation of metallic copper atoms into the ligand, the interaction forces between the two providing guarantees for the anchoring and high dispersion of the active species copper on the support. The reduced activity of tris (2-tolyl) phosphine, tris (4-tolyl) phosphine may be due to the fact that the melting point is closer to the reaction temperature, and there is a different degree of loss of ligand as the reaction proceeds, resulting in a reduced catalyst activity.
According to the invention, activity tests on different copper loadings show that the activity is higher when the copper loading is 12.5 wt%; the copper loading is lower, the activity of the catalyst is reduced, and the active site is possibly reduced due to the reduction of the copper content; copper loading is high, copper ions are easy to agglomerate, and dispersibility is poor, so that the catalyst has poor catalytic performance (figure 3). Screening for optimal loadings of 12.5wt% and optimal ligand tris (3-tolyl) phosphine, a molar ratio of copper precursor to ligand was explored (fig. 4). Experiments show that the ligand has strong electron supply capability and electron delocalization transfer capability, coordinates with a metal copper precursor to modulate the electron property of a central metal atom, constructs a microenvironment favorable for electrophilic addition reaction of acetylene and hydrogen chloride, further improves the adsorption activation capability of the catalyst to reactants of hydrogen chloride and acetylene, and inhibits coke deposition and agglomeration of copper active species, thereby remarkably improving the activity and stability of the catalyst.
Example 17
The catalyst was subjected to a long-term stability test of 300 hours because the short-time test showed superior stability.
5mL of the catalyst prepared in example 13 and comparative example 1 was packed in a fixed bed reactor, and a mixed reaction gas of acetylene and hydrogen chloride was introduced, and the reaction temperature was 180℃and the acetylene space velocity (GHSV) was 180 hours -1 And (3) under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.15, reacting for 300 hours, and detecting the conversion rate of acetylene and the selectivity of vinyl chloride. The test results of the hydrochlorination of acetylene catalyzed by each catalyst are shown in Table 2 and FIG. 6.
TABLE 2 Performance of different catalysts to catalyze hydrochlorination of acetylene
Figure BDA0004004904160000101
FIG. 6 is a comparison of the performance of example 13 and comparative example 1 in catalyzing the hydrochlorination of acetylene; wherein, (a) is an acetylene conversion-reaction time diagram, and (b) is a vinyl chloride selectivity-reaction time diagram. As can be seen from table 2 and fig. 6, the long-term stability test for 300h showed good stability of the catalyst.
FIG. 7 is a TEM image of a copper-based catalyst before and after use; wherein, (a) is before the catalyst of comparative example 3 is used and (b) is after the catalyst of comparative example 3 is used; (c) Before the copper-based catalyst of comparative example 1 was used, (d) after the use of comparative example 1; (e) Before the catalyst of example 13 was used, and (f) after the catalyst of example 13 was used. As can be seen from FIG. 7, by adjusting the copper precursor to ligand molar ratio, 12.5Cu-2L 7/1 The strong interaction between copper and ligand in the AC catalyst significantly increases the anchoring degree and dispersibility of the active species copper on the support.
FIG. 8 is a TPD graph of ligand-copper based catalyst (example 13) and comparative catalyst (comparative examples 1, 2, 3) versus reactants hydrogen chloride and acetylene; in the figure, (a) hydrogen chloride and (b) acetylene. As can be seen from fig. 8, the regulation of the electronic properties of the copper species by the structure of the ligand itself makes the adsorption capacity of the catalyst to the reaction gases hydrogen chloride and acetylene stronger.
Based on the above, the catalyst provided by the invention has outstanding advantages in the aspects of activity, selectivity, thermal stability and other performances, and has good stability.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A ligand-copper-based catalyst for catalyzing hydrochlorination of acetylene is characterized in that the catalyst takes coconut shell activated carbon as a carrier, and CuCl 2 The metal copper precursor is the ligand which is a phosphorus ligand compound containing triphenyl assist.
2. The catalyst of claim 1, wherein the phosphorus ligand compound is one of tris (2-tolyl) phosphine, tris (3-methylphenyl) phosphine, or tris (4-methylphenyl) phosphine.
3. The catalyst according to claim 1, wherein the loading of Cu atoms in the catalyst is 5-15wt%, based on the total weight of the catalyst.
4. The catalyst of claim 1 wherein the molar ratio of metallic copper precursor to phosphorus ligand compound is 3-11:1.
5. The method for producing a catalyst according to any one of claims 1 to 4, characterized in that the method comprises: firstly, uniformly mixing a phosphorus ligand compound with isopropanol to obtain a phosphorus ligand-isopropanol mixed solution containing triphenyl assist; and then sequentially adding a copper precursor and coconut shell activated carbon, uniformly stirring, and performing heat activation and drying treatment to obtain the ligand-copper-based catalyst.
6. The preparation method according to claim 5, wherein the phosphorus ligand compound is uniformly mixed with isopropanol by a magnetic stirring method, wherein the magnetic stirring time is 12 hours.
7. The method according to claim 5, wherein the stirring temperature is room temperature and the stirring time is 12 to 36 hours.
8. The method of claim 5, wherein the thermal activation is: sealing and keeping the constant temperature for 3 hours in a water bath kettle at 70 ℃, and then opening the constant temperature water bath for 3 hours at the same temperature.
9. A process for the preparation of vinyl chloride by hydrochlorination of acetylene, said process comprising the reaction of acetylene with hydrogen chloride to give vinyl chloride, characterized in that said reaction is carried out under the catalysis of a catalyst according to any one of claims 1 to 4.
10. The method according to claim 9, wherein the reaction parameters of the acetylene hydrochlorination reaction are: the reaction temperature is 180 ℃, the reaction time is 12h-300h, and the acetylene airspeed is 180h -1 The volume ratio of acetylene to hydrogen chloride is 1:1.15.
CN202211663119.8A 2022-12-18 2022-12-18 Ligand-copper-based catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof Pending CN116351476A (en)

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