CN111203278B - Metal complex catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof - Google Patents
Metal complex catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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Abstract
The invention provides a metal complex catalyst for catalyzing hydrochlorination of acetylene, which is formed by coordination of central atom metal and ligand; the central atom metal is Au, pt, ru or Cu; the ligand is an organic ligand containing a diimide [ - (c=o) -NH- (c=o) - ] structure. The invention also provides a preparation method and application thereof. Compared with the existing metal catalyst for hydrochlorination of acetylene, the active components in the metal complex catalyst of the invention are in a high dispersion state, are not easy to run off and agglomerate, and simultaneously activate the reactants of acetylene and hydrogen chloride, thereby greatly improving the catalytic activity and stability of the existing metal catalyst.
Description
Technical Field
The invention relates to a metal complex catalyst for catalyzing acetylene hydrochlorination, a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is a polymer material produced by polymerization of Vinyl Chloride (VCM), and its global usage amount is the third place of the polymer material, and is widely used in the fields of industry, construction, agriculture, daily life, etc. The method is classified according to the method of obtaining VCM, and can be classified into acetylene method and ethylene method. Based on the energy characteristics of rich coal, lean oil and less gas in China, the proportion (82%) of the calcium carbide acetylene process technology taking coal as a source is far higher than that of the ethylene process technology taking petroleum resources as a source, however,in the existing calcium carbide acetylene method, carbon-supported mercury chloride is still used as an industrial catalyst to catalyze acetylene hydrochlorination, and according to statistics, about 1.02-1.41kg of HgCl is consumed per 1 ton of PVC 2 Catalyst, of which about 25% HgCl 2 And lost during the cycle. Mercury is extremely volatile and highly toxic at the reaction temperature, and the concentration of the mercury generated is only 0.01-0.1mg/L, and the mercury is easy to migrate and has lasting detention, thus causing serious harm and pollution to human health and the global ecological environment. By 2014, 123 countries including China have signed international water regulations for limiting mercury use and emissions, requiring that production processes using mercury or mercury compounds be eliminated by 2025. The annual consumption of the mercury in VCM prepared by the mercuric chloride catalyst accounts for 60 percent of the mercury consumption in China and approximately accounts for 20 percent of the global mercury demand. Therefore, in order to solve the pollution problem caused by mercury catalysts, the green sustainable development of the PVC industry of the acetylene method in China is realized, and the development of the high-efficiency mercury-free catalyst is unprecedented.
Currently, in the research of acetylene hydrochlorination catalysts, two types of non-Hg-based catalysts are being focused on by researchers: (i) a non-metal catalyst and (ii) a metal catalyst. Non-metallic catalysts have many problems on the way of industrialization that need to be addressed due to their low reactivity and short catalyst life. For metal catalysts, although several metal chlorides (e.g., pt 4+ ，Pt 2+ ，Pd 2+ ，Au 3+ ，Ru 3+ ，Cu 2+ ，Sn 2+ Etc.), but the research of the last decades proves that the metal catalyst prepared by taking chloroauric acid, chloroplatinic acid, ruthenium trichloride or cupric chloride as a precursor can catalyze acetylene hydrochlorination, has good catalytic activity and has good potential in the aspect of replacing Hg-based catalyst.
It is known that in order to make a catalyst play an important role in future industrialization, it is necessary to ensure high catalytic activity and stability and low loading, so that a metal catalyst having higher catalytic activity and stability per unit loading is an important point of future research. Agglomeration or valence change of carbon deposition and active materials is a major cause of catalyst deactivation, and for these reasons, researchers have made a lot of work in inhibiting deactivation of metal catalysts and improving their activity and stability by modifying carriers, adding other metals, and the like. In addition, transition metal ions such as Au, pt, ru or Cu have similar peripheral s, p and d equivalent orbitals, so that a hybridization orbit with strong bonding capability is relatively easy to form, so as to accept lone pair electrons provided by hetero atoms, the electrostatic effect of the transition metal ions on the hetero atoms is strong, the effective nuclear charge of the ions is large, the polarization capability of the hetero atoms is also strong, and in addition, due to unsaturated d orbitals, the transition metal ions are favorable for covalent bonding with the hetero atoms, so that a high-dispersion even single-atom catalyst is formed. Therefore, searching different kinds of ligands, preparing active components of the metal complex through unsaturated coordination between the ligands and metal cations, and grasping the coordination mechanism of the ligands to improve the catalytic activity and stability of the metal catalyst is an important point and a difficult point in the future of work in the aspect.
Disclosure of Invention
According to the current situation of the catalyst for the hydrochlorination of acetylene in the background technology, the invention provides a metal complex catalyst for catalyzing the hydrochlorination of acetylene, and a preparation method and application thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a metal complex catalyst for catalyzing hydrochlorination of acetylene, which is formed by coordination of central atom metal and ligand; the central atom metal is Au, pt, ru or Cu; the ligand is an organic ligand containing a diimide [ - (c=o) -NH- (c=o) - ] structure.
After the metal precursor forms a complex with an organic ligand containing a diimide [ - (C=O) -NH- (C=O) - ] structure, active components can be anchored on the surface of the active carbon, so that the active components are not easy to run off, and become difficult to change in price and agglomerate. The ligand in the formed complex interacts with the central metal atom, d empty orbits around the central metal atom nucleus can effectively adsorb and activate the acetylene rich in electrons, and the- (C=O) -structure on the ligand can utilize hydrogen bond formation to adsorb and activate hydrogen chloride, so that a microenvironment favorable for electrophilic addition reaction is integrally formed, and the catalytic activity and stability of the catalyst are greatly improved.
Preferably, the ligand is selected from one of phthalimide, succinimide, glutarimide and maleimide; preferably, the ligand is phthalimide.
Preferably, the loading of Au, pt or Ru atoms is 0.1-3wt%, preferably 0.2-1wt%, based on the total weight of the metal complex catalyst; the Cu atom loading is 3 to 15wt%, preferably 5 to 10wt%.
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 +m Alkali 。
The metal precursor contains crystal water, but the crystal water is removed in the process of thermal activation of the catalyst, besides leaving the crystal water, one molecule of HCl is released, and the steady-state precursor becomes AuCl 3 The steady state precursor here refers to the portion of the metal precursor that is last present in the catalyst.
For example: in example 6, the load amount was calculated by: m is m Ru /(m Carrier body +m Steady state metal precursors +m Ligand +m Alkali )＝0.07734g/(2g+0.15869g+0.29704g+0.12239g)＝3.0wt％。
The invention provides a preparation method of the metal complex catalyst, which comprises the steps of firstly mixing a ligand with sodium hydroxide or potassium hydroxide in a solvent for reaction, then adding a metal precursor into the mixture for reaction, and finally adding an active carbon carrier into a reaction system for thermal activation in a nitrogen environment to obtain the metal complex catalyst; the metal precursor is chloroauric acid, chloroplatinic acid, ruthenium trichloride or copper chloride.
The effect of adding sodium hydroxide or potassium hydroxide is: eliminating H in- (C=O) -NH- (C=O) -and making it coordinate with metal unsaturation, and adsorbing and activating electron-rich acetylene by empty d orbitals in the metal.
Preferably, the molar ratio of the ligand to sodium hydroxide or potassium hydroxide is 1:1-3, and more preferably, the molar ratio of the ligand to sodium hydroxide or potassium hydroxide is 1:1-2;
the molar ratio of the metal precursor to the ligand is 1:1-5, and further preferably, the molar ratio of the metal precursor to the ligand is 1:1-4;
the thermal activation temperature is 140-300 ℃, and further preferably, the thermal activation temperature is 180-280 ℃;
the thermal activation time is 2 to 24 hours, and further preferably, the thermal activation time is 4 to 16 hours.
Preferably, the reaction of the ligand with KOH or NaOH is carried out at room temperature to 80 ℃ for 2-24 hours. The metal precursor is added and then reacts with the ligand, the reaction is required to be completed for 2-24 hours, and the temperature is at room temperature.
The invention 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 metal complex catalyst.
The reaction is a gas phase reaction.
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 polymerization product can be deposited on the surface of the catalyst to form carbon deposit), so that the selectivity of the main reaction is improved, the carbon deposit is reduced, and the metal catalyst has the problem of valence variation and inactivation at high temperature. Taking into consideration the influence of temperature on polymerization side reaction and catalyst reduction deactivation, the reaction temperature is controlled to be 110-300 ℃, more preferably 140-280 ℃, and most preferably 180-260 ℃.
The volume ratio of acetylene to hydrogen chloride is generally used in the art, specifically 1:1-2, more preferably, the volume ratio of acetylene to hydrogen chloride is 1:1-1.5, and most preferably, the volume ratio of acetylene to hydrogen chloride is 1:1.02-1.2.
The gas phase reaction is carried out in a fixed bed reactor, and the metal complex catalyst is filled in the fixed bed reactor. The control range of the acetylene airspeed adopts the control range commonly used in the field, and is particularly 30-2000h -1 Preferably, the space velocity of acetylene is controlled between 30 and 180 hours -1 。
The invention provides an application of a metal complex catalyst as a catalyst in acetylene hydrochlorination; the hydrochlorination of acetylene is that acetylene reacts with hydrogen chloride to generate chloroethylene.
The reaction is a gas phase reaction, and the reaction temperature is 110-300 ℃.
Compared with the existing metal catalyst for hydrochlorination of acetylene, the active components in the metal complex catalyst of the invention are in a high dispersion state, are not easy to run off and agglomerate, and simultaneously activate the reactants of acetylene and hydrogen chloride, thereby greatly improving the catalytic activity and stability of the existing metal catalyst.
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 graph (a) showing the acetylene conversion versus reaction time and a graph (b) showing the vinyl chloride selectivity versus reaction time for the catalysts (examples 1-5 and comparative examples 1-2).
FIG. 2 is a graph (a) of acetylene conversion versus reaction time and a graph (b) of vinyl chloride selectivity versus reaction time for the catalysts (examples 6-10 and comparative examples 3-4).
FIG. 3 is Au-L 1 HAADF-STEM map of catalyst (example 1).
FIG. 4 is a graph of Pt-L 1 HAADF-STEM map of catalyst (example 4).
FIG. 5 is Ru-L 1 HAADF-STEM map of catalyst (example 6).
FIG. 6 is a Cu-L 1 HAADF-STEM map of catalyst (example 8).
FIG. 7 is a HAADF-STEM diagram of an Au/C catalyst (comparative example 1).
FIG. 8 is a HAADF-STEM diagram of a Pt/C catalyst (comparative example 2).
FIG. 9 is a HAADF-STEM diagram of a Ru/C catalyst (comparative example 3).
FIG. 10 is a HAADF-STEM diagram of a Cu/C catalyst (comparative example 4).
FIG. 11 is a TPD curve of the metal complex catalyst of the invention (examples) and the comparative catalysts (comparative examples 1-4) versus the reactants acetylene and hydrogen chloride.
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.
1. The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesizing a metal complex: weighing the ligand, adding the ligand into deionized water, stirring for 2-24 hours at the temperature of room temperature-80 ℃, then adding KOH or NaOH, and continuing stirring for 2-24 hours; and finally, adding the metal precursor into the mixture, and stirring the mixture for 12 hours at room temperature to obtain a metal complex solution.
The above limitations on temperature and time are due to the time required for dissolution or reaction at the above temperatures to complete.
Wherein the ligand is an organic ligand containing a diimide [ - (c=o) -NH- (c=o) - ] structure, preferably one selected from phthalimide, succinimide, glutarimide and maleimide; most preferably, the ligand is phthalimide.
The metal precursor is chloroauric acid, chloroplatinic acid, ruthenium trichloride or copper chloride.
The molar ratio of ligand to sodium hydroxide or potassium hydroxide is 1:1-3, preferably the molar ratio of ligand to sodium hydroxide or potassium hydroxide is 1:1-2.
The molar ratio of the metal precursor to the ligand is 1:1-5, preferably the molar ratio of the metal precursor to the ligand is 1:1-4.
The stirring for a period of time after the addition of the carrier is to evaporate more liquid while supporting the metal component at 70-80 c, facilitating the thermal activation of the sample in the subsequent tube furnace.
Wherein the loading of Au, pt or Ru atoms is 0.1-3wt%, preferably 0.2-1wt%, based on the total weight of the metal complex; the Cu atom loading is 3 to 15wt%, preferably 5 to 10wt%.
The heat activation temperature is preferably 180-280 ℃. The heat activation time is preferably 4 to 16 hours.
2. Hydrochlorination of acetylene
Filling the metal complex catalyst prepared in the first step into a fixed bed reactor as a catalyst, introducing acetylene and hydrogen chloride reaction gas, and controlling the acetylene space velocity (GHSV) to be between 30 and 2000 hours at a temperature of between 110 and 300 DEG C -1 And reacting for 24 hours under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1-2.
Preferably, the reaction temperature is controlled between 140 and 280 ℃, and most preferably, the reaction temperature is controlled between 180 and 260 ℃.
Example 1
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesis of gold complex: 0.0014976g of phthalimide was weighed and added to 30mLAfter stirring in deionized water at 80 ℃ for 2 hours, 0.000571g of KOH is then added and stirring is continued for 12 hours; finally 0.00419g of HAuCl 4 ·xH 2 O was added thereto and stirred at room temperature for 12 hours to obtain a gold complex solution.
Example 2
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesis of gold complex: 0.0471689g of phthalimide is weighed and added into 30mL of deionized water, after stirring for 2 hours at 80 ℃, 0.025645g of NaOH is added, and stirring is continued for 12 hours; finally 0.044012g of HAuCl 4 ·xH 2 O was added thereto and stirred at room temperature for 12 hours to obtain a gold complex solution.
Example 3
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesis of gold complex: 0.03152g of succinimide is weighed and added into 30mL of deionized water, after stirring for 4 hours at room temperature, 0.025449g of NaOH is added, and stirring is continued for 12 hours; finally 0.04368g of HAuCl 4 ·xH 2 O was added thereto and stirred at room temperature for 12 hours to obtain a gold complex solution.
Example 4
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesis of a platinum complex: 0.04762g of phthalimide is weighed and added into 30mL of deionized water, after stirring for 2 hours at 80 ℃, 0.012945g of NaOH is added, and stirring is continued for 12 hours; finally 0.05533gH 2 PtCl 6 ·6H 2 O was added thereto and stirred at room temperature for 12 hours to obtain a platinum complex solution.
Example 5
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesis of a platinum complex: 0.012021g of glutarimide is weighed, added into 30mL of deionized water, stirred for 2 hours at 80 ℃, then 0.017886g of KOH is added, and stirring is continued for 12 hours; finally 0.05451gH 2 PtCl 6 ·6H 2 O was added thereto and stirred at room temperature for 12 hours to obtain a platinum complex solution.
Example 6
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesis of ruthenium complex: 0.17096g of phthalimide is weighed and added into 30mL of deionized water, and stirred for 2 hours at 80 DEG CThen 0.130375g KOH was added and stirring was continued for 12h; finally 0.06076g RuCl 3 ·3H 2 O was added thereto and stirred at room temperature for 12 hours to obtain a ruthenium complex solution.
Example 7
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesis of ruthenium complex: 0.29704g of maleimide is weighed, added into 30mL of deionized water, stirred for 4 hours at 80 ℃, then 0.12239g of NaOH is added, and stirring is continued for 24 hours; finally, 0.2000g RuCl 3 ·3H 2 O was added thereto and stirred at room temperature for 12 hours to obtain a ruthenium complex solution.
Example 8
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesizing a copper complex: 0.16526g of phthalimide is weighed and added into 50mL of deionized water, after stirring for 4 hours at 80 ℃, 0.063012g of KOH is added, and stirring is continued for 12 hours; finally 0.19151g of CuCl 2 ·2H 2 O was added thereto and stirred at room temperature for 12 hours to obtain a copper complex solution.
Example 9
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesizing a copper complex: 3.42415g of phthalimide is weighed and added into 50mL of deionized water, after stirring for 12 hours at 70 ℃, 1.305613g of KOH is added, and stirring is continued for 12 hours; finally 3.96804g of CuCl 2 ·2H 2 O was added thereto and stirred at room temperature for 12 hours to obtain a copper complex solution.
Example 10
The preparation method of the metal complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
step 1, synthesizing a copper complex: 0.23004g of glutarimide is weighed and added into 50mL of deionized water, after stirring for 12 hours at 80 ℃, 0.08135g of NaOH is added, and stirring is continued for 12 hours; finally 0.34676g of CuCl 2 ·2H 2 O was added thereto and stirred at room temperature for 12 hours to obtain a copper complex solution.
Comparative example 1
Preparation of Au catalyst: weigh 0.0430g HAuCl 4 ·xH 2 Mixing O with 30mL deionized water under stirring, adding 2g of active carbon carrier, and stirring at 70deg.C for 12 hr; finally, transferring the catalyst into a tube furnace, and thermally activating the catalyst for 16 hours at 140 ℃ under nitrogen flowing atmosphere to obtain a supported Au catalyst which is named Au/C.
Comparative example 2
Preparation of Pt catalyst: weighing 0.0542g H 2 PtCl 6 ·6H 2 Mixing O with 30mL deionized water under stirring, adding 2g of active carbon carrier, and stirring at 70deg.C for 12 hr; finally, transferring the catalyst into a tube furnace, and thermally activating the catalyst for 16 hours at 200 ℃ under nitrogen flowing atmosphere to obtain a supported Pt catalyst which is named as Pt/C.
Comparative example 3
Preparation of Ru catalyst: 0.0537g RuCl was weighed out 3 ·3H 2 Mixing O with 30mL deionized water under stirring, adding 2g of active carbon carrier, and stirring at 70deg.C for 12 hr; finally transferring the catalyst into a tube furnace, and thermally activating the catalyst for 16 hours at 180 ℃ under nitrogen flowing atmosphere to obtain a supported Ru catalyst which is named Ru/C.
Comparative example 4
Preparing a Cu catalyst: 0.1769g CuCl was weighed out 2 ·2H 2 Mixing O with 50mL deionized water under stirring, adding 2g of active carbon carrier, and stirring at 70deg.C for 12 hr; finally transferring the catalyst into a tube furnace, and thermally activating the catalyst for 16 hours at 280 ℃ under nitrogen flowing atmosphere to obtain a supported Cu catalyst which is named Cu/C.
Example 11
2mL of the catalyst prepared in examples 1 to 5 and comparative examples 1 to 2 were packed in a fixed bed reactor, and acetylene and hydrogen chloride reaction gas were introduced at 200℃with a space velocity of acetylene (GHSV) of 1200h -1 And (3) reacting for 24 hours under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.15, 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 FIG. 1.
FIG. 1 is a graph (a) showing the acetylene conversion versus reaction time and a graph (b) showing the vinyl chloride selectivity versus reaction time for the catalysts (examples 1-5 and comparative examples 1-2).
Example 12
2mL of the catalyst prepared in examples 6 to 10 and comparative examples 3 to 4 were packed in a fixed bed reactor, and acetylene and hydrogen chloride reaction gas were introduced at 200℃and acetylene space velocity (GHSV) for 180 hours -1 Under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.15, reacting for 24 hours,acetylene conversion and vinyl chloride selectivity were measured. The test results of the hydrochlorination of acetylene catalyzed by each catalyst are shown in Table 1 and FIG. 2.
FIG. 2 is a graph (a) of acetylene conversion versus reaction time and a graph (b) of vinyl chloride selectivity versus reaction time for the catalysts (examples 6-10 and comparative examples 3-4).
TABLE 1 conversion and Selectivity of different catalysts for the catalytic hydrochlorination of acetylene
As can be seen from the catalytic test results of the catalyst on the hydrochlorination reaction of acetylene, after the metal precursor and the ligand are coordinated to form a complex, the conversion rate and stability of acetylene are obviously improved (figures 1-2), and the active components are anchored on the surface of the active carbon and are not easy to run off and become difficult to change price and agglomerate (figures 3-10) mainly because the metal precursor forms the complex; more importantly, the ligand in the formed complex interacts with the central metal atom, d empty orbits around the central metal atom nucleus can effectively adsorb and activate electron-rich acetylene (fig. 11 a), and the- (c=o) -structure on the ligand can adsorb and activate hydrogen chloride by utilizing a hydrogen bond (fig. 11 b), so that a microenvironment favorable for electrophilic addition reaction is integrally formed, and the catalytic activity and stability of the catalyst are greatly improved.
FIG. 3 is Au-L 1 HAADF-STEM map of catalyst (example 1).
FIG. 4 is a graph of Pt-L 1 HAADF-STEM map of catalyst (example 4).
FIG. 5 is Ru-L 1 HAADF-STEM map of catalyst (example 6).
FIG. 6 is a Cu-L 1 HAADF-STEM map of catalyst (example 8).
FIG. 7 is a HAADF-STEM diagram of an Au/C catalyst (comparative example 1).
FIG. 8 is a HAADF-STEM diagram of a Pt/C catalyst (comparative example 2).
FIG. 9 is a HAADF-STEM diagram of a Ru/C catalyst (comparative example 3).
FIG. 10 is a HAADF-STEM diagram of a Cu/C catalyst (comparative example 4).
FIG. 11 is a TPD curve of the metal complex catalyst of the invention (examples) and the comparative catalysts (comparative examples 1-4) versus the reactants acetylene and hydrogen chloride.
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 (12)
1. A metal complex catalyst for catalyzing hydrochlorination of acetylene, characterized in that: the metal complex catalyst is formed by coordination of central atom metal and ligand; the central atom metal is Au, pt, ru or Cu; the ligand is an organic ligand containing a diimide [ - (C=O) -NH- (C=O) - ] structure; the preparation method of the metal complex catalyst comprises the following steps: firstly, mixing a ligand with sodium hydroxide or potassium hydroxide in a solvent for reaction, then adding a metal precursor into the mixture for reaction, and finally adding an active carbon carrier into a reaction system for thermal activation in a nitrogen environment to obtain the metal complex catalyst; the metal precursor is chloroauric acid, chloroplatinic acid, ruthenium trichloride or copper chloride.
2. A metal complex catalyst for catalyzing hydrochlorination of acetylene according to claim 1, wherein: the ligand is selected from one of phthalimide, succinimide, glutarimide and maleimide.
3. A metal complex catalyst for catalyzing hydrochlorination of acetylene according to claim 2, wherein: the ligand is phthalimide.
4. A metal complex catalyst for catalyzing hydrochlorination of acetylene according to claim 1, wherein: based on the total weight of the metal complex catalyst, the loading of Au, pt or Ru atoms is 0.1-3wt% and the loading of Cu is 3-15wt%.
5. A metal complex catalyst for catalyzing hydrochlorination of acetylene according to claim 4, wherein: based on the total weight of the metal complex catalyst, the loading of Au, pt or Ru atoms is 0.2-1wt%; the Cu loading is 5-10wt%.
6. A process for the preparation of a metal complex catalyst as claimed in any one of claims 1 to 5, characterized in that: firstly, mixing a ligand with sodium hydroxide or potassium hydroxide in a solvent for reaction, then adding a metal precursor into the mixture for reaction, and finally adding an active carbon carrier into a reaction system for thermal activation in a nitrogen environment to obtain the metal complex catalyst; the metal precursor is chloroauric acid, chloroplatinic acid, ruthenium trichloride or copper chloride.
7. The method for preparing a metal complex catalyst according to claim 6, wherein: the molar ratio of the ligand to sodium hydroxide or potassium hydroxide is 1:1-3;
the molar ratio of the metal precursor to the ligand is 1:1-5;
the thermal activation temperature is 140-300 ℃;
the thermal activation time is 2-24h.
8. The method for producing a metal complex catalyst according to claim 7, characterized in that: the molar ratio of the ligand to sodium hydroxide or potassium hydroxide is 1:1-2;
the molar ratio of the metal precursor to the ligand is 1:1-4;
the thermal activation temperature is 180-280 ℃;
the thermal activation time is 4-16h.
9. The method for preparing vinyl chloride by hydrochlorination of acetylene comprises the steps of mixing acetylene with hydrogen chloride to obtain vinyl chloride, and is characterized in that: the reaction is carried out under the catalysis of the metal complex catalyst according to any one of claims 1 to 5.
10. The method for preparing vinyl chloride by hydrochlorination of acetylene according to claim 9, wherein the method comprises the following steps: the reaction is a gas phase reaction, and the reaction temperature is 110-300 ℃.
11. Use of the metal complex catalyst according to any one of claims 1 to 5 as a catalyst in hydrochlorination of acetylene; the hydrochlorination of acetylene is that acetylene reacts with hydrogen chloride to generate chloroethylene.
12. The use according to claim 11, characterized in that: the reaction is a gas phase reaction, and the reaction temperature is 110-300 ℃.
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| CN113058594A (en) * | 2021-03-29 | 2021-07-02 | 石河子大学 | Polymer-coated ruthenium-based catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
| CN113171789B (en) * | 2021-05-06 | 2022-08-09 | 石河子大学 | Metallic ruthenium monatomic catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
| CN115608415B (en) * | 2021-07-16 | 2024-04-16 | 中国科学院大连化学物理研究所 | Supported catalyst, preparation and application thereof |
| CN113578389B (en) * | 2021-08-03 | 2023-08-25 | 河北美邦工程科技股份有限公司 | Preparation method of fluorine-containing catalyst for hydrochlorination of acetylene |
| CN113578390B (en) * | 2021-08-06 | 2023-05-30 | 河北美邦工程科技股份有限公司 | Preparation method of low noble metal catalyst for hydrochlorination of acetylene |
| CN113813998A (en) * | 2021-08-11 | 2021-12-21 | 贵州重力科技环保有限公司 | Acetylene hydrochlorination ultralow-mercury catalyst and preparation method and application thereof |
| CN115382579B (en) * | 2022-09-01 | 2023-07-07 | 贵州重力科技环保股份有限公司 | Acetylene copper chloride catalyst and preparation method and application thereof |
| CN115722219A (en) * | 2022-11-14 | 2023-03-03 | 浙江工业大学 | Gold-loaded granular carbon material catalyst, preparation method thereof and application thereof in reaction for preparing vinyl chloride by hydrochlorinating acetylene |
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