CN115463692B - N-containing five-membered heterocyclic ligand modified ruthenium-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof - Google Patents
N-containing five-membered heterocyclic ligand modified ruthenium-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN115463692B CN115463692B CN202211195822.0A CN202211195822A CN115463692B CN 115463692 B CN115463692 B CN 115463692B CN 202211195822 A CN202211195822 A CN 202211195822A CN 115463692 B CN115463692 B CN 115463692B
- Authority
- CN
- China
- Prior art keywords
- ruthenium
- acetylene
- membered heterocyclic
- catalyst
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- 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
- B01J31/18—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
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The application relates to a ruthenium-based catalyst modified by N-containing five-membered heterocyclic ligand for hydrochlorination of acetylene, and a preparation method and application thereof. The catalyst takes active carbon as a carrier, ruthenium metal salt as a main active component, and N-containing five-membered heterocyclic ligand is introduced on the basis. Firstly, the N-containing five-membered heterocyclic ligand can be complexed with Ru atoms to form a local active domain, which is favorable for the cooperative adsorption and activation of initial reactants, and secondly, the conjugated structure in the ligand can effectively promote the electron transfer between hetero atoms and ruthenium precursors, so that the electron cloud density around an active center is improved, and the valence state of active Ru species can be effectively stabilized.
Description
Technical Field
The application belongs to the field of chemical catalysis, and particularly relates to a ruthenium-based catalyst modified by N-containing five-membered heterocyclic ligands for acetylene hydrochlorination, and a preparation method and application thereof.
Background
Polyvinyl chloride (Polyvinyl chloride, abbreviated as PVC) is the second most common resin material in the world next to polyethylene, and has wide application, and the industrial production of Vinyl Chloride (VCM) is particularly important. Due to the energy characteristics of rich coal and lean oil in China, more than 79% of vinyl chloride in China is produced by a calcium carbide method using coal as a raw material. HgCl conventionally used in this method 2 The catalyst has the characteristics of high toxicity, high temperature and easy sublimation, and brings serious harm to the environment and human health. Production is forbidden since 2020 in ChinaMercury-containing products, and thus mercury-free catalysts, are not well developed. The mercury-containing catalyst used in industrial acetylene hydrochlorination reaction has the main active component of HgCl 2 The water-soluble glass is extremely easy to sublimate and run off at high temperature, and can cause serious environmental pollution and seriously harm human health. Along with the positive effect of the contract formula of China and the like of the 'water about mercury' in 2017, the use of mercury-containing products is strictly limited, and the mercury-free preparation of the industry for preparing vinyl chloride by a calcium carbide method becomes a necessary way for industry development.
Since the 70 s of the last century, research into mercury-free catalysts for hydrochlorination of acetylene has been initiated by related researchers at home and abroad. A large number of research results show that the mercury-free catalyst with industrial application conditions at the present stage is mainly a catalyst with noble metals (such as Au, pt and Ru) as active components. Gold-based catalysts are considered to be the most excellent and promising mercury-free catalysts after a large number of screening, but high cost clearly puts a great pressure on industrial production because gold active centers are easily reduction deactivated during the reaction and gold is expensive. In addition to the study of extremely low-loading gold catalysts, other noble metals, which are relatively inexpensive, have been intensively studied, wherein ruthenium-based catalysts have been attracting attention from researchers at lower prices and superior catalytic activities thereof. Bin subject group calculated HgCl by DFT 2 、AuCl 3 、RuCl 3 The acetylene hydrochlorination reaction energy barrier of the three materials, wherein RuCl 3 The lowest energy barrier of the reaction indicates that Ru-based catalysts are more suitable for acetylene hydrochlorination. Based on good research prospects, ruthenium-based catalysts have been studied on the rise of hot flashes in recent years, and a large number of documents and patent reports are presented.
The patent application 201811140702.4 discloses a ruthenium-based catalyst for hydrochlorination of acetylene in RuCl 3 As an active component, an oxalic acid additive is added to modify a ruthenium-based catalyst, so that a low ruthenium-content catalyst with the performance equivalent to that of a ruthenium-based catalyst with the loading of 1 percent is developed, under the action of a catalyst with the loading of 0.25 percent by weight of Ru, the conversion rate of acetylene can reach 80.9 percent and the selectivity of vinyl chloride can reach 99.5 percent in the hydrochlorination process of acetylene; application number is202010383863.7 discloses a thiourea modified ruthenium-based catalyst for hydrochlorination of acetylene. The ruthenium ion loading of the catalyst is 0.2-0.6 wt%, and the catalyst can effectively inhibit carbon deposition and also inhibit reduction of high-valence ruthenium species in the hydrochlorination of acetylene by adding thiourea auxiliary agent to modify the ruthenium-based catalyst. Under the action of 0.25wt% Ru supported catalyst, the conversion rate of acetylene is up to 90%. The application of the two patents relatively reduces the load of ruthenium and improves the reactivity of the ruthenium-based catalyst, but the load of 0.25wt% Ru is still low in cost for noble metal ruthenium, and the conversion rate of acetylene is still to be further improved.
The existing ruthenium ethyne hydrochlorination catalyst mainly has the problems that carbon deposition is easy to form in the reaction process, high-valence ruthenium species are easy to be reduced, active substances are agglomerated, and the like, and the factors lead to low catalytic activity and poor stability of the ruthenium-based catalyst, so that industrial production is difficult to carry out; ruthenium is a precious metal, which is cheaper than gold, but its cost is still not insignificant. Based on the background, the application discloses a method which takes active carbon as a carrier and ruthenium salt as an active component, improves the activity and stability of a catalyst through the modification of N-containing five-membered heterocyclic ligands, reduces the load of catalyst metal, and has high economical efficiency and better industrial application prospect.
Disclosure of Invention
Aiming at the defects of the technology and the defects of industrialized application, the application provides the N-containing five-membered heterocyclic ligand modified ruthenium-based catalyst for acetylene hydrochlorination, and the preparation method and application thereof.
Aiming at the problems of low activity and poor stability commonly existing in the current ruthenium-based catalyst, a large number of experiments and researches show that after the N-containing five-membered heterocyclic ligand rich in hetero atoms is introduced, the hetero atoms and metal ions act synergistically to form a complex with stable cation resonance structure and space topology; secondly, the N-containing five-membered heterocyclic ligand can be complexed with Ru atoms to form a local active domain, which is beneficial to the cooperative adsorption and activation of initial reactants; finally, the conjugated structure rich in electrons in the ligand can effectively adsorb and activate acetylene, and simultaneously can effectively promote electron transfer between hetero atoms and ruthenium precursors, so that the electron cloud density around the active center is improved, the valence state of active Ru species is effectively stabilized, and the activity and stability of the ruthenium-based catalyst are improved.
The N-containing five-membered heterocyclic ligand means a ligand having a cyclic structure in which atoms constituting the ring contain at least one hetero atom in addition to carbon and one or more nitrogen atoms are contained as coordinating atoms. The heteroatom refers to one or more of O, S, N, P elements containing lone pair electrons, and the enrichment refers to at least one heteroatom.
The application is realized by the following steps:
the catalyst comprises ruthenium salt, N-containing five-membered heterocyclic ligand and a carrier. Loading ruthenium salt and one or more N-containing five-membered heterocyclic ligands on the surface of a carbon carrier, wherein the ruthenium salt cation is mainly Ru 3+ 。
The N-containing five-membered heterocyclic ligand is a ligand which has a cyclic structure, atoms forming the ring at least contain one hetero atom besides carbon, and one or more nitrogen in the ligand is used as a coordination atom; the heteroatom refers to one or more of O, S, N, P elements containing lone pair electrons.
The N-containing five-membered heterocyclic ligand is pyrrole; imidazole, 1-isopropylimidazole, 3-methylimidazole, 3-chloroimidazole; pyrazole; an oxazole; one or more of thiazole, 2-methylthiazole, 4-methylthiazole, 5-methylthiazole, 2-chlorothiazole, 2-methoxythiazole, 2-aminothiazole, 2-isobutylthiazole, 2, 5-dimethylthiazole, 2, 4-dimethylthiazole, 4, 5-dimethylthiazole, 2,4, 5-trimethylthiazole, 2-chloro-5-nitrothiazole and 1,2, 3-triazole.
The preparation method of the ruthenium-based catalyst modified by the N-containing five-membered heterocyclic ligand for acetylene hydrochlorination reaction comprises the following steps:
step 1: dissolving ruthenium salt and N-containing five-membered heterocyclic ligand in a specific solvent according to a certain proportion at a certain temperature to obtain a mixed solution, wherein the certain temperature is used for enabling the N-containing five-membered heterocyclic ligand to be completely dissolved in the corresponding solvent and obtaining a uniform and stable mixed solution;
step 2: uniformly loading active components in the mixed solution onto an active carbon carrier by adopting methods such as dipping, spraying, precipitation, ion exchange, spray evaporation and the like at the same temperature;
step 3: drying for a certain time under a certain temperature and pressure environment to obtain the catalyst.
Preferably, in step 1, one or more of the following features are further included:
1) The ruthenium salt is selected from one or more of ruthenium trichloride, ruthenium trichloride hydrate, ruthenium acetate, ruthenium iodide and ammonium chlororuthenate; more preferably, the ruthenium salt is ruthenium trichloride hydrate;
2) The N-containing five-membered heterocyclic ligand is pyrrole; imidazole, 1-isopropylimidazole, 3-methylimidazole, 3-chloroimidazole; pyrazole; an oxazole; one or more of thiazole, 2-methylthiazole, 4-methylthiazole, 5-methylthiazole, 2-chlorothiazole, 2-methoxythiazole, 2-aminothiazole, 2-isobutylthiazole, 2, 5-dimethylthiazole, 2, 4-dimethylthiazole, 4, 5-dimethylthiazole, 2,4, 5-trimethylthiazole, 2-chloro-5-nitrothiazole, 1,2, 3-triazole;
3) The molar ratio of the ruthenium salt to the N-containing five-membered heterocyclic ligand in the mixed solution is 1:0.5 to 10; more preferably, the molar ratio of ruthenium salt to N-containing five-membered heterocyclic ligand in the mixed solution is 1:1 to 8;
4) The solvent is a polar solvent; preferably, the solvent is at least one selected from deionized water, absolute ethyl alcohol, acetone, methylene dichloride, ethylene glycol dimethyl ether (DME) and N, N-Dimethylformamide (DMF), and can be a mixed solvent of water/ethylene glycol dimethyl ether (DME) and a mixed solvent of water/DMF, wherein the mass ratio of organic solvent to water in the mixed solvent is 1:0.5-10;
5) The mass of Ru element in the mixed solution accounts for 0.1-0.3% of the mass fraction of the catalyst finished product, such as 0.1-0.15 wt%, 0.1-0.2 wt% and 0.2-0.3 wt%;
6) The stirring and dissolving temperature of the mixed solution is 30-110 ℃, such as 30-45 ℃, 45-60 ℃ and 65-80 ℃.
Preferably, step 2 should include one or more of the following features:
1) The active carbon carrier is one or more of coal active carbon, wood active carbon and asphalt-based active carbon; the wood-based activated carbon is preferably coconut shell activated carbon.
2) The water capacity of the activated carbon is 60-130%, and the bulk density is 0.3-0.8 g/mL;
3) The loading temperature and the stirring and dissolving temperature are 30-110 ℃.
Preferably, step 3 should include one or more of the following features:
1) The process of the catalyst drying treatment is as follows: drying for 6-20 h at the temperature of 5-20 ℃ and 0.1MPa higher than the boiling point of the solvent.
More preferably, in step 3, drying is performed at 15℃above the boiling point of the solvent for 20 hours.
The prepared ruthenium-based catalyst modified by the N-containing five-membered heterocyclic ligand is applied to acetylene hydrochlorination, and preferably, the reaction conditions are as follows: the temperature is 90-250 ℃ and the acetylene volume space velocity is 5-200 h -1 The pressure is 0.01-0.2 Mpa.
The product consisted of gas chromatography analysis and the reactivity was expressed as acetylene conversion.
Compared with the prior art, the application has the beneficial effects that:
1. in the ruthenium-based catalyst applied to the hydrochlorination of acetylene, an N-containing five-membered heterocyclic ligand rich in heteroatoms is introduced, and the N-containing five-membered heterocyclic ligand can be complexed with Ru atoms to form a local active domain, so that the capability of cooperative adsorption and activation of hydrogen chloride is greatly improved, and the activity of the ruthenium-based catalyst is greatly improved.
2. The conjugated structure in the ligand can effectively promote electron transfer between the heteroatom and the ruthenium precursor, improve electron cloud density around the active center and effectively stabilize the valence state of the active Ru species; the reactant acetylene is easy to be adsorbed by a substance containing an aromatic structure, and the N-containing five-membered heterocyclic ligand is a conjugated structure rich in electrons, so that the acetylene can be effectively adsorbed and activated. By the influence of the two aspects, the activity and the stability of the ruthenium-based catalyst are effectively improved.
3. The ruthenium-based catalyst modified by the N-containing five-membered heterocyclic ligand prepared by the preparation method has high catalytic activity, good stability and low loading capacity, and has better scientific research application potential. Under the same evaluation condition, the catalytic effect of the catalyst is better than that of the published thiourea modified ruthenium-based catalyst. Particularly, catalysts which are excellent after ligand modification are screened out, and under more severe evaluation conditions: 0.1wt% Ru loading, reaction temperature of 180 ℃, acetylene airspeed of 160h -1 Hydrogen chloride acetylene volume ratio 1.2:1, the acetylene conversion rate of the catalyst is above 85%, and the catalyst has good industrial application potential.
Description of the drawings:
FIG. 1 is a graph of the results of a ruthenium-based catalyst life performance test.
Detailed Description
The technical scheme of the application is described below through specific examples. The following examples are presented to provide those skilled in the art with a more detailed understanding of the application and are not intended to limit the scope of the application. The protection scope of the application is set forth in the appended claims.
Example 1
(1) 0.0135g of ruthenium trichloride trihydrate and 26 mu L of oxazole are stirred and dissolved in a mixed solvent of 3.5g of water and DME (2.0 g of water) at 50 ℃ to obtain an impregnating solution containing ruthenium ions and ligands;
(2) Impregnating the impregnating solution onto 5g of active carbon by adopting an isovolumetric impregnation method, and sealing and standing for 1 hour at 50 ℃;
(3) And drying the activated carbon at 110 ℃ for 6 hours to obtain the catalyst A1.
A1 at 180℃under a reaction condition, acetylene space velocity of 160h -1 Hydrogen chloride acetylene volume ratio 1.2: at 1, the acetylene conversion was 72%.
Comparative example 1
(1) 0.0135g of ruthenium trichloride trihydrate and 0.0151g of thiourea are stirred and dissolved in 3.5g of a mixed solvent of water and DME at 50 ℃ to obtain an impregnating solution only containing ruthenium ions;
(2) Impregnating the impregnating solution onto 5g of active carbon by adopting an isovolumetric impregnation method, and sealing and standing for 1 hour at 50 ℃;
(3) And drying the activated carbon at 110 ℃ for 6 hours to obtain the catalyst A2.
A2 under the reaction condition of 180 ℃ and acetylene airspeed of 160h -1 Hydrogen chloride acetylene volume ratio 1.2: at 1, the acetylene conversion was 68%. However, under the same conditions, the ruthenium ion is only used as an active component, the overall performance such as stability and service life is poor, and the industrial application cannot be satisfied.
Example 2
(1) Stirring and dissolving 0.0135g of ruthenium trichloride trihydrate and 28 mu L of thiazole into 3.5g of mixed solvent of water and DME at 50 ℃ to obtain an impregnating solution containing ruthenium ions and ligands;
(2) Impregnating the impregnating solution onto 5g of active carbon by adopting an isovolumetric impregnation method, and sealing and standing for 1 hour at 50 ℃;
(3) And drying the activated carbon at 110 ℃ for 6 hours to obtain the catalyst A3.
A3 at 180 ℃ under the reaction condition, the space velocity of acetylene is 160h -1 Hydrogen chloride acetylene volume ratio 1.2: at 1, the acetylene conversion was 75%.
Example 3
(1) 0.0135g of ruthenium trichloride trihydrate and 35 mu L of 4-methylthiazole are stirred and dissolved in 3.5g of mixed solvent of water and DME at 50 ℃ to obtain an impregnating solution containing ruthenium ions and ligands;
(2) Impregnating the impregnating solution onto 5g of active carbon by adopting an isovolumetric impregnation method, and sealing and standing for 1 hour at 50 ℃;
(3) And drying the activated carbon at 110 ℃ for 6 hours to obtain the catalyst A4.
A4 at 180 ℃ under the reaction condition, the space velocity of acetylene is 160h -1 Hydrogen chloride acetylene volume ratio 1.2: at 1, the acetylene conversion was 82%.
Example 4
(1) Stirring and dissolving 0.0135g of ruthenium trichloride trihydrate and 35 mu L of 5-methylthiazole in 3.5g of a mixed solvent of water and DME at 50 ℃ to obtain an impregnating solution containing ruthenium ions and ligands;
(2) Impregnating the impregnating solution onto 5g of active carbon by adopting an isovolumetric impregnation method, and sealing and standing for 1 hour at 50 ℃;
(3) And drying the activated carbon at 110 ℃ for 6 hours to obtain the catalyst A5.
A5 at 180 ℃ under the reaction condition, the space velocity of acetylene is 160h -1 Hydrogen chloride acetylene volume ratio 1.2: at 1, the conversion of acetylene was 85%.
Example 5
(1) Stirring and dissolving 0.0135g of ruthenium trichloride trihydrate and 42 mu L of 4.5-dimethylthiazole into 3.5g of mixed solvent of water and DME at 50 ℃ to obtain an impregnating solution containing ruthenium ions and ligands;
(2) Impregnating the impregnating solution onto 5g of active carbon by adopting an isovolumetric impregnation method, and sealing and standing for 1 hour at 50 ℃;
(3) And drying the activated carbon at 110 ℃ for 6 hours to obtain the catalyst A6.
A6 at 180 ℃ under the reaction condition, the space velocity of acetylene is 160h -1 Hydrogen chloride acetylene volume ratio 1.2: at 1, the acetylene conversion was 90%.
Example 6
(1) Stirring and dissolving 0.0135g of ruthenium trichloride trihydrate and 42 mu L of 4.5-dimethylthiazole into 3.5g of mixed solvent of water and DME at 50 ℃ to obtain an impregnating solution containing ruthenium ions and ligands;
(2) Impregnating the impregnating solution onto 5g of active carbon by adopting an isovolumetric impregnation method, and sealing and standing for 1 hour at 50 ℃;
(3) And drying the activated carbon at 110 ℃ for 6 hours to obtain the catalyst A7.
A7 at 180℃under a reaction condition, acetylene space velocity 80h -1 Hydrogen chloride acetylene volume ratio 1.2: at 1, the conversion of acetylene after 50 hours of reaction was about 95%.
Example 7
(1) Stirring and dissolving 0.0135g of ruthenium trichloride trihydrate and 22.4 mu L of 1-isopropylimidazole in 3.5g of mixed solvent of water and DME at 50 ℃ to obtain an impregnating solution containing ruthenium ions and ligands;
(2) Impregnating the impregnating solution onto 5g of active carbon by adopting an isovolumetric impregnation method, and sealing and standing for 1 hour at 50 ℃;
(3) And drying the activated carbon at 110 ℃ for 6 hours to obtain the catalyst A8.
A8 at 180 ℃ under the reaction condition, the space velocity of acetylene is 80h -1 Hydrogen chloride acetylene volume ratio 1.2: at 1, the conversion of acetylene after 50 hours of reaction was about 92%.
The tail gas composition was analyzed using gas chromatography and sampled every 0.5 hour. Sampling data, represented by the 4-hour point of reaction, compares acetylene conversion rates of ruthenium-based catalysts incorporating different N-containing five-membered heterocyclic ligands, and the results are shown in Table 1. Further, a 50-hour lifetime test was performed for example 6 and example 7, and the experimental results are shown in Table 2:
TABLE 1
TABLE 250 h Life test
1. From the experimental results of comparative example 1 and comparative example 1 and example 2, it can be seen that the introduction of the N-containing five-membered heterocyclic ligand in the present application can improve the activity of ruthenium-based catalyst under the same conditions, and is superior to the published patent modified ruthenium-based catalyst with thiourea, and the loading of ruthenium active component is significantly reduced.
2. From the experimental results of example 3, example 4 and example 5, the N-containing five-membered heterocyclic ligand is further modified by methyl, electron donating groups are added at different positions, the electron density around the metal active center is improved, and the catalyst after ligand modification can effectively improve the conversion rate of acetylene under the same condition. With the industrial requirement of acetylene airspeed 40h -1 Compared with the method, the method realizes high conversion rate of acetylene and higher stability of the catalyst under the condition of evaluating the space velocity of acetylene which is far higher than the industrial requirement.
3. From the 50h lifetime experimental results of example 6 and example 7, it can be seen that acetylene was supported at 0.1wt% Ru for 80h by the N-containing five membered heterocyclic ligand modified ruthenium based catalyst -1 Under the reaction condition, the conversion rate of acetylene can be stabilized to be more than 90% for a long time, and after 50 hours of reaction, the conversion rates of the example 6 and the example 7 are respectively stabilized to be 95% and 92%, so that the method has certain industrial application potential.
The unsaturated d orbit in Ru ions has quite large deformability and is easy to accept lone pair electrons of heteroatom ligands, so that a hybrid orbit with strong bonding capability is formed. The N-containing five-membered heterocyclic ligand introduced by the application is rich in hetero atoms, and the hetero atoms and metal ions can form chelate with stable cation resonance structure and space topology in a synergistic effect; secondly, the N-containing five-membered heterocyclic ligand can be complexed with Ru atoms to form a local active domain, which is beneficial to the cooperative adsorption and activation of initial reactants; finally, the conjugated structure rich in electrons in the ligand can effectively adsorb and activate acetylene, and simultaneously can effectively promote electron transfer between hetero atoms and ruthenium precursors, so that the electron cloud density around an active center is improved, the valence state of active Ru species is effectively stabilized, and the activity and stability of the ruthenium-based catalyst are obviously improved.
5. According to the application, the N-containing five-membered heterocyclic ligand is added to modify the ruthenium-based catalyst, so that the catalytic activity and stability of the catalyst are greatly improved, the Ru-based catalyst can achieve the catalytic effect of the Ru-based catalyst under the extremely low metal load (Ru ion load is 0.1 wt%) with other Ru-based catalysts under the higher Ru load, the catalytic performance of the Ru-based catalyst is better than that of the existing catalyst under the same condition when Ru load is increased, and the industrial cost is effectively reduced.
The application is applicable to the prior art where it is not described.
Claims (7)
1. A method for preparing a ruthenium-based catalyst modified by N-containing five-membered heterocyclic ligands for hydrochlorination of acetylene, which is characterized by comprising the following preparation steps:
(1) Dissolving ruthenium salt and N-containing five-membered heterocyclic ligand in a solvent to obtain a uniform and stable mixed solution;
(2) Uniformly loading active components in the mixed solution onto an active carbon carrier by adopting a dipping method, a spraying method, a precipitation method, an ion exchange method or a spray evaporation method at the same temperature as the dissolution temperature of the step (1);
(3) Drying at a temperature 5-20 ℃ higher than the boiling point of the solvent in the step (1) to obtain the ruthenium-based catalyst modified by the N-containing five-membered heterocyclic ligand for hydrochlorination of acetylene;
ruthenium in the catalyst and N in the N-containing five-membered heterocyclic ligand form a stable space topology complex after being coordinated;
the N-containing five-membered heterocyclic ligand is one or more of 2-methylthiazole, 4-methylthiazole, 5-methylthiazole, 2, 5-dimethylthiazole, 2, 4-dimethylthiazole and 4, 5-dimethylthiazole;
ru accounts for 0.1 to 0.3 weight percent of the total weight of the catalyst.
2. The method of claim 1, wherein the ruthenium salt is selected from one or more of ruthenium trichloride, ruthenium trichloride hydrate, ruthenium acetate, ruthenium iodide, ammonium chlororuthenate;
the carrier is one or more of coconut shell activated carbon, coal activated carbon, wood activated carbon and asphalt-based activated carbon.
3. The preparation method according to claim 1, wherein the activated carbon has a water content of 60 to 130%, a bulk density of 0.3 to 0.8g/mL, and Ru accounts for 0.1 to 0.15wt% of the total weight of the catalyst.
4. The method according to claim 1, wherein in the step (1), the molar ratio of the ruthenium metal to the ligand in the mixed solution is 1:0.5-10, and the solvent is a polar solvent; the dissolution temperature of the mixed solution is 30-110 ℃; the drying process in the step (3) comprises the following steps: drying 5-20 h under the condition of 5-20 ℃ and 0.1MPa higher than the boiling point of the solvent.
5. The method according to claim 1, wherein the molar ratio of metallic ruthenium to ligand in the mixed solution is 1: 1-8; the solvent is one or more selected from deionized water, absolute ethyl alcohol, acetone, methylene dichloride, ethylene glycol dimethyl ether and N, N-dimethylformamide.
6. The preparation method of claim 5, wherein the solvent is a mixed solvent of water/ethylene glycol dimethyl ether and a mixed solvent of water/DMF, and the mass ratio of organic solvent to water in the mixed solvent is 1:0.5-10.
7. The method of preparing a catalyst according to claim 1, wherein the catalyst is used for hydrochlorination of acetylene at a temperature of 90-250 ℃ and an acetylene volume space velocity of 5-200 h -1 The reaction pressure is 0.01-0.2 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211195822.0A CN115463692B (en) | 2022-09-29 | 2022-09-29 | N-containing five-membered heterocyclic ligand modified ruthenium-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211195822.0A CN115463692B (en) | 2022-09-29 | 2022-09-29 | N-containing five-membered heterocyclic ligand modified ruthenium-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115463692A CN115463692A (en) | 2022-12-13 |
| CN115463692B true CN115463692B (en) | 2023-10-10 |
Family
ID=84336063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211195822.0A Active CN115463692B (en) | 2022-09-29 | 2022-09-29 | N-containing five-membered heterocyclic ligand modified ruthenium-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115463692B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB897099A (en) * | 1959-12-08 | 1962-05-23 | American Cyanamid Co | Polymerization of acetylene compounds |
| CN101905157A (en) * | 2010-08-09 | 2010-12-08 | 南开大学 | Method for preparing mercury-free catalyst for preparing chloroethylene by acetylene hydrochlorination |
| CN107803222A (en) * | 2017-09-29 | 2018-03-16 | 浙江工业大学 | A kind of catalyzed by ruthenium complexes agent for acetylene hydrochlorination reaction |
| CN108262072A (en) * | 2017-12-08 | 2018-07-10 | 石河子大学 | It is a kind of for catalyzed by ruthenium complexes agent of acetylene hydrochlorination and its preparation method and application |
| CN112916049A (en) * | 2021-01-27 | 2021-06-08 | 南开大学 | Oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN113546679A (en) * | 2021-06-15 | 2021-10-26 | 石河子大学 | Ionic liquid-ruthenium-based catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
-
2022
- 2022-09-29 CN CN202211195822.0A patent/CN115463692B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB897099A (en) * | 1959-12-08 | 1962-05-23 | American Cyanamid Co | Polymerization of acetylene compounds |
| CN101905157A (en) * | 2010-08-09 | 2010-12-08 | 南开大学 | Method for preparing mercury-free catalyst for preparing chloroethylene by acetylene hydrochlorination |
| CN107803222A (en) * | 2017-09-29 | 2018-03-16 | 浙江工业大学 | A kind of catalyzed by ruthenium complexes agent for acetylene hydrochlorination reaction |
| CN108262072A (en) * | 2017-12-08 | 2018-07-10 | 石河子大学 | It is a kind of for catalyzed by ruthenium complexes agent of acetylene hydrochlorination and its preparation method and application |
| CN112916049A (en) * | 2021-01-27 | 2021-06-08 | 南开大学 | Oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN113546679A (en) * | 2021-06-15 | 2021-10-26 | 石河子大学 | Ionic liquid-ruthenium-based catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Enhanced catalytic performance of activated carbon-supported ru-based catalysts for acetylene hydrochlorination by azole ligands;Jian Li et al.;《Applied Catalysis A, General》;第592卷;第117431(1-10)页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115463692A (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110302769B (en) | Catalyst carrier, supported catalyst, preparation method and application thereof | |
| CN109718806B (en) | Noble metal monoatomic catalyst and preparation method and application thereof | |
| CN111269086B (en) | Application method of atomic-level dispersed ruthenium catalyst in catalytic hydrogenation | |
| Zhang et al. | One‐pot synthesis of platinum–ceria/graphene nanosheet as advanced electrocatalysts for alcohol oxidation | |
| CN113713841B (en) | Acetylene copper chloride-based catalyst and preparation method and application thereof | |
| CN107715914B (en) | Supported sulfide ionic liquid promoted ruthenium catalyst and application thereof in unsaturated hydrocarbon hydrohalogenation | |
| CN111715268A (en) | Catalyst with nitrogen-doped carbon material as carrier and preparation method thereof | |
| CN112916049B (en) | Oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof | |
| CN115594633B (en) | Organic ligand, functionalized metal-organic framework material, and preparation methods and applications thereof | |
| CN109384750B (en) | Method for preparing 2,5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
| CN111330621A (en) | Supported mercury-free catalyst for synthesizing chloroethylene and preparation method thereof | |
| CN112642448A (en) | Preparation method and application of copper catalyst for acetylene hydrochlorination | |
| CN114931981A (en) | Copper-based catalyst for synthesizing vinyl chloride through acetylene hydrochlorination and preparation method thereof | |
| CN111659388A (en) | Platinum-based catalyst containing uranium or uranium compound | |
| CN115463692B (en) | N-containing five-membered heterocyclic ligand modified ruthenium-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof | |
| CN110665546A (en) | Noble metal/amino MOFs selective hydrogenation catalyst, preparation method and application thereof | |
| CN112892560B (en) | Fluorine-containing weakly coordinated anion modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof | |
| Alfonso-Herrera et al. | Novel strategies to tailor the photocatalytic activity of metal—organic frameworks for hydrogen generation: a mini-review | |
| Santos et al. | Physicochemical and electrochemical characterization of Ce/carbonaceous matrices-based composites | |
| CN114011472A (en) | Preparation of supported platinum nanocluster catalyst and application of supported platinum nanocluster catalyst in alkane anaerobic dehydrogenation | |
| CN115779968A (en) | Copper-based catalyst for preparing vinyl chloride through acetylene hydrochlorination reaction and preparation method and application thereof | |
| CN115888716A (en) | Metal organic framework-ionic liquid composite catalyst, preparation method and application | |
| CN111569926B (en) | Boron nitride loaded palladium-gold-tin liquid alloy catalyst and preparation method and application thereof | |
| CN115007214A (en) | Copper-containing metal organic framework catalyst prepared by mechanochemical method and preparation method thereof | |
| CN114522710A (en) | Ti1Preparation method and application of-NC single-atom catalytic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |