CN108262072B - Ruthenium complex catalyst for acetylene hydrochlorination and preparation method and application thereof - Google Patents
Ruthenium complex catalyst for acetylene hydrochlorination and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ruthenium complex catalyst for hydrochlorination of acetylene and a preparation method thereof3And an organic ligand; RuCl3The molar ratio of the organic ligand to the organic ligand is 1:1-6, and Ru accounts for 0.1-5.0 wt% of the total weight of the catalyst; the organic ligand is one or more of triphenylphosphine, pyridine, 2' -bipyridyl, acetylacetone, chlorodiphenylphosphine, chlorobenzene, cyclopentadiene, 4-cymene and 1, 5-cyclooctadiene. The catalyst provided by the invention is simple in preparation process, the catalytic activity and stability of the catalyst are greatly improved, and the catalyst is environment-friendly and high in economy.
Description
Technical Field
The invention relates to the field of ruthenium catalysts, and particularly relates to a ruthenium complex catalyst for acetylene hydrochlorination and a preparation method and application thereof.
Background
With the development of the world economy and the enhancement of the awareness of environmental protection, polyvinyl chloride (PVC) is increasingly demanded as an excellent plastic. The world's process for producing Vinyl Chloride (VCM) is broadly divided into the following three types, depending on the feedstock: acetylene, ethylene, and ethane processes. The acetylene method is basically replaced by an ethylene method route in the country with rich petroleum resources, but the production of VCM by the acetylene method route taking coal as a raw material still occupies a leading position due to the energy structure characteristics of rich coal, poor oil and less gas in China. In the existing calcium carbide acetylene method, mercury chloride loaded by activated carbon is used as a catalyst to catalyze the hydrochlorination of acetylene, and the mercury active component in the catalyst is easy to sublimate and lose. According to statistics, about 1.02-1.41 kgHgCl is consumed for each 1 ton of PVC produced2Catalyst (HgCl)2The content is as follows: 10-12 wt%), but about 25% HgCl2Lost during cycling. Mercury is a heavy metal, is extremely toxic, generates toxicity with the concentration of 0.01-0.1 mg/L, cannot be degraded by microorganisms, can only migrate and convert among water, substrates and organisms in different valence states, is difficult to metabolize after being dispersed and enriched into a human body, is accumulated in the liver, the kidney and the brain, damages the nervous system and causes terrible water-bearing disease. According to the water guarantee convention signed in japan in 2013, it is explicitly stated that for the production of vinyl chloride monomer, the mercury usage per unit product is reduced by 50% on the basis of the usage in 2010 by 2020, and the production process using mercury or mercury compounds is eliminated by 2025. Therefore, there is a need to solve the pollution problem caused by mercury catalysts, and the development of non-mercury catalysts is urgent.
On the other hand, recent studies have shown that AuCl is used as a material for the optical fibers3The Au-based catalyst prepared from the precursor is used for catalyzing acetylene hydrochlorination reaction, and shows better catalytic activity and conversion rate, so that Au becomes a better substitute of Hg catalyst. As is well known, Au is expensive and plays a major role in national economy, and therefore, it is necessary to develop and search for other novel mercury-free catalysts which are environmentally friendly, have high performance, are inexpensive and are easily available. Ru has similar peripheral electron orbital properties to Au and Hg and is much less expensive than Au, thus making Ru catalysts as wellThe replacement of Hg catalyst is more competitive. With RuCl3The Ru-based catalyst prepared from the precursor has better catalytic performance, but the activity and the stability of the Ru-based catalyst still need to be improved. Through the research on the catalytic reaction mechanism, the ruthenium in an oxidation state is considered to be the catalytic active center, but i) the Ru with poor dispersibility is not beneficial to improving the hydrochlorination activity of acetylene; ii) the lower the active component content, the poorer the activity of the catalyst. And the lone pair electrons of hetero atoms in the ligand or the action of the ligand skeleton and Ru can ensure that Ru stably exists in an oxidation state form playing a main catalytic role, and the Ru in the oxidation state becomes an active domain of the Ru-based catalyst for catalyzing the reaction. Therefore, it is a difficult point to make ruthenium exist in a large number of highly dispersed active domains that play a major catalytic role. Therefore, how to make the dispersion degree of the active component in the Ru-based catalyst higher and have more stable active species becomes a focus of further research.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a ruthenium complex catalyst for hydrochlorinating acetylene and a preparation method and application thereof.
Specifically, the invention provides a ruthenium complex catalyst for hydrochlorination of acetylene, which takes active carbon as a catalyst carrier and loads RuCl3And an organic ligand;
RuCl3the molar ratio of the organic ligand to the organic ligand is 1:1-6, and Ru accounts for 0.1-5.0 wt% of the total weight of the catalyst;
the organic ligand is one or more of triphenylphosphine, pyridine, 2' -bipyridyl, acetylacetone, chlorodiphenylphosphine, chlorobenzene, cyclopentadiene, 4-cymene and 1, 5-cyclooctadiene.
Wherein the activated carbon is modified by hydrochloric acid or nitric acid with the excessive volume of 5-12 mol/L. The modification by using 5-12mol/L of hydrochloric acid or nitric acid with excessive volume refers to that when the activated carbon is modified, the activated carbon is modified by using 5-12mol/L of hydrochloric acid or nitric acid, and the volume of the hydrochloric acid or nitric acid used is larger than that of the activated carbon.
The present invention also provides a method for preparing the ruthenium complex catalyst for hydrochlorination of acetylene, which comprises the following steps:
putting the activated carbon into a sealed filter flask, vacuumizing for 1-4 h, and then adding RuCl3And completely dissolving the organic ligand by using a solvent, adding the dissolved organic ligand into the activated carbon subjected to vacuum treatment, stopping vacuumizing, stirring at room temperature for 4-48 h to obtain a solid-liquid mixture, and drying the obtained mixture at the temperature of 100-160 ℃ for 4-24 h to obtain the ruthenium complex catalyst for acetylene hydrochlorination.
Wherein the activated carbon is modified by the following method: adding activated carbon into 5-12mol/L concentrated hydrochloric acid or nitric acid with excessive volume, stirring for 4-24 h at room temperature-80 ℃, performing suction filtration, washing the PH value to 5-7 with deionized water, and drying the treated activated carbon for 4-24 h at 100-160 ℃.
In addition, the solvent is one or more of water, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and acetone.
The invention also provides application of the ruthenium complex catalyst for acetylene hydrochlorination, which is used for catalyzing acetylene hydrochlorination.
2ml of catalyst is taken, and the space velocity of acetylene is 180h at 180 DEG C-1Under the environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, RuCl is used3The activity of the catalyst prepared from the precursor is 50-60%, and the selectivity is 98-99%; in contrast, the catalytic activity of the catalyst of the invention is greatly improved, the highest conversion rate of acetylene is close to 100%, and the selectivity is more than 99%.
The invention uses modified active carbon as a carrier, and adopts a wet impregnation method to load the organic Ru complex precursor on the modified active carbon to obtain more stable active sites, the preparation method has simple and easy process, and the catalyst is environment-friendly and has high economical efficiency, and adopts the organic Ru complex to replace inorganic RuCl3The precursor is loaded on an active carbon carrier, and the Ru species interacts with the surface groups of the active carbon, so that the active components are anchored on the carrier, the content is higher, the dispersity is better, and the high-efficiency Ru-based catalyst with higher activity and stability is obtained, wherein Ru accounts for catalysis0.1 to 5.0 wt% of the total weight of the agent.
The catalyst provided by the invention has the advantages that the preparation process is simple, the surface active sites of the catalyst are increased, the interaction between the surface groups of the active carbon and active species is promoted, the active species are anchored on the carrier, the content is higher, the dispersity is better, the catalytic activity and the stability of the catalyst are greatly improved, and the catalyst is environment-friendly and has high economical efficiency.
Drawings
FIG. 1 is a graph showing the conversion of catalysts in examples 1 to 10 and comparative example.
FIG. 2 is a drawing showing the selectivity in examples 1 to 10 and comparative example.
Detailed Description
The present invention will be described in detail below by way of examples, which are provided for the convenience of understanding and are not intended to limit the present invention in any way.
Example 1
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: weighing 3g of Activated Carbon (AC), adding the Activated Carbon (AC) into 100ml of 12mol/L concentrated hydrochloric acid, stirring at room temperature for 24 hours, carrying out suction filtration, washing the pH value to 5 with deionized water, and drying the treated activated carbon at 100 ℃ for 24 hours to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask and vacuumizing for 1h, and then weighing 0.4651g of RuCl3And 1.0641g of organic ligand pyridine (molar ratio of pyridine to Ru is 6: 1), completely dissolving the organic ligand pyridine with 100ml of water, adding the dissolved organic ligand pyridine into the activated carbon subjected to vacuum treatment, stopping vacuumizing, stirring at room temperature for 4 hours to obtain a solid-liquid mixture, and drying the obtained mixture at 100 ℃ for 24 hours to obtain the efficient ruthenium complex catalyst for acetylene hydrochlorination, which is recorded as C1.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The volume ratio of acetylene to hydrogen chloride is 1:1.15Under the system, the reaction lasts for 48 hours, the acetylene conversion rate can reach 68%, and the selectivity is over 99%.
Example 2
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: 3g of Activated Carbon (AC) is weighed, added into 100ml of 5mol/L nitric acid, stirred for 4 hours at 80 ℃, filtered, washed with deionized water until the pH value reaches 7, and then dried for 4 hours at 160 ℃ to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask, vacuumizing for 4h, and weighing 0.0685g of RuCl3And 0.25986g of organic ligand triphenylphosphine (the molar ratio of triphenylphosphine to Ru is 3: 1), completely dissolving the organic ligand triphenylphosphine with 300ml of ethanol, adding the solution into the activated carbon subjected to vacuum treatment, stopping vacuumizing, stirring at room temperature for 48 hours to obtain a solid-liquid mixture, and drying the obtained mixture at 160 ℃ for 4 hours to obtain the efficient ruthenium complex catalyst for hydrochlorination of acetylene, which is recorded as C2.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 99%, and the selectivity is over 99%.
Example 3
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: 3g of Activated Carbon (AC) is weighed and respectively added into 100ml of 5mol/L nitric acid, after stirring at room temperature for 24h, the activated carbon is filtered by suction and washed with deionized water until the pH value is 7, and then the treated activated carbon is dried at 140 ℃ for 24h to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask and vacuumizing for 2h, and then weighing 0.06604g of RuCl3And 0.14918g of an organic ligand 2, 2' -biPyridine (molar ratio of 2, 2' -bipyridine to Ru is 3: 1), completely dissolved in 300ml of n-propanol, added to the activated carbon treated under vacuum, the vacuum was stopped, the mixture was stirred at room temperature for 12 hours to obtain a solid-liquid mixture, and the obtained mixture was dried at 150 ℃ for 24 hours to obtain a highly efficient ruthenium complex catalyst for hydrochlorination of acetylene, which was designated as C3.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 85 percent, and the selectivity is over 99 percent.
Example 4
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: 3g of Activated Carbon (AC) is weighed and respectively added into 100ml of 5mol/L nitric acid, after stirring at room temperature for 12h, the activated carbon is filtered by suction and washed with deionized water until the pH value is 7, and then the treated activated carbon is dried at 140 ℃ for 12h to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask and vacuumizing for 2h, and then weighing 0.06493g of RuCl3And 0.09402g of organic ligand acetylacetone (the molar ratio of acetylacetone to Ru is 3: 1), which is completely dissolved in 300ml of isopropanol, added to the activated carbon treated under vacuum, the vacuum is stopped, the mixture is stirred at room temperature for 12 hours to obtain a solid-liquid mixture, and the obtained mixture is dried at 140 ℃ for 24 hours to obtain a high-efficiency ruthenium complex catalyst for hydrochlorination of acetylene, which is recorded as C4.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 98%, and the selectivity is more than 99%.
Example 5
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: 3g of Activated Carbon (AC) is weighed and respectively added into 100ml of 5mol/L nitric acid, after stirring at room temperature for 12h, the activated carbon is filtered by suction and washed with deionized water until the pH value is 7, and then the treated activated carbon is dried at 140 ℃ for 12h to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask and vacuumizing for 2h, and then weighing 0.06438g of RuCl3And 0.06848g of organic ligand chlorodiphenylphosphine (the molar ratio of the chlorodiphenylphosphine to Ru is 1: 1), completely dissolving the chlorodiphenylphosphine with 300ml of n-butanol, adding the solution into the activated carbon subjected to vacuum treatment, stopping vacuumizing, stirring at room temperature for 12 hours to obtain a solid-liquid mixture, and drying the obtained mixture at 140 ℃ for 24 hours to obtain the efficient ruthenium complex catalyst for hydrochlorinating acetylene, which is recorded as C5.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 95%, and the selectivity is more than 99%.
Example 6
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: weighing 3g of Activated Carbon (AC), respectively adding into 100ml of 12mol/L concentrated hydrochloric acid, stirring at room temperature for 12h, performing suction filtration, washing with deionized water until the pH value is 7, and drying the treated activated carbon at 140 ℃ for 12h to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask and vacuumizing for 1h, and then weighing 0.006181g of RuCl3And 0.003354g of chlorobenzene, an organic ligand (molar ratio of chlorobenzene to Ru is 1: 1), dissolved completely in 300ml of isobutanol, added to the activated carbon treated in vacuo, the vacuum is stopped, the mixture is stirred at room temperature for 12 hours to obtain a solid-liquid mixture, and the solid-liquid mixture is stirred inDrying at 140 ℃ for 24h to obtain the efficient ruthenium complex catalyst for hydrochlorinating acetylene, which is marked as C6.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 60 percent, and the selectivity is more than 99 percent.
Example 7
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: 3g of Activated Carbon (AC) is weighed and respectively added into 100ml of 5mol/L nitric acid, after stirring at room temperature for 12h, the activated carbon is filtered by suction and washed with deionized water until the pH value is 7, and then the treated activated carbon is dried at 140 ℃ for 12h to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask and vacuumizing for 2h, and then weighing 0.06335g of RuCl3And 0.020188g of cyclopentadiene (the molar ratio of cyclopentadiene to Ru is 1: 1), which is an organic ligand, completely dissolved in 300ml of acetone, added to the activated carbon treated in vacuum, the vacuum pumping is stopped, the mixture is stirred at room temperature for 12 hours to obtain a solid-liquid mixture, and the obtained mixture is dried at 140 ℃ for 24 hours to obtain the efficient ruthenium complex catalyst for hydrochlorination of acetylene, which is recorded as C7.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 70%, and the selectivity is over 99%.
Example 8
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: 3g of Activated Carbon (AC) is weighed and respectively added into 100ml of 5mol/L nitric acid, after stirring at room temperature for 12h, the activated carbon is filtered by suction and washed with deionized water until the pH value is 7, and then the treated activated carbon is dried at 140 ℃ for 12h to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask and vacuumizing for 2h, and then weighing 0.06383g of RuCl3And 0.0413g of organic ligand 4-cymene (the molar ratio of 4-cymene to Ru is 1: 1), completely dissolving the organic ligand 4-cymene with 300 g of ethanol, adding the solution into the activated carbon subjected to vacuum treatment, stopping vacuumizing, stirring at room temperature for 12 hours to obtain a solid-liquid mixture, and drying the obtained mixture at 100 ℃ for 24 hours to obtain the efficient ruthenium complex catalyst for hydrochlorinating acetylene, which is recorded as C8.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 75 percent, and the selectivity is over 99 percent.
Example 9
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: 3g of Activated Carbon (AC) is weighed and respectively added into 100ml of 5mol/L nitric acid, after stirring at room temperature for 12h, the activated carbon is filtered by suction and washed with deionized water until the pH value is 7, and then the treated activated carbon is dried at 140 ℃ for 12h to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: placing the modified activated carbon obtained in the step 1 in a sealed filter flask and vacuumizing for 2h, and then weighing 0.06365g of RuCl3And 0.033195g of organic ligand 1, 5-cyclooctadiene (the molar ratio of cyclooctadiene to Ru is 1: 1), completely dissolving the mixture with 300ml of ethanol, adding the solution into the activated carbon subjected to vacuum treatment, stopping vacuumizing, stirring at room temperature for 12 hours to obtain a solid-liquid mixture, and drying the obtained mixture at 150 ℃ for 24 hours to obtain the efficient ruthenium complex catalyst for acetylene hydrochlorination, which is recorded as C9.
The catalyst is used for the test of the catalytic acetylene hydrochlorination reaction, 2ml of the catalyst is taken,at 180 ℃, the space velocity of acetylene is 180h-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 70%, and the selectivity is over 99%.
Example 10
Preparing a high-efficiency ruthenium complex catalyst for acetylene hydrochlorination:
step 1, preparing modified activated carbon: 3g of Activated Carbon (AC) is weighed and respectively added into 100ml of 5mol/L nitric acid, after stirring at room temperature for 12h, the activated carbon is filtered by suction and washed with deionized water until the pH value is 7, and then the treated activated carbon is dried at 140 ℃ for 12h to obtain the modified activated carbon carrier.
Step 2, preparing the high-efficiency Ru complex catalyst: the modified activated carbon obtained in the step 1 is placed in a sealed filter flask and vacuumized for 2 hours, and then 0.0669g of RuCl is weighed30.02132g of cyclopentadiene and 0.16919g of triphenylphosphine (molar ratio cyclopentadiene: triphenylphosphine: Ru: 1: 2: 1) were completely dissolved in 300ml of ethanol, the solution was added to vacuum-treated activated carbon, the vacuum-pumping was stopped, the mixture was stirred at room temperature for 12 hours to obtain a solid-liquid mixture, and the obtained mixture was dried at 140 ℃ for 24 hours to obtain a highly efficient ruthenium complex catalyst for hydrochlorination of acetylene, which was denoted as C10.
The catalyst is used for the test of the catalytic acetylene hydrochlorination, 2ml of the catalyst is taken, and the acetylene airspeed is 180h at 180 DEG C-1The catalyst is reacted for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, the conversion rate of the catalyst can reach 90 percent, and the selectivity is more than 99 percent.
Comparative example
Preparation with RuCl3The Ru-based catalyst is a precursor and takes active carbon as a carrier, and the Ru loading capacity is 1 wt%; the preparation method comprises the following steps: 0.064g of RuCl was weighed out3Dissolved in 10ml of water, the solution is then added to 3g of activated carbon and after stirring at room temperature for 24h, the resulting mixture is dried at 140 ℃ for 24h to give the Ru-based catalyst, designated Ru/AC.
When the catalyst is used for the test of catalyzing the hydrochlorination of acetylene, 2ml of the catalyst is taken, and the acetylene is heated at 180 DEG CAirspeed of 180h-1And reacting for 48 hours in an environment system with the volume ratio of acetylene to hydrogen chloride being 1:1.15, wherein the conversion rate of acetylene is reduced to 50%, and the selectivity is about 98%.
As is apparent from FIGS. 1 and 2, the conversion of the catalysts of examples 1 to 10 and comparative example is plotted in FIG. 1, and the selectivity of examples 1 to 10 and comparative example is plotted in FIG. 2, and it is evident that RuCl is used in the present invention3The complex formed by organic ligand (triphenylphosphine, pyridine, bipyridine, acetylacetone, chlorodiphenylphosphine, chlorobenzene, cyclopentadiene, 4-cymene, 1, 5-cyclooctadiene, etc.) with certain molar ratio to Ru is used as precursor, the modified active carbon is used as carrier, and the catalytic activity of the novel Ru-based catalyst prepared by using water, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or acetone as solvent is obviously superior to that of RuCl in the comparative example3The Ru-based catalyst prepared for the precursor is mainly characterized in that the Ru complex catalyst has more active sites, and active species and modified active carbon surface groups interact with each other, so that the active species can be anchored on a carrier, the content is higher, the dispersity is better, and the catalytic activity and the stability of the catalyst are greatly improved.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not limiting, and those of ordinary skill in the art, in light of the present teachings, can make various modifications of RuCl without departing from the spirit of the invention3The complex formed by the organic ligand or the Ru complex catalyst prepared by directly taking the commercial Ru complex as a precursor belongs to the protection of the invention.
Claims (5)
1. A ruthenium complex catalyst for hydrochlorination of acetylene is characterized in that active carbon is used as a catalyst carrier and loaded with RuCl3And an organic ligand;
RuCl3the molar ratio of the organic ligand to the organic ligand is 1:1-6, and Ru accounts for 0.1-5.0 wt% of the total weight of the catalyst;
the organic ligand is one or more of triphenylphosphine, pyridine, 2' -bipyridyl, acetylacetone, chlorodiphenylphosphine, chlorobenzene, cyclopentadiene, 4-cymene and 1, 5-cyclooctadiene;
the activated carbon is modified activated carbon modified by hydrochloric acid or nitric acid with the excessive volume of 5-12 mol/L.
2. A method for preparing a ruthenium complex catalyst for hydrochlorination of acetylene according to claim 1, comprising the steps of:
putting the activated carbon into a sealed filter flask, vacuumizing for 1-4 h, and then adding RuCl3And completely dissolving the organic ligand by using a solvent, adding the dissolved organic ligand into the activated carbon subjected to vacuum treatment, stopping vacuumizing, stirring at room temperature for 4-48 h to obtain a solid-liquid mixture, and drying the obtained mixture at the temperature of 100-160 ℃ for 4-24 h to obtain the ruthenium complex catalyst for acetylene hydrochlorination.
3. The method according to claim 2, wherein the activated carbon is modified by: adding activated carbon into 5-12mol/L concentrated hydrochloric acid or nitric acid, stirring for 4-24 h at room temperature of-80 ℃, performing suction filtration, washing the pH value to 5-7 with deionized water, and drying the treated activated carbon for 4-24 h at 100-160 ℃.
4. The preparation method according to claim 2, wherein the solvent is one or more of water, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and acetone.
5. Use of a ruthenium complex catalyst for hydrochlorination of acetylene according to claim 1, characterised in that it is used to catalyse the hydrochlorination of acetylene.
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| GB201811606D0 (en) * | 2018-07-16 | 2018-08-29 | Univ College Cardiff Consultants Ltd | Gold catalyst |
| CN109876864B (en) * | 2019-02-14 | 2021-12-28 | 西安凯立新材料股份有限公司 | Ultralow-content noble metal composite catalyst for acetylene hydrochlorination and preparation method thereof |
| CN111644210B (en) * | 2020-06-22 | 2022-11-15 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Application of composite carrier ruthenium-based catalyst in acetylene hydrochlorination |
| CN112973800A (en) * | 2021-03-01 | 2021-06-18 | 内蒙古大学 | Preparation method and application of nitrogen modified ruthenium-based catalyst |
| 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 |
| CN113546679B (en) * | 2021-06-15 | 2023-04-28 | 石河子大学 | Ionic liquid-ruthenium-based catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof |
| CN114939437B (en) * | 2022-05-24 | 2024-01-09 | 鄂尔多斯市瀚博科技有限公司 | Ru-MOF/AC acetylene hydrochlorination catalyst and preparation method thereof |
| CN115007214B (en) * | 2022-06-20 | 2024-01-09 | 鄂尔多斯市瀚博科技有限公司 | Copper-based metal organic framework catalyst prepared by mechanochemical method and preparation method |
| CN115463692B (en) * | 2022-09-29 | 2023-10-10 | 南开大学 | N-containing five-membered heterocyclic ligand modified ruthenium-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof |
| CN116351476A (en) * | 2022-12-18 | 2023-06-30 | 石河子大学 | Ligand-copper-based catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof |
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