CN115626863B - Method for preparing chloroethylene by hydrochlorination of acetylene in fixed bed by using low-content ruthenium-based catalyst - Google Patents
Method for preparing chloroethylene by hydrochlorination of acetylene in fixed bed by using low-content ruthenium-based catalyst Download PDFInfo
- Publication number
- CN115626863B CN115626863B CN202211270243.8A CN202211270243A CN115626863B CN 115626863 B CN115626863 B CN 115626863B CN 202211270243 A CN202211270243 A CN 202211270243A CN 115626863 B CN115626863 B CN 115626863B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetylene
- ruthenium
- hydrochlorination
- preparing
- 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
Images
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
Abstract
The invention relates to a method for preparing chloroethylene by hydrochlorination of acetylene in a fixed bed by using a low-content ruthenium-based catalyst, belonging to the technical field of catalyst preparation and application. The invention takes 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride as a ligand, mixes and stirs the ligand with a ruthenium precursor, then wets the carrier for the first time, and dries the obtained mixture in a drying oven to obtain the required catalyst. The catalyst has extremely high activity and vinyl chloride selectivity in the reaction of preparing vinyl chloride by hydrochlorination of acetylene in a fixed bed, has low cost, no mercury pollution, simple and expandable preparation method and great potential industrial application value. At a ruthenium loading of 0.3%, the space velocity of the reaction gas was 170h ‑1 ，V (C2H2) /V (HCl) The conversion rate of acetylene can reach 93.2% and the selectivity of chloroethylene is more than 99% under the condition that the reaction temperature is 180 ℃ and the ratio is=1:1.15.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and application, and particularly relates to a method for preparing vinyl chloride by hydrochlorination of acetylene in a fixed bed by using a low-content ruthenium-based catalyst.
Background
Polyvinyl chloride (PVC) is a polymer formed by polymerization of Vinyl Chloride Monomer (VCM), and has been widely used in construction materials, industrial products, daily necessities, flooring, packaging films, foaming materials, and the like. The calcium carbide process is one main method of producing vinyl chloride monomer in China, and is determined by the energy source structure features of rich coal, lean oil and less gas. The traditional acetylene hydrochlorination process is to load HgCl with active carbon 2 As a catalyst. Mercury, however, has a strong volatility and toxicity and is easily harmful to the environment and human health. Since 2013, 140 countries have signed the "mercury in water convention" and called for global mercury control in 2025. Therefore, the development of a novel mercury-free catalyst with low cost, high activity and high stability has become the most urgent and difficult task in the vinyl chloride industry.
In recent decades, a series of mercury-free catalysts have been studied for acetylene hydrochlorination activity, which can be divided into three main categories: noble metal catalysts, non-noble metal catalysts, and metal-free catalysts. At present, noble metal catalysts are mainly focused on the research and development of gold-based and ruthenium-based catalysts. Hutching et al found that there was a more pronounced positive correlation between metal ion catalytic activity and the corresponding standard electrode potential, and predicted that Au had higher catalytic performance. Furthermore, hutching (J.Am. Chem. Soc.2015,137, 14548-14557) developed Na 3 Au(S 2 O 3 ) 2 Supported catalysts (Au loading 0.1 wt%) and commercial production of the catalysts was achieved with Johonson-Mattey. The factory line of the catalyst also reaches the yield of 1000kgVCM/kg catalyst, the test time is more than 4500h, and the conversion rate is always maintained to be more than 90 percentThe selectivity is more than 99%. From the reaction process perspective, the Au-based catalyst can be used as an excellent choice for replacing mercury catalyst, provides a feasible scheme and has potential application value.
Although gold-based catalysts exhibit excellent catalytic activity and stability, there are still significant problems such as: high cost, scarce reserves, great recovery difficulty and the like. Ruthenium-based catalysts are low in cost, green and efficient, and have become a research hotspot for scientific researchers in recent years. A supported ruthenium complex catalyst (0.3% ruthenium loading) was invented as in patent NC 107803222. A. The catalyst is prepared by compounding polypyridine compound with ruthenium, adding metal auxiliary agent and ionic liquid for stabilizing active components, and the catalyst has a temperature of 160deg.C, a pressure of 0.1MPa, and a ratio of V (HCl)/V (C) 2 H 2 ) =1.0/1, acetylene space velocity 50h -1 . In the initial stage of the reaction, the conversion rate of acetylene is 99.5%, and the selectivity of chloroethylene is 99.94%. It can be seen that the addition of the complex and the ionic liquid is favorable for improving the stability of the ruthenium-based catalyst, reducing the load of ruthenium and saving the cost, but the process is too complex and the acetylene airspeed is lower.
The invention discloses a low-content ruthenium-based catalyst for hydrochlorination of acetylene, which takes oxalic acid as an auxiliary agent, the loading of ruthenium is 0.25wt%, and the loading of ruthenium is V (HCl)/V (C) 2 H 2 )＝1.15，T＝170℃，GHSV(C 2 H 2 )＝180h -1 Performance test experiments were performed under the conditions. As a result of the test, it was found that the acetylene conversion of 0.25% Ru/AC was 58.8%, and the activity of all the ruthenium-based catalysts modified by oxalic acid was higher than that of the 0.25% Ru/AC catalysts, wherein the 0.25% Ru-15/AC catalysts exhibited the best performance, and the acetylene conversion was 80.9%, which was 22.1% higher than that of the unmodified catalysts, 0.25 Ru/AC. The catalyst has lower content, effectively saves cost, but has lower space velocity and slightly lower acetylene conversion rate.
Patent CN 113058594A discloses a ruthenium-based catalyst obtained by wrapping a precursor with polymers such as polydopamine and polyethyleneimine and calcining at 100-300 ℃. The catalyst loading was 1wt%, C at t=180℃ 2 H 2 (GHSV)＝180h -1 、 C 2 H 2 Under the reaction condition of/HCl=1:1.15, the conversion rate of acetylene reaches 98.17%, the selectivity reaches 99.74%, and the catalyst contains Ru-N structure, so that the active component Ru in the catalyst is more stable and is not easy to run off. However, the catalyst has higher ruthenium loading and higher cost.
Disclosure of Invention
The invention solves the technical problems that: a method for preparing chloroethylene by hydrochlorination of acetylene in a fixed bed by using a low-content ruthenium-based catalyst is provided. The invention uses an incipient wetness impregnation method to prepare a catalyst with low ruthenium content, high activity and better stability by adding ligand 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, preparing the molar ratio of the ligand to ruthenium to be 4:1, stirring for 5 hours and the like, wherein the loading amount of ruthenium is 0.3 percent at the space velocity of the reaction gas of 170 hours -1 ， V (C2H2) /V (HCl) The acetylene conversion rate can reach 93.2% and the vinyl chloride selectivity is more than 99% at the reaction temperature of 180 ℃ in the range of 1:1.15, so that a unique and effective solution is provided for the industrial low-cost and high-efficiency production of vinyl chloride.
In order to solve the technical problems of the invention, the technical proposal is as follows: a method for preparing chloroethylene by hydrochlorination of acetylene in a fixed bed by using a low-content ruthenium-based catalyst comprises the following steps:
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor, ru:2.6935mg/ml;
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 Dispersing in O, magnetic stirring at room temperature for 350rpm, adding 60mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, stirring at room temperature, covering the beaker with a sealing film, covering with tinfoil, and stirring at room temperature for 350rpm for 5h;
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of active carbon in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) Drying the ground catalyst in a blast drying oven for 12-24 hours;
(5) The prepared ruthenium-based catalyst is used for the reaction of preparing chloroethylene by hydrochlorination of acetylene in a fixed bed.
Preferably, step (1) uses distilled water as a solvent, and an appropriate amount of ruthenium trichloride (RuCl) is added at room temperature 3 More than or equal to 99 percent) of solid is dissolved in distilled water, is oscillated for 10 minutes by a mixer, is treated by ultrasonic for 30 minutes and is prepared into RuCl 3 2.69356mg/ml of the mother liquor of (C), and sealing, shading and preserving at low temperature.
Preferably, the ligand in step (2) is 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride.
Preferably, the ligand is reacted with the ruthenium precursor in step (2) for a period of 5 hours.
Preferably, the molar ratio of ligand to ruthenium in step (2) is 4:1.
Preferably, in the step (3), one of wood activated carbon, coconut activated carbon and coal activated carbon is not pretreated.
Preferably, in the step (3), the activated carbon is columnar, powdery or flaky, has a particle size of 200 meshes, and has a specific surface area of 800-1500, preferably 1200-1500.
Preferably, the ratio of the impregnating solution to the carrier is adjusted: the carrier and RuCl in the step (3) 3 The solution should be guaranteed to be in the ratio of carrier/g: solution/ml = 0.5.
Preferably, the catalyst after grinding in step (3) should ensure a smooth surface, and then dried in a blow drying oven at 90 ℃.
Preferably, the step (5) is specifically as follows:
(1) Filling a catalyst: a layer of quartz cotton with the thickness of 10mm is padded at the middle position of a quartz reaction tube with the diameter of 10mm, a catalyst is added into the reaction tube, the catalyst is ensured to be smooth, and then a layer of quartz cotton with the thickness of 10mm is padded;
(2) Before the reaction: the whole pipeline is treated with 20mL min -1 N of (2) 2 Purging the flow for 60min to remove the systemSimultaneously controlling the temperature of the air and the moisture in the system, raising the temperature to 150 ℃ at 5 ℃/min and keeping the temperature for 30min, and raising the temperature to 180 ℃ at 5 ℃/min; then, hydrogen chloride was introduced at a flow rate of v=20 mL/min and maintained for 30min, followed by V (C 2 H 2 ) The reaction gas is introduced at a flow rate of (16 mL/min) =16.8 mL/min and maintained for 10min, so that the catalyst is ensured to be in the gas atmosphere of acetylene and hydrogen chloride, and then the catalyst is treated with V (C 2 H 2 ) The reaction gas flow rate was reduced by a ratio of/V (HCl) =1:1.15, and detection was started after holding at the reaction flow rate for ten minutes;
(3) After the reaction: the gas phase product was first passed through an absorber flask containing NaOH solution to remove excess HCl and then analyzed on-line by gas chromatography (GC-9790 ii) to evaluate acetylene conversion and selectivity to VCM.
The beneficial effects of the invention are as follows:
the invention provides a preparation method of a low-content ruthenium-based catalyst, which greatly reduces the preparation cost, and has simpler operation and expansion compared with other methods. The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method has the advantages that 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride is used as a ligand, the reaction time and the molar ratio of the ligand to ruthenium are changed, water is selected as a solvent, the ratio between the solvent and a carrier is determined, the Ru content in the catalyst is greatly reduced, and the prepared low-content ruthenium-based catalyst is low. The production cost is effectively saved; the catalyst prepared by the method has excellent catalytic performance on acetylene hydrochlorination reaction and has potential industrial application value.
(1) Specifically, the invention provides a ruthenium complex catalyst for hydrochlorination of acetylene, which takes active carbon as a catalyst carrier and loads RuCl 3 And a ligand. Screening the ligand 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, tetrabutylammonium chloride, pyridine carboxylic acid, vitamin b1, ethylenediamine tetraacetic acid, 1, 3-bis (2, 4, 6-trimethylphenyl) imidazolium chloride in the step (2) through a plurality of experiments; the ligand is preferably 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride
(2) Ligands for use in the present invention: 1, 3-bis (2, 4, 6-trimethylphenyl) imidazolium chloride is selected as the ligand. Under the same conditions, the ligand can stabilize the electronic environment of the high-valence ruthenium so as to stabilize the active center, and meanwhile, the dispersion of the ruthenium can be improved, the catalytic activity can be improved, and the deactivation rate can be reduced. Compared with the prior art: firstly, the ligand selected in the invention is nontoxic and harmless, and has low price; secondly, the ligand in the invention has less usage and lower cost; in addition, the invention has simple operation, green and environment-friendly performance and reduces energy consumption. In a word, the method of the invention obviously improves the catalytic activity and stability of the catalyst by adding the ligand, and the synthetic method in the technology can show excellent catalytic activity and has potential industrial application value.
(3) In the step (2), the reaction time of the ligand and ruthenium is kept to be 5 hours, and the ruthenium complex is obtained, and compared with the catalyst matched with 1 hour, 3 hours and 7 hours, the catalyst has better performance.
(4) In step (2) of the present invention, the molar ratio of ligand to ruthenium is maintained at 4:1, a ruthenium complex is obtained, and the performance of the catalyst is better than that of the catalyst compounded by 1:1, 2:1, 3:1 and 5:1.
(5) In step (3) of the present invention, the catalyst was ground to be smooth in the clockwise direction within 10min, and then dried in a blow drying oven at 90 ℃. Grinding to smooth in a short time can reduce the contact between the catalyst and air at normal temperature and improve the loading rate and dispersity of the active components.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a plot of acetylene conversion versus reaction time for different ligand catalysts.
FIG. 2 is a plot of selectivity versus reaction time for different ligand catalysts.
FIG. 3 is a graph of acetylene conversion versus reaction time for catalysts having different molar ratios of ruthenium to ligand.
FIG. 4 is a plot of selectivity versus reaction time for catalysts having different molar ratios of ruthenium to ligand.
FIG. 5 is a graph of acetylene conversion versus reaction time for a ligand versus ruthenium catalyst at different reaction times.
FIG. 6 is a plot of ligand selectivity versus reaction time for different reaction time catalysts for ruthenium.
Detailed Description
Example 1 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 48mg of tetrabutylammonium chloride was added and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N1/AC (H 2 O)。
(5) The low-content ruthenium-based catalyst is used for the reaction of preparing chloroethylene by hydrochlorination of acetylene in a fixed bed, and comprises the following steps:
1. filling a catalyst: a layer of quartz cotton with the thickness of 10mm is padded at the middle position of a quartz reaction tube with the diameter of 10mm, 500mg of catalyst is added into the reaction tube, the catalyst is ensured to be smooth, and then a layer of quartz cotton with the thickness of 10mm is padded;
2. before the reaction: the whole pipeline is treated with 20mL min -1 N of (2) 2 Purging at a flow rate of 60min to remove air and moisture from the system while controlling the temperature to rise to 150 ℃ at 5 ℃/min and hold for 30min, and then to rise to 180 ℃ at 5 ℃/min; then, hydrogen chloride was introduced at a flow rate of v=20 mL/min and maintained for 30min, followed by V (C 2 H 2 ) The reaction gas is introduced at a flow rate of (HCl) =16.8 mL/min and maintained for 10min, so that the catalysis is ensuredThe agent is in the atmosphere of acetylene, hydrogen chloride, then in V (C 2 H 2 ) The reaction gas flow rate was reduced by a ratio of/V (HCl) =1:1.15, and detection was started after holding at the reaction flow rate for ten minutes;
3. after the reaction: the gas phase product was first passed through an absorber flask containing NaOH solution to remove excess HCl and then analyzed on-line by gas chromatography (GC-9790 ii) to evaluate acetylene conversion and selectivity to VCM.
Example 2 catalyst preparation
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, 42mg of ethylenediamine tetraacetic acid was then added and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N2/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Comparative example 3 catalyst preparation
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 18mg of 2-picolinic acid was added and stirred at room temperature, the beaker was covered with a sealing film and covered with tinfoil and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of coconut shell powder active carbon in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is placed in a blast drying oven to be dried for 12-24 hours.
The catalyst was named catalyst 0.3% Ru-N3/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Example 4 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 60mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (200 meshes, specific surface area about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4/AC.
(5) The low-content ruthenium-based catalyst is used for the reaction of preparing chloroethylene by hydrochlorination of acetylene in a fixed bed, and comprises the following steps:
1. filling a catalyst: a layer of quartz cotton with the thickness of 10mm is padded at the middle position of a quartz reaction tube with the diameter of 10mm, 500mg of catalyst is added into the reaction tube, the catalyst is ensured to be smooth, and then a layer of quartz cotton with the thickness of 10mm is padded;
2. before the reaction: the whole pipeline is treated with 20mL min -1 N of (2) 2 Purging the system at a flow rate for 60 minutes to remove air and moisture from the system while controllingHeating to 150deg.C at 5deg.C/min, maintaining for 30min, and heating to 180deg.C at 5deg.C/min; then, hydrogen chloride was introduced at a flow rate of v=20 mL/min and maintained for 30min, followed by V (C 2 H 2 ) The reaction gas is introduced at a flow rate of (16 mL/min) =16.8 mL/min and maintained for 10min, so that the catalyst is ensured to be in the gas atmosphere of acetylene and hydrogen chloride, and then the catalyst is treated with V (C 2 H 2 ) The reaction gas flow rate was reduced by a ratio of/V (HCl) =1:1.15, and detection was started after holding at the reaction flow rate for ten minutes;
3. after the reaction: the gas phase product was first passed through an absorber flask containing NaOH solution to remove excess HCl and then analyzed on-line by gas chromatography (GC-9790 ii) to evaluate acetylene conversion and selectivity to VCM.
Example 4-1 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 60mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 1 hour.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4-1 h/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Example 4-2 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 60mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 3 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4-3 h/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Example 4-3 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 60mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 7 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4-7 h/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Examples 4-4 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 15mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4- (1:1)/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Examples 4-5 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/m)l)。
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 30.27mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4- (1:2)/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Examples 4-6 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 45.41mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4- (1:3)/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Examples 4-7 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 75.68mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4- (1:5)/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Examples 4-8 catalyst preparation
(1) Preparing a precursor solution: 0.2764g of ruthenium trichloride (RuCl) was first weighed out 3 More than or equal to 99 percent) solid is dissolved in 10ml distilled water, oscillated and sonicated, and fixed-volume is put into a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O, magnetic stirrer (350 rpm) at room temperature, then 60mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperatureThe beaker was covered with a sealing film, covered with a tinfoil, and stirred (350 rpm) at room temperature for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N4/AC. Times. -II.
(5) The low-content ruthenium-based catalyst is used for the reaction of preparing chloroethylene by hydrochlorination of acetylene in a fixed bed, and comprises the following steps:
1. filling a catalyst: a layer of quartz cotton with the thickness of 10mm is padded at the middle position of a quartz reaction tube with the diameter of 10mm, 1.00g of catalyst is added into the reaction tube, the catalyst is ensured to be smooth, and then a layer of quartz cotton with the thickness of 10mm is padded;
2. before the reaction: the whole pipeline is treated with 20mL min -1 N of (2) 2 Purging at a flow rate of 60min to remove air and moisture from the system while controlling the temperature to rise to 150 ℃ at 5 ℃/min and hold for 30min, and then to rise to 180 ℃ at 5 ℃/min; then, hydrogen chloride was introduced at a flow rate of v=20 mL/min and maintained for 30min, followed by V (C 2 H 2 ) The reaction gas is introduced at a flow rate of (16 mL/min) =16.8 mL/min and maintained for 10min, so that the catalyst is ensured to be in the gas atmosphere of acetylene and hydrogen chloride, and then the catalyst is treated with V (C 2 H 2 ) The reaction gas flow rate was reduced by a ratio of/V (HCl) =1:1.15, and detection was started after holding at the reaction flow rate for ten minutes;
3. after the reaction: the gas phase product was first passed through an absorber flask containing NaOH solution to remove excess HCl and then analyzed on-line by gas chromatography (GC-9790 ii) to evaluate acetylene conversion and selectivity to VCM.
Example 5 catalyst preparation
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O, magnetic stirrer (350 rpm) at room temperature,then 48mg of Vb1 was added and stirred at room temperature, the beaker was covered with a sealing film, covered with a tinfoil and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N5/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Example 6 catalyst preparation
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O was dispersed in a magnetic stirrer (350 rpm) at room temperature, then 49mg of 1, 3-bis (2, 4, 6-trimethylphenyl) imidazolium chloride was added and stirred at room temperature, the beaker was covered with a sealing film and covered with a tinfoil, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours.
The catalyst was named 0.3% Ru-N6/AC.
The procedure for the preparation of vinyl chloride by hydrochlorination of acetylene on a fixed bed with a low ruthenium-based catalyst is the same as in example 1 and will not be described again.
Comparative example 1 catalyst preparation
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 O, magnetic stirrer (350 rpm) at room temperature, cover the beaker with sealing filmThen, the mixture was covered with tinfoil and stirred (350 rpm) at room temperature for 5 hours.
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of powdered coconut activated carbon (> 200 mesh with specific surface area of about 1200) in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) The catalyst after grinding is dried in a blast drying oven at 90 ℃ for 12-24 hours. The catalyst was named 0.3% ru/AC.
TABLE 1 test of hydrochlorination Activity of acetylene
TABLE 2 stability test of hydrochlorination of acetylene
The invention is not limited to the specific technical scheme described in the above embodiments, and all technical schemes formed by adopting equivalent substitution are the protection scope of the invention.
Claims (7)
1. A method for preparing chloroethylene by hydrochlorination of acetylene in a fixed bed by using a low-content ruthenium-based catalyst is characterized by comprising the following steps of:
(1) Preparing a precursor solution: firstly, 0.2764g of ruthenium trichloride solid is weighed and dissolved in 10ml of distilled water, and then the mixture is oscillated and sonicated, and the volume is fixed in a 50ml brown round bottom flask, thus obtaining RuCl 3 Mother liquor, ru:2.6935mg/ml;
(2) 1.37ml of mother liquor was dissolved in 1ml of H 2 Dispersing in O, magnetically stirring at room temperature350rpm of a stirrer, then 60mg of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride is added, stirring is carried out at room temperature, the beaker is covered by a sealing film and covered by tinfoil paper, and stirring is carried out at room temperature for 350rpm for 5 hours;
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of active carbon in a mortar; uniformly dripping the solution prepared in the step (2) onto an active carbon carrier, and fully grinding a catalyst in a clockwise direction until the surface is smooth, wherein ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70;
(4) Drying the ground catalyst in a blast drying oven for 12-24 hours;
(5) The prepared ruthenium-based catalyst is used for the reaction of preparing chloroethylene by hydrochlorination of acetylene in a fixed bed.
2. The method for preparing chloroethylene by hydrochlorination of acetylene with a fixed bed, which is characterized in that the low content ruthenium-based catalyst according to claim 1 is used for the reaction: step (1) using distilled water as a solvent, dissolving a proper amount of ruthenium trichloride solid in distilled water at room temperature, oscillating for 10min by using a mixer, and performing ultrasonic treatment for 30min to prepare RuCl 3 2.69356mg/ml of the mother liquor of (C), and sealing, shading and preserving at low temperature.
3. The method for preparing chloroethylene by hydrochlorination of acetylene with a fixed bed by using a low content ruthenium-based catalyst according to claim 1, wherein in the step (3), one of wood activated carbon, coconut activated carbon and coal activated carbon is not pretreated.
4. The method for preparing vinyl chloride by hydrochlorination of acetylene with a fixed bed according to claim 1, wherein in the step (3), the activated carbon is columnar, powdery or flaky, and has a particle size of 200 meshes and a specific surface area of 800-1500.
5. The method for preparing vinyl chloride by hydrochlorination of acetylene with a fixed bed according to claim 4, wherein in the step (3), the activated carbon is columnar, powdery or flaky, and has a particle size of 200 meshes and a specific surface area of 1200-1500.
6. The method for preparing vinyl chloride by hydrochlorination of acetylene with a fixed bed according to claim 1, wherein the catalyst ground in the step (3) is smooth, and is dried in a blast drying oven at 90 ℃.
7. The method for preparing chloroethylene by hydrochlorination of acetylene with a fixed bed by using a ruthenium-based catalyst with a low content according to claim 1, wherein: the step (5) is specifically as follows:
(1) Filling a catalyst: a layer of quartz cotton with the thickness of 10mm is padded at the middle position of a quartz reaction tube with the diameter of 10mm, a catalyst is added into the reaction tube, the catalyst is ensured to be smooth, and then a layer of quartz cotton with the thickness of 10mm is padded;
(2) Before the reaction: n of the whole pipeline at 20mL/min 2 Purging at a flow rate of 60min to remove air and moisture from the system while controlling the temperature to rise to 150 ℃ at 5 ℃/min and hold for 30min, and then to rise to 180 ℃ at 5 ℃/min; then, hydrogen chloride was introduced at a flow rate of v=20 mL/min and maintained for 30min, followed by V (C 2 H 2 ) The reaction gas is introduced at a flow rate of (16 mL/min) =16.8 mL/min and maintained for 10min, so that the catalyst is ensured to be in the gas atmosphere of acetylene and hydrogen chloride, and then the catalyst is treated with V (C 2 H 2 ) The reaction gas flow rate was reduced by a ratio of/V (HCl) =1:1.15, and detection was started after holding at the reaction flow rate for ten minutes;
(3) After the reaction: the gas phase product was first passed through an absorber flask containing NaOH solution to remove excess HCl, and then analyzed on-line by gas chromatography to evaluate acetylene conversion and selectivity to VCM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211270243.8A CN115626863B (en) | 2022-10-18 | 2022-10-18 | Method for preparing chloroethylene by hydrochlorination of acetylene in fixed bed by using low-content ruthenium-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211270243.8A CN115626863B (en) | 2022-10-18 | 2022-10-18 | Method for preparing chloroethylene by hydrochlorination of acetylene in fixed bed by using low-content ruthenium-based catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115626863A CN115626863A (en) | 2023-01-20 |
| CN115626863B true CN115626863B (en) | 2023-06-23 |
Family
ID=84906029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211270243.8A Active CN115626863B (en) | 2022-10-18 | 2022-10-18 | Method for preparing chloroethylene by hydrochlorination of acetylene in fixed bed by using low-content ruthenium-based catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115626863B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716528A (en) * | 2009-10-30 | 2010-06-02 | 于志勇 | Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof |
| WO2012113778A1 (en) * | 2011-02-24 | 2012-08-30 | Solvay Sa | Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN104936933A (en) * | 2012-12-19 | 2015-09-23 | 索尔维公司 | Process for the hydrohalogenation of an unsaturated hydrocarbon |
| CN109422620A (en) * | 2017-08-25 | 2019-03-05 | 浙江工业大学 | A kind of alkynes high-selectivity reduction at Z- type alkene method |
| CN110614093A (en) * | 2019-09-06 | 2019-12-27 | 内蒙古大学 | Preparation method of low-content gold and ruthenium bimetallic catalyst for acetylene hydrochlorination |
-
2022
- 2022-10-18 CN CN202211270243.8A patent/CN115626863B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716528A (en) * | 2009-10-30 | 2010-06-02 | 于志勇 | Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof |
| WO2012113778A1 (en) * | 2011-02-24 | 2012-08-30 | Solvay Sa | Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN103391911A (en) * | 2011-02-24 | 2013-11-13 | 索维公司 | Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN107417487A (en) * | 2011-02-24 | 2017-12-01 | 索维公司 | Method for hydrohalogenation alkynes and for manufacturing chlorination alkene by the hydrochlorination of alkynes |
| CN104936933A (en) * | 2012-12-19 | 2015-09-23 | 索尔维公司 | Process for the hydrohalogenation of an unsaturated hydrocarbon |
| CN109422620A (en) * | 2017-08-25 | 2019-03-05 | 浙江工业大学 | A kind of alkynes high-selectivity reduction at Z- type alkene method |
| CN110614093A (en) * | 2019-09-06 | 2019-12-27 | 内蒙古大学 | Preparation method of low-content gold and ruthenium bimetallic catalyst for acetylene hydrochlorination |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115626863A (en) | 2023-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107803222A (en) | A kind of catalyzed by ruthenium complexes agent for acetylene hydrochlorination reaction | |
| CN110743613B (en) | Supported metal catalyst and preparation method and application thereof | |
| CN107803225B (en) | Ruthenium catalyst for producing vinyl chloride and preparation method thereof | |
| CN113070061B (en) | Rare earth element doped monatomic catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof | |
| CN105036289B (en) | Method for degrading high-concentration unsym-dimethylhydrazine wastewater | |
| CN110743619B (en) | Supported ionic liquid catalyst and preparation method and application thereof | |
| CN107744836A (en) | A kind of preparation method and applications of load-type ion liquid catalyst | |
| CN111151294B (en) | Peroxide catalytic oxidation catalyst and method for treating propylene oxide and styrene co-production wastewater by using same | |
| CN106861758A (en) | A kind of preparation method of the MOF catalyst for PHOTOCATALYTIC AIR-PURIFYING | |
| CN107456990B (en) | High-dispersity ruthenium-based catalyst for acetylene hydrochlorination and preparation method thereof | |
| CN110743616B (en) | Environment-friendly acetylene hydrochlorination catalyst and preparation method thereof | |
| CN111644210B (en) | Application of composite carrier ruthenium-based catalyst in acetylene hydrochlorination | |
| CN110743617B (en) | Graphite alkynyl composite material catalyst and preparation method and application thereof | |
| CN113713841B (en) | Acetylene copper chloride-based catalyst and preparation method and application thereof | |
| CN115626863B (en) | Method for preparing chloroethylene by hydrochlorination of acetylene in fixed bed by using low-content ruthenium-based catalyst | |
| CN110743614A (en) | High-dispersion catalyst for vinyl chloride synthesis and preparation method and application thereof | |
| CN107715914A (en) | The ruthenium catalyst and its application in unsaturated hydrocarbons hydrogenates halogenation that a kind of supported sulfided ionic liquid promotes | |
| CN113680355A (en) | Preparation method and application of copper-containing catalyst for hydrochlorination of alkyne | |
| US20230381747A1 (en) | Method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material | |
| CN115155573B (en) | Method for preparing vinyl chloride by hydrochlorination of acetylene in fixed bed by using ultralow-content gold-based catalyst modified by nitrogen and sulfur | |
| CN110743615B (en) | Multi-component metal catalyst for synthesizing vinyl chloride monomer and preparation method thereof | |
| CN113145175B (en) | Preparation method and application of catalyst with pyridine copper chloride as active component | |
| CN115501732B (en) | Porous liquid with small molecular gas adsorption function, preparation method thereof, method for removing small molecular gas by using porous liquid and application of porous liquid | |
| CN111250117B (en) | Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in catalyzing acetylene hydrochlorination reaction | |
| CN113634280A (en) | Preparation method of carbon-supported gold-based mercury-free catalyst for acetylene hydrochlorination |
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 |