Method for preparing ruthenium-based catalyst by utilizing sectional type continuous flow technology and applying ruthenium-based catalyst to reaction for preparing vinyl chloride by acetylene hydrochlorination

Abstract

The invention belongs to the technical field of continuous flow preparation of catalysts, and particularly relates to a method for preparing a ruthenium-based catalyst by using a sectional continuous flow technology in a reaction for preparing vinyl chloride through acetylene hydrochlorination. According to the catalyst, activated carbon is used as a carrier, ruthenium is used as a main active component, water is used as a solvent, a sectional type continuous flow technology is utilized, the dispersity of Ru species is accurately regulated and controlled by adjusting the gas flow rate, the high-dispersion and high-activity ruthenium-based catalyst is prepared, and the catalytic performance is optimized while the production efficiency of the catalyst is improved. Meanwhile, by adopting a sectional type continuous flow preparation method, automatic continuous production is realized, the reaction flow rate can be accurately controlled, materials can be uniformly mixed, personal errors are reduced, and the method has remarkable industrial application potential.

Description

Technical Field

[0001] The present invention belongs to the technical field of continuous flow preparation of catalysts, and specifically relates to a method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride by using segmented continuous flow technology. The catalyst uses activated carbon as a carrier, ruthenium as a main active component, and water as a solvent. The segmented continuous flow technology is used to achieve precise control of the dispersion of Ru species by adjusting the gas flow rate, thereby preparing a highly dispersed and highly active ruthenium-based catalyst, which improves the production efficiency of the catalyst and optimizes the catalytic performance. At the same time, the segmented continuous flow preparation method not only realizes automated continuous production, but also can accurately control the reaction flow rate, evenly mix materials, and reduce human errors, and has significant industrial application potential. Background Art

[0002] As a new reaction technology, the continuous flow reactor aims to enhance the continuity of chemical reactions. The reaction takes place in a narrow channel with an inner diameter of micrometers to millimeters. Continuous flow technology has the characteristics of high mass and heat transfer efficiency, precise control of reaction parameters, good reaction repeatability, and high degree of integrated automation. It has received extensive attention in recent years. At present, it is mainly used in the fields of organic synthesis, preparation of nanomaterials and nanoparticles, etc., providing an efficient and stable reaction platform for scientific research and industrial production.

[0003] Polyvinyl chloride (PVC) is a general-purpose plastic made from vinyl chloride monomer (VCM), which is widely used in construction, medical equipment, electronic products, transportation facilities and other industries. The main processes for preparing VCM are acetylene hydrochlorination, ethylene oxychlorination and ethane method. Based on my country's energy structure of rich coal and poor oil, my country mainly uses acetylene hydrochlorination to prepare VCM monomer. At present, the industrial application of acetylene hydrochlorination is highly dependent on mercuric chloride (HgCl 2 / AC) catalyst. However, HgCl 2 It has the disadvantages of being highly toxic and easy to sublimate, which seriously pollutes the environment and endangers human health, and global mercury resources are scarce. In 2013, the United Nations adopted the Minamata Convention, which aims to control and reduce global mercury emissions. Therefore, the development of a new, green, and efficient mercury-free catalyst is the key to achieving green and sustainable development in the polyvinyl chloride industry in my country. There are three main types of mercury-free catalysts reported in the literature. The first type is precious metal catalysts represented by gold, ruthenium, and palladium; the second type is non-precious metal catalysts represented by copper and bismuth; the third type is non-metal catalysts represented by heteroatom-doped carbon materials.

[0004] Among the many mercury-free catalysts, precious metal catalysts are considered to be potential alternatives to mercury-based catalysts due to their high activity and stability. In the laboratory research and development stage, the incipient wetness impregnation method (IWI) is mainly used to synthesize ruthenium-based catalysts in small batches. However, in the industrial production process, intermittent reactors are usually used to synthesize ruthenium-based catalysts in large quantities, which will lead to uneven mixing and thus affect the catalyst performance. In addition, the dispersion of Ru species determines the number of active sites and is an important factor affecting the activity of the catalyst. Therefore, a simple, easy to scale-up, and multi-site high-activity catalyst synthesis method will help realize the industrial application of mercury-free catalysts. Summary of the invention

[0005] The present invention provides a method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride using a segmented continuous flow technology. The segmented continuous flow method is used to precisely control the dispersion of Ru species by changing the gas flow rate, thereby preparing a highly active ruthenium-based catalyst in a simple and efficient manner. -1 ,V(C 2 H 2 ) / V(HCl)=1:1.05, under the condition of reaction temperature of 180℃, the acetylene conversion rate reached 86.0%, VCM selectivity was greater than 99.9%, and each segmented continuous flow device could produce 144 g / d of ruthenium-based catalyst.

[0006] In order to solve the technical problem of the present invention, a technical solution is proposed: a method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride using a segmented continuous flow technology, comprising the following steps:

[0007] A ruthenium-based catalyst is prepared using a segmented continuous flow device: the segmented continuous flow device is composed of a peristaltic pump (5), a nitrogen bottle (7), a gas flow meter (8), a magnetic stirrer (1), a polytetrafluoroethylene tee (6), a polytetrafluoroethylene pipeline (4) and a collection device (10);

[0008] The inlet pipeline of the peristaltic pump (5) is respectively introduced into the two containers (2) and (3), and the outlet pipeline of the peristaltic pump (5) is connected to the two end interfaces of the polytetrafluoroethylene tee (6), and the lower interface of the polytetrafluoroethylene tee (6) is connected to the polytetrafluoroethylene pipeline; the pipeline and the gas flowing through the flow meter (8) merge at the second tee to form a stable gas-liquid segmented flow; the lower interface of the second tee is connected to a section of polytetrafluoroethylene pipeline, and the pipeline is fixed on the pipeline bracket (9); the outlet end of the polytetrafluoroethylene pipeline is fixed above the collecting device (10) to collect the mixed liquid;

[0009] (1) Preparation of RuCl3 Mother solution: weigh 0.6700 g of ruthenium trichloride (RuCl 3 ) solid was dissolved in 10 mL of distilled water, shaken, and ultrasonicated to make RuCl 3 Completely dissolved; then it was diluted to a 50 mL brown round-bottom flask to obtain RuCl 3 Mother solution, Ru: 13.4 mg / mL;

[0010] (2) Weigh 2970 mg of activated carbon into a container, add an appropriate amount of distilled water and ultrasonically disperse to obtain an activated carbon slurry; take an appropriate amount of RuCl 3 The mother liquor is added to another container, and an appropriate volume of distilled water is added to disperse the mother liquor to obtain a ruthenium precursor solution. The volume ratio of distilled water used in preparing the activated carbon slurry and the ruthenium precursor solution in steps (1) and (2) is 2:1, and the activated carbon is wood activated carbon.

[0011] (3) placing the containers containing the activated carbon slurry and the ruthenium precursor solution in step (2) under the peristaltic pump (5) respectively, sucking the pipe through the peristaltic pump (5) and mixing at the first tee; after flowing through a section of polytetrafluoroethylene pipe, merging with the gas flowing through the gas flow meter (8) at the second tee to form a stable gas-liquid diversion section; connecting the lower interface of the second tee to a section of polytetrafluoroethylene pipe, waiting for a period of time, and collecting with a collecting device; the flow rate ratio of the activated carbon slurry, the ruthenium precursor solution and the nitrogen in the preparation process of the segmented continuous flow technology is 2:1:7;

[0012] (4) filtering the collected solid-liquid mixture with a positive pressure filter, and finally drying it in a forced air drying oven for 12-24 hours, wherein the mass ratio of ruthenium to activated carbon in the catalyst is 0.1-1:99-99.9;

[0013] (5) The prepared ruthenium-based catalyst is used in the acetylene hydrochlorination reaction to produce vinyl chloride.

[0014] Preferably, the catalyst is prepared as follows: 2970 mg activated carbon (AC 1 , wood activated carbon, specific surface area SBET = 1078 m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively. The flow rates of the activated carbon slurry and the ruthenium precursor solution were set to 2 mL / min and 1 mL / min, respectively. The peristaltic pump switch was started at the same time. The activated carbon slurry and the ruthenium precursor solution were mixed at the first tee. After flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with N at a flow rate of 7 mL / min. 2 The gases were mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst was obtained. After separation by positive pressure filtration, it was placed in a culture dish. Finally, the culture dish was placed in a 90°C forced air drying oven and dried for 12 hours. After drying, it was sealed and stored. The mass ratio of ruthenium to activated carbon in the catalyst was 1:99, and the catalyst was named 1%Ru / AC 1 -SMF 7 .

[0015] Preferably, step (1) uses distilled water as a solvent, and an appropriate amount of ruthenium trichloride (RuCl 3 ≥ 99%) solid was dissolved in distilled water, shaken for 10 min using a mixer, and then ultrasonicated for 30 min to prepare RuCl 3 The mother solution (Ru: 13.4 mg / mL) was sealed and stored in a light-proof and low-temperature place.

[0016] Preferably, the gas in step (3) is N 2 ; The filtering method of the solid-liquid mixture in step (4) is positive pressure filtration.

[0017] Preferably, the container and the collecting device are beakers, the polytetrafluoroethylene pipe connected to the lower interface of the second tee is circularly wound, and this section of polytetrafluoroethylene pipe is fixed on the pipe bracket.

[0018] Preferably, the acetylene hydrochlorination to vinyl chloride reaction in step (5) comprises the following specific steps:

[0019] (1) Catalyst loading: Place a layer of quartz wool with a thickness of 10 mm in the middle of a quartz reaction tube with a diameter of 10 mm, add a certain amount of catalyst into the reaction tube and ensure that the catalyst is flat, and then place another layer of quartz wool with a thickness of 10 mm;

[0020] (2) Before the reaction: N 2The entire pipeline was purged at a flow rate of 20 mL / min for 60 min to remove air and moisture in the reaction system. At the same time, the temperature was raised to 150 °C at 5 °C / min and maintained for 30 min, and then the temperature was further raised to 180 °C at 5 °C / min. Then, HCl gas was introduced at a flow rate of 20 mL / min and maintained for 30 min, and then V C2H2 =16mL / min, V HCl =16.8 mL / min flow rate of the reaction gas and maintain for 10 min to ensure that the catalyst is in the gas atmosphere of acetylene and hydrogen chloride, and then V C2H2 / V HCl =1:1.05 ratio to reduce the reaction gas flow rate, at V C2H2 =4 mL / min, V HCl =4.2 mL / min reaction flow rate, maintained for 10 min, and then began detection;

[0021] (3) After the reaction: The gaseous product first passed through an absorption bottle containing NaOH solution to remove excess HCl, and then was analyzed online by gas chromatography GC-9790Ⅱ to evaluate the acetylene conversion rate and VCM selectivity.

[0022] Beneficial effects of the present invention:

[0023] The present invention provides a segmented millifluidic flow method (SMF) for preparing ruthenium-based catalysts. Compared with the impregnation method, this method greatly reduces the preparation cost, improves production efficiency and catalytic performance, reduces human errors, is simpler and more efficient to operate, and can be produced continuously. Compared with the continuous continuous flow method, this method further enhances the mixing of ruthenium species and activated carbon in the droplets, reduces the deposition of activated carbon in the pipeline, uniformly mixes materials, and accurately controls the dispersion of ruthenium species on activated carbon. First, this method uses a millimeter-level pipe diameter, which greatly increases the contact area of ​​the reaction liquid, and can quickly transfer mass and heat to achieve uniform mixing of materials.

[0024] Secondly, this method screened different gas flow rates and determined the activated carbon slurry, ruthenium precursor solution, gas (N 2 ) was 2:1:7 mL / min, the ruthenium-based catalyst prepared by the segmented continuous flow method had the best catalytic effect, with a conversion rate of 86.0% and a VCM selectivity of more than 99.9% in the acetylene hydrochlorination reaction.

[0025] Finally, the automated operation of the segmented continuous flow device can avoid human errors, ensure product quality, and greatly improve production efficiency. Each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst. The present invention efficiently prepares ruthenium-based catalyst (1%Ru / AC 1 -SMF 7 ), significantly saving production costs, showing excellent catalytic performance in acetylene hydrochlorination reaction, and has the potential for industrial application.

[0026] As can be seen from Table 1, in Example 3, the catalyst 1%Ru / AC was prepared by a segmented continuous flow method using wood activated carbon as a carrier. 1 -SMF 7 , at a reaction temperature of 180°C, GHSV (C 2 H 2 ) = 340 h -1 Under the same conditions, the acetylene conversion rate reached 86.0%, and the VCM selectivity was higher than 99.9%, which was the best activity compared with other types of activated carbon. 1 -IWI acetylene conversion (80.7%) increased by 5.3% (e.g. Figure 2-4 as shown).

[0027] Depend on Figure 5 It can be seen that Examples 3, 18-20 prepared ruthenium-based catalysts with loading amounts of 1%, 0.5%, 0.3%, and 0.1%, indicating that the segmented continuous flow method can be used to prepare ruthenium-based catalysts with different loading amounts, and the catalyst with a loading amount of 1% prepared in Example 3 has the best activity. 1 -SMF 7 , at a reaction temperature of 180°C, industrial space velocity GHSV (C 2 H 2 ) = 60 h -1 Under these conditions, the acetylene conversion rate reached 92.2% and the VCM selectivity was higher than 99.9% (such as Figure 7-8 as shown). BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Schematic diagram of the segmented continuous flow device.

[0029] Including: magnetic stirrer-1, activated carbon slurry-2, precursor solution-3, polytetrafluoroethylene pipeline-4, peristaltic pump-5, polytetrafluoroethylene tee-6, nitrogen bottle-7, nitrogen flowmeter-8, pipeline bracket-9, collection device-10.

[0030] Figure 2 For the catalyst (Examples 1-5 and Comparative Example 1) at GHSV (C2 H 2 ) = 340 h -1 The relationship between reaction time and acetylene conversion under different conditions.

[0031] Figure 3 For the catalyst (Examples 1-5 and Comparative Example 1) at GHSV (C 2 H 2 ) = 340 h -1 Relationship between reaction time and VCM selectivity under different conditions.

[0032] Figure 4 For the catalyst (Examples 3, 7, 10, 13, 16 and Comparative Examples 1-5) at GHSV (C 2 H 2 ) = 340 h -1 Comparison of acetylene conversion under different conditions.

[0033] Figure 5 For the catalysts (Examples 3, 18-20) at GHSV (C 2 H 2 ) = 340 h -1 The relationship between reaction time and acetylene conversion under different conditions.

[0034] Figure 6 For the catalysts (Examples 3, 18-20) at GHSV (C 2 H 2 ) = 340 h -1 Relationship between reaction time and VCM selectivity under different conditions.

[0035] Figure 7 For the catalyst (Example 20) at GHSV (C 2 H 2 ) = 60 h -1 The relationship between reaction time and acetylene conversion under different conditions.

[0036] Figure 8 For the catalyst (Example 20) at GHSV (C 2 H 2 ) = 60 h -1 Relationship between reaction time and VCM selectivity under different conditions.

[0037] Fig. 9 Gas (N) for the catalyst (Examples 1, 3, 5-17) 2 ) Relationship diagram between flow rate and metal Ru dispersion.

[0038] Fig.10 Gas (N) for the catalyst (Examples 1, 3, 5-17) 2) Flow rate-acetylene conversion rate relationship diagram. DETAILED DESCRIPTION

[0039] Example 1 Catalyst Preparation

[0040] A ruthenium-based catalyst is prepared using a segmented continuous flow device: the segmented continuous flow device is composed of a peristaltic pump (5), a nitrogen bottle (7), a gas flow meter (8), a magnetic stirrer (1), a polytetrafluoroethylene tee (6), a polytetrafluoroethylene pipeline (4) and a collection device (10);

[0041] The inlet pipeline of the peristaltic pump (5) is respectively introduced into the two containers (2) and (3), and the outlet pipeline of the peristaltic pump (5) is connected to the two end interfaces of the polytetrafluoroethylene tee (6), and the lower interface of the polytetrafluoroethylene tee (6) is connected to the polytetrafluoroethylene pipeline; the pipeline and the gas flowing through the flow meter (8) merge at the second tee to form a stable gas-liquid segmented flow; the lower interface of the second tee is connected to a section of polytetrafluoroethylene pipeline, and the pipeline is fixed on the pipeline bracket (9); the outlet end of the polytetrafluoroethylene pipeline is fixed above the collecting device (10) to collect the mixed liquid;

[0042] Preparation of RuCl 3 Mother solution: weigh 0.6700 g of ruthenium trichloride (RuCl 3 ) solid was dissolved in 10 mL of distilled water, shaken, and ultrasonicated to make RuCl 3 It was completely dissolved. Then it was diluted to a 50 mL brown round-bottom flask to obtain RuCl 3 Mother solution, Ru: 13.4 mg / mL;

[0043] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pump respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time. The activated carbon slurry and the ruthenium precursor solution were mixed at the three-way. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst was obtained; after separation by positive pressure filtration, it was placed in a culture dish; finally, the culture dish was placed in a 90 ° C forced air drying oven for 12 hours, and then sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0044] The catalyst is named 1%Ru / AC 1 -SMF 0 .

[0045] Comparative Example 1 Catalyst Preparation

[0046] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0047] Preparation of catalyst by impregnation method: Weigh 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078 m 2 / g) in a mortar, take 2239 uL of the prepared RuCl 3 The mother liquor was added to distilled water to prepare 8 mL solution, oscillated for 10 min, and then ultrasonicated at room temperature for 30 min at an ultrasonic frequency of 40 KHz to quickly dissolve and mix; then it was added dropwise and evenly to the activated carbon, and after the addition was completed, it was quickly ground in a clockwise direction until the surface of the catalyst was smooth. Then it was transferred to a watch glass and placed in a 90°C forced air drying oven to dry for 12 h. After drying, it was sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99.

[0048] The catalyst is named 1%Ru / AC 1 -IWI.

[0049] Example 2 Catalyst Preparation

[0050] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0051] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 3 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0052] The catalyst is named 1%Ru / AC 1 -SMF 3 .

[0053] Example 3 Catalyst Preparation

[0054] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0055] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 7 mL / min. 2) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0056] The catalyst is named 1%Ru / AC 1 -SMF 7 .

[0057] Example 4 Catalyst Preparation

[0058] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0059] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 10 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0060] The catalyst is named 1%Ru / AC 1 -SMF 10 .

[0061] Example 5 Catalyst Preparation

[0062] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0063] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 13 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0064] The catalyst is named 1%Ru / AC 1 -SMF 13 .

[0065] Example 6 Catalyst Preparation

[0066] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0067] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 2 , coconut shell activated carbon, S BET = 1158m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pump respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time. The activated carbon slurry and the ruthenium precursor solution were mixed at the three-way. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst was obtained; after separation by positive pressure filtration, it was placed in a culture dish; finally, the culture dish was placed in a 90 ° C forced air drying oven for 12 hours, and then sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0068] The catalyst is named 1%Ru / AC 2 -SMF 0 .

[0069] Comparative Example 2 Catalyst Preparation

[0070] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0071] Preparation of catalyst by impregnation method: Weigh 2970 mg activated carbon (AC 2 , coconut shell activated carbon, S BET = 1158 m 2 / g) in a mortar, take 2239 uL of the prepared RuCl 3 The mother liquor was added to distilled water to prepare 8 mL solution, oscillated for 10 min, and then ultrasonicated at room temperature for 30 min at an ultrasonic frequency of 40 KHz to quickly dissolve and mix; then it was added dropwise and evenly to the activated carbon, and after the addition was completed, it was quickly ground in a clockwise direction until the surface of the catalyst was smooth. Then it was transferred to a watch glass and placed in a 90°C forced air drying oven to dry for 12 h. After drying, it was sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99.

[0072] The catalyst is named 1%Ru / AC 2 -IWI.

[0073] Example 7 Catalyst Preparation

[0074] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0075] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 2 , coconut shell activated carbon, S BET = 1158m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 7 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0076] The catalyst is named 1%Ru / AC 2 -SMF 7 .

[0077] Example 8 Catalyst Preparation

[0078] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0079] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 2 , coconut shell activated carbon, S BET = 1158m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 13 mL / min. 2) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0080] The catalyst is named 1%Ru / AC 2 -SMF 13 .

[0081] Example 9 Catalyst Preparation

[0082] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0083] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 3 , coconut shell activated carbon, S BET = 1051m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pump respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time. The activated carbon slurry and the ruthenium precursor solution were mixed at the three-way. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst was obtained; after separation by positive pressure filtration, it was placed in a culture dish; finally, the culture dish was placed in a 90 ° C forced air drying oven for 12 hours, and then sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0084] The catalyst is named 1%Ru / AC 3 -SMF 0 .

[0085] Comparative Example 3 Catalyst Preparation

[0086] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0087] Preparation of catalyst by impregnation method: Weigh 2970 mg activated carbon (AC 3 , coconut shell activated carbon, S BET = 1051 m 2 / g) in a mortar, take 2239 uL of the prepared RuCl 3 The mother liquor was added to distilled water to prepare 8 mL solution, oscillated for 10 min, and then ultrasonicated at room temperature for 30 min at an ultrasonic frequency of 40 KHz to quickly dissolve and mix; then it was added dropwise and evenly to the activated carbon, and after the addition was completed, it was quickly ground in a clockwise direction until the surface of the catalyst was smooth. Then it was transferred to a watch glass and placed in a 90°C forced air drying oven to dry for 12 h. After drying, it was sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99.

[0088] The catalyst is named 1%Ru / AC 3 -IWI.

[0089] Example 10 Catalyst Preparation

[0090] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0091] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 3 , coconut shell activated carbon, S BET = 1051m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 7 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0092] The catalyst is named 1%Ru / AC 3 -SMF 7 .

[0093] Example 11 Catalyst Preparation

[0094] Preparation of RuCl 3Mother liquor: Same as in Example 1, no further details are given.

[0095] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 3 , coconut shell activated carbon, S BET = 1051m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 13 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0096] The catalyst is named 1%Ru / AC 3 -SMF 13 .

[0097] Example 12 Catalyst Preparation

[0098] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0099] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 4 , coconut shell activated carbon, S BET = 1104m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pump respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time. The activated carbon slurry and the ruthenium precursor solution were mixed at the three-way. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst was obtained; after separation by positive pressure filtration, it was placed in a culture dish; finally, the culture dish was placed in a 90 ° C forced air drying oven for 12 hours, and then sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0100] The catalyst is named 1%Ru / AC 4 -SMF 0 .

[0101] Comparative Example 4 Catalyst Preparation

[0102] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0103] Preparation of catalyst by impregnation method: Weigh 2970 mg activated carbon (AC 4 , coconut shell activated carbon, S BET = 1104 m 2 / g) in a mortar, take 2239 uL of the prepared RuCl 3 The mother liquor was added to distilled water to prepare 8 mL solution, oscillated for 10 min, and then ultrasonicated at room temperature for 30 min at an ultrasonic frequency of 40 KHz to quickly dissolve and mix; then it was added dropwise and evenly to the activated carbon, and after the addition was completed, it was quickly ground in a clockwise direction until the surface of the catalyst was smooth. Then it was transferred to a watch glass and placed in a 90°C forced air drying oven to dry for 12 h. After drying, it was sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99.

[0104] The catalyst is named 1%Ru / AC 4 -IWI.

[0105] Example 13 Catalyst Preparation

[0106] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0107] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 4 , coconut shell activated carbon, S BET = 1104m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 7 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0108] The catalyst is named 1%Ru / AC 4 -SMF 7 .

[0109] Example 14 Catalyst Preparation

[0110] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0111] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 4 , coconut shell activated carbon, S BET = 1104m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 13 mL / min. 2) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0112] The catalyst is named 1%Ru / AC 4 -SMF 13 .

[0113] Example 15 Catalyst Preparation

[0114] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0115] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 5 , coal-based activated carbon, S BET = 1000m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pump respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time. The activated carbon slurry and the ruthenium precursor solution were mixed at the three-way. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst was obtained; after separation by positive pressure filtration, it was placed in a culture dish; finally, the culture dish was placed in a 90 ° C forced air drying oven for 12 hours, and then sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0116] The catalyst is named 1%Ru / AC 5 -SMF 0 .

[0117] Comparative Example 5 Catalyst Preparation

[0118] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0119] Preparation of catalyst by impregnation method: Weigh 2970 mg activated carbon (AC 5 , coal-based activated carbon, S BET = 1000 m 2 / g) in a mortar, take 2239 uL of the prepared RuCl 3 The mother liquor was added to distilled water to prepare 8 mL solution, oscillated for 10 min, and then ultrasonicated at room temperature for 30 min at an ultrasonic frequency of 40 KHz to quickly dissolve and mix; then it was added dropwise and evenly to the activated carbon, and after the addition was completed, it was quickly ground in a clockwise direction until the surface of the catalyst was smooth. Then it was transferred to a watch glass and placed in a 90°C forced air drying oven to dry for 12 h. After drying, it was sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 1:99.

[0120] The catalyst is named 1%Ru / AC 5 -IWI.

[0121] Example 16 Catalyst Preparation

[0122] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0123] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 5 , coal-based activated carbon, S BET = 1000m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 7 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0124] The catalyst is named 1%Ru / AC 5 -SMF 7 .

[0125] Example 17 Catalyst Preparation

[0126] Preparation of RuCl 3Mother liquor: Same as in Example 1, no further details are given.

[0127] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 5 , coal-based activated carbon, S BET = 1000m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 13 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass ratio of ruthenium in the catalyst to activated carbon is 1:99, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0128] The catalyst is named 1%Ru / AC 5 -SMF 13 .

[0129] Example 18 Catalyst Preparation

[0130] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0131] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 1120 uL of the prepared RuCl 3The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 7 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 0.5:99.5, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0132] The catalyst is named 0.5%Ru / AC 1 -SMF 7 .

[0133] Example 19 Catalyst Preparation

[0134] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0135] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 672 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 7 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90 ℃ forced air drying oven for 12 hours, and then sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 0.3:99.7, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0136] The catalyst is named 0.3%Ru / AC 1 -SMF 7 .

[0137] Example 20 Catalyst Preparation

[0138] Preparation of RuCl 3 Mother liquor: Same as in Example 1, no further details are given.

[0139] Preparation of catalyst by segmented continuous flow method: 2970 mg activated carbon (AC 1 , wood activated carbon, S BET = 1078m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonic to obtain activated carbon slurry. Measure 224 uL of the prepared RuCl 3 The mother liquor was placed in a beaker containing 45 mL of distilled water and dispersed evenly by ultrasonication to obtain a ruthenium precursor solution. The two beakers containing the activated carbon slurry and the ruthenium precursor solution were placed under the peristaltic pumps respectively, and the flow rate of the activated carbon slurry was set to 2 mL / min and the flow rate of the ruthenium precursor solution was set to 1 mL / min. The peristaltic pump switch was started at the same time, and the activated carbon slurry and the ruthenium precursor solution were mixed at the first tee; after flowing through a section of polytetrafluoroethylene pipe, the activated carbon slurry was mixed with a gas (N) at a flow rate of 7 mL / min. 2 ) are mixed at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven for 12 hours, and then sealed and stored. The mass of ruthenium in the catalyst: activated carbon is 0.1:99.9, and each segmented continuous flow device can produce 144 g / d of ruthenium-based catalyst.

[0140] The catalyst is named 0.1%Ru / AC 1 -SMF 7 .

[0141] The evaluation process and conditions of all catalysts in Example 21 are as follows:

[0142] (1) Catalyst loading: Place a 10 mm thick layer of quartz wool in the middle of a 10 mm diameter quartz reaction tube, and add 0.5 g of catalyst (GHSV (C 2 H 2 ) = 340 h -1 ) and ensure that the catalyst is flat, and then pad it with a layer of 10 mm thick quartz wool;

[0143] (2) Before the reaction: N 2The entire pipeline was purged at a flow rate of 20 mL / min for 60 min to remove air and moisture in the reaction system. At the same time, the temperature was raised to 150 °C at 5 °C / min and maintained for 30 min, and then the temperature was further raised to 180 °C at 5 °C / min. Then, HCl gas was introduced at a flow rate of 20 mL / min and maintained for 30 min, and then V C2H2 =16mL / min, V HCl =16.8 mL / min flow rate of the reaction gas and maintain for 10 min to ensure that the catalyst is in the gas atmosphere of acetylene and hydrogen chloride, and then V C2H2 / V HCl =1:1.05 ratio to reduce the reaction gas flow rate, at V C2H2 =4 mL / min, V HCl =4.2 mL / min reaction flow rate, maintained for 10 min, and then began detection;

[0144] (3) After the reaction: The gaseous product first passed through an absorption bottle containing NaOH solution to remove excess HCl, and then was analyzed online by gas chromatography GC-9790Ⅱ to evaluate the acetylene conversion rate and selectivity to VCM.

[0145] Example 22 The evaluation process and conditions of the catalyst (Example 20) are:

[0146] (1) Catalyst loading: Place a 10 mm thick layer of quartz wool in the middle of a 10 mm diameter quartz reaction tube, and add 2.8 g of catalyst (GHSV (C 2 H 2 ) = 60 h -1 ) and ensure that the catalyst is flat, and then pad it with a layer of 10 mm thick quartz wool;

[0147] (2) Before the reaction: N 2 The entire pipeline was purged at a flow rate of 20 mL / min for 60 min to remove air and moisture in the reaction system. At the same time, the temperature was raised to 150 °C at 5 °C / min and maintained for 30 min, and then the temperature was further raised to 180 °C at 5 °C / min. Then, HCl gas was introduced at a flow rate of 20 mL / min and maintained for 30 min, and then V C2H2 =16mL / min, V HCl =16.8 mL / min flow rate of the reaction gas and maintain for 10 min to ensure that the catalyst is in the gas atmosphere of acetylene and hydrogen chloride, and then V C2H2 / V HCl =1:1.05 ratio to reduce the reaction gas flow rate, at V C2H2=4 mL / min, V HCl =4.2 mL / min reaction flow rate, maintained for 10 min, and then began detection;

[0148] (3) After the reaction: The gaseous product first passed through an absorption bottle containing NaOH solution to remove excess HCl, and then was analyzed online by gas chromatography GC-9790Ⅱ to evaluate the acetylene conversion rate and selectivity to VCM.

[0149] The catalyst test results are shown in Table 1.

[0150] Table 1 Acetylene hydrochlorination reaction activity test

[0151]

[0152]

[0153] As can be seen from Table 1, in Example 3, the catalyst 1%Ru / AC was prepared by a segmented continuous flow method using wood activated carbon as a carrier. 1 -SMF 7 , at a reaction temperature of 180°C, GHSV (C 2 H 2 ) = 340 h -1 Under the same conditions, the acetylene conversion rate reached 86.0%, and the VCM selectivity was higher than 99.9%, which was the best activity compared with other types of activated carbon. 1 -IWI acetylene conversion (80.7%) increased by 5.3% (e.g. Figure 2-4 as shown).

[0154] Depend on Figure 5 It can be seen that Examples 3, 18-20 prepared ruthenium-based catalysts with loading amounts of 1%, 0.5%, 0.3%, and 0.1%, indicating that the segmented continuous flow method can be used to prepare ruthenium-based catalysts with different loading amounts, and the catalyst with a loading amount of 1% prepared in Example 3 has the best activity. 1 -SMF 7 , at a reaction temperature of 180°C, industrial space velocity GHSV (C 2 H 2 ) = 60 h -1 Under these conditions, the acetylene conversion rate reached 92.2% and the VCM selectivity was higher than 99.9% (such as Figure 7-8 as shown).

[0155] The ICP test results of Comparative Example 1 and Example 3 are shown in Table 2.

[0156] Table 2 ICP test results

[0157]

[0158] From the ICP analysis results in Table 2, it can be seen that the catalyst Example 3 prepared by the segmented continuous flow technology maintains a relatively high Ru loading.

[0159] The test results of the dispersion of metal Ru in the catalysts of Examples 1, 3, and 5-17 are shown in Table 3.

[0160] Table 3 Test results of the dispersion of metal Ru in the catalyst

[0161]

[0162] Combined with Table 3, it can be seen that with the increase of gas flow rate, the liquid segment volume is smaller and the distribution is wider, the dispersion of Ru species on the activated carbon carrier is higher, and the dispersion of Ru species is precisely controlled. When the activated carbon slurry flow rate is 2 mL / min, the ruthenium precursor solution flow rate is 1 mL / min, and the gas flow rate is 7 mL / min, the ruthenium-based catalyst has the best catalytic activity (such as Figure 9-10 As shown). The segmented continuous flow technology not only improves the production efficiency of the catalyst, optimizes the catalytic performance, but also achieves precise control of the dispersion of Ru species. This shows that the method of the present invention has significant practical value.

[0163] The present invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent replacement are within the protection scope required by the present invention.

Claims

1. A method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride using a segmented continuous flow technology, characterized in that: The following steps are involved: A ruthenium-based catalyst is prepared using a segmented continuous flow device: the segmented continuous flow device is composed of a peristaltic pump (5), a nitrogen bottle (7), a gas flow meter (8), a magnetic stirrer (1), a polytetrafluoroethylene tee (6), a polytetrafluoroethylene pipeline (4) and a collection device (10); The inlet pipeline of the peristaltic pump (5) is respectively introduced into the two containers (2) and (3), and the outlet pipeline of the peristaltic pump (5) is connected to the two end interfaces of the polytetrafluoroethylene tee (6), and the lower interface of the polytetrafluoroethylene tee (6) is connected to the polytetrafluoroethylene pipeline; the pipeline and the gas flowing through the flow meter (8) merge at the second tee to form a stable gas-liquid segmented flow; the lower interface of the second tee is connected to a section of polytetrafluoroethylene pipeline, and the pipeline is fixed on the pipeline bracket (9); the outlet end of the polytetrafluoroethylene pipeline is fixed above the collecting device (10) to collect the mixed liquid; (1) Preparation of RuCl3 mother solution: Weigh 0.6700 g of ruthenium trichloride RuCl3 solid and dissolve it in 10 mL of distilled water. Shake and sonicate to completely dissolve the RuCl3. Then, add the solution to a 50 mL brown round-bottom flask to obtain RuCl3 mother solution with a Ru content of 13.4 mg / mL. (2) Weighing 2970 mg of activated carbon into a container, adding an appropriate amount of distilled water for ultrasonic dispersion to obtain an activated carbon slurry; taking an appropriate amount of RuCl3 mother liquor prepared in step (1) and adding it into another container, adding an appropriate amount of distilled water for dispersion to obtain a ruthenium precursor solution; the volume ratio of distilled water used in preparing the activated carbon slurry and the ruthenium precursor solution in steps (1) and (2) is 2:1, and the activated carbon is wood activated carbon; (3) placing the containers containing the activated carbon slurry and the ruthenium precursor solution in step (2) under the peristaltic pump (5) respectively, sucking the pipe through the peristaltic pump (5) and mixing at the first tee; after flowing through a section of polytetrafluoroethylene pipe, merging with the gas flowing through the gas flow meter (8) at the second tee to form a stable gas-liquid diversion section; connecting the lower interface of the second tee to a section of polytetrafluoroethylene pipe, waiting for a period of time, and collecting with a collecting device; the flow rate ratio of the activated carbon slurry, the ruthenium precursor solution and the nitrogen in the preparation process of the segmented continuous flow technology is 2:1:7; (4) filtering the collected solid-liquid mixture with a positive pressure filter, and finally drying it in a forced air drying oven for 12-24 hours, wherein the mass ratio of ruthenium to activated carbon in the catalyst is 0.1-1:99-99.9; (5) The prepared ruthenium-based catalyst is used in the acetylene hydrochlorination reaction to produce vinyl chloride.

2. The method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride using a segmented continuous flow technology according to claim 1, characterized in that: The catalyst was prepared as follows: 2970 mg of activated carbon (AC1, wood activated carbon, specific surface area S BET = 1078 m 2 / g) in a beaker, add 90 mL of distilled water, stir and disperse evenly by ultrasonication to obtain activated carbon slurry. Measure 2239 uL of the prepared RuCl3 mother liquor and place it in a beaker containing 45 mL of distilled water, disperse evenly by ultrasonication to obtain a ruthenium precursor solution; place the two beakers containing activated carbon slurry and ruthenium precursor solution under the peristaltic pump respectively, set the flow rate of activated carbon slurry to 2 mL / min, and the flow rate of ruthenium precursor solution to 1 mL / min, and start the peristaltic pump switch at the same time, and the activated carbon slurry and ruthenium precursor solution are mixed at the first tee; After flowing through a section of polytetrafluoroethylene pipe, it is mixed with N2 gas at a flow rate of 7 mL / min at the second tee to form a stable gas-liquid segmented flow. After waiting for 30 minutes, a solid-liquid mixture of the ruthenium-based catalyst is obtained; after separation by positive pressure filtration, it is placed in a culture dish; finally, the culture dish is placed in a 90°C forced air drying oven and dried for 12 hours, and then sealed and stored; the mass ratio of ruthenium to activated carbon in the catalyst is 1:99, and the catalyst is named 1%Ru / AC1-SMF7.

3. The method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride using a segmented continuous flow technology according to claim 1, characterized in that: Step (1) Using distilled water as a solvent, dissolve an appropriate amount of ruthenium trichloride (RuCl3 ≥ 99%) solid in distilled water at room temperature, oscillate using a mixer for 10 min, and then ultrasonicate for 30 min to prepare a RuCl3 mother solution (Ru: 13.4 mg / mL), which is then sealed, shielded from light, and stored at low temperature.

4. The method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride using a segmented continuous flow technology according to claim 1, characterized in that: The gas in step (3) is N2; and the filtering method of the solid-liquid mixture in step (4) is positive pressure filtration.

5. The method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride using a segmented continuous flow technology according to claim 1, characterized in that: The container and the collecting device are beakers, the polytetrafluoroethylene pipe connected to the lower interface of the second tee is circularly wound, and this section of polytetrafluoroethylene pipe is fixed on the pipe bracket.

6. The method for preparing a ruthenium-based catalyst for use in the reaction of acetylene hydrochlorination to vinyl chloride using a segmented continuous flow technology according to claim 1, characterized in that: In step (5), the acetylene hydrochlorination reaction to prepare vinyl chloride is specifically carried out as follows: (1) Catalyst loading: Place a layer of quartz wool with a thickness of 10 mm in the middle of a quartz reaction tube with a diameter of 10 mm, add a certain amount of catalyst into the reaction tube and ensure that the catalyst is flat, and then place another layer of quartz wool with a thickness of 10 mm; (2) Before the reaction: N2 was purged throughout the pipeline at a flow rate of 20 mL / min for 60 min to remove air and moisture in the reaction system. At the same time, the temperature was raised to 150 °C at a flow rate of 5 °C / min and maintained for 30 min, and then the temperature was further raised to 180 °C at a flow rate of 5 °C / min. Then, HCl gas was introduced at a flow rate of 20 mL / min and maintained for 30 min, and then V C2H2 =16 mL / min, V HCl =16.8 mL / min flow rate of the reaction gas and maintain for 10 min to ensure that the catalyst is in the gas atmosphere of acetylene and hydrogen chloride, and then V C2H2 / V HCl =1:1.05 ratio to reduce the reaction gas flow rate, at V C2H2 =4 mL / min, V HCl =4.2mL / min reaction flow rate, then maintain for 10 min and start detection; (3) After the reaction: The gaseous product first passed through an absorption bottle containing NaOH solution to remove excess HCl, and then was analyzed online by gas chromatography GC-9790Ⅱ to evaluate the acetylene conversion rate and VCM selectivity.

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