An integrated closed recycling device and process for a flammable solid catalyst

Abstract

The present invention discloses an integrated closed recycling device and process for a flammable solid catalyst. The device includes a closed transfer module, a solvent replacement module, a recycling and reuse module, and a catalyst usage end; the catalyst inlet of the closed transfer module is connected to the solvent replacement module through a pipeline. The closed transfer module is used to quantitatively provide a solid catalyst containing water to the solvent replacement module, and the solid catalyst is sealed in water; the catalyst outlet of the solvent replacement module is connected to the catalyst usage end, and the solvent replacement module replaces water with an organic solvent under the protection of an inert gas; the catalyst outlet of the catalyst usage end is connected to the recycling and reuse module, and the recycling and reuse module is used to collect the used solid catalyst and seal it with water. The device of the present invention ensures that the solid catalyst is under the protection of water seal or inert gas during use, effectively reducing the contact between the solid catalyst and air, and improving the safety and efficiency during the use of the catalyst.

Description

Technical Field

[0001] The present invention belongs to the technical field of fine chemical safety, and particularly relates to an integrated closed recycling device and process for flammable solid catalysts. Background Art

[0002] A catalyst can change the chemical reaction rate of reactants in a chemical reaction without changing the chemical equilibrium, and its own mass and chemical properties do not change before and after the chemical reaction. A chemical reaction carried out under the action of a catalyst is called a catalytic reaction. With the help of a catalyst, beneficial purposes such as accelerating the chemical reaction rate, improving production capacity, inhibiting side reactions, increasing the yield of target products, improving operating conditions, and reducing equipment costs can be achieved.

[0003] Solid catalysts are a commonly used type of reaction catalyst. Due to their easy separation from products, simple post-treatment processes, recyclability and controllable usage, and relative stability at room temperature and easy storage, they are widely used. Media such as lithium metal, Raney nickel, and palladium on carbon are all solid catalysts with excellent performance. However, these substances are relatively active and may self-ignite in air. Therefore, they are generally stored in a water-sealed environment, and actual reactions are often carried out in organic solvents. Therefore, when using these catalysts, the operating environment often inevitably contains Class A and Class B flammable and explosive gases. Moreover, the catalysts themselves are flammable in air, and it is very difficult to prevent the situation where the catalyst self-ignites, ignites the surrounding flammable and explosive gases, and causes an explosion accident during the process of taking them out of the water seal and putting them into the reaction system.

[0004] Currently, the use of such air-flammable catalysts often mainly relies on manual feeding. By carefully and in small batches transferring the materials, the probability of catalyst self-ignition is reduced, and the scale of damage that may be caused by accidental self-ignition is minimized. This not only affects production efficiency but also greatly increases the risk coefficient of using solid catalysts. The filtration and recovery of catalysts generally use equipment such as candle filters, and open operation is required when discharging solid materials. Although soft connections are used to isolate air, accidents where solids cut through the soft connections and mix in air to ignite the catalysts often occur. Moreover, to prevent catalyst residues, a large amount of water is needed to wash the filter, and the collection bucket may need to be replaced multiple times for one batch of recovery, which increases the labor intensity and also poses safety hazards.

[0005] With the increasingly widespread application of air-flammable catalysts and the increasing scale of reactions, developing a process method that can quickly and safely recycle and reuse catalysts not only has objective economic returns such as improving production efficiency but also can effectively reduce the probability of accidents and increase the safety of the process. Summary of the Invention

[0006] To solve the above problems, the purpose of the present invention is to provide an integrated closed recycling device and process for flammable solid catalysts.

[0007] To achieve the above object, the following technical solutions are proposed:

[0008] An integrated closed recycling device for a flammable solid catalyst, comprising a closed transfer module, a solvent replacement module, a recycling and reuse module, and a catalyst usage end; the closed transfer module is connected to the catalyst inlet of the solvent replacement module through a pipeline, and the closed transfer module is used to quantitatively supply a solid catalyst containing water to the solvent replacement module, and the solid catalyst is sealed in water; the catalyst outlet of the solvent replacement module is connected to the catalyst usage end, and the solvent replacement module replaces water with an organic solvent under the protection of an inert gas; the catalyst outlet of the catalyst usage end is connected to the recycling and reuse module, and the recycling and reuse module is used to collect the used solid catalyst and seal it with water.

[0009] Furthermore, the closed transfer module includes an automatic water replenishing system and a catalyst discharging barrel. The automatic water replenishing system passes through the sealed barrel cover above the catalyst discharging barrel and extends into the catalyst discharging barrel. The automatic water replenishing system measures the water level in the catalyst discharging barrel through a liquid level gauge and automatically replenishes water to ensure that the water level in the catalyst discharging barrel exceeds the solid catalyst, playing a role of water seal.

[0010] Furthermore, an overflow port is opened on the side of the catalyst discharging barrel, and a filter screen is provided at the overflow port.

[0011] Furthermore, the solvent replacement module includes a replacement feeding tank, an inert gas replacement system, and an organic solvent inlet. The solid catalyst inlet of the replacement feeding tank is connected to the discharge port below the catalyst discharging barrel. The inert gas replacement system is connected above the replacement feeding tank. The inert gas replacement system has multiple branches for introducing different inert gases respectively. An organic solvent inlet is also provided above the replacement feeding tank. Water outlets are provided on the side and bottom of the replacement feeding tank, and filter screens are provided at the water outlets. The filter screen on the side is used to prevent overflow, and the filter screen at the bottom is used to discharge the water in the replacement feeding tank.

[0012] Furthermore, the catalyst usage end includes a reactor and a filter. The reactor is connected to the catalyst outlet at the bottom of the replacement feeding tank through a pipeline. The outlet of the reactor is connected to the filter. A washing water inlet is provided on the filter, and the filter is connected to the recycling and reuse module.

[0013] Furthermore, the recycling and reuse module includes a catalyst recycling barrel and a U-shaped overflow pipe. The discharge port of the filter is connected to the sealed barrel cover above the catalyst recycling barrel through a pipeline. An overflow port is opened on the side of the catalyst recycling barrel, and the overflow port is connected to the U-shaped overflow pipe. A filter screen is provided between the overflow port and the U-shaped overflow pipe.

[0014] Furthermore, on the connecting pipeline between the catalyst discharging bucket and the replacement feeding tank, on the pipeline of the organic solvent inlet, on the connecting pipeline between the inert gas replacement system and the replacement feeding tank, on the pipeline of the water outlet at the bottom of the replacement feeding tank, on the connecting pipeline between the replacement feeding tank and the reactor, and on the connecting pipeline between the filter and the catalyst recycling bucket, opening and closing valves are provided.

[0015] An integrated closed recycling process for a flammable solid catalyst includes the following steps:

[0016] 1) Pre-seal the solid catalyst in the catalyst discharging bucket with water. After the catalyst discharging bucket is connected to the replacement feeding tank, connect the automatic water replenishment system to the catalyst discharging bucket. The opening and closing valve on the connecting pipeline between the catalyst discharging bucket and the replacement feeding tank is in the closed state. After the replacement feeding tank is evacuated and filled with inert gas by the inert gas replacement system for multiple times, open the opening and closing valve. The solid catalyst in the catalyst discharging bucket enters the replacement feeding tank together with the water seal water. Under the protection of the automatic water replenishment system, ensure that the liquid level of the catalyst discharging bucket is always at a safe height, completely isolate the air, and the excess water seal water is discharged from the overflow port on the side of the catalyst discharging bucket;

[0017] 2) After a quantitative amount of solid catalyst enters the replacement feeding tank, cut off the feed. Under the protection of the inert gas replacement system, open the opening and closing valve on the pipeline of the water outlet at the bottom of the replacement feeding tank to discharge the water seal water, then close this opening and closing valve, and open the opening and closing valve on the pipeline of the organic solvent inlet to inject the organic solvent to the required liquid level;

[0018] 3) Open the opening and closing valve on the connecting pipeline between the replacement feeding tank and the reactor, and let the solid catalyst enter the reactor together with the organic solvent for reaction. Use the organic solvent to rinse the replacement feeding tank multiple times to ensure that there is no catalyst residue. After the reaction is completed, the liquid phase obtained by filtering the product enters other processes;

[0019] 4) The washing water enters the filter through the washing water inlet, so as to rinse the filter multiple times. The solid catalyst and the washing water enter the catalyst recycling bucket together. The excess washing water is discharged through the U-shaped overflow pipe. The catalyst recycling bucket containing the recovered catalyst can directly re-enter the closed transfer module and be used as the catalyst discharging bucket.

[0020] Furthermore, the solid catalyst is Raney nickel, palladium carbon, ruthenium / carbon, metallic lithium, cobalt, iron or zinc.

[0021] Furthermore, the gas used for filling with inert gas in the inert gas replacement system is nitrogen, argon or helium, and the organic solvent is one or more of methanol, ethanol, acetone, ethyl acetate, acetonitrile and tetrahydrofuran.

[0022] The beneficial effects of the present invention are as follows: By configuring an automatic water replenishment system on the raw material barrel with a relatively high original risk coefficient, the possibility of contact between the catalyst and air during the transfer of raw materials from the raw material barrel is effectively reduced, and the safety and efficiency during the transfer of raw materials are greatly improved; By taking the measure of replacing the aqueous phase with the required solvent in the feeding tank under an inert gas protection condition, the path for air to enter the feeding tank and ignite the catalyst during the solvent replacement is effectively blocked, increasing the safety and purity of the solvent replacement; By setting airtight lids on the catalyst discharging barrel and the catalyst recycling barrel, the hidden dangers of connection damage and air entering the system, which may lead to fire and explosion when using flexible connections, are eliminated, ensuring the safety of the recycling process; By setting a U-shaped overflow pipe at an appropriate height on the catalyst recycling barrel, it is ensured that the liquid level of the receiving tank does not overflow, so that the amount of water used by the backflush filter is no longer limited, and it is no longer necessary to frequently replace the receiving tank. It can not only ensure the cleaning effect, eliminate residues and increase the recovery rate, but also not reduce the efficiency; Through the integration of several systems, device integration is achieved, providing a standardized and modular device and process for the air-flammable catalyst closed feeding. Brief Description of the Drawings

[0023] Figure 1 It is a schematic structural diagram of the present invention.

[0024] In the figure: a, airtight transfer module; b, solvent replacement module; c, recycling and reuse module; d, catalyst usage end; 1, automatic water replenishment system; 2, catalyst discharging barrel; 3, filter screen; 4, replacement feeding tank; 5, inert gas replacement system; 6, organic solvent inlet; 7, reactor; 8, filter; 9, washing water inlet; 10, U-shaped overflow pipe; 11, catalyst recycling barrel. Detailed Embodiments

[0025] The present invention will be further described below in conjunction with the specification drawings and embodiments, but the protection scope of the present invention is not limited thereto.

[0026] As Figure 1As shown in the figure, an integrated closed recycling device for a flammable solid catalyst includes a closed transfer module a, a solvent replacement module b, a recycling and reuse module c, and a catalyst usage end d. The closed transfer module a includes an automatic water replenishment system 1 and a catalyst discharge bucket 2. The lower end of the automatic water replenishment system 1 passes through the sealed bucket cover above the catalyst discharge bucket 2 and extends into the catalyst discharge bucket 2. The automatic water replenishment system 1 measures the water level in the catalyst discharge bucket 2 through a level gauge and automatically replenishes water to ensure that the water level in the catalyst discharge bucket 2 exceeds the solid catalyst, playing a role of water seal. This level gauge can be a radar level gauge or an ultrasonic level gauge. The level gauge can measure the liquid level without extending into the water. An overflow port is opened on the side of the catalyst discharge bucket 2, and a filter screen 3 is provided at the overflow port; The solvent replacement module b includes a replacement charging tank 4, an inert gas replacement system 5, and an organic solvent inlet 6. The solid catalyst inlet of the replacement charging tank 4 is connected to the discharge port below the catalyst discharge bucket 2, and an opening and closing valve is provided on the connecting pipeline. The inert gas replacement system 5 is connected above the replacement charging tank 4, and an opening and closing valve is provided on the connecting pipeline. The inert gas replacement system 5 has multiple branches, which are respectively used to introduce different inert gases. An organic solvent inlet 6 is also provided above the replacement charging tank 4, and an opening and closing valve is provided on the connecting pipeline. The side and bottom of the replacement charging tank 4 are provided with water outlets, and filter screens 3 are provided at the water outlets. The filter screen 3 on the side is used to prevent overflow, and the filter screen 3 at the bottom is used to drain the water in the replacement charging tank 4; An opening and closing valve is provided on the pipeline of the bottom water outlet; The catalyst usage end d includes a reactor 7 and a filter 8. The reactor 7 is connected to the catalyst outlet at the bottom of the replacement charging tank 4 through a pipeline, and an opening and closing valve is provided on the connecting pipeline. The outlet of the reactor 7 is connected to the filter 8, and a washing water inlet 9 is provided on the filter 8; The recycling and reuse module c includes a catalyst recycling bucket 11 and a U-shaped overflow pipe 10. The discharge port of the filter 8 is connected to the sealed bucket cover above the catalyst recycling bucket 11 through a pipeline, and an opening and closing valve is provided on the connecting pipeline. An overflow port is opened on the side of the catalyst recycling bucket 11, and the overflow port is connected to the U-shaped overflow pipe 10. A filter screen 3 is provided between the overflow port and the U-shaped overflow pipe 10.

[0027] 1) Pre-seal the solid catalyst with water in the catalyst discharge bucket 2. After the catalyst discharge bucket 2 is connected to the replacement charging tank 4, connect the automatic water replenishment system 1 to the catalyst discharge bucket 2. The opening and closing valve on the connecting pipeline between the catalyst discharge bucket 2 and the replacement charging tank 4 is in the closed state. After the replacement charging tank 4 is evacuated and refilled with gas multiple times through the inert gas replacement system 5, open the opening and closing valve. The solid catalyst in the catalyst discharge bucket 2 enters the replacement charging tank 4 together with the water seal water. Under the protection of the automatic water replenishment system 1, ensure that the liquid level of the catalyst discharge bucket 2 is always at a safe height, completely isolating the air. The excess water seal water is discharged from the overflow port on the side of the catalyst discharge bucket 2;

[0028] 2) After the quantitative solid catalyst enters the displacement charging tank 4, the feeding is cut off. Under the protection of the inert gas displacement system 5, the on-off valve on the pipeline of the water outlet at the bottom of the displacement charging tank 4 is opened to discharge the water seal water, then the on-off valve is closed, and the on-off valve on the pipeline of the organic solvent inlet 6 is opened to inject the organic solvent to the required liquid level;

[0029] 3) Open the on-off valve on the pipeline connecting the displacement charging tank 4 and the reactor 7, and let the solid catalyst enter the reactor 7 together with the organic solvent for reaction. The displacement charging tank 4 is rinsed with the organic solvent multiple times to ensure that there is no catalyst residue. After the reaction, the liquid phase obtained by filtering the product enters other processes;

[0030] 5) The washing water enters the filter 8 through the washing water inlet 9, so as to rinse the filter 8 multiple times. The solid catalyst and the washing water enter the catalyst reuse barrel 11 together. The excess washing water is discharged through the U-shaped overflow pipe 10. The catalyst reuse barrel 11 containing the recovered catalyst can directly re-enter the closed transfer module a and be used as the catalyst discharging barrel 2.

[0031] Example 1

[0032] Using the device and process of the present invention to produce a certain cardiovascular disease drug, the catalyst used is palladium-carbon. 2.5 kg of catalyst is put in at one time. The catalyst discharging barrel 2 with water seal is connected to the automatic water replenishing system 1, and while adding materials to the displacement charging tank 4, water is replenished to ensure the liquid level in the catalyst discharging barrel 2. The inert gas for protection is nitrogen, and the organic solvent is methanol for water displacement; after the quantitative palladium-carbon enters the displacement charging tank 4, the feeding is cut off. Other reaction media such as p-hydroxycinnamic acid and methanol are added to the reactor 7. The water phase is discharged from the displacement charging tank 4, and a certain amount of methanol is added. The palladium-carbon catalyst is put into the reactor 7 from the displacement charging tank 4 for reaction. After the reaction, the product is filtered, and the liquid phase material enters the next process. The palladium-carbon catalyst is rinsed with 800 L of water to recover 2.26 kg of catalyst, and the recovery rate is 90.4%.

[0033] Example 2

[0034] When the present invention is used for the production of a certain diabetes drug, the catalyst used is Raney nickel. 4.0 kg of the catalyst is charged at one time. After the water-sealed catalyst discharge tank 2 is connected to the automatic water replenishment system 1, it feeds the replacement feeding tank 4 while replenishing water to ensure the liquid level in the catalyst discharge tank 2. The inert gas for protection is nitrogen, the organic solvent is ethanol, and water is replaced; after a fixed amount of Raney nickel enters the replacement feeding tank 4, the feeding is cut off. Ethanol, ethanolamine, glucose and other reaction media are added to the reactor 7. The aqueous phase is discharged from the replacement feeding tank 4, and a fixed amount of ethanol is added. The Raney nickel catalyst is fed from the replacement feeding tank 4 into the reactor 7 for reaction. After the reaction is completed, the product is filtered, and the liquid-phase material enters the next process. The Raney nickel catalyst is rinsed with 1350 L of water to recover 3.77 kg of the catalyst, and the recovery rate is 94.3%.

[0035] Example 3

[0036] When the present invention is used for the reaction of catalytic hydrogenation of glucose to synthesize sorbitol, the catalyst used is ruthenium / carbon. 5.0 kg of the catalyst is charged at one time. After the water-sealed catalyst discharge tank 2 is connected to the automatic water replenishment system 1, it feeds the replacement feeding tank 4 while replenishing water to ensure the liquid level in the catalyst discharge tank 2. The inert gas for protection is nitrogen. Since the reaction is carried out in the aqueous phase, there is no need to replace it with other solvents; after a fixed amount of ruthenium / carbon enters the replacement feeding tank 4, the feeding is cut off. Glucose aqueous solution and other reaction media are added to the reactor 7. The ruthenium / carbon catalyst is fed from the replacement feeding tank 4 into the reactor 7 for reaction. After the reaction is completed, the product is filtered, and the liquid-phase material enters the next process. The ruthenium / carbon catalyst is rinsed with 1500 L of water to recover 4.62 kg of the catalyst, and the recovery rate is 92.4%.

Claims

1. An integrated airtight recycling device for a flammable solid catalyst, characterized in that, It includes a closed transfer module (a), a solvent replacement module (b), a recycling and reuse module (c), and a catalyst usage end (d); The catalyst inlet of the closed transfer module (a) is connected to the solvent replacement module (b) through a pipeline. The closed transfer module (a) is used to quantitatively supply a solid catalyst containing water to the solvent replacement module (b), and the solid catalyst is sealed in water; The catalyst outlet of the solvent replacement module (b) is connected to the catalyst usage end (d). The solvent replacement module (b) replaces water with an organic solvent under the protection of an inert gas; The catalyst outlet of the catalyst usage end (d) is connected to the recycling and reuse module (c). The recycling and reuse module (c) is used to collect the used solid catalyst and seal it with water; The closed transfer module (a) includes an automatic water replenishment system (1) and a catalyst discharging bucket (2). The automatic water replenishment system (1) passes through the sealed bucket cover above the catalyst discharging bucket (2) and extends into the catalyst discharging bucket (2). The automatic water replenishment system (1) measures the water level in the catalyst discharging bucket (2) through a liquid level gauge and automatically replenishes water to ensure that the water level in the catalyst discharging bucket (2) exceeds the solid catalyst, playing a role of water seal; The solvent replacement module (b) includes a replacement charging tank (4), an inert gas replacement system (5), and an organic solvent inlet (6). The solid catalyst inlet of the replacement charging tank (4) is connected to the discharge port below the catalyst discharging bucket (2). The inert gas replacement system (5) is connected above the replacement charging tank (4). The inert gas replacement system (5) has multiple branches, which are respectively used to introduce different inert gases. The organic solvent inlet (6) is also provided above the replacement charging tank (4). The side and bottom of the replacement charging tank (4) are provided with water outlets, and filter meshes (3) are provided at the water outlets. The filter mesh (3) on the side is used to prevent overflow, and the filter mesh (3) at the bottom is used to discharge the water in the replacement charging tank (4); The catalyst usage end (d) includes a reactor (7) and a filter (8). The reactor (7) is connected to the catalyst outlet at the bottom of the replacement charging tank (4) through a pipeline. The outlet of the reactor (7) is connected to the filter (8). A washing water inlet (9) is provided on the filter (8). The filter (8) is connected to the recycling and reuse module (c). The bottom of the replacement charging tank (4) is V-shaped; The recycling and reuse module (c) includes a catalyst reuse bucket (11) and a U-shaped overflow pipe (10). The discharge port of the filter (8) is connected to the sealed bucket cover above the catalyst reuse bucket (11) through a pipeline. An overflow port is provided on the side of the catalyst reuse bucket (11), and the overflow port is connected to the U-shaped overflow pipe (10). A filter mesh (3) is provided between the overflow port and the U-shaped overflow pipe (10).

2. The integrated airtight recycling device for a flammable solid catalyst according to claim 1, characterized in that, An overflow port is provided on the side of the catalyst discharging bucket (2), and a filter mesh (3) is provided at the overflow port.

3. The integrated closed recycling device for a flammable solid catalyst according to claim 1, characterized in that, On the connecting pipeline between the catalyst discharging bucket (2) and the replacement charging tank (4), on the pipeline of the organic solvent inlet (6), on the connecting pipeline between the inert gas replacement system (5) and the replacement charging tank (4), on the pipeline of the water outlet at the bottom of the replacement charging tank (4), on the connecting pipeline between the replacement charging tank (4) and the reactor (7), and on the connecting pipeline between the filter (8) and the catalyst recycling bucket (11), on-off valves are provided.

4. A process carried out using an integrated closed recycling device with a flammable solid catalyst as described in claim 3, characterized in that, It includes the following steps: 1) Pre-seal the solid catalyst with water in the catalyst discharging bucket (2). After connecting the catalyst discharging bucket (2) to the replacement charging tank (4), connect the automatic water replenishing system (1) to the catalyst discharging bucket (2). The on-off valve on the connecting pipeline between the catalyst discharging bucket (2) and the replacement charging tank (4) is in the closed state. After the replacement charging tank (4) is evacuated and refilled with inert gas by the inert gas replacement system (5) for multiple times, open the on-off valve. The solid catalyst in the catalyst discharging bucket (2) enters the replacement charging tank (4) together with the water seal water. Under the protection of the automatic water replenishing system (1), ensure that the liquid level of the catalyst discharging bucket (2) is always at a safe height, completely isolate the air, and the excess water seal water is discharged from the overflow port on the side of the catalyst discharging bucket (2); 2) After a certain amount of solid catalyst enters the replacement charging tank (4), cut off the feed. Under the protection of the inert gas replacement system (5), open the on-off valve on the pipeline of the water outlet at the bottom of the replacement charging tank (4) to discharge the water seal water, then close this on-off valve, and open the on-off valve on the pipeline of the organic solvent inlet (6) to inject the organic solvent to the required liquid level; 3) Open the on-off valve on the connecting pipeline between the replacement charging tank (4) and the reactor (7), and let the solid catalyst enter the reactor (7) together with the organic solvent for reaction. Use the organic solvent to rinse the replacement charging tank (4) multiple times to ensure that there is no catalyst residue. After the reaction ends, the liquid phase obtained by filtering the product enters other processes; 4) The washing water enters the filter (8) through the washing water inlet (9), thereby flushing the filter (8) multiple times. The solid catalyst and the washing water enter the catalyst recycling bucket (11) together. The excess washing water is discharged through the U-shaped overflow pipe (10). The catalyst recycling bucket (11) containing the recovered catalyst can directly re-enter the closed transfer module (a) and be used as the catalyst discharging bucket (2).

5. The process carried out by an integrated airtight recycling device using a flammable solid catalyst as described in claim 4, characterized in that, The solid catalyst is Raney nickel, palladium on carbon, ruthenium / carbon, metallic lithium, cobalt, iron or zinc.

6. The process carried out by an integrated closed recycling device using a flammable solid catalyst as described in claim 4, characterized in that, The gas used for refilling in the inert gas replacement system (5) is nitrogen, argon or helium, and the organic solvent is one or more of methanol, ethanol, acetone, ethyl acetate, acetonitrile and tetrahydrofuran.

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