Regeneration system, regeneration method and application of supported copper-bismuth catalyst

Abstract

The present invention relates to the technical field of catalyst regeneration, and specifically provides a regeneration system and method for a supported copper-bismuth catalyst, as well as an application for controlling the LOI of an acetylation reactor. The method system comprises: an acetylation reactor, a catalyst concentration device, a catalyst separator, a catalyst preparation device, a regeneration reactor, a cooler, and a reduction reactor. The present invention aims to reduce the LOI in the acetylation reactor and restores the performance of the catalyst through a two-step process. No chemical substances outside the reaction system need to be added. The copper active center of the catalyst itself decomposes organic coatings on the surface through catalytic oxidation, while simultaneously completing the controlled conversion of different valence states of the copper active species. The sintering and agglomeration of copper during the catalytic decomposition process is suppressed by precisely controlling the pyrolysis temperature, thereby avoiding damage to the catalyst performance. The method has low energy consumption and does not damage the microstructure of the catalyst. Through catalyst recycling and regeneration, the reactor LOI is controlled at a low level, which can significantly improve the reaction efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of catalyst regeneration, and specifically provides a regeneration system and method for a supported copper-bismuth catalyst, as well as application of the system and method of the present invention in controlling the ablation amount of the catalyst. Background Art

[0002] The acetylene-aldehyde process for producing 1,4-butanediol (BDO) originated in the 1820s and has gradually become the primary method for BDO production over the past century. The three-stage slurry bed reaction system, using a supported copper-bismuth catalyst based on a silica-alumina composite, has become a classic route for this BDO process due to its high production efficiency and continuous, reliable operation. This copper-bismuth catalyst has a high diffusion coefficient, enabling high conversion and selectivity under relatively mild reaction conditions.

[0003] The primary issue affecting the efficiency of the acetylation reaction during operation of this type of reaction system is the gradual decline in catalyst activity over time. This is primarily due to the coating of the catalyst surface with organic matter during the reaction, which reduces the catalyst contact area and leads to a decrease in formaldehyde conversion. Catalytic activity is assessed by measuring the mass of the organic coating on the catalyst surface, also known as the loss on ignition (LOI). The primary method for maintaining catalyst activity in industrial production is to regularly replenish new catalyst and discharge spent catalyst to maintain a stable LOI. Discharged spent catalyst contains not only the catalyst but also various compounds such as copper acetylene, residual butynediol, formaldehyde, and polyacetylene. It cannot be stored long-term and must be disposed of as hazardous waste by specialized manufacturers. For a 100,000-ton unit, to maintain an LOI of approximately 50%, approximately 60-80 tons of catalyst are discharged annually, incurring costs of approximately 20-30 million yuan. Amidst increasingly fierce competition in the BDO market, some manufacturers are recycling spent catalysts to reduce production costs.

[0004] Research on the regeneration mechanism of copper-based catalysts has shown that sintering and agglomeration are the primary cause of permanent damage to copper-based catalysts. This is primarily manifested by the aggregation of copper grains at high temperatures, resulting in Ostwald ripening, which reduces their specific surface area. Sintering and agglomeration begin at the Hüttig temperature. As the temperature rises, the copper-based catalyst sintering accelerates, until a severe in-situ sintering transformation occurs at the Tamman temperature. While the appearance remains unchanged, the phases undergo a transformation. Therefore, temperature control during the regeneration of copper-based catalysts is crucial. Existing treatment technologies for spent catalysts primarily involve removing organic matter from the catalyst surface through high-temperature incineration and strong oxidation to restore catalyst activity. For example, patents CN109647544A and CN113209980A, although the treatment order and process are different, both remove organic inclusions by incineration. Although such methods can remove organic matter on the catalyst surface more thoroughly, they ignore the serious agglomeration of catalyst particles caused by high temperature conditions, which changes the microstructure and causes irreversible damage to catalyst performance. This is also contrary to the original intention of catalyst recovery to control LOI in the reactor.

[0005] Therefore, it is necessary to develop a technology that aims to reduce the LOI in the reactor without damaging the microstructure of the catalyst and allowing large amounts of catalyst to be recycled. Summary of the Invention

[0006] In order to overcome the above-mentioned defects, the present invention provides a regeneration system, regeneration method and application of a supported copper-bismuth catalyst, which does not damage the microstructure of the catalyst during the catalyst regeneration process, so that the catalyst can be returned to the acetylation reactor for recycling after regeneration, and ultimately the LOI in the acetylation reactor is controlled within a preset range, thereby improving the reaction efficiency.

[0007] In a first aspect, the present invention provides a regeneration system for a supported copper-bismuth catalyst, comprising: an acetylation reactor, a catalyst concentration device, a catalyst separator, a catalyst preparation device, a regeneration reactor, a catalyst cooler, and a reduction reactor connected in sequence;

[0008] Wherein, the catalyst separator is provided with a rotating shaft and a plurality of filter plates for intercepting the catalyst, and the filter plates are connected to the rotating shaft;

[0009] The catalyst preparation device is provided with a first desalted water input port;

[0010] The regeneration reactor is connected to a gas delivery pipe for inputting regeneration gas, wherein the regeneration gas is nitrogen or a mixed gas, wherein the mixed gas is a mixture of nitrogen and air;

[0011] The reduction reactor is provided with a formaldehyde aqueous solution input port; the discharge port of the reduction reactor is connected to the acetylation reactor.

[0012] Furthermore, the discharge port at the bottom of the acetylation reactor is connected to the feed port of the catalyst concentration device;

[0013] The material output port of the catalyst concentration device is connected to the feed port of the catalyst separator;

[0014] The rotating shaft in the catalyst separator is vertically arranged and has a hollow structure, and the multiple filter plates are arranged at intervals and communicated with the rotating shaft;

[0015] The feed port of the catalyst preparation device is connected to the discharge port at the bottom of the catalyst separator, the discharge port of the catalyst preparation device is connected to the feed port of the regeneration reactor, the catalyst discharge port of the regeneration reactor is connected to the feed port of the catalyst cooler, and the discharge port of the catalyst cooler is connected to the feed port of the reduction reactor.

[0016] Furthermore, the regeneration reactor is a rotary kiln pyrolysis reactor; and / or

[0017] The acetylation reactor is an acetylation reactor for synthesizing 1,4-butynediol.

[0018] Furthermore, the system further comprises: a wire mesh demister, a collector, a gas compressor and a collector circulation cooler; the regeneration reactor is further provided with a gas phase discharge port and a gas phase reflux port; the gas phase discharge port, the wire mesh demister and the collector feed port are sequentially connected;

[0019] The collector is also provided with a second desalted water inlet, a gas phase outlet, a liquid phase outlet and a liquid phase reflux port. The gas phase outlet, the gas compressor and the gas phase reflux port are connected in sequence, and the liquid phase outlet, the collector circulating cooler and the liquid phase reflux port are connected in sequence.

[0020] Furthermore, the catalyst concentration device is also provided with a catalyst reflux port and a clear liquid outlet, and the catalyst reflux port is connected to the acetylation reactor.

[0021] In a second aspect, the present invention provides a method for regenerating a supported copper-bismuth catalyst using the system described in the first aspect, comprising:

[0022] S1, controlling the acetylation reactor to transport the slurry containing the copper-bismuth catalyst to the catalyst concentration device;

[0023] S2, controlling the catalyst concentration device to concentrate the slurry to obtain a concentrated liquid;

[0024] S3, inputting the concentrated liquid into a catalyst separator to separate the catalyst to be regenerated;

[0025] S4, inputting the catalyst to be regenerated into a catalyst preparation device to be prepared into a preset solid content, and then inputting it into a regeneration reactor;

[0026] S5, controlling the regeneration gas to be input into the regeneration reactor according to a preset input flow rate, performing catalyst regeneration treatment in the regeneration reactor, and inputting the treated catalyst into the catalyst cooler for cooling;

[0027] S6, feeding the cooled material into a reduction reactor and feeding a formaldehyde aqueous solution with a preset concentration into the reduction reactor to perform catalyst reduction;

[0028] S7, inputting the materials after the reaction in the reduction reactor into the acetylation reactor.

[0029] Furthermore, the controlling the regeneration gas to be input into the regeneration reactor according to a preset input flow rate comprises:

[0030] S51, inputting regeneration gas into the regeneration reactor, wherein the regeneration gas in step S51 is nitrogen, and then controlling the regeneration reactor to reach 60-180°C at a heating rate of 30-180°C / hour, and maintaining the temperature for 3-8 hours;

[0031] S52, inputting the regeneration gas into the regeneration reactor, wherein the regeneration gas in step S52 is a mixture of nitrogen and air, and controlling the temperature to rise at a heating rate of 5-60°C / hour until the temperature reaches 300-500°C, and maintaining the constant temperature for 3-12 hours; wherein the molar ratio of nitrogen to air is in the range of (1-100000):1.

[0032] Furthermore, the amount of regeneration gas added is calculated based on the gas hourly space velocity GHSV. In step S51, the GHSV of the nitrogen is N2 50~1000 hours -1 In step S52, the total airspeed GHSV of the mixture sum 300~2000 hours -1 , preferably 500~1500 hours -1 .

[0033] Furthermore, the pyrolysis temperature is controlled by the amount of air added, GHSV air The adjustment rate range is 0.00001~100h -1 / Hour.

[0034] Furthermore, in step S5, the cooling temperature is 60-120°C.

[0035] Furthermore, during the process of separating the catalyst to be regenerated from the catalyst separator, the temperature is controlled to be 90-98° C. and the pressure is controlled to be 0.6-1.0 MPaG; and / or

[0036] The formaldehyde aqueous solution of the preset concentration has a formaldehyde mass fraction of 40-55% and a pH of 6-8.

[0037] The mass ratio of the added amount of the formaldehyde aqueous solution to the catalyst in the reduction reactor is 5-20:1, and the reaction residence time is 5-120 minutes.

[0038] In a third aspect, the present invention provides a use of the regeneration system according to the first aspect or the method according to the second aspect in controlling the amount of catalyst ablation.

[0039] The above one or more technical solutions of the present invention have at least one or more of the following beneficial effects:

[0040] In implementing the technical solution of this invention, with the goal of reducing the LOI within the acetylation reactor, the catalyst's inherent activity is utilized to catalytically oxidize organic inclusions from the surface, while simultaneously achieving controlled conversion of copper valence states. A specialized process design and controlled pyrolysis conditions, such as temperature, suppress copper agglomeration and sintering during the regeneration process, thus preventing irreversible damage to catalyst performance. This approach utilizes low energy consumption, does not damage the catalyst's microstructure, and, through a constant amount of catalyst recycling, maintains the reactor's LOI at a low level, significantly improving reaction efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The disclosure of the present invention will be more easily understood with reference to the accompanying drawings. Those skilled in the art will readily appreciate that these drawings are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Furthermore, similar numbers in the drawings represent similar components, wherein:

[0042] Figure 1 is a schematic diagram of the main structure of a catalyst regeneration system according to one embodiment of the present invention;

[0043] Figure 2 This is a schematic diagram of the main process of a catalyst regeneration method according to one embodiment of the present invention;

[0044] Figure 3 is a scanning electron microscope image of the catalyst at 1 μm after the reaction in step S7 according to Example 1 of the present invention;

[0045] Figure 4 is a 1 μm scanning electron microscope image of the fresh catalyst according to Comparative Example 1 of the present invention;

[0046] Figure 5This is a 1 μm scanning electron microscope image of the regenerated catalyst obtained in Comparative Example 2 of the present invention;

[0047] Figure 6 is a scanning electron microscope image of a 200 nm catalyst after the reaction in step S7 according to Example 1 of the present invention;

[0048] Figure 7 is a 200 nm scanning electron microscope image of the fresh catalyst according to Comparative Example 1 of the present invention;

[0049] Figure 8 is a scanning electron microscope image of 200 nm of the regenerated catalyst obtained according to Comparative Example 2 of the present invention;

[0050] Figure 9 This is a 0.2 μm transmission electron microscope image of the catalyst after the reaction in step S7 according to Example 1 of the present invention;

[0051] Figure 10 is a transmission electron microscope image of a fresh catalyst at 0.2 μm according to Comparative Example 1 of the present invention;

[0052] Figure 11 This is a 0.2 μm transmission electron microscope image of the regenerated catalyst obtained in Comparative Example 2 of the present invention;

[0053] Figure 12 is a transmission electron microscopy image of a 50 nm catalyst after the reaction in step S7 according to Example 1 of the present invention;

[0054] Figure 13 is a transmission electron microscope image of a 50 nm fresh catalyst according to Comparative Example 1 of the present invention;

[0055] Figure 14 This is a transmission electron microscope image of a 50 nm regenerated catalyst obtained in Comparative Example 2 of the present invention;

[0056] Figure 15 It is a comparison chart of XPS spectra of Comparative Example 1 and Comparative Example 2 according to the present invention.

[0057] List of reference numerals:

[0058] 1: Acetylation reactor; 2: Catalyst concentration device; 2-1: Catalyst reflux port; 2-2 Clear liquid outlet; 3: Catalyst separator; 3-1: Rotating shaft; 3-2: Filter plate; 4: Catalyst preparation device; 4-1 First desalted water inlet; 5: Regeneration reactor; 5-1: Gas delivery pipe; 511: Air delivery pipe; 512: Nitrogen delivery pipe; 5-2: Wire mesh demister; 5-3: Gas phase discharge port; 5-4: Gas phase reflux port; 6: Catalyst cooler; 7: Reduction reactor; 7-1: Formaldehyde aqueous solution inlet; 8: Online analytical chromatograph; 9: Collector; 9-1: Gas phase outlet; 9-2: Liquid phase outlet; 9-3: Liquid phase reflux port; 9-4 Second desalted water inlet; 10: Collector circulating cooler; 11: Gas compressor; 12: Circulating gas cooler; 13: BYD delivery pipe. DETAILED DESCRIPTION

[0059] Some embodiments of the present invention are described below with reference to the accompanying drawings. Those skilled in the art should understand that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the scope of protection of the present invention.

[0060] The term "A and / or B" refers to all possible combinations of A and B, such as just A, just B, or A and B. The term "at least one of A or B" or "at least one of A and B" has a similar meaning to "A and / or B" and may include just A, just B, or A and B. The singular forms "a" and "the" may also include plural forms.

[0061] Reference Figure 1 The present invention provides a regeneration system for a loaded copper-bismuth catalyst, comprising: an acetylation reactor 1, a catalyst concentration device 2, a catalyst separator 3, a catalyst preparation device 4, a regeneration reactor 5, a catalyst cooler 6 and a reduction reactor 7 connected in sequence.

[0062] The acetylation reactor 1 of the present invention is a reaction device for completing the reaction of acetylene and formaldehyde to produce butynediol. In this reaction system, a supported copper-bismuth catalyst with a silicon-aluminum composite as a carrier is used. However, during the reaction process, as the chemical reaction continues, the catalyst surface is gradually covered by organic matter, which leads to a reduction in the effective contact area of ​​the catalyst. After exceeding a certain limit, the catalytic activity is significantly reduced, the conversion rate is reduced, and filtration and separation are difficult. In industrial production, the degree of organic matter coating the catalyst is characterized by the LOI. By regularly withdrawing a certain amount of catalyst for regeneration and then recycling it back to the reactor, the LOI index in the acetylation reactor 1 can be controlled at a low level without adding a large amount of new catalyst.

[0063] In one embodiment, the acetylation reactor 1 is used for synthesizing 1,4-butynediol. Formaldehyde and acetylene are fed into the acetylation reactor 1, the reaction temperature is 98±1°C, and the reaction pressure is 180 kPa±5. The catalyst is a supported copper-bismuth catalyst on a silicon-aluminum composite support, typically BASF supported copper catalyst Cu6081P. The slurry after the reaction in the acetylation reactor 1 consists of water, the catalyst to be regenerated, butynediol (BYD), and other organic matter.

[0064] The following describes in detail the equipment used to restore the activity of the catalyst and the system it constitutes;

[0065] The discharge port at the bottom of the acetylation reactor 1 is connected to the feed port of the catalyst concentration device 2 .

[0066] The catalyst concentration device 2 is used to concentrate the material.

[0067] In one embodiment, the catalyst concentration device 2 is a complete equipment system capable of continuously withdrawing a supernatant and continuously returning a concentrated slurry to the acetylation reactor 1. Such equipment may include a dynamic cross-flow filter, a disc filter, or the like. Examples include BOKELA's dynamic cross-flow filter, PALL's SCHENK filter, and other similar devices. These devices not only effectively separate the catalyst concentrate from the supernatant, but also ensure the continuity and efficiency of the entire process, thereby meeting the requirements for catalyst recovery and reuse in industrial production.

[0068] In one embodiment, the catalyst concentration device 2 is further provided with a catalyst reflux port 2-1 and a clear liquid outlet 2-2. The catalyst reflux port 2-1 is connected to the acetylation reactor 1 for refluxing a portion of the catalyst concentrate. The clear liquid outlet 2-2 is used to discharge the concentrated clear liquid. The clear liquid outlet 2-2 is connected to the BYD delivery pipe 13 and is used to discharge the BYD solution, which is collected and transported within the BYD delivery pipe 13. The concentrated catalyst concentrate is transported to the catalyst separator 3 via the material outlet of the catalyst concentration device 2.

[0069] The catalyst concentration device 2 has three output ports: a material outlet, a catalyst reflux port 2-1, and a clear liquid outlet 2-2. The process is as follows: After the discharge from the bottom of the acetylation reactor 1 is concentrated by the catalyst concentration device 2, the concentrated catalyst slurry is partially recycled back to the acetylation reactor 1 via the catalyst reflux port 2-1, and a portion is delivered to the catalyst separator 3 via the material outlet according to a preset extraction ratio. The concentrated clear liquid, namely the BYD solution, is then delivered from the clear liquid outlet 2-2 to the BYD delivery pipe 13.

[0070] Catalyst separation and filtration are performed in the catalyst separator 3 in order to recover the BYD (butynediol) solution remaining in the spent catalyst.

[0071] The catalyst separator 3 is provided with a rotating shaft 3-1 and a plurality of filter plates 3-2 for intercepting the catalyst, and the filter plates 3-2 are connected to the rotating shaft 3-1. The rotating shaft 3-1 is arranged vertically and has a hollow structure. The plurality of filter plates 3-2 are arranged at intervals and are connected to the rotating shaft 3-1. The catalyst separator 3 is a hollow cavity, and the rotating shaft 3-1 and the filter plates 3-2 are located in the cavity. The filter plates 3-2 are spaced apart in the vertical direction and need to be spaced at certain intervals to accommodate the catalyst. The filter plates 3-2 can be arranged in a disc shape according to actual needs.

[0072] The concentrated catalyst slurry is obtained by passing through the catalyst concentration device 2. The concentrated liquid is fed from the top of the catalyst separator 3. The slurry flows from top to bottom through each filter plate 3-2. The filter plates 3-2 are hollow and have filter material on their surfaces to intercept the catalyst. The rotation of the rotating shaft 3-1 drives the filter plates 3-2 to rotate at high speed. Under high-speed stirring, the filtered clear liquid penetrates the filter plates 3-2 and is collected in the rotating shaft 3-1. The BYD solution is mainly composed of the BYD solution, which is discharged from the bottom of the rotating shaft for product recovery.

[0073] The catalyst in the concentrated liquid is intercepted by the surface of the filter plate 3-2, contained in the cavity between the filter plates 3-2, and discharged from the cavity of the catalyst separator 3 through the discharge port at the bottom of the catalyst separator 3 by high-speed centrifugal rotation and input into the catalyst preparation device 4.

[0074] In one embodiment, the bottom end of the rotating shaft 3 - 1 is connected to a BYD delivery pipe 13 , and the BYD delivery pipe 13 collects the BYD solution from the rotating shaft 3 - 1 and the BYD solution from the clear liquid output port 2 - 2 of the catalyst concentration device 2 .

[0075] The feed port of the catalyst preparation device 4 is connected to the discharge port at the bottom of the catalyst separator 3, and the discharge port of the catalyst preparation device 4 is connected to the feed port of the regeneration reactor 5; a desalted water input port is provided on the catalyst preparation device 4. In order to distinguish it from the desalted water input ports of other components, the desalted water input port on the catalyst preparation device 4 is recorded as the first desalted water input port 4-1.

[0076] The regeneration reactor 5 is connected to a gas delivery pipe 5-1 for inputting regeneration gas. Depending on the different stages of the reaction in the regeneration reactor 5, the regeneration gas may include only nitrogen or a mixed gas consisting of nitrogen and air.

[0077] The catalyst discharge port 5 - 5 of the regeneration reactor 5 is connected to the feed port of the catalyst cooler 6 .

[0078] In one embodiment, the regeneration reactor 5 is provided with a heating facility for heating the regeneration reactor 5 to increase the temperature.

[0079] In one embodiment, the regeneration reactor 5 is a rotary kiln pyrolysis reactor, which can be heated electrically or by gas.

[0080] In one embodiment, gas delivery pipe 5-1 is connected to air delivery pipe 511 and nitrogen delivery pipe 512, respectively. Control valves are provided on air delivery pipe 511 and nitrogen delivery pipe 512 to control the opening and closing of the pipes. Air flow meters and nitrogen flow meters are provided on air delivery pipe 511 and nitrogen delivery pipe 512, respectively, to accurately measure the flow rates of the input air and nitrogen, facilitating regulation of the input amounts of air and nitrogen.

[0081] The catalyst regenerated in the regeneration reactor 5 is cooled in the catalyst cooler 6 to 60-120° C. before being fed into the reduction reactor 7 . The discharge port of the catalyst cooler 6 is connected to the feed port of the reduction reactor 7 .

[0082] The reduction reactor 7 is provided with a formaldehyde aqueous solution input port; the discharge port of the reduction reactor 7 is connected to the acetylation reactor 1 .

[0083] In one embodiment, the reduction reactor 7 is a stirred tank reactor.

[0084] In one embodiment, the system further comprises: a wire mesh demister 5-2, a collector 9, a gas compressor 11, and a collector circulating cooler 10. The regeneration reactor 5 is further provided with a gas phase discharge port 5-3 and a gas phase reflux port 5-4. The gas phase discharge port 5-3, the wire mesh demister 5-2, and the feed port of the collector 9 are connected in sequence. The liquid phase outlet 9-2, the collector circulating cooler 10, and the liquid phase reflux port 9-3 are connected in sequence.

[0085] The collector 9 is also provided with a second desalted water inlet 9-4, a gas phase outlet 9-1, a liquid phase outlet 9-2 and a liquid phase reflux port 9-3. The gas phase outlet 9-1, the gas compressor 11 and the gas phase reflux port 5-4 are connected in sequence.

[0086] In order to distinguish it from the desalted water inlet on the catalyst preparation device 4 , the desalted water inlet on the collector 9 is recorded as the second desalted water inlet 9 - 4 .

[0087] In one embodiment, an online analytical chromatograph 8 is further provided between the wire mesh demister 5 - 2 and the collector 9 for testing the composition of the gas phase.

[0088] The functions of the wire mesh demister 5-2, the collector 9 and the gas compressor 11 are explained below in conjunction with the process method.

[0089] The material in the catalyst preparation unit 4 is prepared into a slurry of a certain concentration and transported to the regeneration reactor 5. Regeneration gas is then introduced into the regeneration reactor 5. The composition of the regeneration gas is determined according to the reaction stage, and the oxygen content in the regeneration gas is precisely controlled by two mass flow meters. The regeneration reactor 5 is a rotary kiln-type reactor heated by electricity or gas. In the regeneration reactor 5, the slurry and regeneration gas are in full contact, achieving catalyst regeneration.

[0090] During the regeneration process, the gas phase is discharged from the gas phase discharge port 5-3 of the regeneration reactor 5, passes through the wire mesh demister 5-2, and enters the collector 9. In the collector 9, after desalted water is input through the second desalted water input port 9-4, the gas phase input into the collector 9 is sprayed, and the desalted water is used to absorb the organic matter carried in the tail gas (the gas phase in the regeneration reactor 5), such as water, THF, formaldehyde, methanol, ethanol, etc. After the organic matter is removed, the regenerated gas is discharged from the gas phase outlet 9-1 at the top of the collector 9, further pressurized by the gas compressor 11, and returned to the gas phase reflux port 5-4 to enter the regeneration reactor 5 for recycling. The gas phase discharged from the gas phase outlet 9-1 can also be partially discharged out of the system regularly.

[0091] Inside the collector 9, the tail gas, that is, the gas phase from the regeneration reactor 5, is sprayed with desalted water to form a waste liquid containing organic matter. When the organic content in these waste liquids is relatively low, they still have a certain absorption capacity, so these waste liquids can be refluxed to the liquid phase reflux port 9-3. After being replenished with new desalted water, these waste liquids will be used for the spraying process again. However, as the organic content in the liquid phase after spraying in the collector 9 gradually increases, in order to maintain the normal operation and efficiency of the system, it is necessary to regularly discharge these waste liquids rich in organic matter from the system. In one embodiment, a sewage discharge pipe is provided between the liquid phase reflux port 9-3 and the collector circulating cooler 10, and a control valve is provided on the pipe. Opening the control valve can discharge the waste liquid rich in organic matter from the system.

[0092] In one embodiment, the system further comprises a circulating gas cooler 12, wherein the collector circulating cooler 10 is connected to the liquid phase outlet 9-2 and the liquid phase reflux port 9-3, respectively. The circulating gas cooler 12 is connected to the gas compressor 11 and the gas phase reflux port 5-4, respectively.

[0093] In one embodiment, a vent pipe is provided between the circulating gas cooler 12 and the gas compressor 11 , and a control valve is provided on the vent pipe. The gas phase can be discharged by opening the control valve.

[0094] In one embodiment, the gas delivery pipe 5 - 1 may be connected to the pipeline between the circulating gas cooler 12 and the gas phase reflux port 5 - 4 .

[0095] The present invention discloses a method for regenerating a copper-bismuth catalyst using the above system, referring to Figure 2 ,include:

[0096] S1, controlling the acetylation reactor 1 to transport the slurry containing the copper-bismuth catalyst to the catalyst concentration device 2;

[0097] S2, controlling the catalyst concentration device 2 to concentrate the slurry to obtain a concentrated liquid;

[0098] S3, inputting the concentrated liquid into the catalyst separator 3 to separate the catalyst to be regenerated;

[0099] S4, the catalyst to be regenerated is input into the catalyst preparation device 4 and prepared into a preset solid content, and then input into the regeneration reactor 5;

[0100] S5, controlling the regeneration gas to be input into the regeneration reactor 5 according to a preset input flow rate, performing catalyst regeneration treatment in the regeneration reactor 5, and inputting the treated catalyst into the catalyst cooler 6 for cooling;

[0101] S6, the cooled material is fed into the reduction reactor 7 and a formaldehyde aqueous solution with a preset concentration is fed into the reduction reactor 7 to perform catalyst reduction;

[0102] S7, inputting the materials after the reaction in the reduction reactor 7 into the acetylation reactor 1.

[0103] In one embodiment, in step S1, the acetylation reactor 1 is a reaction unit for producing butynediol using a BDO unit through the acetylenic aldehyde process. The acetylation reaction in the acetylation reactor 1 is as follows: butynediol is produced using formaldehyde and acetylene as raw materials in the presence of a catalyst. The reaction temperature is controlled at 98±1°C and the reaction pressure is controlled at 180 kPa±5. The catalyst is a supported copper-bismuth catalyst supported on a silicon-aluminum composite, typically such as BASF's supported copper catalyst Cu6081P. During production, the catalyst surface is gradually coated with organic matter, resulting in a reduction in the catalyst contact area, necessitating regeneration.

[0104] The slurry containing the copper-bismuth catalyst is the slurry after the reaction in the acetylation reactor 1, and includes water, the copper-bismuth catalyst, BYD and other organic substances.

[0105] In one embodiment, in step S2, the copper-bismuth catalyst-containing slurry is conveyed to a catalyst concentration unit 2 for concentration using a dynamic cross-flow filtration or disc filtration system. After passing through the catalyst concentration unit 2, the slurry is concentrated. This concentration can reduce the amount of BYD discharged with the catalyst.

[0106] In one embodiment, step S2 is concentrated by the catalyst concentration device 2 to obtain a concentrated liquid. A portion of the concentrated liquid is recycled back to the acetylation reactor 1, while a portion is discharged through the material outlet according to the required recovery ratio and pumped to the catalyst separator 3. Furthermore, the concentrated clear liquid, i.e., the BYD solution, is conveyed from the clear liquid outlet 2-2 to the BYD delivery pipe 13. In this step, the valence state of the copper in the catalyst in the slurry is primarily monovalent Cu(I).

[0107] In one embodiment, in step S3, the concentrated liquid output from the catalyst concentration device 2 is fed into the catalyst separator 3 for separation and filtration to separate the spent catalyst to be regenerated, i.e., the catalyst to be regenerated, and to recover the residual BYD solution. After separation in the catalyst separator 3, the clear liquid, a BYD (butynediol) solution, is withdrawn from the axis of the catalyst separator 3, i.e., the rotating shaft 3-1, for reuse as the BYD product. The regenerated catalyst to be subsequently regenerated is then ejected from the cavity between the filter plates 3-2 via high-speed centrifugal rotation and enters the catalyst preparation device 4. The solution withdrawn from the rotating shaft 3-1 for reuse as the BYD product can be connected to the BYD delivery pipe 13.

[0108] In one embodiment, during the filtration separation process, the catalyst separator 3 controls the temperature to 90-98° C. and the pressure to 0.6-1.0 MPaG. By adjusting the temperature and pressure in this manner, the BYD solution in the waste catalyst can be effectively recovered.

[0109] In one embodiment, in step S4, desalted water is added through the first desalted water inlet 4-1 of the catalyst preparation device 4 and mixed with the catalyst to be regenerated separated from the catalyst separator 3, and the regenerated catalyst slurry is prepared into a solution with a solid content of about 80% to 95%.

[0110] In one embodiment, in step S5, pure nitrogen or a mixture of nitrogen and air is selectively fed according to the reaction stage within the regeneration reactor 5. The low-temperature catalytic oxidation process in the regeneration reactor 5 regenerates the catalyst, removing moisture and organic inclusions from the catalyst. At the end of the oxidative decomposition, the catalyst is mostly copper (II).

[0111] In step S5, the catalyst is regenerated in the regeneration reactor 5. The main purpose of this step is to remove moisture and catalytically decompose organic inclusions in different stages. After the catalyst to be regenerated from step S4 is input into the regeneration reactor 5, the regeneration gas is continuously introduced. + 、Cu 2+ 、Cu 0) Under the catalytic action of the mixed active species, at a certain temperature, the organic coating on the catalyst surface undergoes thermal decomposition and oxidation reaction under the action of the catalytic active species, generating CO2, H2O and other volatile light components. The reaction mechanism is as follows:

[0112] There are two stages in the regeneration of the catalyst in the regeneration reactor 5. First, there is physical separation. The regeneration gas in the first stage is nitrogen. At a lower temperature, the water and volatile organic compounds (such as methanol, acetylene, formaldehyde, etc.) in the catalyst are removed by nitrogen stripping. The second stage is catalytic oxidation decomposition. The temperature continues to rise. The regeneration gas is a mixture of nitrogen and air. The lattice oxygen in the catalyst is activated by adsorbing oxygen in the regeneration gas, and the monovalent copper Cu is removed. + Forming a metastable active phase CuO with lattice oxygen x It is activated and provides lattice oxygen to CH, CO bonds in organic inclusions, converting them into CO2, H2O and small molecular compounds, and metastable CuO x It is also eventually oxidized to divalent copper (II), and the oxygen in the regeneration gas quickly replenishes the oxygen vacancies of the catalyst and continues to oxidize Cu+ to form the intermediate active CuO x In this way, when the organic inclusions are completely decomposed, the copper valence state in the catalyst is also converted to mainly divalent copper.

[0113] In one embodiment, in step S5, according to the first stage and the second stage, controlling the regeneration gas to be input into the regeneration reactor 5 according to a preset input flow rate includes:

[0114] In the first stage, S51, regeneration gas is fed into the regeneration reactor 5. The regeneration gas in step S51 is referred to as the first regeneration gas and is pure nitrogen. The regeneration reactor 5 is then heated to a temperature of 60-180°C at a rate of 30-180°C / hour and maintained at this temperature for 3-8 hours until the exhaust gas composition remains constant. Preferably, the temperature is heated to a temperature of 80-150°C at a rate of 60-120°C / hour until the exhaust gas composition remains constant.

[0115] In the second stage, S52, regeneration gas is fed into the regeneration reactor 5. The regeneration gas in step S52 is referred to as the second regeneration gas. The second regeneration gas is a mixture of nitrogen and air. The temperature is raised at a controlled rate of 5-60°C / hour until the temperature reaches 300-500°C, preferably 350-450°C, and the temperature is maintained constant for 3-12 hours. The molar ratio of nitrogen to air is (100-20,000):1. Preferably, the temperature is raised at a controlled rate of 10-30°C / hour until the temperature reaches 350-450°C, and the temperature is maintained constant for 3-12 hours.

[0116] In one embodiment, the amount of regeneration gas added is calculated based on the gas hourly space velocity (GHSV). In step S51, the GHSV of the nitrogen is N2 50~1000 hours -1 In step S52, the total airspeed GHSV of the mixture sum 300~2000 hours -1 , preferably 500~1500 hours -1 The pyrolysis temperature is controlled by the amount of air added, GHSV air The adjustment rate range is 0.00001~100h -1 / Hour.

[0117] After the catalytic oxidation stage of the regeneration reactor 5 is completed, the organic coatings on the catalyst surface have been removed, and most of the copper in the catalyst exists in the form of divalent copper.

[0118] The two-stage reaction process is described in more detail below.

[0119] The control of the mixed gas or nitrogen input to the regeneration reactor 5 according to the preset input flow rate includes the first stage and the second stage:

[0120] S51, the first stage, inputs nitrogen into the regeneration reactor 5, and the specific process is as follows:

[0121] After the catalyst to be regenerated is prepared to a preset solid content in the catalyst preparation device 4, it is input into the regeneration reactor 5. Then, nitrogen gas is started to be introduced into the regeneration reactor 5. Under heating, the regeneration reactor 5 requires that the catalyst to be regenerated fully contact with the regeneration gas to react and achieve catalyst regeneration. The gas phase is discharged from the gas phase discharge port 5-3 and passes through the wire mesh demister 5-2 before entering the collector 9. An online analytical chromatograph 8 is set in the pipeline between the wire mesh demister 5-2 and the collector 9 to monitor the gas phase composition and determine the completion of activation based on the changes in the components.

[0122] The operating pressure of the collector 9 is 10-100 kPa, and the temperature is 20±5°C. Desalted water is added as the absorption liquid from the top of the collector 9, where it comes into countercurrent contact with the gas phase, absorbing organic matter carried in the gas phase, such as water, THF, formaldehyde, methanol, and ethanol. The regenerated gas, free of organic matter, is further pressurized by the gas compressor 11 and circulated back to the regeneration reactor 5 for reuse. The liquid phase containing organic matter is partially cooled to 20±1°C by the collector recirculation cooler 10 and then circulated back to the collector 9 to continue absorbing organic matter from the exhaust gas, while a portion is periodically sent off-site for treatment. After the organic matter is removed from the gas at the top of the collector 9, it is returned to the regeneration reactor 5 for recycling via the gas compressor 11.

[0123] The first stage of step S51 is physical separation, the regeneration gas is nitrogen gas alone, and the GHSV of nitrogen gas is N2 Can be set between 50-1000hr -1 Once the gas establishes a stable circulation according to the illustrated flow, the heating device in the regeneration reactor 5 begins heating. The heating rate can be set between 30°C and 180°C / hr, and after reaching 150°C, the temperature is maintained for three hours. During this stage, as the temperature rises, water (including surface water and freely bound water) and volatile organic compounds (such as methanol, ethanol, THF, and formaldehyde) in the catalyst pass through the wire mesh demister 5-2 along with the nitrogen to prevent the catalyst from being carried away by the gas. The gases are then transported to the collector 9, where the organic matter in the gas phase is separated and discharged as organic waste liquid. The nitrogen, free of organic matter and water, is pressurized by the gas compressor 11 and circulated back to the regeneration reactor 5 through the gas phase reflux port 5-4 for reuse. The composition of the gas phase is monitored by the online analytical chromatograph 8 in the pipeline.

[0124] The second stage is catalytic oxidation decomposition. The regeneration gas is a mixture of nitrogen and air. In order to ensure accurate control of the reaction, the input of nitrogen and air in the two stages must be monitored in real time. The completion of catalyst regeneration is determined by the change in oxygen content in the gas phase. A temperature measurement point is set in the regeneration reactor 5. Figure 1 The dashed line indicates that the regeneration reactor 5 is equipped with a temperature acquisition device (such as a temperature sensor) for obtaining the internal temperature of the regeneration reactor 5. A control circuit is provided between the air delivery pipe 511 and the temperature sensor of the regeneration reactor 5 to control the air flow rate delivered by the air delivery pipe 511 based on the temperature acquired by the temperature acquisition device. The reaction pressure within the regeneration reactor 5 can be set to 1-100 kPa. In step S52, a mixture of nitrogen and air is introduced into the regeneration reactor 5. The reaction temperature is increased at a rate of 5-60°C / hour until it reaches 300-500°C, preferably 350-450°C, and maintained at this temperature for 3-5 hours. The molar ratio of nitrogen to air is (1-100,000):1. When the oxygen supply is stable and the temperature no longer rises, decomposition is essentially complete.

[0125] In one embodiment, the total space velocity GHSV of the regeneration gas in the second stage is sum Control 300-2000hr -1 , preferably 500-1500hr -1 When the total air velocity is constant, the pyrolysis temperature is controlled by adjusting the amount of air added. air Growth rate range 0.0001~100h -1 / Hour.

[0126] In one embodiment, after the first stage ends, the second stage begins. While continuing to introduce nitrogen, a certain amount of air is introduced, and the temperature continues to rise, controlled at a rate of 5-60°C / hour. The N2 and air are mixed and added to the regeneration reactor 5. Upon contact between the regeneration gas containing oxygen and the catalyst, the high specific surface area and rich pore structure of the catalyst trigger a catalytic oxidation reaction. The reaction heat is rapidly transferred, causing the temperature to rise rapidly, further accelerating the reaction. Organic matter is oxidized to CO, CO2, and small molecule volatile organic compounds (VOCs). A control loop is formed with the reaction temperature and nitrogen flowmeter to maintain the temperature rise rate at 5-60°C / hr. If the temperature rise rate is too fast, the air intake can be reduced. Once the temperature stabilizes, the air intake is increased and the temperature is further increased. Once the temperature reaches 300-500°C, the temperature is maintained constant for 3-12 hours. During the above process, as the reaction proceeds, the oxygen content in the gas phase gradually increases from low to high. As the reaction proceeds, most of the organic matter is decomposed, and the oxygen content gradually increases, eventually reaching the same level as the intake air, indicating that the reaction is essentially complete. Finally, when the organic matter is completely decomposed and the catalyst is regenerated, a sample can be taken to test the catalyst's LOI.

[0127] In the second stage, the molar ratio of nitrogen to air ranges from 1:1 to 100,000. This ratio is adjusted based on temperature fluctuations. Precise control of the oxidation reaction requires precise air flow. As the air flow increases, the oxidation reaction accelerates, leading to a rapid temperature rise.

[0128] The catalyst regeneration technology involved in the present invention is divided into two stages, and different process parameters are applied in each stage. This staged treatment method plays a vital role in improving the regeneration effect of the catalyst. There are two major challenges in the catalyst regeneration process, which are often difficult to properly handle and balance at the same time. The first challenge is that the organic matter coated on the catalyst surface is difficult to completely separate and needs to be removed by high temperature. The second challenge is that the catalytic oxidation decomposition reaction is violent and releases a large amount of heat. During the process of removing the organic matter, how to effectively control the temperature to avoid overheating, which will cause the copper in the catalyst to agglomerate and permanently damage the catalyst performance. To address these problems, the present invention proposes a special regeneration process method that successfully overcomes the above-mentioned difficulties. Through this method, relying on the self-activity of the regenerated catalyst, the active metal multivalent copper in the catalyst is regulated and converted while removing the organic matter coated on the catalyst. By regulating the temperature of the catalytic decomposition, the microstructure of the catalyst is protected from damage and the performance of the catalyst is restored to the maximum extent. The present invention adopts different gas hourly space velocities and heating rates for different regeneration stages, balances the reaction rate with the amount of air added, controls the heat release, and effectively avoids the problems of local overheating or incomplete decomposition of organic matter. By comprehensively controlling various process parameters as defined in the present invention, the uniformity of the bed temperature distribution in the regenerator can be maintained, and the performance of the catalyst can be restored to the maximum extent.

[0129] In one embodiment, for step S51 in which the components in the exhaust gas are constant, the judgment method is to test the composition of the gas phase through the online analytical chromatograph 8 arranged between the wire mesh demister 5-2 and the collector 9. When the gas phase components no longer change, it indicates that the components in the exhaust gas are constant. The constant temperature time of this process is 3 to 8 hours. After the components are constant, step S52 can be entered.

[0130] In step S52, after the catalytic oxidation phase in regeneration reactor 5 is complete, the organic coatings on the catalyst surface have been removed, the oxygen content in online analytical chromatograph 8 is stable and essentially equal to the intake air volume, and the regeneration reaction is essentially complete. At this point, the copper in the active bulk of the catalyst is primarily present in the form of divalent copper. The regenerated catalyst slurry, cooled in catalyst cooler 6, is then fed into reduction reactor 7.

[0131] In one embodiment, in step S5, when the catalyst cooler 6 is cooling, the cooling temperature is 60-120° C. At this time, the LOI of the regenerated catalyst is ≤15%, preferably ≤10%.

[0132] In one embodiment, in step S6, the formaldehyde solution of the predetermined concentration added to the reduction reactor 7 has a formaldehyde mass fraction of 40-55%, a pH of 6-8, a mass ratio of the formaldehyde solution added to the catalyst in the reduction reactor 7 of 5-20:1, and a reaction residence time of 5-120 minutes. By utilizing the reducing properties of formaldehyde in this environment, divalent copper (II) is reduced to monovalent copper (I) in the absence of acetylene.

[0133] In one embodiment, in step S7, the catalyst activated and reduced by formaldehyde in the reduction reactor 7, in which copper mainly exists in the form of monovalent copper, is fed into the acetylation reactor 1 in the form of a slurry. In the presence of acetylene, monovalent copper (I) combines with acetylene groups to form more catalytic cuprous acetylene active species, thereby completing catalyst regeneration.

[0134] The present invention also proposes the use of the above-mentioned system or method for controlling catalyst ablation. In particular, the system or method is suitable for controlling catalyst ablation in a reaction apparatus for producing butynediol using the acetylene-aldehyde process (BDO) to reduce the ablation amount to a preset range.

[0135] The present invention can be adjusted according to the requirements of LOI control in the acetylation reactor 1, and the LOI in the acetylation reactor can be controlled within the range of 10-45%, preferably 10-40%.

[0136] In one embodiment, the catalyst concentration device 2 is further provided with a catalyst reflux port 2-1 and a clear liquid outlet 2-2. The outlet of the catalyst concentration device 2 is connected to the catalyst separator 3. The concentrated liquid from the catalyst concentration device 2 flows in two different directions. The two portions are distributed in a mass ratio of 1:(1-200) between the concentrated liquid produced to the catalyst separator 3 and the concentrated liquid returned to the acetylation reactor 1. This distribution ratio is designed to meet the requirements for LOI control within the reactor. The specific ratio is dynamically adjusted based on the LOI control requirements within the acetylation reactor 1. By controlling the ratio, the LOI within the acetylation reactor 1 can be maintained within an ideal range of 10% to 45%. In some cases, to achieve optimal reaction results, the LOI is controlled within the range of 10% to 40%, ensuring both reaction efficiency and the economical operation of the device.

[0137] The present invention aims to reduce the LOI in the acetylation reactor 1 and restore the performance of the catalyst through a two-step method. This method does not require the addition of other chemical substances outside the reaction system and only controls the pyrolysis temperature to achieve different valence states of Cu 2+ / Cu +This controlled conversion relies on the catalyst's inherent activity to remove organic coatings from the surface through catalytic oxidation, eliminating the need for additional energy consumption. By controlling the pyrolysis temperature, overheating and the resulting copper agglomeration in the catalyst are avoided, maximizing catalyst performance. This method, through the recycling of a certain amount of catalyst, can control the LOI of the acetylation reactor to below 10-45wt%, significantly improving reaction efficiency and reducing catalyst consumption.

[0138] In the chemical reaction process carried out in the currently widely used acetylation reactor 1, the active metallic copper in the new copper-bismuth catalyst mainly exists in the form of divalent copper, which can be in the form of oxide to ensure the safety of the catalyst. In the existing technology, it usually goes through a series of complex activation steps before it is finally converted into the active monovalent Cu (I) state. From the perspective of microstructure, it can be found that the reduction in catalyst activity is mainly due to the encapsulation of surface organic matter, while its microstructure is not damaged, in which copper is still in the form of Cu 2+ , Cu + and Cu 0 The present invention proposes a new catalyst activity recovery method, which regenerates a certain proportion of the extracted catalyst and recycles it back to the acetylation reactor, thereby controlling the LOI in the reactor to a low level, as low as 10%.

[0139] The catalyst regeneration method of the present invention is particularly suitable for supported copper-bismuth catalysts.

[0140] The following examples illustrate the catalyst treatment and regeneration process of the present invention.

[0141] Example 1

[0142] use Figure 1 The system is used to regenerate the catalyst and control the LOI in the acetylation reactor.

[0143] Acetylation Reactor 1 has a production capacity of 60,000 tons / year, corresponding to a feed rate of 15.0 m³ / hr of formaldehyde (45 ± 5%). The reaction temperature is 98 ± 1°C, and the pressure is 180 kPa ± 5. The catalyst is BASF supported copper catalyst Cu6081P. The physicochemical properties of the slurry output from the acetylation reactor are shown in Table 1.

[0144] Table 1 Physicochemical properties of the slurry output from the alkyne reactor

[0145] project unit Numerical Catalyst concentration wt% 10±0.5% Reaction solution density <![CDATA[kg / m 3 ]]> 990 LOI in the acetylation reactor % 35±2% Particle size distribution D50 mm 10-13 Specific surface area <![CDATA[m 2 / g]]> ≤15 Reaction supernatant composition wt% Water 50.11, methanol 0.87, formaldehyde 0.70, propargyl alcohol 0.47, BYD 47.83, acetylene 0.02

[0146] use Figure 1 The activation and regeneration treatment of the catalyst is carried out according to the following steps.

[0147] S1, controlling the acetylation reactor 1 to output the slurry containing the copper-bismuth catalyst and then transporting it to the catalyst concentration device 2.

[0148] S2, the catalyst concentration device 2 concentrates the slurry to obtain a concentrated liquid. Part of the concentrated liquid is refluxed to the acetylation reactor 1, and part is pumped to the catalyst separator 3 according to a preset extraction ratio. The concentrated liquid is a concentrated catalyst slurry, mainly composed of high-concentration catalyst, water, BYD, and other organic matter. In Example 1, the extraction ratio of these two parts is 1:50 for the concentrated liquid extracted to the catalyst separator 3 and the concentrated liquid refluxed to the acetylation reactor 1. The concentrated liquid flow rate returned to the reactor by the catalyst concentration device is 8333 kg / hr, and the extracted concentrated liquid is 166.7 kg / hr. The catalyst concentration of the concentrated liquid is 28%.

[0149] S3, the concentrated liquid is fed into the catalyst separator 3 to separate the catalyst to be regenerated, and the BYD solution remaining in the catalyst to be regenerated is recovered, and the spent catalyst, i.e., the catalyst to be regenerated, is separated at the same time. The operating temperature is 90°C and the pressure is 0.6 MPaG.

[0150] In step S4, the desalted water and the catalyst to be regenerated separated in step S3 are respectively fed into a catalyst preparation device 4 and prepared to a predetermined solid content. In this embodiment, a predetermined solid content of 85 wt% is prepared as a regenerated catalyst slurry to reduce water evaporation during the subsequent regeneration process. The slurry is then fed into a regeneration reactor 5 for regeneration.

[0151] S5, controlling the regeneration gas to be input into the regeneration reactor 5 according to a preset input flow rate, performing catalyst regeneration treatment in the regeneration reactor 5, and inputting the treated catalyst into the catalyst cooler 6 for cooling;

[0152] The specific process is:

[0153] In the first stage, S51, the slurry prepared by the catalyst preparation device 4 is input into the regeneration reactor 5, and nitrogen is introduced into the regeneration reactor 5. The slurry in the regeneration reactor 5 is fully contacted with the nitrogen through the stirrer in the regeneration reactor 5. The collector 9 is a tail gas collector, in which desalted water is added as a circulating liquid and circulated stably. The circulation volume is 30m 3 / hr, circulating liquid temperature 20℃±1. The gas phase discharged from the regeneration reactor 5 is circulated through the gas compressor 11. After the gas is circulated stably, the GHSV of nitrogen is N2 Controlled within 100 hours -1The regeneration reactor 5 is heated electrically using the regeneration reactor's heater. Heating is performed at a rate of 60°C / hr. After reaching 120°C, the temperature is maintained constant for 3 hours, with the pressure controlled at 50 kPa. At this point, water (including surface water and freely bound water) and volatile organic compounds (such as methanol, ethanol, THF, and formaldehyde) in the catalyst begin to evaporate. The evaporated substances, along with nitrogen, are transported via the regeneration reactor 5's gas phase discharge line to a collector 9. Within the collector 9, desalinated water is sprayed to separate the organic matter, which is then discharged as organic waste liquid. The nitrogen, free of organic matter and water, is pressurized by a compressor and recycled back to the reactor for reuse. An online analytical chromatograph 8 is installed on the regeneration reactor 5's gas phase line, located between the regeneration reactor 5 and the collector 9. The online analytical chromatograph 8 can monitor the content of evaporated organic matter in real time. When the organic matter content detected by the online analytical chromatograph 8 begins to decrease and stabilizes at a low level, and the gas phase components no longer change, it indicates that the removal of water and volatile organic matter is basically completed at this stage, and the process can proceed to step S52.

[0154] The second stage, S52, is controlled to heat up at a rate of 20°C / hour, and a mixture of nitrogen and air is used as the regeneration gas. The molar ratio of nitrogen to air ranges from (1 to 100,000):1 and is adjusted according to temperature changes. The total space velocity (GHSV) of the regeneration gas in the second stage is sum 1000 hours -1 The pyrolysis temperature is controlled by the amount of air added, GHSV air The adjustment rate range is 0.00001~100h -1 / hour. Initial air feed space velocity GHSV air 0.02 hours -1 When the regeneration gas containing oxygen comes into contact with the catalyst, the catalytic oxidation reaction is initiated due to the high specific surface area and rich pore structure of the catalyst. The reaction heat is quickly transferred and the temperature rises rapidly, further accelerating the reaction. The organic matter is oxidized into CO, CO2 and small molecular volatile organic compounds. In this process, the temperature control and air flow of the regeneration reactor 5 are switched to automatic control, and the heating rate is controlled at 20℃ / hr. If the heating rate starts to rise too quickly, the air feed rate can be adjusted. The air feed rate adjustment rate is 1 h. -1 / hour. When the temperature reaches 400°C, maintain the constant temperature for 5 hours. The oxygen content in the gas phase is monitored in real time by an online analytical chromatograph 8. As the reaction proceeds, the oxygen content in the gas phase shows a trend of gradually increasing from low to high. As the reaction proceeds, most of the organic matter is decomposed, and the oxygen content gradually increases. When the oxygen content in the gas phase measured by the online analytical chromatograph 8 is stable and the ratio of the basic intake air volume is maintained, it indicates that the catalytic oxidation stage reaction is basically complete. At this time, the oxygen content in the tail gas is approximately 10-12 mol%. At this time, the copper in the active catalyst body is mainly present in the form of divalent copper.

[0155] The catalyst after the reaction in the regeneration reactor 5 is fed into the catalyst cooler 6. After the reaction in the regeneration reactor 5 is completed, the liquid phase is fed into the catalyst cooler 6 for cooling. The catalyst is cooled to 80° C. The LOI of the regenerated catalyst is measured, and the LOI content is 8.5.

[0156] S6, the cooled material is fed into the reduction reactor 7 and a formaldehyde aqueous solution of a preset concentration is fed into the reduction reactor 7 to perform catalyst reduction; 45% formaldehyde aqueous solution is added to the reduction reactor 7, the pH range of the formaldehyde aqueous solution is 7±0.5, the mass ratio of the formaldehyde added amount to the catalyst in the reduction reactor 7 is 10:1, the reaction residence time is 30 minutes, and at 180 kPa and 80° C., relying on the reducing property of formaldehyde in this environment, divalent copper ions are reduced to monovalent copper in the absence of acetylene.

[0157] S7, inputting the materials after the reaction in the reduction reactor 7 into the acetylation reactor 1.

[0158] The LOI in the acetylation reactor 1 is controlled within the range of 35%±2 by the catalyst regeneration cycle method of the present invention.

[0159] Example 2

[0160] The only difference between Example 2 and Example 1 is:

[0161] In S2, the extraction ratio is that the concentrated liquid extracted to the catalyst separator 3 and the concentrated liquid refluxed to the acetylation reactor 1 are distributed in a mass ratio of 1:1.

[0162] In S3, during the process of separating the catalyst to be regenerated in the catalyst separator 3, the temperature is controlled at 95° C. and the pressure is controlled at 0.9 MPaG.

[0163] S4, the desalted water and the catalyst to be regenerated separated in step S3 are respectively input into the catalyst preparation device 4 to prepare a catalyst slurry to be regenerated with a solid content of 80 wt%.

[0164] In S51, the regeneration reactor 5 is controlled to reach 180°C at a heating rate of 30°C / hour and kept at this temperature for 5 hours; the GHSV of the nitrogen N2 50 hours -1 .

[0165] S52, the regeneration gas is fed into the regeneration reactor 5, wherein the regeneration gas in step S52 is a mixture of nitrogen and air, and the temperature is raised at a rate of 5°C / hour until the temperature reaches 300°C, and the temperature is kept constant for 3 hours. In step S52, the total space velocity GHSV of the mixed gas is sum 2000 hours -1 ;

[0166] In S5, the catalyst cooler 6 cools the catalyst to 60° C. The LOI of the regenerated catalyst is measured, and the LOI content is 12.5%.

[0167] In S6, a 40% formaldehyde aqueous solution is added to the reduction reactor 7, and the pH range of the formaldehyde aqueous solution is 6. The mass ratio of the added formaldehyde to the catalyst in the reduction reactor 7 is 5:1, and the reaction residence time is 120 minutes.

[0168] Under the conditions in Example 2, the LOI in the reactor can be maintained at 40±2%.

[0169] Example 3

[0170] The only difference between Example 3 and Example 1 is that:

[0171] In S2, the extraction ratio is that the concentrated liquid extracted to the catalyst separator 3 and the concentrated liquid refluxed to the acetylation reactor 1 are distributed in a mass ratio of 1:200.

[0172] In S3, during the process of separating the catalyst to be regenerated in the catalyst separator 3, the temperature is controlled at 98° C. and the pressure is controlled at 1.0 MPaG.

[0173] S4, the desalted water and the catalyst to be regenerated separated in step S3 are respectively input into the catalyst preparation device 4 to prepare a catalyst slurry to be regenerated with a solid content of 95 wt%.

[0174] In S51, the regeneration reactor 5 is controlled to reach 180°C at a heating rate of 180°C / hour and kept at this temperature for 8 hours; the GHSV of the nitrogen N2 1000 hours -1 .

[0175] S52, the regeneration gas is fed into the regeneration reactor 5, wherein the regeneration gas in step S52 is a mixture of nitrogen and air, and the temperature is raised at a rate of 60°C / hour until the temperature reaches 500°C, and the temperature is kept constant for 12 hours. In step S52, the total space velocity GHSV of the mixed gas issum 300 hours -1 .

[0176] In S5, the catalyst cooler 6 cools the catalyst to 120° C. The LOI of the regenerated catalyst is measured, and the LOI content is 4.5%.

[0177] In S6, a 55% formaldehyde aqueous solution is added to the reduction reactor 7, and the pH range of the formaldehyde aqueous solution is 8. The mass ratio of the added formaldehyde to the catalyst in the reduction reactor 7 is 20:1, and the reaction residence time is 5 minutes.

[0178] In Example 3, the LOI in the reactor can be maintained at 25±2%.

[0179] Example 4

[0180] The only difference between Example 4 and Example 1 is:

[0181] In S51, the regeneration reactor 5 is controlled to reach 60°C at a heating rate of 30°C / hour and kept at this temperature for 4 hours; the GHSV of the nitrogen N2 800 hours -1 .

[0182] S52, the regeneration gas is fed into the regeneration reactor 5, wherein the regeneration gas in step S52 is a mixture of nitrogen and air, and the temperature is raised at a rate of 60°C / hour until the temperature reaches 450°C, and the temperature is kept constant for 12 hours. In step S52, the total space velocity GHSV of the mixed gas is sum 500 hours -1 .

[0183] In S6, a 55% formaldehyde aqueous solution is added to the reduction reactor 7, and the pH range of the formaldehyde aqueous solution is 8. The mass ratio of the added formaldehyde to the catalyst in the reduction reactor 7 is 18:1, and the reaction residence time is 10 minutes.

[0184] Example 5

[0185] The only difference between Example 5 and Example 1 is that:

[0186] S52, the regeneration gas is fed into the regeneration reactor 5, wherein the regeneration gas in step S52 is a mixture of nitrogen and air, and the temperature is raised at a rate of 40°C / hour until the temperature reaches 450°C, and the temperature is kept constant for 10 hours. In step S52, the total space velocity GHSV of the mixed gas is sum 1500 hours -1 .

[0187] In S6, a 55% formaldehyde aqueous solution is added to the reduction reactor 7, and the pH range of the formaldehyde aqueous solution is 8. The mass ratio of the added formaldehyde to the catalyst in the reduction reactor 7 is 9:1, and the reaction residence time is 60 minutes.

[0188] Comparative Example 1: Fresh catalyst without regeneration cycle

[0189] Following steps S1-S4 in Example 1, using data from a current domestic production facility, fresh catalyst (BASF Cu6081P) was regularly added and discharged. The discharged catalyst was not recycled and treated as hazardous waste. Based on current production data, the LOI of the fresh catalyst was ≤1%. A feed rate of 13.1 kg / hr maintained an LOI of 35 ± 2% in the reactor.

[0190] Comparative Example 2 High-temperature calcined regenerated catalyst

[0191] Comparative Example 2 regenerated the discharged catalyst by high-temperature calcination. Following steps S1-S4 of Example 1, the same mass of regenerated catalyst was obtained. The catalyst was dried at 120°C for 5 hours and then calcined at 800°C for 3 hours. The regenerated catalyst had an LOI content of 4.2%. The regenerated catalyst was returned to the acetylation reactor.

[0192] In Comparative Example 2, the LOI in the reactor can be maintained at 35±2%.

[0193] The reaction conditions of the acetylation reactors of Example 1, Comparative Example 1 and Comparative Example 2 were compared. The comparison results are shown in Table 2 below:

[0194] Table 2 Comparison of reaction conditions in the acetylation reactors of Example 1, Comparative Example 1 and Comparative Example 2

[0195] project name unit Example 1 Comparative Example 1 Comparative Example 2 1 LOI control method -　 Low temperature catalytic decomposition and recycling Add new catalyst High temperature roasting and returning to the reactor 2 Solid content wt% 10±0.5 10±0.5 10±0.5 3 LOI % 35.8 34.8 34.2 4 water wt% 49.94 49.98 49.99 5 formaldehyde wt% 0.23 0.28 3.57 6 BYD wt% 48.67 48.57 45.19 7 Propynol wt% 0.09 0.08 0.16 8 Methanol wt% 1.07 1.09 1.09 9 Formaldehyde conversion rate % 99.54 99.44 92.86 10 Total catalyst investment cost Ten thousand yuan / month Low, about 409,000, and the replenishment amount is about 2kg per hour Very high, about 2.35 million Higher, about 818,000, and the addition amount is about 4.5kg / hour

[0196] The above comparison results show that Example 1 can control the LOI in the reactor at a low level and achieve the highest conversion rate, without the need to add large amounts of fresh catalyst to achieve the same reaction effect. In contrast, although the LOI value in Comparative Example 2 was also reduced to the same level, the conversion rate of the reaction did not improve. This also indicates that the activity of the catalyst regenerated by the method in Comparative Example 2 has been severely damaged, and the efficiency of the acetylation reaction has not been significantly improved. It is not worth recycling, thus negatively affecting the economic benefits of the entire industrial process. The regeneration equipment and regeneration method involved in the present invention, through innovative and efficient technical means, can cleverly transform the valence state of the discarded catalyst, allowing it to be put back into use after regeneration. This process achieves high conversion rate, reduces the amount of fresh catalyst replenished, and significantly reduces the cost of controlling the reactor LOI, thus making the recycling of catalyst more economical and feasible.

[0197] Test Example 1

[0198] The catalyst after regeneration by S6 in Example 1, the fresh catalyst in Comparative Example 1, and the catalyst regenerated by high temperature calcination in Comparative Example 2 were observed by scanning electron microscopy (SEM). The SEM images were obtained by using a Thermo Fisher apreo-2s, EHT5kv, and scanning electron microscopy at 1 μm and 200 nm. Figure 3-Figure 8 0.2μm and 50nm transmission electron microscopy observations were performed using JEOL JEM2100 with an accelerating voltage of 200 kV. The transmission electron microscopy images are shown in Figures 9-14 .

[0199] Figure 3 This is a 1 μm scanning electron microscope image of the regenerated catalyst in Example 1. Figure 4 This is a 1 μm scanning electron microscope image of the catalyst of Comparative Example 1. Figure 5 This is a 1μm scanning electron microscope image of the high-temperature calcined regenerated catalyst in comparative example 2. Figure 6 This is a 200nm scanning electron microscope image of the catalyst in Example 1. Figure 7 This is a 200nm scanning electron microscope image of the catalyst in Comparative Example 1. Figure 8 200nm scanning electron microscope image of the catalyst of Comparative Example 2. Figure 9 This is a 0.2μm transmission electron microscope image of the catalyst in Example 1. Figure 10 This is a 0.2μm transmission electron microscope image of the catalyst in Comparative Example 1. Figure 11 This is a 0.2μm transmission electron microscope image of the catalyst in Comparative Example 2. Figure 12 This is a 50nm transmission electron microscope image of the catalyst in Example 1. Figure 13 This is a 50nm transmission electron microscope image of the catalyst in comparative example 1. Figure 14This is a 50nm transmission electron micrograph of the catalyst from Comparative Example 2. As can be seen from the above SEM images, when comparing the uncalcined materials and the materials calcined at different temperatures, the regenerated catalyst from Example 1 shows no significant change in particle shape and size compared to the fresh catalyst from Comparative Example 1. The particle size is relatively uniform, and the dispersion is still relatively good. However, the regenerated catalyst from Comparative Example 2 calcined at high temperature exhibits significant agglomeration. Figure 5 The boundaries between the catalyst particles in Comparative Example 2 are no longer visible, showing a blurred morphology. Under a higher magnification, this agglomeration phenomenon is more obvious. Combined with transmission electron microscopy (TEM), the morphological characteristics of the material are observed at a more microscopic scale. Figures 9-11 and Figure 12-14 As can be seen, the regenerated catalyst in Example 1 not only maintained its internal pore structure compared to the fresh catalyst, but also exhibited a richer pore structure and a rougher surface. In contrast, the catalyst in Comparative Example 2 exhibited severe sintering and agglomeration, indicating that during the regeneration process, the oxidative decomposition gases within the catalyst overflowed, affecting the pore size and enriching the pore structure of the regenerated catalyst. More nanoscale pores can increase the material's specific surface area. The strict temperature control of 500°C during the regeneration process in Example 1 explains the absence of catalyst agglomeration and the restoration of catalytic activity.

[0200] Test Example 2

[0201] XPS analysis of the surface composition and valence state of the catalyst regenerated in Example 1 after S5 and the catalyst regenerated by high-temperature calcination in Comparative Example 2 was performed using an X-ray photoelectron spectrometer (Thermo Fisher Scientific K-Alpha, USA). The analysis chamber vacuum was 5×10-10 Pa, the excitation source was Al ka radiation (hv = 1486.68 eV), the operating voltage was 15 kV, the filament current was 10 mA, and 5-10 cycles of signal accumulation were performed. The test pass energy was 50 eV, the step size was 0.05 eV, and charge correction was performed using the binding energy of C1s = 284.80 eV as the energy standard.

[0202] Figure 15 Figure 1 (the upper part) is the XPS analysis of the Cu valence state of the catalyst of Example 1, and Figure 3 (the lower part) is the XPS analysis of the Cu valence state of the catalyst regenerated by high-temperature calcination in Comparative Example 2. The analysis results are shown in Table 3.

[0203] Table 3 Valence analysis of Cu in the catalysts of Example 1 and Comparative Example 2

[0204]

[0205] In Table 3, Atomic % is atomic percentage. From the XPS spectra, it can be seen that all catalysts have two main peaks, Cu2p3 / 2 (930-937.5ev) and Cu2p1 / 2 (950-958.5ev), and the shock peak is concentrated in the range of 940-945ev. The coexistence of Cu2p3 / 2 high binding energy (930ev) and shock peak is Cu 2+ There are two main features, and the low binding energy (932.5ev) of Cu2p3 / 2 and the absence of shock peak are Cu + species exist, proving that Cu 2+ and Cu + Two valence states, combined with the composition ratio in Table 3, it can be seen that the Cu 2 + / Cu + It is close to prove that the method of Example 1 is effective for Cu + Converted to Cu 2+ The effect is equivalent, but high temperature conditions are not required to achieve the conversion of copper valence state, avoiding the damage of high temperature to the microstructure of the catalyst.

[0206] Test Example 3

[0207] The specific surface area and pore structure of the catalyst regenerated after steps S1-S6 in Example 1, the fresh catalyst, and the catalyst regenerated by high-temperature calcination in Comparative Example 1 were analyzed using a Mini X surface area analyzer manufactured by Microtrac Instruments, Japan. The adsorption gas was nitrogen, the relative pressure range was 0.1, and the test temperature was 77K. Test sample preparation: Depending on the test sample, degassing was performed at 300°C under vacuum for 8 hours. The test results are shown in Table 4.

[0208] Table 4 Specific surface area analysis structure of Example 1, fresh catalyst and comparative example 1 catalyst

[0209] Serial number Sample name <![CDATA[BET specific surface area (m 2 / g)]]> <![CDATA[Total pore volume (cm 3 / g)]]> Average pore size (nm) 1 Example 1 6.5083 0.0771 22.14 2 Comparative Example 1 8.3621 0.0968 15.08 3 Comparative Example 2 1.3002 0.0187 13.44

[0210] From the results of the BET test in Table 4, it can be seen that the pore size of Example 1 is slightly lower than that of the fresh catalyst of Comparative Example 1, but the pore size is larger than that of Comparative Example 2, which also confirms the test results of SEM and TEM. The outward escape of organic matter during the decomposition process causes the expansion of the pores, but the specific surface area is about 5 times higher than that of Comparative Example 2. This shows that due to the control of the pyrolysis temperature in Example 1, the sintering and agglomeration of copper in the catalyst is avoided, the number of pores is reduced, and a favorable microenvironment is created for the recovery of catalyst performance.

[0211] The catalyst regeneration process in regeneration reactor 5 in S5 of Example 1 was tested, and the content of copper in different valence states during the catalyst regeneration process was detected by XPS. The test results are shown in Table 5 (Atomic represents atomic percentage).

[0212] Table 5. Valence transformation and content of copper at different stages

[0213]

[0214] Test Example 4

[0215] The catalyst regenerated in step S7 of Example 1, the fresh catalyst of Comparative Example 1, and the regenerated catalyst calcined at high temperature in Comparative Example 2 were compared, and the performance of the catalysts was characterized by the formaldehyde conversion rate. The test process is described below.

[0216] Equipment used

[0217] 1. 50% formaldehyde, acetylene gas cylinder instrument;

[0218] 2. Reactor (maximum capacity: 500ml, maximum temperature: 500℃, maximum pressure: 27MpaG);

[0219] 3. T70 potentiometric titrator (for analyzing formaldehyde content);

[0220] 4. Gas chromatograph (Agilent 7890B for analyzing the content of methanol, propynyl alcohol, and butynediol);

[0221] 5. Centrifuge (catalyst separation).

[0222] Steps

[0223] 1. Measure 200 ml of 50% formaldehyde solution (adjust pH to 6.5) and place it in a reaction kettle.

[0224] 2. Weigh 28 g of catalyst sample and add it into the reactor.

[0225] 3. Cover the reactor lid and tighten the bolts to ensure that the reactor is leak-proof.

[0226] 4. After nitrogen replacement is qualified, introduce acetylene gas (pay attention to tail gas emissions).

[0227] 5. Reaction temperature: 98°C, pressure: 1.1 barG, stirring rate: 1200 rpm.

[0228] 6. The first sampling time is 30 seconds after the acetylene enters, and then the timing starts. The reaction is stopped after 3 hours.

[0229] 7. Test the formaldehyde concentration in the reaction solution. The test results are shown in Table 6.

[0230] Table 6 Formaldehyde concentration test results

[0231] project name unit Example 1 Comparative Example 1 Comparative Example 2 1 Solid content g / 100ml 27.4 27.8 27.2 2 formaldehyde wt% 0.58 1.18 36.3 3 BYD wt% 48.23 47.65 12.11 4 Propynol wt% 0.095 0.12 0.41 5 Methanol wt% 1.12 1.06 1.19

[0232] The results in Table 6 show that the catalyst in Example 1 achieved the highest conversion rate. After removing the organic matter encapsulating the catalyst, the catalyst was not damaged, and its catalytic performance was well restored. However, since Comparative Example 1 was not activated, the copper in the catalyst was still primarily divalent copper, requiring activation with formaldehyde during the reaction. At the same reaction residence time, the conversion rate was slightly lower than that in Example 1. However, both conversion rates were significantly higher than those in Comparative Example 2, indicating that high-temperature calcination significantly impacted catalyst performance.

[0233] The regeneration system and method of the present invention regenerate the catalyst. By precisely controlling the catalytic cracking temperature, organic matter such as butynediol, formaldehyde, propargyl alcohol, methanol, and other polymers can be effectively removed from the catalyst surface. This effectively avoids catalyst agglomeration and sintering during traditional high-temperature roasting and incineration processes, preserving catalyst performance to the maximum extent possible. Furthermore, a cyclic regeneration process is established with the acetylation reactor, controlling the reactor's LOI below 40%, and optimally below 20%, thereby improving reaction efficiency. Furthermore, this method significantly reduces catalyst consumption from 1.0 kg / ton BDO to a minimum of 0.3 kg / ton BDO.

[0234] The method of the present invention is highly energy-efficient, eliminating the need for high-temperature incineration to regenerate the catalyst. This not only improves safety, providing a safer working environment for operators and equipment, but also reduces energy consumption and potential environmental impacts.

[0235] It should be pointed out that although the various steps in the above embodiments are described in a specific order, those skilled in the art will understand that in order to achieve the effects of the present invention, different steps do not have to be performed in such an order. They can be performed simultaneously (in parallel) or in other orders. These changes are within the scope of protection of the present invention.

[0236] Thus far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it will be readily understood by those skilled in the art that the scope of protection of the present invention is obviously not limited to these specific embodiments. Without departing from the principles of the present invention, those skilled in the art may make equivalent changes or substitutions to the relevant technical features, and the technical solutions after such changes or substitutions will fall within the scope of protection of the present invention.

Claims

1. A method for regenerating a supported copper-bismuth catalyst, characterized in that: include: S1, controlling the acetylation reactor (1) to transport the slurry containing the copper-bismuth catalyst to the catalyst concentration device (2); S2, controlling the catalyst concentration device (2) to concentrate the slurry to obtain a concentrated solution; S3, inputting the concentrated liquid into a catalyst separator (3) to separate the catalyst to be regenerated; S4, inputting the catalyst to be regenerated into a catalyst preparation device (4) to be prepared into a preset solid content, and then inputting into a regeneration reactor (5); S5, controlling the regeneration gas to be input into the regeneration reactor (5) according to a preset input flow rate, performing catalyst regeneration treatment in the regeneration reactor (5), and inputting the treated catalyst into the catalyst cooler (6) for cooling; S6, inputting the cooled material into the reduction reactor (7) and inputting a formaldehyde aqueous solution of a preset concentration into the reduction reactor (7) to perform catalyst reduction; S7, inputting the materials after the reaction in the reduction reactor (7) into the acetylation reactor (1); The control of the regeneration gas input into the regeneration reactor (5) according to the preset input flow rate comprises: S51, inputting regeneration gas into the regeneration reactor (5), wherein the regeneration gas in step S51 is nitrogen; S52, inputting regeneration gas into the regeneration reactor (5), wherein the regeneration gas in step S52 is a mixture of nitrogen and air; The first stage of step S51 is physical separation. In this stage, water and volatile organic matter in the catalyst are sent to the trap (9) along with nitrogen, where the organic matter in the gas phase is separated, and the nitrogen free of organic matter and water is recycled back to the regeneration reactor for reuse; After the first stage is completed, the second stage S52 begins; after the regeneration gas containing oxygen contacts the catalyst, a catalytic oxidation reaction is initiated, the organic matter is oxidized, and finally the organic matter is completely decomposed; The system used in the regeneration method comprises: an acetylation reactor (1), a catalyst concentration device (2), a catalyst separator (3), a catalyst preparation device (4), a regeneration reactor (5), a catalyst cooler (6) and a reduction reactor (7) connected in sequence; The catalyst separator (3) is provided with a rotating shaft (3-1) and a plurality of filter plates (3-2) for intercepting the catalyst, and the filter plates (3-2) are connected to the rotating shaft (3-1); The catalyst preparation device (4) is provided with a first desalted water inlet (4-1); The regeneration reactor (5) is connected to a gas delivery pipe (5-1) for inputting regeneration gas, wherein the regeneration gas is nitrogen or a mixed gas, wherein the mixed gas is a mixture of nitrogen and air; The reduction reactor (7) is provided with a formaldehyde aqueous solution input port (7-1); the discharge port of the reduction reactor (7) is connected to the acetylation reactor (1); The system further comprises: a wire mesh demister (5-2), a collector (9), a gas compressor (11) and a collector circulation cooler (10); a gas phase discharge port (5-3) and a gas phase reflux port (5-4) are further provided on the regeneration reactor (5); the gas phase discharge port (5-3), the wire mesh demister (5-2) and the feed port of the collector (9) are connected in sequence; The collector (9) is also provided with a second desalted water input port (9-4), a gas phase outlet (9-1), a liquid phase outlet (9-2) and a liquid phase reflux port (9-3); the gas phase outlet (9-1), a gas compressor (11) and the gas phase reflux port (5-4) are connected in sequence; the liquid phase outlet (9-2), a collector circulating cooler (10) and the liquid phase reflux port (9-3) are connected in sequence; The gas delivery pipe (5-1) is connected to the air delivery pipe (511) and the nitrogen delivery pipe (512) respectively. The air delivery pipe (511) and the nitrogen delivery pipe (512) are respectively provided with control valves to control the opening and closing of the pipes. The air delivery pipe (511) and the nitrogen delivery pipe (512) are respectively provided with air flow meters and nitrogen flow meters to accurately measure the flow rates of the input air and nitrogen respectively. An online analytical chromatograph (8) is arranged on the pipeline between the wire mesh demister (5-2) and the collector (9).

2. The method according to claim 1, characterized in that The control of the regeneration gas input into the regeneration reactor (5) according to the preset input flow rate comprises: S51, controlling the regeneration reactor (5) to reach 60-180°C at a heating rate of 30-180°C / hour, and maintaining the temperature for 3-8 hours; S52, controlling the temperature to rise at a rate of 5 to 60°C / hour until the temperature reaches 300 to 500°C, and maintaining the constant temperature for 3 to 12 hours; wherein the molar ratio of nitrogen to air is in the range of (1 to 100,000):

1.

3. The method according to claim 1, characterized in that In step S5, the cooling temperature is 60 to 120°C.

4. The method according to claim 1, wherein During the process of separating the catalyst to be regenerated from the catalyst separator (3), the temperature is controlled to be 90-98° C. and the pressure is controlled to be 0.6-1.0 MPaG; and / or The formaldehyde aqueous solution of the preset concentration has a formaldehyde mass fraction of 40-55% and a pH of 6-8; The mass ratio of the added amount of the formaldehyde aqueous solution to the catalyst in the reduction reactor (7) is 5 to 20:1, and the reaction residence time is 5 to 120 minutes.

5. Use of the method according to any one of claims 1 to 4 in controlling the amount of catalyst ablation.

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