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

Abstract

The invention relates to the technical field of catalyst regeneration, and particularly provides a regeneration system and a regeneration method of a supported copper-bismuth catalyst and an application of controlling LOI of an ethynylation reactor. The system comprises an ethynylation reactor, a catalyst concentration device, a catalyst separator, a catalyst preparation device, a regeneration reactor, a cooler and a reduction reactor. The method aims at reducing LOI in an ethynylation reactor, recovers the performance of the catalyst through a two-step method, does not need to add other chemical substances outside a reaction system, decomposes organic inclusions on the surface through catalytic oxidation by means of a copper active center of the catalyst, and completes regulation and control conversion of different valence states of copper active species at the same time. The sintering agglomeration of copper in the catalytic decomposition process is inhibited by accurately controlling the pyrolysis temperature, the performance of the catalyst is prevented from being damaged, the energy consumption is low, the microstructure of the catalyst is not damaged, the LOI of the reactor is controlled at a lower level through cyclic regeneration of the catalyst, and the reaction efficiency can be greatly improved.

Description

Technical Field

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

[0002] The process for preparing 1,4-butanediol by the alkynal method began in the 1920s of the 19th century. During the development process of nearly a century, it has gradually become the main method for BDO production. The three-stage slurry bed reaction system of the supported copper-bismuth catalyst based on a silica-aluminum composite as the carrier has become a classic route for the alkynal method BDO process with the characteristics of high production efficiency and continuous and reliable operation. This copper-bismuth catalyst has a high diffusion coefficient and can achieve high conversion and selectivity under relatively mild reaction conditions.

[0003] The main problem affecting the efficiency of the alkynylation reaction during the operation of this type of reaction system is that the activity of the catalyst gradually decreases as the operation time increases. The main reason is that during the reaction process, the surface of the catalyst is wrapped by organic substances, resulting in a decrease in the contact area of the catalyst and a decrease in the conversion rate of formaldehyde. The method for evaluating the catalytic activity is to measure the mass of the organic coating on the catalyst surface, which is also called the ablation amount LOI (English full name Loss on ignition). The main means to maintain the activity of the catalyst in industrial production is to regularly supplement new catalysts and discharge waste catalysts to maintain the stability of the LOI index. In addition to the catalyst, the discharged waste catalyst also contains various compounds such as copper acetylide, residual butynediol, formaldehyde, and polyalkynes, and cannot be stored for a long time. It can only be handed over to a professional manufacturer for treatment as hazardous waste. Calculated based on a set of 100,000 tons / unit, in order to control the LOI of the unit at about 50%, the annual catalyst discharge is about 60 - 80 tons, and the cost is about 20 - 30 million yuan. In the increasingly competitive situation of BDO, some existing manufacturers have carried out recycling treatment of this waste catalyst to reduce the production cost of products.

[0004] Studies on the regeneration mechanism of copper-based catalysts have shown that sintering and agglomeration are the primary causes of permanent damage to copper-based catalysts. This is mainly manifested in the fact that copper grains will aggregate and undergo the Ostwald ripening effect at high temperatures, resulting in a reduction in their specific surface area. Sintering and agglomeration begin at the Hüttig temperature. As the temperature increases, the sintering of copper-based catalysts accelerates until severe in-situ sintering transformation occurs at the Tamman temperature. Although there is no obvious change in the appearance, its phase has changed. Therefore, temperature control during the regeneration of copper-based catalysts is crucial. Existing treatment technical solutions for waste catalysts mainly remove the organic matter on the catalyst surface through means such as high-temperature incineration and strong oxidation in order to restore the activity of the catalyst. For example, in patents CN109647544A and CN113209980A, although the treatment sequences and processes are different, both remove the organic coatings through incineration. Although such methods can remove the organic matter on the catalyst surface relatively thoroughly, they ignore the serious agglomeration of catalyst particles and the change in the microstructure caused by high-temperature working conditions, which instead causes irreversible damage to the catalyst performance. This also contradicts the original intention of catalyst recovery, which is to control the LOI in the reactor.

[0005] Therefore, there is a need to develop a technology that aims to reduce the LOI in the reactor, does not damage the microstructure of the catalyst, and enables a large amount of catalyst to be recycled. Summary of the Invention

[0006] To overcome the above defects, the present invention provides a regeneration system, regeneration method, and application of a supported copper-bismuth catalyst. During the catalyst regeneration process, the microstructure of the catalyst is not damaged, so that the catalyst can be recycled back into the acetylene reactor after regeneration, and finally the LOI in the acetylene reactor is controlled within a preset range, and the reaction efficiency is improved.

[0007] In the first aspect, the present invention provides a regeneration system for a supported copper-bismuth catalyst, comprising: an acetylene 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; Wherein, a rotating shaft and a plurality of filter plates for intercepting the catalyst are arranged in the catalyst separator, and the filter plates are connected to the rotating shaft; A first demineralized water input port is arranged on the catalyst preparation device; A gas delivery pipe is connected to the regeneration reactor for inputting a regeneration gas, wherein the regeneration gas is nitrogen or a mixed gas, and the mixed gas is a nitrogen and air mixed gas; A formaldehyde aqueous solution input port is arranged on the reduction reactor; the discharge port of the reduction reactor is connected to the acetylene reactor.

[0008] Further, the discharge port at the bottom of the acetylenation reactor is connected to the feed port of the catalyst concentration device; The material output port of the catalyst concentration device is connected to the feed port of the catalyst separator; The rotating shaft inside the catalyst separator is vertically arranged and has a hollow structure, and the plurality of filter plates are arranged at intervals and communicated with the rotating shaft; 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.

[0009] Further, the regeneration reactor is a rotary kiln pyrolysis reactor; and / or The acetylenation reactor is an acetylenation reactor for synthesizing 1,4-butyne diol.

[0010] Further, the system further includes: a wire mesh demister, a trap, a gas compressor, and a trap circulating cooler. A gas phase discharge port and a gas phase reflux port are further provided on the regeneration reactor, and the gas phase discharge port, the wire mesh demister, and the feed port of the trap are connected in sequence; A second desalted water input port, a gas phase outlet, a liquid phase outlet, and a liquid phase reflux port are further provided on the trap. The gas phase outlet, the gas compressor, and the gas phase reflux port are connected in sequence, and the liquid phase outlet, the trap circulating cooler, and the liquid phase reflux port are connected in sequence.

[0011] Further, a catalyst reflux port and a clear liquid output port are further provided on the catalyst concentration device, and the catalyst reflux port is connected to the acetylenation reactor.

[0012] In a second aspect, the present invention provides a method for regenerating a copper-bismuth supported catalyst using the system described in the first aspect, including: S1, controlling the acetylenation reactor to convey the slurry containing the copper-bismuth catalyst to the catalyst concentration device; S2, controlling the catalyst concentration device to concentrate the slurry to obtain a concentrated solution; S3, inputting the concentrated solution into the catalyst separator to separate the catalyst to be regenerated; S4, inputting the catalyst to be regenerated into the catalyst preparation device to prepare a preset solid content, and then inputting it into the regeneration reactor; 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; S6. Input the cooled material into the reduction reactor and input the aqueous formaldehyde solution with a preset concentration into the reduction reactor for catalyst reduction; S7. Input the material after reaction in the reduction reactor into the alkynylation reactor.

[0013] Further, the control of the regeneration gas input into the regeneration reactor according to a preset input flow rate includes: S51. Input the regeneration gas into the regeneration reactor. The regeneration gas in step S51 is nitrogen, and then control the regeneration reactor to reach 60 - 180 °C at a heating rate of 30 - 180 °C / hour and keep the temperature constant for 3 - 8 hours; S52. Input the regeneration gas into the regeneration reactor. The regeneration gas in step S52 is a mixture of nitrogen and air. Control the temperature to rise at a heating rate of 5 - 60 °C / hour until the temperature reaches 300 - 500 °C and keep the temperature constant for 3 - 12 hours. The molar ratio of nitrogen to air ranges from (1 - 100000):1.

[0014] Further, the addition amount of the regeneration gas is calculated according to the gas hourly space velocity GHSV. In step S51, the GHSV of the nitrogen N2 is 50 - 1000 hours -1 ; in step S52, the total space velocity GHSV of the mixture sum is 300 - 2000 hours -1 , preferably 500 - 1500 hours -1 .

[0015] Further, the control of the pyrolysis temperature is achieved by the addition amount of air, and the adjustment rate range of GHSV air is 0.00001 - 100 h -1 / hour.

[0016] Further, in step S5, the cooling temperature is 60 - 120 °C.

[0017] Further, during the process of separating the catalyst to be regenerated in the catalyst separator, control the temperature to be 90 - 98 °C and the pressure to be 0.6 - 1.0 MPaG; and / or In the aqueous formaldehyde solution with the preset concentration, the mass fraction of formaldehyde is 40 - 55% and the pH is 6 - 8.

[0018] The mass ratio of the addition amount of the aqueous formaldehyde solution to the catalyst in the reduction reactor is 5 - 20:1, and the reaction residence time is 5 - 120 min.

[0019] In the third aspect, the present invention provides an application of the regeneration system according to the first aspect or the method according to the second aspect in controlling the ablation amount of the catalyst.

[0020] One or more of the above technical solutions of the present invention have at least one or more of the following beneficial effects: In implementing the technical solution of the present invention, aiming at reducing the LOI in the alkynylation reactor, relying on the activity of the catalyst itself, the organic coatings on the surface are removed through catalytic oxidation reactions, and at the same time, the regulation and conversion of different valence states of copper are realized. By designing a special process and controlling pyrolysis conditions such as temperature, the agglomeration and sintering of copper during the regeneration process are inhibited, avoiding irreparable damage to the catalyst performance. The energy consumption is low, the microscopic structure of the catalyst is not damaged, and through the recycling and regeneration of a certain amount of catalyst, the LOI of the reactor is controlled at a low level, greatly improving the reaction efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Referring to the accompanying drawings, the disclosure of the present invention will become more understandable. It is easily understood by those skilled in the art that these drawings are only for illustrative purposes and are not intended to limit the scope of protection of the present invention. In addition, similar numbers in the figures are used to represent similar components, where: Figure 1 is a schematic diagram of the main structure of a catalyst regeneration system according to an embodiment of the present invention; Figure 2 is a schematic diagram of the main process flow of a catalyst regeneration method according to an embodiment of the present invention; Figure 3 is a scanning electron micrograph of 1 μm of the catalyst after the reaction in step S7 according to Example 1 of the present invention; Figure 4 is a scanning electron micrograph of 1 μm of the fresh catalyst of Comparative Example 1 according to the present invention; Figure 5 is a scanning electron micrograph of 1 μm of the regenerated catalyst obtained from Comparative Example 2 according to the present invention; Figure 6 is a scanning electron micrograph of 200 nm of the catalyst after the reaction in step S7 according to Example 1 of the present invention; Figure 7 is a scanning electron micrograph of 200 nm of the fresh catalyst of Comparative Example 1 according to the present invention; Figure 8 is a scanning electron micrograph of 200 nm of the regenerated catalyst obtained from Comparative Example 2 according to the present invention; Figure 9 is a transmission electron micrograph of 0.2 μm of the catalyst after the reaction in step S7 according to Example 1 of the present invention; Figure 10 is a transmission electron micrograph of 0.2 μm of the fresh catalyst of Comparative Example 1 according to the present invention; Figure 11 is a transmission electron micrograph of 0.2 μm of the regenerated catalyst obtained from Comparative Example 2 according to the present invention; Figure 12 It is a transmission electron micrograph of 50 nm of the catalyst after the reaction in step S7 according to Embodiment 1 of the present invention; Figure 13 It is a transmission electron micrograph of 50 nm of the fresh catalyst of Comparative Example 1 according to the present invention; Figure 14 It is a transmission electron micrograph of 50 nm of the regenerated catalyst obtained in Comparative Example 2 according to the present invention; Figure 15 It is a comparison chart of XPS spectra of Comparative Example 1 and Comparative Example 2 according to the present invention.

[0022] List of reference numerals: 1: Alkynylation 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 input port; 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 input port; 8: On-line analysis chromatograph; 9: Trap; 9-1: Gas phase outlet; 9-2: Liquid phase outlet; 9-3: Liquid phase reflux port; 9-4: Second desalted water input port; 10: Trap circulation cooler; 11: Gas compressor; 12: Recirculating gas cooler; 13: BYD delivery pipe. Detailed embodiments

[0023] Some embodiments of the present invention will be 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 principle of the present invention and are not intended to limit the protection scope of the present invention.

[0024] The term "A and / or B" represents all possible combinations of A and B, such as only A, only B, or A and B. The term "at least one A or B" or "at least one of A and B" has a meaning similar to "A and / or B" and can include only A, only B, or A and B. The singular terms "a", "this" can also include the plural form.

[0025] Referring to Figure 1 , the present invention provides a regeneration system for a copper-bismuth supported catalyst, including: an alkynylation 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.

[0026] The acetylenation 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 the carrier is used. However, during the reaction process, as the chemical reaction progresses, the surface of the catalyst is gradually covered by organic substances, 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 wrapping of the catalyst is characterized by the ablation amount LOI. By regularly extracting a certain amount of the catalyst for regeneration and then recycling it back to the reactor, the ablation amount LOI index in the acetylenation reactor 1 can be controlled at a relatively low level without replenishing a large amount of new catalyst.

[0027] In one embodiment, the acetylenation reactor 1 is an acetylenation reactor for synthesizing 1,4-butynediol. The feed in the acetylenation reactor 1 is formaldehyde and acetylene, the reaction temperature is 98 ± 1 °C, and the reaction pressure is 180 kPa ± 5. The catalyst is a supported copper-bismuth catalyst with a silicon-aluminum composite as the carrier, typically such as BASF supported copper catalyst Cu6081P. The slurry after the reaction in the acetylenation reactor 1 consists of water, the catalyst to be regenerated, butynediol (BYD), and other organic substances.

[0028] The equipment and the system composed thereof for restoring the activity of the above catalyst will be described in detail below; The discharge port at the bottom of the acetylenation reactor 1 is connected to the feed port of the catalyst concentration device 2.

[0029] The catalyst concentration device 2 is used to concentrate the material.

[0030] In one embodiment, the catalyst concentration device 2 is a complete equipment system capable of continuously extracting the clear liquid and continuously returning the concentrated slurry to the acetylenation reactor 1. Such equipment can be a dynamic cross-flow filter, a disk filter, etc. For example, the dynamic cross-flow filter of BOKELA, the SCHENK filter of PALL, and other similar equipment. These equipments can not only effectively separate the catalyst concentrate and the clear liquid, but also ensure the continuity and efficiency of the whole process, thus meeting the requirements for catalyst recovery and reuse in industrial production.

[0031] In one embodiment, a catalyst concentration device 2 is further provided with a catalyst reflux port 2-1 and a supernatant output port 2-2. The catalyst reflux port 2-1 is connected to the alkynylation reactor 1 and is used to reflux a part of the concentrated catalyst solution. The supernatant output port 2-2 is used to output the concentrated supernatant. The supernatant output port 2-2 is connected to a BYD delivery pipe 13, and the supernatant output port 2-2 is used to output a BYD solution, which is collected and conveyed in the BYD delivery pipe 13. The concentrated catalyst solution after concentration is conveyed to a catalyst separator 3 through the material output port of the catalyst concentration device 2.

[0032] The catalyst concentration device 2 has three output ports, namely a material output port, a catalyst reflux port 2-1, and a supernatant output port 2-2. The processing procedure is as follows: After the material discharged from the bottom of the alkynylation reactor 1 is concentrated by the catalyst concentration device 2, a part of the concentrated catalyst slurry is recycled back to the alkynylation reactor 1 through the catalyst reflux port 2-1, and a part is sent to the catalyst separator 3 through the material output port according to a preset extraction ratio. The supernatant obtained by concentration, that is, the BYD solution, is conveyed from the supernatant output port 2-2 to the BYD delivery pipe 13.

[0033] Catalyst separation and filtration are carried out in the catalyst separator 3, and the purpose is to recover the BYD (butynediol) solution remaining in the waste catalyst.

[0034] A rotating shaft 3-1 and a plurality of filter plates 3-2 for intercepting catalysts are arranged in the catalyst separator 3, and the filter plates 3-2 are connected to the rotating shaft 3-1. The rotating shaft 3-1 is vertically arranged and is of a hollow structure. The plurality of filter plates 3-2 are arranged at intervals and communicate with 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 distributed at intervals in the vertical direction and need to be provided with a certain interval to accommodate the catalyst. The filter plates 3-2 can be set in a disc shape according to actual needs.

[0035] The concentrated liquid obtained after concentration by the catalyst concentration device 2, that is, the concentrated catalyst slurry, is input from the upper part of the catalyst separator 3. The slurry flows through each filter plate 3-2 from top to bottom. The filter plates 3-2 are of a hollow structure, and a filtering material for intercepting catalysts is arranged on the surface of the filter plates 3-2. The rotating shaft 3-1 rotates to drive the filter plates 3-2 to rotate at a high speed. In this way, under high-speed stirring of the slurry, the filtered supernatant penetrates into the filter plates 3-2 and is collected into the rotating shaft 3-1. The main component is the BYD solution, and the BYD solution is sent out from the bottom of the rotating shaft for product recovery.

[0036] 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 means of high-speed centrifugal rotation, and then input into the catalyst preparation device 4.

[0037] In one embodiment, the bottom end of the rotating shaft 3-1 is connected to the BYD delivery pipe 13, and the BYD delivery pipe 13 collects the BYD solution from the rotating shaft 3-1 and the BYD solution at the clear liquid outlet 2-2 of the catalyst concentration device 2.

[0038] 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. To distinguish it from the desalted water input ports of other components, the desalted water input port on the catalyst preparation device 4 is denoted as the first desalted water input port 4-1.

[0039] A gas delivery pipe 5-1 is connected to the regeneration reactor 5 for inputting regeneration gas. According to different reaction stages in the regeneration reactor 5, the regeneration gas can include only nitrogen or can be a mixed gas, and the mixed gas is composed of nitrogen and air.

[0040] The catalyst discharge port 5-5 of the regeneration reactor 5 is connected to the feed port of the catalyst cooler 6.

[0041] In one embodiment, the regeneration reactor 5 is equipped with heating facilities for heating and raising the temperature of the regeneration reactor 5.

[0042] In one embodiment, the regeneration reactor 5 is a rotary kiln type pyrolysis reactor, which can be electrically heated or gas heated.

[0043] In one embodiment, the gas delivery pipe 5-1 is respectively connected to the air delivery pipe 511 and the nitrogen delivery pipe 512. Control valves are respectively provided on the air delivery pipe 511 and the nitrogen delivery pipe 512 to control the opening and closing of the pipeline. An air flow meter and a nitrogen flow meter are respectively provided on the air delivery pipe 511 and the nitrogen delivery pipe 512 to accurately measure the respective flow rates of the input air and nitrogen, facilitating the regulation of the input amounts of air and nitrogen.

[0044] The catalyst regenerated by the regeneration reactor 5 is cooled in the catalyst cooler 6. After being cooled to 60~120°C, it is input into the reduction reactor 7. The discharge port of the catalyst cooler 6 is connected to the feed port of the reduction reactor 7.

[0045] A formaldehyde aqueous solution input port is provided on the reduction reactor 7; the discharge port of the reduction reactor 7 is connected to the ethynylation reactor 1.

[0046] In one embodiment, the reduction reactor 7 is a stirred tank reactor.

[0047] In one embodiment, the system further includes: a wire mesh demister 5-2, a trap 9, a gas compressor 11, and a trap 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 trap 9 are connected in sequence. The liquid phase outlet 9-2, the trap circulation cooler 10, and the liquid phase reflux port 9-3 are connected in sequence.

[0048] 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 are further provided on the trap 9. The gas phase outlet 9-1, the gas compressor 11, and the gas phase reflux port 5-4 are connected in sequence.

[0049] To distinguish it from the desalted water input port on the catalyst preparation device 4, the desalted water input port on the trap 9 is denoted as the second desalted water input port 9-4.

[0050] In one embodiment, an on-line analytical chromatograph 8 is further provided between the wire mesh demister 5-2 and the trap 9 for testing the composition of the gas phase.

[0051] The functions of the wire mesh demister 5-2, the trap 9, and the gas compressor 11 are described below in conjunction with the process method.

[0052] The materials in the catalyst preparation device 4 are formulated into a slurry with a certain concentration and transported to the regeneration reactor 5. Then, the regeneration gas is introduced into the regeneration reactor 5, and the composition of the regeneration gas is determined according to the reaction stage. The oxygen content in the regeneration gas is accurately controlled by two mass flow meters. The regeneration reactor 5 is a rotary kiln reactor and is heated by electric heating or gas. In the regeneration reactor 5, the slurry and the regeneration gas are in full contact to achieve the regeneration of the catalyst.

[0053] 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 trap 9. In the trap 9, after desalted water is input through the second desalted water input port 9-4, the gas phase input into the trap 9 is sprayed. The desalted water is used to absorb the organic substances carried in the tail gas (the gas phase in the regeneration reactor 5), such as water, THF, formaldehyde, methanol, ethanol, etc. After the organic substances are removed, the regeneration gas is discharged from the gas phase outlet 9-1 at the top of the trap 9, further boosted by the gas compressor 11, and then sent back 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.

[0054] Inside the trap 9, the tail gas, i.e., the gas phase from the regeneration reactor 5, is sprayed with demineralized water to form a waste liquid containing organic matter. When the organic matter 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 replenishing new demineralized water, these waste liquids will be used for the spraying process again. However, as the organic matter content in the liquid phase after spraying in the trap 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 trap circulating cooler 10, and a control valve is provided on this pipe. Opening this control valve can discharge the waste liquid rich in organic matter from the system.

[0055] In one embodiment, the system further includes a circulating gas cooler 12. The trap circulating cooler 10 is respectively connected to the liquid phase outlet 9-2 and the liquid phase reflux port 9-3. The circulating gas cooler 12 is respectively connected to the gas compressor 11 and the gas phase reflux port 5-4.

[0056] 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 it. Opening this control valve can discharge the gas phase.

[0057] In one embodiment, the gas delivery pipe 5-1 can be connected to the pipeline between the circulating gas cooler 12 and the gas phase reflux port 5-4.

[0058] The present invention discloses a method for regenerating a supported copper-bismuth catalyst by using the above system. Refer to Figure 2 , including: S1, controlling the alkynylation 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 liquid; S3, inputting the concentrated liquid into the catalyst separator 3 to separate the catalyst to be regenerated; S4, inputting the catalyst to be regenerated into the catalyst preparation device 4 to be formulated into a preset solid content, and then inputting it into the 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 with a preset concentration into the reduction reactor 7 for catalyst reduction; S7, inputting the material after the reaction in the reduction reactor 7 into the alkynylation reactor 1.

[0059] In one embodiment, in step S1, the ethynylation reactor 1 is a reaction device for producing butynediol in an aldehyde-acetylene BDO plant. The process of the ethynylation reaction in the ethynylation reactor 1 is as follows: using formaldehyde and acetylene as raw materials, butynediol is produced under the action of a catalyst. The reaction temperature is controlled at 98 ± 1 °C, the reaction pressure is controlled at 180 kPa ± 5, and the catalyst is a supported copper-bismuth catalyst with a silicon-aluminum composite as the carrier, typically such as BASF supported copper catalyst Cu6081P. During the production operation, the surface of the catalyst is gradually wrapped by organic substances, resulting in a decrease in the contact area of the catalyst, and regeneration treatment is required.

[0060] The slurry containing the copper-bismuth catalyst is the slurry after the reaction in the ethynylation reactor 1, and it consists of water, copper-bismuth catalyst, BYD, and other organic substances.

[0061] In one embodiment, in step S2, the slurry containing the copper-bismuth catalyst is transported to the catalyst concentration device 2 for concentration. The concentration method is to use dynamic cross-flow filtration or a disk filtration complete set of equipment. After passing through the catalyst concentration device 2, the slurry is concentrated. After concentration, the discharge amount of BYD with the catalyst can be reduced.

[0062] In one embodiment, after the slurry is concentrated by passing through the catalyst concentration device 2 in step S2, a concentrated solution is obtained. Part of the concentrated solution is recycled back to the ethynylation reactor 1, and part is discharged through the material output port according to the required extraction ratio and transported to the catalyst separator 3 by a pump. In addition, the clarified liquid obtained by concentration, that is, the BYD solution, is transported from the clarified liquid output port 2-2 to the BYD delivery pipe 13. In this step, the valence state of copper in the catalyst in the slurry is mainly monovalent Cu(I).

[0063] In one embodiment, in step S3, the concentrated solution output from the catalyst concentration device 2 is input into the catalyst separator 3 for separation and filtration, separating the waste catalyst to be regenerated, that is, the catalyst to be regenerated, and recovering the residual BYD liquid. After the separation by the catalyst separator 3, the clarified liquid is a BYD (butynediol) solution, which is taken out from the axis of the catalyst separator 3, that is, the rotating shaft 3-1, for reuse as a BYD product. The catalyst to be regenerated to be regenerated later is thrown out from the cavity between the filter plates 3-2 by high-speed centrifugal rotation and enters the catalyst preparation device 4. The solution taken out from the rotating shaft 3-1 for reuse as a BYD product can be connected to the BYD delivery pipe 13.

[0064] In one embodiment, during the filtration and separation process of the catalyst separator 3, the temperature is controlled at 90 - 98 °C, and the pressure is 0.6 - 1.0 MPaG. By such temperature and pressure adjustment, the BYD solution in the waste catalyst can be effectively recovered.

[0065] In one embodiment, in step S4, after demineralized water is added through the first demineralized water inlet 4-1 of the catalyst preparation device 4 and mixed with the catalyst to be regenerated separated from the catalyst separator 3, the catalyst slurry to be regenerated is formulated into a solution with a solid content of about 80% to 95%.

[0066] In one embodiment, in step S5, pure nitrogen or a mixture of nitrogen and air is selectively input according to the reaction stage in the regeneration reactor 5. Through the low-temperature catalytic oxidation process in the regeneration reactor 5, the regeneration treatment of the catalyst is realized, the moisture and organic inclusions in the catalyst are removed, and most of the catalyst is divalent copper (II) at the end of the oxidative decomposition.

[0067] In step S5, the main purpose of the step of carrying out the catalyst regeneration treatment in the regeneration reactor 5 is to remove moisture and catalytically decompose organic inclusions in different stages. The catalyst to be regenerated from step S4 is input into the regeneration reactor 5, and then the regeneration gas is continuously introduced. Under the catalytic action of the active species existing in the mixed state of multivalent copper (Cu + 、Cu 2+ 、Cu 0 ), at a certain temperature, the organic inclusions on the catalyst surface undergo pyrolysis oxidation reaction under the action of the catalytic active species, generating CO2, H2O and other volatile light components, etc. The reaction mechanism is as follows: There are two stages for regenerating the catalyst in the regeneration reactor 5. First is physical separation. The regeneration gas in the first stage is nitrogen. At a relatively low temperature, the moisture and volatile organic substances (such as methanol, acetylene, formaldehyde, etc.) in the catalyst are removed by nitrogen stripping. The second stage is catalytic oxidative decomposition. As the temperature continues to rise, the regeneration gas is a mixture of nitrogen and air. By adsorbing the oxygen in the regeneration gas to activate the lattice oxygen in the catalyst, the monovalent copper Cu + forms a metastable active phase CuO with the lattice oxygen x and is activated, providing lattice oxygen to the C-H and C-O bonds in the organic inclusions, converting them into CO2, H2O and small molecule compounds and removing them. The metastable CuO x is also finally oxidized to divalent copper (II), and the oxygen in the regeneration gas quickly replenishes the oxygen vacancies of the catalyst, continuing to oxidize Cu+ to form the intermediate active CuO x . In this way, when the decomposition of the organic inclusions is completed, the copper valence state in the catalyst also changes to mainly divalent copper.

[0068] 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: In the first stage, S51, the regeneration gas is input into the regeneration reactor 5. Herein, the regeneration gas in step S51 is denoted as the first regeneration gas, and the first regeneration gas is pure nitrogen. Then, the regeneration reactor 5 is controlled to reach 60 - 180°C at a heating rate of 30 - 180°C per hour, and kept at a constant temperature for 3 - 8 hours until the components in the exhaust gas are constant. Preferably, it reaches 80 - 150°C at a heating rate of 60 - 120°C per hour until the components in the exhaust gas are constant.

[0069] In the second stage, S52, the regeneration gas is input into the regeneration reactor 5. Herein, the regeneration gas in step S52 is denoted as the second regeneration gas, and the second regeneration gas is a mixture of nitrogen and air. It is controlled to heat up at a heating rate of 5 - 60°C per hour until the temperature reaches 300 - 500°C, preferably 350 - 450°C, and kept at a constant temperature for 3 - 12 hours. Among them, the molar ratio of nitrogen to air is (100 - 20000):1. Preferably, it is controlled to heat up at a heating rate of 10 - 30°C per hour until the temperature reaches 350 - 450°C, and kept at a constant temperature for 3 - 12 hours.

[0070] In one embodiment, the addition amount of the regeneration gas is calculated according to the gas hourly space velocity GHSV. In step S51, the GHSV of the nitrogen N2 is 50 - 1000 h -1 ; in step S52, the total space velocity GHSV of the mixed gas sum is 300 - 2000 h -1 preferably 500 - 1500 h -1 . The control of the pyrolysis temperature is achieved by the addition amount of air, and the adjustment rate range of GHSV air is 0.00001 - 100 h -1 / h.

[0071] 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 also exists in the form of divalent copper.

[0072] The reaction processes of the two stages are described in more detail below.

[0073] Controlling the input of the mixed gas or nitrogen into the regeneration reactor 5 according to the preset input flow rate includes a first stage and a second stage: S51, the first stage, input nitrogen into the regeneration reactor 5, and the specific process is as follows: After the catalyst to be regenerated is formulated into a preset solid content in the catalyst preparation device 4, it is input into the regeneration reactor 5, and then nitrogen is started to be introduced into the regeneration reactor 5. Under heating, the catalyst to be regenerated in the regeneration reactor 5 needs to be in full contact with the regeneration gas for reaction to achieve catalyst regeneration. The gas phase is discharged from the gas-phase discharge port 5-3, passes through the wire mesh demister 5-2, and then enters the trap 9. An on-line analytical chromatograph 8 is provided on the pipeline between the wire mesh demister 5-2 and the trap 9 to monitor the gas-phase composition and judge the activation completion process according to the component change.

[0074] The operating pressure of the trap 9 is 10-100 kPa, and the temperature is 20±5°C. Desalted water is used as the absorbent and added from the top of the trap 9 to contact the gas phase countercurrently, absorbing the organic substances carried in the gas phase, such as water, THF, formaldehyde, methanol, ethanol, etc. The regeneration gas from which the organic substances are removed is further pressurized by the gas compressor 11 and recycled to the regeneration reactor 5 for reuse. The liquid phase containing organic substances is partially cooled to 20±1°C by the trap circulating cooler 10 and then recycled back to the trap 9 to continue absorbing the organic substances in the exhaust gas, and part of it is regularly sent out of the boundary for treatment. After the organic substances are removed from the gas at the top of the trap 9, it returns to the regeneration reactor 5 through the gas compressor 11 for recycling.

[0075] The first stage of step S51 is physical separation. The regeneration gas is pure nitrogen, and the GHSV of nitrogen N2 can be set at 50-1000 hr -1 . After the gas establishes a stable cycle according to the illustrated process, the heating device of the regeneration reactor 5 starts to heat up, and the heating rate can be set at 30~180°C / hr. After reaching 150°C, it is kept at a constant temperature for 3 hours. In this stage, as the temperature rises, the water (including surface water and free-bound water) and volatile organic substances (such as methanol, ethanol, THF, formaldehyde, etc.) in the catalyst pass through the wire mesh demister 5-2 together with nitrogen to prevent the catalyst from being carried out by the gas, and then are sent to the trap 9. The organic substances in the gas phase are separated and sent out in the form of organic waste liquid. The nitrogen from which the organic substances and water are removed is pressurized by the gas compressor 11 and recycled back into the regeneration reactor 5 through the gas-phase reflux port 5-4 for reuse. The on-line analytical chromatograph 8 on the pipeline is used to monitor the composition of the gas phase.

[0076] The second stage is catalytic oxidative decomposition. The regeneration gas is a mixture composed of nitrogen and air. To ensure the precise control of the reaction, the input amounts of nitrogen and air in the two stages need to be monitored in real time. The completion of catalyst regeneration is determined according to the change in the oxygen content in the gas phase. Temperature measurement points are set in the regeneration reactor 5. Refer to Figure 1The dashed part indicates that a temperature acquisition device (such as a temperature sensor, etc.) is provided on the regeneration reactor 5 to obtain the internal temperature of the regeneration reactor 5. A control loop 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 according to the temperature collected by the temperature acquisition device. The reaction pressure in the regeneration reactor 5 can be set to 1 - 100 kPa. In step S52, a mixture of nitrogen and air is input into the regeneration reactor 5, and the temperature increase rate of the reaction is controlled at 5 - 60 °C / hour until the temperature reaches 300 - 500 °C, preferably 350 - 450 °C, and kept at a constant temperature for 3 - 5 hours. Among them, the molar ratio of nitrogen to air is (1 - 100000):1. When the oxygen supply is stable and the temperature no longer rises, it indicates that the decomposition is basically completed.

[0077] In one embodiment, the total space velocity GHSV of the secondary stage regeneration gas sum is controlled at 300 - 2000 hr -1 , preferably 500 - 1500 hr -1 . When the total space velocity is constant, the control of the pyrolysis temperature is achieved by adjusting the air addition amount. The growth rate range of GHSV air is 0.0001 - 100 h -1 / hour.

[0078] In one embodiment, when the first stage ends, the second stage begins. While continuing to introduce nitrogen, a certain amount of air is started to be introduced, and the temperature is continued to be raised, controlling the temperature increase rate at 5 - 60 °C / hour. After N2 and air are mixed, they are added to the regeneration reactor 5. After the regeneration gas containing oxygen contacts the catalyst, the catalytic oxidation reaction is initiated under the high specific surface area and rich pore structure of the catalyst. The reaction heat is rapidly conducted, the temperature will rise rapidly, further accelerating the reaction, and the organic matter is oxidized to CO, CO2, and gas small molecule volatile organic compounds, etc. The reaction temperature and the nitrogen flowmeter form a control loop, still controlling the reaction temperature increase rate at 5 - 60 °C / hr. When the temperature increase rate is too fast, the air intake can be reduced. When the temperature is stable, the air intake is increased to further raise the temperature. When it reaches 300 - 500 °C, it is kept at a constant temperature for 3 - 12 hours. During the above process, due to the progress of the reaction, the oxygen content in the gas phase shows a gradually increasing trend from low to high. As the reaction progresses, most of the organic matter is decomposed, the oxygen content gradually rises, and finally levels off with the intake amount, proving that the reaction is basically completed. Finally, the organic matter is completely decomposed and the catalyst regeneration is completed. At this time, a sample can be taken to test the LOI of the catalyst.

[0079] In the second stage, the molar ratio of nitrogen to air ranges from (1 - 100000):1. The specific setting of this ratio is adjusted based on the need for temperature change. To achieve precise control of the oxidation reaction, an appropriate amount of air needs to be accurately input. As the amount of air introduced increases, the degree of the oxidation reaction will correspondingly increase, leading to a rapid rise in temperature.

[0080] 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 crucial role in improving the regeneration effect of the catalyst. During the regeneration process of the catalyst, there are two main challenges that are often difficult to be properly handled and balanced simultaneously. The first challenge is that the organic matter wrapped on the catalyst surface is difficult to be completely separated and needs to be removed by high temperature. The second challenge is that the catalytic oxidation decomposition reaction is intense and releases a large amount of heat. During the process of removing organic matter, how to effectively control the temperature and avoid over-temperature, which may cause the copper in the catalyst to agglomerate and the performance of the catalyst to be permanently damaged. In response to these problems, the present invention proposes a special regeneration process method that successfully overcomes the above-mentioned problems. Through this method, relying on the self-activity of the regenerated catalyst, while removing the organic matter wrapped on the catalyst, the regulation and conversion of the multivalent copper of the active metal in the catalyst are realized. By regulating the temperature of 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 defined by 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.

[0081] In one embodiment, for the determination of the component constancy in the exhaust gas until the components in the exhaust gas are constant in step S51, the determination method is to test the components of the gas phase through the on-line analytical chromatograph 8 provided between the wire mesh demister 5-2 and the trap 9. When the gas phase components no longer change, it indicates that the components in the exhaust gas are constant. The constant temperature time for this process is 3 - 8 hours. After the components are constant, step S52 can be entered.

[0082] For step S52, after the catalytic oxidation stage of the regeneration reactor 5 is completed, the organic wrapping on the catalyst surface has been removed. The oxygen content in the on-line analytical chromatograph 8 is stable and basically equal to the intake air volume, and the regeneration reaction is basically completed. At this time, the copper in the active body of the catalyst mainly exists in the form of divalent copper. The regenerated catalyst slurry cooled by the catalyst cooler 6 is sent to the reduction reactor 7.

[0083] 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%.

[0084] In one embodiment, in step S6, in the formaldehyde aqueous solution of the preset concentration added to the reduction reactor 7, the mass fraction of formaldehyde is 40-55%, the pH is 6-8, the mass ratio of the amount of the formaldehyde aqueous solution added to the catalyst in the reduction reactor 7 is 5-20:1, and the reaction residence time is 5-120 minutes. Relying on the reducing property of formaldehyde in this environment, divalent copper (II) is reduced to monovalent copper (I) in the absence of acetylene.

[0085] 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 slurry. In the presence of acetylene, monovalent copper (I) combines with acetylene groups to form more catalytic cuprous acetylide active species, and the catalyst regeneration is completed.

[0086] The present invention also proposes the use of the above system or method in controlling the amount of catalyst ablation, especially in a reaction device for producing butynediol by an acetylene-aldehyde process BDO device, to control the amount of catalyst ablation and reduce the ablation amount to a preset range.

[0087] 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%.

[0088] 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, and the outlet of the catalyst concentration device 2 is connected to the catalyst separator 3. The concentrated liquid after being concentrated by the catalyst concentration device 2 will flow in two different directions, and the extraction ratio of these two parts is that the concentrated liquid extracted to the catalyst separator 3 and the concentrated liquid refluxed to the acetylation reactor 1 are distributed according to the mass ratio of 1: (1~200), and such a proportional distribution is to meet the requirements of the LOI control index in the reactor. The specific proportional value will be dynamically adjusted according to the LOI control requirements in the acetylation reactor 1. By controlling a certain ratio, the LOI in the acetylation reactor 1 can be maintained in an ideal range, that is, between 10% and 45%. In some cases, in order to achieve a better reaction effect, the LOI is controlled in the range of 10% to 40%, which not only ensures the efficiency of the reaction, but also ensures the economy of the operation of the device.

[0089] The present invention aims to reduce the LOI in the alkynylation reactor 1, and restores the performance of the catalyst by a two-step method. This method does not require adding chemical substances outside other reaction systems, and only realizes the regulation and conversion of different valence states of Cu 2+ / Cu + by controlling the pyrolysis temperature. Relying on the activity of the catalyst itself, the organic coatings on the surface are removed through catalytic oxidation reactions, without additional energy consumption. By controlling the pyrolysis temperature, the agglomeration of copper in the catalyst caused by overheating is avoided, and the performance of the catalyst is restored to the greatest extent. Through this method, by recycling a certain amount of catalyst, the LOI of the alkynylation reactor 1 is controlled below 10-45 wt%, greatly improving the reaction efficiency and reducing the consumption of the catalyst.

[0090] In the chemical reaction process carried out in the currently widely used alkynylation reactor 1, the active metal copper in the new copper-bismuth catalyst mainly exists in the form of divalent copper, and they can be presented in the form of oxides to ensure the safety of the catalyst. In the prior art, a series of complex activation steps are usually required to finally convert it into the active monovalent Cu(I) state. From the perspective of the microstructure analysis, it can be found that the reduction of the catalyst activity is mainly due to the encapsulation of surface organic substances, and its microstructure is not damaged, in which copper still exists in the mixed valence state of Cu 2+ ,Cu + and Cu 0 . The present invention proposes a brand-new idea for restoring the activity of the catalyst. Through this idea, a certain proportion of the withdrawn catalyst is regenerated and recycled back to the alkynylation reactor, and the LOI in the reactor can be controlled at a lower level, up to 10% at the lowest.

[0091] The catalyst regeneration method of the present invention is particularly applicable to supported copper-bismuth catalysts.

[0092] The following illustrates the treatment and regeneration process of the catalyst of the present invention through various examples.

[0093] Example 1 Adopt Figure 1 the system to carry out the regeneration cycle of the catalyst and control the LOI in the alkynylation reactor.

[0094] The production capacity of the alkynylation reactor 1 is 60,000 tons / year, corresponding to the feed formaldehyde (45±5%) of 15.0 m³ / hr. The reaction temperature is 98±1°C, and the reaction pressure is 180 kPa±5. The catalyst is BASF supported copper catalyst Cu6081P, and the relevant physical and chemical properties of the slurry output from the alkynylation reactor are shown in Table 1.

[0095] Table 1 Relevant physical and chemical properties of the slurry output from the alkynylation reactor Item Unit Value Catalyst Concentration wt% 10±0.5% Reaction Liquid Density <![CDATA[kg / m 3 > 990 LOI in Alkynylation Reactor % 35±2% Particle Size Distribution D50 mm 10-13 Specific Surface Area <![CDATA[m 2 / g]]> ≤15 Composition of Reaction Clear Liquid wt% Water 50.11, Methanol 0.87, Formaldehyde 0.70, Propargyl Alcohol 0.47, BYD 47.83, Acetylene 0.02 AdoptFigure 1 For the system, the activation and regeneration treatment of the catalyst is carried out according to the following steps.

[0096] S1, Control the output of the alkyne reactor 1 to send the slurry containing the copper-bismuth catalyst to the catalyst thickening device 2.

[0097] S2, The catalyst thickening device 2 concentrates the slurry to obtain a concentrated solution. Part of the concentrated solution is refluxed to the alkyne reactor 1, and part is pumped to the catalyst separator 3 according to a preset extraction ratio. The concentrated solution is a concentrated catalyst slurry, mainly composed of a high concentration of catalyst, water, BYD, and other organic substances. In Example 1, the extraction ratio of these two parts is that the concentrated solution extracted to the catalyst separator 3 and refluxed to the alkyne reactor 1 is distributed according to a mass ratio of 1:50. The flow rate of the concentrated solution returned from the catalyst thickening device to the reactor is 8333 kg / hr, the extracted concentrated solution is 166.7 kg / hr, and the catalyst concentration of the concentrated solution is 28%.

[0098] S3, Input the concentrated solution into the catalyst separator 3 to separate the catalyst to be regenerated, and recover the residual BYD solution in the catalyst to be regenerated, and at the same time separate the waste catalyst, i.e., the catalyst to be regenerated. The operating temperature is 90 °C and the pressure is 0.6 MPaG.

[0099] S4, Input the demineralized water and the catalyst to be regenerated separated in step S3 into the catalyst preparation device 4 respectively to prepare a preset solid content. In this example, the preset solid content is prepared into a catalyst slurry to be regenerated with 85 wt%, in order to reduce the water evaporation amount in the subsequent regeneration process, and then input it into the regeneration reactor 5 for regeneration.

[0100] S5, Control the regeneration gas to be input into the regeneration reactor 5 according to a preset input flow rate, carry out catalyst regeneration treatment in the regeneration reactor 5, and the treated catalyst is input into the catalyst cooler 6 for cooling; The specific process is as follows: The first stage, S51, The slurry prepared by the catalyst preparation device 4 is input into the regeneration reactor 5, start to introduce nitrogen into the regeneration reactor 5, and make the slurry in the regeneration reactor 5 fully contact with nitrogen through the stirrer in the regeneration reactor 5. The trap 9 is a tail gas trap, in which demineralized water is added as a circulating liquid and circulates stably, and the circulation amount is 30 m 3 / hr, and the temperature of the circulating liquid is 20 °C ± 1. The gas phase discharged from the regeneration reactor 5 is circulated through the gas compressor 11. After the gas circulates stably, the GHSV of nitrogen N2 is controlled at 100 hr -1, the heater of the regeneration reactor heats the regeneration reactor 5 by electric heating. The heating is carried out at a heating rate of 60 °C / hr. After heating up to 120 °C, it is kept at a constant temperature for 3 hours, and the pressure is controlled at 50 KPa. At this time, the water (including surface water and free bound water), volatile organic compounds (such as methanol, ethanol, THF, formaldehyde, etc.) in the catalyst start to evaporate. The evaporated substances are sent to the trap 9 together with nitrogen through the gas-phase discharge pipeline of the regeneration reactor 5. In the trap 9, desalted water is sprayed to separate the organic substances in it, which are sent out in the form of organic waste liquid. The nitrogen gas from which the organic substances and water have been removed is pressurized by a compressor and then recycled back to the reactor for reuse. An on-line analytical chromatograph 8 is installed on the gas-phase pipeline of the regeneration reactor 5. The on-line analytical chromatograph 8 is located between the regeneration reactor 5 and the trap 9. The content of the volatilized organic substances can be detected in real time through the on-line analytical chromatograph 8. When the content of the organic substances detected by the on-line analytical chromatograph 8 starts to decrease and stabilizes at a relatively low level, and the gas-phase components no longer change, it indicates that the removal of water and volatile organic substances in this stage is basically completed. Step S52 can be entered.

[0101] In the second stage, S52, the second stage is controlled to heat up at a heating rate of 20 °C / hour, and a mixture of nitrogen and air is used as the regeneration gas. The molar ratio range of nitrogen to air is (1~100000):1, which is adjusted according to the temperature change. The total space velocity GHSV of the regeneration gas in the second stage sum is 1000 hours -1 . The control of the pyrolysis temperature is achieved by the amount of air added. The adjustment rate range of GHSV air is 0.00001~100 h -1 / hour. The initial space velocity GHSV of the air feed air is 0.02 hour -1 . When the regeneration gas containing oxygen contacts the catalyst, under the high specific surface area and rich pore structure of the catalyst, the catalytic oxidation reaction is initiated, the reaction heat is rapidly conducted, the temperature will rise rapidly, further accelerating the reaction, and the organic substances are oxidized to CO, CO2 and small-molecule volatile organic compounds in the gas. In this process, the temperature control of the regeneration reactor 5 and the air flow are switched to automatic control, and the heating rate is controlled at 20 °C / hr. If it is found that the heating rate starts to rise too fast, the air feed amount can be adjusted. The adjustment rate of the air feed amount is 1 h -1 / h. When the temperature reaches 400 °C, keep it at a constant temperature for 5 h. Monitor the content of components in the gas phase in real time through an on-line analytical chromatograph 8 for the oxygen content. Due to the progress of the reaction, the oxygen content in the gas phase shows a gradually increasing trend 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 measured in the on-line analytical chromatograph 8 is stable and basically levels off with the proportion of the inlet gas volume, it indicates that the catalytic oxidation stage reaction is basically completed. At this time, the oxygen content in the tail gas is about 10 - 12 mol%, and at this time, the copper in the active body of the catalyst mainly exists in the form of divalent copper.

[0102] Input the catalyst after the reaction in the regeneration reactor 5 into the catalyst cooler 6. After the reaction in the regeneration reactor 5 is completed, the liquid phase is sent to the catalyst cooler 6 for cooling, and the catalyst is cooled to 80 °C. Measure the LOI of the regenerated catalyst, and the LOI content is 8.5.

[0103] S6, input the cooled material into the reduction reactor 7 and input an aqueous formaldehyde solution with a preset concentration into the reduction reactor 7 for catalyst reduction; add a 45% aqueous formaldehyde solution to the reduction reactor 7, the pH range of the aqueous formaldehyde solution is 7 ± 0.5, the mass ratio of the formaldehyde addition amount to the catalyst in the reduction reactor 7 is 10:1, the reaction residence time is 30 min, at 180 kPa and 80 °C, relying on the reducibility of formaldehyde in this environment, reduce divalent copper ions to monovalent copper under the condition of no acetylene.

[0104] S7, input the material after the reaction in the reduction reactor 7 into the acetylenation reactor 1.

[0105] Control the LOI in the acetylenation reactor 1 within the range of 35% ± 2 through the catalyst regeneration cycle method of the present invention.

[0106] Example 2 The difference between Example 2 and Example 1 is only that: In S2, the extraction ratio is that the concentrated liquid extracted to the catalyst separator 3 and the concentrated liquid refluxed to the acetylenation reactor 1 are distributed according to a mass ratio of 1:1.

[0107] In S3, during the process of separating the catalyst to be regenerated in the catalyst separator 3, control the temperature at 95 °C and the pressure at 0.9 MPaG.

[0108] S4, input the demineralized water and the catalyst to be regenerated separated in step S3 into the catalyst preparation device 4 respectively to prepare a catalyst slurry to be regenerated with a solid content of 80 wt%.

[0109] In S51, control the regeneration reactor 5 to reach 180 °C at a heating rate of 30 °C / h and keep it at a constant temperature for 5 hours; the GHSV of the nitrogen N2 is 50 h-1 .

[0110] S52, Feed the regeneration gas into the regeneration reactor 5. Among them, the regeneration gas in step S52 is a mixture of nitrogen and air. Control the temperature increase rate at 5 °C per hour until the temperature reaches 300 °C, and maintain a constant temperature for 3 hours. In step S52, the total space velocity GHSV of the mixed gas sum is 2000 h -1 ; In S5, the catalyst cooler 6 cools the catalyst to 60 °C. Measure the LOI of the regenerated catalyst, and the LOI content is 12.5%.

[0111] In S6, add 40% aqueous formaldehyde solution to the reduction reactor 7, and the pH range of the aqueous formaldehyde solution is 6. The mass ratio of the formaldehyde addition amount to the catalyst in the reduction reactor 7 is 5:1, and the reaction residence time is 120 min.

[0112] Under the conditions of Example 2, the LOI in the reactor can be maintained at 40±2%.

[0113] Example 3 The difference between Example 3 and Example 1 is only that: In S2, the extraction ratio is that the concentrated liquid extracted to the catalyst separator 3 and the concentrated liquid refluxed to the alkynylation reactor 1 are distributed according to a mass ratio of 1:200.

[0114] In S3, during the process of separating the catalyst to be regenerated in the catalyst separator 3, control the temperature at 98 °C and the pressure at 1.0 MPaG.

[0115] S4, Feed the demineralized water and the catalyst to be regenerated separated in step S3 into the catalyst preparation device 4 respectively to prepare a catalyst slurry to be regenerated with a solid content of 95 wt%.

[0116] In S51, control the regeneration reactor 5 to reach 180 °C at a heating rate of 180 °C per hour and maintain a constant temperature for 8 hours; the GHSV of the nitrogen N2 is 1000 h -1 .

[0117] S52, Feed the regeneration gas into the regeneration reactor 5. Among them, the regeneration gas in step S52 is a mixture of nitrogen and air. Control the temperature increase rate at 60 °C per hour until the temperature reaches 500 °C, and maintain a constant temperature for 12 hours. In step S52, the total space velocity GHSV of the mixed gas sum is 300 h -1 .

[0118] In S5, the catalyst cooler 6 cools the catalyst to 120 °C. Measure the LOI of the regenerated catalyst, and the LOI content is 4.5%.

[0119] In S6, 55% aqueous formaldehyde solution is added to the reduction reactor 7, and the pH range of the aqueous formaldehyde solution is 8. The mass ratio of the amount of formaldehyde added to the catalyst in the reduction reactor 7 is 20:1, and the reaction residence time is 5 min.

[0120] In Example 3, the LOI in the reactor can be maintained at 25 ± 2%.

[0121] Example 4 The difference between Example 4 and Example 1 is only that: In S51, the regeneration reactor 5 is controlled to reach 60 °C at a heating rate of 30 °C / hour and kept at a constant temperature for 4 hours; the GHSV of the nitrogen N2 is 800 hours -1 .

[0122] In S52, the regeneration gas is input into the regeneration reactor 5. Among them, the regeneration gas in step S52 is a mixture of nitrogen and air, and it is controlled to heat up at a heating rate of 60 °C / hour until the temperature reaches 450 °C and kept at a constant temperature for 12 hours. In step S52, the total space velocity GHSV of the mixture sum is 500 hours -1 .

[0123] In S6, 55% aqueous formaldehyde solution is added to the reduction reactor 7, and the pH range of the aqueous formaldehyde solution is 8. The mass ratio of the amount of formaldehyde added to the catalyst in the reduction reactor 7 is 18:1, and the reaction residence time is 10 min.

[0124] Example 5 The difference between Example 5 and Example 1 is only that: In S52, the regeneration gas is input into the regeneration reactor 5. Among them, the regeneration gas in step S52 is a mixture of nitrogen and air, and it is controlled to heat up at a heating rate of 40 °C / hour until the temperature reaches 450 °C and kept at a constant temperature for 10 hours. In step S52, the total space velocity GHSV of the mixture sum is 1500 hours -1 .

[0125] In S6, 55% aqueous formaldehyde solution is added to the reduction reactor 7, and the pH range of the aqueous formaldehyde solution is 8. The mass ratio of the amount of formaldehyde added to the catalyst in the reduction reactor 7 is 9:1, and the reaction residence time is 60 min.

[0126] Comparative Example 1 The fresh catalyst is not equipped with a regeneration cycle According to the steps of S1 - S4 in Example 1, using the data of a domestic production device at present, fresh catalyst (BASF Cu6081P) is regularly added, and the catalyst is regularly discharged. The discharged catalyst is no longer regenerated and recycled, but is treated as hazardous waste. According to the current production data, the LOI of the fresh catalyst is ≤1%, and the addition amount is 13.1 kg / hr, which can maintain the LOI in the reactor at 35 ± 2%.

[0127] The regenerated catalyst calcined at high temperature in Comparative Example 2 In Comparative Example 2, the discharged catalyst is regenerated by high - temperature roasting. The same - quality catalyst to be regenerated is obtained according to the steps of S1 - S4 in Example 1, dried at 120°C for 5 hr, and then roasted at 800°C for 3 hr. After obtaining the regenerated catalyst, the LOI content of the regenerated catalyst is 4.2%. The catalyst regenerated by this method is returned to the alkynylation reactor.

[0128] In Comparative Example 2, the LOI in the reactor can be maintained at 35 ± 2%.

[0129] Compare the reaction conditions of the alkynylation reactors in Example 1, Comparative Example 1, and Comparative Example 2. The comparison results are as follows in Table 2: Table 2 Comparison results of the reaction conditions of the alkynylation reactors in Example 1, Comparative Example 1, and Comparative Example 2 Item Name Unit Example 1 Comparative Example 1 Comparative Example 2 1 LOI Control Method -　 Low - temperature Catalytic Decomposition and Recycling Supplementary Addition of New Catalyst High - temperature Calcination and Return to 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 Propargyl Alcohol 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 Input Cost of Catalyst 10,000 Yuan / Month Low, about 409,000 Yuan, supplementary addition amount about 2 kg per hour Very high, about 2,350,000 Yuan Relatively high, about 818,000 Yuan, supplementary addition amount about 4.5 kg / hour From the above comparison results, it can be seen that in Example 1, the LOI in the reactor can be controlled at a lower level, and the highest conversion rate can be obtained. Without adding a large amount of fresh catalyst, the same reaction effect can be achieved. Although the LOI value in Comparative Example 2 is also reduced to the same level, the conversion rate of the reaction has not been improved. This also shows that the activity of the catalyst regenerated by the method in Comparative Example 2 has been severely damaged, and the efficiency of the alkynylation reaction has not been significantly improved, so it does not have the value of reuse, which has a negative impact on the economic benefits of the entire industrial process. The regeneration equipment and regeneration method involved in the present invention can, through innovative and efficient technical means, cleverly transform the valence state of the waste catalyst so that it can be reused after regeneration treatment. This process has a high conversion rate, reduces the supplement amount of fresh catalyst, significantly reduces the cost of controlling the LOI in the reactor, and thus makes the recycling of the catalyst more economically feasible.

[0130] Test Example 1 The catalyst after the regeneration in Example 1 is completed through S6, the fresh catalyst in Comparative Example 1, and the catalyst regenerated by high - temperature roasting in Comparative Example 2 are observed by scanning electron microscopy (SEM). Using Thermo Fisher apreo - 2s, EHT5kv, scanning electron microscopy observations at 1μm and 200nm are carried out, and the scanning electron micrographs are shown in Figures 3 - 8Transmission electron microscopy (TEM) observations at 0.2 μm and 50 nm were carried out using a JEOL JEM2100 with an accelerating voltage of 200 kV, and the TEM images are shown in Figures 9 - 14 。

[0131] Figure 3 Figure Figures 9 - 14 is the 1-μm scanning electron microscopy (SEM) image of the regenerated catalyst in Example 1, Figure 4 Figure Figure 4 is the 1-μm SEM image of the catalyst in Comparative Example 1, Figure 5 Figure Figure 5 is the 1-μm SEM image of the regenerated catalyst by high-temperature calcination in Comparative Example 2. Figure 6 Figure Figure 6 is the 200-nm SEM image of the catalyst in Example 1, Figure 7 Figure Figure 7 is the 200-nm SEM image of the catalyst in Comparative Example 1, Figure 8 Figure Figure 8 is the 200-nm SEM image of the catalyst in Comparative Example 2. Figure 9 Figure Figure 9 is the 0.2-μm TEM image of the catalyst in Example 1, Figure 10 Figure Figure 10 is the 0.2-μm TEM image of the catalyst in Comparative Example 1, Figure 11 Figure Figure 11 is the 0.2-μm TEM image of the catalyst in Comparative Example 2. Figure 12 Figure Figure 12 is the 50-nm TEM image of the catalyst in Example 1, Figure 13 Figure Figure 13 is the 50-nm TEM image of the catalyst in Comparative Example 1, Figure 14 Figure Figure 14 is the 50-nm TEM image of the catalyst in Comparative Example 2. It can be seen from the above SEM images that, when comparing the materials without calcination and at different calcination temperatures, for the regenerated catalyst in Example 1 compared with the fresh catalyst in Comparative Example 1, there are no obvious changes in the shape and size of the particles, the particle size is relatively uniform, and the dispersibility is still relatively good. However, for the regenerated catalyst by high-temperature calcination in Comparative Example 2, obvious agglomeration and caking phenomena are presented. Figure 5 For the catalyst in Comparative Example 2, the boundaries between particles cannot be observed, presenting a blurred morphology. At a larger magnification, this agglomeration phenomenon is more obvious. Combining with the transmission electron microscopy (TEM) to observe the morphological characteristics inside the material at a more microscopic scale, from Figures 9 - 11 and Figures 12 - 14 it can be seen that for the regenerated catalyst in Example 1, not only the internal pore structure matrix is not reduced compared with the fresh catalyst, but also a more abundant pore structure is presented, and the surface is rougher. However, for the catalyst in Comparative Example 2, the sintering and agglomeration phenomena are serious, indicating that during the regeneration process, the oxidation and decomposition of organic matter inside the catalyst and the outward overflow of gas have an impact on the pore diameter, making the pore structure of the regenerated catalyst more abundant. More nano-scale pore structures can increase the specific surface area of the material, and the strict control of the temperature within 500 °C during the regeneration process in Example 1 is the reason why the catalyst does not agglomerate and the catalyst activity is restored.

[0132] Test Example 2 The surface composition and valence states of the catalyst after the regeneration of Example 1 was completed in S5 and the catalyst regenerated by high-temperature calcination in Comparative Example 2 were analyzed by XPS, and the test was carried out using an X-ray photoelectron spectrometer (Thermo Fisher Scientific K-Alpha, USA). Among them, the vacuum degree of the analysis chamber was 5×10⁻¹⁰ Pa, the excitation source used Al Kα ray (hv = 1486.68 eV), the working voltage was 15 kV, the filament current was 10 mA, and the signal was accumulated for 5 - 10 cycles. The test passing energy was 50 eV, the step size was 0.05 eV, and the charge correction was carried out with the binding energy of C1s = 284.80 eV as the energy standard.

[0133] Figure 15 1 (the figure in the upper half) is the XPS analysis of the valence state of Cu for the catalyst of Example 1, and 3 (the figure in the lower half) is the XPS analysis of the valence state of Cu for the catalyst regenerated by high-temperature calcination in Comparative Example 2. The analysis results are shown in Table 3.

[0134] Table 3 Valence state analysis of Cu in the catalysts of Example 1 and Comparative Example 2

[0135] In Table 3, Atomic % is the atomic percentage, Atomic Percent. It can be seen from the XPS spectra that two main peaks of Cu2p3 / 2 (930 - 937.5 eV) and Cu2p1 / 2 (950 - 958.5 eV) appear in each catalyst, and the shake-up peaks are concentrated in the range of 940 - 945 eV. The coexistence of the high binding energy (930 eV) of Cu2p3 / 2 and the shake-up peak is one of the two main characteristics of the existence of Cu 2+ while the low binding energy (932.5 eV) of Cu2p3 / 2 and the absence of the shake-up peak are the + characteristics of the existence of Cu species, which proves that both Cu 2+ and Cu + valence states exist in the regenerated catalyst. Combining the composition ratios in Table 3, it can be seen that the Cu 2 + / Cu + in Example 1 and Comparative Example 1 are relatively close, which proves that the method of Example 1 has an equivalent effect on the conversion of Cu + to Cu 2+ , but the conversion of copper valence states can be achieved without high-temperature conditions, avoiding the damage to the microstructure of the catalyst caused by high temperature.

[0136] Test Example 3 After the regeneration of Example 1 was completed through S1 - S6, the specific surface area and pore structure of the catalyst, fresh catalyst, and the catalyst regenerated by high - temperature calcination in Comparative Example 1 were analyzed. A Mini X - type specific surface area analyzer produced by Mac Science Co., Ltd. of Japan was used. The adsorbed gas was nitrogen, the relative pressure range was 0.1, and the test temperature was 77K. Preparation method of the test sample: According to different test samples, degassing was carried out at 300 °C under vacuum for 8 hours. The test results are shown in Table 4.

[0137] Table 4 Analysis results of the specific surface area of the catalysts in Example 1, fresh catalyst, and Comparative Example 1 Serial Number Sample Name <![CDATA[BET specific surface area (m 2 / g)]]> <![CDATA[Total pore volume (cm 3 / g)]]> Average Pore Diameter (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 It can be seen from the BET test results in Table 4 that compared with the fresh catalyst in Comparative Example 1, the specific surface area of Example 1 decreased slightly. However, compared with Comparative Example 2, the pore diameter was larger, which also confirmed the test results of SEM and TEM. During the decomposition process of organic matter, the outward escape caused the expansion of the pore channels, but the specific surface area was 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 reduction in the number of pores caused by the sintering and agglomeration of copper in the catalyst was avoided, creating a favorable micro - environment for the restoration of the catalyst performance.

[0138] In S5 of Example 1, the regeneration process of the catalyst in the regeneration reactor 5 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 is the atomic percentage).

[0139] Table 5 Valence state transformation and content of copper at different stages

[0140] Test Example 4 The catalyst after the regeneration treatment of Example 1 through step S7, the fresh catalyst of Comparative Example 1, and the regenerated catalyst obtained by high - temperature calcination of Comparative Example 2 were compared, and the performance of the catalyst was characterized by the formaldehyde conversion rate. The test process is described below.

[0141] Equipment used 1. 50% formaldehyde, cylinder acetylene gas instrument; 2. Reaction kettle (maximum capacity: 500 ml, maximum temperature: 500 °C, maximum pressure: 27 MpaG); 3. T70 potentiometric titrator (for analyzing formaldehyde content); 4. Gas chromatograph (Agilent 7890B for analyzing methanol, propargyl alcohol, and butynediol content); 5. Centrifuge (for separating the catalyst).

[0142] Operation steps 1. Measure 200 ml of 50% formaldehyde solution (pH adjusted to 6.5) into the reactor.

[0143] 2. Weigh 28 g of the catalyst sample and add it to the reactor.

[0144] 3. Cover the reactor lid and tighten the bolts to ensure that the reactor is airtight.

[0145] 4. After passing the nitrogen replacement test, introduce acetylene gas (pay attention to the tail gas emission).

[0146] 5. Reaction temperature: 98 °C, pressure: 1.1 barG, stirring rate: 1200 rpm.

[0147] 6. The first sampling starts 30 s after the acetylene enters, then start timing, and stop the reaction after 3 hours.

[0148] 7. Test the formaldehyde concentration in the reaction solution. The test results are shown in Table 6.

[0149] Table 6 Test Results of Formaldehyde Concentration Item 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 Propargyl Alcohol wt% 0.095 0.12 0.41 5 Methanol wt% 1.12 1.06 1.19 As can be seen from the results in Table 6, the catalyst in Example 1 obtained the highest conversion rate. After the organic matter wrapped by the catalyst was removed, the structure of the catalyst was not damaged, and the catalytic performance was well restored. In Comparative Example 1, since it was not activated, the copper in the catalyst was mainly divalent copper, and it needed to be activated with formaldehyde first during the reaction. Under the same reaction residence time, the conversion rate was slightly lower than that in Example 1. However, both were much higher than that in Comparative Example 2, indicating that the agglomeration and sintering of the catalyst caused by high-temperature calcination had a greater impact on the catalyst performance.

[0150] Using the regeneration system and regeneration method of the present invention to regenerate the catalyst, by precisely controlling the catalytic cracking temperature, it is possible to effectively remove the organic matter on the catalyst surface, such as butynediol, formaldehyde, propargyl alcohol, methanol and other polymers, etc., and avoid the agglomeration and sintering of the catalyst caused by traditional high-temperature calcination and high-temperature incineration processes, maximize the retention of the catalyst performance, and form a cyclic regeneration process with the acetylation reactor, control the LOI of the reactor below 40%, and optimally reach below 20%, thereby improving the reaction efficiency. At the same time, through this method, the consumption of the catalyst can be greatly reduced, from the original catalyst consumption of 1.0 kg / ton BDO to a minimum of 0.3 kg / ton BDO, and the lowest can reach 0.3 kg / ton BDO.

[0151] The method involved in the present invention performs very well in terms of energy consumption. It does not rely on high-temperature incineration process to achieve catalyst regeneration, which not only improves safety and provides a safer working environment for operators and equipment, but also reduces energy consumption and potential impact on the environment.

[0152] It should be noted that although the above embodiments describe the various steps in a specific order, those skilled in the art can understand that in order to achieve the effects of the present invention, it is not necessary for different steps to be executed in such an order. They can be executed simultaneously (in parallel) or in other orders, and these variations are all within the protection scope of the present invention.

[0153] So far, the technical solution of the present invention has been described in combination with the preferred embodiments shown in the drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will all fall within the protection scope of the present invention.

Claims

1. A regeneration system for a supported copper-bismuth catalyst, characterized in that Comprising: An acetylenation 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; Wherein, a rotating shaft (3-1) and a plurality of filter plates (3-2) for intercepting the catalyst are arranged in the catalyst separator (3), and the filter plates (3-2) are connected to the rotating shaft (3-1); A first desalted water input port (4-1) is arranged on the catalyst preparation device (4); A gas delivery pipe (5-1) is connected to the regeneration reactor (5) for inputting regeneration gas, wherein the regeneration gas is nitrogen or a mixed gas, and the mixed gas is a nitrogen and air mixed gas; A formaldehyde aqueous solution input port (7-1) is arranged on the reduction reactor (7); the discharge port of the reduction reactor (7) is connected to the acetylenation reactor (1).

2. The system according to claim 1, wherein The discharge port at the bottom of the acetylenation reactor (1) is connected to the feed port of the catalyst concentration device (2); The material output port of the catalyst concentration device (2) is connected to the feed port of the catalyst separator (3); The rotating shaft (3-1) in the catalyst separator (3) is vertically arranged and has a hollow structure, and the plurality of filter plates (3-2) are arranged at intervals and communicated with the rotating shaft (3-1); The feed port of the catalyst preparation device (4) is connected to the discharge port at the bottom of the catalyst separator (3), the discharge port of the catalyst preparation device (4) is connected to the feed port of the regeneration reactor (5), the catalyst discharge port (5-5) of the regeneration reactor (5) is connected to the feed port of the catalyst cooler (6), and the discharge port of the catalyst cooler (6) is connected to the feed port of the reduction reactor (7).

3. The system according to claim 1, wherein The regeneration reactor (5) is a rotary kiln type pyrolysis reactor; and / or The acetylenation reactor (1) is an acetylenation reactor for synthesizing 1,4-butyne diol.

4. The system according to claim 1, characterized in that, The system further includes: a wire mesh demister (5-2), a trap (9), a gas compressor (11) and a trap circulating cooler (10), and a gas phase discharge port (5-3) and a gas phase reflux port (5-4) are further arranged on the regeneration reactor (5), and the gas phase discharge port (5-3), the wire mesh demister (5-2) and the feed port of the trap (9) are connected in sequence; 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) are further arranged on the trap (9), the gas phase outlet (9-1), the gas compressor (11) and the gas phase reflux port (5-4) are connected in sequence, and the liquid phase outlet (9-2), the trap circulating cooler (10) and the liquid phase reflux port (9-3) are connected in sequence.

5. The system according to claim 1, characterized in that, A catalyst reflux port (2-1) and a clear liquid output port (2-2) are further arranged on the catalyst concentration device (2), and the catalyst reflux port (2-1) is connected to the acetylenation reactor (1).

6. A method for regenerating a copper-bismuth catalyst under load using the system according to any one of claims 1-5, characterized in that, Comprising: S1, controlling the acetylenation reactor (1) to transport the slurry containing the copper-bismuth catalyst to the catalyst concentration device (2); S2, control the catalyst concentration increasing device (2) to concentrate the slurry to obtain a concentrated liquid; S3, input the concentrated liquid into the catalyst separator (3) to separate the catalyst to be regenerated; S4, input the catalyst to be regenerated into the catalyst preparation device (4) to prepare a preset solid content, and then input it into the regeneration reactor (5); S5, control the regeneration gas to be input into the regeneration reactor (5) according to a preset input flow rate, perform catalyst regeneration treatment in the regeneration reactor (5), and input the treated catalyst into the catalyst cooler (6) for cooling; S6, input the cooled material into the reduction reactor (7) and input a formaldehyde aqueous solution with a preset concentration into the reduction reactor (7) to perform catalyst reduction; S7, input the material after the reaction in the reduction reactor (7) into the ethynylation reactor (1).

7. The method according to claim 6, characterized in that The control of the regeneration gas being input into the regeneration reactor (5) according to a preset input flow rate includes: S51, input the regeneration gas into the regeneration reactor (5), wherein the regeneration gas in step S51 is nitrogen, and then control the regeneration reactor (5) to reach 60 - 180°C at a heating rate of 30 - 180°C per hour and keep the temperature constant for 3 - 8 hours; S52, input the regeneration gas into the regeneration reactor (5), wherein the regeneration gas in step S52 is a mixture of nitrogen and air, control the temperature to rise at a heating rate of 5 - 60°C per hour until the temperature reaches 300 - 500°C, and keep the temperature constant for 3 - 12 hours; wherein, the molar ratio range of nitrogen to air is (1 - 100000):

1.

8. The method according to claim 6, wherein In step S5, the cooling temperature is 60 - 120°C.

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

10. An application of the system according to any one of claims 1 - 5 or the method according to any one of claims 6 - 9 in controlling the ablation amount of the catalyst.

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