Separation and purification system for synthesizing propargyl alcohol

Abstract

The utility model relates to the field of chemical separation, in particular to a separation and purification system for synthesizing propargyl alcohol, which comprises a gas mixing device, an acetylene gas pressurizing device, an ethynylation reaction device, a gas-liquid separator, a butynediol separation tower, a formaldehyde recovery tower, a methanol separation tower, a propargyl alcohol product tower and a chromatography device which are connected in sequence. The system disclosed by the utility model can improve the selectivity of propargyl alcohol in the production process of butynediol under the condition of ensuring the safety of high-pressure acetylene, and effectively realize the separation of propargyl alcohol, so that the supply capacity of propargyl alcohol in the market is obviously improved. The device disclosed by the utility model not only improves the yield of the byproduct propargyl alcohol in BYD production, but also separates and extracts important chemical raw materials such as 1, 4 butynediol.

Description

Technical Field

[0001] The utility model relates to the field of chemical separation, and particularly provides a separation and purification system for synthesizing propargyl alcohol. Background Art

[0002] Propargyl alcohol, also known as 2-propyn-1-ol, is an important chemical raw material and has a wide range of applications in the fields of medicine, chemical industry, electroplating, pesticides, steel, oil extraction, etc. As an important intermediate in the organic synthesis industry, propargyl alcohol can be used to synthesize sodium fosfomycin, calcium fosfomycin, sulfadiazine, etc., and can also be used to produce products such as vitamin A, allyl alcohol, and acrolein. In the pesticide industry, propargyl alcohol is an important intermediate for synthesizing propargite. At present, the demand for propargyl alcohol in the pharmaceutical and pesticide industries has exceeded 10,000 tons / year. In addition, propargyl alcohol can also be used as a solvent, herbicide, fungicide, stabilizer for chlorinated hydrocarbons, etc.

[0003] The general reaction technology of propargyl alcohol was discovered by German scholar Reppet in the 1940s. The method uses formaldehyde and acetylene to react. The reaction uses an acetylene metal compound catalyst and is carried out at a certain temperature and pressure to obtain propargyl alcohol. To avoid the danger of acetylene explosion, the reaction process is generally carried out in the liquid phase, and water, alcohols, aldehydes, etc. can be used as solvents or diluents. When using aldehydes, the reaction is usually carried out in a weakly acidic or neutral environment; when using ketones, the solvent can also be alkaline. If the reaction solution is too alkaline, the formed alkynol may decompose into acetylene-based compounds or carbonyl compounds; if the reaction solution is too acidic, the catalyst will decompose with the formation of acetylene-based compounds, resulting in a very low conversion rate. In the production process of 1,4-butyne diol (BYD), using acetylene and formaldehyde as raw materials, under the action of a catalyst, the obtained reaction solution contains an aqueous solution mixed with about 47.8% of butyne diol, unreacted formic acid, reaction by-product propargyl alcohol, and trace amounts of methanol and other materials. In such a reaction system, propargyl alcohol often circulates back to the reactor as a by-product through rectification, wasting the economic value it contains.

[0004] Therefore, it is necessary to develop a separation and purification system that can improve the yield of propargyl alcohol, ensure the maximum utilization of by-products in the production process, maximize production profits, and enhance product competitiveness. Summary of the Utility Model

[0005] In order to overcome the above defects, the utility model provides a separation and purification system for synthesizing propargyl alcohol, which improves the yields of propargyl alcohol and by-products through specific separation processes.

[0006] In a first aspect, the present utility model provides a system for the separation and purification of propargyl alcohol synthesis, comprising: a gas mixing device, an acetylene gas pressurizing device, an alkynylation reaction device, a gas-liquid separator, a butynediol separation column, a formaldehyde recovery column, a methanol separation column, a propargyl alcohol product column, and a chromatography device connected in sequence; wherein, the gas mixing device includes a first gas inlet, a second gas inlet, a mixing tank, and a mixed gas outlet, the mixed gas outlet is connected to the inlet of the acetylene gas pressurizing device, the alkynylation reaction device is provided with a formaldehyde delivery pipe and an acetylene delivery pipe, the outlet of the acetylene gas pressurizing device is connected to the acetylene delivery pipe, the alkynylation reaction device is further connected to a heat exchange device, the outlet at the bottom of the alkynylation reaction device is connected to the inlet of the gas-liquid separator, the liquid phase outlet of the gas-liquid separator is connected to the feed inlet of the butynediol separation column, the tops of the butynediol separation column, the formaldehyde recovery column, the methanol separation column, and the propargyl alcohol product column are respectively provided with a condensation reflux device, and the bottoms of the butynediol separation column, the formaldehyde recovery column, the methanol separation column, and the propargyl alcohol product column are respectively provided with a heating device;

[0007] The inlet of the chromatography device is connected to the condensation device of the propargyl alcohol product column, the first outlet of the chromatography device is connected to the inlet of the propargyl alcohol product column, and the second outlet of the chromatography device is connected to the inlet of the methanol separation column.

[0008] Further, the alkynylation reaction device is a tubular reactor, and a plurality of tubes for filling copper-bismuth catalysts with a catalyst particle size of 3 mm to 6 mm are arranged in the tubular reactor. The top of each tube is respectively connected to the formaldehyde delivery pipe and the acetylene delivery pipe, and a liquid outlet is provided at the bottom of each tube; the diameter range of each tube is 50 mm to 200 mm; the tubes are arranged at intervals in the vertical direction;

[0009] A plurality of baffle plates for heat exchange are arranged on the shell side of the tubular reactor.

[0010] Further, the tubular reactor includes a reaction liquid collecting pipe and a plurality of reaction units. Each reaction unit includes a reaction liquid delivery pipe and a plurality of tubes; wherein, the liquid outlets of all the tubes in each reaction unit are connected to the reaction liquid delivery pipe in the reaction unit, one end of the collecting pipe is respectively connected to the reaction liquid delivery pipes of each reaction unit, and the other end of the reaction liquid collecting pipe is connected to the gas-liquid separator;

[0011] Each reaction unit is respectively connected to a formaldehyde delivery pipe and an acetylene delivery pipe.

[0012] Further, the gas-liquid separator includes: a centrifugal separator; and / or

[0013] The gas-liquid separator includes a liquid phase outlet and a gas phase outlet. The liquid phase outlet is located at the bottom of the gas-liquid separator, and the gas phase outlet of the gas-liquid separator is located at the top of the gas-liquid separator. The gas phase outlet is connected to the inlet of the acetylene gas pressurizing device and / or the outlet of the gas mixing device.

[0014] Further, the feed inlet of the butynediol separation column is located in the upper or middle part of the butynediol separation column. A first top outlet is provided at the top of the butynediol separation column. The first top outlet is sequentially connected to a first condenser and a first reflux drum. The outlet of the first reflux drum is respectively connected to the upper part of the butynediol separation column and the feed inlet of the formaldehyde recovery column. A butynediol discharge outlet is provided at the bottom of the butynediol separation column.

[0015] Further, the feed inlet of the formaldehyde recovery column is located in the upper or middle part of the formaldehyde recovery column. A second top outlet is provided at the top of the formaldehyde recovery column. The second top outlet is sequentially connected to a second condenser and a second reflux drum. The outlet of the second reflux drum is respectively connected to the upper part of the formaldehyde recovery column and the feed inlet of the methanol separation column. A formaldehyde discharge outlet is provided at the bottom of the formaldehyde recovery column.

[0016] Further, the feed inlet of the methanol separation column is located in the upper or middle part of the methanol separation column. A third top outlet is provided at the top of the methanol separation. The third top outlet is sequentially connected to a third condenser and a third reflux drum. The outlet of the third reflux drum is connected to the upper part of the methanol separation column. The discharge outlet in the middle of the methanol separation column is connected to the feed inlet of the propargyl alcohol product column. A methanol discharge outlet is provided at the bottom of the methanol separation column.

[0017] Further, a first cooler is provided between the discharge outlet in the middle of the methanol separation column and the propargyl alcohol product column.

[0018] Further, the feed inlet of the propargyl alcohol product column is located in the upper or middle part of the propargyl alcohol product column. A fourth top outlet is provided at the top of the propargyl alcohol product column. The fourth top outlet is sequentially connected to a fourth condenser and a fourth reflux drum. The outlet of the fourth reflux drum is respectively connected to the upper part of the propargyl alcohol product column and the chromatography device.

[0019] A fifth condenser and a propargyl alcohol delivery pump are sequentially connected to the middle of the propargyl alcohol product column.

[0020] Further, the top of the chromatography device is connected to the feed inlet of the propargyl alcohol product column, and the bottom of the chromatography device is connected to the feed inlet of the methanol separation column.

[0021] One or more of the above technical solutions of the present utility model have at least one or more of the following beneficial effects:

[0022] In implementing the technical solution of the present utility model, the system constructed by the present utility model can improve the selectivity of propargyl alcohol in the production process of synthesizing butynediol, effectively separate propargyl alcohol, and thus significantly enhance the supply capacity of propargyl alcohol in the market.

[0023] The present utility model not only improves the yield of by-product propargyl alcohol in the production of BYD, but also separates and purifies important chemical raw materials such as 1,4-butynediol, formaldehyde, and methanol.

[0024] The system of the present utility model significantly improves the product quality of propargyl alcohol, with a purity of ≥99.8%.

[0025] The present utility model effectively reduces the co-production ratio of 1,4-butynediol and propargyl alcohol, thereby increasing the output of propargyl alcohol. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Referring to the accompanying drawings, the disclosure of the present utility model will become more readily understood. 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 utility model. In addition, similar numbers in the figures are used to represent similar components, where:

[0027] Figure 1 is a schematic diagram of the main structure of a separation and purification system for synthesizing propargyl alcohol according to an embodiment of the present utility model;

[0028] Figure 2 is a schematic diagram of the distribution of the tubes in the alkynylation reaction device according to an embodiment of the present utility model;

[0029] Figure 3 is a top view schematic diagram of the alkynylation reaction device according to an embodiment of the present utility model.

[0030] LIST OF REFERENCE NUMERALS:

[0031] 1 Gas mixing device; 1-1 First gas inlet; 1-2 Second gas inlet; 1-3 Mixing tank; 1-4 Mixed gas outlet; 2 Acetylene gas pressurizing device; 3 Alkynylation reaction device; 3-1 Formaldehyde delivery pipe; 3-2 Acetylene delivery pipe; 3-3 Tube bundle; 3-4 Liquid outlet; 3-5 Reaction liquid delivery pipe; 3-6 Reaction liquid collecting pipe; 3-7 Baffle plate; 4 Gas-liquid separator; 5 Butynediol separation column; 5-1 First condenser; 5-2 First reflux tank; 5-3 First reboiler; 6 Formaldehyde recovery column; 6-1 Second condenser; 6-2 Second reflux tank; 6-3 Second reboiler; 7 Methanol separation column; 7-1 Third condenser; 7-2 Third reflux tank; 7-3 Third reboiler; 8 Propargyl alcohol product column; 8-1 Fourth condenser; 8-2 Fourth reflux tank; 8-3 Fifth condenser; 8-4 Propargyl alcohol transfer pump; 8-5 Total condenser; 8-6 Fourth reboiler; 9 Chromatography device; 10 First cooler; 11 Vacuum equipment; 12 Heat exchange device; 13 First heat exchange medium delivery pipe; 14 Second heat exchange medium delivery pipe; and 15 Heat exchange medium transfer pump. Detailed implementation manners

[0032] Some implementation manners of the present utility model will be described below with reference to the accompanying drawings. Those skilled in the art should understand that these implementation manners are only used to explain the technical principle of the present utility model and are not intended to limit the protection scope of the present utility model.

[0033] Refer to Figure 1 , the present utility model provides a system for separating propargyl alcohol, including: a gas mixing device 1, an acetylene gas pressurizing device 2, an alkynylation reaction device 3, a gas-liquid separator 4, a butynediol separation column 5, a formaldehyde recovery column 6, a methanol separation column 7, a propargyl alcohol product column 8, and a chromatography device 9 that are connected in sequence.

[0034] The functions and necessary connection relationships of each component in the above system will be described below.

[0035] The gas mixing device 1 is used to mix two gases, namely propane and acetylene, and the acetylene is preferably purified acetylene. The gas mixing device 1 includes a first gas inlet 1-1, a second gas inlet 1-2, a mixing tank 1-3 and a mixed gas outlet 1-4. The first gas inlet 1-1 is for propane intake, and the second gas inlet 1-2 is for acetylene intake. The mixing tank 1-3 is a feed buffer tank, where acetylene and propane are mixed. Here, propane is used as an inert diluent to prevent the overpressure decomposition of acetylene. The subsequent actual reaction is carried out by acetylene. Here, propane is used as a diluent to reduce the partial pressure of acetylene. This is crucial for enhancing the safety of the entire system. Due to the characteristic that acetylene is prone to decomposition and detonation, especially high-pressure acetylene, once it decomposes, the expanding pressure increases exponentially. Therefore, the high-pressure acetylene process of continuous transportation and continuous reaction faces many challenges, and its safe use is the primary factor to be considered in the design and production process. Therefore, by mixing propane, the partial pressure of acetylene can be effectively reduced, and it operates below the decomposition pressure of acetylene, thereby greatly reducing the risk of decomposition or explosion and ensuring the intrinsically safe use of acetylene. In addition, the buffer tank can also eliminate the fluctuations during the feeding process, such as pressure or flow fluctuations, which is beneficial to accurately control the reaction conditions.

[0036] The mixed gas outlet 1-4 is connected to the inlet of the acetylene gas pressurizing device 2. The mixed gas of propane and acetylene is pressurized in the acetylene gas pressurizing device 2, and the pressurized mixed gas of propane and acetylene is input into the alkynylation reaction device 3.

[0037] A formaldehyde delivery pipe 3-1 and an acetylene delivery pipe 3-2 are provided on the alkynylation reaction device. The outlet of the acetylene gas pressurizing device is connected to the acetylene delivery pipe 3-2. The formaldehyde delivery pipe 3-1 is used to input formaldehyde into the alkynylation reaction device 3. Although it is named the acetylene delivery pipe 3-2, the gas entering the interior of the alkynylation reaction device 3 through the acetylene delivery pipe 3-2 includes both acetylene and propane. The pressurized mixed gas of propane and acetylene is input into the alkynylation reaction device 3 through the acetylene delivery pipe 3-2. The alkynylation reaction device 3 is also connected to a heat exchange device 12.

[0038] In the alkynylation reaction device 3, under high-pressure conditions, the acetylene supplied from the acetylene gas pressurizing device 2 and the formaldehyde input from the formaldehyde delivery pipe 3-1 enter the top of the alkynylation reaction device 3 and mix. A copper-bismuth catalyst is provided in the alkynylation reaction device. In the alkynylation reaction device 3, a reaction occurs under the action of the copper-bismuth catalyst to generate an aqueous solution of butynediol and propargyl alcohol, and the pressure is set to 2.0 MPaG.

[0039] By using the heat exchange device 12, the acetylenation reaction device 3 can be heated during the start-up phase of the system, and during normal operation, the heat exchange device 12 is used for cooling, thereby effectively maintaining the temperature stability inside the acetylenation reaction device 3. The start-up phase of the system is the transitional phase from the completion of installation and commissioning to the normal and stable operation of the system of the present utility model.

[0040] In one embodiment, referring to Figure 2 , the acetylenation reaction device 3 is a tubular reactor. A number of tubes 3-3 are arranged inside the tubular reactor, and each tube 3-3 is filled with a copper-bismuth catalyst. The top of each tube is respectively connected to the formaldehyde delivery pipe 3-1 and the acetylene delivery pipe 3-2, and an outlet is provided at the bottom of each tube 3-3.

[0041] In one embodiment, the diameter range of each tube 3-3 is 50 mm to 200 mm; the tubes 3-3 are arranged at intervals in the vertical direction; a plurality of baffle plates 3-7 for heat exchange are arranged on the shell side of the tubular reactor for heat exchange during the reaction.

[0042] In one embodiment, the copper-bismuth catalyst filled in the tube 3-3 is a large-particle copper-bismuth catalyst.

[0043] In one embodiment, the copper-bismuth catalyst filled in the tube 3-3 is a copper-bismuth catalyst with a catalyst particle size of 3 mm to 6 mm. The tubular reactor is composed of a plurality of tubes arranged at intervals. When the large-particle catalyst is filled, the catalyst particles can play a role in filling the high-pressure acetylene space, filling the space required for the decomposition of high-pressure acetylene, greatly reducing the risk of high-pressure acetylene decomposition, and being of great significance for the safe use of high-pressure acetylene.

[0044] In each tube of the present utility model, in addition to the catalyst, there are formaldehyde and acetylene gas in a high-pressure state. By filling large-particle catalysts in the tubes, the complex catalyst separation and filtration process of the traditional slurry bed reactor can also be solved, and the production efficiency can be greatly improved.

[0045] The structural design of the acetylenation reaction device involved in the present utility model plays a crucial role in realizing the efficient and intrinsically safe synthesis of butynediol and propynol from high-pressure acetylene.

[0046] The working process of the tubes will be described below

[0047] The top ends of each of the said tube bundles 3-3 are respectively connected to the formaldehyde delivery pipe 3-1 and the acetylene delivery pipe 3-2. The pressurized propane and acetylene mixture is input into the tube bundle 3-3 through the acetylene delivery pipe 3-2, and formaldehyde is input into the tube bundle 3-3 from the formaldehyde delivery pipe 3-1. The tube bundle 3-3 is filled with large-particle copper-bismuth catalyst. Acetylene and formaldehyde are received in each tube bundle, and then react under the action of the catalyst in the tube bundle 3-3. Specifically, after acetylene and formaldehyde enter the tube bundle simultaneously, under the action of the catalyst, the reaction liquid generated mainly includes butynediol solution and propargyl alcohol solution. This process is an exothermic reaction, and the heat needs to be dissipated in time. The generated product flows vertically downward along the tube bundle 3-3 into the bottom of the tube bundle 3-3. The bottom of the tube bundle 3-3 is located at the bottom of the acetylation reaction device 3. Each bottom of the tube bundle is provided with a liquid outlet 3-4. Finally, after collecting the reaction liquid output from the liquid outlets 3-4 at the bottoms of all the tube bundles, it is transported to the gas-liquid separator 4.

[0048] The tubular reactor is composed of N tube bundles. The specific value of N is determined according to the production capacity. The tube bundle is filled with large-particle catalyst. After acetylene and formaldehyde enter the tube bundle simultaneously, under the action of the catalyst, butynediol solution and propargyl alcohol solution are generated by reaction.

[0049] Figure 2 In the figure, the dotted part is the heat exchange baffle 3-7 on the shell side. The shell side refers to the space surrounding the tube side and is composed of a large outer shell, which is responsible for guiding the fluid into the tube bundle 3-3 and wrapping the tube bundle 3-3 inside. In the tubular reactor, the "shell side" refers to the external closed space wrapping the tube bundle, which together with the "tube side" (tube pass) constitutes the heat transfer interface.

[0050] Since the baffle 3-7 is arranged horizontally, in order to avoid ambiguity caused by line crossing when showing it together with the vertical tube bundle 3-3, the baffle 3-7 in the acetylation reaction device 3 is shown by a dotted line. The setting method of the baffle 3-7 in the present utility model is as follows: the distance between adjacent two tube bundles 3-3 is L1, and the tube diameter is L2. L1 is 1 to 5 times of L2. In the present utility model, aiming at the characteristics of the reaction materials (acetylene and formaldehyde react to generate butynediol and propargyl alcohol solution under the action of the catalyst), within the specific range of baffle spacing and tube diameter, the design pressure on the tube side can be greatly increased, ensuring the safe use of high-pressure acetylene and meeting the high-pressure conditions required for increasing the yield of propargyl alcohol. At the same time, the gas-liquid-solid three-phase mixing inside the tubular reactor is more uniform, the contact is more sufficient, and the mass transfer and heat generation efficiency are greatly improved. On the shell side, under the low-pressure working condition, the reaction heat can be easily removed, and the temperature of each tube bundle is more balanced, avoiding local overheating. It also solves the economic problems such as high equipment investment caused by the significant increase in the equipment wall thickness under the condition of high-pressure acetylene.

[0051] In one embodiment, referring to Figure 3, the alkynylation reaction device 3 is a tubular reactor, and the tubular reactor includes a reaction liquid collecting pipe 3-6 and a plurality of reaction units. Each reaction unit includes a reaction liquid delivery pipe 3-5 and a number of tubes 3-3. The reaction liquid collecting pipe 3-6 is used to collect the reaction liquid after the reaction of all reaction units and then output it to the gas-liquid separator 4. Each reaction unit has a reaction liquid delivery pipe 3-5 for outputting the reaction liquid in the reaction unit.

[0052] The liquid outlets 3-4 of all the tubes 3-3 in each reaction unit are connected to the reaction liquid delivery pipe 3-5 in the reaction unit. One end of the reaction liquid collecting pipe 3-6 is respectively connected to the reaction liquid delivery pipes 3-5 of each reaction unit, and the other end of the reaction liquid collecting pipe 3-6 is connected to the gas-liquid separator 4. Finally, the reaction liquid delivery pipes 3-5 of each reaction unit are connected to the inlet of the reaction liquid collecting pipe 3-6 and are output from the outlet of the reaction liquid collecting pipe 3-6.

[0053] Each reaction unit is respectively connected to a formaldehyde delivery pipe 3-1 and an acetylene delivery pipe 3-2. The formaldehyde delivery pipe 3-1 is used to deliver formaldehyde to all the tubes 3-3 in the reaction unit. Structurally, all the tubes 3-3 in the reaction unit are connected to the formaldehyde delivery pipe 3-1 in the reaction unit. Similarly, the acetylene delivery pipe 3-2 is used to deliver acetylene to all the tubes 3-3 in the reaction unit. More precisely, it receives the mixed gas of propane and acetylene after pressurization. Since acetylene is the reaction raw material, acetylene is taken as the main object for description. Structurally, all the tubes 3-3 in the reaction unit are connected to the acetylene delivery pipe 3-2 in the reaction unit.

[0054] In an application scenario, referring to Figure 3 , an example is given to illustrate the structure of the alkynylation reaction device as a tubular reactor. The tubular reactor includes 7 groups of reaction units and 1 reaction liquid collecting pipe 3-6. Each reaction unit includes a different number of tubes 3-3, and each reaction unit includes 2 to 6 tubes. The number of tubes included in the reaction units can be the same or different.

[0055] The 7 groups of reaction units are respectively denoted as the first unit, the second unit, the third unit, the fourth unit, the fifth unit, the sixth unit, and the seventh unit.

[0056] There are 2 tube bundles in the first unit (denoted as tube bundle - 1 and tube bundle - 2), 1 acetylene delivery pipe (denoted as acetylene delivery pipe - 1), 1 formaldehyde delivery pipe (denoted as formaldehyde delivery pipe - 1), and 1 reaction liquid delivery pipe (denoted as reaction liquid delivery pipe - 1); the acetylene delivery pipe - 1 in the first unit delivers acetylene to tube bundle - 1 and tube bundle - 2 in the first unit, and the formaldehyde delivery pipe - 1 in the first unit delivers formaldehyde to tube bundle - 1 and tube bundle - 2 in the first unit. The reaction liquid delivery pipe - 1 in the first unit collects the reaction liquid from tube bundle - 1 and tube bundle - 2.

[0057] There are 4 tube bundles in the second unit (denoted as tube bundle - 3, tube bundle - 4, tube bundle - 5, and tube bundle - 6), 1 acetylene delivery pipe (denoted as acetylene delivery pipe - 2), 1 formaldehyde delivery pipe (denoted as formaldehyde delivery pipe - 2), and 1 reaction liquid delivery pipe (denoted as reaction liquid delivery pipe - 2); the acetylene delivery pipe - 2 in the second unit delivers acetylene to tube bundle - 3, tube bundle - 4, tube bundle - 5, and tube bundle - 6 in the second unit, and the formaldehyde delivery pipe - 2 in the second unit delivers formaldehyde to tube bundle - 3, tube bundle - 4, tube bundle - 5, and tube bundle - 6 in the second unit. The reaction liquid delivery pipe - 2 in the second unit collects the reaction liquid from tube bundle - 3, tube bundle - 4, tube bundle - 5, and tube bundle - 6.

[0058] The number of tube bundles in the third unit is 5, and the reaction liquid delivery pipe in the third unit is denoted as reaction liquid delivery pipe - 3.

[0059] The number of tube bundles in the fourth unit is 6, and the reaction liquid delivery pipe in the fourth unit is denoted as reaction liquid delivery pipe - 4.

[0060] The number of tube bundles in the fifth unit is 5, and the reaction liquid delivery pipe in the fifth unit is denoted as reaction liquid delivery pipe - 5.

[0061] The number of tube bundles in the sixth unit is 4, and the reaction liquid delivery pipe in the sixth unit is denoted as reaction liquid delivery pipe - 6.

[0062] The number of tube bundles in the seventh unit is 2, and the reaction liquid delivery pipe in the seventh unit is denoted as reaction liquid delivery pipe - 7.

[0063] The structures of the third to seventh units can be deduced by referring to the first and second units.

[0064] The reaction liquid collecting pipes 3 - 6 are respectively connected to the reaction liquid delivery pipes - 1, reaction liquid delivery pipe - 2, reaction liquid delivery pipe - 3, reaction liquid delivery pipe - 4, reaction liquid delivery pipe - 5, reaction liquid delivery pipe - 6, and reaction liquid delivery pipe - 7. The 7 reaction liquid delivery pipes in the 7 reaction units input the reaction liquid of their respective reaction units into the collecting pipe 3 - 6, and the reaction liquid collecting pipe 3 - 6 outputs to the gas - liquid separator 4.

[0065] The heat exchange process will be further described below. In the acetylenation reaction device 3 of the present utility model, there are two kinds of fluids, hot and cold, for heat exchange. One is the tube-side fluid flowing inside the tube of the tube bundle, which is the reaction slurry of the acetylenation reaction device 3; the other is the shell-side fluid flowing outside the tube of the tube bundle, which is an ethylene glycol aqueous solution. The acetylenation reaction device 3 exchanges heat through the ethylene glycol aqueous solution outside the tube bundle 3-3. The heat exchange medium, ethylene glycol aqueous solution, is introduced into the gap outside the tube 3-3 of the tube bundle. By cooling the tube wall of the tube bundle, the temperature of the acetylenation reaction device 3 is maintained within a preset range, preventing overheating and ensuring the quality of the reaction products.

[0066] In one embodiment, still referring to Figure 1 , a first heat exchange medium delivery pipe 13 and a second heat exchange medium delivery pipe 14 are respectively connected between the acetylenation reaction device 3 and the heat exchange device 12. The two heat exchange medium delivery pipes connect the heat exchange device 12 and the acetylenation reaction device 3 together.

[0067] In one embodiment, the first heat exchange medium delivery pipe 13 and the second heat exchange medium delivery pipe 14 are used to convey the heat exchange medium. The heat exchange medium is an ethylene glycol aqueous solution. The tube wall of the tube bundle is cooled by using the heat exchange medium, ethylene glycol aqueous solution. The heat is carried out by forced circulation into the acetylenation reaction device 3 by a pump, and then enters the heat exchange device 12 for cooling with circulating water, and circulates for temperature reduction.

[0068] The output end of the first heat exchange medium delivery pipe 13 is connected to the acetylenation reaction device 3, and the input end of the first heat exchange medium delivery pipe 13 is connected to the heat exchange device 12. The output end of the second heat exchange medium delivery pipe 14 is connected to the heat exchange device 12, and the input end of the second heat exchange medium delivery pipe 14 is connected to the acetylenation reaction device 3. The first heat exchange medium delivery pipe 13 and the second heat exchange medium delivery pipe 14 are used to transfer and recover the flowing heat exchange medium, ethylene glycol aqueous solution, to the acetylenation reaction device 3. The ethylene glycol aqueous solution is introduced outside the tube 3-3 of the tube bundle. The ethylene glycol aqueous solution flows between the outer walls of multiple tube bundles, enabling the ethylene glycol aqueous solution to dissipate heat from the tube bundle 3-3, thereby cooling the acetylenation reaction device 3 during the normal operation of the system.

[0069] In one embodiment, the heat exchange device 12 is a shell-and-tube heat exchanger. The shell-and-tube heat exchanger includes a shell and a plurality of heat exchange tubes arranged at intervals inside the shell.

[0070] In one embodiment, the system is further provided with a heat exchange medium delivery pump 15. The heat exchange medium delivery pump 15 is arranged between the first heat exchange medium delivery pipe 13 and the heat exchange device 12 or the heat exchange medium delivery pump 15 is arranged between the second heat exchange medium delivery pipe 14 and the heat exchange device 12.

[0071] The output end of the first heat exchange medium transfer pipe 13 is connected to the ethynylation reaction device 3, and the input end of the first heat exchange medium transfer pipe 13 is connected to the outlet of the heat exchange pipe of the heat exchange device 12. The output end of the second heat exchange medium transfer pipe 14 is connected to the inlet of the heat exchange pipe of the heat exchange device 12, and the input end of the second heat exchange medium transfer pipe 14 is connected to the ethynylation reaction device 3. The heat exchange medium, ethylene glycol aqueous solution, flows in the heat exchange pipes inside the shell-and-tube heat exchanger. During normal operation of the system, circulating water serves as the cooling medium and flows in the shell outside the heat exchange pipes of the shell-and-tube heat exchanger to cool the heat exchange medium. After the cooled heat exchange medium is re-input into the heat exchange device 12, the ethylene glycol aqueous solution flows outside the tubes 3-3 of the ethynylation reaction device 3 to carry away the heat. Under the pumping action, the heated ethylene glycol aqueous solution after absorbing heat is transported through the second heat exchange medium transfer pipe 14 to flow in the heat exchange pipes inside the heat exchange device 12. The cooling medium, circulating water, cools the ethylene glycol aqueous solution. The cooled ethylene glycol aqueous solution is then input into the space between the tubes of the ethynylation reaction device 3 through the first heat exchange medium transfer pipe 13 to maintain the temperature of the tubes within a preset range. In this way, the heat exchange medium is forced to circulate through the heat exchange medium transfer pump 15 into the tubular reactor to carry out the heat, and then enters the heat exchange device 12 to be cooled by the cooling medium, circulating water, for cooling. Thus, by regulating the temperatures of the cooling medium and the heat exchange medium, cooling is achieved during normal operation of the system.

[0072] In addition, by adaptively changing the temperatures of the cooling medium (the cooling medium becomes the heating medium after the temperature is increased) and the heat exchange medium, the ethynylation reaction device 3 can also be heated during the start-up stage of the system.

[0073] The outlet at the bottom of the ethynylation reaction device 3 is connected to the inlet of the gas-liquid separator 4.

[0074] In one embodiment, the outlet at the bottom of the ethynylation reaction device 3 is the outlet of the reaction liquid collecting pipe 3-6, and the gas-liquid separator 4 is connected to the reaction liquid collecting pipe 3-6.

[0075] The reaction liquid output from the outlet at the bottom of the ethynylation reaction device 3 mainly includes butynediol and propynol aqueous solution. The reaction liquid output from the outlet at the bottom of the ethynylation reaction device 3 needs to be further separated and purified subsequently.

[0076] Gas-liquid separation is carried out in the gas-liquid separator 4. The separated gas phase is discharged from the top of the gas-liquid separator 4, and the separated liquid phase is discharged from the bottom of the gas-liquid separator 4 and enters the butynediol separation column 5 for rectifying butynediol. The liquid phase outlet of the gas-liquid separator 4 is connected to the feed inlet of the butynediol separation column 5.

[0077] The butynediol separation column 5 needs to operate under pressure. The column bottom is about 35 wt% butynediol, and the main components of the overhead vapor phase are water, formaldehyde, methanol, and propynol solution. Condensing and reflux devices are respectively arranged at the tops of the butynediol separation column 5, formaldehyde recovery column 6, methanol separation column 7, and propynol product column 8, and heating devices are respectively arranged at the bottoms of the butynediol separation column 5, formaldehyde recovery column 6, methanol separation column 7, and propynol product column 8.

[0078] The butynediol separation column 5 is a valve-tray column. The butynediol separation column 5 includes several trays with valves for butynediol separation.

[0079] Through the purification and separation functions of the butynediol separation column 5, formaldehyde recovery column 6, methanol separation column 7, and propynol product column 8, important chemical raw material products can be separated step by step.

[0080] The inlet of the chromatography device 9 is connected to the condensing device of the propynol product column 8. The first outlet of the chromatography device is connected to the inlet of the propynol product column 8, and the second outlet of the chromatography device 9 is connected to the inlet of the methanol separation column 7.

[0081] The distillate after condensation at the top of the propynol product column 8 enters the chromatography device 9 for further separation and material reuse. In the chromatography device 9, according to the different densities in the material system, the azeotropic agent propyl acetate and water are separated into layers, and the azeotropic agent is recovered and reused.

[0082] In one embodiment, the heating device is a reboiler.

[0083] In one embodiment, the gas mixing device 1 is a high-pressure tubular reactor.

[0084] In one embodiment, the gas-liquid separator 4 includes: a centrifugal separator. The centrifugal separator uses the action of centrifugal force to separate the liquid from the gas. Since the centrifugal force received by the liquid is greater than that of the gas, the liquid adheres to the separation wall surface and falls to the bottom under the action of gravity and is discharged through a pipeline. In one embodiment, the gas-liquid separator 4 includes a liquid phase outlet and a gas phase outlet. The liquid phase outlet is located at the bottom of the gas-liquid separator 4, and the gas phase outlet of the gas-liquid separator 4 is located at the top of the gas-liquid separator 4. The gas phase outlet is connected to the inlet of the acetylene gas pressurizing device 2 and / or the outlet of the gas mixing device 1. In other words, the gas phase outlet can be set at the inlet position of the acetylene gas pressurizing device 2, or at the outlet position of the gas mixing device 1, or at the connection position of the inlet of the acetylene gas pressurizing device 2 and the outlet of the gas mixing device 1.

[0085] After the gas-liquid separation in the gas-liquid separator 4, the unreacted acetylene / propane mixed gas is led out from the top and returned to the inlet of the acetylene gas pressurizing device 2 for recycling, and the reaction liquid output from the liquid phase outlet below enters the refining system for refining through a transfer pump.

[0086] In one embodiment, the composition of the reaction liquid output from the liquid phase outlet below the gas-liquid separator 4 is shown in Table 1.

[0087] Table 1 Composition of the materials output from the liquid phase outlet of the gas-liquid separator

[0088] Name Butynediol Water Formaldehyde Methanol Propargyl alcohol Content 47.8 wt% 50.2 wt% 0.7 wt% 0.8 wt% 0.5 wt%

[0089] The separation and rectification equipment of the present utility model will be described below.

[0090] In one embodiment, the feed inlet of the butynediol separation tower 5 is located in the upper or middle part of the butynediol separation tower 5. A first tower top outlet is provided at the top of the butynediol separation tower 5, and the first tower top outlet is sequentially connected to a first condenser 5-1 and a first reflux tank 5-2. The first condenser 5-1 is a butynediol tower top condenser, and the condensate after condensation by the first condenser 5-1 is collected in the first reflux tank 5-2. The outlet of the first reflux tank 5-2 is respectively connected to the upper part of the butynediol separation tower 5 and the feed inlet of the methanol separation tower 7; a butynediol discharge outlet is provided at the bottom of the butynediol separation tower 5; the butynediol separation tower 5 includes a point disk type liquid distributor and a number of valve trays.

[0091] The point disk type liquid distributor can perform uniform initial distribution, which is used to increase the effective surface for mass transfer and heat transfer, improve the interfacial contact, and thus improve the efficiency of the tower. The function of the valve tray is to have high gas-liquid contact efficiency, strong anti-blocking property, low manufacturing cost, and convenient maintenance.

[0092] A first reboiler 5-3 is provided at the bottom of the butynediol separation tower 5, and the first reboiler 5-3 is used to heat the butynediol separation tower 5. After the bottom of the butynediol separation tower 5 is heated for rectification, the main components of the vapor phase at the top of the butynediol separation tower 5 are water, formaldehyde, methanol, and propargyl alcohol solution. After being condensed by the first condenser 5-1, they are collected in the first reflux tank 5-2, and a part of them is refluxed to the upper part of the butynediol separation tower 5 under the pumping action, and the other part is sent to the formaldehyde recovery tower 6.

[0093] The butynediol is output from the bottom of the butynediol separation tower 5 through the transfer of a pump.

[0094] In one embodiment, the condensate collected in the first reflux tank 5-2 is respectively transported to the formaldehyde recovery tower 6 and the butynediol separation tower 5 through the pumping action of a liquid pump.

[0095] In one embodiment, the feed inlet of the formaldehyde recovery column 6 is located in the upper or middle part of the formaldehyde recovery column 6. A second top outlet is provided at the top of the formaldehyde recovery column 6, which is successively connected to a second condenser 6-1 and a second reflux drum 6-2. The second condenser 6-1 is a top condenser of the formaldehyde recovery column. The outlet of the second reflux drum 6-2 is respectively connected to the upper part of the formaldehyde recovery column 6 and the feed inlet of the methanol separation column 7; the condensate condensed by the second condenser 6-1 is collected in the second reflux drum 6-2. A formaldehyde discharge port is provided at the bottom of the formaldehyde recovery column 6, and the formaldehyde at the bottom of the formaldehyde recovery column 6 is output under the conveying action of a pump.

[0096] The formaldehyde recovery column 6 operates under a vacuum state. A second reboiler 6-3 is provided at the bottom of the formaldehyde recovery column 6 for heating the formaldehyde recovery column 6. After the formaldehyde recovery column 6 is heated, about 20 wt% of propargyl alcohol is separated from the top of the formaldehyde recovery column 6. After being condensed by the second condenser 6-1, it is collected in the second reflux drum 6-2. Under the conveying action of a liquid pump, a part of it is refluxed to the formaldehyde recovery column 6, and a part is sent to the methanol separation column 7. A formaldehyde discharge port is provided at the bottom of the formaldehyde recovery column 6, and the formaldehyde of the formaldehyde recovery column 6 is output under the conveying action of a pump for formaldehyde recovery.

[0097] In one embodiment, the feed inlet of the methanol separation column 7 is located in the upper or middle part of the methanol separation column 7. A third top outlet is provided at the top of the methanol separation column, which is successively connected to a third condenser 7-1 and a third reflux drum 7-2. The third condenser 7-1 is a condenser of the methanol separation column. The outlet of the third reflux drum 7-2 is connected to the upper part of the methanol separation column 7; the discharge port in the middle of the methanol separation column 7 is connected to the feed inlet of the propargyl alcohol product column; a methanol discharge port is provided at the bottom of the methanol separation column 7, and the methanol at the bottom of the methanol separation column 7 is output under the conveying action of a pump.

[0098] A third reboiler 7-3 is further provided at the bottom of the methanol separation column 7.

[0099] The methanol separation column 7 needs to operate under normal pressure. The overhead distillate is lower-boiling alcohols. The middle draw is about 50 wt% aqueous solution of propargyl alcohol, which is output through the discharge port in the middle of the methanol separation column 7. The bottom liquid is an aqueous solution containing a small amount of propargyl alcohol and is output under the conveying action of a pump and sent to the dilute formaldehyde tank for recycling.

[0100] In one embodiment, a first cooler 10 is further provided between the discharge port in the middle of the methanol separation column 7 and the propargyl alcohol product column 8. According to the temperature requirement of the feed condition of the propargyl alcohol product column 8, cooling of the feed is required. Therefore, in order to improve the efficiency of the system, the first cooler 10 is provided to cool the material entering the propargyl alcohol product column 8.

[0101] The aqueous solution of propargyl alcohol taken from the middle of the methanol separation column 7 enters the propargyl alcohol product column 8 after cooling through the pumping action of a liquid pump.

[0102] In one embodiment, the feed inlet of the propargyl alcohol product column 8 is located in the upper or middle part of the propargyl alcohol product column 8. A fourth top outlet is provided at the top of the propargyl alcohol product column 8, and the fourth top outlet is sequentially connected to a fourth condenser 8-1 and a fourth reflux drum 8-2. The fourth condenser 8-1 is a top condenser for the propargyl alcohol product column, and the fourth reflux drum 8-2 collects the liquid condensed by the fourth condenser 8-1. The outlet of the fourth reflux drum 8-2 is respectively connected to the upper part of the propargyl alcohol product column 8 and a chromatography device 9; a fourth reboiler 8-6 is provided at the bottom of the propargyl alcohol product column 8 for heating the propargyl alcohol product column 8.

[0103] The middle part of the propargyl alcohol product column 8 has a gas-phase draw. The middle part of the propargyl alcohol product column 8 is sequentially connected to a fifth condenser 8-3 and a propargyl alcohol transfer pump 8-4. The fifth condenser 8-3 is a middle-draw condenser for the propargyl alcohol product column. Since the gas-phase draw temperature in the middle part of the propargyl alcohol product column 8 is about 90 °C, it needs to enter the fifth condenser 8-3 to be cooled to 40 °C and then be pumped to the product storage tank.

[0104] An aqueous solution of propargyl alcohol with a content of about 50 wt% taken from the methanol separation column 7 is cooled and sent to the propargyl alcohol product column 8. The propargyl alcohol product column 8 operates under a vacuum state. Propargyl alcohol with a purity of ≥99.8 wt% is drawn from the side line of the propargyl alcohol column, and a small amount of propargyl alcohol and some high-boiling substances are in the bottom of the column and need to be discharged regularly.

[0105] The bottom of the propargyl alcohol product column 8 discharges the propargyl alcohol residue at the bottom of the propargyl alcohol product column 8 through a bottom liquid pump.

[0106] The condensed liquid stored in the fourth reflux drum 8-2 is, through a liquid pump, partly transported into the propargyl alcohol product column 8 and partly input into the chromatography device 9.

[0107] In one embodiment, the top of the chromatography device 9 is connected to the feed inlet of the propargyl alcohol product column 8, and the bottom of the chromatography device 9 is connected to the feed inlet of the methanol separation column 7.

[0108] Ethyl acetate is added as an azeotropic agent to the overhead distillate of the propargyl alcohol product column 8 and enters the chromatography device 9. Or there is an azeotropic agent input port provided in the chromatography device 9 for inputting an azeotropic agent. Ethyl acetate is pre-charged as an azeotropic agent in the chromatography device 9 through the azeotropic agent input port. After the overhead distillate enters the chromatography device 9, it is mixed with the azeotropic agent.

[0109] In the chromatography device 9, propyl acetate and water are separated into layers. The upper-layer propyl acetate and part of propargyl alcohol are continuously recycled back to the propargyl alcohol product tower 8 through the top outlet of the chromatography device 9, and the lower-layer water and part of propyl acetate are returned to the methanol separation tower 7.

[0110] In one embodiment, the condensation device of the propargyl alcohol product tower 8 further includes a total condenser 8-5. The total condenser 8-5 is respectively connected to the fourth condenser 8-1 and the fourth reflux tank 8-2. Specifically, the vapor outlet of the fourth condenser 8-1 is connected to the inlet of the total condenser 8-5, the liquid outlet of the fourth condenser 8-1 is connected to the fourth reflux tank 8-2, the discharge port at the top of the fourth reflux tank 8-2 is connected to the inlet of the total condenser 8-5, and the liquid outlet of the total condenser 8-5 is connected to the fourth reflux tank 8-2.

[0111] The working process is as follows:

[0112] The vapor at the top of the propargyl alcohol product tower 8 is condensed by the fourth condenser 8-1. In order to better recover propyl acetate, the vapor of the fourth condenser 8-1 enters the total condenser 8-5 for further cooling. The condensate condensed by the total condenser 8-5 is collected in the fourth reflux tank 8-2, and the liquid phase condensed by the fourth condenser 8-1 is also collected in the fourth reflux tank 8-2. Through the reflux pump, a part of the condensate in the fourth reflux tank 8-2 is returned to the propargyl alcohol product tower 8, and the other part of the condensate is sent to the chromatography device 9 for separating and recovering propyl acetate.

[0113] In one embodiment, a discharge port is provided at the top of the fourth reflux tank 8-2 and is connected to the inlet of the total condenser 8-5. The vapor of the fourth condenser 8-1 is sent to the total condenser 8-5 through the vapor outlet, the liquid phase of the fourth condenser 8-1 is sent into the fourth reflux tank 8-2, and the inlet of the total condenser 8-5 is respectively connected to the vapor outlet of the fourth condenser 8-1 and the discharge port at the top of the fourth reflux tank 8-2.

[0114] In one embodiment, the total condenser 8-5 and the second condenser 6-1 are respectively connected to the vacuum device 11 to establish the required vacuum environment for the propargyl alcohol product tower 8 and the formaldehyde recovery tower 6.

[0115] Through the separation system of the present invention, the yield of propargyl alcohol taken out from the middle of the propargyl alcohol product tower 8 and output by the propargyl alcohol transfer pump can reach 40%.

[0116] In one embodiment, in order to improve the conveying efficiency of the material, the present invention is also provided with liquid pumps, including but not limited to the following:

[0117] A liquid pump is provided between the alkynylation reaction device 3 and the heat exchange device 12 for pumping the heat exchange medium.

[0118] The material at the bottom of the gas-liquid separator 4 is transported to the butynediol separation tower 5 through a liquid pump.

[0119] The liquid stored in the first reflux drum 5-2 is partially refluxed to the butynediol separation column 5 through a liquid pump, and the rest is sent to the formaldehyde recovery column 6.

[0120] The liquid stored in the second reflux drum 6-2 is partially refluxed to the formaldehyde recovery column 6 through a liquid pump, and the rest is refluxed to the methanol separation column 7.

[0121] The liquid stored in the third reflux drum 7-2 is partially refluxed to the methanol separation column 7 through a liquid pump, and the rest is output.

[0122] The liquid stored in the fourth reflux drum 8-2 is partially refluxed to the propargyl alcohol product column 8 through a liquid pump, and the rest is transported to the chromatography device 9.

[0123] The coolant of the fifth condenser 8-3 is output through a liquid pump.

[0124] The coolant of the first cooler 10 is transported to the propargyl alcohol product column 8 through a liquid pump.

[0125] Liquid pumps are respectively arranged at the bottoms of the butynediol separation column 5, the formaldehyde recovery column 6, the methanol separation column 7, and the propargyl alcohol product column 8 for outputting the materials in each column still.

[0126] The system constructed by the present utility model can ensure the safe transportation of high-pressure acetylene at a relatively high acetylene pressure, improve the selectivity of propargyl alcohol in the production process of butynediol, and effectively realize the separation of propargyl alcohol, thus significantly enhancing the supply capacity of propargyl alcohol in the market. The separation system involved in the present utility model has the following advantages:

[0127] First, it is conducive to the industrial promotion, making the production process of propargyl alcohol safer and more reliable, and ensuring the safety after expanding the production scale. Based on the production process of 1,4-butynediol (BYD), using acetylene and formaldehyde as raw materials, under the action of a catalyst, a new type of tubular reactor is adopted to ensure the intrinsically safe production of high-pressure acetylene, which is easy to realize and has no potential safety hazards.

[0128] In addition, the present utility model not only improves the yield of the by-product propargyl alcohol in the production of BYD, but also extracts important chemical raw materials such as 1,4-butynediol, formaldehyde, and methanol.

[0129] Secondly, the system significantly improves the product quality of propargyl alcohol, with a purity of ≥99.8%.

[0130] Thirdly, the system effectively reduces the co-production ratio of 1,4-butynediol and propargyl alcohol, thereby increasing the output of propargyl alcohol and further enhancing the market competitiveness. The co-production ratio of the existing system for separating propargyl alcohol is about 250:1, while the co-production ratio of the present utility model is 100:1.

[0131] 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 utility model, 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 utility model.

[0132] So far, the technical solution of the present utility model 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 utility model is obviously not limited to these specific embodiments. Without departing from the principle of the present utility model, 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 utility model.

Claims

1. A separation and purification system for synthesizing propargyl alcohol, characterized in that, Comprising: A gas mixing device, an acetylene gas pressurizing device, an alkynylation reaction device, a gas-liquid separator, a butynediol separation column, a formaldehyde recovery column, a methanol separation column, a propargyl alcohol product column, and a chromatography device connected in sequence; wherein, the gas mixing device includes a first gas inlet, a second gas inlet, a mixing tank, and a mixed gas outlet, the mixed gas outlet is connected to the inlet of the acetylene gas pressurizing device, a formaldehyde delivery pipe and an acetylene delivery pipe are arranged on the alkynylation reaction device, the outlet of the acetylene gas pressurizing device is connected to the acetylene delivery pipe, the alkynylation reaction device is further connected to a heat exchange device, the outlet at the bottom of the alkynylation reaction device is connected to the inlet of the gas-liquid separator, the liquid phase outlet of the gas-liquid separator is connected to the feed inlet of the butynediol separation column, and condensation reflux devices are respectively arranged at the tops of the butynediol separation column, the formaldehyde recovery column, the methanol separation column, and the propargyl alcohol product column, and heating devices are respectively arranged at the bottoms of the butynediol separation column, the formaldehyde recovery column, the methanol separation column, and the propargyl alcohol product column; The inlet of the chromatography device is connected to the condensation device of the propargyl alcohol product column, the first outlet of the chromatography device is connected to the inlet of the propargyl alcohol product column, and the second outlet of the chromatography device is connected to the inlet of the methanol separation column.

2. The system according to claim 1, characterized in that, The alkynylation reaction device is a tubular reactor, and a plurality of tubes for loading copper-bismuth catalyst are arranged in the tubular reactor, the top ends of each tube are respectively connected to the formaldehyde delivery pipe and the acetylene delivery pipe, and a liquid outlet is arranged at the bottom of each tube; The diameter range of each tube is 50 mm to 200 mm; the tubes are arranged at intervals in the vertical direction; a plurality of baffle plates for heat exchange are arranged on the shell side of the tubular reactor.

3. The system according to claim 2, wherein The tubular reactor includes a reaction liquid collecting pipe and a plurality of reaction units, and each reaction unit includes a reaction liquid delivery pipe and a plurality of tubes; wherein, The liquid outlets of all the tubes in each reaction unit are connected to the reaction liquid delivery pipe in the reaction unit, one end of the collecting pipe is respectively connected to the reaction liquid delivery pipes of each reaction unit, and the other end of the reaction liquid collecting pipe is connected to the gas-liquid separator; Each reaction unit is respectively connected to a formaldehyde delivery pipe and an acetylene delivery pipe.

4. The system according to claim 1, wherein The gas-liquid separator includes: a centrifugal separator; and / or The gas-liquid separator includes a liquid phase outlet and a gas phase outlet, the liquid phase outlet is located at the bottom of the gas-liquid separator, the gas phase outlet of the gas-liquid separator is located at the top of the gas-liquid separator, and the gas phase outlet is connected to the inlet of the acetylene gas pressurizing device and / or the outlet of the gas mixing device.

5. The system according to claim 1, characterized in that, The feed inlet of the butynediol separation column is located in the upper or middle part of the butynediol separation column, a first top outlet is arranged at the top of the butynediol separation column, the first top outlet is sequentially connected to a first condenser and a first reflux tank, the outlet of the first reflux tank is respectively connected to the upper part of the butynediol separation column and the feed inlet of the formaldehyde recovery column; a butynediol discharge outlet is arranged at the bottom of the butynediol separation column.

6. The system according to claim 1, wherein The feed inlet of the formaldehyde recovery column is located in the upper or middle part of the formaldehyde recovery column. A second top outlet is provided at the top of the formaldehyde recovery column. The second top outlet is sequentially connected to a second condenser and a second reflux drum. The outlet of the second reflux drum is respectively connected to the upper part of the formaldehyde recovery column and the feed inlet of the methanol separation column. A formaldehyde discharge outlet is provided at the bottom of the formaldehyde recovery column.

7. The system according to claim 1, wherein The feed inlet of the methanol separation column is located in the upper or middle part of the methanol separation column. A third top outlet is provided at the top of the methanol separation column. The third top outlet is sequentially connected to a third condenser and a third reflux drum. The outlet of the third reflux drum is connected to the upper part of the methanol separation column. The discharge outlet in the middle of the methanol separation column is connected to the feed inlet of the propargyl alcohol product column. A methanol discharge outlet is provided at the bottom of the methanol separation column.

8. The system according to claim 7, wherein A first cooler is further provided between the discharge outlet in the middle of the methanol separation column and the propargyl alcohol product column.

9. The system according to claim 1, wherein The feed inlet of the propargyl alcohol product column is located in the upper or middle part of the propargyl alcohol product column. A fourth top outlet is provided at the top of the propargyl alcohol product column. The fourth top outlet is sequentially connected to a fourth condenser and a fourth reflux drum. The outlet of the fourth reflux drum is respectively connected to the upper part of the propargyl alcohol product column and the chromatography device. A fifth condenser and a propargyl alcohol transfer pump are sequentially connected in the middle of the propargyl alcohol product column.

10. The system according to claim 1 or 9, characterized in that, The top of the chromatography device is connected to the feed inlet of the propargyl alcohol product column, and the bottom of the chromatography device is connected to the feed inlet of the methanol separation column.

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