A tail gas resource utilization and urea co-production system in a process of producing pyrazole alcohol

Abstract

The application discloses a tail gas resource utilization and urea co-production system in a pyrazole alcohol production process, relates to the technical field of tail gas treatment, and comprises a pyrazole ketone oxidation product purification module, an oxygen-argon recycling module and a co-production urea and potassium salt recycling module; the pyrazole ketone oxidation product purification module comprises a first gas-liquid separation unit and a hydrochloric acid generation unit, the former receives the material at the outlet of a production system, separates a first separation liquid, a first separation mixed gas and condensed water, and the latter prepares hydrochloric acid by using part of the condensed water; the oxygen-argon recycling module separates oxygen and argon from the first separation mixed gas by sequentially connecting oxygen and argon separation units, and discharges a first remaining mixed gas; the co-production urea and potassium salt recycling module is provided with a urea preparation reactor into which the first remaining mixed gas is fed to generate a urea crude product solution; and a second gas-liquid separation unit separates the urea crude product solution into a second separation mixed gas and a second separation liquid. The application reduces pollutant emission and realizes resource cascade utilization.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of tail gas treatment, in particular to a tail gas resource utilization and urea co-production system in the production of pyrazolol. BACKGROUND

[0002] 1-(4-chlorophenyl)-3-pyrazolol prepared by air oxidation method is a green synthesis process with good development prospect. Compared with traditional synthesis method, the advantages of air oxidation method are mild reaction conditions, higher economy and good process safety. At present, the tail gas treatment method of 1-(4-chlorophenyl)-3-pyrazolol prepared by air oxidation method mainly relies on traditional waste gas treatment technology, but there are still problems such as large tail gas emission and low resource utilization rate in actual industrial application. Therefore, it is urgent to develop green and efficient tail gas treatment technology to promote process optimization and upgrading. SUMMARY

[0003] The purpose of the present application is to provide a tail gas resource utilization and urea co-production system in the production of pyrazolol to solve the problems existing in the prior art, reduce pollutant emissions and realize resource cascade utilization.

[0004] To achieve the above purpose, the present application provides the following scheme:

[0005] The present application provides a tail gas resource utilization and urea co-production system in the production of pyrazolol, which comprises a pyrazolidone oxidation product purification module, an oxygen-argon recovery and recycling module and a co-production urea and potassium salt recycling module. The pyrazolidone oxidation product purification module comprises a first gas-liquid separation unit and a hydrochloric acid generation unit. The first gas-liquid separation unit is used to receive the outlet material of the reactor of the pyrazolol production system by air oxidation method. The first gas-liquid separation unit can separate the received outlet material into a first separated liquid, a first separated mixed gas and condensed water. The hydrochloric acid generation unit is used to receive part of the condensed water, and the hydrochloric acid generation unit is used to prepare hydrochloric acid. The oxygen-argon recovery and recycling module comprises an oxygen separation unit for separating out oxygen and an argon separation unit for separating out argon. The oxygen separation unit and the argon separation unit are connected in sequence, the inlet of the oxygen separation unit is connected to the first separated mixed gas, and the gas discharged after passing through the argon separation unit is a first remaining mixed gas. The co-production urea and potassium salt recycling module comprises a urea preparation reactor and a second gas-liquid separation unit connected in sequence. The inlet of the urea preparation reactor is connected to the first remaining mixed gas, and the urea preparation reactor can generate a urea crude product solution containing urea. The second gas-liquid separation unit is used to separate the urea crude product solution into a second separated mixed gas and a second separated liquid.

[0006] Preferably, the first gas-liquid separation unit comprises a first gas-liquid separator, a heat exchanger and a gravity gas-liquid separator connected in sequence; the inlet of the first gas-liquid separator is used for receiving the outlet material of the reactor in the production of pyrazole alcohol by air oxidation method, the liquid phase outlet of the first gas-liquid separator is used for discharging the first separation liquid, the gas phase outlet of the first gas-liquid separator is communicated with the shell side inlet of the heat exchanger; the shell side outlet of the heat exchanger is communicated with the inlet of the gravity gas-liquid separator, the liquid phase outlet of the gravity gas-liquid separator is used for discharging the condensed water, and the gas phase outlet of the gravity gas-liquid separator is used for discharging the first separation mixed gas.

[0007] Preferably, the co-production of urea and potassium salt recycling module further comprises a gas separation module, a first conical crystallization filtration drying all-in-one machine and a second conical crystallization filtration drying all-in-one machine; the gas separation module is used for receiving the second separation mixed gas of the second gas-liquid separation unit, and the gas separation module can separate and store oxygen and hydrogen in the second separation mixed gas, and the remaining gas after separation of the gas separation module is a third remaining mixed gas, which is used for being introduced into the urea preparation reactor; the first conical crystallization filtration drying all-in-one machine is used for receiving the second separation liquid of the second gas-liquid separation unit, and the first conical crystallization filtration drying all-in-one machine is used for separating potassium salt in the second separation liquid; the second conical crystallization filtration drying all-in-one machine is used for separating urea in the liquid discharged by the first conical crystallization filtration drying all-in-one machine.

[0008] Preferably, the working medium of the tube side outlet of the heat exchanger is used for being introduced into the heat exchange jacket of the second conical crystallization filtration drying all-in-one machine after secondary heating.

[0009] Preferably, the hydrochloric acid generation unit comprises an absorption tower and a hydrochloric acid storage tank; the absorption tower is communicated with the liquid phase outlet of the gravity gas-liquid separator, and volatile hydrogen chloride is introduced into the absorption tower, the absorption tower is used for preparing hydrochloric acid, and the hydrochloric acid prepared by the absorption tower is stored in the hydrochloric acid storage tank; the outlet of the hydrochloric acid storage tank can be communicated with the liquid phase outlet of the first gas-liquid separator through a hydrochloric acid introduction pipeline; a second single-way valve is arranged on the hydrochloric acid introduction pipeline.

[0010] Preferably, the oxygen separation unit comprises a first membrane separator and a first gas storage tank; the argon separation unit comprises a second membrane separator and a second gas storage tank; the inlet of the first membrane separator is used for receiving the first separation mixed gas; the oxygen outlet of the first membrane separator is communicated with the first gas storage tank; the mixed gas outlet of the first membrane separator is communicated with the inlet of the second membrane separator; the argon outlet of the second membrane separator is communicated with the second gas storage tank.

[0011] Preferably, the potassium salt separated by the first conical crystallization filter-drying integrated machine is stored in a potassium salt storage tank, which is connected to a first storage tank through a pipeline, and part of the condensed water separated by the first gas-liquid separation unit is passed into the first storage tank; the first storage tank is used to prepare a potassium salt solution, and the outlet of the first storage tank is connected to a second storage tank, and the outlet of the second storage tank is connected to the urea preparation reactor through a pipeline with a third one-way valve.

[0012] Preferably, the second gas-liquid separation unit includes a second gas-liquid separator; the gas separation module includes a third membrane separator, a hydrogen storage tank and a fourth membrane separator; the second gas-liquid separator is used to receive the crude urea solution of the urea preparation reactor; the second gas-liquid separator can separate the second separated mixed gas and the second separated liquid; the second separated mixed gas is used to pass into the third membrane separator, and the third membrane separator is used to separate the hydrogen in the second separated mixed gas and store it in the hydrogen storage tank; the remaining gas after passing through the third membrane separator is passed into the fourth membrane separator, and the fourth membrane separator is used to separate the oxygen in the passed gas and store it in the first gas storage tank; the remaining gas after passing through the fourth membrane separator is used to pass into the urea preparation reactor.

[0013] Preferably, the remaining gas after passing through the fourth membrane separator is passed through a condenser and then introduced into the urea preparation reactor.

[0014] Preferably, ethanol for separating potassium salt is introduced into the first conical crystallization-filtration-drying integrated machine; and the ethanol solution separated in the second conical crystallization-filtration-drying integrated machine is introduced into the first conical crystallization-filtration-drying integrated machine.

[0015] Compared with the prior art, the present invention has achieved the following technical effects:

[0016] The application provides a tail gas resource utilization and urea co-production system in a process of producing pyrazole alcohol, through the first gas-liquid separation unit of the pyrazole ketone oxidation product purification module, the gas-liquid separation of the outlet material of the reactor of the air oxidation method for producing pyrazole alcohol system can effectively capture the liquid phase components such as 1-(4-chlorophenyl)-3-pyrazole alcohol droplets and inorganic alkali solution entrained in the gas phase, avoiding solvent loss and environmental pollution caused by the exhaust gas; at the same time, the condensed water separated is used by the hydrochloric acid generating unit, reacts with volatile hydrogen chloride to generate hydrochloric acid, realizes the directional recovery of hydrogen chloride, reduces the corrosion and pollution risk of direct emission of acid gas; the first gas-liquid separation unit removes water vapor and other impurities in the gas phase, provides the first separation mixed gas with low water content for the oxygen-argon recovery and reuse module, avoids the influence of water on the membrane separation efficiency, and ensures the accuracy and stability of oxygen and argon separation; the oxygen-argon recovery and reuse module is sequentially connected through "oxygen separation unit-argon separation unit", and the first separation mixed gas is directionally and step by step separated: oxygen can be reused in the air oxidation reaction section (reducing fresh oxygen consumption), and argon can be used as inert gas in industrial protection gas scenes, avoiding the resource waste of the two in the traditional process, and improving the utilization rate of gas resources; in the co-production of urea and potassium salt recycling module, the first remaining mixed gas (containing nitrogen and carbon dioxide) remaining after argon separation is used as raw material in the urea preparation reactor, and the nitrogen and carbon elements originally discharged are converted into urea crude liquid through a synthesis reaction, realizing the "resource co-production and value-added" of waste gas; at the same time, potassium salt as a reaction medium can be recycled through subsequent separation, reducing the amount of external potassium salt supplement and reducing raw material cost; each module is accurately connected through material flow (such as the gas phase of the first gas-liquid separation unit-oxygen-argon recovery and reuse module, and the gas phase after argon separation-urea preparation reactor), forming a closed loop process, avoiding the redundant links of "multiple transportation and repeated treatment" in the traditional dispersed treatment, shortening the processing path, and reducing equipment investment and operation energy consumption; the hydrochloric acid prepared by the hydrochloric acid generating unit can be reused in the initial raw material system, the co-production of urea and potassium salt recycling module realizes the closed loop reuse of potassium salt medium, and the condensed water is used as a water supplement to participate in the reaction, forming a "material-medium-energy" synergistic cycle, reducing the consumption of fresh water, hydrochloric acid and potassium salt and other external raw materials, and reducing the comprehensive operation cost; the system integrates the three functions of "tail gas purification", "resource recovery" and "product co-production", solves the problems of large exhaust gas emission and serious pollution in the production of pyrazole alcohol by the air oxidation method, realizes the positive cycle of "environmental treatment-resource utilization-economic benefit" through the recovery of oxygen and argon and the co-production of urea, meets the needs of green and sustainable development of the chemical industry, and provides an integrated solution of "environmentally friendly-resource efficient-economic feasible" for tail gas treatment. BRIEF DESCRIPTION OF DRAWINGS

[0017] In order to make the technical solutions in the embodiments of the present application or the prior art clearer, the accompanying drawings needed in the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below only represent some of the embodiments of the present application, and all other embodiments obtained by those of ordinary skill in the art without any creative effort based on the embodiments in the present application shall fall within the protection scope of the present application.

[0018] Figure 1 The schematic diagram of the tail gas resource utilization and urea co-production system in the process of producing pyrazole alcohol provided by the present application is shown.

[0019] In the figure:

[0020] 101-initial raw material inlet; 102-first gas-liquid separator; 103-heat exchanger; 104-cold working medium inlet; 105-hot working medium outlet; 106-gravity gas-liquid separator; 107-absorption tower; 108-volatile hydrogen chloride inlet; 109-first single-way valve; 110-hydrochloric acid storage tank; 111-second single-way valve; 112-initial raw material liquid phase outlet;

[0021] 201-first membrane separator; 202-first gas storage tank; 203-oxygen storage tank outlet; 204-second membrane separator; 205-second gas storage tank; 206-argon storage tank outlet;

[0022] 301-carbon dioxide inlet; 302-urea preparation reactor; 303-second gas-liquid separator; 304-third membrane separator; 305-hydrogen storage tank; 306-fourth membrane separator; 307-condenser; 308-first conical crystallization, filtration and drying all-in-one machine; 309-ethanol inlet; 310-potassium salt storage tank; 311-first storage tank; 312-second storage tank; 313-third single-way valve; 314-second conical crystallization, filtration and drying all-in-one machine; 315-urea crude product storage tank. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments only represent some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without any creative effort shall fall within the protection scope of the present application.

[0024] The present application aims to provide a tail gas resource utilization and urea co-production system in the process of producing pyrazole alcohol, so as to solve the problems in the prior art, reduce pollutant emissions, and realize resource cascade utilization.

[0025] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0026] Example 1

[0027] This embodiment provides a system for resource utilization of tail gas and co-production of urea during the production of pyrazole alcohol. Figure 1 As shown, it includes a pyrazolidone oxidation product purification module, an oxygen-argon recovery and reuse module, and a co-production urea and potassium salt recycling module; the pyrazolidone oxidation product purification module includes a first gas-liquid separation unit and a hydrochloric acid generation unit; the first gas-liquid separation unit is used to receive the outlet material of the reactor of the pyrazolol production system by air oxidation; the first gas-liquid separation unit can separate the received outlet material into a first separated liquid, a first separated mixed gas, and condensed water; the hydrochloric acid generation unit is used to receive part of the condensed water, and the hydrochloric acid generation unit is used to prepare hydrochloric acid; the oxygen-argon recovery and reuse module includes an oxygen separation unit for separating oxygen and a hydrochloric acid generation unit for separating the oxygen. An argon separation unit for separating argon; an oxygen separation unit is connected to the argon separation unit in sequence, and a first separated mixed gas is introduced into the inlet of the oxygen separation unit; and the gas discharged after passing through the argon separation unit is a first residual mixed gas; a co-production urea and potassium salt recycling module includes a urea preparation reactor 302 and a second gas-liquid separation unit that are connected in sequence; the first residual mixed gas is introduced into the inlet of the urea preparation reactor 302, and the urea preparation reactor 302 can generate a crude urea solution containing urea; the second gas-liquid separation unit is used to perform gas-liquid separation on the crude urea solution and generate a second separated mixed gas and a second separated liquid.

[0028] The first gas-liquid separation unit of the pyrazolidone oxidation product purification module can effectively capture the liquid phase components such as 1-(4-chlorophenyl)-3-pyrazolol droplets and inorganic alkali solution entrained in the gas phase by gas-liquid separation of the outlet material of the air oxidation method pyrazolol system reactor, avoiding solvent loss and environmental pollution caused by exhaust gas emission; at the same time, the condensed water separated out is used by the hydrochloric acid generation unit to react with volatile hydrogen chloride to generate hydrochloric acid, realizing the directional recovery of hydrogen chloride and reducing the corrosion and pollution risk of direct emission of acid gas; the first gas-liquid separation unit removes water vapor and other impurities in the gas phase, providing a first separated mixed gas with low water content for the oxygen-argon recovery and reuse module, avoiding the influence of water on the efficiency of membrane separation, and ensuring the accuracy and stability of oxygen and argon separation; the oxygen-argon recovery and reuse module connects in sequence "oxygen separation unit→argon separation unit" to perform directional and staged separation on the first separated mixed gas: oxygen can be reused in the air oxidation reaction section (reducing fresh oxygen consumption), and argon can be used as inert gas in industrial protection gas scenes, avoiding the waste of resources caused by the emission of oxygen and argon in the traditional process, and improving the utilization rate of gas resources; in the co-production of urea and potassium salt recycling module, the urea preparation reactor 302 uses the first remaining mixed gas (containing nitrogen and carbon dioxide) remaining after argon separation as raw material, and converts the originally emitted nitrogen and carbon elements into urea crude liquid through a synthesis reaction, realizing the "resourceization co-production value-added" of waste gas; at the same time, potassium salt as a reaction medium can be recycled through subsequent separation, reducing the amount of external potassium salt supplement and reducing raw material cost; each module is accurately connected through material flow (such as the gas phase of the first gas-liquid separation unit→the oxygen-argon recovery and reuse module, and the gas phase after argon separation→the urea preparation reactor 302), forming a closed loop process, avoiding the redundant links of "multiple transportation and repeated treatment" in the traditional dispersed treatment, shortening the treatment path, and reducing equipment investment and operating energy consumption; the hydrochloric acid prepared by the hydrochloric acid generation unit can be reused in the initial raw material system, the co-production of urea and potassium salt recycling module realizes the closed loop reuse of potassium salt medium, and the condensed water is used as a water source to participate in the reaction, forming a "material-medium-energy" synergistic cycle, reducing the consumption of fresh water, hydrochloric acid, potassium salt and other external raw materials, and reducing the comprehensive operating cost; the system integrates the three functions of "tail gas purification", "resource recovery" and "product co-production", not only solves the problems of large exhaust gas emission and serious pollution in the production of pyrazolol by air oxidation method, but also realizes the positive cycle of "environmental treatment→resource utilization→economic benefit" through the recovery of oxygen and argon and the co-production of urea, meeting the needs of green and sustainable development of the chemical industry, and providing an integrated solution of "environmentally friendly+resource efficient+economically feasible" for tail gas treatment.

[0029] Specifically:

[0030] (1) This embodiment relies on the pyrazolidone oxidation product purification module, the oxygen-argon recycling module, and the co-production of urea and potassium salt recycling module. The three core modules are integrated and embedded in the air oxidation method for producing pyrazolol system, realizing the high integration of the process flow. The functional modules can be flexibly replaced and combined according to different production needs, making the system have good adaptability and scalability.

[0031] (2) This embodiment builds a set of efficient and energy-saving material and waste heat recycling system for the treatment of entrained liquid phase, waste heat, condensed water and potassium salt. Through the collaborative optimization of materials and energy, the maximum recovery of reaction materials and the efficient use of process heat energy are realized, achieving the dual purposes of resource recovery efficiency and energy utilization optimization.

[0032] (3) This embodiment directly converts nitrogen and carbon dioxide in the process tail gas into urea products by supplementing part of carbon dioxide, realizing the resource co-production and value-added of industrial waste gas, and organically integrating environmental protection, resource utilization and economic benefits, providing a new solution for the sustainable development of chemical industry.

[0033] Among them, the related setting of the pyrazolidone oxidation product purification module is as follows:

[0034] Specifically, the pyrazolidone oxidation product purification module is used to separate the gas and liquid of the outlet material of the air oxidation method for producing pyrazolol system reactor, and realize the recycling of hydrochloric acid.

[0035] In the optional scheme of this embodiment, as shown in Figure 1 The first gas-liquid separation unit includes a first gas-liquid separator 102 (for gas-liquid separation of the feed), a heat exchanger 103 and a gravity gas-liquid separator 106 connected in sequence; the inlet of the first gas-liquid separator 102 (i.e. the initial raw material inlet 101) is used to receive the outlet material of the air oxidation method for producing pyrazolol system reactor, the liquid phase outlet of the first gas-liquid separator 102 is used to discharge the first separated liquid (i.e. the initial raw material liquid phase outlet 112), and the gas phase outlet of the first gas-liquid separator 102 is communicated with the shell side inlet of the heat exchanger 103; the shell side outlet of the heat exchanger 103 is communicated with the inlet of the gravity gas-liquid separator 106, and the liquid phase outlet of the gravity gas-liquid separator 106 is used to discharge condensed water, and the gas phase outlet of the gravity gas-liquid separator 106 is used to discharge the first separated mixed gas.

[0036] Specifically, the heat exchanger 103 has a cold working medium inlet 104 and a hot working medium outlet 105, and the cold working medium inlet 104 and the hot working medium outlet 105 are communicated with the tube side of the heat exchanger 103.

[0037] In the optional scheme of this embodiment, as shown in Figure 1As shown, the hydrochloric acid generating unit includes an absorption tower 107 (for generating hydrochloric acid from the volatilized hydrogen chloride and condensed water) and a hydrochloric acid storage tank 110; the absorption tower 107 is in communication with the liquid phase outlet of the gravity gas-liquid separator 106, and the volatilized hydrogen chloride is introduced into the absorption tower 107 through the volatilized hydrogen chloride inlet 108 (the source of the volatilized hydrogen chloride is explained as follows: the generated product of the pH adjustment tank for pH adjustment after the reaction of the air oxidation method for producing pyrazol alcohol system, part of which volatilizes, so the volatilized hydrogen chloride is introduced into the absorption tower 107 for the preparation of hydrochloric acid, which is combined with the air oxidation method for producing pyrazol alcohol system and realizes the full utilization of the material), the absorption tower 107 is used for preparing hydrochloric acid (absorption tower), and the hydrochloric acid prepared by the absorption tower 107 is stored in the hydrochloric acid storage tank 110; the outlet of the hydrochloric acid storage tank 110 can be in communication with the liquid phase outlet of the first gas-liquid separator 102 through a hydrochloric acid introduction pipeline; a second single-way valve 111 is arranged on the hydrochloric acid introduction pipeline.

[0038] Specifically, the outlet of the absorption tower 107 is in communication with the inlet of the absorption tower 107 through the first single-way valve 109, and the outlet of the absorption tower 107 is in communication with the inlet of the hydrochloric acid storage tank 110.

[0039] Among them, the related setting of the oxygen-argon recovery and recycling module is explained as follows:

[0040] Specifically, the oxygen-argon recovery and recycling module is used for separating oxygen and argon from the exhaust gas at the outlet of the pyrazolidone oxidation product purification module, and recycling the resources.

[0041] In the optional scheme of the present embodiment, more preferably, as shown in the figure, Figure 1 As shown, the oxygen separation unit includes a first membrane separator 201 and a first gas storage tank 202 (a oxygen storage tank outlet 203 is arranged on the first gas storage tank 202); the argon separation unit includes a second membrane separator 204 and a second gas storage tank 205 (an argon storage tank outlet 206 is arranged on the second gas storage tank 205); the inlet of the first membrane separator 201 is used for receiving the first separated mixed gas; the oxygen outlet of the first membrane separator 201 is in communication with the first gas storage tank 202; the mixed gas outlet of the first membrane separator 201 is in communication with the inlet of the second membrane separator 204; the argon outlet of the second membrane separator 204 is in communication with the second gas storage tank 205.

[0042] Specifically, the first membrane separator 201 and the second membrane separator 204 are respectively used for separating oxygen and argon from the tail gas.

[0043] Among them, the related setting of the co-production of urea and potassium salt recycling module is explained as follows:

[0044] Specifically, the co-production of urea and potassium salt recycling module is used for synthesizing urea crude product solution from nitrogen and carbon dioxide, and recycling potassium salt medium.

[0045] Specifically, the urea preparation reactor 302 is also provided with a carbon dioxide inlet 301 for supplementing carbon dioxide.

[0046] Specifically, the urea preparation reactor 302 is an existing device, which is composed of a series of variable diameter pipe type reaction units and double cavity H type electrolytic cell units in series. Sulzer SMX type static mixer is arranged in the variable diameter pipe type reaction unit to strengthen the premixing, rely on the fluid division and the rotating turbulent mixing to ensure the uniform dispersion of the gas to the electrolyte, avoid the accumulation of gas film on the electrode surface, and simultaneously realize the optimization of mass transfer and heat transfer process and the improvement of reaction efficiency. The electrolytic cell is a double cavity H type electrolytic cell. Carbon dioxide and nitrogen are directly generated into urea in an electrocatalytic coupling manner. The anode material is a carbon rod, and the cathode material is one of Pd1Cu1 / TiO2-400 and CuNi / CeO2, which provides a core catalytic site to realize the synergistic activation of N2 and CO2 and C-N coupling. The electrolyte adopts one of potassium hydroxide, potassium chloride and potassium bicarbonate solution. The cathode area and the anode area are separated by an anion exchange membrane or a bipolar membrane to realize the regulation of the reaction environment and balance the proton transfer and product selectivity.

[0047] In the optional scheme of the present embodiment, as shown in Figure 1 The co-production of urea and potassium salt recycling module also includes a gas separation module, a first conical crystallization filtration and drying all-in-one machine 308 and a second conical crystallization filtration and drying all-in-one machine 314. The gas separation module is used for receiving the second separation mixed gas of the second gas-liquid separation unit, and the gas separation module can separate and store oxygen and hydrogen in the second separation mixed gas. The remaining gas after separation of the gas separation module is the third remaining mixed gas, which is used for entering the urea preparation reactor 302. The first conical crystallization filtration and drying all-in-one machine 308 is used for receiving the second separation liquid of the second gas-liquid separation unit (the liquid phase outlet of the second gas-liquid separator 303 is communicated with the liquid phase inlet of the first conical crystallization filtration and drying all-in-one machine 308), and the first conical crystallization filtration and drying all-in-one machine 308 is used for separating potassium salt in the second separation liquid. The second conical crystallization filtration and drying all-in-one machine 314 is used for separating urea in the liquid discharged from the first conical crystallization filtration and drying all-in-one machine 308.

[0048] In the optional scheme of the present embodiment, as shown in Figure 1 The working medium (such as hot water) at the outlet of the tube side of the heat exchanger 103 is used for entering the heat exchange jacket of the second conical crystallization filtration and drying all-in-one machine 314 after secondary heating, which is used for evaporating ethanol.

[0049] In the optional solution of the embodiment, preferably, as shown in Figure 1 The potassium salt separated by the first conical crystallization, filtration and drying integrated machine 308 is stored in a potassium salt storage tank 310 (the solid phase outlet of the first conical crystallization, filtration and drying integrated machine 308 is communicated with the inlet of the potassium salt storage tank 310), and the potassium salt storage tank 310 is connected with a first storage tank 311 through a pipeline, and part of the condensed water separated by the first gas-liquid separation unit is introduced into the first storage tank 311; the first storage tank 311 is used for preparing a potassium salt solution, and the outlet of the first storage tank 311 is connected with a second storage tank 312, and the outlet of the second storage tank 312 is communicated with the urea preparation reactor 302 through a pipeline with a third single-way valve 313.

[0050] Specifically, the first conical crystallization, filtration and drying integrated machine 308 is further provided with an ethanol inlet 309.

[0051] Specifically, the liquid phase inlet of the second conical crystallization, filtration and drying integrated machine 314 is communicated with the liquid phase outlet of the first conical crystallization, filtration and drying integrated machine 308, and the solid phase outlet of the second conical crystallization, filtration and drying integrated machine 314 is communicated with the inlet of a urea crude product storage tank 315.

[0052] In the optional solution of the embodiment, preferably, as shown in Figure 1 The second gas-liquid separation unit includes a second gas-liquid separator 303 (used for separating the reaction product into a gas phase and a liquid phase); the gas separation module includes a third membrane separator 304, a hydrogen storage tank 305 and a fourth membrane separator 306; the second gas-liquid separator 303 is used for receiving the urea crude product solution of the urea preparation reactor 302; the second gas-liquid separator 303 can separate out a second separation mixed gas and a second separation liquid; the second separation mixed gas is used for being introduced into the third membrane separator 304 (the gas phase outlet of the second gas-liquid separator 303 is communicated with the inlet of the third membrane separator 304), and the third membrane separator 304 is used for separating the hydrogen in the second separation mixed gas and storing the hydrogen into the hydrogen storage tank 305; the remaining gas after passing through the third membrane separator 304 is introduced into the fourth membrane separator 306 (the mixed gas outlet of the third membrane separator 304 is communicated with the inlet of the fourth membrane separator 306), and the fourth membrane separator 306 is used for separating the oxygen in the introduced gas and storing the oxygen into the first gas storage tank 202; the remaining gas after passing through the fourth membrane separator 306 is used for being introduced into the urea preparation reactor 302.

[0053] Specifically, the third membrane separator 304 and the fourth membrane separator 306 are respectively used for separating the hydrogen and the oxygen in the by-products.

[0054] In the optional solution of the embodiment, preferably, as shown in Figure 1As shown, the remaining gas after the fourth membrane separator 306 passes through the condenser 307 and enters the urea preparation reactor 302 (the mixed gas outlet of the fourth membrane separator 306 is connected to the inlet of the condenser 307, and the outlet of the condenser 307 is connected to the gas-liquid inlet of the urea preparation reactor 302).

[0055] In the optional scheme of the present embodiment, it is more preferred that Figure 1 As shown, ethanol is introduced into the first conical crystallization filtration drying all-in-one machine 308; and the ethanol solution separated from the second conical crystallization filtration drying all-in-one machine 314 is used to be introduced into the first conical crystallization filtration drying all-in-one machine 308.

[0056] Specifically, the first conical crystallization filtration drying all-in-one machine 308 and the second conical crystallization filtration drying all-in-one machine 314 are both existing devices, such as the washing liquid collection and recycling device of the filtration washing and drying all-in-one machine in patent CN214130662U, or the conical filtration washing and drying three-in-one multifunctional device in patent CN214913864U, and the like, which will not be described in more detail here.

[0057] Specific operation method 1 is described as follows:

[0058] S1, the material (including components such as oxidation product mother liquor, oxygen, nitrogen, carbon dioxide, argon, water vapor, and 1-(4-chlorophenyl)-3-pyrazol liquid droplets carried by gas phase, inorganic alkali solution, and transition metal ion catalyst solution) at the outlet of the pyrazol alcohol system reactor produced by air oxidation method is used as feed material to perform gas-liquid separation through the first gas-liquid separator 102. The gas phase is oxygen, nitrogen, carbon dioxide, argon, and water vapor, and the remaining components are in the liquid phase.

[0059] S2, the water vapor in the gas phase is condensed and separated through the heat exchanger 103 and the gravity gas-liquid separator 106, the separated liquid phase is condensed water, and the mixed gas is oxygen, nitrogen, carbon dioxide, and argon, with a temperature of 25-35 ℃ and a pressure of 1.0-1.3 MPa.

[0060] S3, volatile hydrogen chloride is reacted with condensed water in the absorption tower 107 to generate hydrochloric acid, which is then introduced into the initial raw material liquid phase outlet 112 through the hydrochloric acid storage tank 110 and the second single-way valve 111, and part of the hydrochloric acid is circulated into the absorption tower 107 through the first single-way valve 109 when necessary;

[0061] S4, oxygen and argon in the mixed gas are separated by the first membrane separator 201 and the second membrane separator 204 and stored in the first gas storage tank 202 and the second gas storage tank 205; wherein the inlet temperature and pressure of the first membrane separator 201 and the second membrane separator 204 are both in the range of 25-35 ℃ and 1.0-1.3 MPa, and the outlet temperature and pressure are both in the range of 25-30 ℃ and 0.1-0.5 MPa.

[0062] S5, the remaining components of the mixed gas (nitrogen, a small amount of carbon dioxide, carbon dioxide gas source) are made into a urea crude liquid by a urea production reactor 302.

[0063] S6, the reaction product is separated into gas and liquid phases by a second gas-liquid separator 303, the gas phase is nitrogen, carbon dioxide and byproduct carbon monoxide, hydrogen, oxygen and water vapor; the liquid phase is a second separation liquid; wherein the temperature and pressure of the gas-liquid separation product are both 25-30 ℃, 0.1-0.5 MPa.

[0064] S7, the hydrogen and oxygen in the gas phase are separated by a third membrane separator 304 and a fourth membrane separator 306 after being pressurized and are respectively stored in a hydrogen storage tank 305 and a first gas storage tank 202, the remaining gas phase components are condensed by a condenser 307 and then introduced into the reactor. The inlet temperature and pressure of the third membrane separator 304 and the fourth membrane separator 306 are both 25-30 ℃, 1.0-1.3 MPa, and the outlet temperature and pressure are both 25-30 ℃, 0.1-0.5 MPa.

[0065] S8, by slowly and gradiently adding anhydrous ethanol to the first conical crystallization, filtration and drying all-in-one machine 308 to a concentration of 65-75%, the temperature is controlled at 25-35 ℃, while maintaining the stirring speed at 150-200 rpm to promote crystallization, the potassium salt in the liquid phase is precipitated, and then the potassium salt precipitate is separated by filtration, and finally the obtained potassium salt precipitate is introduced into a potassium salt storage tank 310, the potassium salt storage tank 310 has a heat exchange jacket to separate ethanol and potassium salt (the working medium in the heat exchange jacket of the potassium salt storage tank 310 can be sourced from the working medium at the outlet of the tube side of the heat exchanger 103, and the ethanol separated in the potassium salt storage tank 310 is used to circulate into the first conical crystallization, filtration and drying all-in-one machine 308). Then through the first storage tank 311, the second storage tank 312 and the third single-way valve 313 to the urea production reactor 302 to supplement potassium salt.

[0066] S9, the working medium (such as hot water) at the outlet of the tube side of the heat exchanger 103 is heated again, the temperature is controlled at 70-80 ℃, and is introduced into the heat exchange jacket of the second conical crystallization, filtration and drying all-in-one machine 314 for waste heat utilization, the remaining liquid phase is heated, the temperature and pressure are controlled at 60-65 ℃, -0.05~-0.07 MPa by vacuum evaporation, ethanol is preferentially recovered, and the recovered ethanol is introduced into the first conical crystallization, filtration and drying all-in-one machine 308, then the temperature is continuously controlled for evaporation, the temperature is controlled at 85-90 ℃, the urea solution is concentrated to near saturation, the concentrated liquid is naturally cooled to room temperature, and is placed for 4-6 h, then filtered, finally the temperature and pressure are controlled at 50-60 ℃, -0.091~-0.071 MPa for vacuum drying of urea crystallization, and the urea crude product is stored in a urea crude product storage tank 315.

[0067] The operation method 2 is different from the operation method 1 in that the liquid phase separated from the second gas-liquid separator 303 is directly stored in a corresponding tank as a crude product containing nitrogen and potassium, so that the energy consumption is saved.

[0068] The operation methods 1 and 2 realize near-zero emission and resource full recovery of the tail gas in the production of pyrazolol by air oxidation method through gradient separation and resource utilization of the tail gas, and promote the development of green chemical industry.

[0069] The principles and implementation manners of the present application are described by using specific examples in the present application, and the above examples are only used to help understand the method of the present application and its core idea; meanwhile, for those skilled in the art, the specific implementation manners and application ranges will be changed according to the idea of the present application. In conclusion, the content of the present specification should not be understood as a limitation of the present application.

Claims

1. A system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol, characterized by: It includes a pyrazolidone oxidation product purification module, an oxygen-argon recovery and reuse module, and a co-production urea and potassium salt recycling module; The pyrazolidone oxidation product purification module includes a first gas-liquid separation unit and a hydrochloric acid generation unit; the first gas-liquid separation unit is used to receive the outlet material of the reactor of the pyrazolidone production system by air oxidation; the first gas-liquid separation unit is capable of separating the received outlet material into a first separated liquid, a first separated mixed gas and condensed water; The hydrochloric acid generating unit is used to receive part of the condensed water, and the hydrochloric acid generating unit is used to prepare hydrochloric acid; The oxygen-argon recovery and reuse module includes an oxygen separation unit for separating oxygen and an argon separation unit for separating argon; the oxygen separation unit and the argon separation unit are connected in sequence, the first separated mixed gas is introduced into the inlet of the oxygen separation unit; and the gas discharged after passing through the argon separation unit is the first residual mixed gas; The urea co-production and potassium salt recycling module includes a urea preparation reactor and a second gas-liquid separation unit connected in sequence; the first residual mixed gas is introduced into the inlet of the urea preparation reactor, and the urea preparation reactor is capable of generating a crude urea solution containing urea; The second gas-liquid separation unit is used to perform gas-liquid separation on the crude urea solution and generate a second separated mixed gas and a second separated liquid. The potassium salt contained in the second separated liquid can be separated and recycled.

2. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 1, characterized in that: The first gas-liquid separation unit includes a first gas-liquid separator, a heat exchanger and a gravity gas-liquid separator which are connected in sequence; The inlet of the first gas-liquid separator is used to receive the outlet material of the reactor of the air oxidation method for producing pyrazole alcohol, the liquid phase outlet of the first gas-liquid separator is used to discharge the first separated liquid, and the gas phase outlet of the first gas-liquid separator is connected to the shell side inlet of the heat exchanger; the shell side outlet of the heat exchanger is connected to the inlet of the gravity gas-liquid separator, the liquid phase outlet of the gravity gas-liquid separator is used to discharge the condensed water, and the gas phase outlet of the gravity gas-liquid separator is used to discharge the first separated mixed gas.

3. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 2, characterized in that: The urea and potassium salt recycling module also includes a gas separation module, a first conical crystallization filter drying integrated machine and a second conical crystallization filter drying integrated machine; The gas separation module is used to receive the second separated mixed gas from the second gas-liquid separation unit, and the gas separation module is capable of separating and storing oxygen and hydrogen in the second separated mixed gas, and the remaining gas after separation by the gas separation module is a third residual mixed gas, and the third residual mixed gas is used to be passed into the urea preparation reactor; The first conical crystallization filter-drying integrated machine is used to receive the second separated liquid from the second gas-liquid separation unit, and the first conical crystallization filter-drying integrated machine is used to separate the potassium salt in the second separated liquid; the second conical crystallization filter-drying integrated machine is used to separate the urea from the liquid discharged from the first conical crystallization filter-drying integrated machine.

4. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 3, characterized in that: The working medium at the outlet of the tube side of the heat exchanger is heated twice and then passed into the heat exchange jacket of the second conical crystallization, filtration and drying integrated machine.

5. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 2, characterized in that: The hydrochloric acid generation unit includes an absorption tower and a hydrochloric acid storage tank; The absorption tower is connected to the liquid phase outlet of the gravity gas-liquid separator, and volatilized hydrogen chloride is introduced into the absorption tower. The absorption tower is used to prepare hydrochloric acid, and the hydrochloric acid prepared by the absorption tower is stored in the hydrochloric acid storage tank; The outlet of the hydrochloric acid storage tank can be connected to the liquid phase outlet of the first gas-liquid separator through a hydrochloric acid inlet pipeline; a second one-way valve is provided on the hydrochloric acid inlet pipeline.

6. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 3, characterized in that: The oxygen separation unit includes a first membrane separator and a first gas storage tank; the argon separation unit includes a second membrane separator and a second gas storage tank; The inlet of the first membrane separator is used to receive the first separated mixed gas; the oxygen outlet of the first membrane separator is connected to the first gas storage tank; the mixed gas outlet of the first membrane separator is connected to the inlet of the second membrane separator; The argon outlet of the second membrane separator is communicated with the second gas storage tank.

7. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 3, characterized in that: The potassium salt separated by the first conical crystallization filter drying integrated machine is stored in a potassium salt storage tank, which is connected to the first storage tank through a pipeline, and part of the condensed water separated by the first gas-liquid separation unit is passed into the first storage tank; The first storage tank is used to prepare a potassium salt solution, and the outlet of the first storage tank is connected to a second storage tank, and the outlet of the second storage tank is connected to the urea preparation reactor through a pipeline with a third one-way valve.

8. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 6, characterized in that: The second gas-liquid separation unit includes a second gas-liquid separator; the gas separation module includes a third membrane separator, a hydrogen storage tank and a fourth membrane separator; The second gas-liquid separator is used to receive the crude urea solution from the urea preparation reactor; The second gas-liquid separator is capable of separating the second separated mixed gas and the second separated liquid; The second separated mixed gas is used to pass into the third membrane separator, and the third membrane separator is used to separate the hydrogen in the second separated mixed gas and store it in the hydrogen storage tank; The remaining gas after passing through the third membrane separator is passed into the fourth membrane separator, and the fourth membrane separator is used to separate the oxygen in the passed gas and store it in the first gas storage tank; The remaining gas after passing through the fourth membrane separator is used to be introduced into the urea preparation reactor.

9. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 8, characterized in that: The remaining gas after passing through the fourth membrane separator is passed through a condenser and then introduced into the urea preparation reactor.

10. The system for resource utilization of tail gas and co-production of urea in the process of producing pyrazolol according to claim 3, characterized in that: Ethanol for separating potassium salt is introduced into the first conical crystallization-filtration-drying integrated machine; The ethanol solution separated in the second conical crystallization-filtration-drying integrated machine is used to pass into the first conical crystallization-filtration-drying integrated machine.

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