CN111672427A - CO dehydrogenation circulation reaction device capable of controlling reactant ratio in real time - Google Patents
CO dehydrogenation circulation reaction device capable of controlling reactant ratio in real time Download PDFInfo
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- CN111672427A CN111672427A CN202010416774.8A CN202010416774A CN111672427A CN 111672427 A CN111672427 A CN 111672427A CN 202010416774 A CN202010416774 A CN 202010416774A CN 111672427 A CN111672427 A CN 111672427A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0278—Feeding reactive fluids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00212—Plates; Jackets; Cylinders
Abstract
A CO dehydrogenation circulating reaction device for controlling the proportion of reactants in real time belongs to the technical field of dehydrogenation and purification of CO feed gas, and is applied to performance evaluation of a dehydrogenation and purification catalyst of the CO feed gas. The invention comprises a gas control system (A), a fixed bed reaction system (B), an analysis system (C) and a central processing system (D); the problem of current CO feed gas dehydrogenation purifier existence is solved: 1. the reaction gas cannot circulate stably; 2. when the circulating gas enters the reaction system again, the content of hydrogen and oxygen in the reaction gas can not be controlled in real time, and the safety risk is increased. The device can solve the problems and adjust H in the reaction gas in real time2And O2The safety coefficient is improved.
Description
Technical Field
The invention belongs to the technical field of dehydrogenation and purification of CO raw material gas, and particularly relates to a design method of a circulating reaction device capable of controlling the proportion of reactants in real time, which is applied to performance evaluation of a dehydrogenation and purification catalyst of the CO raw material gas.
Background
Ethylene glycol is a strategic and large chemical basic raw material, has wide application, and is mainly used for producing polyester, antifreeze, adhesive, paint solvent, cold-resistant lubricating oil, surfactant, polyester polyol and the like. Although the production capacity and the yield of ethylene glycol in China are rapidly increased, the ethylene glycol can not meet the increasing market demands of domestic polyester and the like, a large amount of ethylene glycol is imported every year, the import quantity is increased year by year, and the contradiction between supply and demand is very prominent. Therefore, the technology for preparing ethylene glycol from coal has great significance for relieving the current situation of ethylene glycol in China.
The CO raw material gas obtained by water gas shift in the process of preparing the ethylene glycol from the coal contains a certain amount of H2And H is2The catalyst for synthesizing the oxalate through CO catalytic coupling is poisoned and deactivated. Therefore, in order to ensure the process for synthesizing oxalate by CO catalytic coupling, H in the CO feed gas is used2The removal of impurities below 100ppm is of great significance. The most effective means at present is to remove H from the CO feed gas by a selective oxidative dehydrogenation process2。
The preparation, evaluation and screening work of the high-efficiency catalyst is the core of the CO dehydrogenation process, and a safe, stable and high-efficiency reaction device is the key for guaranteeing the implementation of the high-efficiency catalyst. Several CO raw material gas oxidative dehydrogenation reactors provided by patents CN201110045204.3, CN201110045647.2, CN201110046318.X, CN201110045473.X and CN201110047240.3 are mainly designed for controlling reaction heat release-heat transfer rate, wherein a heat exchange medium is saturated steam, and the temperature of a catalyst bed of the reactor is controlled by controlling the pressure of the saturated steam. And patents CN201110045647.2 and cn201110046318.x adopt a double-pipe structure of an inner pipe and an outer pipe and a catalyst loading method of a composite bed structure. Patent CN201110045060.1 provides a fluidized bed reactor.
Since most CO does not participate in the oxidation reaction in the reaction process, the raw materials are wasted, the environment is polluted, and the poisoning risk and the potential safety hazard are greatly caused by directly discharging the CO from the tail gas. Patent CN20140436486.3 provides a CO raw material gas oxidative dehydrogenation reactionProvided is a device. Meanwhile, in actual working conditions, H in CO raw material gas obtained by water gas shift2The content of (A) is not constant and has large fluctuation, and O2From H in the feed gas2Content determination, so that a certain amount of H remains in the gas after the reaction2And O2When the recycle gas is re-introduced into the reaction system, the hydrogen and oxygen content in the reaction gas is increased, and the safety risk is increased.
Therefore, the above device needs to be further optimized, and a CO dehydrogenation circulating reaction device capable of controlling the reactant ratio in real time is designed.
Disclosure of Invention
The invention aims to provide a CO dehydrogenation circulating reaction device for controlling the proportion of reactants in real time, which is mainly used for solving the problems of the existing CO raw material gas dehydrogenation purification device: 1. the reaction gas cannot circulate stably; 2. when the circulating gas enters the reaction system again, the content of hydrogen and oxygen in the reaction gas can not be controlled in real time, and the safety risk is increased.
The invention provides a CO dehydrogenation circulating reaction device capable of controlling the proportion of reactants in real time, which is characterized in that:
comprises a gas control system (A), a fixed bed reaction system (B), an analysis system (C) and a central processing system (D); wherein:
(1) the gas control system (A) comprises seven parts of a raw material gas pipeline, an oxygen pipeline, an inert gas pipeline, an analysis pipeline, a circulation pipeline, a gas storage pipeline and an emptying pipeline:
the raw material gas pipeline comprises a CO pipeline and H2The pipeline and the CO pipeline are connected with a switch valve (1 a) in sequence3) A first pressure gauge (2 a)3) And a pressure maintaining valve (3 a)3) A second pressure gauge (2b)3) And a stop valve (1 b)3) A flowmeter (4d) and a one-way valve (5 a)3) And a stop valve (1 c)3) Entering a circulating low-pressure tank (8), a stop valve (1h), a circulating pneumatic pump (9), a stop valve (1k), a circulating high-pressure tank (10) and a stop valve (1n), and entering a reaction gas path from a first three-way valve (6a), namely the stop valve (1 b)5) A first pressure gauge (2 a)5) And a pressure maintaining valve (3 a)5) A second pressure gauge (2b)5) And a stop valve (1 c)5)、A flow meter (4c), a second three-way valve (6b), a one-way valve (5 a)5) A third three-way valve (6c), a gas mixer (1) and then enters a fixed bed reaction system (B). H2The pipeline is connected with a switch valve (1 a) in sequence2) A first pressure gauge (2 a)2) And a pressure maintaining valve (3 a)2) A second pressure gauge (2b)2) And a stop valve (1 b)2) A flowmeter (4b) and a one-way valve (5 a)2) And a stop valve (1 c)2) And enters a reaction gas circuit through a second three-way valve (6 b).
O2The pipeline is connected with a switch valve (1 a) in sequence1) A first pressure gauge (2 a)1) And a pressure maintaining valve (3 a)1) A second pressure gauge (2b)1) And a stop valve (1 b)1) A flowmeter (4a) and a one-way valve (5 a)1) And a stop valve (1 c)1) And the mixture is mixed with a raw gas pipeline by a third three-way valve (6c) and enters a reaction gas pipeline.
The inert gas pipeline is connected with a switch valve (1 a) in sequence4) A first pressure gauge (2 a)4) And a pressure maintaining valve (3 a)4) A second pressure gauge (2b)4) And a stop valve (1 b)4) A flowmeter (4e), a check valve (5 a)4) And a stop valve (1 c)4) The system comprises a circulating low-pressure tank (8), a stop valve (1s), a needle valve (12c), a stop valve (1t), a circulating high-pressure tank (10) and a stop valve (1n), wherein the stop valve (1n) enters a reaction gas circuit through a first three-way valve (6a) and then enters a fixed bed reaction system (B).
The reacted gas is divided into three paths in a first four-way valve (7 a): one path is an air storage pipeline which is sequentially connected with a stop valve (1w), a one-way valve (5e) and an air storage tank (16), wherein the air storage tank is divided into two paths, and the other path is the stop valve (1x) to a next reaction system; the other path is an analysis pipeline, and is sequentially connected with a stop valve (1y) and an eighth three-way valve (6h) to enter an analysis system (C). The eighth three-way valve (6h) further comprises a path of analysis pipeline which is from the gas mixer (1), is sequentially connected with the gas mixer (1), the one-way valve (5f) and the stop valve (1z), and enters the analysis system (C) through the eighth three-way valve (6 h); one path is a circulating pipeline, and is sequentially connected with a stop valve (1f), a circulating flow meter (4f), a one-way valve (5d), a stop valve (1g), a circulating low-pressure tank (8), a stop valve (1h), a circulating pneumatic pump (9), a stop valve (1k), a circulating high-pressure tank (10), a stop valve (1n) and a gas concentration feedback module (17) connected with the circulating low-pressure tank (8), and enters a fixed bed reaction system (B) after being mixed with a reaction pipeline through a first three-way valve (6 a); one path is an emptying pipeline, and is sequentially connected with a system pressure gauge (2c), a system backpressure valve (9a), a stop valve (1e) and a fourth three-way valve (6g) to enter the emptying pipeline. The fourth three-way valve (6g) also comprises a 2-way emptying pipeline: one path is a circulating low-pressure tank (8), a pressure gauge (2d), a stop valve (1j), a needle valve (12a), a fifth three-way valve (6d), a safety valve (8a) and a seventh three-way valve (6f) and enters an emptying pipeline; one path is a circulating high-pressure tank (10), a pressure gauge (2e), a stop valve (1m), a needle valve (12b), a sixth three-way valve (6e), a safety valve (8b) and a seventh three-way valve (6f) and enters an emptying pipeline.
(2) The fixed bed reaction system (B) comprises a gas preheater (2), a first temperature sensor (10a), a heating jacket (3), a second temperature sensor (10B), a reactor (4), a first gas-liquid separation tank (5), a second gas-liquid separation tank (6), a circulating condenser (11), a dryer (7), a one-way valve (5B) and a gas-liquid separation tank liquid emptying valve (1 d).
(3) The analysis system (C) is a gas product analysis unit and is composed of an analysis pipeline one-way valve (5C) and a sampling switch valve (1v) which are connected with a six-way valve (12), a quantitative tube (13), a packed chromatographic column (14) and a thermal conductivity detector (15).
(4) And the central control system (D) monitors all components of the whole reaction system, including a temperature sensor, a pressure sensor, a flow control device and a thermal conductivity detector.
The inert gas of the gas control system (A) is N2Any one of He and Ar;
the pressure range of each pipeline of the gas control system (A) after pressure stabilization is 0.1-5MPa, and the system pressure range is 0.1-5 MPa. The pressure range of the circulating low-pressure tank is 0.1-3MPa, and the pressure range of the circulating high-pressure tank is 0.1-5 MPa.
The preheating temperature range of a preheater in the fixed bed reaction system (B) is 30-200 ℃; the heating temperature is between room temperature and 500 ℃; the refrigerant fluid is water or glycol.
The chromatographic packed column of the analysis system (C) is one of a 5A molecular sieve and TDX-01.
The invention provides a CO dehydrogenation circulating reaction method for controlling the proportion of reactants in real time, which comprises the following steps:
(1) measuring a catalyst, filling the catalyst into the reactor (4), sealing the reactor (4) after filling, and connecting the reactor with a central processing system (D);
(2) opening an emptying pipeline switch valve (1e), opening a circulating condenser (11) and ensuring that liquid emptying valves (1d) of gas-liquid separation tanks (5) and (6) are in a closed state; opening the inert gas switching valve (1 a)4) Regulating pressure stabilizing valve (3 a)4) Opening the stop valve (1 b)4) Adjusting the flow rate of the flow meter (4e) and opening the stop valve (1 c)4) Entering a circulating low-pressure tank (8), opening a stop valve (1s), adjusting a needle valve (12c), opening a stop valve (1t), entering a circulating high-pressure tank (10), opening stop valves (1n), (1 b)5) Regulating pressure stabilizing valve (3 a)5) Opening the stop valve (1 c)5) Adjusting the air in a system back pressure valve (9a), a replacement gas mixer (1), a preheater (2) and a reactor (4);
(3) after the inert gas is replaced, setting the preheating temperature of the preheater (2) and the temperature of the heating sleeve (3);
(4) after the reactor temperature stabilized, H was opened2On-off valve (1 a)2) Regulating pressure stabilizing valve (3 a)2) Opening the stop valve (1 b)2) Adjusting the flow rate of the flow meter 4b and opening the stop valve (1 c)2) Entering a gas mixer (1); h2Preparing reducing gas with inert gas in gas mixer (1), opening stop valve (1z), getting into analytic system (C) through eighth three-way valve (6h), analysis reducing gas ratio, opening sample stop valve (1v) and getting into sample six-way valve (12), dosing pipe (13), packed column (14), get into thermal conductivity detector (15) analysis back, the analysis is finished and is closed stop valve (1 z). Reducing gas enters a reaction system for catalyst reduction, and H is closed after the reduction is finished2Switching all pipelines;
(5) the heating switches of the preheater (2) and the heating jacket (3) are closed, when the temperature of the reactor is reduced to about room temperature, the switch in front of a first three-way valve (6a) of an inert gas pipeline is closed, stop valves (1j) and (1m) on the circulating low-pressure tank (8) and the circulating high-pressure tank (10) are opened, needle valves (12a) and (12b) are adjusted, when the pressures of pressure gauges (2d) and (2e) are reduced to 0.1MPa, the stop valves (1j) and (1m) and the needle valves (12a) and (12b) are closed, and the inert gas in the circulating low-pressure tank (8) and the circulating high-pressure tank (10) is emptied;
(6) on-off valve (1 a) for opening CO pipeline3) Regulating pressure stabilizing valve (3 a)3) Opening the stop valve (1 b)3) Adjusting the flow rate of the flow meter (4d) and opening the stop valve (1 c)3) CO enters a circulating low-pressure tank (8), a stop valve (1h) is opened, a circulating pneumatic pump (9) and a stop valve (1k) are arranged, the CO enters a circulating high-pressure tank (10), enters a reaction gas path through the stop valve (1n), and a pressure stabilizing valve (3 a) is adjusted5) Introducing the mixture into a fixed bed reaction system (B) through a gas mixer (1);
(7) setting the temperature of the preheater (2) and the heating jacket (3) in a CO atmosphere, and raising the temperature of the reactor (4) to a reaction temperature;
(8) after the temperature of the reactor (4) is stabilized, H is opened2On-off valve (1 a)2) Regulating pressure stabilizing valve (3 a)2) Opening the stop valve (1 b)2) Adjusting the flow rate of the flow meter (4b) and opening the stop valve (1 c)2) Enters a reaction gas path through a second three-way valve (6B), is mixed with CO in a gas mixer (1) and then is introduced into a fixed bed reaction system (B);
(9) wait for H2After the flow rate (4b) has stabilized, O is opened2On-off valve (1 a)1) Regulating pressure stabilizing valve (3 a)1) Opening the stop valve (1 b)1) Adjusting the flow rate of the flow meter (4a) and opening the stop valve (1 c)1) Enters a reaction gas path through a third three-way valve (6c), O2With CO, H2Preparing reaction gas in a gas mixer (1);
(10) the reaction gas enters an analysis system (C) through a stop valve (1z) and an eighth three-way valve (6h), and the mixture ratio of each component of the reaction gas is analyzed. After the analysis is completed, the stop valve (1z) is closed. After the mixture ratio is stable, the circulating pipeline switch valve (1f) is opened, the flow of the circulating flowmeter (4f) is adjusted, the stop valve (1g) is opened, the flow of the flowmeter (4d) is adjusted, and the flow stability of the flowmeter (4c) is ensured.
(11) The system back pressure valve (9a) is adjusted to ensure that the reaction system pressure (2c) is stable. Turning on a gas concentration feedback module (17) provided withO with gas concentration feedback module (17)2And H2By volume ratio of (a). And sampling and analyzing the gas after the reaction is stabilized every 1-5h after the reaction is started. Gas after reaction enters an analysis system (C) through gas-liquid separation tanks (5) and (6), a dryer (7), a gas storage tank (16), a stop valve (1y) and an eighth three-way valve (6h) to be subjected to gas analysis, a sampling stop valve (1v) is opened and passes through a sampling six-way valve (12), a quantitative pipe (13) and a packed column (14) to enter a thermal conductivity detector (15) to be analyzed, and the stop valves (1y) and (1v) are closed after sampling is finished;
(12) the gas concentration feedback module (17) analyzes H in the result according to the gas after the reaction in the step (11)2、O2Content, real-time adjustment of H2、O2The flow rate of (c). The gas in the gas mixer (1) was analyzed in accordance with the step (4) every 0.5 to 2 hours after the start of the reaction, and H was monitored2And O2The content of (A);
(13) after the reaction is finished, the heating switches of the preheater (2) and the heating jacket (3) are closed, the switch of the circulating condenser (11) is closed, and the O is closed2Air passage switch (1 a)1)、(1b1)、(1c1) Closing H2Air passage switch (1 a)2)、(1b2)、(1c2) Closing the circulating pipeline switches (1f) and (1g) and the gas concentration feedback module (17), and closing the CO pipeline switch (1 a)3)、(1b3)、(1c3) (1h), (1k) and a circulating pneumatic pump (9). Opening the inert gas pipeline switch (1 a)4) Regulating pressure stabilizing valve (3 a)4) Opening the stop valve (1 b)4) Adjusting the flow rate of the flow meter (4e) and opening the stop valve (1 c)4) The device comprises a circulating low-pressure tank (8), a stop valve (1s) is opened, a needle valve (12c) is adjusted, a stop valve (1t) is opened, the circulating high-pressure tank (10) is entered, the stop valve (1n) is opened to enter a fixed bed reaction system through a reaction pipeline to replace and cool gas in a reactor, after the temperature of the reactor is reduced to room temperature, a switch in front of the inert gas pipeline circulating low-pressure tank (8) is closed, a back pressure valve (9a) of an emptying pipeline system is adjusted, and when the pressure (2c) of the reaction system is reduced to be below 0.05MPa, all switches of the device are closed. And opening liquid emptying valves (1d) of the gas-liquid separation tanks (5) and (6) to empty the liquid, and closing the liquid in time after the liquid is emptied.
Said step (4) H2In a reducing gas with an inert gas, H2The volume content of the catalyst is 5-20 percent, the content of inert gas is 80-95 percent, and the reduction time is 0.5-5 h;
the step (8) is carried out by reacting CO with H2The volume content of CO in the raw material gas is 80-99.5%, and H2The volume content of (A) is 0.5-20%;
said step (9) O2And H2The volume ratio of (A) to (B) is 0.5: 1-3;
o of the gas concentration feedback module (17) in the step (12)2And H2The volume ratio of (a) is in the range of 0.5: 1-3;
compared with the existing CO dehydrogenation purification device, the CO dehydrogenation circulating reaction device capable of controlling the reactant ratio in real time has the beneficial effects that:
1. reaction gas can be stably circulated;
2. increase circulating gas line and H2、O2The gas flow of the pipeline is automatically controlled, and when the circulating gas enters the reaction system again, the content of hydrogen and oxygen in the reaction gas is controlled in real time, so that the safety risk is reduced, and the safety factor is improved.
Drawings
Fig. 1 is a schematic structural diagram of a CO dehydrogenation cyclic reaction apparatus for controlling reactant ratio in real time, wherein: 1a1-5Z is an on-off valve, 2a1-5E is a pressure gauge, 3a1-5Is a pressure stabilizing valve, 4a-f is a flow meter, 5a1-5F is a one-way valve, 6a-h is a three-way valve, 7a is a four-way valve, 8a-b is a safety valve, 9a is a back pressure valve, 10a-b is a temperature sensor, 11a-b is a pressure sensor, 1 is a gas mixture, 2 is a gas preheater, 3 is a heating jacket, 4 is a reactor, 5 and 6 are gas-liquid separation tanks, 7 is a gas drier, 8 is a circulating low-pressure tank, 9 is a circulating compressor, 10 is a circulating high-pressure tank, 11 is a circulating condenser, 12 is a six-way valve, 13 is a quantitative pipe, 14 is a packed chromatographic column, 15 is a thermal conductivity detector, 16 is a gas storage tank, and 17 is a gas concentration feedback module.
Detailed Description
Example 1:
the invention provides a CO dehydrogenation circulating reaction device capable of controlling the proportion of reactants in real time, which is characterized in that:
comprises a gas control system (A), a fixed bed reaction system (B), an analysis system (C) and a central processing system (D); wherein:
(1) the gas control system (A) comprises seven parts of a raw material gas pipeline, an oxygen pipeline, an inert gas pipeline, an analysis pipeline, a circulation pipeline, a gas storage pipeline and an emptying pipeline:
the raw material gas pipeline comprises a CO pipeline and H2The pipeline and the CO pipeline are connected with a switch valve (1 a) in sequence3) A first pressure gauge (2 a)3) And a pressure maintaining valve (3 a)3) A second pressure gauge (2b)3) And a stop valve (1 b)3) A flowmeter (4d) and a one-way valve (5 a)3) And a stop valve (1 c)3) Entering a circulating low-pressure tank (8), a stop valve (1h), a circulating pneumatic pump (9), a stop valve (1k), a circulating high-pressure tank (10) and a stop valve (1n), and entering a reaction gas path from a first three-way valve (6a), namely the stop valve (1 b)5) A first pressure gauge (2 a)5) And a pressure maintaining valve (3 a)5) A second pressure gauge (2b)5) And a stop valve (1 c)5) A flowmeter (4c), a second three-way valve (6b) and a one-way valve (5 a)5) A third three-way valve (6c), a gas mixer (1) and then enters a fixed bed reaction system (B). H2The pipeline is connected with a switch valve (1 a) in sequence2) A first pressure gauge (2 a)2) And a pressure maintaining valve (3 a)2) A second pressure gauge (2b)2) And a stop valve (1 b)2) A flowmeter (4b) and a one-way valve (5 a)2) And a stop valve (1 c)2) And enters a reaction gas circuit through a second three-way valve (6 b).
O2The pipeline is connected with a switch valve (1 a) in sequence1) A first pressure gauge (2 a)1) And a pressure maintaining valve (3 a)1) A second pressure gauge (2b)1) And a stop valve (1 b)1) A flowmeter (4a) and a one-way valve (5 a)1) And a stop valve (1 c)1) And the mixture is mixed with a raw gas pipeline by a third three-way valve (6c) and enters a reaction gas pipeline.
The inert gas pipeline is connected with a switch valve (1 a) in sequence4) A first pressure gauge (2 a)4) And a pressure maintaining valve (3 a)4) A second pressureWatch (2b)4) And a stop valve (1 b)4) A flowmeter (4e), a check valve (5 a)4) And a stop valve (1 c)4) The system comprises a circulating low-pressure tank (8), a stop valve (1s), a needle valve (12c), a stop valve (1t), a circulating high-pressure tank (10) and a stop valve (1n), wherein the stop valve (1n) enters a reaction gas circuit through a first three-way valve (6a) and then enters a fixed bed reaction system (B).
The reacted gas is divided into three paths in a first four-way valve (7 a): one path is an air storage pipeline which is sequentially connected with a stop valve (1w), a one-way valve (5e) and an air storage tank (16), wherein the air storage tank is divided into two paths, and the other path is the stop valve (1x) to a next reaction system; the other path is an analysis pipeline, and is sequentially connected with a stop valve (1y) and an eighth three-way valve (6h) to enter an analysis system (C). The eighth three-way valve (6h) further comprises a path of analysis pipeline which is from the gas mixer (1), is sequentially connected with the gas mixer (1), the one-way valve (5f) and the stop valve (1z), and enters the analysis system (C) through the eighth three-way valve (6 h); one path is a circulating pipeline, and is sequentially connected with a stop valve (1f), a circulating flow meter (4f), a one-way valve (5d), a stop valve (1g), a circulating low-pressure tank (8), a stop valve (1h), a circulating pneumatic pump (9), a stop valve (1k), a circulating high-pressure tank (10), a stop valve (1n) and a gas concentration feedback module (17) connected with the circulating low-pressure tank (8), and enters a fixed bed reaction system (B) after being mixed with a reaction pipeline through a first three-way valve (6 a); one path is an emptying pipeline, and is sequentially connected with a system pressure gauge (2c), a system backpressure valve (9a), a stop valve (1e) and a fourth three-way valve (6g) to enter the emptying pipeline. The fourth three-way valve (6g) also comprises a 2-way emptying pipeline: one path is a circulating low-pressure tank (8), a pressure gauge (2d), a stop valve (1j), a needle valve (12a), a fifth three-way valve (6d), a safety valve (8a) and a seventh three-way valve (6f) and enters an emptying pipeline; one path is a circulating high-pressure tank (10), a pressure gauge (2e), a stop valve (1m), a needle valve (12b), a sixth three-way valve (6e), a safety valve (8b) and a seventh three-way valve (6f) and enters an emptying pipeline.
(2) The fixed bed reaction system (B) comprises a gas preheater (2), a first temperature sensor (10a), a heating jacket (3), a second temperature sensor (10B), a reactor (4), a first gas-liquid separation tank (5), a second gas-liquid separation tank (6), a circulating condenser (11), a dryer (7), a one-way valve (5B) and a gas-liquid separation tank liquid emptying valve (1 d).
(3) The analysis system (C) is a gas product analysis unit and is composed of an analysis pipeline one-way valve (5C) and a sampling switch valve (1v) which are connected with a six-way valve (12), a quantitative tube (13), a packed chromatographic column (14) and a thermal conductivity detector (15).
(4) And the central control system (D) monitors all components of the whole reaction system, including a temperature sensor, a pressure sensor, a flow control device and a thermal conductivity detector.
The inert gas of the gas control system (A) is N2Any one of He and Ar;
the pressure range of each pipeline of the gas control system (A) after pressure stabilization is 0.1-5MPa, and the system pressure range is 0.1-5 MPa. The pressure range of the circulating low-pressure tank is 0.1-3MPa, and the pressure range of the circulating high-pressure tank is 0.1-5 MPa.
The preheating temperature range of a preheater in the fixed bed reaction system (B) is 30-200 ℃; the heating temperature is between room temperature and 500 ℃; the refrigerant fluid is water or glycol.
The chromatographic packed column of the analysis system (C) is one of a 5A molecular sieve and TDX-01.
The invention provides a method for controlling a CO dehydrogenation circulating reaction device of reactant proportion in real time, which comprises the following steps:
(1) measuring PdO/Al2O3Catalyst 20ml (PdO/Al)2O3The mass content of pd in the catalyst is 1 percent, the same as other embodiments), the catalyst is filled into a reactor (4), and the reactor (4) is sealed after the filling is finished and is connected with a central processing system (D);
(2) opening an emptying pipeline switch valve (1e), opening a circulating condenser (11) and ensuring that liquid emptying valves (1d) of gas-liquid separation tanks (5) and (6) are in a closed state; opening the inert gas Ar switch valve (1 a)4) Regulating pressure stabilizing valve (3 a)4) Controlling Ar post-pressure stabilization pressure (2b)4) 0.5MPa, the stop valve (1 b) is opened4) Adjusting the flow rate of the flow meter (4e) to 333.3ml/min, and opening the stop valve (1 c)4) Entering a circulating low-pressure tank (8), opening a stop valve (1s), adjusting a needle valve (12c), opening a stop valve (1t), entering a circulating high-pressure tank (10), opening stop valves (1n), (1 b)5) Enter into reactionGas path, regulating pressure stabilizing valve (3 a)5) Opening the stop valve (1 c)5) Adjusting a system back pressure valve (9a) to ensure that the pressure (2c) of the reaction system is stabilized at 0.25MPa, and replacing the air in the gas mixer (1), the preheater (2) and the reactor (4);
(3) after Ar gas is replaced for 0.5h, setting the preheating temperature of the preheater (2) to be 100.0 ℃ and the temperature of the heating sleeve (3) to be 150.0 ℃;
(4) after the temperature of the reactor (4) is stabilized, H is opened2On-off valve (1 a)2) By adjusting the pressure stabilizing valve (3 a)2) Control H2Pressure gauge (2b)2) Is 0.5MPa, and the stop valve (1 b) is opened2) Opening the stop valve (1 c)2) The flow rate of the flow meter (4b) is adjusted to be 16.7ml/min, and reduction gas is prepared by the flow meter and Ar gas in the gas mixer (1). The stop valve (1z) is opened, and the gas enters an analysis system (C) through an eighth three-way valve (6H) to analyze the reducing gas ratio H2The content is 5%. And the reducing gas enters the reaction system to reduce the catalyst. The reduction time is 5H, and after the reduction is finished, H is closed2Switching all pipelines;
(5) after the reduction is finished, the heating switches of the preheater (2) and the heating jacket (3) are closed, when the temperature of the reactor (4) is reduced to about room temperature, the switch in front of the first three-way valve (6a) of the inert gas pipeline is closed, the stop valves (1j) and (1m) on the circulating low-pressure tank (8) and the circulating high-pressure tank (10) are opened, the needle valves (12a) and (12b) are adjusted, when the pressures of the pressure gauges (2d) and (2e) are reduced to 0.1MPa, the stop valves (1j) and (1m) and the needle valves (12a) and (12b) are closed, and the inert gas in the circulating low-pressure tank (8) and the circulating high-pressure tank (10);
(6) on-off valve (1 a) for opening CO pipeline3) Regulating pressure stabilizing valve (3 a)3) Controlling the pressure of the CO pressure gauge (2b) to be 0.5MPa, and opening the stop valve (1 b)3) The flow rate of the flow meter 4d was adjusted to 1666.7ml/min, and the stop valve (1 c) was opened3) CO enters a circulating low-pressure tank (8), a stop valve (1h) is opened, a circulating pneumatic pump (9) and a stop valve (1k) are arranged, the CO enters a circulating high-pressure tank (10), enters a reaction gas path through the stop valve (1n), and a pressure stabilizing valve (3 a) is adjusted5) Enters a fixed bed reaction system B from a gas mixer (1);
(7) in a CO atmosphere, setting the preheating temperature of a preheater (2) to be 90.0 ℃, setting the temperature of a heating sleeve (3) to be 110.0 ℃, and raising the temperature of a reactor (4) to be 110.0 ℃;
(8) after the temperature of the reactor (4) is stabilized, H is opened2On-off valve (1 a)2) Regulating pressure stabilizing valve (3 a)2) Control H2Pressure gauge (2b)2) 0.5MPa, the stop valve (1 b) is opened2) The flow rate of the flow meter (4b) is adjusted to 8.3ml/min, and the stop valve (1 c) is opened2) Enters a reaction gas path through a second three-way valve (6B), is mixed with CO in a gas mixer (1) and then is introduced into a fixed bed reaction system (B);
(9) wait for H2After the flow rate (4b) has stabilized, O is opened2On-off valve (1 a)1) Regulating pressure stabilizing valve (3 a)1) Control of O2Pressure gauge (2b)3) 0.5MPa, the stop valve (1 b) is opened1) The flow rate of the flow meter (4a) is adjusted to 10.5ml/min, and the stop valve (1 c) is opened1) Enters a reaction gas path through a third three-way valve (6c), O2With CO, H2Preparing reaction gas in a gas mixer (1);
(10) opening the stop valve (1z), and allowing the reaction gas to enter an analysis system (C) with an analysis reaction gas ratio of H2:CO＝0.5％，O2:H21.25: 1; after the mixture ratio is stable, the circulating pipeline switch valve (1f) is opened, the flow of the circulating flowmeter (4f) is adjusted to be 1333.4ml/min, the stop valve (1g) is opened, the flow of the flowmeter (4d) is adjusted to be 333.3ml/min, and the flow of the flowmeter (4c) is ensured to be 1666.7 ml/min.
(11) The system back pressure valve (9a) is adjusted to ensure that the reaction system pressure (2c) is stabilized at 0.25 MPa. A gas concentration feedback module (17) for opening the circulation pipeline, and O of the gas concentration feedback module (17)2And H2Is 1.25. 1h after the start of the reaction, the reacted gas was sampled and analyzed. Gas after reaction enters an analysis system (C) through gas-liquid separation tanks (5) and (6), a dryer (7), a gas storage tank (16), a stop valve (1y) and an eighth three-way valve (6h) to be subjected to gas analysis, a sampling stop valve (1v) is opened and passes through a sampling six-way valve (12), a quantitative pipe (13) and a packing column (14) to enter a thermal conductivity detector (15) to be analyzed, and the stop valve is closed after sampling is finished(1y), (1v), analysis results residual H after reaction2Content 85ppm, O2The content of (B) is 0.33%.
(12) After reacting for 1H, the gas concentration feedback module (17) adjusts H in real time according to the analysis result of the step (11)2The mass flow meter (4b) of the pipeline is 8.2ml/min, O2The mass flow meter (4a) of the line was 6.1 ml/min. After reacting for 20h, analyzing the gas in the gas mixer (1), and analyzing the result to obtain O in the reaction gas2And H2Is 1.24.
(13) After the reaction is finished, the heating switches of the preheater (2) and the heating jacket (3) are closed, the switch of the circulating condenser (11) is closed, and the O is closed2Air passage switch (1 a)1)、(1b1)、(1c1) Closing H2Air passage switch (1 a)2)、(1b2)、(1c2) Closing circulating pipeline switches (1f) and (1g), a gas concentration feedback module (17) and a CO pipeline switch (1 a)3)、(1b3)、(1c3) (1h), (1k) and a circulating pneumatic pump (9). Opening the inert gas pipeline switch (1 a)4) Regulating pressure stabilizing valve (3 a)4) Controlling Ar post-pressure stabilization pressure (2b)4) 0.5MPa, the stop valve (1 b) is opened4) Adjusting the flow rate of the flow meter (4e) to 333.3ml/min, and opening the stop valve (1 c)4) The device comprises a circulating low-pressure tank (8), a stop valve (1s) is opened, a needle valve (12c) is adjusted, a stop valve (1t) is opened, the circulating high-pressure tank (10) is entered, the stop valve (1n) is opened to enter a fixed bed reaction system through a reaction pipeline to replace and cool gas in a reactor, after the temperature of the reactor is reduced to room temperature, a switch in front of the inert gas pipeline circulating low-pressure tank (8) is closed, a back pressure valve (9a) of an emptying pipeline system is adjusted, and when the pressure (2c) of the reaction system is reduced to be below 0.05MPa, all switches of the device are closed. And opening liquid emptying valves (1d) of the gas-liquid separation tanks (5) and (6) to empty the liquid, and closing the liquid in time after the liquid is emptied.
Example 2:
the other steps are the same as those of the embodiment 1, except that:
measuring 50ml of catalyst in the step (1);
step (3), the preheating temperature of the preheater (2) is 120.0 ℃, and the temperature of the heating sleeve (3) is 150 ℃;
step (4) H2The flow rate of the flow meter (4b) is 83.3ml/min, and H in reducing gas2The volume content of (A) is 10%, and the reduction time is 2 h;
the flow rate of the CO flow meter (4d) in the step (6) is 833.3 ml/min;
step (7), setting the preheating temperature of the preheater (2) to be 130.0 ℃;
step (8) H2The flow of the flow meter (4b) is 12.5 ml/min;
step (9) O2The flow of the flowmeter (4a) is 25 ml/min;
the reaction gas proportion in the step (10) is H2:CO＝1.5％，O2:H22: 1; the flow rate of the circulation flow meter (4f) is 666.3ml/min, and the flow rate of the flow meter (4d) is adjusted to 167ml/min, so that the flow rate of the flow meter (4c) is ensured to be 833.3 ml/min.
Step (11) setting O of gas concentration feedback module (17)2And H2Is 2. Analysis results residual H after reaction2Content 27ppm, O2The content was 2.22%.
Step (12) of automatically adjusting H2The mass flow meter (4b) of the pipeline is 12.5ml/min, O2The mass flow meter (4a) of the pipeline is 10.33ml/min, and after 20 hours of reaction, the reaction gas O in the gas mixer (1)2And H2Is 2.02.
Example 3:
the other steps are the same as those of the embodiment 1, except that:
step (1) measuring PdCl2/Al2O310ml of catalyst;
step (4) H2The flow rate of the flow meter (4b) is 33.3ml/min, and H in reducing gas2The volume content of (A) is 20%, and the reduction time is 1 h;
the flow rate of the CO flowmeter (4d) in the step (6) is 333.3 ml/min;
step (8) H2The flow of the flow meter (4b) is 66.7 ml/min;
step (9) O2The flow of the flowmeter (4a) is 50 ml/min;
the reaction gas proportion in the step (10) is H2:CO＝20％，O2:H20.75: 1; the flow rate of the circulation flow meter (4f) is 266.6ml/min, and the flow rate of the flow meter (4d) is adjusted to be 66.7ml/min, so that the flow rate of the flow meter (4c) is ensured to be 333.3 ml/min.
Step (11) setting O of gas concentration feedback module (17)2And H2Volume ratio of (3) was 0.75, and analysis result shows that H remains after the reaction2Content of 1.23%, O2The content was 5.11%.
Step (12) of automatically adjusting H2The mass flow meter (4b) of the pipeline is 63.5ml/min, O2The mass flow meter (4a) of the pipeline is 36.4ml/min, and after 20 hours of reaction, the reaction gas O in the gas mixer (1)2And H2Is 0.74.
Example 4:
the other steps are the same as those of the embodiment 1, except that:
step (1) measuring PdO/Al2O310ml of catalyst;
in the step (2), the flow of the Ar flowmeter (4e) is 333.3 ml/min;
step (4) H2The flow rate of the flow meter (4b) is 33.3ml/min, and H in reducing gas2The volume content of (A) is 10%, and the reduction time is 3 h;
the flow rate of the CO flowmeter (4d) in the step (6) is 333.3 ml/min;
step (8) H2The flow of the flow meter (4b) is 33.3 ml/min;
step (9) O2The flow of the flowmeter (4a) is 100.0 ml/min;
the reaction gas proportion in the step (10) is H2:CO＝10％，O2:H21: 3; the flow rate of the circulation flow meter (4f) was adjusted to 266.6ml/min, and the flow rate of the flow meter (4d) was adjusted to 66.7ml/min, ensuring that the flow rate of the flow meter (4c) was 333.3 ml/min.
Step (11) setting O of gas concentration feedback module (17)2And H2Volume ratio of (3), analytical results remaining H after reaction2Content 65ppm, O2The content was 24.51%.
Step (12) of automatically adjusting H2The mass flow meter (4b) of the pipeline is 33.3ml/min, O2The mass flow meter (4a) of the pipeline is 34.7ml/min, and after 20 hours of reaction, the reaction gas O in the gas mixer (1)2And H2Is 2.97.
Comparative example 1:
the other steps are the same as those of the embodiment 1, except that:
the flow rate of the CO flowmeter (4d) in the step (6) is 333.3 ml/min;
step (8) H2The flow of the flow meter (4b) is 33.3 ml/min;
step (9) O2The flow of the flowmeter (4a) is 100.0 ml/min;
the reaction gas proportion in the step (10) is H2:CO＝10％，O2:H21: 3; the flow rate of the circulation flow meter (4f) was adjusted to 266.6ml/min, and the flow rate of the flow meter (4d) was adjusted to 66.7ml/min, ensuring that the flow rate of the flow meter (4c) was 333.3 ml/min.
Step (11) without opening the gas concentration feedback module (17), analyzing the residual H after the result reaction2A content of 55ppm, O2The content was 18.15%.
After the reaction for 20 hours in the step (12), carrying out chromatographic analysis on the reaction gas, namely the reaction gas O in the gas mixer (1)2And H2Is 8.52.
Claims (9)
1. A CO dehydrogenation circulation reaction unit of real time control reactant ratio which characterized in that:
comprises a gas control system (A), a fixed bed reaction system (B), an analysis system (C) and a central processing system (D); wherein:
(1) the gas control system (A) comprises seven parts of a raw material gas pipeline, an oxygen pipeline, an inert gas pipeline, an analysis pipeline, a circulation pipeline, a gas storage pipeline and an emptying pipeline:
the raw material gas pipeline comprises a CO pipeline and H2The pipeline and the CO pipeline are connected with a switch valve (1 a) in sequence3) A first pressure gauge (2 a)3) And a pressure maintaining valve (3 a)3) A second pressure gauge (2b)3) And a stop valve (1 b)3) A flowmeter (4d) and a one-way valve (5 a)3) And a stop valve (1 c)3) Enters a circulating low-pressure tank (8) and is stoppedThe valve (1h), the circulating pneumatic pump (9), the stop valve (1k), the circulating high-pressure tank (10), the stop valve (1n) and the reaction gas path from the first three-way valve (6a), namely the stop valve (1 b)5) A first pressure gauge (2 a)5) And a pressure maintaining valve (3 a)5) A second pressure gauge (2b)5) And a stop valve (1 c)5) A flowmeter (4c), a second three-way valve (6b) and a one-way valve (5 a)5) The third three-way valve (6c) and the gas mixer (1) enter a fixed bed reaction system (B); h2The pipeline is connected with a switch valve (1 a) in sequence2) A first pressure gauge (2 a)2) And a pressure maintaining valve (3 a)2) A second pressure gauge (2b)2) And a stop valve (1 b)2) A flowmeter (4b) and a one-way valve (5 a)2) And a stop valve (1 c)2) And enters a reaction gas path through a second three-way valve (6 b);
O2the pipeline is connected with a switch valve (1 a) in sequence1) A first pressure gauge (2 a)1) And a pressure maintaining valve (3 a)1) A second pressure gauge (2b)1) And a stop valve (1 b)1) A flowmeter (4a) and a one-way valve (5 a)1) And a stop valve (1 c)1) The mixture is mixed with a raw gas pipeline by a third three-way valve (6c) and enters a reaction gas pipeline;
the inert gas pipeline is connected with a switch valve (1 a) in sequence4) A first pressure gauge (2 a)4) And a pressure maintaining valve (3 a)4) A second pressure gauge (2b)4) And a stop valve (1 b)4) A flowmeter (4e), a check valve (5 a)4) And a stop valve (1 c)4) The system comprises a circulating low-pressure tank (8), a stop valve (1s), a needle valve (12c), a stop valve (1t), a circulating high-pressure tank (10), a reaction gas circuit which is fed by a first three-way valve (6a) through a stop valve (1n), and a fixed bed reaction system (B);
the reacted gas is divided into three paths in a first four-way valve (7 a): one path is an air storage pipeline which is sequentially connected with a stop valve (1w), a one-way valve (5e) and an air storage tank (16), wherein the air storage tank is divided into two paths, and the other path is the stop valve (1x) to a next reaction system; the other path is an analysis pipeline which is sequentially connected with a stop valve (1y) and an eighth three-way valve (6h) and enters an analysis system (C); the eighth three-way valve (6h) further comprises a path of analysis pipeline which is from the gas mixer (1), is sequentially connected with the gas mixer (1), the one-way valve (5f) and the stop valve (1z), and enters the analysis system (C) through the eighth three-way valve (6 h); one path is a circulating pipeline, and is sequentially connected with a stop valve (1f), a circulating flow meter (4f), a one-way valve (5d), a stop valve (1g), a circulating low-pressure tank (8), a stop valve (1h), a circulating pneumatic pump (9), a stop valve (1k), a circulating high-pressure tank (10), a stop valve (1n) and a gas concentration feedback module (17) connected with the circulating low-pressure tank (8), and enters a fixed bed reaction system (B) after being mixed with a reaction pipeline through a first three-way valve (6 a); one path is an emptying pipeline, and is sequentially connected with a system pressure gauge (2c), a system backpressure valve (9a), a stop valve (1e) and a fourth three-way valve (6g) to enter the emptying pipeline; the fourth three-way valve (6g) also comprises a 2-way emptying pipeline: one path is a circulating low-pressure tank (8), a pressure gauge (2d), a stop valve (1j), a needle valve (12a), a fifth three-way valve (6d), a safety valve (8a) and a seventh three-way valve (6f) and enters an emptying pipeline; one path is a circulating high-pressure tank (10), a pressure gauge (2e), a stop valve (1m), a needle valve (12b), a sixth three-way valve (6e), a safety valve (8b) and a seventh three-way valve (6f) and enters an emptying pipeline;
(2) the fixed bed reaction system (B) comprises a gas preheater (2), a first temperature sensor (10a), a heating jacket (3), a second temperature sensor (10B), a reactor (4), a first gas-liquid separation tank (5), a second gas-liquid separation tank (6), a circulating condenser (11), a dryer (7), a one-way valve (5B) and a gas-liquid separation tank liquid emptying valve (1 d);
(3) the analysis system (C) is a gas product analysis unit and is composed of an analysis pipeline one-way valve (5C) and a sampling switch valve (1v) which are connected with a six-way valve (12), a quantitative tube (13), a packed chromatographic column (14) and a thermal conductivity detector (15);
(4) and the central control system (D) monitors all components of the whole reaction system, including a temperature sensor, a pressure sensor, a flow control device and a thermal conductivity detector.
2. The apparatus of claim 1, wherein: the inert gas of the gas control system (A) is N2Any one of He and Ar;
after the pressure of each pipeline of the gas control system (A) is stabilized, the pressure range is 0.1-5MPa, and the system pressure range is 0.1-5 MPa; the pressure range of the circulating low-pressure tank is 0.1-3MPa, and the pressure range of the circulating high-pressure tank is 0.1-5 MPa.
3. The apparatus of claim 1, wherein: the preheating temperature range of a preheater in the fixed bed reaction system (B) is 30-200 ℃; the heating temperature is between room temperature and 500 ℃; the refrigerant fluid is water or glycol.
4. The apparatus of claim 1, wherein: the chromatographic packed column of the analysis system (C) is one of a 5A molecular sieve and TDX-01.
5. A CO dehydrogenation circulating reaction method for controlling the proportion of reactants in real time is characterized by comprising the following steps:
(1) measuring a catalyst, filling the catalyst into the reactor (4), sealing the reactor (4) after filling, and connecting the reactor with a central processing system (D);
(2) opening an emptying pipeline switch valve (1e), opening a circulating condenser (11) and ensuring that liquid emptying valves (1d) of gas-liquid separation tanks (5) and (6) are in a closed state; opening the inert gas switching valve (1 a)4) Regulating pressure stabilizing valve (3 a)4) Opening the stop valve (1 b)4) Adjusting the flow rate of the flow meter (4e) and opening the stop valve (1 c)4) Entering a circulating low-pressure tank (8), opening a stop valve (1s), adjusting a needle valve (12c), opening a stop valve (1t), entering a circulating high-pressure tank (10), opening stop valves (1n), (1 b)5) Regulating pressure stabilizing valve (3 a)5) Opening the stop valve (1 c)5) Adjusting the air in a system back pressure valve (9a), a replacement gas mixer (1), a preheater (2) and a reactor (4);
(3) after the inert gas is replaced, setting the preheating temperature of the preheater (2) and the temperature of the heating sleeve (3);
(4) after the reactor temperature stabilized, H was opened2On-off valve (1 a)2) Regulating pressure stabilizing valve (3 a)2) Opening the stop valve (1 b)2) Adjusting the flow rate of the flow meter 4b and opening the stop valve (1 c)2) Entering a gas mixer (1); h2Preparing reducing gas with inert gas in a gas mixer (1), opening a stop valve1z) entering an analysis system (C) through an eighth three-way valve (6h), analyzing the proportion of reducing gas, opening a sampling stop valve (1v), entering a sampling six-way valve (12), a quantitative tube (13) and a packed column (14), entering a thermal conductivity detector (15) for analysis, and closing the stop valve (1z) after the analysis is finished; reducing gas enters a reaction system for catalyst reduction, and H is closed after the reduction is finished2Switching all pipelines;
(5) the heating switches of the preheater (2) and the heating jacket (3) are closed, when the temperature of the reactor is reduced to about room temperature, the switch in front of a first three-way valve (6a) of an inert gas pipeline is closed, stop valves (1j) and (1m) on the circulating low-pressure tank (8) and the circulating high-pressure tank (10) are opened, needle valves (12a) and (12b) are adjusted, when the pressures of pressure gauges (2d) and (2e) are reduced to 0.1MPa, the stop valves (1j) and (1m) and the needle valves (12a) and (12b) are closed, and the inert gas in the circulating low-pressure tank (8) and the circulating high-pressure tank (10) is emptied;
(6) on-off valve (1 a) for opening CO pipeline3) Regulating pressure stabilizing valve (3 a)3) Opening the stop valve (1 b)3) Adjusting the flow rate of the flow meter (4d) and opening the stop valve (1 c)3) CO enters a circulating low-pressure tank (8), a stop valve (1h) is opened, a circulating pneumatic pump (9) and a stop valve (1k) are arranged, the CO enters a circulating high-pressure tank (10), enters a reaction gas path through the stop valve (1n), and a pressure stabilizing valve (3 a) is adjusted5) Introducing the mixture into a fixed bed reaction system (B) through a gas mixer (1);
(7) setting the temperature of the preheater (2) and the heating jacket (3) in a CO atmosphere, and raising the temperature of the reactor (4) to a reaction temperature;
(8) after the temperature of the reactor (4) is stabilized, H is opened2On-off valve (1 a)2) Regulating pressure stabilizing valve (3 a)2) Opening the stop valve (1 b)2) Adjusting the flow rate of the flow meter (4b) and opening the stop valve (1 c)2) Enters a reaction gas path through a second three-way valve (6B), is mixed with CO in a gas mixer (1) and then is introduced into a fixed bed reaction system (B);
(9) wait for H2After the flow rate (4b) has stabilized, O is opened2On-off valve (1 a)1) Regulating pressure stabilizing valve (3 a)1) Opening the stop valve (1 b)1) Adjusting the flow rate of the flow meter (4a) and opening the stop valve (1 c)1) Via the thirdThe three-way valve (6c) enters a reaction gas path O2With CO, H2Preparing reaction gas in a gas mixer (1);
(10) the reaction gas enters an analysis system (C) through a stop valve (1z) and an eighth three-way valve (6h), and the mixture ratio of each component of the reaction gas is analyzed; after the analysis is finished, closing the stop valve (1 z); after the mixture ratio is stable, opening a circulating pipeline switch valve (1f), adjusting the flow of a circulating flowmeter (4f), opening a stop valve (1g), adjusting the flow of a flowmeter (4d) and ensuring the flow of a flowmeter (4c) to be stable;
(11) adjusting a system backpressure valve (9a) to ensure that the reaction system pressure (2c) is stable; opening the gas concentration feedback module (17), and setting O of the gas concentration feedback module (17)2And H2The volume ratio of (A) to (B); sampling and analyzing the gas after the reaction is stable every 1-5h after the reaction starts; gas after reaction enters an analysis system (C) through gas-liquid separation tanks (5) and (6), a dryer (7), a gas storage tank (16), a stop valve (1y) and an eighth three-way valve (6h) to be subjected to gas analysis, a sampling stop valve (1v) is opened and passes through a sampling six-way valve (12), a quantitative pipe (13) and a packed column (14) to enter a thermal conductivity detector (15) to be analyzed, and the stop valves (1y) and (1v) are closed after sampling is finished;
(12) the gas concentration feedback module (17) analyzes H in the result according to the gas after the reaction in the step (11)2、O2Content, real-time adjustment of H2、O2The flow rate of (a); the gas in the gas mixer (1) was analyzed in accordance with the step (4) every 0.5 to 2 hours after the start of the reaction, and H was monitored2And O2The content of (A);
(13) after the reaction is finished, the heating switches of the preheater (2) and the heating jacket (3) are closed, the switch of the circulating condenser (11) is closed, and the O is closed2Air passage switch (1 a)1)、(1b1)、(1c1) Closing H2Air passage switch (1 a)2)、(1b2)、(1c2) Closing the circulating pipeline switches (1f) and (1g) and the gas concentration feedback module (17), and closing the CO pipeline switch (1 a)3)、(1b3)、(1c3) (1h), (1k) and a circulating pneumatic pump (9); opening the inert gas pipeline switch (1 a)4) Regulating pressure stabilizing valve (3 a)4) Opening the stop valve (1 b)4) Adjusting the flow meter (4e) Opening the stop valve (1 c)4) The reaction system enters a circulating low-pressure tank (8), a stop valve (1s) is opened, a needle valve (12c) is adjusted, a stop valve (1t) is opened, the reaction system enters a fixed bed reaction system through a reaction pipeline to replace gas in a reactor and cool the gas, after the temperature of the reactor is reduced to room temperature, a switch in front of the inert gas pipeline circulating low-pressure tank (8) is closed, a back pressure valve (9a) of a venting pipeline system is adjusted, and when the pressure (2c) of the reaction system is reduced to be below 0.05MPa, all switches of the device are closed; and opening liquid emptying valves (1d) of the gas-liquid separation tanks (5) and (6) to empty the liquid, and closing the tanks after the liquid is emptied.
6. The method of claim 5, wherein: said step (4) H2In a reducing gas with an inert gas, H2The volume content of the catalyst is 5-20 percent, the content of inert gas is 80-95 percent, and the reduction time is 0.5-5 h.
7. The method of claim 5, wherein: the step (8) is carried out by reacting CO with H2The volume content of CO in the raw material gas is 80-99.5%, and H2The content of (A) is 0.5-20% by volume.
8. The method of claim 5, wherein: said step (9) O2And H2The volume ratio of (A) to (B) is 0.5: 1-3.
9. The method of claim 5, wherein: o of the gas concentration feedback module (17) in the step (12)2And H2The volume ratio of (a) is in the range of 0.5: 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010416774.8A CN111672427B (en) | 2020-05-15 | 2020-05-15 | CO dehydrogenation circulation reaction device capable of controlling reactant ratio in real time |
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