Self-heating type hydrogen deoxidization, dehydration and purification system and method for hydrolysis hydrogen production process

Abstract

The invention relates to a gas purification system, in particular to a self-heating type hydrogen deoxidizing, dehydrating and purifying system and method for a hydrolysis hydrogen production process, and aims to solve the problems that an existing hydrogen purification system is high in operation difficulty, relatively high in energy consumption and incomplete in dehydration. The system comprises a deoxidation and preliminary dehydration unit and a deep dehydration unit, the deep dehydration unit comprises a second heater, a second cooler, a regenerated gas separator, an adjustable ejector, a first dehydration tower, a second dehydration tower, a third dehydration tower, a pressure reducer and a post-filter; the first dehydrating tower, the second dehydrating tower and the third dehydrating tower are respectively provided with three input end pipelines and three output end pipelines, the first dehydrating tower, the second dehydrating tower and the third dehydrating tower are used for adsorbing moisture in fluid, the pressure reducer is used for reducing the pressure of the fluid, and the adjustable ejector is used for increasing the pressure of the fluid; and the rear filter is used for filtering adsorbent dust entrained in the fluid.

Description

Technical Field

[0001] The invention relates to a gas purification system, and in particular to a self-heating hydrogen deoxygenation and dehydration purification system and method for a hydrolysis hydrogen production process. Background Art

[0002] Hydrogen is a widely used raw material. It can be used as raw gas, reducing gas, cooling gas, protective gas or combustion gas in industry, and has a wide range of uses in scientific research fields such as chemical industry, petrochemical industry, metallurgy, mechanical processing, electricity and medicine. Water electrolysis is a common method for preparing hydrogen in industry. The reaction is carried out in an electrolytic cell. The liquid in the electrolytic cell is a dilute hydroxide solution (such as KOH or NaOH solution). The reduction reaction occurring at the cathode is: 4H 2 O+4e - =2H 2 ↑+4OH - The oxidation reaction at the anode is: 4OH - -4e - =2H 2 O+O 2 ↑, where +e - Represents electrons, -e - represents the loss of electrons, and the overall reaction equation is: The raw gas prepared by this method usually contains impurities O 2 , H 2 O(g), trace amounts of hydroxide solution, and other impurities, which need to be removed, (g) represents the gaseous state.

[0003] In this regard, Chinese patent CN108910824A discloses a high-purity hydrogen purification system and purification method, the system includes a main PSA hydrogen extraction device and an auxiliary PSA hydrogen extraction device, the main PSA hydrogen extraction device includes an adsorption unit A, a raw gas buffer tank A, a product gas buffer tank A, a forward discharge tank, a reverse discharge tank and a decomposition gas tank, the auxiliary PSA hydrogen extraction device includes an adsorption unit B, a raw gas buffer tank B, a product gas buffer tank B and a tail gas tank, the decomposition gas tank is connected to the raw gas buffer tank B, and the raw gas buffer tank A is connected to the product gas buffer tank B. The tail gas of the main PSA hydrogen extraction device is compressed and used as the raw gas of the auxiliary PSA hydrogen extraction device. The product gas of the auxiliary PSA hydrogen extraction device is used as the raw gas of the main PSA hydrogen extraction device, which improves the hydrogen yield, effectively removes carbon monoxide, carbon dioxide, methane, nitrogen, water vapor and nitrogen in the crude hydrogen, and improves the product purity. However, the shortcomings of this patent are: a large number of tanks are used, the structure is complex, the operation is difficult, and the energy consumption is high, and the dehydration is not thorough. Summary of the invention

[0004] The purpose of the present invention is to solve the problems of difficult operation, high energy consumption and incomplete dehydration of existing hydrogen purification systems, and to provide a self-heating hydrogen deoxygenation and dehydration purification system and method for the hydrolysis hydrogen production process.

[0005] To achieve the above purpose, the technical solution provided by the present invention is:

[0006] A self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process, which is special in that:

[0007] The invention comprises a deoxygenation and preliminary dehydration unit whose input end is connected to the raw gas input pipeline, and a deep dehydration unit connected to the output end of the deoxygenation and preliminary dehydration unit; the deoxygenation and preliminary dehydration unit is used to remove hydroxide solution and O in the raw gas. 2 impurities, and perform preliminary dehydration to obtain a third intermediate gas; the deep dehydration unit is used to perform deep dehydration on the third intermediate gas to obtain a finished gas;

[0008] The deep dehydration unit comprises a second heater, a second cooler, a regeneration gas separator, an adjustable ejector, a first dehydration tower, a second dehydration tower, a third dehydration tower, a pressure reducer and a post-filter;

[0009] The first dehydration tower, the second dehydration tower and the third dehydration tower are respectively provided with three input end pipelines and three output end pipelines; the first dehydration tower, the second dehydration tower and the third dehydration tower are all provided with an adsorbent for absorbing water;

[0010] The output pipeline of the deoxygenation and preliminary dehydration unit is provided with a diversion point, and a control valve is arranged on the diversion point to divide the output pipeline into two paths with different flow rates. The flow rate is q 1 One of the channels is connected to the first input of the adjustable ejector, and the flow rate is q 2 The other route is divided into three routes, which are respectively connected to the first input end pipeline of each dehydration tower, q 1 >q 2 ; The second input end of the adjustable ejector is connected to the output end pipeline of the regeneration gas separator; the output end of the adjustable ejector is divided into three paths, which are respectively connected to the second input end pipeline of each dehydration tower; the first output end pipeline of each dehydration tower is connected to the input end of the post-filter, and the second output end pipeline of each dehydration tower is connected to the input end of the second heater; the output end of the post-filter is connected to the finished gas output pipeline, and the finished gas output pipeline is used to output the obtained finished gas; the output end of the second heater is connected to the input end of the pressure reducer, and the output end of the pressure reducer is divided into three paths, which are respectively connected to the third input end pipeline of each dehydration tower; the third output end pipeline of each dehydration tower is connected to the input end of the second cooler; the output end pipeline of the second cooler is connected to the input end of the regeneration gas separator;

[0011] The first dehydration tower, the second dehydration tower and the third dehydration tower are used to adsorb moisture in the fluid, the pressure reducer is used to reduce the fluid pressure, and the adjustable ejector is used to increase the fluid pressure; the post-filter is used to filter out the adsorbent dust entrained in the fluid; the regeneration gas separator is used to separate moisture in the regeneration gas.

[0012] Furthermore, the deoxidation and preliminary dehydration unit includes an alkali filter for removing impurities from the hydroxide solution, a deoxidation heat recovery device, a first heater, and a deoxidation and preliminary dehydration unit. 2 The deoxidation tower for impurities, the first cooler and the deoxidation separation filter for preliminary dehydration; wherein the deoxidation heat recovery device includes two sets of input ends and two sets of output ends;

[0013] The input end of the alkali liquid filter is connected to the raw gas input pipeline, and the output end pipeline is divided into two paths, wherein the first output end pipeline is connected to the first input end of the deoxygenation heat recovery device, and the second output end pipeline is connected to the input end of the first heater, and the raw gas input pipeline is used to input the raw gas to be decontaminated; the output end pipeline of the first heater is connected to the input end of the deoxygenation tower, and the output end pipeline of the deoxygenation tower is connected to the second input end of the deoxygenation heat recovery device; the first output end pipeline of the deoxygenation heat recovery device is connected to the input end of the first heater, and the second output end pipeline of the deoxygenation heat recovery device is connected to the input end of the first cooler, and the output end pipeline of the first cooler is connected to the input end of the deoxygenation separation filter, and the output end pipeline of the deoxygenation separation filter serves as the output end pipeline of the deoxygenation and preliminary dehydration unit, and is used to output the third intermediate gas;

[0014] The raw gas input pipeline is provided with a first valve; the first output end pipeline of the alkali solution filter is provided with a second valve, and the second output end pipeline thereof is provided with a third valve.

[0015] Furthermore, the first heater, the second heater, the first cooler, the second cooler, and the output end of the deoxidation tower are all provided with a temperature sensor;

[0016] The third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the first dehydration tower are respectively provided with a fourth valve, a fifth valve, a sixth valve, a seventh valve, an eighth valve, and a ninth valve; the third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the second dehydration tower are respectively provided with a tenth valve, an eleventh valve, a twelfth valve, a thirteenth valve, a fourteenth valve, and a fifteenth valve; the third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the third dehydration tower are respectively provided with a sixteenth valve, a seventeenth valve, an eighteenth valve, a nineteenth valve, a twentieth valve, and a twenty-first valve;

[0017] Define the set consisting of the fourth valve, the fifth valve, the sixth valve, the seventh valve, the eighth valve, the ninth valve, the tenth valve, the eleventh valve, the twelfth valve, the thirteenth valve, the fourteenth valve, the fifteenth valve, the sixteenth valve, the seventeenth valve, the eighteenth valve, the nineteenth valve, the twentieth valve and the twenty-first valve as the tower valve set C.

[0018] Further, the first valve, the second valve, the third valve, the fourth valve, the fifth valve, the sixth valve, the seventh valve, the eighth valve, the ninth valve, the tenth valve, the eleventh valve, the twelfth valve, the thirteenth valve, the fourteenth valve, the fifteenth valve, the sixteenth valve, the seventeenth valve, the eighteenth valve, the nineteenth valve, the twentieth valve and the twenty-first valve are all electric control valves, and are electrically connected to the external control device.

[0019] Further, it also includes a condensed water tank;

[0020] The deoxygenation separation filter and the regeneration gas separator are both provided with drainage ports, and the drainage ports of the deoxygenation separation filter and the regeneration gas separator are both connected to the input end of the condensed water tank.

[0021] Furthermore, the catalyst in the deoxygenation tower is a palladium catalyst; the first dehydration tower, the second dehydration tower and the third dehydration tower are all packed towers, and the packings of the packed towers are all molecular sieves, and the molecular sieves are used as adsorbents for absorbing moisture.

[0022] At the same time, the present invention also provides a method for autothermal hydrogen deoxygenation and dehydration purification for a hydrolysis hydrogen production process, which uses the above-mentioned autothermal hydrogen deoxygenation and dehydration purification system for a hydrolysis hydrogen production process, and its special feature is that it includes the following steps:

[0023] Step 1: The raw gas is deoxygenated and preliminarily dehydrated to remove hydroxide solution and O 2 impurities, and initially dehydrate to obtain a third intermediate gas;

[0024] Step 2: The third intermediate gas reaches the diversion point and is divided into two paths with different flow rates. The flow rate is defined as q 1 The gas in one path is the original gas, and the flow rate is q 2 The gas in one path is the first regeneration gas, q 1 >q 2 Execute step 2a and step 2b at the same time, define the state when step 2a and step 2b are executed at the same time as state I, when the execution state I is the first preset time t 1 Then, proceed to step 3;

[0025] Step 2a, the raw gas enters from the first input end pipeline of the first dehydration tower through the pressure of the adjustable ejector, flows out from the first output end pipeline thereof after being dehydrated in the first dehydration tower, and enters the post-filter. After the post-filter filters out the adsorbent dust in the raw gas, the finished gas is obtained at the output end thereof;

[0026] Step 2b, the first regenerated gas enters from the second input end pipeline of the second dehydration tower, flows out from the second output end pipeline after being dehydrated in the second dehydration tower, enters from the third input end pipeline of the third dehydration tower through the second heater and the pressure reducer in sequence, is output from the third output end pipeline after being dehydrated in the third dehydration tower, passes through the second cooler and the regenerated gas separator in sequence, and then enters from the second input end of the adjustable ejector as the original gas;

[0027] Step 3: Monitor the output temperature T of the second heater 4 and the output temperature T of the second cooler 5 , set T 4 The allowable temperature range [t 41 ,t 42 ]、T 5 The allowable temperature range [t 51 ,t 52 ], t 41 <t 42 , t 51 <t 52 ; Execute step 3a and step 3b at the same time, define the state when executing step 3a and step 3b at the same time as state II, during the execution of state II, according to T 4 and T 5 The operating power of the second heater and the second cooler is dynamically adjusted to make T 4 and T 5 Always in the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; in the fourth preset time t 4 After that, the heating power of the second heater is turned off; after running for the fifth preset time t 5 After that, the cooling power of the second cooler is turned off; when the second preset time length t of the execution state II 2 After that, execute step 4; t 4 <t 5 <t 2 ;

[0028] Step 3a, the raw gas enters from the first input end pipeline of the second dehydration tower through the pressure of the adjustable ejector, flows out from the first output end pipeline of the second dehydration tower after being dehydrated in the second dehydration tower, and enters the post-filter. After the post-filter filters out the adsorbent dust in the raw gas, the finished gas is obtained at the output end;

[0029] Step 3b, the first regeneration gas enters from the second input end pipeline of the third dehydration tower, flows out from the second output end pipeline after being dehydrated in the third dehydration tower, forms the second regeneration gas after passing through the second heater, enters the third input end pipeline of the first dehydration tower through the pressure reducer, flows out from the third output end pipeline after the adsorbent is desorbed in the first dehydration tower, enters the regeneration gas separator after being cooled in the second cooler, separates the water carried by the second regeneration gas through the regeneration gas separator, and then enters from the second input end of the adjustable ejector as the original gas;

[0030] Step 4: Execute step 4a and step 4b simultaneously. Define the state when step 4a and step 4b are executed simultaneously as state III. During the execution of state III, according to T 4 and T 5 The operating power of the second heater and the second cooler is dynamically adjusted to make T 4 and T 5 Always in the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; in the sixth preset time t 6 After that, the heating power of the second heater is turned off; after running for the seventh preset time t 7 After that, the cooling power of the second cooler is turned off; when the third preset time t is executed 3 After that, execute step 5; t 6 <t 7 <t 3 ;

[0031] Step 4a, the raw gas enters from the first input end pipeline of the third dehydration tower through the pressure of the adjustable ejector, flows out from the first output end pipeline of the third dehydration tower after being dehydrated in the third dehydration tower, and enters the post-filter. After the post-filter filters out the adsorbent dust in the raw gas, the finished gas is obtained at the output end;

[0032] Step 4b, the first regeneration gas enters from the second input end pipeline of the first dehydration tower, flows out from the second output end pipeline after being dehydrated in the first dehydration tower, forms the second regeneration gas after passing through the second heater, passes through the pressure reducer and enters the third input end pipeline of the second dehydration tower, flows out from the third output end pipeline after the adsorbent is desorbed in the second dehydration tower, reaches the second cooler for cooling, and then reaches the regeneration gas separator, the second regeneration gas separates the water it carries through the regeneration gas separator, and then enters from the second input end of the adjustable ejector as the original gas;

[0033] Step 5: Execute step 5a and step 5b simultaneously. Define the state when step 5a and step 5b are executed simultaneously as state I. During the execution of state I, according to T 4 and T 5 The operating power of the second heater and the second cooler is dynamically adjusted to make T 4 and T 5 Always in the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; in the eighth preset time t 8 After that, the heating power of the second heater is turned off; after running for the ninth preset time t 9 After that, the cooling power of the second cooler is turned off; when the first preset time t is executed 1 Then, execute step 6; 8 <t 9 <t 1 ;

[0034] Step 5a, the raw gas enters from the first input end pipeline of the first dehydration tower through the pressure of the adjustable ejector, flows out from the first output end pipeline thereof after being dehydrated in the first dehydration tower, and enters the post-filter. After the post-filter filters out the adsorbent dust in the raw gas, the finished gas is obtained at the output end thereof;

[0035] Step 5b, the first regeneration gas enters from the second input end pipeline of the second dehydration tower, flows out from the second output end pipeline after being dehydrated in the second dehydration tower, forms the second regeneration gas after passing through the second heater, enters the third input end pipeline of the third dehydration tower through the pressure reducer, flows out from the third output end pipeline after the adsorbent is desorbed in the third dehydration tower, enters the regeneration gas separator after being cooled in the second cooler, separates the water carried by the second regeneration gas through the regeneration gas separator, and then enters from the second input end of the adjustable ejector as the original gas;

[0036] Step 6: Repeat steps 3 to 5 until the supply of raw gas is stopped, and the hydrogen deoxygenation and dehydration purification is completed.

[0037] Furthermore, step 1 is specifically as follows:

[0038] Step 1.1, open the first valve with O 2 , H 2 The raw gas containing O(g) and a trace amount of hydroxide solution enters the alkali filter, and the alkali filter removes the trace amount of hydroxide solution in the raw gas to obtain a raw gas containing O(g). 2 and H 2 O(g) first intermediate gas with impurities;

[0039] Step 1.2, open the third valve and the first heater, the first intermediate gas enters the first heater through the second output end pipeline of the alkali liquid filter, and the first heater heats the first intermediate gas to a first preset temperature T 1 The first intermediate gas enters the deoxidation tower, which removes O in the first intermediate gas. 2 , get 2 The second intermediate gas containing O(g) impurities enters the second input end of the deoxidation heat recovery device; at the same time, the temperature sensor at the output end of the deoxidation tower is turned on to monitor the temperature T at the output end of the deoxidation tower. out When T out <Third preset temperature T 3 When T out ≥T 3 When , execute step 1.3;

[0040] Step 1.3, open the second valve and close the third valve, the first intermediate gas enters from the first input end of the deoxidation heat recovery device, flows out from the first output end of the deoxidation heat recovery device, and then enters the first heater, and the first heater heats the first intermediate gas to a first preset temperature T 1 When the gas flows through the deoxidation heat recovery device, the multiple heat exchange plates of the deoxidation heat recovery device transfer heat energy to the first intermediate gas; the first intermediate gas enters the deoxidation tower, and the deoxidation tower removes O in the first intermediate gas. 2 , get 2 The second intermediate gas containing O(g) impurities enters the second input end of the deoxygenation heat recovery device, and then performs step 1.4;

[0041] Step 1.4, after the second intermediate gas undergoes heat exchange in the deoxygenation heat recovery device, it flows out from the second output end of the deoxygenation heat recovery device; when flowing through the interior of the deoxygenation heat recovery device, the second intermediate gas transfers heat energy to the multiple heat exchange plates of the deoxygenation heat recovery device;

[0042] Step 1.5: Turn on the first cooler, and the second intermediate gas enters the first cooler and is cooled to the second preset temperature T 2 , and then flows into the deoxygenation separation filter, which removes H 2 O(g) undergoes preliminary dehydration to obtain a third intermediate gas.

[0043] Furthermore, the first preset temperature T 1 =100°C, the second preset temperature T 2 =30°C, the third preset temperature T 3 =140℃~160℃.

[0044] Furthermore, in step 2 and step 5, when in state I:

[0045] In the tower valve set C, the fifth valve, the eighth valve, the twelfth valve, the fifteenth valve, the sixteenth valve and the nineteenth valve are all in the open state, and the remaining valves are all in the closed state;

[0046] When in state II:

[0047] In the tower valve set C, the eleventh valve, the fourteenth valve, the eighteenth valve, the twenty-first valve, the fourth valve and the seventh valve are all in the open state, and the remaining valves are all in the closed state;

[0048] When in state III:

[0049] In the tower valve set C, the seventeenth valve, the twentieth valve, the sixth valve, the ninth valve, the tenth valve and the thirteenth valve are all in the open state, and the remaining valves are all in the closed state.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] 1. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention, the deep dehydration unit of which, according to the adsorption equilibrium theory, utilizes the difference in the adsorption capacity of gas components on solid materials and the change of adsorption capacity at different temperatures and pressures, and performs a cyclic operation of adsorption at low temperature and high pressure and desorption at high temperature and low pressure, thereby achieving H 2 deep dehydration; the device used for fluid pressurization is an adjustable ejector, and the device used for fluid decompression is a pressure reducer, which can realize desorption at elevated temperature and desorption at low pressure at the same time, and can maximize the adsorption and desorption efficiency of the three dehydration towers, reducing the desorption time by more than 20%; at the same time, the adjustable ejector can automatically adjust the ejection coefficient according to the pressure after decompression and the pipeline resistance loss, to ensure that the regenerated gas can return to the system.

[0052] 2. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention has a deep dehydration unit that adopts a first dehydration tower, a second dehydration tower and a third dehydration tower, which can perform adsorption, pre-adsorption and desorption operations simultaneously. During stable operation, if the first dehydration tower is performing adsorption work, then the second dehydration tower is performing pre-adsorption (also called blowing cold) work, and the third dehydration tower is performing desorption work. After running for a certain period of time, the work is rotated, and the system has high operating efficiency.

[0053] 3. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention is provided with a condensed water tank, which can meet the drainage volume for several hours under the maximum load conditions and ensure the timely removal of the condensed water generated by the regeneration gas separator and the deoxygenation separation filter.

[0054] 4. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention has an alkali liquid filter at the front stage of the deoxygenation and preliminary dehydration unit to protect the deoxygenation catalyst in the rear stage deoxygenation tower as much as possible and avoid the reduction of its activity to a certain extent.

[0055] 5. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention is provided with a deoxygenation heat recovery device in the deoxygenation and preliminary dehydration unit. The path of the first intermediate gas after dealkalization is determined according to the output end temperature of the deoxygenation tower. At the beginning, the first intermediate gas directly enters the heater for direct heating. When the output end temperature of the deoxygenation tower is high enough, the second intermediate gas can be used to preheat the first intermediate gas, and then the first intermediate gas enters the heater for heating. In this way, the heat generated in the reaction process can be fully utilized, the electric power of the heater can be reduced, the energy consumption can be reduced, the heat self-sustaining in the deoxygenation catalytic process can be realized, and the system structure is simple.

[0056] 6. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention can save more than 30% of heat and more than 20% of circulating water in its deoxygenation and preliminary dehydration units. At the same time, the deoxygenation tower and the heater are independently set up, which can greatly reduce the structural complexity of the tower and effectively solve the problems of local overheating, uneven heat transfer, multiple fault points and high energy consumption in the tower.

[0057] 7. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention has a deoxygenation heat recovery device in the deoxygenation and preliminary dehydration unit as a plate heat exchanger with high heat exchange efficiency and small footprint.

[0058] 8. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention has the temperature sensor, the second valve and the third valve in the deoxygenation and preliminary dehydration units electrically connected to the control module, and the second valve and the third valve are both electric control valves. The automatic control method is adopted, which can save manpower and greatly reduce the difficulty of operation.

[0059] 9. The self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention has a palladium catalyst in the deoxygenation tower of the deoxygenation and preliminary dehydration unit, which has the advantages of low activation temperature and long service life.

[0060] 10. In the self-heating hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention, the power of the second heater and the second cooler in the deep dehydration unit can be dynamically adjusted to save energy consumption.

[0061] 11. The autothermal hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process provided by the present invention can produce finished gas that meets the quality requirements of 5N or above in (GB / T3634.2-2011) "Hydrogen Part 2: Pure Hydrogen, High-Purity Hydrogen and Ultrapure Hydrogen". BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 It is a structural schematic diagram of an embodiment of a self-heating hydrogen deoxygenation and dehydration purification system for a hydrolysis hydrogen production process according to the present invention;

[0063] Figure 2 1 is a fluid flow diagram of the deep dehydration unit at state I of step 5 of an embodiment of the autothermal hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process of the present invention, wherein the blue arrow represents the flow direction of the original gas, the orange arrow represents the flow direction of the first regenerated gas, and the red arrow represents the flow direction of the second regenerated gas;

[0064] Description of reference numerals:

[0065] A-deoxygenation and preliminary dehydration unit; B-dehydration unit; 11-raw gas, 12-finished gas; 2-alkali solution filter; 3-deoxygenation heat recovery device; 41-first heater, 42-second heater; 5-deoxygenation tower; 61-first cooler, 62-second cooler; 7-deoxygenation separation filter; 8-condensate tank; 9-regeneration gas separator; 91-first valve, 92-second valve, 93-third valve, 161-fourth valve, 162-fifth valve, 163-sixth valve, 164-seventh valve, 165-eighth valve, 1 66-the ninth valve, 171-the tenth valve, 172-the eleventh valve, 173-the twelfth valve, 174-the thirteenth valve, 175-the fourteenth valve, 176-the fifteenth valve, 181-the sixteenth valve, 182-the seventeenth valve, 183-the eighteenth valve, 184-the nineteenth valve, 185-the twentieth valve, 186-the twenty-first valve; 10-adjustable ejector; 131-the first dehydration tower, 132-the second dehydration tower, 133-the third dehydration tower; 14-pressure reducer; 15-post-filter; 16-diversion point. DETAILED DESCRIPTION

[0066] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0067] See also Figure 1 A self-heating hydrogen deoxygenation and dehydration purification system for a hydrolysis hydrogen production process, comprising a deoxygenation and preliminary dehydration unit A connected to a raw gas input pipeline at an input end, and a deep dehydration unit B and a condensed water tank 8 connected to an output end of the deoxygenation and preliminary dehydration unit A; the deoxygenation and preliminary dehydration unit A is used to remove hydroxide solution and O in the raw gas 11. 2impurities, and perform preliminary dehydration to obtain a third intermediate gas; the deep dehydration unit B is used to perform deep dehydration on the third intermediate gas to obtain a finished gas 12;

[0068] The deep dehydration unit B includes a second heater 42, a second cooler 62, a regeneration gas separator 9, an adjustable ejector 10, a first dehydration tower 131, a second dehydration tower 132, a third dehydration tower 133, a pressure reducer 14 and a post-filter 15;

[0069] The first dehydration tower 131, the second dehydration tower 132 and the third dehydration tower 133 are provided with three input end pipelines and three output end pipelines respectively; the first dehydration tower 131, the second dehydration tower 132 and the third dehydration tower 133 are all provided with an adsorbent for adsorbing water;

[0070] The output pipeline of the deoxygenation and preliminary dehydration unit A is provided with a diversion point 16, and a control valve is provided on the diversion point 16 to divide the output pipeline into two paths with different flow rates. The flow rate is q 1 One of the channels is connected to the first input end of the adjustable ejector 10, and the flow rate is q 2 The other route is divided into three routes, which are respectively connected to the first input end pipeline of each dehydration tower, q 1 >q 2 ; The second input end of the adjustable ejector 10 is connected to the output end pipeline of the regeneration gas separator 9; the output end of the adjustable ejector 10 is divided into three paths, which are respectively connected to the second input end pipeline of each dehydration tower; the first output end pipeline of each dehydration tower is connected to the input end of the post-filter 15, and the second output end pipeline of each dehydration tower is connected to the input end of the second heater 42; the output end of the post-filter 15 is connected to the finished gas output pipeline, and the finished gas output pipeline is used to output the obtained finished gas 12; the output end of the second heater 42 is connected to the input end of the pressure reducer 14, and the output end of the pressure reducer 14 is divided into three paths, which are respectively connected to the third input end pipeline of each dehydration tower; the third output end pipeline of each dehydration tower is connected to the input end of the second cooler 62; the output end pipeline of the second cooler 62 is connected to the input end of the regeneration gas separator 9;

[0071] The first dehydration tower 131, the second dehydration tower 132 and the third dehydration tower 133 are used to adsorb moisture in the fluid, the pressure reducer 14 is used to reduce the fluid pressure, and the adjustable ejector 10 is used to increase the fluid pressure; the post-filter 15 is used to filter out the adsorbent dust entrained in the fluid; the regeneration gas separator 9 is used to separate the moisture in the regeneration gas.

[0072] The deoxidation and preliminary dehydration unit A comprises an alkali solution filter 2 for removing impurities from the hydroxide solution, a deoxidation heat recovery device 3, a first heater 41, and a deoxidation and preliminary dehydration unit 42. 2The deoxidation tower 5 for impurities, the first cooler 6 and the deoxidation separation filter 7 for preliminary dehydration; wherein the deoxidation heat recovery device 3 includes two sets of input ends and output ends;

[0073] The input end of the alkali liquid filter 2 is connected to the raw gas input pipeline, and the output end pipeline is divided into two paths, wherein the first output end pipeline is connected to the first input end of the deoxygenation heat recovery device 3, and the second output end pipeline is connected to the input end of the first heater 41, and the raw gas input pipeline is used to input the raw gas 11 to be decontaminated; the output end pipeline of the first heater 41 is connected to the input end of the deoxygenation tower 5, and the output end pipeline of the deoxygenation tower 5 is connected to the second input end of the deoxygenation heat recovery device 3; the first output end pipeline of the deoxygenation heat recovery device 3 is connected to the input end of the first heater 41, and the second output end pipeline of the deoxygenation heat recovery device 3 is connected to the input end of the first cooler 6, and the output end pipeline of the first cooler 6 is connected to the input end of the deoxygenation separation filter 7, and the output end of the deoxygenation separation filter 7 is used to output the obtained third intermediate gas;

[0074] The deoxygenation heat recovery device 3 of this embodiment adopts a plate heat exchanger including two sets of input ends and output ends. The plate heat exchanger can actually also be a shell and tube heat exchanger. The hydroxide solution removed is usually in the form of droplets. A filter element is provided in the alkali liquid filter 2. The special coalescing material of the filter element will coalesce and separate the trace hydroxide aqueous solution droplets that may exist in the raw gas 11, and protect the catalyst in the later stage as much as possible.

[0075] A first valve 91 is provided on the raw gas input pipeline; a second valve 92 is provided on the first output end pipeline, and a third valve 93 is provided on the second output end pipeline.

[0076] The first heater 41, the second heater 42, the first cooler 62, the second cooler 62, and the output end of the deoxidation tower 5 are all provided with temperature sensors;

[0077] The fourth valve 161, the fifth valve 162, the sixth valve 163, the seventh valve 164, the eighth valve 165, and the ninth valve 166 are respectively arranged on the third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the first dehydration tower 131; the tenth valve 171, the eleventh valve 172, the twelfth valve 173, the thirteenth valve 174, the fourteenth valve 175, and the fifteenth valve 176 are respectively arranged on the third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the second dehydration tower 132; the sixteenth valve 181, the seventeenth valve 182, the eighteenth valve 183, the nineteenth valve 184, the twentieth valve 185, and the twenty-first valve 186 are respectively arranged on the third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the third dehydration tower 133;

[0078] Define the set consisting of the fourth valve 161, the fifth valve 162, the sixth valve 163, the seventh valve 164, the eighth valve 165, the ninth valve 166, the tenth valve 171, the eleventh valve 172, the twelfth valve 173, the thirteenth valve 174, the fourteenth valve 175, the fifteenth valve 176, the sixteenth valve 181, the seventeenth valve 182, the eighteenth valve 183, the nineteenth valve 184, the twentieth valve 185 and the twenty-first valve 186 as the tower valve set C.

[0079] The first valve 91, the second valve 92, the third valve 93, the fourth valve 161, the fifth valve 162, the sixth valve 163, the seventh valve 164, the eighth valve 165, the ninth valve 166, the tenth valve 171, the eleventh valve 172, the twelfth valve 173, the thirteenth valve 174, the fourteenth valve 175, the fifteenth valve 176, the sixteenth valve 181, the seventeenth valve 182, the eighteenth valve 183, the nineteenth valve 184, the twentieth valve 185 and the twenty-first valve 186 are all electric control valves, which are electrically connected to the external control device.

[0080] The deoxygenation heat recovery device 3 is a plate heat exchanger including two sets of input ends and output ends; the deoxygenation separation filter 7 and the regeneration gas separator 9 are both provided with drainage ports, and the drainage ports of the deoxygenation separation filter 7 and the regeneration gas separator 9 are both connected to the input end of the condensed water tank 8.

[0081] The catalyst in the deoxidation tower 5 is a palladium catalyst; the first dehydration tower 131, the second dehydration tower 132 and the third dehydration tower 133 are all packed towers, and the packings of the packed towers are all molecular sieves, which are used as adsorbents for absorbing moisture. The reaction occurring in the deoxidation tower 5 is: A small amount of O 2 Under the catalytic action of the catalyst, H 2 The reaction generates H 2 O, the catalyst can be a palladium catalyst, which has the advantages of low activation temperature and long service life. In the actual application scenario, the design pressure of the condensate tank 8 is designed according to the maximum load pressure of the entire system. The condensate tank is equipped with a safety valve and a flame arrester to ensure that it will not operate at overpressure. The condensate tank is also equipped with a liquid level transmitter, an automatic drain valve and a condensate drain pump to ensure the timely discharge of cooling water.

[0082] At the same time, this embodiment also provides a method for autothermal hydrogen deoxygenation and dehydration purification for a hydrolysis hydrogen production process, using the above-mentioned autothermal hydrogen deoxygenation and dehydration purification system for a hydrolysis hydrogen production process, comprising the following steps:

[0083] Step 1.1, open the first valve 91, with O 2 , H2 The raw gas 11 containing O(g) and a trace amount of hydroxide solution enters the alkali filter 2, and the alkali filter 2 removes the trace amount of hydroxide solution in the raw gas 11 to obtain a raw gas containing O(g) and a trace amount of hydroxide solution. 2 and H 2 O(g) first intermediate gas with impurities;

[0084] Step 1.2, open the third valve 93 and the first heater 41, the first intermediate gas enters the first heater 41 through the second output end pipeline of the alkali liquid filter 2, and the first heater 41 heats the first intermediate gas to a first preset temperature T 1 =100°C; the first intermediate gas enters the deoxidation tower 5, which removes O in the first intermediate gas 2 , get 2 The second intermediate gas containing O(g) impurities enters the second input end of the deoxidation heat recovery device 3; at the same time, the temperature sensor at the output end of the deoxidation tower 5 is turned on to monitor the temperature T at the output end of the deoxidation tower 5. out When T out <Third preset temperature T 3 When T out ≥T 3 When T 3 =140℃~160℃;

[0085] Step 1.3, open the second valve 92 and close the third valve 93, the first intermediate gas enters from the first input end of the deoxidation heat recovery device 3, flows out from the first output end of the deoxidation heat recovery device 3, and then enters the first heater 41, and the first heater 41 heats the first intermediate gas to the first preset temperature T 1 When the gas flows through the deoxidation heat recovery device 3, the multiple heat exchange plates of the deoxidation heat recovery device 3 transfer heat energy to the first intermediate gas; the first intermediate gas enters the deoxidation tower 5, and the deoxidation tower 5 removes O in the first intermediate gas. 2 , get 2 The second intermediate gas containing O(g) impurities enters the second input end of the deoxygenation heat recovery device 3, and then performs step 1.4;

[0086] Step 1.4, after the second intermediate gas is heat exchanged in the deoxygenation heat recovery device 3, it flows out from the second output end of the deoxygenation heat recovery device 3; when flowing through the interior of the deoxygenation heat recovery device 3, the second intermediate gas transfers heat energy to the multiple heat exchange plates of the deoxygenation heat recovery device 3;

[0087] Step 1.5: Turn on the first cooler 61, and the second intermediate gas enters the first cooler 61 and is cooled to the second preset temperature T 2=30°C, and then flows into the deoxygenation separation filter 7, which removes H in the second intermediate gas. 2 O(g) undergoes preliminary dehydration to obtain a third intermediate gas;

[0088] Step 2: The third intermediate gas reaches the diversion point 16 and is divided into two paths with different flow rates, and the flow rate is defined as q 1 The gas in one path is the original gas, and the flow rate is q 2 The gas in one path is the first regeneration gas, q 1 >q 2 Execute step 2a and step 2b at the same time, define the state when step 2a and step 2b are executed at the same time as state I, when the execution state I is the first preset time t 1 Then, proceed to step 3;

[0089] Step 2a, the raw gas enters from the first input end pipeline of the first dehydration tower 131 through the pressure of the adjustable ejector 10, flows out from the first output end pipeline of the first dehydration tower 131 after being dehydrated, and enters the post-filter 15. After the post-filter 15 filters out the adsorbent dust in the raw gas, the finished gas 12 is obtained at its output end;

[0090] Step 2b, the first regenerated gas enters from the second input end pipeline of the second dehydration tower 132, flows out from the second output end pipeline thereof after being dehydrated in the second dehydration tower 132, passes through the second heater 42 and the pressure reducer 14 in sequence to enter the third input end pipeline of the third dehydration tower 133, is dehydrated in the third dehydration tower 133 and is output from the third output end pipeline thereof, passes through the second cooler 62 and the regenerated gas separator 9 in sequence, and then enters from the second input end of the adjustable ejector 10 as the original gas;

[0091] Step 3: Monitor the output temperature T of the second heater 42 4 and the output temperature T of the second cooler 62 5 , set T 4 The allowable temperature range [t 41 ,t 42 ]、T 5 The allowable temperature range [t 51 ,t 52 ], t 41 <t 42 , t 51 <t 52 ; Execute step 3a and step 3b at the same time, define the state when executing step 3a and step 3b at the same time as state II, during the execution of state II, according to T 4 and T 5 The operating power of the second heater 42 and the second cooler 62 is dynamically adjusted so that T 4 and T 5Always in the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; in the fourth preset time t 4 After that, the heating power of the second heater 42 is turned off; during the fifth preset time t 5 After that, the cooling power of the second cooler 62 is turned off; when the second preset time length t of the execution state II 2 After that, execute step 4; t 4 <t 5 <t 2 ;

[0092] Step 3a, the raw gas enters from the first input end pipeline of the second dehydration tower 132 after being pressurized by the adjustable ejector 10, flows out from the first output end pipeline of the second dehydration tower 132 after being dehydrated, and enters the post-filter 15. After the post-filter 15 filters out the adsorbent dust in the raw gas, the finished gas 12 is obtained at its output end;

[0093] Step 3b, the first regeneration gas enters from the second input end pipeline of the third dehydration tower 133, flows out from the second output end pipeline thereof after being dehydrated in the third dehydration tower 133, forms the second regeneration gas after passing through the second heater 42, enters the third input end pipeline of the first dehydration tower 131 through the pressure reducer 14, flows out from the third output end pipeline thereof after the adsorbent is desorbed in the first dehydration tower 131, reaches the second cooler 62 for cooling, and then enters the regeneration gas separator 9, the moisture carried by the second regeneration gas is separated by the regeneration gas separator 9, and then enters from the second input end of the adjustable ejector 10 as the original gas;

[0094] Step 4: Execute step 4a and step 4b simultaneously. Define the state when step 4a and step 4b are executed simultaneously as state III. During the execution of state III, according to T 4 and T 5 The operating power of the second heater 42 and the second cooler 62 is dynamically adjusted so that T 4 and T 5 Always in the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; in the sixth preset time t 6 After that, the heating power of the second heater 42 is turned off; after running for the seventh preset time t 7 After that, the cooling power of the second cooler 62 is turned off; when the third preset time t is executed 3 After that, execute step 5; t 6 <t 7 <t 3;

[0095] Step 4a, the raw gas enters from the first input end pipeline of the third dehydration tower 133 after being pressurized by the adjustable ejector 10, flows out from the first output end pipeline of the third dehydration tower 133 after being dehydrated, and enters the post-filter 15. After the post-filter 15 filters out the adsorbent dust in the raw gas, the finished gas 12 is obtained at its output end;

[0096] Step 4b, the first regeneration gas enters from the second input end pipeline of the first dehydration tower 131, flows out from the second output end pipeline thereof after being dehydrated in the first dehydration tower 131, forms the second regeneration gas after passing through the second heater 42, passes through the pressure reducer 14 and enters the third input end pipeline of the second dehydration tower 132, flows out from the third output end pipeline thereof after the adsorbent is desorbed in the second dehydration tower 132, reaches the second cooler 62 for cooling, and then reaches the regeneration gas separator 9, the moisture carried by the second regeneration gas is separated by the regeneration gas separator 9, and then enters from the second input end of the adjustable ejector 10 as the original gas;

[0097] Step 5: Execute step 5a and step 5b simultaneously. Define the state when step 5a and step 5b are executed simultaneously as state I. Figure 2 , in the process of executing state I, according to T 4 and T 5 The operating power of the second heater 42 and the second cooler 62 is dynamically adjusted so that T 4 and T 5 Always in the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; in the eighth preset time t 8 After that, the heating power of the second heater 42 is turned off; after running for the ninth preset time t 9 After that, the cooling power of the second cooler 62 is turned off; when the first preset time t is executed 1 Then, execute step 6; 8 <t 9 <t 1 ;

[0098] Step 5a, the raw gas enters from the first input end pipeline of the first dehydration tower 131 after being pressurized by the adjustable ejector 10, flows out from the first output end pipeline thereof after being dehydrated in the first dehydration tower 131, and enters the post-filter 15. After the post-filter 15 filters out the adsorbent dust in the raw gas, the finished gas 12 is obtained at its output end;

[0099] Step 5b, the first regeneration gas enters from the second input end pipeline of the second dehydration tower 132, flows out from the second output end pipeline thereof after being dehydrated in the second dehydration tower 132, forms the second regeneration gas after passing through the second heater 42, enters the third input end pipeline of the third dehydration tower 133 through the pressure reducer 14, flows out from the third output end pipeline thereof after the adsorbent is desorbed in the third dehydration tower 133, reaches the second cooler 62 for cooling, and then enters the regeneration gas separator 9, the moisture carried by the second regeneration gas is separated by the regeneration gas separator 9, and then enters from the second input end of the adjustable ejector 10 as the original gas;

[0100] Step 6: Repeat steps 3 to 5 until the supply of the raw gas 11 is stopped, and the hydrogen deoxygenation and dehydration purification is completed.

[0101] In step 2 and step 5, when in state I:

[0102] In the tower valve set C, the fifth valve 162, the eighth valve 165, the twelfth valve 173, the fifteenth valve 176, the sixteenth valve 181 and the nineteenth valve 184 are all in the open state, and the remaining valves are all in the closed state;

[0103] When in state II:

[0104] In the tower valve set C, the eleventh valve 172, the fourteenth valve 175, the eighteenth valve 183, the twenty-first valve 186, the fourth valve 161 and the seventh valve 164 are all in the open state, and the remaining valves are all in the closed state;

[0105] When in state III:

[0106] In the tower valve set C, the seventeenth valve 182, the twentieth valve 185, the sixth valve 163, the ninth valve 166, the tenth valve 171 and the thirteenth valve 174 are all in the open state, and the remaining valves are all in the closed state.

[0107] The following table provides a clear description of the working status of each dehydration tower in steps 3 to 5:

[0108] Table 1 Working status of each dehydration tower in steps 3 to 5

[0109]

[0110] It should be noted that in actual application scenarios, the switch states of the first valve 91, the second valve 92, the third valve 93, the fourth valve 161, the fifth valve 162, the sixth valve 163, the seventh valve 164, the eighth valve 165, the ninth valve 166, the tenth valve 171, the eleventh valve 172, the twelfth valve 173, the thirteenth valve 174, the fourteenth valve 175, the fifteenth valve 176, the sixteenth valve 181, the seventeenth valve 182, the eighteenth valve 183, the nineteenth valve 184, the twentieth valve 185 and the twenty-first valve 186, as well as the start and stop of the first heater 41, the second heater 42, the first cooler 62 and the second cooler 62 can all be controlled manually or automatically, and there are many scenarios for automatic control, which saves manpower. If manual control is adopted, a control cabinet connected to the external control device can also be added, on which a liquid crystal screen is provided for the operator to input instructions.

[0111] When T out ≥T 3 The operating power of the post-heater 4 is greatly reduced and is basically in a shutdown state. The heating task of the first intermediate gas is largely completed by the heat energy transferred by multiple heat exchange plates, which saves the energy consumption of the heater 4 and realizes "self-heating". After the raw gas passes through the deoxidation and preliminary dehydration unit of this embodiment, H 2 Hydroxide solution and O 2 Removal of impurities and H 2 The removal of O(g) can meet the H requirements of most application scenarios. 2 Purity requirements, after passing through the deep dehydration unit, can meet the quality requirements of 5N or above in (GB / T3634.2-2011) "Hydrogen Part 2: Pure Hydrogen, High-Purity Hydrogen and Ultra-Pure Hydrogen".

Claims

1. An autothermal hydrogen deoxygenation and dehydration purification system for a hydrolysis hydrogen production process, characterized in that: It comprises a deoxygenation and preliminary dehydration unit (A) whose input end is connected to a raw gas input pipeline, and a deep dehydration unit (B) connected to the output end of the deoxygenation and preliminary dehydration unit (A); the deoxygenation and preliminary dehydration unit (A) is used to remove hydroxide solution and O2 impurities in the raw gas (11), and perform preliminary dehydration to obtain a third intermediate gas; the deep dehydration unit (B) is used to perform deep dehydration on the third intermediate gas to obtain a finished gas (12); The deep dehydration unit (B) comprises a second heater (42), a second cooler (62), a regeneration gas separator (9), an adjustable ejector (10), a first dehydration tower (131), a second dehydration tower (132), a third dehydration tower (133), a pressure reducer (14) and a post-filter (15); The first dehydration tower (131), the second dehydration tower (132) and the third dehydration tower (133) are respectively provided with three input end pipelines and three output end pipelines; the first dehydration tower (131), the second dehydration tower (132) and the third dehydration tower (133) are all provided with an adsorbent for adsorbing water; The output pipeline of the deoxygenation and preliminary dehydration unit (A) is provided with a branch point (16), and a control valve is arranged on the branch point (16) to divide the output pipeline into two paths with different flow rates, one path with a flow rate of q1 is connected to the first input end of the adjustable ejector (10), and the other path with a flow rate of q2 is divided into three paths, which are respectively connected to the first input end pipeline of each dehydration tower, q1>q2; the second input end of the adjustable ejector (10) is connected to the output end pipeline of the regeneration gas separator (9); the output end of the adjustable ejector (10) is divided into three paths, which are respectively connected to the second input end pipeline of each dehydration tower; the first output end pipeline of each dehydration tower is connected to the rear The input end of the filter (15) is connected, and the second output end pipeline of each dehydration tower is connected to the input end of the second heater (42); the output end of the post-filter (15) is connected to the finished gas output pipeline, and the finished gas output pipeline is used to output the obtained finished gas (12); the output end of the second heater (42) is connected to the input end of the pressure reducer (14), and the output end of the pressure reducer (14) is divided into three paths, which are respectively connected to the third input end pipeline of each dehydration tower; the third output end pipeline of each dehydration tower is connected to the input end of the second cooler (62); the output end pipeline of the second cooler (62) is connected to the input end of the regeneration gas separator (9); The first dehydration tower (131), the second dehydration tower (132) and the third dehydration tower (133) are used to adsorb moisture in the fluid, the pressure reducer (14) is used to reduce the fluid pressure, and the adjustable ejector (10) is used to increase the fluid pressure; the post-filter (15) is used to filter out adsorbent dust entrained in the fluid; and the regeneration gas separator (9) is used to separate moisture in the regeneration gas.

2. The autothermal hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process according to claim 1, characterized in that: The deoxygenation and preliminary dehydration unit (A) comprises an alkali solution filter (2) for removing impurities of the hydroxide solution, a deoxygenation heat recovery device (3), a first heater (41), a deoxygenation tower (5) for removing O2 impurities, a first cooler (61) and a deoxygenation separation filter (7) for preliminary dehydration; wherein the deoxygenation heat recovery device (3) comprises two sets of input ends and two sets of output ends; The input end of the alkali liquid filter (2) is connected to the raw gas input pipeline, and the output end pipeline is divided into two paths, wherein the first output end pipeline is connected to the first input end of the deoxygenation heat recovery device (3), and the second output end pipeline is connected to the input end of the first heater (41). The raw gas input pipeline is used to input the raw gas (11) to be decontaminated; the output end pipeline of the first heater (41) is connected to the input end of the deoxygenation tower (5), and the output end pipeline of the deoxygenation tower (5) is connected to the second input end of the deoxygenation heat recovery device (3); the first output end pipeline of the deoxygenation heat recovery device (3) is connected to the input end of the first heater (41), and the second output end pipeline of the deoxygenation heat recovery device (3) is connected to the input end of the first cooler (61); the output end pipeline of the first cooler (61) is connected to the input end of the deoxygenation separation filter (7), and the output end pipeline of the deoxygenation separation filter (7) serves as the output end pipeline of the deoxygenation and preliminary dehydration unit (A) for outputting the third intermediate gas; A first valve (91) is arranged on the raw gas input pipeline; a second valve (92) is arranged on the first output end pipeline of the alkali liquid filter (2), and a third valve (93) is arranged on the second output end pipeline.

3. The autothermal hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process according to claim 2, characterized in that: The output ends of the first heater (41), the second heater (42), the first cooler (61), the second cooler (62), and the deoxidation tower (5) are all provided with temperature sensors; A fourth valve (161), a fifth valve (162), a sixth valve (163), a seventh valve (164), an eighth valve (165), and a ninth valve (166) are respectively disposed on the third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the first dehydration tower (131); and a tenth valve (171) is respectively disposed on the third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the second dehydration tower (132). , an eleventh valve (172), a twelfth valve (173), a thirteenth valve (174), a fourteenth valve (175), and a fifteenth valve (176); a sixteenth valve (181), a seventeenth valve (182), an eighteenth valve (183), a nineteenth valve (184), a twentieth valve (185), and a twenty-first valve (186) are respectively arranged on the third output end, the second input end, the first input end, the third input end, the first output end, and the second output end of the third dehydration tower (133); The set consisting of the fourth valve (161), the fifth valve (162), the sixth valve (163), the seventh valve (164), the eighth valve (165), the ninth valve (166), the tenth valve (171), the eleventh valve (172), the twelfth valve (173), the thirteenth valve (174), the fourteenth valve (175), the fifteenth valve (176), the sixteenth valve (181), the seventeenth valve (182), the eighteenth valve (183), the nineteenth valve (184), the twentieth valve (185) and the twenty-first valve (186) is defined as the tower valve set C.

4. The autothermal hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process according to claim 3, characterized in that: The first valve (91), the second valve (92), the third valve (93), the fourth valve (161), the fifth valve (162), the sixth valve (163), the seventh valve (164), the eighth valve (165), the ninth valve (166), the tenth valve (171), the eleventh valve (172), the twelfth valve (173), the thirteenth valve (174), the fourteenth valve (175), the fifteenth valve (176), the sixteenth valve (181), the seventeenth valve (182), the eighteenth valve (183), the nineteenth valve (184), the twentieth valve (185) and the twenty-first valve (186) are all electrically controlled valves and are electrically connected to an external control device.

5. The autothermal hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process according to any one of claims 2 to 4, characterized in that: Also includes a condensate tank (8); The deoxygenation separation filter (7) and the regeneration gas separator (9) are both provided with drainage ports, and the drainage ports of the deoxygenation separation filter (7) and the regeneration gas separator (9) are both connected to the input end of the condensed water tank (8).

6. The autothermal hydrogen deoxygenation and dehydration purification system for the hydrolysis hydrogen production process according to claim 5, characterized in that: The catalyst in the deoxygenation tower (5) is a palladium catalyst; the first dehydration tower (131), the second dehydration tower (132) and the third dehydration tower (133) are all packed towers, and the packings of the packed towers are all molecular sieves, which serve as adsorbents for absorbing moisture.

7. A method for the purification of autothermal hydrogen deoxygenation and dehydration for the process of producing hydrogen by hydrolysis, using the autothermal hydrogen deoxygenation and dehydration purification system for the process of producing hydrogen by hydrolysis according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1, the raw gas (11) is subjected to a deoxygenation and preliminary dehydration unit (A) to remove hydroxide solution and O2 impurities, and is preliminarily dehydrated to obtain a third intermediate gas; Step 2, the third intermediate gas reaches the diversion point (16) and is divided into two paths with different flow rates, the gas path with a flow rate of q1 is defined as the original gas, and the gas path with a flow rate of q2 is defined as the first regeneration gas, q1>q2; step 2a and step 2b are performed simultaneously, and the state when step 2a and step 2b are performed simultaneously is defined as state I, and after the first preset time t1 of state I is performed, step 3 is performed; Step 2a, the raw gas is pressurized by the adjustable ejector (10) and enters the first input end pipeline of the first dehydration tower (131), and after being dehydrated in the first dehydration tower (131), it flows out from the first output end pipeline thereof and enters the post-filter (15). After the post-filter (15) filters out the adsorbent dust in the raw gas, the finished gas (12) is obtained at its output end; Step 2b, the first regenerated gas enters from the second input end pipeline of the second dehydration tower (132), is dehydrated in the second dehydration tower (132), flows out from the second output end pipeline thereof, passes through the second heater (42) and the pressure reducer (14) in sequence, enters the third input end pipeline of the third dehydration tower (133), is dehydrated in the third dehydration tower (133), is output from the third output end pipeline thereof, passes through the second cooler (62) and the regenerated gas separator (9) in sequence, and then enters from the second input end of the adjustable ejector (10) as the original gas; Step 3: Monitor the output temperature T4 of the second heater (42) and the output temperature T5 of the second cooler (62), and set the allowable temperature range of T4 [t 41 ,t 42 ]、T5 allowable temperature range [t 51 ,t 52 ], t 41 <t 42 , t 51 <t 52 ; Execute step 3a and step 3b simultaneously, define the state when executing step 3a and step 3b simultaneously as state II, and in the process of executing state II, dynamically adjust the operating power of the second heater (42) and the second cooler (62) according to the temperature values ​​of T4 and T5, so that T4 and T5 are always in the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; after running the fourth preset time t4, turn off the heating power of the second heater (42); after running the fifth preset time t5, turn off the cooling power of the second cooler (62); when the execution state II second preset time t2, execute step 4; t4 <t5<t2; Step 3a, the raw gas is pressurized by the adjustable ejector (10) and enters the first input end pipeline of the second dehydration tower (132), and after being dehydrated in the second dehydration tower (132), it flows out from the first output end pipeline thereof and enters the post-filter (15). After the post-filter (15) filters out the adsorbent dust in the raw gas, the finished gas (12) is obtained at its output end; Step 3b, the first regeneration gas enters from the second input end pipeline of the third dehydration tower (133), is dehydrated in the third dehydration tower (133), and flows out from the second output end pipeline thereof, passes through the second heater (42) to form the second regeneration gas, the second regeneration gas passes through the pressure reducer (14) and enters the third input end pipeline of the first dehydration tower (131), desorbs the adsorbent in the first dehydration tower (131), flows out from the third output end pipeline thereof, reaches the second cooler (62) for cooling, and then enters the regeneration gas separator (9), the moisture carried by the second regeneration gas is separated by the regeneration gas separator (9), and then enters from the second input end of the adjustable ejector (10) as the original gas; Step 4: Execute step 4a and step 4b simultaneously, define the state when step 4a and step 4b are executed simultaneously as state III, and in the process of executing state III, dynamically adjust the operating power of the second heater (42) and the second cooler (62) according to the temperature values ​​of T4 and T5, so that T4 and T5 are always within the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; after running the sixth preset time t6, turn off the heating power of the second heater (42); after running the seventh preset time t7, turn off the cooling power of the second cooler (62); after executing the third preset time t3, execute step 5; t6 <t7<t3; Step 4a, the raw gas is pressurized by the adjustable ejector (10) and enters the first input end pipeline of the third dehydration tower (133), and after being dehydrated in the third dehydration tower (133), it flows out from the first output end pipeline thereof and enters the post-filter (15). After the post-filter (15) filters out the adsorbent dust in the raw gas, the finished gas (12) is obtained at its output end; Step 4b, the first regeneration gas enters from the second input end pipeline of the first dehydration tower (131), is dehydrated in the first dehydration tower (131), and flows out from the second output end pipeline thereof, passes through the second heater (42) to form the second regeneration gas, the second regeneration gas passes through the pressure reducer (14) and enters the third input end pipeline of the second dehydration tower (132), desorbs the adsorbent in the second dehydration tower (132), flows out from the third output end pipeline thereof, reaches the second cooler (62) for cooling, and then reaches the regeneration gas separator (9), the moisture carried by the second regeneration gas is separated by the regeneration gas separator (9), and then enters from the second input end of the adjustable ejector (10) as the original gas; Step 5: Execute step 5a and step 5b simultaneously, define the state when step 5a and step 5b are executed simultaneously as state I, and in the process of executing state I, dynamically adjust the operating power of the second heater (42) and the second cooler (62) according to the temperature values ​​of T4 and T5, so that T4 and T5 are always within the interval [t 41 ,t 42 ] and the interval [t 51 ,t 52 ]; after running the eighth preset time t8, turn off the heating power of the second heater (42); after running the ninth preset time t9, turn off the cooling power of the second cooler (62); after executing the first preset time t1, execute step 6; t8 <t9<t1; Step 5a, the raw gas is pressurized by the adjustable ejector (10) and enters the first input end pipeline of the first dehydration tower (131), and after being dehydrated in the first dehydration tower (131), it flows out from the first output end pipeline thereof and enters the post-filter (15). After the post-filter (15) filters out the adsorbent dust in the raw gas, the finished gas (12) is obtained at its output end; Step 5b, the first regeneration gas enters from the second input end pipeline of the second dehydration tower (132), is dehydrated in the second dehydration tower (132), and flows out from the second output end pipeline thereof, passes through the second heater (42) to form the second regeneration gas, the second regeneration gas passes through the pressure reducer (14) and enters the third input end pipeline of the third dehydration tower (133), desorbs the adsorbent in the third dehydration tower (133), flows out from the third output end pipeline thereof, reaches the second cooler (62) for cooling, and then enters the regeneration gas separator (9), the moisture carried by the second regeneration gas is separated by the regeneration gas separator (9), and then enters from the second input end of the adjustable ejector (10) as the original gas; Step 6: Repeat steps 3 to 5 until the supply of the raw gas (11) is stopped, and the hydrogen deoxygenation and dehydration purification is completed.

8. The method for autothermal hydrogen deoxygenation and dehydration purification for hydrogen production by hydrolysis according to claim 7, characterized in that: Step 1 is as follows: Step 1.1, opening the first valve (91), the raw gas (11) containing O2, H2O(g) and a trace amount of hydroxide solution enters the alkali solution filter (2), the alkali solution filter (2) removes the trace amount of hydroxide solution in the raw gas (11), and obtains the first intermediate gas containing O2 and H2O(g) impurities; Step 1.2, open the third valve (93) and the first heater (41), the first intermediate gas enters the first heater (41) through the second output end pipeline of the alkali liquid filter (2), the first heater (41) heats the first intermediate gas to a first preset temperature T1; the first intermediate gas enters the deoxidation tower (5), the deoxidation tower (5) removes O2 in the first intermediate gas, and the second intermediate gas with H2O(g) impurities enters the second input end of the deoxidation heat recovery device (3); at the same time, the temperature sensor at the output end of the deoxidation tower (5) is turned on to monitor the temperature T1 at the output end of the deoxidation tower (5). out When T out < the third preset temperature T3, execute step 1.4; when T out When ≥T3, execute step 1.3; Step 1.3, open the second valve (92) and close the third valve (93), the first intermediate gas enters from the first input end of the deoxygenation heat recovery device (3), flows out from the first output end of the deoxygenation heat recovery device (3), and then the first intermediate gas enters the first heater (41), the first heater (41) heats the first intermediate gas to a first preset temperature T1, when flowing through the interior of the deoxygenation heat recovery device (3), a plurality of heat exchange plates of the deoxygenation heat recovery device (3) transfer heat energy to the first intermediate gas; the first intermediate gas enters the deoxygenation tower (5), the deoxygenation tower (5) removes O2 in the first intermediate gas, and the second intermediate gas with H2O(g) impurities enters the second input end of the deoxygenation heat recovery device (3), and then executes step 1.4; Step 1.4, after the second intermediate gas is heat exchanged in the deoxygenation heat recovery device (3), it flows out from the second output end of the deoxygenation heat recovery device (3); when flowing through the interior of the deoxygenation heat recovery device (3), the second intermediate gas transfers heat energy to a plurality of heat exchange plates of the deoxygenation heat recovery device (3); Step 1.5, the first cooler (61) is turned on, the second intermediate gas enters the first cooler (61), is cooled to a second preset temperature T2, and then flows into the deoxygenation separation filter (7), the deoxygenation separation filter (7) performs preliminary dehydration on the H2O (g) in the second intermediate gas to obtain the third intermediate gas.

9. The method for autothermal hydrogen deoxygenation and dehydration purification for hydrogen production by hydrolysis according to claim 8, characterized in that: The first preset temperature T1 = 100°C, the second preset temperature T2 = 30°C, and the third preset temperature T3 = 140°C to 160°C.

10. The method for autothermal deoxygenation and dehydration purification of hydrogen for use in a hydrolysis hydrogen production process according to any one of claims 8 or 9, characterized in that: In step 2 and step 5, when in state I: In the tower valve set C, the fifth valve (162), the eighth valve (165), the twelfth valve (173), the fifteenth valve (176), the sixteenth valve (181) and the nineteenth valve (184) are all in the open state, and the remaining valves are all in the closed state; When in state II: In the tower valve set C, the eleventh valve (172), the fourteenth valve (175), the eighteenth valve (183), the twenty-first valve (186), the fourth valve (161) and the seventh valve (164) are all in the open state, and the remaining valves are all in the closed state; When in state III: In the tower valve set C, the seventeenth valve (182), the twentieth valve (185), the sixth valve (163), the ninth valve (166), the tenth valve (171) and the thirteenth valve (174) are all in the open state, and the remaining valves are all in the closed state.

Images