CN109399564B - Device and method for preparing high-purity hydrogen by directly utilizing high-temperature coke oven crude gas - Google Patents
Device and method for preparing high-purity hydrogen by directly utilizing high-temperature coke oven crude gas Download PDFInfo
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Abstract
The invention discloses a device and a method for preparing high-purity hydrogen by directly utilizing high-temperature coke oven raw gas, wherein the device comprises a tar converter, a waste heat boiler, a spray tower, an array type self-heating reforming membrane reactor, a water-steam converter and a pressure swing adsorption tower, wherein the tar converter comprises a primary air nozzle group, a secondary air nozzle group, a reaction cavity and a heat insulation layer; the device can fully utilize sensible heat carried by high-temperature coke oven gas and rich tar, and efficiently prepare high-purity H with lower energy consumption2Low energy consumption, high efficiency, and is beneficial to CO production while realizing high-purity hydrogen production2Pure state separation provides an effective solution for zero emission of coke oven gas.
Description
Technical Field
The invention belongs to the technical field of coke oven crude gas purification and waste heat recovery, and particularly relates to a device and a method for preparing high-purity hydrogen by directly utilizing high-temperature coke oven crude gas.
Background
Coke oven crude gas (RCOG) is a high-temperature gas byproduct generated by coal coking and mainly comprises H2（>50%）、CH4(24-28%), CO (1-3%), and part of light hydrocarbon compounds, and further contains>30% and a concentration of about 100 g/m3The tar vapor. In actual production, coke oven crude gas at the inlet of the coke oven riser is carriedThe sensible heat accounting for 30-40% of the heat of the coke oven reaches 750-oC. The coke production in 2016 for China was 4.49 million tons, which would yield about 430 Nm per 1 ton of coke produced3The annual output of the coke oven gas is more than 1800 hundred million Nm calculated by the coke oven gas3. Due to the lack of efficient utilization, there are nearly 300 billion Nm/year3The coke oven gas is either directly burned or vented to the atmosphere.
The coke oven raw gas is rich in hydrogen, has high mass concentration of energy-containing components, carries a large amount of sensible heat, and is a high-quality large-scale hydrogen production raw material. The prepared hydrogen can be used as fuel of fuel cells, and can also be widely applied to industries such as petrochemical industry, metal smelting, chemical fertilizer production, electronic industry and the like. The conventional hydrogen production method by using coke oven gas is to cool the coke oven crude gas to<80oAnd C, separating and recovering most of tar after dedusting and desulfurization, and separating the obtained coke oven clean gas (COG) by Pressure Swing Adsorption (PSA) to obtain hydrogen. Most sensible heat of the coke oven raw gas is wasted by cold washing, the content of toluene insoluble substances in the recovered tar is easy to exceed the standard, and the actual recovery rate of hydrogen by a PSA (pressure swing adsorption) separation method is generally less than 80% of a theoretical value. In addition, it is rich in CH4CO and residual H2The desorbed PSA gas is generally directly combusted or exhausted, resulting in energy waste and environmental pollution.
Disclosure of Invention
The invention aims to provide a device for preparing high-purity hydrogen by directly utilizing high-temperature coke oven raw gas, which can realize energy balance utilization.
The invention also aims to provide a method for preparing high-purity hydrogen by directly utilizing the high-temperature coke oven raw gas.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a device for directly utilizing high-temperature coke oven crude gas to prepare high-purity hydrogen comprises a tar converter, a waste heat boiler, a spray tower, an array type autothermal reforming membrane reactor, a water-steam converter and a pressure swing adsorption tower;
the tar converter comprises a primary air nozzle group, a secondary air nozzle group, a reaction cavity and a heat insulation layer; the primary air nozzle group and the secondary air nozzle group are respectively provided with at least three air nozzles which are circumferentially arranged on the wall of the reaction cavity at equal angles, one end of each air nozzle is arranged in the reaction cavity and provided with a porous ceramic aeration port, the other end of each air nozzle is communicated with an air injection pipeline, the axial spacing distance between the primary air nozzle group and the secondary air nozzle group is 1/10-1/5 of the length of the reaction cavity, and the heat insulation layer wraps the outer surface of the reaction cavity;
the array type self-heating reforming membrane reactor comprises a fixed reforming bed and a palladium alloy membrane tube, wherein the fixed reforming bed is of a circular cylindrical structure and is coaxially arranged with the wall of the reactor, a cylindrical cavity formed by the inner circular surface of the fixed reforming bed is a combustion heating chamber, a circular cavity formed between the outer circular surface of the fixed reforming bed and the wall of the reactor is a flue gas heating chamber, the inlet end of the combustion heating chamber is provided with a connecting flange, the tail end of the combustion heating chamber is closed, and the combustion heating chamber is communicated with the flue gas heating chamber through a plurality of flue gas guide tubes at the position close to the; a catalyst bed layer is loaded in the fixed reforming bed, the tail end of the fixed reforming bed is communicated with a tail gas channel through a flange, a plurality of palladium alloy membrane tubes are immersed in the catalyst bed layer in an array mode by taking the axis of the fixed reforming bed as the center, and the tail ends of the palladium alloy membrane tubes are communicated with a gas collection header through a connecting coil; the gas collection header is provided with a header outlet communicated with the hydrogen collection device;
the gas inlet end of the tar converter is connected with the coke oven riser, the gas outlet end of the tar converter is connected with the top inlet of the waste heat boiler, the lower outlet of the waste heat boiler is connected with the lower inlet of the spray tower, one path of the middle outlet of the waste heat boiler is connected with the upper outlet of the waste heat boiler and then connected with the gas inlet channel of the array type self-heating reforming membrane reactor, the tail gas channel of the array type self-heating reforming membrane reactor is connected with the top inlet of the steam converter, the bottom outlet of the steam converter is connected with the inlet of the pressure swing adsorption tower, the top outlet of the pressure swing adsorption tower and the other path of the middle outlet of the waste heat boiler are respectively connected with the proportional valve and then connected with the inlet of the combustion heating chamber, and the connecting pipeline between the waste heat boiler and the spray tower is internally provided with a compressor I and a, and a mixed condenser, a compressor II and a water-vapor separator II which are sequentially connected are arranged in a connecting pipeline between the water-vapor converter and the pressure swing adsorption tower.
Furthermore, the reaction cavity is cylindrical, and the gas inlet end and the gas outlet end of the reaction cavity both shrink towards the inner wall to form a shuttle-like cavity with a wide middle and narrow two ends.
Furthermore, a flame arrester is arranged on a pipeline between the inlet of the combustion heating chamber and the proportional valve.
Furthermore, a plurality of baffle plates which are staggered up and down are arranged in the flue gas heating chamber, so that the residence time of the flue gas can be prolonged, and the heating and heat-preserving effects are improved.
Preferably, the tail end of the combustion heating chamber is closed by an embedded flange.
Preferably, the two flue gas guide pipes are arranged at equal angles in the circumferential direction by taking the axis of the combustion heating chamber as the center.
Further, the palladium alloy membrane tube comprises a porous outer sleeve, a palladium alloy membrane layer and a porous stainless steel substrate, wherein the porous stainless steel substrate is of a cavity structure and is connected with the epitaxial tube of the connecting coil through a clamping sleeve threaded joint, the palladium alloy membrane layer is plated on the outer surface of the porous stainless steel substrate, and the porous outer sleeve is wrapped on the palladium alloy membrane layer.
Preferably, the palladium alloy film layer is a Cu or Ni doped Pd-Ag alloy coating; the hydrogen permeation rate of the hydrogen is improved, the hydrogen embrittlement phenomenon of the permeation separation membrane in the use process is inhibited, and the service life of the membrane can be obviously prolonged.
Preferably, the reforming catalyst loaded in the catalyst bed layer is commercial catalyst NiO/Al2O3。
Further, the smoke exhaust channel is also connected with an explosion-proof Roots blower.
The invention also provides a method for preparing high-purity hydrogen by directly utilizing the high-temperature coke oven raw gas based on the device, which comprises the following steps:
a. high temperature coke from coke oven riserThe raw gas is directly introduced into the reaction cavity of the tar converter, mixed with the primary injection air and mainly subjected to combustion reaction, so that the temperature of the raw gas of the coke oven is raised to 1200 DEGoC; then, under the combined action of secondary jet air and water vapor, the tar is decomposed into small molecular gas to complete tar removal;
b. the high-temperature coke oven gas without tar enters a waste heat boiler, water is heated to form high-temperature steam, meanwhile, the clean coke oven gas discharged from the top of the spray tower is preheated, part of steam contained in the high-temperature coke oven gas in the cooling process is condensed, part of particles are washed away, and formed slurry is discharged from a slag discharge port at the bottom of the waste heat boiler;
c. conveying the coke oven gas from the waste heat boiler to a spray tower after passing through a compressor I and a water-vapor separator I in sequence, washing off impurities such as tar, particulate matters, sulfides and the like which are not completely removed, introducing the obtained clean coke oven gas into the waste heat boiler through an exhaust pipeline at the top of the spray tower, and preheating the coke oven gas to 200-300 DEG CoC, mixing the medium-temperature coke oven gas and the high-temperature steam, introducing the mixture into a fixed reforming bed through an air inlet channel for steam reforming reaction, and in the reaction process, generating H through a palladium alloy membrane tube which is immersed in a catalyst bed layer2Separating from the reaction zone; the separated high-purity hydrogen is collected to a gas collection header through a connecting coil pipe, and then is compressed and stored or is conveyed out through a pipeline;
d. the reformed tail gas from the fixed reforming bed enters a water-steam converter through a tail gas channel for deep conversion so as to further remove CO; then, the product gas of the water-gas converter is conveyed to a pressure swing adsorption tower after sequentially passing through a mixed condenser, a compressor II and a water-gas separator II to obtain high-purity hydrogen and desorbed gas;
e. the desorption gas of the pressure swing adsorption tower and a certain proportion of medium-temperature coke oven gas enter a combustion heating chamber together for combustion and heat release, a heating fixed reforming bed provides heat for steam reforming reaction, the flue gas enters a flue gas heating chamber through a flue gas guide pipe at the position close to the tail end of the combustion heating chamber, and the waste gas is discharged through a smoke discharge channel.
Compared with the prior art, the invention has the following beneficial effects:
the method can be directly applied to the treatment of the raw gas of the high-temperature coke oven. High-temperature coke oven crude gas discharged from a coke oven riser is firstly subjected to tar removal in a tar converter, and is introduced into an array type autothermal reforming membrane reactor to react with high-temperature steam after being cooled, washed and preheated. The high-purity hydrogen in the first process is obtained through on-line separation of a palladium alloy membrane tube; and simultaneously, the steam reforming tail gas enters a steam-water converter to further remove CO, and the high-purity hydrogen of the second process is obtained through condensation, compression, steam-water separation and pressure swing adsorption separation. The heat required by the steam reforming reaction in the array type autothermal reforming membrane reactor is provided by PSA desorption gas and part of coke oven clean gas combustion heat release; the steam required by the reforming reaction is obtained by heating the high-temperature coke oven gas after tar removal to feed water. The whole system realizes the high-efficiency balanced utilization of the energy flow and the material flow of the raw gas of the high-temperature coke oven.
The permeation separation process of the palladium alloy membrane to hydrogen gas follows a dissolution-diffusion mechanism, and comprises (1) dissociation of hydrogen molecules on the surface of the membrane; (2) hydrogen atoms can be reversibly dissolved into the compact palladium-based membrane; (3) diffusion of hydrogen atoms in the film layer is three main steps. The Pd-based alloy membrane has a high selectivity for hydrogen due to the directional selectivity of step (1).
The method can use the conventional commercial nickel-based steam reforming catalyst, thereby saving the production cost. The method has the advantages of system integration, low energy consumption and high efficiency, and is beneficial to CO while realizing the preparation of high-purity hydrogen2And (5) separating a pure state. Compared with the existing coke oven gas treatment method, the method has the advantages of high technical safety, system integration, high product selectivity and low energy consumption, and can be used for continuously treating the coke oven gas of the coke oven plant.
Drawings
FIG. 1 is a schematic view of the apparatus for producing high purity hydrogen by directly using raw coke oven gas of a high temperature coke oven according to the present invention;
FIG. 2 is a schematic diagram of a tar converter configuration of the present invention;
FIG. 3 is a transverse cross-sectional view of an array autothermal reforming membrane reactor of the present invention;
FIG. 4 is a longitudinal cross-sectional view of an array autothermal reforming membrane reactor of the present invention;
fig. 5 is a schematic view of a palladium alloy membrane structure of the present invention.
In the figure, 1-tar converter, 101-primary air nozzle group, 102-secondary air nozzle group, 103-reaction chamber, 104-insulating layer, 105-aeration port, 2-waste heat boiler, 3-compressor I, 4-water vapor separator I, 5-spray tower, 6-array type self-heating reforming membrane reactor, 601-combustion heating chamber, 602-flue gas heating chamber, 603-fixed reforming bed, 604-palladium alloy membrane tube, 6041-porous outer sleeve, 6042-palladium alloy membrane layer, 6043-porous stainless steel substrate, 605-flue gas guide tube, 606-connecting coil, 607-header outlet, 608-tail gas channel, 609-gas collecting header, 6010-baffle plate, 6011-smoke exhaust channel, 6012-gas inlet channel, 6013-embedded flange, 7-steam converter, 8-mixed condenser, 9-compressor II, 10-steam separator II, 11-pressure swing adsorption tower, 12-flame arrester, 13-explosion-proof Roots blower, 14-gas mixer and 15-proportional valve.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
As shown in figure 1, the device for preparing high-purity hydrogen by directly utilizing the high-temperature coke oven raw gas comprises a tar converter 1, a waste heat boiler 2, a spray tower 5, an array type autothermal reforming membrane reactor 6, a water-steam converter 7 and a pressure swing adsorption tower 11.
As shown in fig. 1 and fig. 2, the tar converter 1 includes a primary air nozzle set 101, a secondary air nozzle set 102, a reaction chamber 103 and an insulating layer 104; the primary air nozzle group 101 and the secondary air nozzle group 102 are provided with at least three air nozzles which are circumferentially arranged on the wall of the reaction cavity 103 at equal angles, one end of each air nozzle is arranged in the reaction cavity 103 and provided with a porous ceramic aeration opening 105, the other end of each air nozzle is communicated with an air injection pipeline, the axial spacing distance between the primary air nozzle group 101 and the secondary air nozzle group 102 is 1/10-1/5 of the length of the reaction cavity 103, and the heat insulation layer 104 is wrapped on the outer surface of the reaction cavity 103;
the reaction cavity 103 is cylindrical, and the gas inlet end and the gas outlet end of the reaction cavity 103 both shrink towards the inner wall to form a shuttle-like cavity with a wide middle and narrow two ends.
As shown in fig. 1, 3 and 4, the array-type autothermal reforming membrane reactor 6 includes a fixed reforming bed 603 and a palladium alloy membrane tube 604, the fixed reforming bed 603 is of a circular cylindrical structure and is coaxially disposed with a reactor wall, a cylindrical cavity formed by an inner circular surface of the fixed reforming bed 603 is a combustion heating chamber 601, an annular cavity formed between an outer circular surface of the fixed reforming bed 603 and the reactor wall is a flue gas heating chamber 602, an inlet end of the combustion heating chamber 601 is provided with a connecting flange, a tail end of the combustion heating chamber is closed by an embedded flange 6013, and the combustion heating chamber 601 is communicated with the flue gas heating chamber 602 through a plurality of flue gas guide tubes 605 near the tail end.
The fixed reforming bed 603 is loaded with a catalyst bed, and in order to save production cost, the reforming catalyst loaded in the catalyst bed can be commercial catalyst NiO/Al2O3. The tail end of the fixed reforming bed 603 is communicated with a tail gas channel 608 through a flange, a plurality of palladium alloy membrane tubes 604 are embedded in the catalyst bed layer in an array mode by taking the axis of the fixed reforming bed 603 as the center, and the tail ends of the palladium alloy membrane tubes are communicated with a gas collection header 609 through a connecting coil 606;
a plurality of smoke exhaust channels 6011 communicated with the atmosphere are radially and symmetrically arranged in the smoke heating chamber 602, and the smoke exhaust channels 6011 are connected with the explosion-proof Roots blower 13 to accelerate the discharge of waste gas; the gas inlet end cover of the fixed reforming bed 603 is provided with a plurality of gas inlet channels 6012, and the gas inlet channels 6012 are provided with connecting flanges which are connected with gas inlet pipelines; the gas collection header 609 is provided with a header outlet 607 communicated with a hydrogen collecting device.
A plurality of baffle plates 6010 arranged in a staggered manner up and down are arranged in the flue gas heating chamber 602, so that the residence time of flue gas can be prolonged, and the heating and heat preservation effects can be improved.
As shown in fig. 5, the palladium alloy membrane tube 604 includes a porous outer sleeve 6041, a palladium alloy membrane layer 6042, and a porous stainless steel base 6043, the porous stainless steel base 6043 has a cavity structure inside and is connected to the extension tube of the connection coil 606 through a ferrule screwed joint, the palladium alloy membrane layer 6042 is plated on the outer surface of the porous stainless steel base 6043, the palladium alloy membrane layer 6042 is a Pd-Ag alloy coating doped with Cu or Ni, and the porous outer sleeve 6041 is wrapped on the palladium alloy membrane layer 6042. The palladium alloy membrane tube 604 is connected with the gas collection header 609 through the clamping sleeve connector-connecting coil 606, so that the disassembly is convenient, and the residual pre-tightening stress in the installation is small.
As shown in fig. 1, an air inlet end of the tar converter 1 is connected with a coke oven riser, an air outlet end of the tar converter 1 is connected with a top inlet of the waste heat boiler 2, a lower outlet of the waste heat boiler 2 is connected with a lower inlet of the spray tower 5, one path of a middle outlet of the waste heat boiler 2 and an upper outlet of the waste heat boiler 2 are respectively connected with the gas mixer 14 and then connected with an air inlet channel 6012 of the array type autothermal reforming membrane reactor 6, a tail gas channel 608 of the array type autothermal reforming membrane reactor 6 is connected with a top inlet of the steam reformer 7, a bottom outlet of the steam reformer 7 is connected with an inlet of the pressure swing adsorption tower 11, a top outlet of the pressure swing adsorption tower 11 and a middle outlet of the waste heat boiler 2 are respectively connected with the proportional valve 15 and then connected with an inlet of the combustion heating chamber 601, and a connecting pipeline between the waste heat boiler 2 and the spray tower 5 is provided with a compressor i, And a mixed condenser 8, a compressor II 9 and a water-vapor separator II 10 which are sequentially connected are arranged in a connecting pipeline between the water-vapor converter 7 and the pressure swing adsorption tower 11 of the water-vapor separator I4.
In order to prevent the back fire of the combustible gas, a flame arrester 12 is also installed on the pipeline between the inlet of the combustion heating chamber 601 and the proportional valve 15.
The method for preparing high-purity hydrogen by directly utilizing the raw coke oven gas of the high-temperature coke oven based on the device comprises the following steps:
a. high-temperature coke oven crude gas A (700-900) coming out of coke oven riseroC) Is directly introduced into the reaction chamber 103 of the tar converter 1, is mixed with the primary injection air, mainly undergoes a combustion reaction, and raises the temperature to 1200 deg.foC; then, under the combined action of secondary jet air and water vapor, the tar is decomposed into small molecular gas to complete tar removal;
b. the high-temperature coke oven gas without tar enters the waste heat boiler 2, the fed water C is heated to form high-temperature steam D, meanwhile, the clean coke oven gas discharged from the top of the spray tower 5 is preheated, part of steam contained in the high-temperature coke oven gas in the cooling process is condensed, part of particles are washed away, and formed slurry is discharged from a slag discharge port at the bottom of the waste heat boiler 2;
c. the coke oven gas from the waste heat boiler 2 sequentially passes through a compressor I3 and a water-vapor separator I4 and then is sent to a spray tower 5, impurities such as tar, particles, sulfides and the like which are not completely removed are washed away, the obtained clean coke oven gas enters the waste heat boiler 2 through an exhaust pipeline at the top of the spray tower 5 and is preheated to 200-300 DEGoC, mixing the medium-temperature coke oven gas B and the high-temperature steam D, introducing the mixture into a fixed reforming bed 603 through an air inlet channel 6012 for steam reforming reaction, and in the reaction process, generating H through a palladium alloy membrane tube 604 embedded in a catalyst bed layer2Separating from the reaction zone; the separated high-purity hydrogen G is collected to a gas collection header 609 through a connecting coil 606, and then is compressed, stored or conveyed out through a pipeline;
d. reformed tail gas F from the fixed reforming bed 603 enters a water-steam converter 7 through a tail gas channel 608 for deep conversion so as to further remove CO; then, the product gas of the water-steam converter 7 is conveyed to a pressure swing adsorption tower 11 after sequentially passing through a mixed condenser 8, a compressor II 9 and a water-steam separator II 10 to obtain high-purity hydrogen and desorbed gas;
e. the desorption gas of the pressure swing adsorption tower 11 and a certain proportion of medium-temperature coke oven gas enter a combustion heating chamber 601 together for combustion and heat release, a heating fixed reforming bed 603 provides heat for steam reforming reaction, the flue gas enters the flue gas heating chamber 602 through a flue gas guide pipe 605 at the position close to the tail end of the combustion heating chamber 601, the fixed reforming bed 603 is further heated under the action of a baffle plate 6010, and finally, under the gravity of a high-temperature explosion-proof Roots blower 13, waste gas E is discharged through a smoke discharge channel 6011.
Claims (10)
1. A device for directly utilizing high-temperature coke oven raw gas to prepare high-purity hydrogen is characterized by comprising a tar converter (1), a waste heat boiler (2), a spray tower (5), an array type self-heating reforming membrane reactor (6), a water-steam converter (7) and a pressure swing adsorption tower (11);
the tar converter (1) comprises a primary air nozzle group (101), a secondary air nozzle group (102), a reaction cavity (103) and an insulating layer (104); the primary air nozzle group (101) and the secondary air nozzle group (102) are respectively provided with at least three air nozzles which are circumferentially arranged on the wall of the reaction cavity (103) at equal angles, one end of each air nozzle is arranged in the reaction cavity (103) and provided with a porous ceramic aeration port (105), the other end of each air nozzle is communicated with an air injection pipeline, the axial spacing distance between the primary air nozzle group (101) and the secondary air nozzle group (102) is 1/10-1/5 of the length of the reaction cavity (103), and the heat insulation layer (104) is wrapped on the outer surface of the reaction cavity (103);
the array type autothermal reforming membrane reactor (6) comprises a fixed reforming bed (603) and a palladium alloy membrane tube (604), wherein the fixed reforming bed (603) is of a circular cylindrical structure and is coaxially arranged with the wall of the reactor, a cylindrical cavity formed by the inner circular surface of the fixed reforming bed (603) is a combustion heating chamber (601), a circular cavity formed between the outer circular surface of the fixed reforming bed (603) and the wall of the reactor is a flue gas heating chamber (602), the inlet end of the combustion heating chamber (601) is provided with a connecting flange, the tail end of the combustion heating chamber is closed, and the combustion heating chamber (601) near the tail end is communicated with the flue gas heating chamber (602) through a plurality of flue gas guide tubes (605); a catalyst bed layer is loaded in the fixed reforming bed (603), the tail end of the fixed reforming bed (603) is communicated with a tail gas channel (608) through a flange, a plurality of palladium alloy membrane tubes (604) are embedded in the catalyst bed layer in an array mode by taking the axis of the fixed reforming bed (603) as the center, and the tail ends of the palladium alloy membrane tubes are communicated with a gas collection header (609) through a connecting coil (606); a plurality of smoke exhaust channels (6011) communicated with the atmosphere are radially arranged in the smoke heating chamber (602), a plurality of air inlet channels (6012) are arranged on an air inlet end cover of the fixed reforming bed (603), a connecting flange is arranged on the air inlet channels (6012), and a header outlet (607) communicated with a hydrogen collecting device is arranged in the gas collecting header (609);
the gas inlet end of the tar converter (1) is connected with the coke oven riser, the gas outlet end of the tar converter (1) is connected with the top inlet of the waste heat boiler (2), the lower outlet of the waste heat boiler (2) is connected with the lower inlet of the spray tower (5), one path of the middle outlet of the waste heat boiler (2) is connected with the upper outlet of the waste heat boiler (2) after being respectively connected with the gas mixer (14) and then connected with the gas inlet channel (6012) of the array type autothermal reforming membrane reactor (6), the tail gas channel (608) of the array type autothermal reforming membrane reactor (6) is connected with the top inlet of the steam converter (7), the bottom outlet of the steam converter (7) is connected with the inlet of the pressure swing adsorption tower (11), the top outlet of the pressure swing adsorption tower (11) and the other path of the middle outlet of the waste heat boiler (2) are respectively connected with the proportional valve (15) and then connected with the inlet of the combustion heating chamber (601), a compressor I (3) and a water-vapor separator I (4) which are connected in sequence are arranged in a connecting pipeline between the waste heat boiler (2) and the spray tower (5), and a mixed condenser (8), a compressor II (9) and a water-vapor separator II (10) which are connected in sequence are arranged in a connecting pipeline between the water-vapor converter (7) and the pressure swing adsorption tower (11).
2. The device for preparing high-purity hydrogen by directly utilizing the high-temperature coke oven raw gas as claimed in claim 1, wherein the reaction chamber (103) is cylindrical, and the gas inlet end and the gas outlet end of the reaction chamber (103) both shrink towards the inner wall to form a shuttle-like cavity with a wide middle and narrow two ends.
3. The device for preparing high-purity hydrogen by directly utilizing the raw gas of the high-temperature coke oven as claimed in claim 1 or 2, characterized in that a flame arrester (12) is arranged on a pipeline between the inlet of the combustion heating chamber (601) and the proportional valve (15).
4. The device for preparing high-purity hydrogen by directly utilizing the raw coke oven gas of the high-temperature coke oven according to claim 1 or 2, characterized in that a plurality of baffle plates (6010) which are staggered up and down are arranged in the flue gas heating chamber (602).
5. The device for preparing high-purity hydrogen by directly utilizing the high-temperature coke oven raw gas as claimed in claim 1 or 2, characterized in that the tail end of the combustion heating chamber (601) is closed by an embedded flange (6013).
6. The device for preparing high-purity hydrogen by directly utilizing the raw gas of the high-temperature coke oven according to claim 1 or 2, wherein the two flue gas guide pipes (605) are arranged at equal angles in the circumferential direction by taking the axis of the combustion heating chamber (601) as the center.
7. The device for preparing high-purity hydrogen by directly utilizing the raw coke oven gas of the high-temperature coke oven according to claim 1 or 2, wherein the palladium alloy membrane tube (604) comprises a porous outer sleeve (6041), a palladium alloy membrane layer (6042) and a porous stainless steel substrate (6043), the interior of the porous stainless steel substrate (6043) is of a cavity structure and is connected with an epitaxial tube of the connecting coil (606) through a clamping sleeve threaded joint, the palladium alloy membrane layer (6042) is plated on the outer surface of the porous stainless steel substrate (6043), and the porous outer sleeve (6041) is wrapped on the palladium alloy membrane layer (6042).
8. The device for preparing high-purity hydrogen by directly utilizing the raw coke oven gas of the high-temperature coke oven as claimed in claim 7, wherein the palladium alloy membrane layer (6042) is a Pd-Ag alloy coating doped with Cu or Ni.
9. The device for preparing high-purity hydrogen by directly utilizing the raw coke oven gas of the high-temperature coke oven according to claim 1 or 2, characterized in that the smoke exhaust channel (6011) is also connected with an explosion-proof Roots blower (13).
10. A method for preparing high-purity hydrogen by directly utilizing high-temperature coke oven raw gas based on the device of any one of claims 1 to 9, which is characterized by comprising the following steps:
a. the high-temperature coke oven crude gas coming out of the coke oven riser is directly introduced into a reaction cavity (103) of the tar converter (1) to be mixed with primary injection air, mainly to generate combustion reaction, so that the temperature is raised to 1200 DEGoC; then, under the combined action of secondary jet air and water vapor, the tar is decomposed into small molecular gas to complete tar removal;
b. the high-temperature coke oven gas without tar enters the waste heat boiler (2), the high-temperature coke oven gas is heated to feed water to form high-temperature steam, meanwhile, the clean coke oven gas discharged from the top of the spray tower (5) is preheated, part of steam contained in the high-temperature coke oven gas in the cooling process is condensed, part of particles are washed away, and formed slurry is discharged from a slag discharge port at the bottom of the waste heat boiler (2);
c. the coke oven gas from the waste heat boiler (2) sequentially passes through a compressor I (3) and a water-vapor separator I (4) and then is sent to a spray tower (5), tar, particulate matters and sulfide impurities which are not completely removed are washed away, the obtained clean coke oven gas enters the waste heat boiler (2) through an exhaust pipeline at the top of the spray tower (5) and is preheated to 200-300 DEG CoC, mixing the medium-temperature coke oven gas and the high-temperature steam, introducing the mixture into a fixed reforming bed (603) through an air inlet channel (6012) for steam reforming reaction, and in the reaction process, generating H through a palladium alloy membrane tube (604) which is immersed in a catalyst bed layer2Separating from the reaction zone; the separated high-purity hydrogen is collected to a gas collection header (609) through a connecting coil (606), and then is compressed, stored or conveyed out through a pipeline;
d. reformed tail gas from the fixed reforming bed (603) enters a water-steam converter (7) through a tail gas channel (608) for deep conversion so as to further remove CO; then, the product gas of the water-steam converter (7) is conveyed to a pressure swing adsorption tower (11) after sequentially passing through a mixed condenser (8), a compressor II (9) and a water-steam separator II (10) to obtain high-purity hydrogen and desorbed gas;
e. the desorption gas of the pressure swing adsorption tower (11) and a certain proportion of medium-temperature coke oven gas enter a combustion heating chamber (601) together for combustion and heat release, a heating fixed reforming bed (603) provides heat for steam reforming reaction, the flue gas enters a flue gas heating chamber (602) through a flue gas guide pipe (605) at the position close to the tail end of the combustion heating chamber (601), and the waste gas is discharged through a smoke discharge channel (6011).
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| CN110605089B (en) * | 2019-09-27 | 2024-04-02 | 浙江浙能技术研究院有限公司 | Combined energy-saving stirring-free solvothermal synthesis device and method |
| CN111607418A (en) * | 2020-06-11 | 2020-09-01 | 陕西东鑫垣化工有限责任公司 | Oxygen-enriched pyrolysis device for coal and processing technology thereof |
| CN113476996B (en) * | 2021-07-09 | 2022-05-31 | 北京科技大学 | Double-membrane reformer system for efficiently utilizing fuel gas and control method thereof |
| CN116115794A (en) * | 2022-12-08 | 2023-05-16 | 珠海格力电器股份有限公司 | Sterilizing water generating device and cleaning equipment |
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| JPS57183303A (en) * | 1981-05-07 | 1982-11-11 | Jgc Corp | Hydrogen recovery from coke oven gas |
| MX2016016047A (en) * | 2014-07-15 | 2017-03-28 | Midrex Technologies Inc | Methods and systems for producing direct reduced iron and steel mill fuel gas. |
| CN104495749B (en) * | 2014-12-23 | 2016-05-11 | 东北大学 | A kind of device and method that utilizes coal oven dithio-gas hydrogen making |
| CN107758615A (en) * | 2016-08-22 | 2018-03-06 | 四川天采科技有限责任公司 | A kind of low energy consumption, raw coke oven gas hydrogen production process in high yield |
| CN108117047B (en) * | 2017-12-22 | 2020-02-28 | 新疆宣力环保能源有限公司 | Low-pressure sulfur-tolerant shift and special adsorbent inerting-discharging technology for hydrogen production from raw gas |
| CN108249401B (en) * | 2018-03-22 | 2023-09-26 | 邵阳学院 | Hydrogen purification device for raw gas and biomass gasification products |
| CN108609582A (en) * | 2018-04-11 | 2018-10-02 | 四川省达科特化工科技有限公司 | A kind of raw coke oven gas process for making hydrogen |
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