CN114604829A - System and method for purifying hydrogen from coke oven gas - Google Patents
System and method for purifying hydrogen from coke oven gas Download PDFInfo
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- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
Abstract
The invention relates to the technical field of chemical equipment, and discloses a system and a method for purifying hydrogen from coke oven gas, which comprises an atmospheric adsorption unit, a chemical absorption unit and a membrane separation unit, wherein the atmospheric adsorption unit is provided with a coke oven gas inlet, an air outlet of the atmospheric adsorption unit is connected with an air inlet of the chemical absorption unit, an air outlet of the chemical absorption unit is connected with an air inlet of the membrane separation unit through a first compressor, a low-pressure gas outlet side of the membrane separation unit is connected with an air inlet of the pressure swing adsorption unit through a second compressor, and the pressure swing adsorption unit is provided with a hydrogen outlet. The hydrogen for the fuel cell meeting the requirements is efficiently prepared through the coupling integration of units such as normal pressure adsorption, chemical absorption, membrane separation, pressure swing adsorption and the like, the recovery rate exceeds 90 percent, and the concentration back mixing in the hydrogen purification process is reduced and the separation efficiency is improved through the staged permeation of the membrane separation unit, the staged desorption of the pressure swing adsorption unit and the coupling integration of the membrane separation unit and the pressure swing adsorption unit.
Description
Technical Field
The invention relates to the technical field of chemical equipment, in particular to a system and a method for purifying hydrogen from coke oven gas.
Background
Due to exhaustion of fossil energy, emission of greenhouse gases and the like, a global energy system is coming to a revolution, and hydrogen energy is a key carrier for a new energy system to insist on green and low carbon and realize sustainable development. Firstly, hydrogen energy is recognized as clean energy, basically no pollution is generated in the conversion and utilization processes, energy conversion far higher than the efficiency of a heat engine can be realized by a fuel cell and the like, and the hydrogen energy is compatible and communicated with an electric power system. And secondly, unstable unconventional renewable energy sources such as solar energy, wind energy and the like can be converted into hydrogen energy sources, so that the hydrogen energy sources are favorable for storage, transportation and multi-way use. In addition, solid high-carbon resources with low calorific value, such as oil sand, biomass, peat and the like, can also be converted into hydrogen energy, so that the quality improvement of the energy is realized, and the pipeline transportation and the carbon concentration and emission reduction are facilitated.
In a hydrogen energy system, a new energy vehicle taking hydrogen as fuel occupies an important position, and under the trend of rapid development of the new energy, the hydrogen for fuel cells with reasonable price is produced on a large scale, so that the hydrogen becomes an important bottleneck restricting the development of the hydrogen energy system at the present stage.
The coke oven gas is combustible gas which is a byproduct of high-temperature carbonization of coal in a coke oven. In general, 300-350 standard square coke oven gas can be produced as a byproduct per ton of dry coal, and the main components are hydrogen (55-60%), methane (23-27%), and a small amount of carbon monoxide, light hydrocarbon, naphthalene, tar, carbon dioxide, hydrogen sulfide, oxygen and nitrogen. The heat value of the coke oven gas can reach 17-19 MJ/Nm3, and the coke oven gas is generally used as fuel of high-temperature industrial furnaces and urban gas, and a few projects are used for producing synthetic ammonia. In these conventional uses of coke oven gas, hydrogen resources are regarded as common fuels and do not fully realize their value. If the hydrogen can be separated and purified by an effective separation process to prepare the hydrogen for the fuel cell, the value can be improved by 5 to 10 times. In conclusion, the coke oven gas is a potential raw material for producing hydrogen for fuel cells on a large scale.
Hydrogen fuel cells have stringent requirements for the purity of the hydrogen gas, especially for the specific impurity content. According to the regulations of national standard hydrogen (GB/T37244-2018) which is a fuel for proton exchange membrane fuel cell automobiles, the hydrogen for the fuel cell needs to meet the following key indexes, namely 99.97 mol% of hydrogen, 100ppm of methane, nitrogen and argon, 5ppm of oxygen, 5ppm of water, 2ppm of carbon dioxide and 0.2ppm of carbon monoxide. However, the impurity content of the coke oven gas is far higher than the limit level of the national standard GB/T37244-2018. In order to realize the production of hydrogen with high added value for fuel cells by using coke oven gas as a raw material, an efficient purification technology must be developed to deeply and even ultra-deeply remove various impurities.
The patent with the publication number of CN101850949B discloses a method for purifying hydrogen in coke oven gas with high purity and high recovery rate, wherein the coke oven gas is subjected to temperature swing adsorption to remove naphthalene, tar and NH3、H2After S and other aromatic compounds and other impurities enter a pressure swing adsorption device to obtain hydrogen with the purity of more than 99.9 v%, and after further deoxidation and drying, high-purity hydrogen with the purity of more than 99.999 v%, the oxygen content of less than 3ppm and the dew point of less than minus 70 ℃ is obtained; the purity of hydrogen in the pressure swing adsorption desorption gas is more than 20 v%, the hydrogen enters a membrane separation device after being compressed and cooled, the obtained permeation gas with the purity of 55-65 v% of hydrogen returns to a coke oven gas compressor, and the hydrogen in the permeation gas is further recovered; the residual gas is discharged out of the boundary area of the device.
The method for purifying hydrogen from coke oven gas comprises the steps of,Tar, NH3、H2S and other aromatic compounds and other impurities are removed through temperature swing adsorption, a plurality of adsorbents are required to be filled according to strict distribution, and the operation difficulty is high. The temperature swing adsorption needs to consume extra steam to regenerate the adsorbent, and the energy consumption is high. In addition, the coke oven gas directly enters pressure swing adsorption after temperature swing adsorption, the concentration of fed hydrogen is only 55-60 v%, and according to the operation experience of an industrial pressure swing adsorption device, the condition is not the feeding concentration condition that the pressure swing adsorption can efficiently operate, and the separation efficiency is low.
Disclosure of Invention
The purpose of the invention is: the system for purifying the hydrogen gas from the coke oven gas is provided, various impurity gases are deeply removed through multi-technology integration, and the hydrogen gas for the fuel cell is efficiently produced; the invention also provides a method for purifying hydrogen from coke oven gas.
In order to achieve the purpose, the invention provides a system for purifying hydrogen from coke oven gas, which comprises an atmospheric pressure adsorption unit for absorbing heavy hydrocarbon, a chemical absorption unit for removing acid impurity gas, a membrane separation unit for separating hydrogen and a pressure swing adsorption unit for adsorbing light hydrocarbon, wherein a coke oven gas inlet is arranged on the atmospheric pressure adsorption unit, a gas outlet of the atmospheric pressure adsorption unit is connected with a gas inlet of the chemical absorption unit, a gas outlet of the chemical absorption unit is connected with a gas inlet of the membrane separation unit through a first compressor, a low pressure gas outlet side of the membrane separation unit is connected with a gas inlet of the pressure swing adsorption unit through a second compressor, and a hydrogen outlet is arranged on the pressure swing adsorption unit.
Preferably, the membrane separation unit includes first membrane separation unit and second membrane separation unit, first compressor with the air inlet of first membrane separation unit is connected, the low pressure of first membrane separation unit press the gas side with the second compressor is connected, the high pressure of first membrane separation unit press the gas side with the air inlet of second membrane separation unit is connected, the low pressure of second membrane separation unit give vent to anger the side with the air inlet of chemical absorption unit is connected, the high pressure of second membrane separation unit press the gas side with the air inlet of ordinary pressure adsorption unit is connected.
Preferably, a regenerative heater is connected between the high pressure gas outlet side of the second membrane separation unit and the gas inlet of the atmospheric adsorption unit.
Preferably, the normal pressure desorption outlet of the pressure swing adsorption unit is connected with the air inlet of the first compressor, and the negative pressure desorption outlet of the pressure swing adsorption unit is connected with the air inlet of the second membrane separation unit.
Preferably, a vacuum pump and a third compressor are connected in sequence between the negative pressure desorption outlet of the pressure swing adsorption unit and the air inlet of the second membrane separation unit.
Preferably, the chemical absorption unit includes alkali lye absorption unit and washing unit, the air inlet of the bottom of alkali lye absorption unit with the normal pressure adsorbs the unit connection, the gas outlet at the top of alkali lye absorption unit with the air inlet of the bottom of washing unit is connected, the gas outlet at washing unit top with the air inlet of membrane separation unit is connected, the top of alkali lye absorption unit is connected with alkali lye and advances the pipe, the top of washing unit is connected with the inlet channel.
The invention also provides a method for purifying hydrogen from coke oven gas, and the system for purifying hydrogen from coke oven gas according to any technical scheme comprises the following steps of S1, feeding the coke oven gas into a normal pressure adsorption unit from a gas inlet at the bottom of the normal pressure adsorption unit, and adsorbing heavy hydrocarbon to generate oil-free coke oven gas;
step S2, allowing the oil-free coke oven gas to enter from the bottom of the alkali liquor absorption unit and to be in countercurrent contact with the alkali liquor entering from the top of the tower, discharging the formed desulfurization and decarburization rich liquid from the bottom of the tower, allowing the formed desulfurization coke oven gas to enter a water washing unit from the top of the alkali liquor absorption unit, and washing to form purified coke oven gas;
step S3, pressurizing the purified coke oven gas by a first compressor to form a first membrane separation feed, enabling the first membrane separation feed to enter a first membrane separation unit, forming a first membrane separation hydrogen-rich permeate gas on the low-pressure side of the first membrane separation unit, enabling the first membrane separation hydrogen-rich permeate gas to enter a second compressor, and forming a first membrane separation hydrogen-poor permeate gas on the high-pressure side of the first membrane separation unit;
and step S4, the first membrane separation hydrogen-rich permeate gas is boosted by a second compressor to form pressure swing adsorption feed, the pressure swing adsorption feed enters a pressure swing adsorption unit, and the pressure swing adsorption unit generates hydrogen for the fuel cell.
Preferably, step S5 is further included, the first membrane separation hydrogen-poor retentate is sent to a second membrane separation unit, a low pressure side of the second membrane separation unit forms a second membrane separation hydrogen-rich permeate, the second membrane separation hydrogen-rich permeate is sent to a lye absorption unit, and a high pressure side of the second membrane separation unit forms a second membrane separation hydrogen-poor retentate;
and step S6, enabling the second membrane separation hydrogen-poor residual gas to enter a regenerative heater to form hot regeneration inlet gas, enabling the hot regeneration inlet gas to enter an atmospheric pressure adsorption unit to desorb heavy hydrocarbon, and forming hot regeneration tail gas.
Preferably, when an adsorption tower of the pressure swing adsorption unit is close to a saturated state, the pressure swing adsorption unit is switched to enter a desorption regeneration working state, the first desorption gas is desorbed at normal pressure in a first stage of desorption regeneration and is produced, and the first desorption gas and the purified coke oven gas are mixed and then enter a first compressor; and carrying out negative pressure desorption in a second desorption regeneration stage to generate second desorption gas, boosting the pressure of the second desorption gas by a vacuum pump and a third compressor to form pressurized desorption gas, and plying the pressurized desorption gas and the first membrane separation lean hydrogen permeation residual gas and then entering a second membrane separation unit.
Preferably, the first compressor increases the pressure of the first membrane separation feed to 2.0MPaG, the second compressor increases the pressure of the pressure swing adsorption feed to 2.0MPaG, the third compressor increases the pressure of the pressurized stripping gas to 2.0MPaG, and the regenerative heater increases the temperature of the hot regeneration inlet gas to above 150 ℃.
Compared with the prior art, the system and the method for purifying hydrogen from coke oven gas have the beneficial effects that: the coke oven gas firstly enters an atmospheric pressure adsorption unit, and heavy hydrocarbon molecules with higher boiling points, such as naphthalene, tar and the like, are firstly deeply removed by the atmospheric pressure adsorption unit, so that the heavy hydrocarbon molecules are prevented from contacting with a subsequent compressor and a membrane separation unit; oil-free coke oven gas generated after adsorption treatment by the normal pressure adsorption unit enters a chemical absorption unit, hydrogen sulfide and most of carbon dioxide can be deeply removed, the generated desulfurized coke oven gas enters a membrane separation unit after being pressurized by a first compressor, impurities such as methane, nitrogen, light hydrocarbon, carbon monoxide and the like can be removed by the membrane separation unit, the hydrogen content can reach more than 97.5 mol%, the desulfurized coke oven gas enters a pressure swing adsorption unit after being pressurized by a second compressor, the impurities such as methane, carbon monoxide, nitrogen, light hydrocarbon and the like are adsorbed and intercepted, and hydrogen for fuel cells meeting national standards is generated; the hydrogen for the fuel cell meeting the national standard requirements is efficiently prepared by coupling and integrating units such as normal pressure adsorption, chemical absorption, membrane separation, pressure swing adsorption and the like, the recovery rate exceeds 90 percent, and concentration back mixing in the hydrogen purification process is reduced and the separation efficiency is improved by stage permeation of the membrane separation unit, stage desorption of the pressure swing adsorption unit and coupling and integration of the membrane separation unit and the pressure swing adsorption unit.
Drawings
FIG. 1 is a schematic structural diagram of a system for purifying hydrogen from coke oven gas according to the present invention;
FIG. 2 is a schematic structural diagram of a first membrane separation unit of the system for purifying hydrogen from coke oven gas of the present invention;
FIG. 3 is a schematic structural diagram of a second membrane separation unit of the system for purifying hydrogen from coke oven gas according to the present invention.
In the figure, 1, an atmospheric adsorption unit; 2. an alkali liquor absorption unit; 3. a water washing unit; 4. a first compressor; 5. a first membrane separation unit; 6. a second membrane separation unit; 7. a regenerative heater; 8. a second compressor; 9. a pressure swing adsorption unit; 10. a vacuum pump; 11. a third compressor; 12. a cooler; 13. liquid separating tank; 14. a demister; 15. a heater; 16. a precision filter; 17. a hydrogen separation membrane; s-1, coke oven gas; s-2, oil-free coke oven gas; s-3, an alkaline absorbent; s-4, desulfurizing and decarbonizing the rich solution; s-5, desulfurizing coke oven gas; s-6, softening water; s-7, dilute alkali liquor; s-8, purifying coke oven gas; s-9, feeding a first membrane separation material; s-10, separating the hydrogen-rich permeate gas by using a first membrane; s-11, separating the hydrogen-poor residual gas by a first membrane; s-12, separating the hydrogen-rich permeate gas by a second membrane; s-13, separating the hydrogen-poor residual gas by a second membrane; s-14, hot regeneration air inlet; s-15, thermally regenerating tail gas; s-16, feeding by pressure swing adsorption; s-17, hydrogen for a fuel cell; s-18, first desorption gas; s-19, second desorption gas; s-20, pressurizing desorption gas.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the preferred embodiment of the system for purifying hydrogen from coke oven gas S-1 of the present invention, as shown in FIGS. 1 to 3, the system for purifying hydrogen from coke oven gas S-1 comprises an atmospheric adsorption unit 1, a chemical absorption unit, a membrane separation unit and a pressure swing adsorption unit 9, and the atmospheric adsorption unit 1, the chemical absorption unit, the membrane separation unit and the pressure swing adsorption unit 9 are connected in sequence. Normal pressure adsorption unit 1 is used for absorbing the heavy hydrocarbon, and the chemical absorption unit is used for detaching acid impurity gas, and the membrane separation unit is used for separating hydrogen, and pressure swing adsorption unit 9 is used for adsorbing light hydrocarbon.
The normal pressure adsorption unit 1 is provided with a coke oven gas S-1 inlet, the coke oven gas S-1 inlet is used for the coke oven gas S-1 produced by high-temperature dry distillation of coal to enter, and the gas outlet of the normal pressure adsorption unit 1 is connected with the gas inlet of the chemical absorption unit. The core equipment of the atmospheric adsorption unit 1 consists of two or more adsorption towers, the adsorbent filled in the adsorption towers can be but is not limited to activated carbon, carbon molecular sieve, carbon fiber, silica gel or zeolite molecular sieve, and can also be the combination of the adsorbents, and the abundant pore structure and the surface area in the adsorbent have stronger affinity with heavy hydrocarbon.
When the coke oven gas S-1 enters the adsorption tower in the adsorption working state, naphthalene, tar and other heavy hydrocarbons are adsorbed, the obtained oil-free coke oven gas S-2 enters the chemical absorption unit, and the oil-free coke oven gas S-2 enters the chemical absorption unit. In this embodiment, the coke oven gas S-1 is introduced from the bottom of the adsorption tower of the atmospheric adsorption unit 1 to increase the contact area with the atmospheric adsorption unit 1. The specific structure of the atmospheric adsorption unit 1 is prior art and will not be described in detail herein.
The core equipment of the chemical absorption unit is an absorption tower, oil-free coke oven gas S-2 enters the chemical absorption unit from the bottom, the chemical absorption unit can absorb hydrogen sulfide and most of carbon dioxide in the coke oven gas S-1 to form desulfurized coke oven gas S-5, and the desulfurized coke oven gas S-5 is extracted from the top and sent to the membrane separation unit. The oil-free coke oven gas S-2 forms a desulfurization and decarburization rich solution S-4 in the chemical absorption unit, is extracted from the bottom of the tower and is sent to an absorbent regeneration device, and the absorbent can be recycled.
The gas outlet of the chemical absorption unit is connected with the gas inlet of the membrane separation unit through the first compressor 4, the desulfurized coke oven gas S-5 firstly enters the first compressor 4, the first compressor 4 can increase the pressure to be more than 2.0MPaG to become a first membrane separation feed S-9, the size of hydrogen molecules is far smaller than that of impurity molecules, the diffusion rate in the membrane material is higher, the hydrogen molecules can preferentially permeate in the membrane separation unit under the action of high pressure, the first membrane separation hydrogen-rich permeate gas S-10 is formed on the low-pressure gas outlet side, the hydrogen content reaches more than 97.5 mol%, the first membrane separation hydrogen-poor permeate residual gas S-11 is formed on the high-pressure gas outlet side, and the hydrogen content is lower than 30.0 mol%.
The low pressure outlet side of the membrane separation unit is connected with the air inlet of the pressure swing adsorption unit 9 through a second compressor 8, the second compressor 8 can pressurize the pressure of the first membrane separation hydrogen-rich permeate gas S-10 to more than 1.5MPaG to form a pressure swing adsorption feed S-16, and the pressure swing adsorption feed S-16 enters the pressure swing adsorption unit 9. The membrane separation unit may adopt an existing membrane separation structure, and will not be described in detail herein.
The pressure swing adsorption unit 9 is complete equipment and is used for adsorbing light hydrocarbon in the pressure swing adsorption feeding S-16 to generate hydrogen S-17 for the fuel cell meeting the national standard requirements, and a hydrogen outlet is arranged on the pressure swing adsorption unit 9. The pressure swing adsorption unit 9 is a complete set of equipment, the core equipment is composed of two or more adsorption towers, and activated alumina (for adsorbing water), silica gel (for adsorbing hydrocarbons and carbon dioxide), activated carbon (for adsorbing methane) and zeolite molecular sieves (for adsorbing nitrogen and carbon monoxide) are filled in the adsorption towers in layers from bottom to top. The pressure swing adsorption feed S-16 with pressure raised by the second compressor 8 enters the adsorption tower in the pressure swing adsorption unit 9 from the bottom, which is in an adsorption working state, and impurities such as methane, carbon monoxide, nitrogen, light hydrocarbon and the like are all adsorbed and intercepted, and hydrogen S-17 for the fuel cell meeting the national standard is produced. The specific structure of the pressure swing adsorption unit 9 is prior art and will not be described in detail herein.
When the adsorption tower of the pressure swing adsorption unit 9 is close to a saturated state, the desorption regeneration working state is switched to enter, normal pressure desorption is carried out in the first stage of desorption regeneration, the desorption pressure range is usually from 0.20MPaG to normal pressure, and first desorption gas S-18 with the hydrogen content exceeding 65 mol% is produced; and carrying out negative pressure desorption in a second desorption regeneration stage, wherein the desorption pressure is generally in the range from normal pressure to-0.08 MPaG, and a second desorption gas S-19 with the hydrogen content of more than 30 mol% is produced.
In the application, oil-free coke oven gas S-2 generated after adsorption treatment by the normal pressure adsorption unit 1 enters a chemical absorption unit, hydrogen sulfide and most of carbon dioxide can be deeply removed, generated desulfurized coke oven gas S-5 enters a membrane separation unit after being boosted by a first compressor 4, the membrane separation unit can remove impurities such as methane, nitrogen, light hydrocarbon and carbon monoxide, the hydrogen content can reach more than 97.5 mol%, and finally the desulfurized coke oven gas S-5 enters a pressure swing adsorption unit 9 after being boosted by a second compressor 8, the impurities such as methane, carbon monoxide, nitrogen and light hydrocarbon are adsorbed and intercepted, and hydrogen S-17 for the fuel cell meeting national standards is generated; the hydrogen S-17 for the fuel cell meeting the national standard requirements is efficiently prepared by coupling and integrating units such as normal pressure adsorption, chemical absorption, membrane separation, pressure swing adsorption and the like, the recovery rate exceeds 90 percent, and concentration back mixing in the hydrogen purification process is reduced and the separation efficiency is improved by stage permeation of the membrane separation unit, stage desorption of the pressure swing adsorption unit 9 and coupling and integration of the membrane separation unit and the pressure swing adsorption unit 9.
Preferably, the membrane separation unit comprises a first membrane separation unit 5 and a second membrane separation unit 6, the first compressor 4 is connected with the air inlet of the first membrane separation unit 5, the low pressure outlet side of the first membrane separation unit 5 is connected with the second compressor 8, the high pressure outlet side of the first membrane separation unit 5 is connected with the air inlet of the second membrane separation unit 6, the low pressure outlet side of the second membrane separation unit 6 is connected with the air inlet of the chemical absorption unit, and the high pressure outlet side of the second membrane separation unit 6 is connected with the air inlet of the atmospheric adsorption unit 1.
In the present embodiment, the first membrane separation unit 5 is composed of a cooler 12, a liquid separation tank 13, a demister 14, a heater 15, a precision filter 16, and a hydrogen separation membrane 17, and the cooler 12, the liquid separation tank 13, the demister 14, the heater 15, the precision filter 16, and the hydrogen separation membrane 17 are connected in this order. The first membrane separation feed S-9 forms a first membrane separation hydrogen-rich permeate S-10 on the low pressure side of the hydrogen separation membrane 17 and a first membrane separation hydrogen-lean retentate S-11 on the high pressure side of the hydrogen separation membrane 17. The first membrane separation unit 5 is a complete equipment, and the specific structure thereof is the prior art and will not be described in detail herein.
In the present embodiment, the second membrane separation unit 6 is composed of a precision filter 16 and a hydrogen separation membrane 17, and the size of hydrogen molecules is much smaller than that of impurity molecules, and the diffusion rate in the membrane material is higher and the permeation is preferential. The first membrane separation hydrogen-poor residual gas S-11 forms a second membrane separation hydrogen-rich permeation gas S-12 on the low-pressure side of the hydrogen separation membrane 17, the hydrogen content is about 85.0 mol%, hydrogen sulfide and carbon dioxide are concentrated due to high impurity content, the concentration of hydrogen sulfide is more than 20ppmv, the concentration of carbon dioxide is more than 0.5 vol%, and the hydrogen sulfide and carbon dioxide can be absorbed and then hydrogen gas can be continuously generated after being sent to a chemical absorption unit.
The impurities and a small amount of hydrogen intercepted in the first membrane separation hydrogen-poor residual gas S-11 form a second membrane separation hydrogen-poor residual gas S-13 at the high-pressure side of the hydrogen separation membrane 17, the hydrogen content is lower than 10.0 mol%, the second membrane separation hydrogen-poor residual gas S-13 enters the normal-pressure adsorption unit 1, naphthalene, tar and other heavy hydrocarbons are desorbed at high temperature, and the formed thermal regeneration tail gas S-15 can be sent to a downstream device for use.
Preferably, a regenerative heater 7 is connected between the high pressure gas outlet side of the second membrane separation unit 6 and the gas inlet of the atmospheric adsorption unit 1.
The second membrane separation lean hydrogen permeation residual gas S-13 generated by the second membrane separation unit 6 firstly enters a regenerative heater 7, the regenerative heater 7 can raise the temperature of the gas to be more than 150 ℃ to form hot regeneration inlet gas S-14, the hot regeneration inlet gas S-14 enters an adsorption tower in the normal pressure adsorption unit 1 in a working state, and the desorption efficiency of heavy hydrocarbon can be improved after the temperature is raised. In the present embodiment, the regenerative heater 7 may be, but is not limited to, a shell and tube heat exchanger.
Preferably, the normal pressure desorption outlet of the pressure swing adsorption unit 9 is connected with the gas inlet of the first compressor 4, and the negative pressure desorption outlet of the pressure swing adsorption unit 9 is connected with the gas inlet of the second membrane separation unit 6.
The pressure swing adsorption feeding S-16 enters the pressure swing adsorption unit 9, the adsorption tower of the pressure swing adsorption unit 9 enters a desorption regeneration working state when approaching a saturation state, and the first stage of desorption regeneration is carried out with normal pressure desorption, so as to produce the first desorption gas S-18 with the hydrogen content of more than 65 mol%, and the first desorption gas S-18 and the purified coke oven gas S-8 are jointly sent to the first compressor 4 through the normal pressure desorption outlet, so that the cyclic utilization of the hydrogen-containing gas is realized, and the hydrogen generation efficiency is improved. And the second stage of desorption regeneration is carried out negative pressure desorption, and the produced second desorption gas S-19 with the hydrogen content exceeding 30mol percent can enter the second membrane separation unit 6 to continuously separate hydrogen.
Preferably, a vacuum pump 10 and a third compressor 11 are connected in sequence between the negative pressure desorption outlet of the pressure swing adsorption unit 9 and the gas inlet of the second membrane separation unit 6.
The second desorption gas S-19 is subjected to pressure increase to be more than 2.0MPaG through the vacuum pump 10 and the third compressor 11 to become pressurized desorption gas S-20, then separated from the first membrane to be lean hydrogen permeation residual gas S-11 to be stranded, and the diffusion rate of hydrogen can be increased after the pressure is increased to enable the hydrogen to permeate.
Preferably, the chemical absorption unit includes alkali liquor absorption unit 2 and washing unit 3, and the air inlet and the ordinary pressure of the bottom of alkali liquor absorption unit 2 adsorb unit 1 and be connected, and the gas outlet and the air inlet of the bottom of washing unit 3 at the gas outlet at the top of alkali liquor absorption unit 2 are connected, and the gas outlet at the top of washing unit 3 is connected with the air inlet of membrane separation unit, and the top of alkali liquor absorption unit is connected with alkali liquor and advances the pipe, and the top of washing unit 3 is connected with the inlet channel.
The core equipment of the alkali liquor absorption unit 2 is a filler absorption tower or a sieve plate absorption tower, oil-free coke oven gas S-2 generated by the normal pressure absorption unit 1 enters the alkali liquor absorption unit 2 from the bottom of the tower and is in countercurrent contact with an alkaline absorbent S-3 entering from an alkali liquor inlet pipe at the top of the tower, the alkaline absorbent S-3 can be, but is not limited to, an alcohol amine solution, a sodium hydroxide solution, a calcium hydroxide suspension, a potassium carbonate solution, hydrogen sulfide and most of carbon dioxide are absorbed by reacting with active components in the alkaline absorbent S-3, and the formed desulfurization and decarburization rich liquid S-4 is extracted from the bottom of the tower and sent to an absorbent regeneration device, and meanwhile, the formed desulfurization coke oven gas S-5 is extracted from the top of the tower and sent to the water washing unit 3.
The core equipment of the water washing unit 3 is a filler absorption tower or a sieve plate absorption tower, desulfurized coke oven gas S-5 enters the water washing unit 3 from the bottom of the tower and is in countercurrent contact with softened water S-6 entering from a water inlet pipeline at the top of the tower, alkaline liquid mist carried in a gas phase is absorbed and trapped by the softened water S-6, formed dilute alkaline liquid S-7 is extracted from the bottom of the tower and sent to an alkaline liquid concentrating device, and meanwhile, formed purified coke oven gas S-8 is extracted from the top of the tower and sent to a first compressor 4.
The invention also provides a method for purifying hydrogen from coke oven gas S-1, and a system for purifying hydrogen from coke oven gas S-1 in any embodiment comprises the following steps of S1, wherein the coke oven gas S-1 enters the normal pressure adsorption unit 1 from the air inlet at the bottom of the normal pressure adsorption unit 1, and heavy hydrocarbon is adsorbed to generate oil-free coke oven gas S-2;
step S2, allowing oil-free coke oven gas S-2 to enter from the bottom of the alkali liquor absorption unit 2 and to be in countercurrent contact with alkali liquor entering from the top of the tower, discharging a desulfurization and decarburization rich solution S-4 from the bottom of the tower, allowing formed desulfurization coke oven gas S-5 to enter a washing unit 3 from the top of the alkali liquor absorption unit 2, and washing to form purified coke oven gas S-8;
step S3, pressurizing the purified coke oven gas S-8 by a first compressor 4 to form a first membrane separation feed S-9, enabling the first membrane separation feed S-9 to enter a first membrane separation unit 5, forming a first membrane separation hydrogen-rich permeate gas S-10 on the low-pressure side of the first membrane separation unit 5, enabling the first membrane separation hydrogen-rich permeate gas S-10 to enter a second compressor 8, and forming a first membrane separation hydrogen-poor permeate residual gas S-11 on the high-pressure side of the first membrane separation unit 5;
and step S4, the pressure of the first membrane separation hydrogen-rich permeate gas S-10 is increased by the second compressor 8 to form a pressure swing adsorption feed S-16, the pressure swing adsorption feed S-16 enters the pressure swing adsorption unit 9, and the pressure swing adsorption unit 9 generates hydrogen S-17 for the fuel cell.
Oil-free coke oven gas S-2 generated after adsorption treatment by the normal pressure adsorption unit 1 enters a chemical absorption unit, hydrogen sulfide and most of carbon dioxide can be deeply removed, generated desulfurized coke oven gas S-5 enters a membrane separation unit after being boosted by a first compressor 4, the membrane separation unit can remove impurities such as methane, nitrogen, light hydrocarbon, carbon monoxide and the like, the hydrogen content can reach more than 97.5 mol%, and finally the desulfurized coke oven gas S-5 enters a pressure swing adsorption unit 9 after being boosted by a second compressor 8, the impurities such as methane, carbon monoxide, nitrogen, light hydrocarbon and the like are all adsorbed and intercepted, and hydrogen S-17 for the fuel cell meeting national standards is generated; the hydrogen S-17 for the fuel cell meeting the national standard requirements is efficiently prepared by coupling and integrating units such as normal pressure adsorption, chemical absorption, membrane separation, pressure swing adsorption and the like, the recovery rate exceeds 90 percent, and concentration back mixing in the hydrogen purification process is reduced and the separation efficiency is improved by stage permeation of the membrane separation unit, stage desorption of the pressure swing adsorption unit 9 and coupling and integration of the membrane separation unit and the pressure swing adsorption unit 9.
Preferably, step S5 is further included, wherein the first membrane separation hydrogen-poor retentate S-11 is fed to the second membrane separation unit 6, the low pressure side of the second membrane separation unit 6 forms a second membrane separation hydrogen-rich permeate S-12, the second membrane separation hydrogen-rich permeate S-12 is fed to the lye absorption unit 2, and the high pressure side of the second membrane separation unit 6 forms a second membrane separation hydrogen-poor retentate S-13;
and step S6, feeding the second membrane separation hydrogen-poor residual gas S-13 into a regenerative heater 7 to form hot regeneration inlet gas S-14, feeding the hot regeneration inlet gas S-14 into the normal pressure adsorption unit 1 to desorb heavy hydrocarbon, and forming hot regeneration tail gas S-15.
Preferably, when the adsorption tower of the pressure swing adsorption unit 9 is close to a saturated state, the desorption regeneration working state is switched to enter, the first desorption gas S-18 is desorbed at normal pressure in the first stage of desorption regeneration and is produced, and the first desorption gas S-18 and the purified coke oven gas S-8 are stranded and then enter the first compressor 4; and carrying out negative pressure desorption in a second desorption regeneration stage to generate second desorption gas S-19, boosting the pressure of the second desorption gas S-19 through a vacuum pump 10 and a third compressor 11 to form pressurized desorption gas S-20, and plying the pressurized desorption gas S-20 and the first membrane separation hydrogen-poor residual gas S-11 and then entering a second membrane separation unit 6.
Preferably, the first compressor 4 increases the pressure of the first membrane separation feed S-9 to 2.0MPaG, the second compressor 8 increases the pressure of the pressure swing adsorption feed S-16 to 2.0MPaG, the third compressor 11 increases the pressure of the pressurized stripping gas S-20 to 2.0MPaG, and the regenerative heater 7 increases the temperature of the hot regeneration feed S-14 to above 150 ℃.
In summary, the embodiment of the invention provides a system and a method for purifying hydrogen from coke oven gas, wherein the coke oven gas firstly enters a normal pressure adsorption unit, and heavy hydrocarbon molecules with higher boiling points, such as naphthalene, tar and the like, are firstly deeply removed by using the normal pressure adsorption unit, so that the heavy hydrocarbon molecules are prevented from contacting with a subsequent compressor and a membrane separation unit; oil-free coke oven gas generated after adsorption treatment by the normal pressure adsorption unit enters a chemical absorption unit, hydrogen sulfide and most of carbon dioxide can be deeply removed, the generated desulfurized coke oven gas enters a membrane separation unit after being pressurized by a first compressor, impurities such as methane, nitrogen, light hydrocarbon, carbon monoxide and the like can be removed by the membrane separation unit, the hydrogen content can reach more than 97.5 mol%, the desulfurized coke oven gas enters a pressure swing adsorption unit after being pressurized by a second compressor, the impurities such as methane, carbon monoxide, nitrogen, light hydrocarbon and the like are adsorbed and intercepted, and hydrogen for fuel cells meeting national standards is generated; the hydrogen for the fuel cell meeting the national standard requirements is efficiently prepared by coupling and integrating units such as normal pressure adsorption, chemical absorption, membrane separation, pressure swing adsorption and the like, the recovery rate exceeds 90 percent, and concentration back mixing in the hydrogen purification process is reduced and the separation efficiency is improved by stage permeation of the membrane separation unit, stage desorption of the pressure swing adsorption unit and coupling and integration of the membrane separation unit and the pressure swing adsorption unit.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (10)
1. The system for purifying hydrogen from coke oven gas is characterized by comprising an atmospheric pressure adsorption unit for absorbing heavy hydrocarbon, a chemical absorption unit for removing acid impurity gas, a membrane separation unit for separating hydrogen and a pressure swing adsorption unit for adsorbing light hydrocarbon, wherein a coke oven gas inlet is formed in the atmospheric pressure adsorption unit, a gas outlet of the atmospheric pressure adsorption unit is connected with a gas inlet of the chemical absorption unit, a gas outlet of the chemical absorption unit is connected with a gas inlet of the membrane separation unit through a first compressor, a low-pressure gas outlet side of the membrane separation unit is connected with a gas inlet of the pressure swing adsorption unit through a second compressor, and a hydrogen outlet is formed in the pressure swing adsorption unit.
2. The system for purifying hydrogen from coke oven gas as claimed in claim 1, wherein the membrane separation unit comprises a first membrane separation unit and a second membrane separation unit, the first compressor is connected with the gas inlet of the first membrane separation unit, the low pressure gas outlet side of the first membrane separation unit is connected with the second compressor, the high pressure gas outlet side of the first membrane separation unit is connected with the gas inlet of the second membrane separation unit, the low pressure gas outlet side of the second membrane separation unit is connected with the gas inlet of the chemical absorption unit, and the high pressure gas outlet side of the second membrane separation unit is connected with the gas inlet of the atmospheric adsorption unit.
3. The system for purifying hydrogen from coke oven gas as claimed in claim 2, wherein a regenerative heater is connected between the high pressure gas outlet side of the second membrane separation unit and the gas inlet of the atmospheric adsorption unit.
4. The system for purifying hydrogen from coke oven gas as claimed in claim 2, wherein the normal pressure desorption outlet of the pressure swing adsorption unit is connected with the gas inlet of the first compressor, and the negative pressure desorption outlet of the pressure swing adsorption unit is connected with the gas inlet of the second membrane separation unit.
5. The system for purifying hydrogen from coke oven gas as claimed in claim 4, wherein a vacuum pump and a third compressor are connected in sequence between the negative pressure desorption outlet of the pressure swing adsorption unit and the gas inlet of the second membrane separation unit.
6. The system for purifying hydrogen from coke oven gas as claimed in any one of claims 1 to 5, wherein the chemical absorption unit comprises an alkali liquor absorption unit and a water washing unit, the air inlet at the bottom of the alkali liquor absorption unit is connected with the normal pressure adsorption unit, the air outlet at the top of the alkali liquor absorption unit is connected with the air inlet at the bottom of the water washing unit, the air outlet at the top of the water washing unit is connected with the air inlet of the membrane separation unit, the top of the alkali liquor absorption unit is connected with an alkali liquor inlet pipe, and the top of the water washing unit is connected with an water inlet pipeline.
7. A method for purifying hydrogen from coke oven gas by using the system for purifying hydrogen from coke oven gas as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps,
step S1, the coke oven gas enters the normal pressure adsorption unit from the gas inlet at the bottom of the normal pressure adsorption unit, and the heavy hydrocarbon is adsorbed to generate oil-free coke oven gas;
step S2, allowing the oil-free coke oven gas to enter from the bottom of the alkali liquor absorption unit and to be in countercurrent contact with the alkali liquor entering from the top of the tower, discharging the formed desulfurization and decarburization rich liquid from the bottom of the tower, allowing the formed desulfurization coke oven gas to enter a water washing unit from the top of the alkali liquor absorption unit, and washing to form purified coke oven gas;
step S3, pressurizing the purified coke oven gas by a first compressor to form a first membrane separation feed, enabling the first membrane separation feed to enter a first membrane separation unit, forming a first membrane separation hydrogen-rich permeate gas on the low-pressure side of the first membrane separation unit, enabling the first membrane separation hydrogen-rich permeate gas to enter a second compressor, and forming a first membrane separation hydrogen-poor permeate gas on the high-pressure side of the first membrane separation unit;
and step S4, the first membrane separation hydrogen-rich permeate gas is subjected to pressure rise by the second compressor to form pressure swing adsorption feed, the pressure swing adsorption feed enters the pressure swing adsorption unit, and the pressure swing adsorption unit generates hydrogen for the fuel cell.
8. The method for purifying hydrogen from coke oven gas as claimed in claim 7, further comprising step S5, wherein the first membrane separation hydrogen-poor retentate is fed into a second membrane separation unit, the low pressure side of the second membrane separation unit forms a second membrane separation hydrogen-rich permeate, the second membrane separation hydrogen-rich permeate is fed into a lye absorption unit, and the high pressure side of the second membrane separation unit forms a second membrane separation hydrogen-poor retentate;
and step S6, enabling the second membrane separation hydrogen-poor residual gas to enter a regenerative heater to form hot regeneration inlet gas, enabling the hot regeneration inlet gas to enter an atmospheric pressure adsorption unit to desorb heavy hydrocarbon, and forming hot regeneration tail gas.
9. The method for purifying the hydrogen from the coke oven gas as claimed in claim 8, wherein when the adsorption tower of the pressure swing adsorption unit is close to a saturated state, the desorption regeneration working state is switched to enter, the desorption regeneration first stage is carried out at normal pressure to generate a first desorption gas, and the first desorption gas and the purified coke oven gas enter a first compressor after being combined; and carrying out negative pressure desorption in a second desorption regeneration stage to generate second desorption gas, boosting the pressure of the second desorption gas by a vacuum pump and a third compressor to form pressurized desorption gas, and plying the pressurized desorption gas and the first membrane separation lean hydrogen permeation residual gas and then entering a second membrane separation unit.
10. The method of purifying hydrogen from coke oven gas as claimed in claim 9, wherein the first compressor increases the pressure of the first membrane separation feed to 2.0MPaG, the second compressor increases the pressure of the pressure swing adsorption feed to 2.0MPaG, the third compressor increases the pressure of the pressurized stripping gas to 2.0MPaG, and the regenerative heater increases the temperature of the hot regeneration feed gas to 150 ℃ or higher.
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| US20020181747A1 (en) * | 1999-10-28 | 2002-12-05 | Catherine Topping | Identification system |
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| CN110127613A (en) * | 2019-05-20 | 2019-08-16 | 广东国能中林实业有限公司 | A kind of efficiently advanced hydrogen production from coke oven gas technique |
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| US20020181747A1 (en) * | 1999-10-28 | 2002-12-05 | Catherine Topping | Identification system |
| CN101850949A (en) * | 2010-06-11 | 2010-10-06 | 大连理工大学 | Method with high purity and high recovery rate for purifying hydrogen gas in coke oven gas |
| CN106673014A (en) * | 2016-12-29 | 2017-05-17 | 天津市创举科技有限公司 | Process of removing sulfur and ammonia from coke gas to prepare ammonia water |
| CN109704280A (en) * | 2019-01-24 | 2019-05-03 | 大连理工大学 | A kind of pressure-variable adsorption, absorption, steam reformation gas separating system associated with UF membrane |
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