CN114604829B - 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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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, wherein the system comprises a normal pressure adsorption unit, a chemical absorption unit and a membrane separation unit pressure swing adsorption unit, a coke oven gas inlet is arranged on the normal pressure adsorption unit, an air outlet of the normal pressure 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 air outlet side of the membrane separation unit is connected with an air inlet of the pressure swing adsorption unit through a second compressor, and a hydrogen outlet is arranged on the pressure swing adsorption unit. The hydrogen for the fuel cell meeting the requirements is efficiently prepared through coupling integration of units such as normal pressure adsorption, chemical absorption, membrane separation, pressure swing adsorption and the like, the recovery rate exceeds 90%, and the concentration back mixing in the hydrogen purification process is reduced and the separation efficiency is improved through staged permeation of the membrane separation unit, staged desorption of the pressure swing adsorption unit and 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 the exhaustion of fossil energy sources, emission of greenhouse gases and the like, the global energy system is coming to be transformed, and hydrogen energy is a key carrier for realizing sustainable development by keeping green low carbon of new energy systems. Firstly, hydrogen energy is a recognized clean energy, pollution is not generated basically in the conversion and utilization process, and energy conversion with far higher efficiency than a heat engine can be realized through a fuel cell and other ways, and the 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 storage, transportation and multi-way use are facilitated. In addition, the solid high-carbon resources with low heat value such as oil sand, biomass, peat and the like can be converted into hydrogen energy, so that the energy quality improvement is realized, and meanwhile, the pipeline transportation and the centralized carbon emission reduction are facilitated.
In a hydrogen energy system, a new energy vehicle taking hydrogen as fuel takes an important role, and under the trend of rapid development of the new energy, the large-scale production of hydrogen for fuel cells with reasonable price becomes an important bottleneck for restricting the development of the hydrogen energy system at present.
The coke oven gas is the combustible gas which is a byproduct of high-temperature carbonization of coal in a coke oven. In general, each ton of dry coal can be by-produced into 300-350 standard coke oven gas, and the main components of the coke oven gas comprise hydrogen (55-60%), methane (23-27%), and small amounts of carbon monoxide, light hydrocarbons, naphthalene, tar, carbon dioxide, hydrogen sulfide, oxygen and nitrogen. The calorific value of coke oven gas can reach 17-19MJ/Nm3 generally, and is usually used as fuel of high-temperature industrial furnaces and city gas, and few projects are used for producing synthetic ammonia. In these conventional uses of coke oven gas, hydrogen resources are used as common fuel, and their value is not sufficiently achieved. If the hydrogen can be separated and purified by an effective separation process, the value of the hydrogen for the fuel cell can be improved by 5-10 times. In summary, coke oven gas will be a potential feedstock for large-scale production of hydrogen for fuel cells.
Hydrogen fuel cells have stringent requirements for the purity of hydrogen, especially for specific impurity levels. According to the specification of the national standard proton exchange membrane fuel cell fuel for automobile, namely hydrogen (GB/T37244-2018), the hydrogen for the fuel cell needs to meet the following key indexes of 99.97mol percent 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 for fuel cells with high added value by taking coke oven gas as a raw material, a high-efficiency purification technology must be developed to deeply or 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, and naphthalene, tar and NH are removed from the coke oven gas through temperature swing adsorption 3 、H 2 S, other aromatic compounds and other impurities enter a pressure swing adsorption device to obtain hydrogen with purity of more than 99.9v%, and the hydrogen is further deoxidized and dried to obtain high-purity hydrogen with purity of more than 99.999v%, oxygen content of less than 3ppm and dew point of less than-70 ℃; the purity of hydrogen in pressure swing adsorption desorption gas is more than 20% by volume, the hydrogen enters a membrane separation device after being compressed and cooled, and the obtained permeated gas with the purity of 55-65% by volume returns to a coke oven gas compressor to further recycle the hydrogen therein; and the residual seepage gas is discharged out of the boundary region of the device.
The method for purifying hydrogen from coke oven gas is characterized in that naphthalene, tar and NH are mixed 3 、H 2 S and other aromatic compounds and other impurities are removed through temperature swing adsorption, and various adsorbents are required to be filled according to strict distribution, so that the operation difficulty is high. Temperature swing adsorption requires additional steam to regenerate the adsorbent, and is energy efficient. In addition, coke oven gas directly enters pressure swing adsorption after temperature swing adsorption, the concentration of feed hydrogen is only 55-60 v%, and according to the operation experience of an industrial pressure swing adsorption device, the pressure swing adsorption device is not a feed concentration condition capable of efficiently operating, and the separation efficiency is low.
Disclosure of Invention
The purpose of the invention is that: the system for purifying the hydrogen from the coke oven gas is provided, various impurity gases are deeply removed through multi-technology integration, and the hydrogen 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 above purpose, the invention provides a system for purifying hydrogen from coke oven gas, which comprises a normal 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 absorbing light hydrocarbon, wherein the normal pressure adsorption unit is provided with a coke oven gas inlet, an air outlet of the normal pressure adsorption unit is connected with an air inlet of the chemical absorption unit, an air outlet of the chemical absorption unit is connected with the air inlet of the membrane separation unit through a first compressor, a low pressure air outlet side of the membrane separation unit is connected with the air 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 comprises a first membrane separation unit and a second membrane separation unit, the first compressor is connected with the air inlet of the first membrane separation unit, the low-pressure air outlet side of the first membrane separation unit is connected with the second compressor, the high-pressure air outlet side of the first membrane separation unit is connected with the air inlet of the second membrane separation unit, the low-pressure air outlet side of the second membrane separation unit is connected with the air inlet of the chemical absorption unit, and the high-pressure air outlet side of the second membrane separation unit is connected with the air inlet of the normal-pressure absorption unit.
Preferably, a regeneration heater is connected between the high-pressure air outlet side of the second membrane separation unit and the air inlet of the normal-pressure 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 sequentially connected 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 comprises an alkali liquor absorption unit and a water washing unit, wherein an air inlet at the bottom of the alkali liquor absorption unit is connected with the normal pressure adsorption unit, an air outlet at the top of the alkali liquor absorption unit is connected with an air inlet at the bottom of the water washing unit, an air outlet at the top of the water washing unit is connected with an air inlet of the membrane separation unit, an alkali liquor inlet pipe is connected at the top of the alkali liquor absorption unit, and a water inlet pipe is connected at the top of the water washing unit.
The invention also provides a method for purifying hydrogen by using the coke oven gas, which comprises the following steps that step S1, the coke oven gas enters the normal pressure adsorption unit from an air inlet at the bottom of the normal pressure adsorption unit, and oil-free coke oven gas is generated after heavy hydrocarbon is adsorbed;
s2, enabling oil-free coke oven gas to enter from the bottom of the alkali liquor absorption unit and contact with alkali liquor entering from the top of the tower in a countercurrent manner to form desulfurization decarbonization rich liquor, discharging the desulfurization decarbonization rich liquor from the bottom of the tower to form desulfurization coke oven gas, entering a water washing unit from the top of the alkali liquor absorption unit, and washing the desulfurization coke oven gas to form purified coke oven gas;
step S3, purifying coke oven gas, pressurizing 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 permeation gas at the low pressure side of the first membrane separation unit, enabling the first membrane separation hydrogen-rich permeation gas to enter a second compressor, and forming a first membrane separation hydrogen-poor permeation residual gas at the high pressure side of the first membrane separation unit;
and S4, boosting the first membrane separation hydrogen-rich permeate gas by a second compressor to form pressure swing adsorption feeding, and enabling the pressure swing adsorption feeding to enter a pressure swing adsorption unit to produce hydrogen for the fuel cell.
Preferably, the method further comprises the step S5 of enabling the first membrane separation hydrogen-depleted residual gas to enter a second membrane separation unit, enabling a low-pressure side of the second membrane separation unit to form a second membrane separation hydrogen-enriched permeation gas, enabling the second membrane separation hydrogen-enriched permeation gas to enter an alkali liquor absorption unit, and enabling a high-pressure side of the second membrane separation unit to form a second membrane separation hydrogen-depleted residual gas;
and S6, allowing the hydrogen-depleted residual gas after the second membrane separation to enter a regeneration heater to form hot regeneration air, and allowing the hot regeneration air to enter an atmospheric adsorption unit to desorb heavy hydrocarbon to form hot regeneration tail gas.
Preferably, when the adsorption tower of the pressure swing adsorption unit is close to a saturated state, switching to a desorption regeneration working state, desorbing at normal pressure in a first stage of desorption regeneration and producing a first desorption gas, and enabling the first desorption gas and purified coke oven gas to enter a first compressor after stranding; and in the desorption regeneration second stage, negative pressure desorption is carried out, a second desorption gas is produced, the second desorption gas is boosted by a vacuum pump and a third compressor to form a pressurized desorption gas, and the pressurized desorption gas is stranded with the hydrogen-poor permeation residual gas separated by the first membrane and then enters 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 pressure swing desorption gas to 2.0MPaG, and the regeneration heater increases the temperature of the hot regeneration gas feed to above 150 ℃.
Compared with the prior art, the system and the method for purifying the hydrogen from the coke oven gas have the beneficial effects that: the coke oven gas is firstly subjected to normal pressure adsorption unit, and heavy hydrocarbon molecules with higher boiling points such as naphthalene, tar and the like are deeply removed by the normal pressure adsorption unit, so that the heavy hydrocarbon molecules are prevented from being contacted with a subsequent compressor and a membrane separation unit; the oil-free coke oven gas generated after the adsorption treatment of the normal pressure adsorption unit enters the chemical absorption unit, hydrogen sulfide and most carbon dioxide can be deeply removed, the generated desulfurization coke oven gas enters the membrane separation unit after being boosted by the first compressor, the membrane separation unit can remove impurities such as methane, nitrogen, light hydrocarbon and carbon monoxide, the hydrogen content can reach more than 97.5mol percent, finally the oil-free coke oven gas enters the pressure swing adsorption unit after being boosted by the second compressor, and the impurities such as methane, carbon monoxide, nitrogen and light hydrocarbon are all adsorbed and trapped, so that the hydrogen for the fuel cell meeting the national standard is produced; the hydrogen for the fuel cell meeting the national standard requirement is efficiently prepared through 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 difference back mixing in the hydrogen purification process is reduced and the separation efficiency is improved through staged permeation of the membrane separation unit, staged desorption of the pressure swing adsorption unit and coupling integration of the membrane separation unit and the pressure swing adsorption unit.
Drawings
FIG. 1 is a schematic diagram of the system for purifying hydrogen from coke oven gas according to the present invention;
FIG. 2 is a schematic structural view 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 view of a second membrane separation unit of the system for purifying hydrogen from coke oven gas of 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. a 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 through first membrane separation; s-10, separating hydrogen-rich permeation gas by a first membrane; s-11, separating the hydrogen-depleted residual gas by a first membrane; s-12, separating hydrogen-rich permeation gas by a second membrane; s-13, separating the hydrogen-depleted residual gas by a second membrane; s-14, hot regeneration air intake; s-15, thermally regenerating tail gas; s-16, pressure swing adsorption feeding; s-17, hydrogen for fuel cells; s-18, first desorption gas; s-19, second desorption gas; s-20, pressurizing and desorbing air.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The system for purifying hydrogen from coke oven gas S-1 comprises an atmospheric pressure adsorption unit 1, a chemical absorption unit, a membrane separation unit and a pressure swing adsorption unit 9, wherein the atmospheric pressure adsorption unit 1, the chemical absorption unit, the membrane separation unit and the pressure swing adsorption unit 9 are sequentially connected as shown in fig. 1 to 3. The normal pressure adsorption unit 1 is used for absorbing heavy hydrocarbon, the chemical absorption unit is used for removing acid impurity gas, the membrane separation unit is used for separating hydrogen, and the 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 entering the coke oven gas S-1 produced by high-temperature carbonization of coal, and the air outlet of the normal pressure adsorption unit 1 is connected with the air inlet of the chemical absorption unit. The core equipment of the normal pressure adsorption unit 1 is composed of two or more adsorption towers, the adsorbent filled in the adsorption towers can be, but not limited to, activated carbon, carbon molecular sieve, carbon fiber, silica gel or zeolite molecular sieve, or can be a combination of the above adsorbents, and the abundant pore structure and the surface area of the adsorbent have strong affinity with heavy hydrocarbon.
After the coke oven gas S-1 enters an adsorption tower in an adsorption working state, naphthalene, tar and other heavy hydrocarbons are adsorbed, and the obtained oil-free coke oven gas S-2 enters a chemical absorption unit. In the present embodiment, the coke oven gas S-1 enters from the bottom of the adsorption tower of the normal pressure adsorption unit 1 to increase the contact area with the normal pressure adsorption unit 1. The specific structure of the normal pressure adsorption unit 1 is prior art and will not be described in detail here.
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 carbon dioxide in the coke oven gas S-1 to form desulfurization coke oven gas S-5, and the desulfurization 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 decarbonization rich solution S-4 in the chemical absorption unit, and the desulfurization decarbonization rich solution S-4 is extracted from the bottom of the tower and 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 a first compressor 4, the desulfurized coke oven gas S-5 firstly enters the first compressor 4, the first compressor 4 can raise 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, a first membrane separation hydrogen-rich permeation gas S-10 is formed at the low-pressure outlet side, the hydrogen content is more than 97.5mol%, a first membrane separation hydrogen-poor permeation residual gas S-11 is formed at the high-pressure outlet side, and the hydrogen content is lower than 30.0mol%.
The low pressure gas outlet side of the membrane separation unit is connected with the gas inlet of the pressure swing adsorption unit 9 through the second compressor 8, the second compressor 8 can boost the pressure of the first membrane separation hydrogen-rich permeation gas S-10 to more than 1.5MPaG to form 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 be of a conventional membrane separation structure, and will not be described in detail herein.
The pressure swing adsorption unit 9 is a complete set of equipment and is used for adsorbing light hydrocarbons in the pressure swing adsorption feed S-16 to generate hydrogen S-17 for fuel cells meeting the national standard requirement, and a hydrogen outlet is arranged on the pressure swing adsorption unit 9. The pressure swing adsorption unit 9 is a complete equipment, and the core equipment consists of two or more adsorption towers, wherein the adsorption towers are filled with 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) in a layered manner from bottom to top. The pressure swing adsorption feed S-16 with the pressure increased by the second compressor 8 enters an adsorption tower in an adsorption working state in the pressure swing adsorption unit 9 from the bottom, and impurities such as methane, carbon monoxide, nitrogen, light hydrocarbon and the like are all adsorbed and trapped, so that the hydrogen S-17 for the fuel cell meeting the national standard is produced. The specific construction of the pressure swing adsorption unit 9 is prior art and will not be described in detail here.
When the adsorption tower of the pressure swing adsorption unit 9 is close to a saturated state, switching to a desorption regeneration working state, and performing normal pressure desorption in a desorption regeneration first stage, wherein the desorption pressure range is usually 0.20MPaG to normal pressure, and generating a first desorption gas S-18 with hydrogen content exceeding 65mol percent; in the second stage of desorption regeneration, negative pressure desorption is carried out, the desorption pressure is usually in the range of normal pressure to-0.08 MPaG, and the second desorption gas S-19 with the hydrogen content exceeding 30mol percent is produced.
In the method, 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, the generated desulfurization coke oven gas S-5 enters a membrane separation unit after being boosted by the 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 97.5mol%, and finally enters a pressure swing adsorption unit 9 after being boosted by the second compressor 8, and the impurities such as methane, carbon monoxide, nitrogen and light hydrocarbon are all adsorbed and trapped, so that the hydrogen S-17 for the fuel cell meeting the national standard is produced; the hydrogen S-17 for the fuel cell meeting the national standard requirement is efficiently prepared through 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 staged permeation of the membrane separation unit, staged desorption of the pressure swing adsorption unit 9 and coupling 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 air outlet side of the first membrane separation unit 5 is connected with the second compressor 8, the high-pressure air 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 air outlet side of the second membrane separation unit 6 is connected with the air inlet of the chemical absorption unit, and the high-pressure air outlet side of the second membrane separation unit 6 is connected with the air inlet of the normal-pressure 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 fine filter 16, and a hydrogen separation membrane 17, and the cooler 12, the liquid separation tank 13, the demister 14, the heater 15, the fine 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-depleted retentate S-11 on the high pressure side of the hydrogen separation membrane 17. The first membrane separation unit 5 is a plant, the specific construction of which is prior art and is not described in detail here.
In the present embodiment, the second membrane separation unit 6 is composed of a fine filter 16 and a hydrogen separation membrane 17, the size of hydrogen molecules is much smaller than that of impurity molecules, and the diffusion rate in the membrane material is higher, preferentially permeating. The hydrogen-depleted retentate S-11 of the first membrane separation forms a second membrane separation hydrogen-enriched permeate S-12 on the low pressure side of the hydrogen separation membrane 17, which has a hydrogen content of about 85.0mol% and, due to the higher impurity content, hydrogen sulfide and carbon dioxide are concentrated, the concentration of hydrogen sulfide is greater than 20ppmv, the concentration of carbon dioxide is greater than 0.5vol%, and the hydrogen sulfide and carbon dioxide can be absorbed and then continue to produce hydrogen.
The trapped impurities and a small amount of hydrogen in the first membrane separation hydrogen-lean permeation residual gas S-11 form second membrane separation hydrogen-lean permeation residual gas S-13 on the high pressure side of the hydrogen separation membrane 17, the hydrogen content is lower than 10.0mol%, the second membrane separation hydrogen-lean permeation 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 outlet side of the second membrane separation unit 6 and the inlet of the normal pressure adsorption unit 1.
The second membrane separation hydrogen-lean residual gas S-13 generated by the second membrane separation unit 6 firstly enters the regeneration heater 7, the temperature of the gas can be raised to be more than 150 ℃ by the regeneration heater 7 to become hot regeneration inlet gas S-14, the hot regeneration inlet gas S-14 enters an adsorption tower in a working state in the normal pressure adsorption unit 1, 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 tube type heat exchanger.
Preferably, the normal pressure desorption outlet of the pressure swing adsorption unit 9 is connected to the air inlet of the first compressor 4, and the negative pressure desorption outlet of the pressure swing adsorption unit 9 is connected to the air inlet of the second membrane separation unit 6.
The pressure swing adsorption feed 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 to a saturated state, normal pressure desorption is carried out in a desorption regeneration first stage, a first desorption gas S-18 with the hydrogen content of more than 65mol percent is produced, and the first desorption gas S-18 is stranded with purified coke oven gas S-8 through a normal pressure desorption outlet and is sent to the first compressor 4, so that the recycling of hydrogen-containing gas is realized, and the hydrogen production efficiency is improved. And in the second stage of desorption regeneration, negative pressure desorption is carried out, a second desorption gas S-19 with the hydrogen content exceeding 30mol percent is produced, and the second desorption gas can enter the second membrane separation unit 6 to continuously separate hydrogen.
Preferably, a vacuum pump 10 and a third compressor 11 are sequentially connected between the negative pressure desorption outlet of the pressure swing adsorption unit 9 and the air inlet of the second membrane separation unit 6.
The second desorption gas S-19 is lifted to a pressure above 2.0MPaG by the vacuum pump 10 and the third compressor 11 to become a pressurized desorption gas S-20, and then is stranded with the first membrane separated hydrogen-lean permeation residual gas S-11, and the diffusion rate of hydrogen can be improved after the pressure is lifted, so that the hydrogen is permeated.
Preferably, the chemical absorption unit comprises an alkali liquor absorption unit 2 and a water washing unit 3, wherein an air inlet at the bottom of the alkali liquor absorption unit 2 is connected with the normal pressure adsorption unit 1, an air outlet at the top of the alkali liquor absorption unit 2 is connected with an air inlet at the bottom of the water washing unit 3, an air outlet at the top of the water washing unit 3 is connected with an air inlet of the membrane separation unit, an alkali liquor inlet pipe is connected at the top of the alkali liquor absorption unit, and an air inlet pipe is connected at the top of the water washing unit 3.
The core equipment of the alkali liquor absorbing unit 2 is a packed absorbing tower or a sieve plate absorbing tower, oil-free coke oven gas S-2 generated by the normal pressure absorbing unit 1 enters the alkali liquor absorbing unit 2 from the bottom of the tower and is in countercurrent contact with an alkaline absorbent S-3 entering the alkali liquor inlet pipe at the top of the tower, the alkaline absorbent S-3 can be but not limited to an alcohol amine solution, a sodium hydroxide solution, a suspension of calcium hydroxide and a potassium carbonate solution, hydrogen sulfide and most carbon dioxide are absorbed by reacting with active components in the alkaline absorbent S-3, the formed desulfurization decarbonization rich solution S-4 is extracted from the bottom of the tower and is sent to an absorbent regenerating device, and meanwhile, the formed desulfurization coke oven gas S-5 is extracted from the top of the tower and is sent to the water washing unit 3.
The core equipment of the water washing unit 3 is a packing absorption tower or a sieve plate absorption tower, the 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 a water inlet pipeline at the top of the tower, alkaline liquid mist carried in gas phase is absorbed and trapped by the softened water S-6, formed dilute alkali liquor S-7 is extracted from the bottom of the tower and is sent to an alkali liquor concentration device, and meanwhile, formed purified coke oven gas S-8 is extracted from the top of the tower and is sent to the first compressor 4.
The invention also provides a method for purifying hydrogen by using the coke oven gas S-1, which comprises the following steps that step S1, the coke oven gas S-1 enters the normal pressure adsorption unit 1 from an air inlet at the bottom of the normal pressure adsorption unit 1, and oil-free coke oven gas S-2 is generated after heavy hydrocarbon is adsorbed;
s2, enabling 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 alkali liquor absorption unit 2 to form desulfurization decarbonization rich liquor S-4, discharging the desulfurization decarbonization rich liquor S-4 from the bottom of the alkali liquor absorption unit 2 to form desulfurization coke oven gas S-5, entering a washing unit 3 from the top of the alkali liquor absorption unit 2, and washing the desulfurization coke oven gas S-5 to form purified coke oven gas S-8;
step S3, purifying coke oven gas S-8, pressurizing 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 permeation gas S-10 on the low pressure side of the first membrane separation unit 5, enabling the first membrane separation hydrogen-rich permeation gas S-10 to enter a second compressor 8, and forming a first membrane separation hydrogen-poor permeation residual gas S-11 on the high pressure side of the first membrane separation unit 5;
and S4, the first membrane separation hydrogen-rich permeation gas S-10 is boosted 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.
The oil-free coke oven gas S-2 generated after the adsorption treatment of the normal pressure adsorption unit 1 enters a chemical absorption unit, hydrogen sulfide and most carbon dioxide can be deeply removed, the generated desulfurization 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 97.5mol percent, finally the oil-free coke oven gas S-2 enters a pressure swing adsorption unit 9 after being boosted by a second compressor 8, and the impurities such as methane, carbon monoxide, nitrogen and light hydrocarbon are all adsorbed and trapped to produce hydrogen S-17 for the fuel cell meeting the national standard; the hydrogen S-17 for the fuel cell meeting the national standard requirement is efficiently prepared through 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 staged permeation of the membrane separation unit, staged desorption of the pressure swing adsorption unit 9 and coupling integration of the membrane separation unit and the pressure swing adsorption unit 9.
Preferably, the method further comprises the step S5, wherein the first membrane separation hydrogen-depleted residual gas S-11 enters the second membrane separation unit 6, the low pressure side of the second membrane separation unit 6 forms a second membrane separation hydrogen-enriched permeation gas S-12, the second membrane separation hydrogen-enriched permeation gas S-12 enters the alkali liquor absorption unit 2, and the high pressure side of the second membrane separation unit 6 forms a second membrane separation hydrogen-depleted residual gas S-13;
in the step S6, the hydrogen-depleted residual gas S-13 of the second membrane separation enters a regeneration heater 7 to form a thermal regeneration inlet gas S-14, and the thermal regeneration inlet gas S-14 enters the normal pressure adsorption unit 1 to desorb heavy hydrocarbon to form a thermal regeneration tail gas S-15.
Preferably, when the adsorption tower of the pressure swing adsorption unit 9 is close to a saturated state, the pressure swing adsorption unit is switched to be in a desorption regeneration working state, and is subjected to normal pressure desorption in a first stage of desorption regeneration to produce a first desorption gas S-18, and the first desorption gas S-18 and purified coke oven gas S-8 are stranded and then enter the first compressor 4; in the second stage of desorption regeneration, negative pressure desorption is carried out, a second desorption gas S-19 is produced, the second desorption gas S-19 is boosted by a vacuum pump 10 and a third compressor 11 to form a pressurized desorption gas S-20, and the pressurized desorption gas S-20 is stranded with the first membrane separation hydrogen-poor permeation residual gas S-11 and then enters 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 pressure swing adsorption feed S-20 to 2.0MPaG, and the regeneration 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 is firstly subjected to normal pressure adsorption unit, and heavy hydrocarbon molecules with higher boiling points such as naphthalene, tar and the like are deeply removed by the normal pressure adsorption unit, so that the heavy hydrocarbon molecules are prevented from being contacted with a subsequent compressor and a membrane separation unit; the oil-free coke oven gas generated after the adsorption treatment of the normal pressure adsorption unit enters the chemical absorption unit, hydrogen sulfide and most carbon dioxide can be deeply removed, the generated desulfurization coke oven gas enters the membrane separation unit after being boosted by the first compressor, the membrane separation unit can remove impurities such as methane, nitrogen, light hydrocarbon and carbon monoxide, the hydrogen content can reach more than 97.5mol percent, finally the oil-free coke oven gas enters the pressure swing adsorption unit after being boosted by the second compressor, and the impurities such as methane, carbon monoxide, nitrogen and light hydrocarbon are all adsorbed and trapped, so that the hydrogen for the fuel cell meeting the national standard is produced; the hydrogen for the fuel cell meeting the national standard requirement is efficiently prepared through 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 difference back mixing in the hydrogen purification process is reduced and the separation efficiency is improved through staged permeation of the membrane separation unit, staged desorption of the pressure swing adsorption unit and coupling integration of the membrane separation unit and the pressure swing adsorption unit.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and substitutions can be made by those skilled in the art without departing from the technical principles of the present invention, and these modifications and substitutions should also be considered as being within the scope of the present invention.
Claims (10)
1. The utility model provides a system for coke oven gas purification hydrogen, its characterized in that, including the normal pressure adsorption unit that is used for absorbing heavy hydrocarbon, the chemical absorption unit that is used for getting rid of acid impurity gas, the membrane separation unit that is used for separating hydrogen, the pressure swing adsorption unit that is used for adsorbing light hydrocarbon, be equipped with coke oven gas import on the normal pressure adsorption unit, the gas outlet of normal pressure adsorption unit with the air inlet of chemical absorption unit is connected, the gas outlet of chemical absorption unit with be connected through first compressor between the air inlet of membrane separation unit, the low pressure air outlet side of membrane separation unit with the air inlet of pressure swing adsorption unit is connected through the second compressor, be equipped with the hydrogen export on the pressure swing adsorption unit.
2. The system for purifying hydrogen from coke oven gas according to claim 1, wherein the membrane separation unit comprises a first membrane separation unit and a second membrane separation unit, wherein the first compressor is connected to the gas inlet of the first membrane separation unit, the low-pressure gas outlet side of the first membrane separation unit is connected to the second compressor, the high-pressure gas outlet side of the first membrane separation unit is connected to the gas inlet of the second membrane separation unit, the low-pressure gas outlet side of the second membrane separation unit is connected to the gas inlet of the chemical absorption unit, and the high-pressure gas outlet side of the second membrane separation unit is connected to the gas inlet of the normal-pressure adsorption unit.
3. The system for purifying hydrogen from coke oven gas according to claim 2, wherein a regenerative heater is connected between the high-pressure outlet side of the second membrane separation unit and the inlet of the normal pressure adsorption unit.
4. The system for purifying hydrogen from coke oven gas according to claim 2, wherein the atmospheric pressure desorption outlet of the pressure swing adsorption unit is connected to the gas inlet of the first compressor, and the negative pressure desorption outlet of the pressure swing adsorption unit is connected to the gas inlet of the second membrane separation unit.
5. The system for purifying hydrogen from coke oven gas according to claim 4, wherein a vacuum pump and a third compressor are sequentially connected 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 according to any one of claims 1 to 5, wherein the chemical absorption unit comprises an lye absorption unit and a water washing unit, wherein an air inlet at the bottom of the lye absorption unit is connected with the atmospheric adsorption unit, an air outlet at the top of the lye absorption unit is connected with an air inlet at the bottom of the water washing unit, an air outlet at the top of the water washing unit is connected with an air inlet of the membrane separation unit, an lye inlet pipe is connected at the top of the lye absorption unit, and an air inlet pipe is connected at the top of the water washing unit.
7. A method for purifying hydrogen from coke oven gas, a system for purifying hydrogen from coke oven gas according to any one of claims 1 to 6, comprising the steps of,
step S1, coke oven gas enters an atmospheric adsorption unit from an air inlet at the bottom of the atmospheric adsorption unit, and oil-free coke oven gas is generated after heavy hydrocarbon is adsorbed;
s2, enabling oil-free coke oven gas to enter from the bottom of the alkali liquor absorption unit and contact with alkali liquor entering from the top of the tower in a countercurrent manner to form desulfurization decarbonization rich liquor, discharging the desulfurization decarbonization rich liquor from the bottom of the tower to form desulfurization coke oven gas, entering a water washing unit from the top of the alkali liquor absorption unit, and washing the desulfurization coke oven gas to form purified coke oven gas;
step S3, purifying coke oven gas, pressurizing 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 permeation gas at the low pressure side of the first membrane separation unit, enabling the first membrane separation hydrogen-rich permeation gas to enter a second compressor, and forming a first membrane separation hydrogen-poor permeation residual gas at the high pressure side of the first membrane separation unit;
and S4, boosting the first membrane separation hydrogen-rich permeate gas by a second compressor to form pressure swing adsorption feeding, and enabling the pressure swing adsorption feeding to enter a pressure swing adsorption unit to produce hydrogen for the fuel cell.
8. The method for purifying hydrogen from coke oven gas according to claim 7, further comprising step S5, wherein the first membrane separation hydrogen-depleted retentate enters a second membrane separation unit, the low pressure side of the second membrane separation unit forms a second membrane separation hydrogen-enriched permeate, the second membrane separation hydrogen-enriched permeate enters an alkaline liquor absorption unit, and the high pressure side of the second membrane separation unit forms a second membrane separation hydrogen-depleted retentate;
and S6, allowing the hydrogen-depleted residual gas after the second membrane separation to enter a regeneration heater to form hot regeneration air, and allowing the hot regeneration air to enter an atmospheric adsorption unit to desorb heavy hydrocarbon to form hot regeneration tail gas.
9. The method for purifying hydrogen from coke oven gas according to claim 8, wherein when the adsorption tower of the pressure swing adsorption unit is close to a saturated state, the pressure swing adsorption unit is switched to a desorption regeneration working state, and is subjected to normal pressure desorption in a first stage of desorption regeneration to produce a first desorption gas, and the first desorption gas is stranded with the purified coke oven gas and then enters a first compressor; and in the desorption regeneration second stage, negative pressure desorption is carried out, a second desorption gas is produced, the second desorption gas is boosted by a vacuum pump and a third compressor to form a pressurized desorption gas, and the pressurized desorption gas is stranded with the hydrogen-poor permeation residual gas separated by the first membrane and then enters a second membrane separation unit.
10. The method for purifying hydrogen from coke oven gas according to claim 9, wherein the first compressor increases the pressure of the first membrane separation feed to 2.0mpa g, the second compressor increases the pressure of the pressure swing adsorption feed to 2.0mpa g, the third compressor increases the pressure of the pressurized stripping gas to 2.0mpa g, and the regeneration heater increases the temperature of the hot regeneration gas feed to 150 ℃.
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