CN214734512U - Raw gas hydrogen production system - Google Patents

Raw gas hydrogen production system Download PDF

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CN214734512U
CN214734512U CN202120398074.0U CN202120398074U CN214734512U CN 214734512 U CN214734512 U CN 214734512U CN 202120398074 U CN202120398074 U CN 202120398074U CN 214734512 U CN214734512 U CN 214734512U
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purification
adsorption
concentration
swing adsorption
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宋如昌
李亚军
高玉安
宋涛
张子东
谢庆辉
高宏寅
崔智宇
李斯嘉
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Shaanxi Dongxinyuan Chemical Co ltd
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Abstract

The application discloses a raw gas hydrogen production system, and relates to the field of raw gas hydrogen production equipment. The raw gas hydrogen production system comprises a gas compression device, a temperature swing adsorption device and more than two concentration and purification mechanisms, wherein the outlet end of the gas compression device is connected with the inlet end of the temperature swing adsorption device, and the more than two concentration and purification mechanisms are connected in parallel and are connected to the outlet end of the temperature swing adsorption device; the concentration and purification mechanism comprises a concentration adsorption device, a deoxidation device and a purification adsorption device, and the concentration adsorption device, the deoxidation device and the purification adsorption device are sequentially arranged in series along the flowing direction of the raw coke oven gas. According to the raw gas hydrogen production system, raw material raw gas is subjected to compression separation and temperature swing adsorption, and two paths of parallel concentration adsorption, deoxidation and purification adsorption are carried out, so that the resistance of the raw gas hydrogen production system is reduced, the long-period stable operation of the hydrogen production system is ensured, and the hydrogen yield and the hydrogen purity are greatly improved.

Description

Raw gas hydrogen production system
Technical Field
The application relates to the field of raw gas hydrogen production equipment, in particular to a raw gas hydrogen production system.
Background
Raw coke oven gas is a gas product which is separated out in the coal dry distillation process and is not purified, and the main components of the raw coke oven gas comprise hydrogen, nitrogen, methane, carbon monoxide and the like. In the industry, most of raw gas is used as fuel for power generation, so that not only is the resource waste greatly caused, but also serious environmental pollution is caused in the combustion process due to high sulfide content in the raw gas, and the raw gas is more low-efficiency in utilization of hydrogen rich in the raw gas. Hydrogen is an important chemical raw material and industrial protective gas, has wide application in the industries of ammonia synthesis, oil refining, electronics and metallurgy, has good combustion performance and environmental protection, and has potential huge demand on hydrogen in the future market. Therefore, the industry prepares high-purity hydrogen by taking the raw coke oven gas as a raw material, not only can solve the pollution problem of the emission and/or combustion of the raw coke oven gas, but also can reduce the waste of a large amount of coke resources, is an economic and environment-friendly measure for processing and utilizing the raw coke oven gas, and has obvious competitive advantage.
At present, the industry generally adopts a vacuum pressure swing adsorption method in the preparation of high-purity hydrogen by using raw coke oven gas, and the vacuum pressure swing adsorption method realizes the adsorption and regeneration of gas by using the change of pressure so as to achieve the gas separation technology, and has the advantages of safety, high efficiency, energy conservation and environmental protection.
However, in the existing separation technology for preparing high-purity hydrogen by using a vacuum pressure swing adsorption method, the resistance of a hydrogen production system is increased due to the large processing amount of raw gas, so that the yield and purity of hydrogen are obviously reduced, and the analysis reasons mainly include the following two points: firstly, the pressure of raw material crude gas after compression and temperature swing adsorption is obviously increased, so that the reverse pressure in the concentration vacuum pressure swing adsorption process is far higher than the designed value, and the reverse regeneration in the concentration vacuum pressure swing adsorption process and the regeneration of a subsequent purification adsorbent are not facilitated; and secondly, the regeneration effect of the adsorbent is poor, so that the adsorption capacity of the concentration and purification device is poor due to the linkage effect, and the adsorbent is not regenerated thoroughly, so that on one hand, the hydrogen production system cannot operate stably, and on the other hand, the load is likely to increase, and the yield and the purity of the hydrogen are likely to decrease.
SUMMERY OF THE UTILITY MODEL
The embodiment of the application provides a raw coke oven gas hydrogen production system, and solves the technical problems of large system resistance, small raw coke oven gas treatment capacity, low hydrogen yield and insufficient hydrogen purity in the process of preparing hydrogen by vacuum pressure swing adsorption.
In order to achieve the above purpose, the embodiment of the present application adopts the following technical solutions:
the raw gas hydrogen production system provided by the embodiment of the application comprises a gas compression device, a temperature swing adsorption device and more than two concentration and purification mechanisms;
the outlet end of the gas compression device is connected with the inlet end of the temperature swing adsorption device, and more than two concentration and purification mechanisms are connected in parallel and are connected to the outlet end of the temperature swing adsorption device;
the concentration and purification mechanism comprises a concentration adsorption device, a deoxidation device and a purification adsorption device;
the concentration adsorption device, the deoxidation device and the purification adsorption device are sequentially arranged in series along the flowing direction of the raw coke oven gas.
In some optional embodiments of the examples herein, the raw gas hydrogen production system further comprises a purification apparatus;
the purifying devices are connected in parallel at two ends of any one of the purifying and adsorbing devices.
In some alternative embodiments of the examples herein, the gas compression device comprises a gas compressor and a gas-liquid separator;
the gas-liquid separator is connected to an outlet end of the gas compressor.
In some optional embodiments of the examples herein, the raw gas hydrogen production system further comprises a pretreatment device;
the pretreatment device is arranged between the gas compression device and the temperature swing adsorption device and is used for removing ammonium salt impurities in the raw gas.
In some alternative embodiments of the examples herein, the pretreatment device comprises a water wash spray tower.
In some alternative embodiments of the examples herein, the temperature swing adsorption unit is at least loaded with coke and activated carbon.
In some alternative embodiments of the examples herein, the deoxygenator device comprises a deoxygenator column;
the inside of the deoxidation tower is at least filled with a desulfurizer and a deoxidizer.
Compared with the prior art, the beneficial effects or advantages of the embodiment of the application include:
the raw gas hydrogen production system provided by the embodiment of the application comprises a gas compression device, a temperature swing adsorption device and more than two concentration and purification mechanisms, wherein the outlet end of the gas compression device is connected with the inlet end of the temperature swing adsorption device, and the more than two concentration and purification mechanisms are connected in parallel and are connected to the outlet end of the temperature swing adsorption device; wherein concentration and purification mechanism includes concentration adsorption equipment, deoxidation device and purification adsorption equipment, and concentration adsorption equipment, deoxidation device and purification adsorption equipment set up along the flow direction of raw coke oven gas in proper order in series. In view of this, after raw material raw gas is compressed and subjected to temperature swing adsorption, concentration vacuum pressure swing adsorption, deoxidation and purification vacuum pressure swing adsorption can be simultaneously performed through the concentration and purification mechanisms connected in parallel, so that on one hand, the reverse discharge pressure in the concentration vacuum pressure swing adsorption process is reduced, and the reduction of the resistance of the raw gas hydrogen production system is realized; on the other hand, the treatment capacity of concentrating, deoxidizing and purifying the raw gas is improved, so that the hydrogen yield is increased; meanwhile, the regeneration effect of the adsorbent in the processes of concentration vacuum pressure swing adsorption, deoxidation and purification vacuum pressure swing adsorption is improved, and the adsorption capacity of the concentration vacuum pressure swing adsorption and the purification vacuum pressure swing adsorption is improved, so that the purity of the prepared hydrogen is improved.
According to the system and the process for preparing hydrogen from raw coke oven gas, provided by the embodiment of the application, on one hand, the treatment capacity of the raw coke oven gas can be controlled from 15 ten thousand Nm (nanometers)3Increase in/h to 25 ten thousand Nm3Hydrogen production from 2.7 ten thousand Nm/h3The/h is increased to 4.5 ten thousand Nm3And h, the treatment capacity of the raw gas and the hydrogen yield are improved, and on the other hand, the hydrogen purity is improved to more than 99.9 percent, so that the purity of the prepared hydrogen is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings used in the description of the embodiments will be briefly introduced below. It is obvious that the drawings in the following description are only some of the embodiments described in the present application, and that other drawings can be derived from these drawings by a person skilled in the art without inventive effort.
FIG. 1 is a schematic structural diagram of a raw gas hydrogen production system provided by an embodiment of the present application;
FIG. 2 is another schematic structural diagram of a raw gas hydrogen production system provided by the embodiment of the application;
fig. 3 is a schematic structural diagram of a gas compression device according to an embodiment of the present application.
Icon: 1-a gas compression device; 2-a temperature swing adsorption device; 3-a concentration and purification mechanism; 4-a purification device; 5-a pretreatment device; 11-a gas compressor; 12-a gas-liquid separator; 31-a concentration adsorption device; a 32-deoxygenation device; 33-purification and adsorption device.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In order to solve the problems of large system resistance, small raw gas treatment capacity, low hydrogen yield and insufficient hydrogen purity in the process of preparing hydrogen by using a pressure swing adsorption method, the embodiment of the application provides a raw gas hydrogen production system.
Referring to fig. 1 to fig. 3, fig. 1 is a schematic structural diagram of a raw gas hydrogen production system according to the present embodiment; FIG. 2 is another schematic structural diagram of the raw gas hydrogen production system provided by the embodiment; fig. 3 is a schematic structural diagram of the gas compression device provided in this embodiment.
As shown in fig. 1, the crude gas hydrogen production system comprises a gas compression device 1, a temperature swing adsorption device 2 and more than two concentration and purification mechanisms 3. The outlet end of the gas compression device 1 is connected with the inlet end of the temperature swing adsorption device 2, and more than two concentration and purification mechanisms 3 are connected in parallel and are connected to the outlet end of the temperature swing adsorption device 2. The concentration and purification mechanism 3 comprises a concentration adsorption device 31, a deoxidation device 32 and a purification adsorption device 33, wherein the concentration adsorption device 31, the deoxidation device 32 and the purification adsorption device 33 are sequentially arranged in series along the flowing direction of the raw coke oven gas.
The gas compression device 1 is a device and/or apparatus capable of compressing the volume of raw gas and performing gas-liquid separation, and may be composed of a gas compressor and a gas-liquid separator. Fig. 3 shows a composition structure of a gas compression apparatus 1, wherein the gas compression apparatus 1 includes a gas compressor 11 and a gas-liquid separator 12, and the gas-liquid separator 12 is connected to an outlet end of the gas compressor 11. Accordingly, the gas compression device 1 can compress the raw gas to a pressure of not less than 0.65MPa and then perform gas-liquid separation, thereby separating a part of the impurities such as phenols and tar contained in the raw gas.
It should be noted that the gas compression device 1 may further include more than two gas compressors 11 and a corresponding number of gas-liquid separators 12, wherein the more than two gas compressors 11 are connected in parallel, and the outlet end of each gas compressor 11 is connected to a gas-liquid separator 12, so as to achieve rapid compression and gas-liquid separation of raw material raw gas.
The composition of raw gas is related to the properties and proportion of coal, production operation conditions, raw gas purification method and operation, and other factors, wherein table 1 shows the composition proportion of raw gas. As can be seen from Table 1, the raw coke oven gas has a rather complex composition and a wide variation range. In the embodiment, the gas compression device 1 is adopted to compress and separate gas and liquid from raw crude gas, so that not only can part of phenols and tar in the raw crude gas be removed, but also the subsequent temperature swing adsorption and pressure swing adsorption speed is higher, the effect is better, and the hydrogen production efficiency can be improved.
TABLE 1 raw gas composition ratios
Figure BDA0002949288910000061
The temperature swing adsorption device 2 is a device and/or apparatus capable of performing temperature swing adsorption-desorption on the compressed raw gas, and may be composed of more than two parallel adsorption towers and matched program control valves, etc., and the adsorption and desorption operations are realized by valve switching and temperature change, for example, an activated carbon temperature swing adsorption apparatus. When the temperature swing adsorption device 2 operates, compressed raw gas enters one of the adsorption towers, and is subjected to five steps of adsorption, reverse pressure release, heating desorption, adsorbent cooling and adsorber stamping in sequence, and then exits from a raw gas flow pipeline through valve switching, and the other adsorption tower repeats the five steps, so that the two adsorption towers perform mutual alternate adsorption-desorption, and continuous temperature swing adsorption-desorption of the compressed raw gas is realized. Because each adsorption tower is filled with the adsorbent, the temperature swing adsorption device 2 is adopted to perform temperature swing adsorption treatment on the compressed raw gas in the embodiment, so that naphthalene and residual tar carried in the compressed raw gas can be removed. Wherein, the adsorbent filled in the temperature swing adsorption device at least comprises coke and activated carbon.
The concentration adsorption device 31 is a device and/or apparatus capable of performing vacuum pressure swing adsorption-desorption on the crude gas subjected to temperature swing adsorption, and may include a plurality of parallel adsorption towers and a vacuum pressure swing adsorption-desorption unitAn air pump, a desorption gas buffer tank, a matched program control valve and the like. When the concentration adsorption device 31 operates, the crude gas subjected to temperature swing adsorption enters one of the adsorption towers, and is subjected to the steps of adsorption, pressure equalizing and reducing for many times, sequential and reverse release, vacuumizing and flushing, and pressure equalizing and increasing for many times, and the pressure swing adsorption-desorption steps are alternately repeated through the adsorption towers, so that the vacuum pressure swing adsorption of the crude gas subjected to temperature swing adsorption is realized. Because each adsorption tower is filled with a plurality of special adsorbents, under the selective adsorption of different adsorbents, the raw gas can be removed from H2The majority of impurities other than H, e.g. hydrocarbons2O、CO2、H2S, part N2And CO, to obtain hydrogen-rich gas. The special adsorbent can be reasonably selected according to impurity components of the raw coke oven gas, and the embodiment does not limit the components.
The deoxidation apparatus 32 is a device and/or apparatus capable of desulfurizing and deoxidizing the hydrogen-rich gas, such as a deoxidation tower, in which at least a desulfurizing agent and a deoxidizing agent are filled. When the deoxidizing device 32 is in operation, the hydrogen-rich gas enters the deoxidizing tower, organic sulfur impurities in the hydrogen-rich gas are removed through the inlet desulfurizer, and a small amount of O is contained in the hydrogen-rich gas under the action of the deoxidizing agent2Can be reacted with H2Reaction to form H2O, thereby realizing the purpose of O in the hydrogen-rich gas2To obtain the deoxidized hydrogen-rich gas.
The purification and adsorption device 33 is a device and/or apparatus capable of performing vacuum pressure swing adsorption-desorption and drying on the deoxygenated hydrogen-rich gas, and may be composed of a plurality of adsorption towers, a vacuum pump, a desorption gas buffer tank, a program control valve and the like connected in parallel. When the purification and adsorption device 33 operates, the deoxygenated hydrogen-rich gas enters one of the adsorption towers and undergoes the steps of adsorption, pressure equalization and depressurization for multiple times, forward and reverse release, vacuumizing and flushing and pressure equalization and pressurization for multiple times, and the vacuum pressure swing adsorption-desorption steps are alternately repeated by the multiple adsorption towers, so that the vacuum pressure swing adsorption of the hydrogen-rich gas is realized. Since each adsorption tower is filled with a plurality of special adsorbents, purification is carried out under selective adsorption of different adsorbents, such as silica gel, so that H produced in hydrogen-rich gas can be removed2O; the filled molecular sieve can further remove hydrocarbons and CO2、H2S, part N2And CO and other impurities to realize the preparation of H2The purity is improved. Of course, the special adsorbent can be reasonably selected according to the components to be removed, and this embodiment does not limit this.
Referring to fig. 1 and fig. 2, the raw gas hydrogen production system further includes a purification device 4, and the purification device 4 is connected in parallel to both ends of any one of the purification adsorption devices 33 to purify the deoxidized hydrogen-rich gas. The purification device 4 is equipment and/or a device capable of performing vacuum pressure swing adsorption-desorption on the deoxidized hydrogen-rich gas, and comprises a plurality of adsorption towers, a vacuum pump, a desorbed gas buffer tank, matched program control valves and the like which are connected in parallel. When the purifying device 4 operates, the deoxidized hydrogen-rich gas enters one of the adsorption towers and undergoes the steps of adsorption, pressure equalizing and reducing for many times, forward and reverse release, vacuumizing and flushing and pressure equalizing and increasing for many times, and the vacuum pressure swing adsorption-desorption steps are alternately repeated by the adsorption towers, so that the vacuum pressure swing adsorption purification of the deoxidized hydrogen-rich gas is realized. Because each adsorption tower is filled with a plurality of special adsorbents, H produced in the hydrogen-rich gas can be removed under the selective adsorption of different adsorbents2O and can be further removed such as hydrocarbons, CO2、H2S, part N2And CO and other impurities to realize the preparation of H2The purity is improved. Of course, the special adsorbent can be reasonably selected according to the components to be removed. Specifically, in the embodiment of the application, three-way parallel purification vacuum pressure swing adsorption (including two-way parallel purification vacuum pressure swing adsorption and purification vacuum pressure swing adsorption) is performed on the deoxidized hydrogen-rich gas, and especially a purification vacuum pressure swing adsorption processing path is added to the deoxidized hydrogen-rich gas, so that the reverse release pressure in the purification vacuum pressure swing adsorption process is reduced, the resistance of a hydrogen production system is reduced, and the processing amount of the deoxidized hydrogen-rich gas is increased, so that the hydrogen yield is increased; meanwhile, the loading capacity of the adsorbent is increased, the regeneration effect of the adsorbent is improved, and the adsorption capacity of concentration adsorption and purification adsorption is improved, so that on one hand, the long-period stable operation of equipment can be ensured, and on the other hand, the improvement on the purity of the prepared hydrogen is realized.
As shown in fig. 2, the raw gas hydrogen production system further comprises a pretreatment device 5, wherein the pretreatment device 5 is arranged between the gas compression device 4 and the temperature swing adsorption device 5, and is used for removing ammonium salt impurities in the raw gas, so that the subsequent temperature swing adsorption and the vacuum pressure swing adsorption for concentration and purification are accelerated. Specifically, the pretreatment device 5 is a device capable of performing water washing desalination on the compressed raw gas components, such as a water washing spray tower. In the embodiment, the compressed raw gas is subjected to water washing spraying by using the water washing spraying tower, so that ammonium salt impurities in the raw gas are removed.
As can be seen from the above description, the raw coke oven gas hydrogen production system provided in the embodiment of the present application includes a gas compression device 1, a temperature swing adsorption device 2, and two or more concentration and purification mechanisms 3, an outlet end of the gas compression device 1 is connected to an inlet end of the temperature swing adsorption device 2, and the two or more concentration and purification mechanisms 3 are connected in parallel and are both connected to an outlet end of the temperature swing adsorption device 2; the concentration and purification mechanism 3 comprises a concentration adsorption device 31, a deoxidation device 32 and a purification adsorption device 33, wherein the concentration adsorption device 31, the deoxidation device 32 and the purification adsorption device 33 are sequentially arranged in series along the flowing direction of the raw coke oven gas. In view of this, when the raw gas hydrogen production system operates, raw gas firstly enters the gas compression device 1 for compression and gas-liquid separation, so that part of phenols and tar carried in the raw gas is separated and removed; the wastewater enters a pretreatment device 5 comprising a water washing spray tower, and the water washing spray tower in the pretreatment device 5 can remove ammonium salt impurities; entering a temperature swing adsorption device 2, sequentially carrying out five steps of adsorption, reverse pressure release, heating desorption, adsorbent cooling and adsorber stamping at the working temperature of less than or equal to 40 ℃ to realize continuous temperature swing adsorption-desorption of the raw coke oven gas, thereby removing naphthalene and residual tar impurities carried in the raw coke oven gas; the desorbed gas after temperature swing adsorption is subjected to two-way parallel concentration vacuum pressure swing adsorption, deoxidation and purification vacuum pressure swing adsorption, so that the hydrogen-rich throughput on the original concentration vacuum pressure swing adsorption and deoxidation paths is reduced, the reverse pressure in the concentration vacuum pressure swing adsorption process is reduced, the resistance of the crude gas after temperature swing adsorption in the concentration pressure swing adsorption process is reduced, the loading capacity of the special adsorbent in the concentration adsorption device 31 is increased, the adsorption effect and the regeneration effect of the special adsorbent and the adsorption capacity of the concentration vacuum pressure swing adsorption and the purification vacuum pressure swing adsorption are improved, the long-period stable operation of a hydrogen production system can be ensured, and the purity of the prepared hydrogen can be improved; meanwhile, through two parallel paths of concentration vacuum pressure swing adsorption and deoxidation, the treatment capacity of raw coke oven gas in unit time can be increased, and the yield of prepared hydrogen is improved; and the purification is carried out in parallel in the purification vacuum pressure swing adsorption process, and three paths of purification vacuum pressure swing adsorption and purification vacuum pressure swing adsorption are carried out after the hydrogen-rich gas is deoxidized, so that the passing rate of the hydrogen-rich gas on the original purification vacuum pressure swing adsorption path is reduced, the reverse discharge pressure in the purification vacuum pressure swing adsorption process is reduced, the resistance reduction of the hydrogen-rich gas when the hydrogen-rich gas passes through the purification vacuum adsorption device 33 is realized, the loading capacity of the special adsorbent in the purification adsorption device 33 is increased, the adsorption effect and the regeneration effect of the special adsorbent, the adsorption capacity of the concentration vacuum pressure swing adsorption and the purification vacuum pressure swing adsorption are improved, the long-period stable operation of a hydrogen production system can be ensured, and the purity of the prepared hydrogen can be improved.
According to the crude gas hydrogen production system provided by the embodiment of the application, on one hand, the crude gas can be processed by 15 ten thousand Nm3Increase in/h to 25 ten thousand Nm3Hydrogen production from 2.7 ten thousand Nm/h3The/h is increased to 4.5 ten thousand Nm3And h, the treatment capacity of the raw gas and the hydrogen yield are improved, and on the other hand, the hydrogen purity is improved to more than 99.9 percent, so that the purity of the prepared hydrogen is improved.
The above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the present application; although the present application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art. The technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure.

Claims (5)

1. A raw gas hydrogen production system is characterized by comprising a gas compression device, a temperature swing adsorption device and more than two concentration and purification mechanisms;
the outlet end of the gas compression device is connected with the inlet end of the temperature swing adsorption device, and more than two concentration and purification mechanisms are connected in parallel and are connected to the outlet end of the temperature swing adsorption device;
the concentration and purification mechanism comprises a concentration adsorption device, a deoxidation device and a purification adsorption device;
the concentration adsorption device, the deoxidation device and the purification adsorption device are sequentially arranged in series along the flowing direction of the raw coke oven gas.
2. The raw gas hydrogen production system according to claim 1, further comprising a purification device, wherein the purification device is connected in parallel to two ends of any one of the purification adsorption devices.
3. The raw gas hydrogen production system according to claim 1, wherein the gas compression device comprises a gas compressor and a gas-liquid separator, and the gas-liquid separator is connected to an outlet end of the gas compressor.
4. The raw gas hydrogen production system according to any one of claims 1 to 3, further comprising a pretreatment device, wherein the pretreatment device is disposed between the gas compression device and the temperature swing adsorption device.
5. The raw gas hydrogen production system according to claim 4, wherein the pretreatment device comprises a water-washing spray tower.
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