CN113881464A - Fine desulfurization device and method for coke oven gas - Google Patents
Fine desulfurization device and method for coke oven gas Download PDFInfo
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Abstract
The invention discloses a fine desulfurization device and a fine desulfurization method for coke oven gas, and belongs to the technical field of gas desulfurization. The fine desulfurization device comprises an adsorption tower, a washing tower and a conversion tank, wherein a gas inlet of the adsorption tower is communicated with a gas inlet main pipe, and a gas outlet of the adsorption tower is communicated with a clean gas outlet main pipe; the gas inlet of the conversion tank is communicated with the adsorption tower through a circulating desorption gas inlet pipe, and the gas outlet of the conversion tank is communicated with the adsorption tower through a circulating desorption gas outlet pipe; the circulating analysis gas inlet pipe is provided with a heating device and a desorption fan, and the circulating analysis gas outlet pipe is communicated with the washing tower through an analysis gas exhaust inlet pipe. The invention can effectively prolong the continuous working time of the adsorption tower, prevent the easy blockage of the adsorbent and the easy poisoning of the catalyst, improve the efficiency of removing organic sulfur in the coke oven gas, the blast furnace gas and the gasifier gas and reduce the energy consumption in the whole process.
Description
Technical Field
The invention belongs to the technical field of gas desulfurization, and particularly relates to a fine desulfurization device and a fine desulfurization method for microcrystalline molecular sieves of coke oven gas.
Background
The fuel gas used by the heating furnace and boiler in the iron and steel industry mainly comes from coke oven gas produced by coking and blast furnace gas produced by blast furnace smelting, and the content of sulfide in the gas determines the flue gas SO after combustion2Whether the content can reach the standard or not. The coke oven gas of the steel and iron combined enterprise also contains a certain amount of H after desulfurization and decyanation2S and organic sulfur (carbon disulfide, carbon oxysulfide, thiol, thioether, thiophene, methyl thiol, methyl sulfide, etc.), and a small amount of naphthalene, tar, benzene, ammonia, hydrogen cyanide, etc.; blast furnace gas contains 1.5-3.0% of H20.2-0.5% of CH425-30% of CO and 9-12% of CO255-60% of N20.2-0.4% of O2Also contains 30-60mg/Nm3H of (A) to (B)2S、80-150mg/Nm3Organic sulfur (carbonyl sulfide, carbon disulfide, mercaptans and thioethers), dust, and the like.
The existing coke oven gas desulfurization technology mainly removes inorganic sulfur, and little consideration is given to the removal of organic sulfur, so that the sulfur content is even H2The content of S reaches the standard (less than 20 mg/m)3) And it is difficult to ensure the flue gas SO after gas combustion2The emission can reach the standard; blast furnace caffeine H2The S content is low without removal. H in coke oven gas2The S removal method is more, and the currently domestic common methods comprise vacuum carbonate, AS, HPF and PDS methods, and H of desulfurized coal gas2The S content is generally less than or equal to 300mg/Nm3The content of organic sulfur is no more than 350mg/Nm3. In order to implement the ultralow emission standard of the atmospheric pollutants in the steel industry and reduce the SO of the flue gas of coke oven gas and downstream users of blast furnace gas2Content, source treatment, organic sulfur fine removal of coke oven gas and blast furnace gasSulfur or deep desulfurization treatment. The fine desulfurization or deep desulfurization of coke oven gas comprises the removal of organic sulfur and hydrogen sulfide, and the mature method comprises dry desulfurization and organic sulfur catalytic hydrogenation conversion. The dry desulfurization process has many kinds, such as oxidation process, adsorption-desorption process, etc., but the gas contains tar, naphthalene, benzene, ammonia, hydrogen cyanide, etc., so that the desulfurizer has poisoning failure in different degrees, which is not favorable for the continuous desulfurization process.
Literature [ catalytic hydroconversion of coke oven gas for fine desulfurization process and production practice]The process for fine desulfurization of coke oven gas by catalytic hydrogenation conversion method using ZnO as catalyst is introduced, in the course of said process O in the gas2、H2The over-standard contents of S, tar, dust and other components may cause the damages of ZnO catalyst such as high-temperature inactivation, short service life, equipment blockage and the like, but effective measures for improving the fine desulfurization efficiency and reducing the energy consumption and the operation cost of a system are not provided in the literature.
The document [ flow analysis of coke oven gas fine desulfurization process ], aiming at the problems of high cost of the ferro-manganese catalyst used in the fine desulfurization process, difficult solid waste treatment and the like, proposes to replace the ferro-manganese catalyst with medium-temperature zinc oxide and change the original primary hydrogenation into a secondary hydrogenation flow, belongs to an improvement on the ferro-manganese catalyst fine desulfurization process, but the problems of high operation cost, long process route, frequent catalyst replacement, unsatisfactory thiophene removal and the like of the process are not effectively solved.
Through retrieval, the application with the Chinese patent application number of 201911353163.7 discloses an ultra-deep removal device for organic sulfur in coke oven gas and a removal process thereof, and the application provides the ultra-deep removal device for the organic sulfur, aiming at the weak capability of zinc oxide for removing the organic sulfur in the process of preparing natural gas through methanation of the coke oven gas.
For another example, chinese patent application No. 201710590574.2 discloses a method for removing organic sulfur from coke oven gas, which comprises feeding the gas from coke oven into a crude debenzolization unit, debenzolizing by solvent extraction, feeding the gas into a crude desulfurization unit, and performing crude desulfurization by using at least one desulfurizing agent selected from organic amine, limestone, calcium hydroxide and iron oxide, feeding the gas into a water-gas separator, removing water from the coke oven gas by using at least one of a molecular sieve and activated carbon, feeding the gas from the water-gas separator into a comprehensive purification tower containing a molecular sieve adsorbent, and simultaneously removing aromatic hydrocarbons and organic sulfides in the gas. The method for removing organic sulfur in this application is mainly filtration adsorption, and although it is mentioned that the molecular sieve adsorbent can be regenerated, the process scheme is not shown, and how to regenerate the adsorbent and catalytically convert organic sulfur are not described.
For another example, the application with chinese patent application No. 201810829320.6, which is directed to the problem that trace impurities such as light alkene, organic sulfide and oxygen in coke oven gas generate exothermic reaction on the surface of the synthetic catalyst, and carbon formation blocks the catalyst pore channels, which easily causes catalyst deactivation in the coke oven gas dry purification process, provides a method for removing oxygen and fine desulfurization of coke oven gas, which comprises the following steps: s1), heat exchange and temperature rise, S2), pre-hydrogenation conversion and primary hydrogenation conversion, S3), primary desulfurization, S4), secondary heat exchange and temperature rise, S5), secondary hydrogenation conversion, S6) and secondary fine desulfurization. The essence of the application is also hydroconversion, and the process route is long and the energy consumption is high.
For another example, the chinese patent application No. 201922197621.4 discloses a blast furnace gas desulfurization and regeneration gas pretreatment system, which comprises an electric heating device, an alkali spraying tower and an adsorption tower, wherein the adsorption tower is filled with a purification medium, and after the blast furnace gas enters the adsorption tower, H gas enters the adsorption tower2S, etc. inorganic sulfur, COS and CS2Adsorbing organic sulfur and impurities by a purification medium to obtain purified blast furnace gas; when the adsorption of the purification medium in the adsorption tower reaches saturation, the regenerated gas is heated and then returns to the adsorption tower, so that the regeneration can be carried out, and the organic sulfur can be catalytically converted into inorganic sulfur in situ. The application passes through the purificationAlthough the adsorption and regeneration of the medium can improve the purification effect of the blast furnace gas, the problems that tar, naphthalene, dust and the like in the gas are easy to cause the blockage of an adsorbent and hydrogen cyanide and the like are easy to cause the catalyst poisoning still cannot be effectively solved.
Disclosure of Invention
1. Problems to be solved
The invention provides a device and a method for removing organic sulfur from a microcrystalline molecular sieve catalyst, which can adapt to complex components of coke oven gas, blast furnace gas and gasifier gas, and can effectively prolong the continuous working time of an adsorption tower, improve the efficiency of removing organic sulfur in the coke oven gas, blast furnace gas and gasifier gas, and reduce the energy consumption in the whole process.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention discloses a fine desulfurization device for coke oven gas, which comprises an adsorption tower and a washing tower, wherein a gas inlet of the adsorption tower is communicated with a gas inlet main pipe, and a gas outlet of the adsorption tower is communicated with a purified gas outlet main pipe; the fine desulfurization device also comprises a conversion tank, wherein an air inlet of the conversion tank is communicated with the adsorption tower through a circulating analytic gas inlet pipe, and an air outlet of the conversion tank is communicated with the adsorption tower through a circulating analytic gas outlet pipe; the circulating analysis gas inlet pipe is provided with a heating device and a desorption fan, and the circulating analysis gas outlet pipe is communicated with the washing tower through an analysis gas exhaust inlet pipe.
Furthermore, N adsorption towers are arranged, wherein N is more than or equal to 3; the gas inlets of the N adsorption towers are respectively communicated with a gas inlet main pipe through gas inlet branch pipes; the gas outlets are respectively communicated with the purified gas outlet main pipe through the purified gas outlet branch pipes.
Furthermore, M reforming tanks are arranged, M is more than or equal to 2, the M reforming tanks are arranged in parallel, and at least one of the reforming tanks is used as a standby reforming tank.
Furthermore, all be equipped with analytic gas air inlet and analytic gas outlet on N adsorption towers, analytic gas air inlet is responsible for through analytic gas intake pipe and analytic gas and is linked together, analytic gas outlet is through analytic gas outlet pipe and the intercommunication each other of circulation analytic gas intake pipe.
Furthermore, the washing tower is provided with a desorption gas exhaust outlet pipe, a spraying opening and a condensate outlet opening, the washed regeneration desorption gas is exhausted from the desorption gas exhaust outlet pipe, and the condensate outlet opening is communicated with the clarifying tank through a circulating pump.
Further, the fine desulfurization method of the coke oven gas comprises the following steps:
step one, enabling the coal gas of a coarse desulfurization system to enter an adsorption tower, and adsorbing inorganic sulfur, organic sulfur and organic impurities in the coal gas by using an adsorbent to obtain clean coal gas;
step two, after the adsorbent in the adsorption tower is saturated, taking the clean coal gas at the outlet of the adsorption tower as regeneration desorption gas, and heating and regenerating the adsorbent;
step three, the regenerated desorption gas desorbed by the desorption of the adsorption tower enters a conversion tank, and organic sulfur is converted into H through catalytic hydrogenation or catalytic hydrolysis2S；
Step four, the regenerated desorption gas circularly works between the adsorption tower and the conversion tank, and simultaneously, a part of converted H-rich gas is continuously cut off2And (4) feeding the S gas into a washing tower for cooling treatment, returning the cooled gas to the coarse desulfurization system, and performing coarse desulfurization on the gas and the non-desulfurized gas in the coarse desulfurization system.
Further, in the second step, the heating, analyzing, desorbing and regenerating of the adsorption tower are carried out in turn, and the specific process is as follows:
A. closing a gas inlet and outlet valve of the to-be-desorbed gas of the to-be-desorbed absorption tower, and opening a regenerative desorption gas inlet and outlet valve of the to-be-desorbed absorption tower to form gas path circulation between the to-be-desorbed absorption tower and the conversion tank; meanwhile, a heating device is started to maintain the temperature in the reforming tank;
B. closing a regeneration desorption gas inlet and outlet valve of the desorption adsorption tower, opening a desorption gas inlet valve of the desorption adsorption tower, introducing clean gas into the desorption adsorption tower, cooling the adsorbent, and heating the clean gas to participate in regeneration desorption gas circulation;
C. when the adsorbent in the desorbed adsorption tower is cooled to a certain temperature and has adsorption capacity, the desorption gas inlet valve of the desorbed adsorption tower is closed, the gas inlet and outlet valve of the gas is opened, and the adsorbent is used for adsorbing inorganic sulfur, organic sulfur and organic impurities in the gas again.
Furthermore, at the same time, 1 adsorption tower is in a heating regeneration state, one adsorption tower is in a heat recovery state, and the rest adsorption towers are in a gas organic sulfur adsorption state.
Further, the H-rich fraction fed to the scrubbing column in step four2And the flow rate of the S gas is kept consistent with the flow rate of the purified gas introduced into the desorbed adsorption tower in the step B.
Further, the adsorbent is a microcrystalline molecular sieve catalyst, a microcrystalline molecular sieve or a molecular sieve; the conversion temperature of the conversion tank is 180-320 ℃, and the pressure is 0-8.0 MPa.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the fine desulfurization device for the coke oven gas, the adsorption and conversion functions are separated and are respectively completed in the adsorption tower and the conversion tank without mutual interference, and the blocking of tar, naphthalene, dust and the like in the gas on the adsorbent can be effectively prevented, so that the continuous working time of the adsorption tower is prolonged, and the working efficiency is improved.
(2) According to the fine desulfurization device for the coke oven gas, the large-flow internal circulation of the circularly regenerated desorption gas is realized between the adsorption tower and the conversion tank, the regeneration time of the adsorption tower is shortened to 1/5-1/6 of the existing fine desulfurization process, and the fine desulfurization efficiency is ensured.
(3) The invention relates to a fine desulfurization device for coke oven gas, wherein a desorption gas inlet is communicated with a desorption gas main pipe through a desorption gas inlet pipe, and a desorption gas outlet is communicated with a circulating desorption gas inlet pipe through a desorption gas outlet pipe.
(4) According to the fine desulfurization device for the coke oven gas, provided by the invention, the adsorption towers and the conversion tanks are respectively provided with a plurality of adsorption towers, at least one adsorption tower is used as a spare adsorption tower, and at least one conversion tank is used as a spare conversion tank, so that when a catalyst needs to be replaced, the adsorption towers are not required to be stopped, and continuous desorption and continuous conversion can be realized; meanwhile, the temperature and the operating pressure of the reforming tank are relatively stable, and the service life of the reforming tank can be prolonged to more than 18 months.
Drawings
FIG. 1 is a schematic view showing the construction of a fine desulfurization apparatus according to the present invention;
in the figure: 1. an adsorption tower; 11. a gas inlet main pipe; 12. a gas inlet branch pipe; 13. a clean gas outlet branch pipe; 14. a clean gas outlet main pipe; 15. a desorption gas inlet; 16. a desorption gas outlet;
2. a conversion tank; 21. a circulating desorption gas inlet pipe; 22. a circulating desorption gas outlet pipe;
3. a heating device;
4. a washing tower; 41. a gas inlet pipe for discharging the resolved gas; 42. the gas is discharged out of the gas outlet pipe; 43. a spray port; 44. a condensate drain port; 45. a circulation pump;
5. a main pipe for desorption gas; 51. a desorption gas inlet pipe; 52. a desorption gas outlet pipe;
6. a desorption fan; 7. a clarifying tank.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
As shown in fig. 1, the fine desulfurization device for coke oven gas of the present embodiment includes an adsorption tower 1, a conversion tank 2 and a washing tower 4, wherein a gas inlet of the adsorption tower 1 is communicated with a gas inlet main pipe 11, and a gas outlet is communicated with a clean gas outlet main pipe 14; the gas inlet of the conversion tank 2 is communicated with the adsorption tower 1 through a circulating analytic gas inlet pipe 21, and the gas outlet is communicated with the adsorption tower 1 through a circulating analytic gas outlet pipe 22; the circulating analysis gas inlet pipe 21 is provided with a heating device 3 and a desorption fan 6, and the circulating analysis gas outlet pipe 22 is communicated with the washing tower 4 through an analysis gas outer exhaust inlet pipe 41. Wherein, the adsorption tower 1 is filled with an adsorbent which can be a microcrystalline molecular sieve catalyst, a microcrystalline molecular sieve or a molecular sieve with good adsorption performance; the conversion tank 2 is a hydrogenation conversion tank or a catalytic hydrolysis tank, in the embodiment, the adsorption and conversion or hydrolysis functions are separated and are respectively completed in the adsorption tower and the conversion tank without mutual interference, and the continuous working time of the adsorption tower is effectively prolonged.
According to the actual production requirement, 4-7 adsorption towers 1 can be arranged, wherein 1 adsorption tower is in a heating regeneration state, one adsorption tower is in a heat recovery state, and the rest adsorption towers are in a state of adsorbing coal gas organic sulfur. The number of the conversion tanks 2 can be 1-3, and one standby, two standby or one standby (two conversion tanks) is realized. The air inlets of the adsorption towers 1 are respectively communicated with a coal gas inlet main pipe 11 through a coal gas inlet branch pipe 12; the gas outlets are respectively communicated with a main purified gas outlet pipe 14 through a purified gas outlet branch pipe 13. Further, each of the plurality of adsorption towers 1 is provided with a desorption gas inlet 15 and a desorption gas outlet 16, the desorption gas inlet 15 is communicated with the desorption gas main pipe 5 through a desorption gas inlet pipe 51, and the desorption gas outlet 16 is communicated with the circulating desorption gas inlet pipe 21 through a desorption gas outlet pipe 52.
The fine desulfurization device in this embodiment is composed of 5 microcrystalline molecular sieve or microcrystalline molecular sieve catalyst adsorption towers (hereinafter referred to as adsorption towers) connected in parallel, of which 1 is in a heating regeneration state, one is in a heat recovery state, and the remaining adsorption towers are in a state of adsorbing organic sulfur in coal gas. 2 hydrogenation conversion tanks or catalytic hydrolysis tanks (hereinafter referred to as conversion tanks) connected in parallel realize one use and one standby, so that when the catalyst needs to be replaced, the adsorption tower does not need to be stopped, the continuity of the whole desulfurization process is ensured, and the efficiency can be improved.
In the desulfurization process, the regenerated desorption gas (hereinafter referred to as desorption gas) is divided into three paths, the path 1 is newly added desorption gas with the temperature of 30-45 ℃, the desorption gas comes from a gas inlet main pipe and is clean gas after inorganic sulfur and organic sulfur are adsorbed,the desorption gas firstly enters a regenerated adsorption tower which is not put into operation through a desorption gas main pipe 5, takes away the heat of the adsorbent in the tower, and is sent to a desorption fan to be combined with the 2 nd path of circulating desorption gas; the temperature of the adsorption tower is reduced from 180 ℃ to 320 ℃ to 30-45 ℃. The circulation desorption gas of the 2 nd path realizes the circulation between the adsorption tower 1 and the conversion tank 2 through the circulation desorption gas inlet pipe 21 and the circulation desorption gas outlet pipe 22, the circulation desorption gas flow of the 2 nd path is adjustable, and the adjusting range is 3000-30000m3The temperature of the circulating desorption gas is 200-330 ℃, and the heat of the circulating desorption gas comes from the sensible heat of the adsorbent brought by the desorption gas in the 1 st path and the auxiliary heating of the heating device 3; and (3) the 2 nd path of circulating desorption gas is sent to an adsorption tower to be regenerated and desorbed due to adsorption saturation, and heating regeneration is carried out. The 3 rd way desorption gas is discharged desorption gas, and the discharge flow of the discharged desorption gas is equal to the adding flow of the 1 st way desorption gas; the 3 rd path desorbed gas enters the washing tower 4 through the desorbed gas exhaust inlet pipe 41, is cooled to 60-85 ℃ after being sprayed and cooled by light tar ammonia water, is sent to the front end of the coal gas primary cooler through the desorbed gas exhaust outlet pipe 42, and is sent to the mechanized tar ammonia water clarifying tank 7 through the condensate outlet 44 under the drive of the circulating pump 45.
In the process, the 5 adsorption towers perform alternate flow adsorption-desorption regeneration, and the cyclic desorption gas (the 2 nd path gas) contains high-concentration COS and CS2、H2The temperature of the S acid gas is kept at 320 ℃ for circulating desorption gas, the S acid gas is heated to 330 ℃ for 200 ℃ by auxiliary electric heating, and the S acid gas enters a conversion tank to convert COS and CS2Etc. are converted into H2S gas and the converted desorption gas are discharged continuously, and the S gas contains H2And (4) washing and cooling the discharged desorption gas containing S, and then sending the gas into the front end of the coal gas primary cooler to participate in coarse desulfurization, so as to treat the organic sulfur and the inorganic sulfur separated from the fine desulfurization adsorption tower. The process recipe path can be expressed as: organic sulfur in coal gas after benzene washing tower → microcrystal adsorption → heating desorption → hydrogenation catalytic conversion to H2S → return to the primary cooler → enter the wet desulphurization tower → convert into sulfur product.
The method comprises the following specific steps:
1. coke oven gas from crude desulfurization system (hydrogen sulfide content less than or equal to 300 mg)/Nm3The content of organic sulfur is no more than 350mg/Nm3(ii) a The upper limits of the contents of the hydrogen sulfide and the organic sulfur in practical application can be respectively widened to be less than or equal to 500mg/Nm3, and can also be designed according to the practical contents) to enter the adsorption towers which are connected in parallel;
2. containing H2S and COS, CS2Organic sulfides such as mercaptan and thiophene and a small amount of organic matters such as tar, naphthalene, benzene, ammonia and hydrogen cyanide from a crude desulfurization system enter an adsorption tower, and H in the coal gas is adsorbed by an adsorbent in the tower2S and various organic sulfides, naphthalene, tar, ammonia, HCN and other organic impurities are adsorbed on the inner surface and the outer surface and the pore channels of the adsorption tower, and clean coal gas is discharged from the adsorption tower and enters a clean coal gas outlet main pipe for downstream users to use;
3. heating the adsorbent in the adsorption tower to 300 deg.C after the adsorbent is saturated, taking clean coke oven gas from the outlet of the adsorption tower as regeneration desorption gas, heating and regenerating the adsorbent to desorb H adsorbed by the adsorbent2S, organic sulfide, naphthalene, tar, ammonia, HCN and other impurities;
4. heating, resolving, desorbing and regenerating the adsorption towers in turn;
5. high-concentration sulfur-containing gas and other organic matters desorbed from the adsorption tower enter a conversion tank, and organic sulfur is converted into H through catalytic hydrogenation or catalytic hydrolysis2S；
6. While the regenerated desorption gas is circularly operated between the adsorption tower and the conversion tank, a part of converted H-rich gas is continuously cut off2S gas is sent into a spray tower, after being sprayed, washed and cooled by light tar, the temperature of the gas is reduced to 80 ℃, the gas is sent into a gas primary cooler to be cooled and then returns to the front of a crude desulfurization tower, and the gas which is not desulfurized enter a crude desulfurization system together to be subjected to crude desulfurization; fresh clean coal gas which is equal to the cut gas is supplemented to participate in the regeneration desorption. The bottom of the spray tower is provided with condensate generated in the coal gas cooling process and sent to a mechanical clarifying tank of a blast cooling section;
7. the operation temperature of the conversion tank is 180 ℃, and the operation pressure is 8.0 MPa.
The chemistry involved in this example is as follows:
1. adsorption and desorption
The adsorbent is selectively adsorbed by utilizing the specific surface and pore volume thereof; heating for desorption after adsorbing for a certain time, wherein the regenerated gas is coke oven gas; the desorption gas is coke oven gas, high-concentration organic sulfide and organic matter.
2. Hydroconversion or catalytic hydrolysis
2.1 hydrogenation catalysis of desorbed gases
COS+H2→CO+H2S
CS2+4H2→CH4+2H2S
C4H4S+4H2→C4H10+H2S
RSH+H2→RH+H2S
2.2 catalytic hydrolysis of desorbed gases
COS+H2O→H2S+CO2
CS2+2H2O→2H2S+CO2
3. And returning the desorbed gas after hydroconversion or catalytic hydrolysis to the front-end coarse desulfurization system.
The desulfurization process of the embodiment aims to overcome the defects of easy poisoning, short service life and long regeneration time of the microcrystalline molecular sieve catalyst in the prior art, and reduce the total sulfur content in the coal gas to 10mg/m3And then, regenerating and resolving impurities such as hydrogen sulfide, aromatic hydrocarbon and the like, and sending the impurities back to the crude desulfurization system. The process of the embodiment has the following characteristics:
1. the fine desulfurization system is independently provided with a hydrogenation conversion tank or a catalytic hydrolysis tank for hydrogenation conversion or catalytic hydrolysis, the adsorption and conversion or hydrolysis functions are separated and respectively completed in the adsorption tower and the conversion tank without mutual interference, and the continuous working time of the adsorption tower is effectively prolonged.
2. 1-3 conversion tanks are arranged according to the gas flow, one standby or two standby or one standby (two conversion tanks) is realized, and when the catalyst needs to be replaced, the adsorption tower does not need to be stopped; meanwhile, the use temperature and the operation pressure of the hydrolysis catalyst or the hydro-conversion catalyst are relatively stable, and the service life of the catalyst can be prolonged to more than 18 months.
3. The process can realize continuous desorption, continuous hydrolysis or hydro-conversion, the regenerated desorption gas adopts large-flow internal circulation, the regeneration time of the adsorption tower is shortened to 1/5-1/6 of the existing fine desulfurization process, and the efficiency of the fine desulfurization process is ensured.
4. The adsorbent in the desorption stage contains a large amount of sensible heat, and in the cold blowing process, the cold blowing gas is heated along with the temperature reduction of the adsorbent in the adsorption tower, so that the heat of the cooling tower is transferred to the heating regeneration tower, the heat transfer is realized, and the energy consumption can be reduced by 30-50%.
5. The adsorption regeneration and the hydroconversion or the catalytic hydrolysis are operated separately, the adsorbent can be a microcrystalline molecular sieve catalyst, and can also be a microcrystalline molecular sieve or a molecular sieve with good adsorption performance, so that the singleness that the microcrystalline molecular sieve catalyst can only be used as the adsorbent in the existing fine desulfurization process is avoided, and the process operation cost can be reduced.
6. The regeneration temperature can be selected within the range of 180-320 ℃, and the service life of the molecular sieve can be repeatedly regenerated to reach the service life of 5-7 years according to the calculation of the crystallinity and the adsorption condition of the microcrystalline molecular sieve.
At 10 ten thousand meters3For the example of fine desulfurization of coke oven gas, five adsorption towers and 2 conversion towers (one for use and one for standby) can be designed. Wherein, the 5# (located at the rightmost side in fig. 1) adsorption tower is heated and desorbed and is in a desorbed state, the temperature is 180-; meanwhile, the adsorption tower 1# (located at the leftmost position in the figure 1) needs to be heated, desorbed and regenerated and is in a desorption state, but the initial temperature is only 30-50 ℃. It is proposed that the temperature reduction of the No. 5 adsorption tower and the temperature increase of the No. 1 adsorption tower are completed within 40 hours. The temperature rise of the tower No. 1 and the temperature drop of the tower No. 5 are carried out synchronously. The specific process is as follows:
the first step is as follows: the gas inlet and outlet valve of the No. 5 adsorption tower furnace is in a closed state; the temperature of the conversion tank is maintained at 180 ℃ and 320 ℃;
the second step is that: closing a coal gas inlet and outlet valve of the No. 1 adsorption tower, cutting the groove and preparing for regeneration;
the third step: opening a regenerative desorption gas inlet and outlet valve of the No. 1 adsorption tower to form gas path circulation between the No. 1 adsorption tower and the conversion tank; meanwhile, an electric heater is started to heat the regenerated desorption gas, and the temperature of the reforming tank is ensured to be maintained at 180 ℃;
the fourth step: closing the regenerative desorption gas inlet and outlet valves of the No. 5 adsorption tower, wherein the No. 5 adsorption tower does not participate in the gas path circulation of the regenerative desorption link, so that the gas path circulation of the regenerative desorption gas which is totally concentrated between the No. 1 adsorption tower and the conversion tank is realized, and the circulation gas amount is 0.5-5.0 ten thousand m3/h；
The fifth step: opening 5# adsorption and desorption gas inlet valve, introducing 2000m3The fresh clean coal gas enters a No. 5 adsorption tower for cooling the adsorbent, and the fresh clean coal gas is heated and then participates in the regeneration desorption gas circulation; the temperature of the adsorbent of the No. 5 adsorption tower is 260 ℃, and the adsorption tower does not have adsorption capacity, so that a coal gas inlet and outlet valve cannot be opened immediately for adsorption operation;
and a sixth step: opening the desorption gas exhaust and inlet pipe, and leading out and supplementing fresh clean coal gas by 2000m3H equal amount of enriched H2And (4) introducing the regenerated dirty coal gas of S and other organic matters into a spray tower, and spraying and washing the regenerated dirty coal gas by using coal tar, so that the balance of gas inlet and gas outlet is ensured.
In the above operation, 1 adsorption tower is required to be in a heating state, one adsorption tower is in a cold blowing cooling state at the same time to form a heat transfer passage, and the other three adsorption towers are in a state that coal gas adsorbs organic sulfur.
The present invention and its embodiments have been described above schematically, without limitation, and what is shown in the drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.
Claims (10)
1. A fine desulfurization device for coke oven gas comprises an adsorption tower (1) and a washing tower (4), wherein a gas inlet of the adsorption tower (1) is communicated with a gas inlet main pipe (11), and a gas outlet is communicated with a clean gas outlet main pipe (14); the method is characterized in that: the device is characterized by also comprising a conversion tank (2), wherein the air inlet of the conversion tank (2) is communicated with the adsorption tower (1) through a circulating desorption gas inlet pipe (21), and the air outlet is communicated with the adsorption tower (1) through a circulating desorption gas outlet pipe (22); the circulating analysis gas inlet pipe (21) is provided with a heating device (3) and a desorption fan (6), and the circulating analysis gas outlet pipe (22) is communicated with the washing tower (4) through an analysis gas exhaust inlet pipe (41).
2. The fine desulfurization device for coke oven gas as claimed in claim 1, wherein: n adsorption towers (1) are arranged, wherein N is more than or equal to 3; the gas inlets of the N adsorption towers (1) are respectively communicated with a gas inlet main pipe (11) through gas inlet branch pipes (12); the gas outlets are respectively communicated with a main purified gas outlet pipe (14) through a purified gas outlet branch pipe (13).
3. The fine desulfurization device for coke oven gas as claimed in claim 2, wherein: the number of the conversion tanks (2) is M, M is more than or equal to 2, the M conversion tanks (2) are arranged in parallel, and at least one of the conversion tanks (2) is used as a standby conversion tank.
4. The fine desulfurization device for coke oven gas as claimed in claim 3, wherein: the N adsorption towers (1) are respectively provided with a desorption gas inlet (15) and a desorption gas outlet (16), the desorption gas inlet (15) is communicated with a desorption gas main pipe (5) through a desorption gas inlet pipe (51), and the desorption gas outlet (16) is communicated with a circulating desorption gas inlet pipe (21) through a desorption gas outlet pipe (52).
5. The fine desulfurization device for coke oven gas as claimed in claim 4, wherein: the washing tower (4) is provided with a desorption gas exhaust and outlet pipe (42), a spray opening (43) and a condensate outlet (44), the washed regeneration desorption gas is exhausted from the desorption gas exhaust and outlet pipe (42), and the condensate outlet (44) is communicated with the clarifying tank (7) through a circulating pump (45).
6. The fine desulfurization method of the coke oven gas is characterized by comprising the following steps: the fine desulfurization apparatus according to any one of claims 2 to 5, which comprises the steps of:
step one, coke oven gas of a crude desulfurization system enters an adsorption tower (1), and an adsorbent adsorbs inorganic sulfur, organic sulfur and organic impurities in the coke oven gas to obtain clean gas;
step two, after the adsorbent in the adsorption tower (1) is saturated, taking the clean coal gas at the outlet of the adsorption tower (1) as regenerated desorption gas, and heating and regenerating the adsorbent;
step three, the regenerated desorption gas desorbed by the desorption of the adsorption tower (1) enters a conversion tank (2) and is subjected to catalytic hydrogenation or catalytic hydrolysis to convert organic sulfur into H2S；
Step four, the regenerated desorption gas circularly works between the adsorption tower (1) and the conversion tank (2), and simultaneously, part of converted H-rich gas is continuously cut off2And S gas is sent into the washing tower (4) for cooling treatment, and the cooled gas returns to the coarse desulfurization system to be subjected to coarse desulfurization in the coarse desulfurization system together with the non-desulfurized gas.
7. The fine desulfurization method for coke oven gas as claimed in claim 6, characterized in that: in the second step, the heating, analyzing, desorbing and regenerating of the adsorption tower (1) are carried out in turn, and the specific process is as follows:
A. closing the coke oven gas inlet and outlet valve of the adsorption tower to be desorbed, and opening the regeneration desorption gas inlet and outlet valve of the adsorption tower to be desorbed to form gas path circulation between the adsorption tower to be desorbed and the conversion tank (2); meanwhile, the heating device (3) is started to maintain the temperature in the conversion tank (2);
B. closing a regeneration desorption gas inlet and outlet valve of the desorption adsorption tower, opening a desorption gas inlet valve of the desorption adsorption tower, introducing clean gas into the desorption adsorption tower, cooling the adsorbent, and heating the clean gas to participate in regeneration desorption gas circulation;
C. when the adsorbent in the desorbed adsorption tower is cooled to a certain temperature and has adsorption capacity, the desorption gas inlet valve of the desorbed adsorption tower is closed, the gas inlet and outlet valve of the gas is opened, and the adsorbent is used for adsorbing inorganic sulfur, organic sulfur and organic impurities in the gas again.
8. The fine desulfurization method for coke oven gas as claimed in claim 7, characterized in that: at the same time, 1 adsorption tower (1) is in a heating regeneration state, one adsorption tower is in a heat recovery state, and the rest adsorption towers are in a state that coal gas adsorbs organic sulfur.
9. The fine desulfurization method for coke oven gas as claimed in claim 8, characterized in that: h-rich in the fourth step fed to the washing column (4)2And the flow rate of the S gas is kept consistent with the flow rate of the purified gas introduced into the desorbed adsorption tower in the step B.
10. The fine desulfurization method for coke oven gas as claimed in claim 9, characterized in that: the adsorbent is a microcrystalline molecular sieve catalyst, a microcrystalline molecular sieve or a molecular sieve; the conversion temperature of the conversion tank (2) is 180-320 ℃, and the pressure is 0-8.0 MPa.
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