CN112226251A

CN112226251A - Dry desulfurization system and method for fuel gas containing high-concentration sulfide

Info

Publication number: CN112226251A
Application number: CN202011040095.1A
Authority: CN
Inventors: 郑经堂; 王维汉; 张文效; 张晋; 谢燕青; 王金峰; 刘景贵
Original assignee: Beijing Zhongke Hongfei Environmental Engineering Technology Co ltd
Current assignee: Beijing Zhongke Hongfei Environmental Engineering Technology Co ltd
Priority date: 2020-09-28
Filing date: 2020-09-28
Publication date: 2021-01-15

Abstract

The invention provides a dry desulfurization system and a dry desulfurization method for fuel gas containing high-concentration sulfides. The system comprises a filtering device, a heat exchanger, a cooling device, an organic sulfur hydrogenation converter and a desulfurization device; the inlet of the filtering device is connected with a fuel gas inlet pipeline, the outlet of the filtering device is connected with the low-temperature side inlet of the heat exchanger, the low-temperature side outlet of the heat exchanger is connected with the air inlet of the organic sulfur hydrogenation converter, the air outlet of the organic sulfur hydrogenation converter is connected with the high-temperature side inlet of the heat exchanger, the high-temperature side outlet of the heat exchanger is connected with the air inlet of the desulfurization device, and the cooling device is arranged on an air flow pipeline connecting the heat exchanger and the desulfurization device; the organic sulfur hydrogenation converter comprises a shell, wherein a catalyst bed layer, a heating mechanism for heating the catalyst bed layer, a temperature monitoring mechanism and a cooling mechanism for filling cooling gas into the shell are arranged in the shell. The system and the method can effectively remove sulfide components in the fuel gas and can avoid equipment failure caused by temperature runaway.

Description

Dry desulfurization system and method for fuel gas containing high-concentration sulfide

Technical Field

The invention belongs to the technical field of desulfurization, and particularly relates to a dry desulfurization system and a dry desulfurization method for fuel gas containing high-concentration sulfides.

Background

The raw gas of fuel gas such as natural gas, blast furnace gas, semi-coke furnace gas, ferroalloy furnace gas, coal bed gas, etc. contains not only trace amount of tar, naphthalene, dust, etc. but also various sulfide components such as H₂S、COS、 CS₂、C₄H₄S and the like. In particular to coke oven gas, the total sulfur content of which reaches 3000-8000mg/m³Wherein the organic sulfur accounts for 10-15%.

At present, most of desulfurization technical methods selected for desulfurization of coke oven gas (except for the case of using coke oven gas as a chemical product raw material) are wet oxidation methods, and a few wet absorption methods are adopted. However, such wet desulfurization processes have the following problems: 1. can only remove inorganic sulfur, basically can not remove organic sulfur in coke oven gas, and can cause SO in flue gas after combustion₂The content seriously exceeds the standard; 2. the produced sulfur has low taste and is difficult to sell; 3. the air consumption actually used in the solution regeneration is more than 10 times of the theoretical air consumption, and a large amount of VOC waste gas is generated; 4. the absorption solution generates secondary salts, consuming raw materials and producing solid contaminants.

In order to avoid the drawbacks of wet desulfurization, researchers have attempted to employ dry desulfurization for gas desulfurization treatment,for example, Chinese patent CN201810829320.6 discloses a method for removing oxygen and fine desulfurizing of coke oven gas, but the method can only treat H with low total sulfur content₂S content less than 1mg/m³The coke oven gas can not carry out desulfurization treatment on the fuel gas with high total sulfur content, SO that the purified fuel gas is SO in the flue gas after combustion₂The content meets the national requirement of ultra-low emission. The method needs to carry out crude desulfurization treatment on the raw material gas and a pre-hydrogenation and deoxygenation process, the organic sulfur conversion process needs to be carried out two-stage hydrogenation treatment, the treatment process is complex, the temperature and pressure conditions required by the reaction are high, the cost is high, and the method is not suitable for popularization and application. Meanwhile, because the hydro-conversion reaction of the organic sulfur in the dry desulfurization method is an exothermic reaction, a temperature runaway phenomenon is easy to occur in the conversion process, equipment faults are caused, and the normal operation of the desulfurization process is influenced.

Disclosure of Invention

The invention provides a dry desulfurization system and a dry desulfurization method for fuel gas containing high-concentration sulfides. The dry desulfurization system can perform desulfurization and purification treatment on the fuel gas containing high-concentration sulfide, effectively remove sulfide components in the fuel gas, and ensure that SO in the flue gas generated after the purified fuel gas is combusted₂The content reaches the national current ultralow emission standard, and simultaneously, the equipment failure caused by the temperature runaway phenomenon in the organic sulfur conversion process can be avoided.

In order to achieve the above objects, the present invention provides a dry desulfurization system for fuel gas containing high concentration of sulfides, comprising a filtering means for filtering impurities, a heat exchanger, a cooling means for cooling the gas, an organic sulfur hydroconversion unit, and a desulfurization means for removing hydrogen sulfide; the inlet of the filtering device is connected with a fuel gas inlet pipeline, the outlet of the filtering device is connected with the low-temperature side inlet of the heat exchanger, the low-temperature side outlet of the heat exchanger is connected with the air inlet of the organic sulfur hydrogenation converter, the air outlet of the organic sulfur hydrogenation converter is connected with the high-temperature side inlet of the heat exchanger, the high-temperature side outlet of the heat exchanger is connected with the air inlet of the desulfurization device through an air flow pipeline, and the cooling device is arranged on the air flow pipeline connecting the heat exchanger and the desulfurization device;

organic sulphur hydroconversion ware includes the casing, be provided with the catalyst bed in the casing, organic sulphur hydroconversion ware's air inlet and gas outlet distribute set up in on the casing of catalyst bed top and below, the catalyst bed is including being used for catalyzing organic sulphur and turning into the catalyst of hydrogen sulfide, organic sulphur hydroconversion ware still installs and is used for heating the heating mechanism of catalyst bed is used for the test the temperature monitoring mechanism of catalyst bed temperature, and be used for to fill into cooling body of cooling gas in the casing, cooling body is including setting up in cooling gas entry on the casing to and be used for supplying cooling gas's cooling gas air feed unit, cooling gas air feed unit connects the cooling gas entry.

Preferably, a first buffer layer and a second buffer layer are further arranged in the shell, the first buffer layer is arranged between the air inlet of the organic sulfur hydroconversion device and the catalyst bed layer, and the second buffer layer is arranged between the catalyst bed layer and the air outlet of the organic sulfur hydroconversion device.

Preferably, the first buffer layer comprises a first support ball layer, a second support ball layer, a first stainless steel mesh, a first sieve plate and a first grid which are sequentially arranged from top to bottom, the second support ball layer consists of a plurality of second support ceramic balls which are stacked and paved on the first stainless steel mesh, the first support ball layer consists of a plurality of first support ceramic balls which are stacked and paved on the second support ball layer, and the diameter of each first support ceramic ball is larger than that of each second support ceramic ball; the second buffer layer includes that the third that sets gradually from bottom to top supports ball layer, fourth support ball layer, second stainless steel net, second sieve and second grid, the third supports the ball layer and lays by piling up a plurality of third on the casing bottom surface support the porcelain ball and constitute, the fourth supports the ball layer and lays by piling up a plurality of fourth on the third support ball layer support the porcelain ball and constitute, the diameter that the third supported the porcelain ball is greater than the diameter that the fourth supported the porcelain ball.

Preferably, the cooling mechanism includes a cooling air inlet provided below the second buffer layer, and the cooling air inlet serves as a first cooling air inlet.

Preferably, the temperature monitoring mechanism comprises a plurality of temperature monitoring units for monitoring temperature changes of different height positions of the catalyst bed layer, and the cooling mechanism is provided with a plurality of cooling gas inlets corresponding to the plurality of temperature monitoring units for cooling in a partitioning manner.

Preferably, the temperature monitoring mechanism comprises a first monitoring unit for monitoring the temperature of the upper part of the catalyst bed layer, a second monitoring unit for monitoring the temperature of the middle part of the catalyst bed layer and a third monitoring unit for monitoring the temperature of the lower part of the catalyst bed layer; the cooling mechanism comprises a plurality of cooling gas inlets, wherein the cooling gas inlets comprise a second cooling gas inlet for filling cooling gas into the upper area of the catalyst bed layer, a third cooling gas inlet for filling cooling gas into the middle area of the catalyst bed layer and a fourth cooling gas inlet for filling cooling gas into the lower part of the catalyst bed layer; and the second cooling gas inlet, the third cooling gas inlet and the fourth cooling gas inlet are respectively connected with the cooling gas supply unit through gas flow pipelines, and are connected with the second cooling gas inlet, the third cooling gas inlet and the fourth cooling gas inlet, and the gas flow pipelines are respectively provided with a first control valve, a second control valve and a third control valve.

Preferably, the temperature monitoring mechanism is a multi-probe temperature detector, the first monitoring unit comprises a first temperature probe inserted into the upper part of the catalyst bed layer and used for monitoring whether the catalyst bed layer has a temperature runaway phenomenon, the second monitoring unit comprises a second temperature probe inserted into the middle part of the catalyst bed layer and used for monitoring whether the catalyst bed layer has a temperature runaway phenomenon, and the third monitoring unit comprises a third temperature probe inserted into the lower part of the catalyst bed layer and used for monitoring whether the catalyst bed layer has a temperature runaway phenomenon.

Preferably, the housing comprises a housing body with an open upper end, and a cover body for closing the open upper end of the housing body, and the cover body is connected with the housing body in a flange manner.

Preferably, the cooling mechanism further comprises a controller, and the controller comprises a first control module for controlling the first control valve to open and close, a second control module for controlling the second control valve to open and close, a third control module for controlling the third control valve to open and close, and a fourth control module for controlling the cooling air supply unit to open and close; the first monitoring unit is in signal connection with a signal input end of the first control module, and a control signal output end of the first control module is in signal connection with the first control valve; the second monitoring unit is in signal connection with the signal input end of the second control module, and the control signal output end of the second control module is in signal connection with the second control valve; the third monitoring unit is in signal connection with a signal input end of the third control module, and a control signal output end of the third control module is in signal connection with the third control valve; the first monitoring unit, the second monitoring unit and the third monitoring unit are in signal connection with the signal input end of the fourth control module, and the signal output end of the fourth control module is in signal connection with the cooling gas supply unit.

Preferably, the cooling gas supply unit includes a nitrogen gas cylinder for supplying low-pressure nitrogen gas.

Preferably, the heating mechanism comprises a plurality of electric heating pipes, the electric heating pipes are arranged along the height direction of the shell, the plurality of electric heating pipes are uniformly distributed in the catalyst bed layer, and the heating temperature of the electric heating pipes is more than or equal to 150 ℃.

In another aspect, the present invention provides a dry desulfurization method, which uses the above dry desulfurization system, and comprises the following steps:

and (3) filtering and removing impurities: the fuel gas is introduced into the filtering device through an air inlet pipeline, and the filtering device filters the fuel gas to remove impurities in the fuel gas;

preheating: the filtered and impurity-removed fuel gas flows through the heat exchanger and enters an air inlet of the organic sulfur hydrogenation converter, a heating mechanism is started to preheat the catalyst bed layer, the heating mechanism is closed after the temperature monitoring mechanism detects that the temperature of the catalyst bed layer reaches 150 ℃, and the fuel gas enters the catalyst bed layer and then undergoes hydrogenation conversion under the action of a catalyst so as to convert organic sulfur in the fuel gas into hydrogen sulfide; meanwhile, the olefin is converted into alkane, and oxygen reacts with hydrogen and carbon monoxide to generate water and carbon dioxide;

heat exchange: the fuel gas which flows out of the gas outlet of the organic sulfur hydrogenation converter and is converted by organic sulfur enters the heat exchanger through a high-temperature side inlet, the fuel gas which is filtered and purified enters the heat exchanger through a low-temperature side inlet, the fuel gas and the filtered and purified fuel gas exchange heat in the heat exchanger, so that the temperature of the fuel gas which is filtered and purified is heated to 150-180 ℃, the temperature of the fuel gas which is converted by organic sulfur is reduced, and the fuel gas which is cooled by the heat exchanger is secondarily cooled to 40-80 ℃ through the cooling device;

organic sulfur conversion: the fuel gas heated in the heat exchange step enters a catalyst bed layer through an air inlet of the organic sulfur hydrogenation converter, and is subjected to hydrogenation conversion under the action of a catalyst, so that organic sulfur in the fuel gas is converted into hydrogen sulfide; meanwhile, the olefin is converted into alkane, and oxygen reacts with hydrogen and carbon monoxide to generate water and carbon dioxide; in the step of organic sulfur conversion, when the temperature monitoring mechanism monitors that the catalyst bed layer has a temperature runaway phenomenon, the cooling mechanism is opened to charge cooling gas into the shell to cool the catalyst bed layer, and the cooling mechanism is closed after the temperature monitoring mechanism monitors that the catalyst bed layer is reduced to 250 ℃ of 200-;

and (3) desulfurization: and the fuel gas cooled in the heat exchange step enters the desulfurization device to remove hydrogen sulfide in the fuel gas, so that the purified fuel gas is obtained.

Preferably, the fuel gas is coke oven gas, and the total sulfur of the fuel gas before treatment is 3000-8000mg/m³。

Preferably, the impurities include dust, tar and naphthalene; the total dust content of the fuel gas after being filtered by the filter device is less than or equal to 1mg/m³。

Preferably, the effective components of the fuel gas after the impurity filtering step comprise 20-30% of methane volume fraction, 50-65% of hydrogen volume fraction, 8-15% of carbon monoxide volume fraction, 0.1-0.8% of oxygen volume fraction, 0.5-2.0% of carbon dioxide volume fraction, 0.3-2.0% of ethylene volume fraction, 0.1-0.2% of ethane volume fraction, 0.2-0.5% of propylene volume fraction, 0.1-0.5% of nitrogen gas volume fraction, and the content of tar and dust is less than 1mg/m³The hydrogen sulfide content is 3000-8000mg/m³The organic sulfur content is 300-800mg/m³。

Preferably, the organic sulfur comprises COS and CS₂、RSH、RSR、C₄H₄S。

Preferably, in the organic sulfur conversion step, the catalyst catalyzes the conversion of organic sulfur to > 97%.

Preferably, the desulfurization step adopts an adsorption desulfurization process, and the desorption rate of the adsorbent adopted by the adsorption desulfurization process to the hydrogen sulfide is more than 99.8%.

Preferably, the total sulphur content in the cleaned fuel gas is < 20mg/m³。

Preferably, the filtering and impurity removing step adopts a filtering agent for filtering, the filtering agent, the catalyst and the adsorbent all adopt solid structures, and the dry desulfurization method does not use liquid substances.

Preferably, the adsorbent is activated carbon particles, and the performance parameters of the activated carbon particles are as follows: iodine adsorption number<700mg/g, methylene blue adsorption number>7ml/mg, BET specific surface area>800m²Per g, particle size phi 2.5-3.5mm, water content<Contact angle of 10%>90 degrees; the micropore distribution of the activated carbon particles is as follows: the number of micropores less than 1nm is not less than 60%, the number of micropores less than 2nm is 20%, and the rest are micropores greater than 2 nm.

Preferably, the active component of the catalyst is any one or combination of more of cobalt, molybdenum and nickel, and the carrier of the catalyst is any one or combination of more of titanium dioxide and/or aluminum oxide and/or silicon dioxide.

Preferably, the catalyst adopts a column shapeThe particle catalyst has the particle diameter of 2.5-4 mm, the length of 8-10 mm and the specific surface area of 120-150 m²The specific pore volume is 0.4 to 0.5 ml/g.

Compared with the prior art, the invention has the advantages that: the invention provides a dry desulfurization system and a dry desulfurization method for fuel gas containing high-concentration sulfides. The dry desulfurization system can perform desulfurization and purification treatment on the fuel gas containing high-concentration sulfide, effectively remove sulfide components in the fuel gas, and ensure that SO in the flue gas generated after the purified fuel gas is combusted₂The content reaches the national current ultralow emission standard, and the organic sulfur hydrogenation converter is provided with the cooling mechanism, so that the equipment failure caused by the temperature runaway phenomenon in the organic sulfur conversion process can be avoided through the cooling mechanism.

Drawings

FIG. 1 is a schematic structural diagram of a dry desulfurization system according to the present embodiment;

FIG. 2 is a schematic view of the organic sulfur hydroconversion unit of the present embodiment;

FIG. 3 is a sectional view taken along line A-A of FIG. 2;

FIG. 4 is an enlarged view of portion B of FIG. 2;

FIG. 5 is an enlarged view of portion C of FIG. 2;

fig. 6 shows the temperature monitoring mechanism and the cooling mechanism of the organic sulfur hydroconversion unit according to the present embodiment;

FIG. 7 is an analytical detection diagram for organic sulfur conversion of example 1;

fig. 8 is an analytical detection diagram for organic sulfur conversion of example 2;

in fig. 1: arrows indicate fuel gas flow direction.

Detailed Description

In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described and illustrated below with reference to the accompanying drawings and embodiments. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments provided in the present application without any inventive step are within the scope of protection of the present application.

It is obvious that the drawings in the following description are only examples or embodiments of the present application, and that it is also possible for a person skilled in the art to apply the present application to other similar contexts on the basis of these drawings without inventive effort. Moreover, it should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another.

Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the specification. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of ordinary skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments without conflict.

Unless defined otherwise, technical or scientific terms referred to herein shall have the ordinary meaning as understood by those of ordinary skill in the art to which this application belongs. Reference to "a," "an," "the," and similar words throughout this application are not to be construed as limiting in number, and may refer to the singular or the plural. The present application is directed to the use of the terms "including," "comprising," "having," and any variations thereof, which are intended to cover non-exclusive inclusions; the term "plurality" as referred to herein means two or more. "and/or" describes an association relationship of associated objects, meaning that three relationships may exist, for example, "A and/or B" may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship. Reference herein to the terms "first," "second," "third," and the like, are merely to distinguish similar objects and do not denote a particular ordering for the objects.

As shown in fig. 1 to 5, the embodiment of the present invention provides a dry desulfurization system for fuel gas containing high concentration of sulfides, comprising a filtering device 2 for filtering impurities, a heat exchanger 3, a cooling device 5 for cooling the gas, an organic sulfur hydroconversion device 4, and a desulfurization device 6 for removing hydrogen sulfide; the inlet of the filtering device 2 is connected with a fuel gas inlet pipeline 1, the outlet of the filtering device 2 is connected with a low-temperature side inlet 3-1 of the heat exchanger 3, a low-temperature side outlet 3-2 of the heat exchanger 3 is connected with a gas inlet 4-17 of the organosulfur hydroconversion device 4, a gas outlet 4-18 of the organosulfur hydroconversion device 4 is connected with a high-temperature side inlet 3-3 of the heat exchanger 3, a high-temperature side outlet 3-4 of the heat exchanger 3 is connected with a gas inlet of the desulphurization device 6 through a gas flow pipeline 7, and the cooling device 5 is installed on the gas flow pipeline 7 connecting the heat exchanger 3 and the desulphurization device 6;

the organic sulfur hydroconversion device 4 comprises a shell 4-1, a catalyst bed layer 4-4 is arranged in the shell 4-1, an air inlet 4-17 and an air outlet 4-18 of the organic sulfur hydroconversion device 4 are distributed on the shell 4-1 above and below the catalyst bed layer 4-4, the catalyst bed layer 4-4 comprises a catalyst for catalyzing organic sulfur to be converted into hydrogen sulfide, the organic sulfur hydroconversion device 4 is also provided with a heating mechanism for heating the catalyst bed layer 4-4, a temperature monitoring mechanism 4-8 for testing the temperature of the catalyst bed layer 4-4, and a cooling mechanism 4-9 for filling cooling gas into the shell 4-1, the cooling mechanism 4-9 comprises a cooling gas inlet 4-16 arranged on the shell 4-1, and a cooling gas supply unit for supplying cooling gas, the cooling gas supply unit being connected to the cooling gas inlets 4-16.

The dry desulfurization method adopting the dry desulfurization system comprises the following steps:

and (3) filtering and removing impurities: the fuel gas is introduced into the filtering device 2 through the gas inlet pipeline 1, and the filtering device 2 filters the fuel gas to remove impurities in the fuel gas;

preheating: the filtered and impurity-removed fuel gas flows through the heat exchanger 3 and enters an air inlet 4-17 of the organic sulfur hydrogenation converter 4, a heating mechanism is started to preheat the catalyst bed layer 4-4, the heating mechanism is closed after the temperature monitoring mechanism 4-8 detects that the temperature of the catalyst bed layer 4-4 reaches 150 ℃, and the fuel gas enters the catalyst bed layer 4-4 and then undergoes hydrogenation conversion under the action of a catalyst, so that organic sulfur in the fuel gas is converted into hydrogen sulfide; meanwhile, the olefin is converted into alkane, and oxygen reacts with hydrogen and carbon monoxide to generate water and carbon dioxide;

heat exchange: the fuel gas converted by organic sulfur and flowing out from the air outlet 4-18 of the organic sulfur hydrogenation converter 4 enters the heat exchanger 3 through the high-temperature side inlet 3-3, the fuel gas filtered and purified enters the heat exchanger 3 through the low-temperature side inlet 3-1, the fuel gas filtered and purified is subjected to heat exchange in the heat exchanger 3, the temperature of the fuel gas filtered and purified is increased to 150-180 ℃, the temperature of the fuel gas converted by organic sulfur is reduced, and the temperature of the fuel gas cooled by the heat exchanger 3 is secondarily reduced to 40-80 ℃ through the cooling device 5; because the organic sulfur conversion reaction is an exothermic reaction, the temperature of a bed layer can be increased from 250 ℃ to 350 ℃ in the reaction process, so that the temperature of the gas discharged from the gas outlet 4-18 is obviously higher than the temperature required by the conversion reaction, the heat source used for the heat exchanger 3 can preheat the fuel gas to the temperature of 150 ℃ and 180 ℃ required by the conversion reaction before the fuel gas enters the organic sulfur hydrogenation converter 4, the heat generated by the subsequent organic sulfur conversion reaction can be continuously used for preheating the fuel gas by the heat exchanger 3, and the heat source of the heat exchanger 3 is not required to be additionally provided for heating the fuel gas, so that the energy;

organic sulfur conversion: the fuel gas heated in the heat exchange step enters a catalyst bed layer 4-4 through an air inlet 4-17 of the organic sulfur hydrogenation converter 4, and is subjected to hydrogenation conversion under the action of a catalyst, so that organic sulfur in the fuel gas is converted into hydrogen sulfide; meanwhile, the olefin is converted into alkane, and oxygen reacts with hydrogen and carbon monoxide to generate water and carbon dioxide; in the step of converting organic sulfur, when the temperature monitoring mechanism 4-8 monitors that the catalyst bed layer 4-4 has a temperature runaway phenomenon, the cooling mechanism 4-9 is started to charge cooling gas into the shell 4-1 to cool the catalyst bed layer 4-4, and the cooling mechanism 4-9 is closed after the temperature monitoring mechanism 4-8 monitors that the temperature of the catalyst bed layer 4-4 is reduced to 250 ℃ of 200-;

and (3) desulfurization: and the fuel gas cooled in the heat exchange step enters the desulfurization device 6, and hydrogen sulfide in the fuel gas is removed, so that purified fuel gas is obtained.

The dry desulfurization system and the dry desulfurization method are adopted to carry out desulfurization treatment on the fuel gas, in the treatment process, the heating mechanism can be closed only by starting the heating mechanism to preheat the catalyst bed layer 4-4 in the preheating step, the heat required by preheating the fuel gas is forwarded and reacted by the subsequent organic sulfur, the heat can be provided by conversion reaction, a heat exchanger 3 is not required to be additionally provided for heating the fuel gas, and the energy consumption in the desulfurization process can be effectively reduced. Meanwhile, the organic sulfur hydrogenation converter 4 of the system is also provided with a temperature monitoring mechanism 4-8 and a cooling mechanism 4-9, when the temperature monitoring mechanism 4-8 detects that the temperature of the catalyst bed layer 4-4 has a temperature runaway phenomenon, the cooling mechanism 4-9 can be opened, the cooling mechanism 4-9 can charge low-temperature cooling gas into the shell 4-1 through the independently arranged cooling gas inlet 4-16, the cooling gas is charged into the catalyst bed 4 to reduce the temperature of the cooling gas, the cooling of the catalyst bed 4 is realized, and the organic sulfur hydrogenation converter 4 can still continue to work in the cooling process, namely, when the temperature runaway phenomenon occurs in the organic sulfur hydrogenation converter 4, the catalyst bed layer 4 can be effectively cooled through the cooling mechanism 9 without stopping the operation of the equipment, so that the equipment faults are reduced, and the normal operation of the desulfurization process is ensured. And experiments show that the system and the method are applied to the total sulfur content of 3000-8000mg/m³The total sulfur content in the purified coke oven gas is less than 20mg/m³Can lead SO in the flue gas after the purified coke oven gas is burnt₂The content reaches the current ultra-low emission of ChinaAnd (4) standard. The method has simple process, can carry out organic sulfur conversion under normal pressure, has low requirement on reaction conditions in the desulfurization process, and is beneficial to reducing energy consumption and cost.

In the heat exchange step, the fuel gas converted from organic sulfur flowing out from the air outlet 4-18 of the organic sulfur hydroconversion device 4 enters the heat exchanger 3 through the high-temperature side inlet 3-3, the fuel gas subjected to filtration and impurity removal enters the heat exchanger 3 through the low-temperature side inlet 3-1, the fuel gas and the fuel gas are subjected to heat exchange in the heat exchanger 3, so that the temperature of the fuel gas subjected to filtration and impurity removal is raised to 150 ℃, the temperature of the fuel gas converted from organic sulfur is reduced, and the temperature of the fuel gas cooled by the heat exchanger 3 is secondarily reduced to 40 ℃ through the cooling device 5; as the organic sulfur conversion reaction is an exothermic reaction, the temperature of a bed layer can be raised from 150 ℃ to 250 ℃ in the reaction process, so that the temperature of the gas discharged from the gas outlet 4-18 is obviously higher than the temperature required by the conversion reaction, and the gas can be used as a heat source of the heat exchanger 3, the fuel gas can be preheated to the temperature of 150 ℃ required by the conversion reaction before entering the organic sulfur hydrogenation converter 4, and the heat generated by the subsequent organic sulfur conversion reaction.

Specifically, in the catalyst bed 4-4, an organic sulfur conversion reaction occurs, and the organic sulfur is converted into inorganic sulfur, and the reaction equation is as follows:

COS+H₂→CO+H₂S

CS₂+4H₂→CH₄+2H₂S

RSH+H₂→RH+H₂S

RSR+2H₂→RH+RH+H₂S

C₄H₄S+4H₂→C₄H₁₀+H₂S

oxygen and olefins to H₂O、CO₂And alkanes.

Specifically, the cooling device 5 is a water cooler.

Specifically, the air inlet 4-17 is arranged at the top of the shell, and the air outlet 4-18 is arranged at the bottom of the shell.

Specifically, the housing 4-1 is a cylindrical housing made of carbon steel.

Specifically, the shell is also provided with a vent 4-19 and a pressure gauge port 4-110 for installing a pressure gauge; the vent 4-19 and the pressure gauge 4-110 are arranged at the top of the shell 1, the pressure gauge is used for displaying the pressure inside the converter, and when the pressure inside the shell 4-1 exceeds a limit value, the gas is discharged from the vent 4-19 through a safety valve so as to avoid overpressure of the system.

Specifically, the shell 4-1 is further provided with a manhole 4-111, the manhole 4-111 is arranged on the side face of the lower portion of the shell 4-1, and a manhole cover used for closing the manhole 4-111 is installed on the manhole 4-111. The manholes 4-111 are provided for maintenance personnel to service in the event of a catalyst loading/unloading or converter failure.

Specifically, a plurality of legs 4-2 for supporting the housing 4-1 are installed at the bottom of the housing 4-1.

Specifically, a first buffer layer 4-5 and a second buffer layer 4-7 are further arranged in the shell 4-1, the first buffer layer 4-5 is arranged between the air inlet 4-17 of the organic sulfur hydroconversion device 4 and the catalyst bed layer 4-4, and the second buffer layer is arranged between the catalyst bed layer and the air outlet of the organic sulfur hydroconversion device. After the fuel gas containing organic sulfur enters the shell 4-1 from the air inlet 4-17 and is buffered by the first buffer layer 4-5, the flow speed is reduced and the fuel gas uniformly enters the catalyst bed layer 4-4, so that the contact between the fuel gas and the catalyst is better ensured, the catalytic effect of the catalyst is ensured, and the conversion reaction of the organic sulfur is promoted.

Specifically, as shown in fig. 4, the first buffer layer 4-5 includes a first support ball layer 4-51, a second support ball layer 4-52, a first stainless steel mesh 4-53, a first sieve plate 4-54 and a first grid 4-55, which are sequentially disposed from top to bottom, the second support ball layer 4-52 is composed of a plurality of second support ceramic balls stacked on the first stainless steel mesh 4-53, the first support ball layer 4-51 is composed of a plurality of first support ceramic balls stacked on the second support ball layer 4-52, and a diameter of the first support ceramic balls is greater than a diameter of the second support ceramic balls; as shown in fig. 5, the second buffer layer 4-7 includes a third support ball layer 4-71, a fourth support ball layer 4-72, a second stainless steel wire mesh 4-73, a second sieve plate 4-74 and a second grid 4-75, which are sequentially disposed from bottom to top, the third support ball layer 4-71 is composed of a plurality of third support ceramic balls stacked and laid on the bottom surface of the housing 4-1, the fourth support ball layer 4-72 is composed of a plurality of fourth support ceramic balls stacked and laid on the third support ball layer 4-71, and the diameter of the third support ceramic balls is greater than that of the fourth support ceramic balls. The stainless steel wire net, the sieve plate and the grid are used for separating the support ceramic balls from the catalyst bed layer 4-4, preventing the support ceramic balls from entering the catalyst bed layer 4-4, further promoting the gas to be treated to be uniformly distributed and avoiding the bias flow phenomenon. Meanwhile, the sieve plate and the grating can ensure that the first buffer layer 4-5 and the second buffer layer 4-7 have enough strength, and the first buffer layer 4-5 and the second buffer layer 4-7 are prevented from generating obvious deformation in the long-term operation process of the device.

Specifically, the first supporting ceramic ball and the third supporting ceramic ball are ceramic balls with the diameter of 25mm, and the second supporting ceramic ball and the fourth supporting ceramic ball are ceramic balls with the diameter of 10 mm; the specifications of the first stainless steel wire mesh 4-53 and the second stainless steel wire mesh 4-73 are set to be 20 meshes, and the aperture is 0.85mm, so that the support ceramic balls cannot leak into the catalyst bed layer 4-4.

Specifically, the cooling mechanism 4-9 includes a cooling gas inlet provided at 4-7 below the second buffer layer, and the cooling gas inlet serves as a first cooling gas inlet 4-16. The first cooling gas inlet 4-16 is arranged below the second buffer layer 4-7, and cooling gas entering from the first cooling gas inlet 4-16 can pass through the buffer of the second buffer layer 4-7 before entering the catalyst bed layer 4-4, so that the cooling gas can flow through the catalyst bed layer 4-4 more uniformly and at a low speed and is in full contact with the catalyst bed layer 4-4, and the cooling effect is improved.

Specifically, the temperature monitoring mechanism 4-8 includes a plurality of temperature monitoring units for monitoring temperature changes at different height positions of the catalyst bed layer 4-4, and the cooling mechanism 9 is provided with a plurality of cooling gas inlets corresponding to a plurality of temperature monitoring unit positions for cooling in a partitioned manner. The temperature of the catalyst bed layer 4-4 is monitored in a subarea mode, the temperature-runaway position of the catalyst bed layer 4-4 is determined more accurately, and then the cooling mechanism 4-9 is started to introduce cooling gas through a cooling gas inlet arranged corresponding to the area, so that the temperature-runaway area can be cooled rapidly, equipment faults are solved rapidly, and the normal operation of the converter is guaranteed better.

Specifically, the temperature monitoring mechanism comprises a first monitoring unit for monitoring the temperature of the upper part of the catalyst bed layer 4-4, a second monitoring unit for monitoring the temperature of the middle part of the catalyst bed layer 4-4, and a third monitoring unit for monitoring the temperature of the lower part of the catalyst bed layer 4-4; the cooling mechanism 4-9 comprises a plurality of cooling gas inlets, wherein the cooling gas inlets comprise a second cooling gas inlet 4-13 for charging cooling gas into the upper area of the catalyst bed 4-4, a third cooling gas inlet 4-14 for charging cooling gas into the middle area of the catalyst bed 4-4, and a fourth cooling gas inlet 4-15 for charging cooling gas into the lower part of the catalyst bed 4-4; the second cooling air inlet 4-13, the third cooling air inlet 4-14 and the fourth cooling air inlet 4-15 are respectively connected with the cooling air supply unit through an air flow pipeline 4-93, and a first control valve 4-96, a second control valve 4-95 and a third control valve 4-94 are respectively installed on the air flow pipeline 4-93 which is connected with the second cooling air inlet 4-13, the third cooling air inlet 4-14 and the fourth cooling air inlet 4-15. The communication state of the second cooling air inlet 4-13, the third cooling air inlet 4-14 and the fourth cooling air inlet 4-15 and the cooling air supply unit can be controlled by controlling the opening and closing states of the first control valve 4-96, the second control valve 4-95 and the third control valve 4-94, so that the temperature can be reduced in a subarea mode. For example, when the first monitoring unit detects that the temperature runaway state occurs in the upper region of the catalyst bed 4-4, the first control valve 4-96 is controlled to be opened, the second control valve 4-95 and the third control valve 4-94 are closed, and the cooling gas can be charged from the second cooling gas inlet 4-13, so that the temperature of the upper region of the catalyst bed 4-4 can be reduced more quickly and accurately. In addition, the cooling gas sprayed into the shell 4-1 by the cooling mechanism 4-9 not only can cool the catalyst bed layer, but also can be used for blowing equipment in the early stage, filling the catalyst and the like.

Specifically, the second cooling air inlet 4-13 is disposed below the first buffer layer 4-5 and is close to the first buffer layer 4-5, the third cooling air inlet 4-14 is disposed at the middle position of the housing 4-1 in the height direction, and the fourth cooling air inlet 4-15 is disposed above the second buffer layer 4-7 and is close to the second buffer layer 4-7.

Specifically, the temperature monitoring mechanism 4-8 is a multi-probe temperature detector, the first monitoring unit comprises a first temperature probe 4-81 inserted into the upper part of the catalyst bed 4-4 and used for monitoring whether the catalyst bed has a temperature runaway phenomenon, the second monitoring unit comprises a second temperature probe 4-82 inserted into the middle part of the catalyst bed 4-4 and used for monitoring whether the catalyst bed has a temperature runaway phenomenon, and the third monitoring unit comprises a third temperature probe 4-83 inserted into the lower part of the catalyst bed 4-4 and used for monitoring whether the catalyst bed has a temperature runaway phenomenon.

Specifically, the first temperature probe 4-81, the second temperature probe 4-82 and the third temperature probe 4-83 are sequentially inserted into the catalyst bed 4-4 from top to bottom and used for testing the temperature of the upper part, the middle part and the lower part of the catalyst bed 4-4. The insertion directions of the first temperature probe 4-81, the second temperature probe 4-82 and the third temperature probe 4-83 are sequentially arranged at 90 degrees difference in the horizontal direction from top to bottom so as to more uniformly display the temperature of the catalyst bed layer 4-4, thereby objectively displaying the temperature distribution in the converter.

Specifically, the shell 4-1 comprises a shell body 4-12 with an open upper end, and a cover body 4-11 for closing the open upper end of the shell body 4-12, wherein the cover body 4-11 is connected with the shell body 4-12 through a flange. The shell 4-1 is designed to be of the structure so as to facilitate the loading and unloading of the first buffer layer 4-5, the catalyst bed layer 4-4 and the second buffer layer 4-7.

Specifically, as shown in fig. 6, the cooling mechanism 4-9 further includes a controller, where the controller includes a first control module for controlling the opening and closing of the first control valve 4-96, a second control module for controlling the opening and closing of the second control valve 4-95, a third control module for controlling the opening and closing of the third control valve 4-93, and a fourth control module for controlling the opening and closing of the cooling air supply unit; the first monitoring unit is in signal connection with a signal input end of the first control module, and a control signal output end of the first control module is in signal connection with the first control valve 4-96, so that when the first monitoring unit monitors that a temperature runaway phenomenon occurs, the first control module automatically controls the first control valve 4-96 to be opened, and cooling gas is filled into an upper area of the catalyst bed layer 4-4; the second monitoring unit is in signal connection with a signal input end of the second control module, and a control signal output end of the second control module is in signal connection with the second control valve 4-95, so that when the second monitoring unit monitors that a temperature runaway phenomenon occurs, the second control module automatically controls the second control valve 4-96 to be opened, and cooling gas is filled into the middle area of the catalyst bed layer 4-4; the third monitoring unit is in signal connection with a signal input end of the third control module, and a control signal output end of the third control module is in signal connection with the third control valves 4-94, so that when the third monitoring unit monitors that a temperature runaway phenomenon occurs, the third control module automatically controls the third control valves 4-96 to be opened, and cooling gas is filled into the lower area of the catalyst bed layer 4-4; first monitoring unit, second monitoring unit and the equal signal connection of third monitoring unit fourth control module signal input part, fourth control module control signal output part signal connection cooling gas air feed unit, in order when any one or more in first monitoring unit, second monitoring unit and the third monitoring unit monitor the temperature runaway phenomenon, automatic control cooling gas air feed unit opens the supply cooling gas. The cooling system adopting the structure can realize automatic control.

Specifically, the cooling gas supply unit includes a nitrogen gas cylinder for supplying low-pressure nitrogen gas.

Besides being set as a nitrogen cylinder, the cooling gas supply unit can also be set as the following structure: the cooling gas supply unit comprises gas storage parts 4-91 for storing cooling gas (such as nitrogen), main gas supply pipelines communicated with the gas flow pipelines, and gas pumps 4-92 arranged on the main gas supply pipelines.

Specifically, the heating mechanism comprises a plurality of electric heating pipes 4-3, the electric heating pipes 4-3 are arranged along the height direction of the shell 4-1, the plurality of electric heating pipes 4-3 are uniformly distributed in the catalyst bed layer 4-4, and the heating temperature of the electric heating pipes 4-3 is more than or equal to 150 ℃. The heating mechanism can determine the uniform heating of the catalyst bed layer 4-4 by adopting the structure, ensure that the gas entering the catalyst bed layer 4-4 is uniformly heated to the reaction temperature in the preheating process, and ensure the heating effect and the reaction temperature. The electric heating pipe 4-3 is used for heating the catalyst bed layer 4-4 in the preheating step, heating the fuel gas to the activation temperature required by the catalyst, and after the normal operation is carried out, the electric heating pipe 4-3 can stop heating.

Specifically, a heating mechanism body 4-6 of the heating mechanism is mounted at the top of the shell 4-1, an electric heating pipe inlet for penetrating the electric heating pipe 4-3 is formed at the top of the shell 4-1, the electric heating pipe 4-3 is inserted into the shell 4-1 through the electric heating pipe inlet, and a heating section of the electric heating pipe 4-3 is embedded in the catalyst bed layer 4-4. The electric heating pipe 4-3 heats the catalyst bed layer 4-4 to the required temperature, so that the temperature of the catalytic conversion bed layer 4-4 can be kept uniform, and compared with a mode of preheating fuel gas to be fed into the converter by adopting an additional heat source arranged outside the converter, the electric heating pipe can also improve the heat efficiency, reduce the heat loss and reduce the energy consumption.

Specifically, the electric heating tube 4-3 is made of 304 stainless steel or 316 stainless steel, and the outer diameter of the electric heating tube 4-3 is 10 mm-16 mm.

Specifically, a plurality of electric heating pipes 4-3 are arranged in an equidistant and uniform distribution manner, so as to achieve the effect of uniform heating.

Specifically, the fuel gas to be desulfurized is coke oven gas, and the total sulfur of the fuel gas before treatment is 3000-8000mg/m³。

Specifically, in the step of filtering and removing impurities, the impurities comprise dust, tar and naphthalene; the total dust content of the fuel gas after being filtered by the filter device is less than or equal to 1mg/m³。

Specifically, after the impurity filtering step, the effective components of the fuel gas comprise 20-30% of methane volume fraction, 50-65% of hydrogen volume fraction, 8-15% of carbon monoxide volume fraction, 0.1-0.8% of oxygen volume fraction, 0.5-2.0% of carbon dioxide volume fraction, 0.3-2.0% of ethylene volume fraction and 0% of ethane volume fraction1-0.2%, propylene volume fraction 0.2-0.5%, nitrogen gas integral rate 0.1-0.5%, and tar and dust content less than 1mg/m³The hydrogen sulfide content is 3000-8000mg/m³The organic sulfur content is 300-800mg/m³。

Specifically, the organic sulfur comprises COS and CS₂、RSH、RSR、C₄H₄S。

Specifically, in the step of converting organic sulfur, the catalyst catalyzes the conversion rate of the organic sulfur to be more than 97%.

Specifically, the active component of the catalyst is any one or combination of more of cobalt, molybdenum and nickel, and the carrier of the catalyst is any one or combination of more of titanium dioxide and/or aluminum oxide and/or silicon dioxide. The catalyst is a columnar particle catalyst, the particle diameter of the catalyst is 2.5-4 mm, the length of the catalyst is 8-10 mm, and the specific surface area of the catalyst is 120-150 m²The specific pore volume is 0.4 to 0.5 ml/g. Said catalyst has the advantages of no fear of oxygen, no sulfation reaction, long service life, high selectivity and low activation temperature.

Specifically, the desulfurization step can adopt an adsorption desulfurization process, a metal oxide desulfurization process or other micro-nano material desulfurization.

Specifically, the desulfurization step adopts an adsorption desulfurization process, and the desorption rate of the adsorbent adopted by the adsorption desulfurization process to the hydrogen sulfide is more than 99.8%.

Specifically, the adsorbent is activated carbon particles, and the performance parameters of the activated carbon particles are as follows: iodine adsorption number<700mg/g, methylene blue adsorption number>7ml/mg, BET specific surface area>800m²Per g, particle size phi of 2.5-3.5mm, preferably 3mm, water content<Contact angle of 10%>90 degrees; the micropore distribution of the activated carbon particles is as follows: the number of micropores with the diameter less than 1nm is more than or equal to 60 percent, the number of micropores with the diameter less than 2nm accounts for 20 percent preferably, and the rest is micropores with the diameter more than 2 nm. The active carbon particles adopted by the adsorbent can be customized active carbon products purchased according to performance parameters, and the active carbon adopting the performance parameters has the advantages of large adsorption capacity, good selectivity and easy regeneration. The product of the desorption of the adsorbent may beHigh purity H₂The S gas can also be matched with a Claus process to produce high-purity sulfur and can also be processed into sulfuric acid. More importantly, the high concentration of H₂When S gas passes through, the purification degree of the gas can be ensured, namely the total sulfur content is less than 20mg/m³。

Specifically, the total sulfur content in the purified fuel gas is less than 20mg/m³。

Specifically, the filtering and impurity removing step adopts a filtering agent for filtering, the filtering agent, the catalyst and the adsorbent all adopt solid structures, and the dry desulfurization method does not use liquid substances. The dry desulfurization process is adopted in the embodiment, so that the defects of the wet desulfurization process can be effectively avoided, and the dry desulfurization process has the technical advantages of no secondary pollution, short flow, small occupied area and investment saving.

The adsorbents used in the following examples are customized activated carbon granules, the performance parameters of which are: iodine adsorption number<700mg/g, methylene blue adsorption number>7ml/mg, BET specific surface area>800m²A particle size of 3mm, water content<Contact angle of 10%>90 degrees; the micropore distribution of the activated carbon particles is as follows: the number of micropores less than 1nm is not less than 60%, the number of micropores less than 2nm is 20%, and the rest are micropores greater than 2 nm.

The catalyst used in the following examples was purchased from Zibosky environmental protection technologies, Inc., and was made as HSO-35 hydrogen sulfide selective oxidation catalyst.

Example 1

The fuel gas containing high-concentration sulfide to be treated is coke oven gas, and the fuel gas comprises the following components by test: o is₂： 0.22％；N₂：2.08％；CH₄：17.76％；CO：9.26％；CO₂: 1.09%; ethylene: 0.55 percent; ethane: 0.12 percent; propylene: 0.37 percent; h₂: 68.56 percent. Dust content 10mg/m³Hydrogen sulfide content 4395mg/m³Organic sulfur content 397.45mg/m³Pressure 0.02Mpa, gas flow 1560m³/h。

The dry desulfurization system and the desulfurization method are adopted to carry out desulfurization treatment on the coke oven gas, and the process is briefly described as follows: the coke oven coalAfter the gas is filtered and impurity-removed, the impurities of dust, tar, naphthalene and the like are removed, so that the dust content is 1mg/m³. Coke oven gas from the filter device 2 enters the organic sulfur hydrogenation converter 4 through the heat exchanger 3 to be preheated, the heating mechanism preheats the catalyst bed layer, the heating mechanism is closed after the temperature monitoring mechanism detects that the temperature of the catalyst bed layer reaches 150 ℃, the preheating step is completed, the preheated fuel gas reacts in the organic sulfur hydrogenation converter 4, and under the action of the catalyst, COS and CS react₂、RSH、RSR、C₄H₄Conversion of organic sulfur such as S to H₂S; then the fuel gas discharged from the organic sulfur hydrogenation converter 4 passes through the heat exchanger 3 as the heat source of the heat exchanger 3, the fuel gas which subsequently passes through the heat exchanger 3 and is ready to enter the organic sulfur hydrogenation converter 4 is heated, the temperature of the fuel gas is raised to 150 ℃, the fuel gas then enters the organic sulfur hydrogenation converter 4, and under the action of a catalyst, COS and CS of organic sulfur in the organic sulfur hydrogenation converter 4₂、RSH、RSR、C₄H₄Conversion of organic sulfur such as S to H₂S; at the same time, O is converted into organic sulfur₂With olefins to H₂O、CO₂And alkane, the temperature of the catalyst bed layer 4-4 is raised to 230 ℃ by the reaction heat, the high-temperature coke oven gas which is discharged from the organic sulfur hydrogenation converter 4 exchanges heat with the low-temperature coke oven gas which enters the heat exchanger 3 in the heat exchanger 3, and the high-temperature coke oven gas is cooled to 40 ℃ by a water cooler and then enters the desulfurization device 6; in the desulfurization unit 6, the adsorbent converts H₂The purified fuel gas obtained after S adsorption and removal is discharged from the gas outlet of the desulfurizing device 6.

And (3) effect testing:

analyzing sulfide with HY-6800 type trace sulfur analyzer, which is FPD high-precision detector for detecting hydrogen sulfide (H) in coke oven gas₂S), carbonyl sulfide (COS), carbon disulfide (CS)₂) Thiophene (C)₄H₄S) and the like for accurate analysis. The abscissa in the chromatogram is the time to peak in minutes (min); the ordinate in the chromatogram is the signal value in millivolts (mv). The concentration data of each component in the chromatogram map is composed of trace sulfurAnd (4) automatically integrating and calculating by a chromatographic workstation matched with the analyzer.

The analytical detection results of the organic sulfur conversion chromatographic detection in this example are shown in fig. 7, (a) shows analytical data of hydrogen sulfide and carbonyl sulfide at the gas inlets 4 to 17 of the organic sulfur hydroconversion unit 4, (b) shows analytical data of hydrogen sulfide and carbonyl sulfide of the purified fuel gas (at the gas outlet of the desulfurization unit 6), (c) shows analytical data of carbon disulfide and thiophene at the gas inlets 4 to 17, and (d) shows analytical data of carbon disulfide and thiophene of the purified fuel gas.

As can be seen from the analysis of FIG. 7, the gas inlets 4-17 are used to supply fuel gas H₂The S content is 4395mg/m³Organic sulfur content 397.45mg/m³Purified fuel gas H₂The S content is 3.1mg/m³Organic sulfur content 1.1mg/m³The content of the organic sulfur is reduced to 1.1mg/m after the conversion of the organic sulfur is finished³The conversion rate reaches 99.7 percent, the adsorption rate of the adsorbent to the total sulfur (the percentage of the total sulfide concentration of the purified fuel gas divided by the total sulfide concentration at the gas inlet 4-17) is 99.91 percent, and the SO in the flue gas after the purified coke oven gas is combusted can be ensured₂The content reaches the national current ultra-low emission standard.

Example 2

The fuel gas containing high-concentration sulfide to be treated is coke oven gas, and the fuel gas comprises the following components by test: o is₂： 0.64％；N₂：3.77％；CH₄：20.14％；CO：11.39％；CO₂: 1.359%; ethylene: 1.62 percent; ethane: 1.56 percent; propylene: 0.30 percent; h₂: 59.22% and dust content 10mg/m³，H₂The S content is 5959mg/m³The organic sulfur is 565.4mg/m³Pressure 0.25Kpa, flow 2000m³/h。

The dry desulfurization system and the desulfurization method are adopted to carry out desulfurization treatment on the coke oven gas, and the process is briefly described as follows: after the coke oven gas is filtered and impurity-removed, impurities such as dust, tar, naphthalene and the like are removed, so that the dust content is 1mg/m³. The coke oven gas from the filter device 2 enters the organic sulfur hydrogenation converter through the heat exchanger 34, preheating the catalyst bed layer by a heating mechanism, closing the heating mechanism after the temperature monitoring mechanism detects that the temperature of the catalyst bed layer reaches 150 ℃, completing the preheating step, reacting the preheated fuel gas in the organic sulfur hydrogenation converter 4, and under the action of a catalyst, COS and CS₂、RSH、RSR、C₄H₄Conversion of organic sulfur such as S to H₂S; then the fuel gas discharged from the organic sulfur hydrogenation converter 4 passes through the heat exchanger 3 as the heat source of the heat exchanger 3, the fuel gas which subsequently passes through the heat exchanger 3 and is ready to enter the organic sulfur hydrogenation converter 4 is heated, the temperature of the fuel gas is raised to 150 ℃, the fuel gas then enters the organic sulfur hydrogenation converter 4, and under the action of a catalyst, COS and CS of organic sulfur in the organic sulfur hydrogenation converter 4₂、RSH、RSR、C₄H₄Conversion of organic sulfur such as S to H₂S, at the same time, O in the organic sulfur conversion step₂With olefins to H₂O、CO₂And alkane, the temperature of the catalyst bed layer 4-4 is raised to about 240 ℃ by the reaction heat, the high-temperature coke oven gas which is discharged from the organic sulfur hydrogenation converter 4 exchanges heat with the low-temperature coke oven gas which enters the heat exchanger 3 in the heat exchanger 3, and then the high-temperature coke oven gas is cooled to 40 ℃ by a water cooler and enters a desulfurization device; in the desulfurization unit 6, the adsorbent is fed with H in the desulfurization unit 6₂The purified fuel gas obtained after S adsorption and removal is discharged from the gas outlet of the desulfurizing device 6.

And (3) effect testing:

the analytical and detection results of the chromatographic detection of organic sulfur conversion in this example are shown in fig. 8, wherein in fig. 8, (a) shows the analytical data of hydrogen sulfide and carbonyl sulfide at the inlet 4-17 of the organic sulfur hydroconversion unit 4, (b) shows the analytical data of hydrogen sulfide and carbonyl sulfide of the purified fuel gas (at the outlet of the desulfurization unit 6), (c) shows the analytical data of carbon disulfide and thiophene at the inlet 4-17, and (d) shows the analytical data of carbon disulfide and thiophene of the purified fuel gas.

As can be seen from the analysis of FIG. 8, the gas inlets 4 to 17 are supplied with fuel gas H₂The S content is 5959mg/m³Organic sulfur(sum of carbonyl sulfide, carbon disulfide and thiophene) content 565.4mg/m³Purified fuel gas H₂The S content is 7.4mg/m³Organic sulfur content 9.5mg/m³The content of the organic sulfur is reduced to 9.5mg/m after the conversion of the organic sulfur is finished³The conversion rate reaches 98.3 percent, the adsorption rate of the adsorbent to the total sulfur (the percentage of the total sulfide concentration of the purified fuel gas divided by the total sulfide concentration at the gas inlet 4-17) is 99.72 percent, and the SO in the flue gas after the purified coke oven gas is combusted can be ensured₂The content reaches the national current ultra-low emission standard.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein. In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on the realization of those skilled in the art; where combinations of features are mutually inconsistent or impractical, such combinations should not be considered as being absent and not within the scope of the claimed invention.

Claims

1. A dry desulfurization system for fuel gas containing high concentration of sulfides, characterized by comprising a filtering device for filtering impurities, a heat exchanger, a cooling device for cooling the gas, an organic sulfur hydroconversion device, and a desulfurization device for removing hydrogen sulfide; the inlet of the filtering device is connected with a fuel gas inlet pipeline, the outlet of the filtering device is connected with the low-temperature side inlet of the heat exchanger, the low-temperature side outlet of the heat exchanger is connected with the air inlet of the organic sulfur hydrogenation converter, the air outlet of the organic sulfur hydrogenation converter is connected with the high-temperature side inlet of the heat exchanger, the high-temperature side outlet of the heat exchanger is connected with the air inlet of the desulfurization device through an air flow pipeline, and the cooling device is arranged on the air flow pipeline connecting the heat exchanger and the desulfurization device;

2. The system for dry desulfurization of high concentration sulfide-containing fuel gas according to claim 1, wherein a first buffer layer and a second buffer layer are further provided in the housing, the first buffer layer is provided between the inlet of the organosulfur hydroconversion unit and the catalyst bed, and the second buffer layer is provided between the catalyst bed and the outlet of the organosulfur hydroconversion unit; the first buffer layer comprises a first support ball layer, a second support ball layer, a first stainless steel wire mesh, a first sieve plate and a first grid which are sequentially arranged from top to bottom, the second support ball layer consists of a plurality of second support ceramic balls which are stacked and paved on the first stainless steel mesh, the first support ball layer consists of a plurality of first support ceramic balls which are stacked and paved on the second support ball layer, and the diameter of each first support ceramic ball is larger than that of each second support ceramic ball; the second buffer layer includes that the third that sets gradually from bottom to top supports ball layer, fourth support ball layer, second stainless steel net, second sieve and second grid, the third supports the ball layer and lays by piling up a plurality of third on the casing bottom surface support the porcelain ball and constitute, the fourth supports the ball layer and lays by piling up a plurality of fourth on the third support ball layer support the porcelain ball and constitute, the diameter that the third supported the porcelain ball is greater than the diameter that the fourth supported the porcelain ball.

3. The system for dry desulfurization of a fuel gas containing a high concentration of sulfides according to claim 1, characterized in that the cooling mechanism comprises a cooling gas inlet provided below the second buffer layer as the first cooling gas inlet.

4. The system for dry desulfurization of fuel gas containing high concentration of sulfides according to claim 1, wherein the temperature monitoring means comprises a plurality of temperature monitoring units for monitoring temperature changes at different height positions of the catalyst bed, and the cooling means is provided with a plurality of cooling gas inlets corresponding to the plurality of temperature monitoring units for zoned cooling.

5. The system for dry desulfurization of fuel gas containing sulfur compounds in high concentration according to claim 4, characterized in that said temperature monitoring means comprises a first monitoring unit for monitoring the temperature of the upper part of said catalyst bed, a second monitoring unit for monitoring the temperature of the middle part of said catalyst bed, and a third monitoring unit for monitoring the temperature of the lower part of said catalyst bed; the cooling mechanism comprises a plurality of cooling gas inlets, wherein the cooling gas inlets comprise a second cooling gas inlet for filling cooling gas into the upper area of the catalyst bed layer, a third cooling gas inlet for filling cooling gas into the middle area of the catalyst bed layer and a fourth cooling gas inlet for filling cooling gas into the lower part of the catalyst bed layer; and the second cooling gas inlet, the third cooling gas inlet and the fourth cooling gas inlet are respectively connected with the cooling gas supply unit through gas flow pipelines, and are connected with the second cooling gas inlet, the third cooling gas inlet and the fourth cooling gas inlet, and the gas flow pipelines are respectively provided with a first control valve, a second control valve and a third control valve.

6. The system for dry desulfurization of a fuel gas containing a high concentration of sulfides according to claim 5, characterized in that said cooling mechanism further comprises a controller, said controller comprising a first control module for controlling the opening and closing of said first control valve, a second control module for controlling the opening and closing of said second control valve, a third control module for controlling the opening and closing of said third control valve, and a fourth control module for controlling the opening and closing of said cooling gas supply unit; the first monitoring unit is in signal connection with a signal input end of the first control module, and a control signal output end of the first control module is in signal connection with the first control valve; the second monitoring unit is in signal connection with the signal input end of the second control module, and the control signal output end of the second control module is in signal connection with the second control valve; the third monitoring unit is in signal connection with a signal input end of the third control module, and a control signal output end of the third control module is in signal connection with the third control valve; the first monitoring unit, the second monitoring unit and the third monitoring unit are in signal connection with the signal input end of the fourth control module, and the signal output end of the fourth control module is in signal connection with the cooling gas supply unit.

7. The system for dry desulfurization of high concentration sulfide-containing fuel gas according to claim 1, characterized in that the cooling gas supply unit comprises a nitrogen gas cylinder for supplying low pressure nitrogen gas; the heating mechanism comprises a plurality of electric heating pipes, the electric heating pipes are arranged along the height direction of the shell, the electric heating pipes are uniformly distributed in the catalyst bed layer, and the heating temperature of the electric heating pipes is more than or equal to 150 ℃.

8. A dry desulfurization method characterized by using the dry desulfurization system according to any one of claims 1 to 7, the dry desulfurization method comprising the steps of:

preheating: the filtered and impurity-removed fuel gas enters an air inlet of the organic sulfur hydroconversion device, a heating mechanism is started to preheat the catalyst bed layer, the heating mechanism is closed after the temperature monitoring mechanism detects that the temperature of the catalyst bed layer reaches 150 ℃, and the fuel gas enters the catalyst bed layer and then is subjected to hydroconversion under the action of a catalyst, so that the organic sulfur in the fuel gas is converted into hydrogen sulfide;

organic sulfur conversion: the fuel gas heated in the heat exchange step enters a catalyst bed layer through an air inlet of the organic sulfur hydrogenation converter, and is subjected to hydrogenation conversion under the action of a catalyst, so that organic sulfur in the fuel gas is converted into hydrogen sulfide; when the temperature monitoring mechanism monitors that the catalyst bed layer has a temperature runaway phenomenon, the cooling mechanism is started to charge cooling gas into the shell to cool the catalyst bed layer, and the cooling mechanism is closed when the temperature monitoring mechanism monitors that the temperature of the catalyst bed layer is reduced to 200-250 ℃;

9. The dry desulfurization method as claimed in claim 8, wherein the fuel gas is coke oven gas, and the total sulfur of the fuel gas before treatment is 3000-8000mg/m³The impurities include dust, tar and naphthalene; the total dust content of the fuel gas after being filtered by the filter device is less than or equal to 1mg/m³After impurity filtering step, the effective components of the fuel gas comprise 20-30% of methane volume fraction, 50-65% of hydrogen volume fraction, 8-15% of carbon monoxide volume fraction, 0.1-0.8% of oxygen volume fraction, 0.5-2.0% of carbon dioxide volume fraction, 0.3-2.0% of ethylene volume fraction, 0.1-0.2% of ethane volume fraction, 0.2-0.5% of propylene volume fraction, 0.1-0.5% of nitrogen volume fraction, and the content of tar and dust is less than 1mg/m³The hydrogen sulfide content is 3000-8000mg/m³The organic sulfur content is 300-800mg/m³(ii) a The organic sulfur comprises COS and CS₂、RSH、RSR、C₄H₄S; in the step of converting the organic sulfur, the conversion rate of the catalyst for catalyzing the organic sulfur is more than 97 percent; the desulfurization step adopts an adsorption desulfurization process, and the desorption rate of the adsorbent adopted by the adsorption desulfurization process to the hydrogen sulfide is more than 99.8 percent; the total sulfur content in the purified fuel gas is less than 20mg/m³(ii) a And in the filtering and impurity removing step, a filtering agent is adopted for filtering, the filtering agent, the catalyst and the adsorbent are all in a solid structure, and a liquid substance is not used in the dry desulfurization method.

10. The dry desulfurization method according to claim 9, wherein the adsorbent is activated carbon particles, and the performance parameters of the activated carbon particles are as follows: iodine adsorption number<700mg/g, methylene blue adsorption number>7ml/mg, BET specific surface area>800m²Per g, particle size phi 2.5-3.5mm, water content<Contact angle of 10%>90 degrees; the micropore distribution of the activated carbon particles is as follows: the number of micropores less than 1nm is more than or equal to 60 percent, the number of micropores less than 2nm accounts for 20 percent, and the balance is micropores more than 2 nm; the catalyst is a cylindrical particle catalyst, the particle diameter of the catalyst is 2.5-3.5mm, and the length of the catalyst is 8-10 mm; the active component of the catalyst is any one or combination of more of cobalt, molybdenum and nickel, and the carrier of the catalyst is any one or combination of more of titanium dioxide andor aluminum oxide and/or silicon dioxide.