CN114196448B

CN114196448B - Full-flow dry type blast furnace gas fine desulfurization system and method

Info

Publication number: CN114196448B
Application number: CN202210139581.1A
Authority: CN
Inventors: 康东娟; 陈晶; 张�杰; 邓云波; 赵长波; 刘玉鹇
Original assignee: Beijing Zhty Technology Co ltd
Current assignee: Beijing Zhty Technology Co ltd
Priority date: 2022-02-16
Filing date: 2022-02-16
Publication date: 2022-05-10
Anticipated expiration: 2042-02-16
Also published as: CN114196448A

Abstract

The invention discloses a full-flow dry type blast furnace gas fine desulfurization system and a method, which comprises a pretreatment system, a hydrolysis system and a desulfurization system which are connected in sequence; be equipped with the preliminary treatment tower among the pretreatment systems, be equipped with the tower of hydrolysising in the system of hydrolysising, be equipped with the desulfurizing tower among the desulfurization system, the preliminary treatment tower the tower of hydrolysising with the desulfurizing tower is the vertical tower that the structure is the same, the middle part of vertical tower is equipped with the filler storehouse, the filler storehouse of preliminary treatment tower is the pretreatment storehouse of filling the pretreating agent, the filler storehouse of the tower of hydrolysising is the storehouse of hydrolysising of filling the hydrolytic agent, the filler storehouse of desulfurizing tower is the desulfurization storehouse of filling the pre-desulfurization agent. The invention adopts full-flow dry desulfurization, no wastewater is discharged in the treatment process, the water content of the coal gas cannot be increased, and the calorific value of the coal gas cannot be reduced. The pretreatment system, the hydrolysis system and the desulfurization system all adopt similar structural designs, the three systems can be mutually standby, and the aim of blast furnace gas fine desulfurization under various working conditions can be achieved.

Description

Full-flow dry type blast furnace gas fine desulfurization system and method

Technical Field

The invention relates to the technical field of blast furnace gas desulfurization, in particular to a full-flow dry type blast furnace gas fine desulfurization system and a full-flow dry type blast furnace gas fine desulfurization method.

Background

The blast furnace gas is used as the combustible gas with the largest output of the iron and steel enterprises, and the statistical output of the blast furnace gas is 700-800 billion cubic meters per month. The existing blast furnace gas purification and subsequent application mainly adopts bag type dust removal to remove particles, and the particles are sent to a blast furnace hot blast stove, a steel rolling heating furnace and a coal gas generator after TRT (blast furnace top gas recovery turbine) residual pressure power generationConsumer units such as electricity are used as fuel, but blast furnace gas still contains harmful substances such as sulfur and chlorine. 22.4.2019, the department of ecological environment issued an opinion on the promotion of ultra-low emissions in the iron and steel industry (environmental atmosphere [2019 ]]35) for the first time, clearly proposes that 'the source control is strengthened, the blast furnace gas and the coke oven gas should be subjected to fine desulfurization', and the tail end flue gas SO is simultaneously subjected to₂The emission of the steel also provides a tighter standard, and the steel industry formally enters an ultra-low emission era. The air pollution control key areas such as Jingjin Ji, peripheral areas, Yanwei plain and the like are the first to promote the index requirements of the steel enterprises on ultra-low emission. In 2019, in 5 months, the ecological environment bureau of Tangshan City in Hebei province has established a working scheme for treating the smoke reaching the standard in the whole process of steel, coking and cement industries (Tanghuaqi [2019 ]]Number 3), the blast furnace gas hydrogen sulfide (H) of iron and steel enterprises₂S) concentration less than or equal to 20mg/Nm³And encourages enterprises to implement organic sulfur treatment, and comprehensively reduces the sulfur content in the gas. However, the existing blast furnace gas purification process cannot reach SO₂Ultra low emission requirements.

Under the background of ultralow emission, the conventional tail end treatment mode is adopted, the investment cost is high, and the tail end cannot be completely discharged according to the standard, so that the source treatment is carried out, and the blast furnace gas desulfurization is the most economic and convenient technical means for the management of iron and steel plants. Meanwhile, the nation will classify iron and steel enterprises, and blast furnace gas desulfurization is an important judgment of a class a enterprise. Therefore, the method for implementing the blast furnace gas fine desulfurization is a more effective and more economic technical means.

The sulfide in the blast furnace gas is mainly carbonyl sulfide (COS) and hydrogen sulfide (H)₂S), wherein the content of COS is about 70%, and the COS is chemically stable and cannot be removed in a simple absorption or adsorption mode, so the difficulty of the fine desulfurization of the blast furnace gas mainly lies in the removal of the COS.

At present, the fine desulfurization of blast furnace gas is a new technical development direction. Although the blast furnace gas fine desulfurization can refer to the coke oven gas fine desulfurization and the CO feed gas desulfurization technology and engineering application cases in the chemical industry, the blast furnace gas fine desulfurization technology cannot be directly applied to the desulfurization technology in the industry due to the particularity of the blast furnace gas, so that the blast furnace gas fine desulfurization technology still belongs to the front exploration stage. The development of the blast furnace gas fine desulfurization technology suitable for the steel industry has important scientific significance and economic value.

Patent CN 112852504A discloses a system and a process for prolonging the service life of a blast furnace gas fine desulfurization reactant, which comprises a carbonyl sulfide hydrolysis catalysis system, an inorganic sulfur removal system and a NaOH solution circulating supply system. The process firstly utilizes a hydrolysis reaction device to complete the conversion of carbonyl sulfide to H₂S conversion and then inorganic sulfur removal using NaOH solution spray system, but the process does not consider the following two aspects: 1. the high-content acid gas such as hydrogen chloride in blast furnace gas can cause poisoning of carbonyl sulfide hydrolysis catalyst, thereby reducing the hydrolysis efficiency of the whole system and shortening the service life of the hydrolysis catalyst; 2. high concentration CO in blast furnace gas₂The alkali liquor consumption of the rear-end wet-method inorganic sulfur removal system is increased, the wastewater discharge is increased, the heat value of blast furnace gas is reduced, the system resistance is large, and a pressure boosting device is required to be arranged.

Therefore, in view of the above problems, it is desirable to develop a system and a method for fine desulfurization of blast furnace gas, which do not affect the existing process and cause secondary environmental pollution.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a full-flow dry blast furnace gas fine desulfurization system and a full-flow dry blast furnace gas fine desulfurization method.

In order to achieve the purpose, the invention adopts the following technical scheme:

a full-flow dry blast furnace gas fine desulfurization system comprises a pretreatment system, a hydrolysis system and a desulfurization system which are connected in sequence; be equipped with the preliminary treatment tower among the pretreatment system, be equipped with the tower of hydrolysising in the system of hydrolysising, be equipped with the desulfurizing tower among the desulfurization system, the preliminary treatment tower the tower of hydrolysising with the desulfurizing tower is the vertical tower that the structure is the same, the middle part of vertical tower is equipped with the filler storehouse, the filler storehouse of preliminary treatment tower is the preliminary treatment storehouse of filling the pretreating agent, the filler storehouse of the tower of hydrolysising is the storehouse of hydrolysising of filling the hydrolytic agent, the filler storehouse of desulfurizing tower is the desulfurization storehouse of filling the desulfurizer in advance.

The coal gas inlet rectifying grid is connected with a blast furnace gas inlet, the coal gas outlet rectifying grid is connected with a blast furnace gas outlet, a feeding buffer bin is arranged above the filling bin, a conical hopper is arranged below the filling bin, a filling feeding port is arranged at the top of the feeding buffer bin, a filling discharging port is arranged at the bottom of the conical hopper, and a rotary telescopic cloth bag is arranged at the top of the feeding buffer bin, so that feeding is facilitated, and the thickness of a material layer in the bin is uniform.

A feeding isolating valve is arranged between the filler feeding hole and the feeding buffer bin, a buffer bin isolating valve is arranged between the feeding buffer bin and the filler bin, a bin isolating valve is arranged between the filler bin and the conical hopper, and a discharging isolating valve is arranged between the conical hopper and the filler discharging hole; and the middle part of the vertical tower is provided with an access hole which is convenient for overhauling in case of failure.

Wherein, still include medicament conveying system, medicament conveying system includes storage silo, electronic loading attachment, medicament delivery track and medicament recovery storehouse, the storage silo electronic loading attachment with the medicament delivery track connects gradually, the medicament delivery track is connected respectively the preliminary treatment tower hydrolysising the tower with the filler feed inlet of desulfurizing tower, the medicament recovery storehouse is used for retrieving the medicament that became invalid, respectively with the preliminary treatment tower hydrolysising the tower with the filler discharge opening of desulfurizing tower links to each other.

The gas replacement system is composed of a first gas replacement system and a second gas replacement system; the first gas replacement system comprises a first blowing pipeline, a first blowing inlet, a first gas diffusing pipeline and a first blowing outlet, the first blowing inlet is arranged at one side of the feeding buffer bin, the first blowing outlet is arranged at the other side of the feeding buffer bin, the gas inlet end of the first blowing pipeline is connected with a first compressed air pipeline and a first nitrogen pipeline, the gas outlet end of the first blowing pipeline is communicated with the first blowing inlet, and a first gas replacement valve is arranged on the first blowing pipeline; the gas inlet end of the first gas diffusion pipeline is connected with the first purge gas outlet, and a first gas diffusion valve is arranged on the first gas diffusion pipeline; the second gas replacement system comprises a second purging pipeline, a second purging gas inlet, a second gas diffusing pipeline and a second purging gas outlet, the second purging gas inlet is arranged at one side of the tapered hopper, the second purging gas outlet is arranged at the other side of the tapered hopper, the gas inlet end of the second purging pipeline is connected with a second compressed air pipeline and a second nitrogen pipeline, the gas outlet end of the second purging pipeline is communicated with the second purging gas inlet, and a second gas replacement valve is arranged on the second purging pipeline; and the gas inlet end of the second gas diffusion pipeline is connected with the second purge gas outlet, and a second gas diffusion valve is arranged on the second gas diffusion pipeline.

Wherein, still including being used for the regenerated regeneration system of desulfurizer, constitute by connecting gradually compressed air pipeline, draught fan, cold air inlet pipeline, heat exchanger, hot-air outlet pipeline, cold air inlet pipeline with the upper portion of heat exchanger links to each other, hot-air outlet pipeline with the lower part of heat exchanger links to each other, be equipped with regeneration valve on the hot-air outlet pipeline, hot-air outlet pipeline links to each other with desulfurization system's inlet pipeline.

The system comprises a reaction pipeline unit, a bypass pipeline unit, a gas pipeline system and a gas pipeline system, wherein the gas pipeline system comprises the reaction pipeline unit and the bypass pipeline unit; the reaction pipeline unit comprises a gas pipeline, an inlet reducing cone and an outlet reducing cone, the pretreatment tower, the hydrolysis tower and the desulfurization tower are sequentially connected through the gas pipeline, a reduction section of the inlet reducing cone is connected with the gas pipeline, an expansion section of the inlet reducing cone is connected with a gas inlet rectifying grid, an inlet gas distribution plate is arranged in the inlet reducing cone, a reduction section of the outlet reducing cone is connected with the gas pipeline, an expansion section of the outlet reducing cone is connected with the gas outlet rectifying grid, an outlet gas distribution plate is arranged in the outlet reducing cone, and the gas pipeline is provided with a gas component detection device and a flow regulating valve; the bypass pipeline unit comprises a bypass main pipe and four bypass branch pipes, one end of each bypass branch pipe is connected with four gas pipelines connected with the pretreatment tower, the hydrolysis tower and the desulfurization tower, and the other end of each bypass branch pipe is connected with the bypass main pipe.

A full-flow dry type blast furnace gas fine desulfurization method comprises the following steps:

s1, allowing the blast furnace gas to enter a pretreatment system through a gas pipeline, an inlet reducing cone and an inlet rectifying grating in sequence, removing acid gases such as hydrogen chloride, carbon dioxide, hydrogen fluoride and the like in the blast furnace gas under the action of a pretreatment agent in a pretreatment bin, and allowing the blast furnace gas to flow out of the pretreatment system through an outlet rectifying grating and an outlet reducing cone outlet gas distribution plate;

s2, the pretreated blast furnace gas enters a hydrolysis system through a gas pipeline, an inlet reducing cone and an inlet rectifying grid, and organic sulfur (mainly carbonyl sulfur (COS)) is converted into inorganic sulfur (H) under the action of a hydrolytic agent in a hydrolysis bin₂S), performing hydrolysis conversion, and then enabling the mixture to flow out of a hydrolysis system through an outlet rectification grid and an outlet reducing cone;

s3, making the hydrolyzed blast furnace gas enter a desulfurization system through a gas inlet pipeline inlet reducing cone, inlet gas distribution and an inlet rectifying grid, and realizing H under the action of a desulfurizing agent in a desulfurization bin₂And S is removed, then the gas passes through an outlet rectification grid and an outlet reducing cone on the side surface of the desulfurizing tower and enters a gas pipeline to finish fine desulfurization of the gas, and the purified gas enters a pipe network for a rear-end user to use.

Wherein the hydrolytic agent is one of clover-shaped, columnar and spherical, and is used for catalytically hydrolyzing carbonyl sulfide (COS) in blast furnace gas and converting the COS into H₂S; the hydrolysis agent comprises the following components in parts by weight: 60-85 parts of a porous carrier, 5-15 parts of an active component, 5-15 parts of a modifier and 5-20 parts of a binder; the porous carrier is one or two of defective alumina and defective titanium oxide; the active component is one or more of copper nitrate, zinc nitrate and nickel nitrate; the modifier is potassium nitrate or potassium carbonateOne of potassium hydroxide and potassium bicarbonate; the binder is one or two of kaolin, bentonite and pseudo-boehmite.

The preparation method of the hydrolytic agent is implemented according to the following steps:

step 1, preparing a porous carrier: weighing a certain amount of aluminum isopropoxide (or titanium isopropoxide) and dissolving the aluminum isopropoxide (or titanium isopropoxide) in glacial acetic acid, ultrasonically mixing for 15-30 minutes, placing the formed uniform solution in a high-pressure reaction kettle, and reacting for 2-8 hours in a constant-temperature air-blast drying oven at 150-200 ℃; taking out the reaction product after the reaction is finished, naturally cooling the reaction product, and washing, drying and roasting the reaction product to obtain a sample, namely the porous carrier defect alumina or defect titanium oxide;

step 2, preparing an active component solution: mixing 5-15 parts of the weighed active component with 5-15 parts of a modifier, then adding a certain amount of water, and stirring for 15 minutes;

step 3, putting 60-85 parts of the porous carrier obtained in the step 1 into the active component solution prepared in the step 2, and soaking at normal temperature for 12-24 hours to obtain a wet mixture;

step 4, mixing the wet mixture obtained in the step 3 with 5-20 parts of the weighed binder, then adding a certain amount of water, stirring, and performing extrusion molding to obtain a molding material;

step 5, drying the formed material obtained in the step 4 in a constant-temperature air-blast drying oven to obtain a primary product;

and 6, roasting the primary product dried in the step 5 in a muffle furnace, and naturally cooling to room temperature to obtain a catalyst sample.

The drying temperature in the step 1 and the step 5 is 80-180 ℃, and the drying time is 1-8 hours.

The mass ratio of the total mass of the active components and the modifier to the water in the step 2 is 10: (2-5).

In the step 1 and the step 6, the roasting temperature is 350-550 ℃, and the roasting time is 2-6 hours.

Wherein the pretreating agent is one of clover-shaped, columnar and spherical, and is used for treating hydrogen chloride (HCl) and carbon dioxide (CO) in blast furnace gas₂) And Hydrogen Fluoride (HF) and other acidic gases are removed, so that a rear-end pipeline and equipment are protected from being corroded, and the service life of a rear-end hydrolytic agent is prolonged. The pretreating agent comprises the following components in parts by weight: 40-65 parts of calcium hydroxide, 5-15 parts of active component, 5-25 parts of modifier and 5-20 parts of binder; the active component is one or two of zinc oxide and copper oxide; the modifier is one or two of potassium hydroxide, sodium carbonate and sodium bicarbonate; the binder is one or two of cement, kaolin and polyvinyl alcohol;

the preparation method of the pretreating agent is implemented according to the following steps:

step 1, putting 40-65 parts of calcium hydroxide, 5-15 parts of active component, 5-25 parts of modifier and 5-20 parts of binder into a stirring device for stirring, and fully mixing uniformly to obtain mixed powder;

step 2, putting the mixed powder obtained in the step 1 into a ball mill for grinding until all the mixed powder passes through a screen;

step 3, adding water into the sieved mixed powder obtained in the step 2, stirring, extruding and forming to obtain a formed material;

and 4, drying the formed material obtained in the step 3 in a drying box, and naturally cooling to room temperature to obtain the pretreating agent sample.

In the step 1, the stirring time is 10-45 minutes.

In the step 2, a sieve with 150-350 meshes is adopted for sieving.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: (1-4) stirring for 10-60 minutes.

In the step 4, the drying temperature is 50-200 ℃, and the drying time is 1-10 hours.

The desulfurizer is one of clover-shaped, columnar and spherical, and is used for generating H after hydrolysis₂S is removed; the desulfurizer consists of the following components in parts by weight: 45-70 parts of soluble ferrite, 15-35 parts of a modifier and 5-20 parts of a binder; the soluble ferrous salt is ferrous sulfateOne or both of iron and ferrous chloride; the modifier is one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide and sodium carbonate; the binder is one or two of kaolin, bentonite and pseudo-boehmite.

The preparation method of the desulfurizer is implemented according to the following steps:

step 1, putting 45-70 parts of soluble ferrous salt, 15-35 parts of modifier and 5-20 parts of binder into a stirring device for stirring, and fully mixing uniformly to obtain mixed powder;

and 4, drying the formed material obtained in the step 3 in a drying oven, and naturally cooling to room temperature to obtain the desulfurizer sample.

In the step 1, the stirring time is 10-30 minutes.

In the step 2, a sieve with 150-350 meshes is adopted for sieving.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: (1-4) stirring for 10-30 minutes.

In the step 4, the drying temperature is 25-150 ℃, and the drying time is 1-10 hours.

The blast furnace gas desulfurization method firstly removes hydrogen chloride (HCl) and carbon dioxide (CO) in the blast furnace gas₂) Hydrogen Fluoride (HF), and the like, and then carbonyl sulfide (COS) is catalytically hydrolyzed and converted into hydrogen sulfide (H)₂S); finally, the solid desulfurizer is utilized to remove H₂And S. Compared with the prior art, the method has the advantages and positive effects that the blast furnace gas fine desulfurization is carried out by adopting a full-flow dry method, the desulfurization efficiency is high, the service life of the catalyst is long, organic sulfur and inorganic sulfur can be simultaneously removed, and the requirement of a terminal user on SO is met₂Ultra-low emission requirements; can remove HCl and CO synergistically₂When acid gas is used, the rear end is protectedPipelines and equipment are prevented from being corroded; the whole process has no waste water, and the heat value of the coal gas is ensured.

The innovation of the invention is that:

1. the arrangement of the pretreatment system effectively solves the problems that the hydrolysis efficiency of the whole system is reduced and the service life of the hydrolysis catalyst is shortened due to the poisoning of the carbonyl sulfide hydrolysis catalyst caused by high-content acidic gases such as hydrogen chloride and the like in blast furnace gas;

2. the full-flow dry desulfurization has no wastewater discharge in the treatment process, the water content of the coal gas cannot be increased, and the heat value of the coal gas cannot be reduced.

3. The pretreatment system, the hydrolysis system and the desulfurization system all adopt similar structural designs, the three systems can be mutually standby, and the aim of blast furnace gas fine desulfurization under various working conditions can be achieved.

4. The method makes full use of the unique structures of the porous carrier defect alumina and the defect titanium oxide with rich defects on the surface, on one hand, promotes the dissociation and activation of water and the generation of active hydroxyl in the COS hydrolysis process; on the other hand, the metal active component is anchored on the defect site on the surface of the porous carrier, so that the activity of metal-oxygen at the interface of the catalyst is improved, and the hydrolysis conversion of COS is accelerated. The hydrolysis catalyst prepared by the invention has higher low-temperature hydrolysis conversion rate and longer service life for carbonyl sulfide in blast furnace gas.

Drawings

FIG. 1 is a schematic structural diagram of a full-flow dry blast furnace gas fine desulfurization system;

FIG. 2 is a scanning electron microscope photograph of a hydrolytic agent in example 1 of the method of the present invention;

FIG. 3 is a graph of COS conversion by the hydrolyzing agent in example 1 of the process of the present invention as a function of time;

FIG. 4 is a graph showing the COS conversion rate of the hydrolyzing agent of the present invention in comparative example 1 as a function of time.

In the figure, 1, a pretreatment system, 1-1, a pretreatment tower, 1-2, a pretreatment bin, 1-3, an inlet rectification grid, 1-4, an outlet rectification grid, 1-5, a feeding buffer bin, 1-6, a conical hopper, 1-7, a filler feeding port, 1-8, a filler discharging port, 1-9, a feeding isolating valve, 1-10, a buffer bin isolating valve, 1-11, a bin isolating valve, 1-12, a discharging isolating valve, 1-13, an access hole, 2, a hydrolysis system, 2-1, a hydrolysis tower, 2-2, a hydrolysis bin, 3, a desulfurization system, 3-1, a desulfurization tower, 3-2, a desulfurization bin, 4, a storage bin, 5, an electric feeding device, 6, a medicament conveying track, 7, a medicament recovery bin, 8, a first blowing and sweeping pipeline, 9. a first purge gas inlet, 10, a first gas discharge pipe, 11, a first purge gas outlet, 12, a first compressed air pipe, 13, a first nitrogen gas pipe, 14, a first gas replacement valve, 15, a first gas discharge valve, 16, a second purge pipe, 17, a second purge gas inlet, 18, a second gas discharge pipe, 19, a second purge gas outlet, 20, a second compressed air pipe, 21, a second nitrogen gas pipe, 22, a second gas replacement valve, 23, a second gas discharge valve, 24, a compressed air pipe, 25, an induced draft fan, 26, a cold air inlet pipe, 27, a heat exchanger, 28, a hot air outlet pipe, 29, a regeneration valve, 30, a gas pipe, 31, an inlet variable-diameter cone, 32, an outlet variable-diameter cone, 33, an inlet gas distribution plate, 34, an outlet gas distribution plate, 35, a gas component detection device, 36, a flow control valve, 37. bypass manifold, 38 bypass branch, 39 bypass pipeline regulating valve, 40 rotary telescopic cloth bag.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

As shown in fig. 1, the present embodiment provides a full-flow dry blast furnace gas fine desulfurization system, which comprises a pretreatment system 1, a hydrolysis system 2 and a desulfurization system 3 connected in sequence; the pretreatment system 1, the hydrolysis system 2 and the desulfurization system 3 are similar in structure, and the three systems can be mutually standby. Be equipped with pretreatment tower 1-1 in the pretreatment system 1, be equipped with among the system of hydrolysising 2 and hydrolysise tower 2-1, be equipped with desulfurizing tower 3-1 among the desulfurization system 3, pretreatment tower 1-1 hydrolysis tower 2-1 with desulfurizing tower 3-1 is the vertical tower that the structure is the same, the middle part of vertical tower is equipped with the filler bin, pretreatment tower 1-1's filler bin is pretreatment bin 1-2 for filling the pretreating agent, hydrolysis tower 2-1's filler bin is hydrolysis bin 2-2 for filling the hydrolyzing agent, desulfurizing tower 3-1's filler bin is desulfurization bin 3-2 for filling the desulfurizing agent in advance.

The coal gas inlet rectifying grid device comprises a filling bin and is characterized in that a coal gas inlet rectifying grid 1-3 connected with a blast furnace gas inlet is arranged on one side of the filling bin, a coal gas outlet rectifying grid 1-4 connected with a blast furnace gas outlet is arranged on the other side of the filling bin, a feeding buffer bin 1-5 is arranged above the filling bin, a conical hopper 1-6 is arranged below the filling bin, a filling feeding port 1-7 is arranged at the top of the feeding buffer bin 1-5, a filling discharging port 1-8 is arranged at the bottom of the conical hopper 1-6, and a rotary telescopic cloth bag 40 is arranged at the top of the feeding buffer bin 1-5, so that feeding is facilitated, and the thickness of a material layer in the bin is uniform.

Wherein, a feeding isolating valve 1-9 is arranged between the filler feeding port 1-7 and the feeding buffer bin 1-5, a buffer bin isolating valve 1-10 is arranged between the feeding buffer bin 1-5 and the filler bin, a bin isolating valve 1-11 is arranged between the filler bin and the conical hopper 1-6, and a discharging isolating valve 1-12 is arranged between the conical hopper 1-6 and the filler discharging port 1-8; and the middle part of the vertical tower is provided with access holes 1-13 which are convenient for overhauling in case of failure.

The device comprises a pretreatment tower 1-1, a hydrolysis tower 2-1, a desulfurizing tower 3-1, a storage bin 4, an electric feeding device 5, a medicament conveying track 6 and a medicament recovery bin 7, wherein the storage bin 4, the electric feeding device 5 and the medicament conveying track 6 are sequentially connected, the medicament conveying track 6 is respectively connected with the pretreatment tower 1-1, the hydrolysis tower 2-1 and a filler feed inlet of the desulfurizing tower 3-1, and the medicament recovery bin 7 is used for recovering ineffective medicaments and is respectively connected with the pretreatment tower 1-1, the hydrolysis tower 2-1 and a filler discharge outlet 1-8 of the desulfurizing tower 3-1. A medicament conveying system is utilized to respectively provide a pretreating agent, a hydrolyzing agent and a desulfurizing agent for the pretreating tower 1-1, the hydrolyzing tower 2-1 and the desulfurizing tower 3-1, and a recycling bin is utilized to recycle the waste medicament.

The gas replacement system is composed of a first gas replacement system and a second gas replacement system; the first gas replacement system comprises a first blowing pipeline 8, a first blowing gas inlet 9, a first gas diffusing pipeline 10 and a first blowing gas outlet 11, wherein the first blowing gas inlet 9 is arranged on one side of the feeding buffering bin 1-5, the first blowing gas outlet 11 is arranged on the other side of the feeding buffering bin 1-5, the gas inlet end of the first blowing pipeline 8 is connected with a first compressed air pipeline 12 and a first nitrogen pipeline 13, the gas outlet end of the first blowing pipeline 8 is communicated with the first blowing gas inlet 9, and a first gas replacement valve 14 is arranged on the first blowing pipeline 8; the gas inlet end of the first gas diffusion pipeline 10 is connected with the first purge gas outlet 11, and a first gas diffusion valve 15 is arranged on the first gas diffusion pipeline 10; the second gas replacement system comprises a second purge pipeline 16, a second purge gas inlet 17, a second gas diffusing pipeline 18 and a second purge gas outlet 19, the second purge gas inlet 17 is arranged at one side of the tapered hopper 1-6, the second purge gas outlet 19 is arranged at the other side of the tapered hopper 1-6, the gas inlet end of the second purge pipeline 16 is connected with a second compressed air pipeline 20 and a second nitrogen pipeline 21, the gas outlet end of the second purge pipeline 16 is communicated with the second purge gas inlet 17, and a second gas replacement valve 22 is arranged on the second purge pipeline 16; the gas inlet end of the second gas diffusion pipeline 18 is connected with the second purge gas outlet 19, and a second gas diffusion valve 23 is arranged on the second gas diffusion pipeline 18. And the gas replacement system is connected with the purging ports of the pretreatment tower 1-1, the hydrolysis tower 2-1 and the desulfurization tower 3-1 and is used for purging and replacing coal gas in the three towers with replacement gas before medicament replacement and maintenance so as to ensure safety.

Wherein, still including the regeneration system who is used for desulfurizer regeneration, by compressed air pipeline 24, draught fan 25, cold air inlet pipeline 26, heat exchanger 27, the hot-air outlet pipeline 28 that connect gradually constitute, cold air inlet pipeline 26 with the upper portion of heat exchanger 27 links to each other, hot-air outlet pipeline 28 with the lower part of heat exchanger 27 links to each other, be equipped with regeneration valve 29 on the hot-air outlet pipeline 28, hot-air outlet pipeline 28 links to each other with desulfurization system 3's inlet pipeline. And (4) regenerating the invalid desulfurizer by using hot air of a regeneration system.

The system comprises a reaction pipeline unit, a bypass pipeline unit, a gas pipeline system and a gas pipeline system, wherein the gas pipeline system comprises the reaction pipeline unit and the bypass pipeline unit; the reaction pipeline unit comprises a gas pipeline 30, an inlet reducing cone 31 and an outlet reducing cone 32, the pretreatment tower 1-1, the hydrolysis tower 2-1 and the desulfurization tower 3-1 are sequentially connected through the gas pipeline 30, a reduction section of the inlet reducing cone 31 is connected with the gas pipeline 30, an expansion section of the inlet reducing cone 31 is connected with a gas inlet rectifying grid 1-3, an inlet gas distribution plate 33 is arranged inside the inlet reducing cone 31, a reduction section of the outlet reducing cone 32 is connected with the gas pipeline 30, an expansion section of the outlet reducing cone 32 is connected with the gas outlet rectifying grid 1-4, an outlet gas distribution plate 34 is arranged inside the outlet reducing cone 32, and the gas pipeline 30 is provided with a gas component detection device 35 and a flow regulating valve 36; the bypass pipeline unit comprises a bypass main pipe 37 and four bypass branch pipes 38, one end of each bypass branch pipe 38 is connected with four gas pipelines 30 connected with the pretreatment tower 1-1, the hydrolysis tower 2-1 and the desulfurization tower 3-1, the other end of each bypass branch pipe 38 is connected with the bypass main pipe 37, and a bypass pipeline adjusting valve 39 is arranged on each bypass branch pipe 38.

According to the concentration of chloride and sulfide in the gas component detection device 35 on the gas pipeline 30, whether each system can be mutually standby or not is judged. The following are the most common cases: 1. according to the detection result of the gas component detection device 35 arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the concentration of the chloride in the gas is lower than the concentration of the chloride in the gas>10 mg/Nm³Organic sulfur concentration>25 mg/Nm³And the concentration of inorganic sulfur>5 mg/Nm³When in use, the pretreatment system 1, the hydrolysis system 2 and the desulfurization system 3 are required to be arranged at the same time for ensuring that the concentration of chloride in coal gas at the outlet of the system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³(ii) a 2. According to the detection result of the gas component detection device arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the gas component is detected to be gasThe concentration of the medium chloride is less than or equal to 10mg/Nm³Concentration of organic sulfur>50 mg/Nm³In the process, the pretreatment system 1 can be used as a second hydrolysis system to meet the requirement of organic sulfur hydrolysis conversion and ensure that the concentration of chloride in the coal gas at the outlet of the system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³(ii) a 3. According to the detection result of the gas component detection device arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the concentration of chloride in the gas is less than or equal to 10mg/Nm³And the concentration of organic sulfur is less than or equal to 25 mg/Nm³But H₂Concentration of S>20 mg/Nm³When in use, the pretreatment system and the hydrolysis system can be used as a second desulfurization system and a third desulfurization system to meet the requirement that the concentration of chloride in the coal gas at the outlet of the system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³The need of (c); 4. according to the detection result of the gas component detection device 35 arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the concentration of the chloride in the gas is lower than the concentration of the chloride in the gas>10 mg/Nm³And the concentration of inorganic sulfur>20 mg/Nm³But the concentration of organic sulfur is less than or equal to 25 mg/Nm³In the process, the hydrolysis system 2 can be used as a second desulfurization system to meet the condition that the concentration of chloride in the coal gas at the outlet of the system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³The requirements of (a).

The conditions for judging whether the medicament needs to be replaced in the running processes of the pretreatment system 1, the hydrolysis system 2 and the desulfurization system are as follows: 1. combining the detection result of the gas component detection device 35, if the concentration of the chloride in the outlet gas of the pretreatment system 1 is less than or equal to 10mg/Nm³When in use, the coal gas can be directly discharged into the rear-end hydrolysis system 2 through the outlet of the pretreatment system 1; otherwise, the pretreating agent needs to be replaced when the pretreating agent fails; 2. if the concentration of organic sulfur in the coal gas at the outlet of the hydrolysis system 2 is less than or equal to 25 mg/Nm by combining the detection result of the coal gas component detection device 35³When in use, the coal gas can be directly discharged into the rear-end desulfurization system through the outlet of the hydrolysis system 2; otherwise, the hydrolysis agent is needed to be replaced when the hydrolysis agent is failed; 3. converting the concentration of organic sulfur in the gas at the outlet of the desulfurization system into H according to the detection result of the gas component detection device 35₂After concentration of S (conversion factor 0.57), if H₂The concentration of S is less than or equal to 20mg/Nm³The coal gas can be directly discharged into a rear-end coal gas outlet through an outlet of the desulfurization system; on the contrary, the desulfurization agent needs to be regenerated when the desulfurization agent fails. After the desulfurizer is regenerated, if the concentration of sulfide in the coal gas at the outlet of the desulfurization system is completely converted into H₂After S concentration (conversion coefficient 0.57), H₂The concentration of S is less than or equal to 20mg/Nm³If the desulfurization agent is successfully regenerated, the desulfurization system can normally operate; after multiple regeneration, the concentration of organic sulfur in the coal gas at the outlet of the desulfurization system is completely converted into H₂After concentration of S (conversion factor 0.57), if H₂The concentration of S is more than 20 mg/m³The desulfurizer is poisoned and deactivated, and the desulfurizer needs to be replaced at the moment; 4. when the gas component detection device 35 is arranged on the gas pipeline connected with the inlet of the pretreatment system 1 to detect sulfide (converted into H)₂S concentration is standard, organic sulfur is converted into H₂Coefficient of S is 0.57) concentration is less than or equal to 20mg/Nm³And the concentration of chloride is less than or equal to 10mg/Nm³When the method is used, the subsequent pretreatment system 1, the hydrolysis system 2 and the desulfurization system can be skipped, and the bypass pipeline stop valve is opened to directly discharge the blast furnace gas into the blast furnace gas outlet for a rear-end user to use.

In the normal operation process of the pretreatment tower 1-1, the hydrolysis tower 2-1 and the desulfurization tower 3-1, the feed inlet block valve, the buffer bin block valve 1-10, the pretreatment bin 1-2 block valve and the discharge port block valve are all in a closed state. Taking the hydrolysis system 2 as an example, when the hydrolysis agent needs to be replaced, firstly opening a closing valve of the hydrolysis bin 2-2, discharging the hydrolysis agent in the hydrolysis bin 2-2 into the conical hopper 1-6, then closing the closing valve of the hydrolysis bin 2-2, opening a second gas replacement valve 22 and a second bleeding valve of the gas replacement system, introducing nitrogen into the conical hopper 1-6 through a second purge gas inlet 17, replacing and bleeding coal gas in the discharging hopper; the second gas replacement valve 22 and the second blow-off valve are then closed, the discharge port block valve is opened, the hydrolyzat in the hopper is discharged through the discharge port to the waste hydrolyzat recovery bin, and the discharge port block valve is closed until the discharge is completed, and the waste hydrolyzat is preferably carried away by a truck.

When the hydrolytic agent is required to be filled, the hydrolytic agent in the storage bin 4 is conveyed to a hydrolytic agent feeding hole through the electric feeding device 5 and the feeding sliding track, at the moment, the nitrogen stop valve, the first gas replacement valve 14 and the first diffusion valve are opened, nitrogen is introduced into the hydrolytic agent buffer bin, and the coal gas in the discharging bin is replaced and diffused; then closing the nitrogen stop valve, the first gas replacement valve 14 and the first diffusion valve, opening the feed inlet isolating valve, discharging the hydrolytic agent into the buffer bin from the rotary retractable material distribution bag, closing the feed inlet isolating valve, opening the first gas replacement valve 14 and the first diffusion valve under the condition that the buffer bin isolating valve is kept closed by 1-10, introducing nitrogen into the hydrolysis buffer bin, and replacing and diffusing air brought in by the hydrolytic agent in the bin; after the diffusion is finished, the first diffusion valve and the first gas replacement valve 14 are closed in sequence, the buffer bin isolating valve 1-10 is opened, the hydrolytic agent is discharged into the hydrolytic bin 2-2, and the buffer bin isolating valve 1-10 is closed until the hydrolytic agent is completely filled. The mode of gas replacement of the surge bin and the hopper can prevent the blast furnace gas from leaking and ensure the operation safety of the system.

When the hydrolysis tower 2-1 needs to be overhauled, after the hydrolytic agent is emptied according to the mode, the feed inlet block valve and the discharge outlet block valve are closed, the buffer bin block valve 1-10 and the hydrolysis bin 2-2 block valve are opened, the first gas replacement valve 14, the second bleeding valve and the nitrogen cut-off valve are opened, nitrogen is introduced into the whole hydrolysis tower 2-1 to replace coal gas in the tower and bleed the coal gas, then the nitrogen cut-off valve is closed, the compressed air cut-off valve is opened, and the whole system is blown by compressed air until the overhaul is finished, so that the safety of overhaul personnel is ensured.

Method example 1

Detecting the components of the coal gas to be treated: according to the detection result of the gas component detection device 35 arranged on the gas pipeline connected with the inlet of the pretreatment system 1, the concentration of chloride in the gas is 18mg/Nm³Organic sulfur concentration of 30mg/Nm³And the concentration of inorganic sulfur is 8mg/Nm³In this embodiment, a full-flow dry type blast furnace gas fine desulfurization method is provided, which comprises the following steps:

s1, allowing the blast furnace gas to enter a pretreatment system 1 through a gas pipeline, an inlet reducing cone 31 and an inlet rectifying grating 1-3 in sequence, removing acid gases such as hydrogen chloride, carbon dioxide, hydrogen fluoride and the like in the blast furnace gas under the action of a pretreatment agent in a pretreatment bin 1-2, and allowing the blast furnace gas to flow out of the pretreatment system 1 through an outlet rectifying grating 1-4 and an outlet reducing cone 32 and an outlet gas distribution plate 34;

s2, the pretreated blast furnace gas enters the hydrolysis system 2 through the gas pipeline, the inlet reducing cone 31 and the inlet rectifying grid 1-3, and organic sulfur (mainly carbonyl sulfur (COS)) is converted into inorganic sulfur (H) under the action of the hydrolytic agent in the hydrolysis bin 2-2₂S), then the mixture flows out of the hydrolysis system 2 through an outlet rectification grid 1-4 and an outlet reducing cone 32;

s3, making the hydrolyzed blast furnace gas enter a desulfurization system 3 from a gas inlet pipeline inlet reducing cone 31 and an inlet gas distribution and inlet rectification grid 1-3, and realizing H under the action of a desulfurizing agent in a desulfurization bin 3-2₂S is removed, then the gas passes through an outlet rectification grid 1-4 and an outlet reducing cone 32 on the side surface of a desulfurizing tower 3-1 and enters a gas pipeline to finish fine desulfurization of the gas, and the purified gas enters a pipe network for a back-end user to use.

Wherein the hydrolytic agent is in the shape of clover and is used for catalyzing and hydrolyzing carbonyl sulfide (COS) in blast furnace gas to convert the COS into H₂S; the hydrolysis agent comprises the following components in parts by weight: 70 parts of porous carrier, 10 parts of active component, 10 parts of modifier and 10 parts of binder; the porous carrier is defect alumina; the active component is copper nitrate; the modifier is potassium nitrate; the binder is kaolin.

step 1, preparing a porous carrier: weighing a certain amount of aluminum isopropoxide, dissolving the aluminum isopropoxide in glacial acetic acid, ultrasonically mixing for 20 minutes, placing the formed uniform solution in a high-pressure reaction kettle, and reacting for 5 hours in a constant-temperature air-blast drying oven at 180 ℃; taking out the reaction product after the reaction is finished, naturally cooling the reaction product, and washing, drying and roasting the reaction product to obtain a sample, namely porous carrier defect alumina;

step 2, preparing an active component solution: mixing the weighed active components with a modifier, then adding a certain amount of water, and stirring for 15 minutes;

step 3, putting the porous carrier obtained in the step 1 into the active component solution prepared in the step 2, and soaking the porous carrier for 18 hours at normal temperature to obtain a wet mixture;

step 4, mixing the wet mixture obtained in the step 3 with the weighed binder, then adding a certain amount of water, stirring, extruding and forming to obtain a formed material;

The drying temperature in the step 1 and the step 5 is 130 ℃, and the drying time is 4 hours.

The mass ratio of the total mass of the active components and the modifier to the water in the step 2 is 10: 3.5.

the roasting temperature in the step 1 and the step 6 is 450 ℃, and the roasting time is 4 hours.

Wherein the pretreating agent is in the shape of clover and is used for treating hydrogen chloride (HCl) and carbon dioxide (CO) in blast furnace gas₂) And Hydrogen Fluoride (HF) and other acidic gases are removed, so that a rear-end pipeline and equipment are protected from being corroded, and the service life of a rear-end hydrolytic agent is prolonged. The pretreating agent comprises the following components in parts by weight: 50 parts of calcium hydroxide, 10 parts of active component, 25 parts of modifier and 15 parts of binder; the active components comprise 7 parts of copper oxide and 3 parts of zinc oxide; the modifier is 10 parts of potassium hydroxide and 15 parts of sodium bicarbonate; the binder comprises 5 parts of cement and 10 parts of kaolin.

step 1, putting 50 parts of calcium hydroxide, 7 parts of copper oxide, 3 parts of zinc oxide, 10 parts of potassium hydroxide, 15 parts of sodium bicarbonate, 5 parts of cement and 10 parts of kaolin into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 10 minutes.

In the step 2, a sieve with 150 meshes is adopted for sieving.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: 4, the stirring time is 10 minutes.

In the step 4, the drying temperature is 175 ℃, and the drying time is 1 hour.

The desulfurizer is clover-shaped and is used for generating H after hydrolysis₂S is removed; the desulfurizer consists of the following components in parts by weight: 45 parts of soluble ferrous salt, 35 parts of modifier and 5 parts of binder; the soluble ferrous salt comprises 40 parts of ferrous sulfate and 5 parts of ferrous chloride; the modifier is 15 parts of potassium hydroxide, 5 parts of calcium hydroxide and 15 parts of sodium carbonate; the binder is 3 parts of bentonite and 2 parts of pseudo-boehmite.

step 1, putting 40 parts of ferrous sulfate, 5 parts of ferrous chloride, 15 parts of potassium hydroxide, 5 parts of calcium hydroxide, 15 parts of sodium carbonate, 3 parts of bentonite and 2 parts of pseudo-boehmite into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 15 minutes.

In the step 2, a 350-mesh screen is adopted for screening.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: 3, the stirring time is 30 minutes.

In the step 4, the drying temperature is 50 ℃ and the drying time is 8 hours.

Detecting that the concentration of chloride in the coal gas at the outlet of the desulfurization system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³。

Method example 2

Detecting the components of the coal gas to be treated: according to the detection result of the gas component detection device 35 arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the concentration of the chloride in the gas is 15 mg/Nm³The concentration of organic sulfur is 32 mg/Nm³And the concentration of inorganic sulfur is 7mg/Nm³In the present embodiment, a full-flow dry type blast furnace gas fine desulfurization method is provided, which includes the following steps:

s2, the pretreated blast furnace gas enters the hydrolysis system 2 through the gas pipeline, the inlet reducing cone 31 and the inlet rectifying grating 1-3, and organic sulfur (mainly carbonyl sulfur (COS)) is converted into inorganic sulfur (H) under the action of a hydrolytic agent in the hydrolysis bin 2-2₂S), then the mixture flows out of the hydrolysis system 2 through an outlet rectification grid 1-4 and an outlet reducing cone 32;

s3, making the hydrolyzed blast furnace gas enter a desulfurization system 3 from a gas inlet pipeline inlet reducing cone 31 and an inlet gas distribution and inlet rectification grid 1-3, and realizing H under the action of a desulfurizing agent in a desulfurization bin 3-2₂S is removed, then the coal gas passes through an outlet rectification grid 1-4 and an outlet reducing cone 32 on the side surface of a desulfurizing tower 3-1 and enters a gas pipeline to finish fine desulfurization of the coal gas, and the purified coalThe gas enters the pipe network for the back-end user to use.

Wherein the hydrolytic agent is columnar and is used for catalytically hydrolyzing carbonyl sulfide (COS) in the blast furnace gas and converting the COS into H₂S; the hydrolysis agent comprises the following components in parts by weight: 60 parts of porous carrier, 15 parts of active component, 5 parts of modifier and 20 parts of binder; the porous carrier is defect titanium oxide; the active component is zinc nitrate; the modifier is potassium carbonate; the binder is bentonite.

step 1, preparing a porous carrier: weighing a certain amount of titanium isopropoxide in glacial acetic acid, carrying out ultrasonic mixing for 15 minutes, placing the formed uniform solution in a high-pressure reaction kettle, and reacting for 2 hours in a constant-temperature air-blast drying oven at 200 ℃; taking out the reaction product after the reaction is finished, naturally cooling the reaction product, and washing, drying and roasting the reaction product to obtain a sample, namely the porous carrier defect alumina or defect titanium oxide;

step 3, putting the porous carrier obtained in the step 1 into the active component solution prepared in the step 2, and soaking the porous carrier for 24 hours at normal temperature to obtain a wet mixture;

The drying temperature in the step 1 and the step 5 is 80 ℃, and the drying time is 8 hours.

The mass ratio of the total mass of the active components and the modifier to the water in the step 2 is 10: 2.

the roasting temperature in the step 1 and the step 6 is 350 ℃, and the roasting time is 6 hours.

Wherein the pretreating agent is one of clover-shaped, columnar and spherical, and is used for treating hydrogen chloride (HCl) and carbon dioxide (CO) in blast furnace gas₂) And Hydrogen Fluoride (HF) and other acidic gases are removed, so that a rear-end pipeline and equipment are protected from being corroded, and the service life of a rear-end hydrolytic agent is prolonged. The pretreating agent comprises the following components in parts by weight: 40 parts of calcium hydroxide, 5 parts of active component, 25 parts of modifier and 20 parts of binder; the active components comprise 2 parts of copper oxide and 3 parts of zinc oxide; the modifier is 15 parts of sodium hydroxide and 10 parts of sodium carbonate; the binder is 10 parts of kaolin and 10 parts of polyvinyl alcohol;

step 1, putting 40 parts of calcium hydroxide, 2 parts of copper oxide, 3 parts of zinc oxide, 15 parts of sodium hydroxide, 10 parts of sodium carbonate, 10 parts of kaolin and 10 parts of polyvinyl alcohol into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 20 minutes.

In the step 2, a sieve with 150 meshes is adopted for sieving.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: 2, the stirring time is 20 minutes.

In the step 4, the drying temperature is 50 ℃ and the drying time is 1 hour.

The desulfurizer is columnar and is used for generating H after hydrolysis₂S removing; the desulfurizer consists of the following components in parts by weight: soluble ferrous salt 7015 parts of modifier and 20 parts of binder; the soluble ferrous salt comprises 45 parts of ferrous sulfate and 25 parts of ferrous chloride; the modifier is 10 parts of sodium hydroxide and 5 parts of sodium carbonate; the binder is 10 parts of kaolin and 10 parts of pseudo-boehmite.

step 1, putting 45 parts of ferrous sulfate, 25 parts of ferrous chloride, 10 parts of sodium hydroxide, 5 parts of sodium carbonate, 10 parts of kaolin and 10 parts of pseudo-boehmite into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 30 minutes.

In the step 2, a 300-mesh screen is adopted for screening.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: 1, the stirring time is 15 minutes.

In the step 4, the drying temperature is 150 ℃ and the drying time is 4 hours.

Method example 3

Detecting the components of the coal gas to be treated: according to the detection result of the gas component detection device 35 arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the concentration of the chloride in the gas is 16 mg/Nm³The concentration of organic sulfur was 34mg/Nm³And the concentration of inorganic sulfur is 8mg/Nm³In the present embodiment, a full-flow dry type blast furnace gas fine desulfurization method is provided, which includes the following steps:

Wherein the hydrolytic agent is spherical and converts carbonyl sulfide (COS) in blast furnace gas into H by catalytic hydrolysis₂S; the hydrolysis agent comprises the following components in parts by weight: 75 parts of porous carrier, 5 parts of active component, 15 parts of modifier and 5 parts of binder; the porous carrier is defect titanium oxide; the active component is nickel nitrate; the modifier is potassium hydroxide; the binder is pseudo-boehmite.

step 1, preparing a porous carrier: weighing a certain amount of aluminum isopropoxide (or titanium isopropoxide) and dissolving the aluminum isopropoxide (or titanium isopropoxide) in glacial acetic acid, ultrasonically mixing for 30 minutes, placing the formed uniform solution in a high-pressure reaction kettle, and reacting for 8 hours in a constant-temperature air-blast drying oven at 150 ℃; taking out the reaction product after the reaction is finished, naturally cooling the reaction product, and washing, drying and roasting the reaction product to obtain a sample, namely the porous carrier defect alumina or defect titanium oxide;

The drying temperature in the step 1 and the step 5 is 180 ℃, and the drying time is 1 hour.

The mass ratio of the total mass of the active components and the modifier to the water in the step 2 is 10: 5.

the roasting temperature in the step 1 and the step 6 is 550 ℃, and the roasting time is 2 hours.

Wherein the pretreating agent is spherical and is used for treating hydrogen chloride (HCl) and carbon dioxide (CO) in the blast furnace gas₂) And Hydrogen Fluoride (HF) and other acidic gases are removed, so that a rear-end pipeline and equipment are protected from being corroded, and the service life of a rear-end hydrolytic agent is prolonged. The pretreating agent comprises the following components in parts by weight: 65 parts of calcium hydroxide, 15 parts of active component, 5 parts of modifier and 5 parts of binder; the active components comprise 7 parts of copper oxide and 8 parts of zinc oxide; the modifier is 3 parts of potassium hydroxide and 2 parts of sodium bicarbonate; the binder is 3 parts of cement and 2 parts of polyvinyl alcohol;

step 1, putting 65 parts of calcium hydroxide, 7 parts of copper oxide, 8 parts of zinc oxide, 5 parts of potassium hydroxide, 10 parts of sodium bicarbonate, 5 parts of cement and 5 parts of polyvinyl alcohol into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 45 minutes.

In the step 2, a 350-mesh screen is adopted for screening.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: 1, the stirring time is 10 minutes.

In the step 4, the drying temperature is 75 ℃, and the drying time is 10 hours.

The desulfurizer is spherical and is used for generating H after hydrolysis₂S removing; the desulfurizer consists of the following components in parts by weight: 65 parts of soluble ferrite, 28 parts of a modifier and 7 parts of a binder; the soluble ferrous salt is 35 parts of ferrous sulfate and 30 parts of ferrous chloride; the modifier comprises 5 parts of potassium hydroxide, 15 parts of calcium hydroxide and 8 parts of sodium carbonate; the binder is 5 parts of bentonite and 2 parts of pseudo-boehmite.

step 1, putting 35 parts of ferrous sulfate, 30 parts of ferrous chloride, 5 parts of potassium hydroxide, 15 parts of calcium hydroxide, 8 parts of sodium carbonate, 5 parts of bentonite and 2 parts of pseudo-boehmite into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 30 minutes.

In the step 2, a 200-mesh screen is adopted for screening.

In the step 4, the drying temperature is 150 ℃ and the drying time is 2 hours.

Method example 4

Detecting the components of the coal gas to be treated: according to the detection result of the gas component detection device 35 arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the concentration of the chloride in the gas is 6mg/Nm³The organic sulfur concentration was 66mg/Nm³In the present embodiment, a full-flow dry type blast furnace gas fine desulfurization method is provided, which includes the following steps:

s1, allowing blast furnace gas to enter a first hydrolysis system through a gas pipeline, an inlet reducing cone 31 and an inlet rectifying grating 1-3, completing the hydrolysis conversion of organic sulfur (mainly carbonyl sulfur (COS)) to inorganic sulfur (H2S) under the action of a hydrolysis agent in a hydrolysis bin 2-2, and allowing the blast furnace gas to flow out of the first hydrolysis system through an outlet rectifying grating 1-4 and an outlet reducing cone 32;

s2, allowing blast furnace gas passing through the first hydrolysis system to enter a second hydrolysis system through a gas pipeline, the inlet reducing cone 31 and the inlet rectifying grating 1-3, completing the hydrolysis conversion of organic sulfur (mainly carbonyl sulfur (COS)) to inorganic sulfur (H2S) under the action of a hydrolyzing agent in the hydrolysis bin 2-2, and then allowing the blast furnace gas to flow out of the second hydrolysis system through the outlet rectifying grating 1-4 and the outlet reducing cone 32;

s3, making the hydrolyzed blast furnace gas enter a desulfurization system 3 from a gas inlet pipeline inlet reducing cone 31 and an inlet gas distribution and inlet rectification grid 1-3, and realizing H under the action of a desulfurizing agent in a desulfurization bin 3-2₂S is removed and then passes through an outlet on the side surface of a desulfurizing tower 3-11-4 of the rectifying grating, the outlet reducing cone 32 and the gas pipeline, finish the fine desulfurization of the gas, and the purified gas enters the pipe network for the back-end user to use.

Wherein the hydrolytic agent is one of clover-shaped, columnar and spherical, and is used for catalytically hydrolyzing carbonyl sulfide (COS) in blast furnace gas and converting the COS into H₂S; the hydrolysis agent comprises the following components in parts by weight: 75 parts of porous carrier, 8 parts of active component, 12 parts of modifier and 5 parts of binder; the porous carrier is defect alumina; the active component is nickel nitrate; the modifier is potassium bicarbonate; the binder is kaolin.

step 1, preparing a porous carrier: weighing a certain amount of aluminum isopropoxide (or titanium isopropoxide) and dissolving the aluminum isopropoxide (or titanium isopropoxide) in glacial acetic acid, ultrasonically mixing for 25 minutes, placing the formed uniform solution in a high-pressure reaction kettle, and reacting for 5 hours in a constant-temperature air-blast drying oven at 180 ℃; taking out the reaction product after the reaction is finished, naturally cooling the reaction product, and washing, drying and roasting the reaction product to obtain a sample, namely the porous carrier defect alumina or defect titanium oxide;

step 3, putting the porous carrier obtained in the step 1 into the active component solution prepared in the step 2, and soaking at normal temperature for 18 hours to obtain a wet mixture;

The drying temperature in the step 1 and the step 5 is 150 ℃, and the drying time is 5 hours.

The mass ratio of the total mass of the active components and the modifier to the water in the step 2 is 10: 3.

the roasting temperature in the step 1 and the step 6 is 400 ℃, and the roasting time is 5 hours.

The desulfurizer is one of clover-shaped, columnar and spherical, and is used for generating H after hydrolysis₂S is removed; the desulfurizer consists of the following components in parts by weight: 70 parts of soluble ferrous salt, 18 parts of modifier and 12 parts of binder; the soluble ferrous salt comprises 25 parts of ferrous sulfate and 45 parts of ferrous chloride; the modifier comprises 5 parts of sodium hydroxide, 8 parts of calcium hydroxide and 5 parts of sodium carbonate; the binder is 7 parts of kaolin and 5 parts of pseudo-boehmite.

step 1, putting 25 parts of ferrous sulfate, 45 parts of ferrous chloride, 5 parts of sodium hydroxide, 8 parts of calcium hydroxide, 5 parts of sodium carbonate, 7 parts of kaolin and 5 parts of pseudo-boehmite into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 20 minutes.

In the step 2, a screen with 150 meshes is adopted for screening.

In the step 4, the drying temperature is 75 ℃, and the drying time is 6 hours.

Method example 5

Detecting the components of the coal gas to be treated: according to the detection result of the gas component detection device 35 arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the concentration of the chloride in the gas is 8mg/Nm³And the concentration of organic sulfur is 20mg/Nm³But H₂The S concentration was 28 mg/Nm³In the present embodiment, a full-flow dry type blast furnace gas fine desulfurization method is provided, which includes the following steps:

s1, allowing blast furnace gas to enter a first desulfurization system through a gas inlet pipeline, an inlet reducing cone 31 and inlet gas distribution and inlet rectifying grids 1-3, and realizing H under the action of a desulfurizing agent in a desulfurization bin 3-2₂S is removed, and then the S passes through an outlet rectification grid 1-4 on the side surface of a desulfurizing tower 3-1, an outlet reducing cone 32 and enters a gas pipeline;

s2, allowing the blast furnace gas to enter a second desulfurization system through a gas inlet pipeline, an inlet reducing cone 31 and inlet gas distribution and inlet rectifying grids 1-3, and realizing H under the action of a desulfurizing agent in a desulfurization bin 3-2₂S is removed, and then the S passes through an outlet rectification grid 1-4 on the side surface of a desulfurizing tower 3-1, an outlet reducing cone 32 and enters a gas pipeline;

s3, allowing blast furnace gas to enter a third desulfurization system through a gas inlet pipeline, an inlet reducing cone 31 and inlet gas distribution and inlet rectifying grids 1-3, and realizing H under the action of a desulfurizing agent in a desulfurization bin 3-2₂S is removed, and then the S passes through an outlet rectification grid 1-4 on the side surface of a desulfurizing tower 3-1, an outlet reducing cone 32 and enters a gas pipeline; and finishing fine desulfurization of the coal gas, and enabling the purified coal gas to enter a pipe network for a rear-end user to use.

The desulfurizer is clover-shaped; the desulfurizer consists of the following components in parts by weight: 60 parts of soluble ferrite, 28 parts of a modifier and 12 parts of a binder; the soluble ferrous salt is 10 parts of ferrous sulfate and 50 parts of ferrous chloride; the modifier comprises 8 parts of potassium hydroxide, 10 parts of calcium hydroxide and 10 parts of sodium carbonate; the binder is 5 parts of kaolin and 7 parts of pseudo-boehmite.

step 1, putting 10 parts of ferrous sulfate, 50 parts of ferrous chloride, 8 parts of potassium hydroxide, 10 parts of calcium hydroxide, 10 parts of sodium carbonate, 5 parts of kaolin and 7 parts of pseudo-boehmite into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 10 minutes.

In the step 2, a screen with 250 meshes is adopted for screening.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: 2, the stirring time is 10 minutes.

In the step 4, the drying temperature is 25 ℃ and the drying time is 10 hours.

Method example 6

Detecting the components of the coal gas to be treated: according to the detection result of the gas component detection device 35 arranged on the gas pipeline connected with the inlet of the pretreatment system 1, if the concentration of the chloride in the gas is lower than the concentration of the chloride in the gas>10 mg/Nm³And the concentration of inorganic sulfur is 25 mg/Nm³But the concentration of organic sulfur was 19 mg/Nm³In the present embodiment, a full-flow dry type blast furnace gas fine desulfurization method is provided, which includes the following steps:

s2, enabling the pretreated blast furnace gas to enter a first desulfurization system from a gas pipeline, the inlet reducing cone 31 and the inlet rectifying grating 1-3, and realizing H under the action of a desulfurizing agent in the desulfurization bin 3-2₂S is removed, and then the S passes through an outlet rectification grid 1-4 on the side surface of a desulfurizing tower 3-1, an outlet reducing cone 32 and enters a gas pipeline;

s3, allowing the blast furnace gas passing through the first desulfurization system to enter the second desulfurization system through the gas inlet pipeline inlet reducing cone 31, the inlet gas distribution and the inlet rectifying grating 1-3, and realizing H under the action of a desulfurizer in the desulfurization bin 3-2₂S is removed, then the gas passes through an outlet rectification grid 1-4 and an outlet reducing cone 32 on the side surface of a desulfurizing tower 3-1 and enters a gas pipeline to finish fine desulfurization of the gas, and the purified gas enters a pipe network for a back-end user to use.

Wherein the pretreating agent is in the shape of clover and is used for treating hydrogen chloride (HCl) and carbon dioxide (CO) in blast furnace gas₂) And Hydrogen Fluoride (HF) and other acidic gases are removed, so that a rear-end pipeline and equipment are protected from being corroded, and the service life of a rear-end hydrolytic agent is prolonged. The pretreating agent comprises the following components in parts by weight: 65 parts of calcium hydroxide, 5 parts of active component, 15 parts of modifier and 15 parts of binder; the active component is 5 parts of zinc oxide; the modifier is 10 parts of sodium hydroxide and 5 parts of sodium bicarbonate; the binder is 15 parts of polyvinyl alcohol;

step 1, putting 65 parts of calcium hydroxide, 5 parts of zinc oxide, 10 parts of sodium hydroxide, 5 parts of sodium bicarbonate and 15 parts of polyvinyl alcohol into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 40 minutes.

In the step 2, a 300-mesh screen is adopted for screening.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: 3, the stirring time is 50 minutes.

The desulfurizer is columnar and is used for generating H after hydrolysis₂S is removed; the desulfurizer consists of the following components in parts by weight: 65 parts of soluble ferrous, 23 parts of modifier and 12 parts of binder; the soluble ferrous salt is ferrous sulfate; the modifier is sodium carbonate; the binder is pseudo-boehmite.

step 1, putting 20 parts of ferrous sulfate, 45 parts of ferrous chloride, 7 parts of sodium hydroxide, 8 parts of calcium hydroxide, 8 parts of sodium carbonate, 2 parts of kaolin and 10 parts of bentonite into a stirring device for stirring, and fully and uniformly mixing to obtain mixed powder;

In the step 1, the stirring time is 30 minutes.

In the step 2, a 300-mesh screen is adopted for screening.

In the step 3, the mass ratio of the sieved mixed powder to water is 10: 4, stirring time 25 minutes.

In the step 4, the drying temperature is 50 ℃ and the drying time is 10 hours.

Hydrolytic Agents comparative example 1

A hydrolytic agent for blast furnace gas fine desulfurization is different from that of example 1 only in that commercial alumina is used instead of defective alumina to obtain a hydrolysis catalyst product.

Hydrolytic Agents comparative example 2

A hydrolytic reagent for blast furnace gas fine desulfurization is different from example 1 only in that commercially available titanium oxide is used instead of defective titanium oxide to obtain a hydrolysis catalyst product.

Examples of the experiments

The following performance indicators of the hydrolyzates obtained in examples 1 to 4 and comparative examples 1 to 2 were examined: bulk density, radial crush strength and conversion. The specific detection method is as follows:

(1) method for detecting bulk density reference is made to: measuring the bulk density of the HGT 4680-2014 fertilizer catalyst;

(2) the radial crushing strength detection method refers to: measuring the crushing resistance of the HGT 2782-2011 fertilizer catalyst particles;

(3) the conversion was calculated as follows:

wherein the content of the first and second substances,C ₀COS concentration of blast furnace gas before passing through hydrolysis catalyst, mg/Nm³；CCOS concentration of blast furnace gas after passing through hydrolysis catalyst, mg/Nm³。

And (3) testing conditions are as follows: the catalyst was charged in a fixed bed reactor (phi 10 mm. times.200 mm) at a reaction temperature of 80 ℃ and a COS concentration of 300mg/Nm³The contact time of the gas and the catalyst was 4.0s, and the concentration of COS in the inlet and outlet gas was measured every 10 minutes by a gas chromatograph, and the average of the 4-hour measurement data was taken. The results of detection of each index are shown in table 1.

TABLE 1 detection results of performance index of hydrolytic agent

A scanning electron microscope photograph of the hydrolytic agent in example 1 is shown in fig. 2, a time-varying graph of the COS conversion rate of the hydrolytic agent is shown in fig. 3, and a time-varying graph of the COS conversion rate of the hydrolytic agent in comparative example 1 is shown in fig. 4.

The experimental results of the embodiment and the comparative example show that the hydrolysis catalyst provided by the invention is suitable for catalytic hydrolysis of COS in blast furnace gas, and has the advantages of high hydrolysis conversion rate and long service life; the preparation method of the catalyst provided by the invention has the advantages of mild reaction conditions, simplicity, convenience, easiness in operation, lower cost and higher feasibility; the catalyst provided by the invention has good repeatability, and is easy to realize large-scale production. The catalyst prepared by the invention has low-temperature activity, and can still realize catalytic hydrolysis of COS even at the temperature lower than 60 ℃.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. A full-flow dry type blast furnace gas fine desulfurization system is characterized in that: comprises a pretreatment system, a hydrolysis system and a desulfurization system which are connected in sequence; the pretreatment system is internally provided with a pretreatment tower, the hydrolysis system is internally provided with a hydrolysis tower, the desulfurization system is internally provided with a desulfurization tower, the pretreatment tower, the hydrolysis tower and the desulfurization tower are vertical towers with the same structure, the middle part of the vertical tower is provided with a filler bin, the filler bin of the pretreatment tower is a pretreatment bin filled with a pretreatment agent, the filler bin of the hydrolysis tower is a hydrolysis bin filled with a hydrolysis agent, and the filler bin of the desulfurization tower is a desulfurization bin filled with a pre-desulfurizing agent;

according to the concentration of chloride and sulfide in the gas component detection device on the gas pipeline, whether each system can be mutually standby or not is judged: (1) according to the detection result of the gas component detection device arranged on the gas pipeline connected with the inlet of the pretreatment system, if the concentration of the chloride in the gas is lower than the concentration of the chloride in the gas>10 mg/Nm³Organic sulfur concentration>25 mg/Nm³And the concentration of inorganic sulfur>5 mg/Nm³When in use, a pretreatment system, a hydrolysis system and a desulfurization system are required to be arranged at the same time for ensuring that the concentration of chloride in coal gas at the outlet of the system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³(ii) a (2) According to the detection result of the gas component detection device arranged on the gas pipeline connected with the inlet of the pretreatment system, if the concentration of chloride in the gas is less than or equal to 10mg/Nm³Concentration of organic sulfur>50 mg/Nm³In the process, the pretreatment system can be used as a second hydrolysis system to meet the requirement of organic sulfur hydrolysis conversion and ensure that the concentration of chloride in the coal gas at the outlet of the system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³(ii) a (3) According to the detection result of the gas component detection device arranged on the gas pipeline connected with the inlet of the pretreatment system, if the concentration of chloride in the gas is less than or equal to 10mg/Nm³And the concentration of organic sulfur is less than or equal to 25 mg/Nm³But H₂Concentration of S>20 mg/Nm³When in use, the pretreatment system and the hydrolysis system can be used as a second desulfurization system and a third desulfurization system to meet the requirement that the concentration of chloride in the coal gas at the outlet of the system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³The need of (c); (4) according to the detection result of the gas component detection device arranged on the gas pipeline connected with the inlet of the pretreatment system, if the concentration of chloride in the gas is lower than the preset concentration, the concentration of chloride in the gas is detected>10 mg/Nm³And the concentration of inorganic sulfur>20 mg/Nm³But the concentration of organic sulfur is less than or equal to 25 mg/Nm³When the method is used, the hydrolysis system can be used as a second desulfurization system to meet the condition that the concentration of chloride in the coal gas at the outlet of the system is less than or equal to 10mg/Nm³And H₂S concentration is less than or equal to 20mg/Nm³The requirements of (a).

2. The full-flow dry type blast furnace gas fine desulfurization system according to claim 1, characterized in that: the coal gas inlet rectifying grid is connected with a blast furnace gas inlet, the coal gas outlet rectifying grid is connected with a blast furnace gas outlet, a feeding buffer bin is arranged above the filling bin, a conical hopper is arranged below the filling bin, a filling feeding port is arranged at the top of the feeding buffer bin, a filling discharging port is arranged at the bottom of the conical hopper, a rotary telescopic cloth bag is arranged at the top of the feeding buffer bin, feeding is facilitated, and the thickness of a material layer in the bin is uniform.

3. The full-flow dry type blast furnace gas fine desulfurization system according to claim 2, characterized in that: a feeding isolating valve is arranged between the filler feeding hole and the feeding buffer bin, a buffer bin isolating valve is arranged between the feeding buffer bin and the filler bin, a bin isolating valve is arranged between the filler bin and the conical hopper, and a discharging isolating valve is arranged between the conical hopper and the filler discharging hole; and the middle part of the vertical tower is provided with an access hole which is convenient for overhauling in case of failure.

4. The full-flow dry type blast furnace gas fine desulfurization system according to claim 2, characterized in that: still include medicament conveying system, medicament conveying system includes storage silo, electronic loading attachment, medicament delivery track and medicament recovery storehouse, the storage silo electronic loading attachment with the medicament delivery track connects gradually, the medicament delivery track connects respectively the preliminary treatment tower hydrolysising the tower with the filler feed inlet of desulfurizing tower, the medicament recovery storehouse is used for retrieving the medicament that became invalid, respectively with the preliminary treatment tower hydrolysising the tower with the filler discharge opening of desulfurizing tower links to each other.

5. The full-flow dry type blast furnace gas fine desulfurization system according to claim 2, characterized in that: the gas replacement system is composed of a first gas replacement system and a second gas replacement system; the first gas replacement system comprises a first blowing pipeline, a first blowing inlet, a first gas diffusing pipeline and a first blowing outlet, the first blowing inlet is arranged at one side of the feeding buffer bin, the first blowing outlet is arranged at the other side of the feeding buffer bin, the gas inlet end of the first blowing pipeline is connected with a first compressed air pipeline and a first nitrogen pipeline, the gas outlet end of the first blowing pipeline is communicated with the first blowing inlet, and a first gas replacement valve is arranged on the first blowing pipeline; the gas inlet end of the first gas diffusion pipeline is connected with the first purge gas outlet, and a first gas diffusion valve is arranged on the first gas diffusion pipeline; the second gas replacement system comprises a second purging pipeline, a second purging gas inlet, a second gas diffusing pipeline and a second purging gas outlet, the second purging gas inlet is arranged at one side of the tapered hopper, the second purging gas outlet is arranged at the other side of the tapered hopper, the gas inlet end of the second purging pipeline is connected with a second compressed air pipeline and a second nitrogen pipeline, the gas outlet end of the second purging pipeline is communicated with the second purging gas inlet, and a second gas replacement valve is arranged on the second purging pipeline; and the gas inlet end of the second gas diffusion pipeline is connected with the second purge gas outlet, and a second gas diffusion valve is arranged on the second gas diffusion pipeline.

6. The full-flow dry type blast furnace gas fine desulfurization system according to claim 1, characterized in that: still including being used for the regenerated regeneration system of desulfurizer, constitute by connecting gradually compressed air pipeline, draught fan, cold air inlet pipeline, heat exchanger, hot-air outlet pipeline, cold air inlet pipeline with the upper portion of heat exchanger links to each other, hot-air outlet pipeline with the lower part of heat exchanger links to each other, be equipped with regeneration valve on the hot-air outlet pipeline, hot-air outlet pipeline links to each other with desulfurization system's inlet pipeline.

7. The full-flow dry type blast furnace gas fine desulfurization system according to claim 2, characterized in that: the system also comprises a gas pipeline system, wherein the gas pipeline system comprises a reaction pipeline unit and a bypass pipeline unit; the reaction pipeline unit comprises a gas pipeline, an inlet reducing cone and an outlet reducing cone, the pretreatment tower, the hydrolysis tower and the desulfurization tower are sequentially connected through the gas pipeline, a reduction section of the inlet reducing cone is connected with the gas pipeline, an expansion section of the inlet reducing cone is connected with a gas inlet rectifying grid, an inlet gas distribution plate is arranged in the inlet reducing cone, a reduction section of the outlet reducing cone is connected with the gas pipeline, an expansion section of the outlet reducing cone is connected with the gas outlet rectifying grid, an outlet gas distribution plate is arranged in the outlet reducing cone, and a gas component detection device and a flow regulating valve are arranged on the gas pipeline; the bypass pipeline unit comprises a bypass main pipe and four bypass branch pipes, one end of each bypass branch pipe is connected with four gas pipelines connected with the pretreatment tower, the hydrolysis tower and the desulfurization tower, and the other end of each bypass branch pipe is connected with the bypass main pipe.

8. A blast furnace gas fine desulfurization method using the full-flow dry type blast furnace gas fine desulfurization system according to any one of claims 1 to 7, characterized by comprising the following steps:

s1, enabling the blast furnace gas to enter a pretreatment system through a gas pipeline, an inlet reducing cone and an inlet rectifying grating in sequence, removing acid gas in the blast furnace gas under the action of a pretreatment agent in a pretreatment bin, and then enabling the blast furnace gas to flow out of the pretreatment system through an outlet rectifying grating and an outlet reducing cone outlet gas distribution plate;

s2, the pretreated blast furnace gas enters a hydrolysis system through a gas pipeline, an inlet reducing cone and an inlet rectifying grating, the hydrolysis conversion of organic sulfur to inorganic sulfur is completed under the action of a hydrolyzing agent in a hydrolysis bin, and then the pretreated blast furnace gas flows out of the hydrolysis system through an outlet rectifying grating and an outlet reducing cone;

s3, making the hydrolyzed blast furnace gas enter a desulfurization system through a gas inlet pipeline inlet reducing cone, inlet gas distribution and an inlet rectifying grid, and realizing H under the action of a desulfurizing agent in a desulfurization bin₂Removal of S, thenThe purified gas enters a pipe network for a rear-end user to use.

9. The blast furnace gas fine desulfurization method according to claim 8, characterized in that: the hydrolytic agent is one of clover-shaped, columnar and spherical, and is used for catalytically hydrolyzing carbonyl sulfide (COS) in blast furnace gas and converting the COS into H₂S; the hydrolysis agent comprises the following components in parts by weight: 60-85 parts of a porous carrier, 5-15 parts of an active component, 5-15 parts of a modifier and 5-20 parts of a binder; the porous carrier is one or two of defective alumina and defective titanium oxide; the active component is one or more of copper nitrate, zinc nitrate and nickel nitrate; the modifier is one of potassium nitrate, potassium carbonate, potassium hydroxide and potassium bicarbonate; the binder is one or two of kaolin, bentonite and pseudo-boehmite;

10. The blast furnace gas fine desulfurization method according to claim 8, characterized in that: the pretreatment agent is one of clover-shaped, columnar and spherical and is used for removing acid gas in blast furnace gas; the pretreating agent comprises the following components in parts by weight: 40-65 parts of calcium hydroxide, 5-15 parts of active component, 5-25 parts of modifier and 5-20 parts of binder; the active component is one or two of zinc oxide and copper oxide; the modifier is one or two of potassium hydroxide, sodium carbonate and sodium bicarbonate; the binder is one or two of cement, kaolin and polyvinyl alcohol;

the desulfurizer is one of clover-shaped, columnar and spherical, and is used for generating H after hydrolysis₂S is removed; the desulfurizer consists of the following components in parts by weight: 45-70 parts of soluble ferrite, 15-35 parts of a modifier and 5-20 parts of a binder; the soluble ferrous salt is one or two of ferrous sulfate and ferrous chloride; the modifier is one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide and sodium carbonate; the binder is one or two of kaolin, bentonite and pseudo-boehmite.