CN111334341A - Method for desulfurizing blast furnace gas - Google Patents
Method for desulfurizing blast furnace gas Download PDFInfo
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- CN111334341A CN111334341A CN202010180550.1A CN202010180550A CN111334341A CN 111334341 A CN111334341 A CN 111334341A CN 202010180550 A CN202010180550 A CN 202010180550A CN 111334341 A CN111334341 A CN 111334341A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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Abstract
The invention relates to a desulfurization method for blast furnace gas, which mainly solves the technical problems that in the prior art, sulfide and dust in the blast furnace gas purification cannot be completely removed, so that a gas pipeline is easy to corrode, and the emission of sulfur dioxide after the blast furnace gas is combusted exceeds the standard. The invention adopts the following steps: a. blast furnace gas from a blast furnace enters a dry dedusting unit, and a material flow I is formed after dedusting; b. the material flow I enters an organic sulfur conversion device filled with a medium-temperature hydrolysis catalyst, the catalyst is a microcrystalline material catalyst, and the material flow I is subjected to catalytic conversion to form a material flow II; c. the material flow II enters a TRT power generation unit to generate power to form a material flow III; d. the material flow III enters a desulfurizing tower and forms a material flow IV after being absorbed by active carbon or an iron oxide fine desulfurizing agent; e. the material flow IV enters a subsequent blast furnace gas use workshop section, so that the problem is better solved, and the method can be used for industrial production of blast furnace gas purification.
Description
Technical Field
The present invention relates to a method for purifying blast furnace gas, and more particularly to a method for desulfurizing and purifying blast furnace gas used for power generation.
Background
Blast furnace gas is a byproduct of iron and steel enterprises in the iron making process, namely low-calorific-value combustible gas containing carbon monoxide, carbon dioxide, nitrogen and hydrogen. Raw blast furnace gas also contains a large amount of dust and sulfides, which are mainly divided into organic sulfur and inorganic sulfur, and the organic sulfur accounts for a higher proportion than the inorganic sulfur. The main components of the organic sulfur comprise carbonyl sulfide, carbon disulfide, thioether mercaptan, thiophene and the like, and the carbonyl sulfide is taken as the main component; the inorganic sulfur mainly contains hydrogen sulfide, sulfur dioxide, etc. The emission of sulfur dioxide in flue gas of blast furnace gas after untreated combustion exceeds the standard. Therefore, the blast furnace gas needs to be purified to remove dust and sulfides carried in the gas before combustion and power generation.
In the existing blast furnace gas purification process, the dust removal link is a dry dust removal process which replaces the traditional wet process. In the aspect of sulfide removal, a wet scrubbing device is arranged behind a TRT device in the mature method at present. The method can effectively remove inorganic sulfur such as H in blast furnace gas2S，SO2，SO3But the organic sulfur in the blast furnace gas can not be removed, resulting in SO in the flue gas after combustion2The discharge is not up to standard, and the moisture carried by the wet desulphurization can enter subsequent pipeline equipment to cause corrosion. The removal of organic sulfur, especially COS, is an important link of blast furnace gas fine desulfurization, and the currently effective solution is to convert COS into H through catalytic hydrolysis2And removing the S.
Chinese patent CN201910042224.1 discloses a method for desulfurizing and purifying blast furnace gas, which comprises the following steps: s1, the blast furnace gas enters an organic sulfur conversion device after being dedusted by a dry cloth bag dedusting device, and the organic sulfur is converted into H2S; s2, then, the mixed gas enters a residual pressure turbine power generation device to recover pressure energy and heat energy; and S3, removing hydrogen sulfide in the cooled blast furnace gas by a wet desulphurization device, and then removing hydrogen sulfide in each user unit. The organic sulfur conversion device comprises a purification furnace and a hydrolysis furnace connected with the purification furnace through a pipeline, the dedusted blast furnace gas is subjected to dust removal and chlorine removal through a purification furnace filled with a protective agent after cloth bag dedusting, and then the blast furnace gas enters a hydrolysis furnace filled with a multifunctional purifying agent and a medium-temperature hydrolysis catalyst to convert organic sulfur to convert the organic sulfur. The medium-temperature hydrolysis catalyst used in the method is easy to be poisoned, an anti-poisoning step (a purifying furnace filled with a protective agent) is required to be added before the medium-temperature hydrolysis catalyst is used, the process is complex, and the blast furnace gas after TRT is removed by a wet methodHydrogen sulfide can reduce the calorific value of the gas, and cause corrosion of subsequent pipeline equipment.
The prior art does not disclose a report of using a microcrystalline material catalyst to remove organic sulfides from blast furnace gas. The blast furnace gas purification method of the invention can completely remove organic sulfur and hydrogen sulfide and remove dust in the blast furnace gas. The technical problem that the existing blast furnace gas is not completely desulfurized and purified is solved in a targeted manner.
Disclosure of Invention
The invention aims to solve the technical problems that the removal of sulfides and dust in blast furnace gas is not clean, especially the organic sulfur in the sulfides is difficult to remove, so that the emission of sulfur dioxide exceeds the standard, and a gas pipeline in a subsequent working section is easy to corrode after wet desulphurization. The invention provides a new blast furnace gas desulfurization and purification method, which is used for production by adopting gas heating or power generation and has the advantages of clean purification, simple process, low sulfur emission, difficult corrosion of subsequent pipeline equipment and stable operation of a power generation device.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for desulphurizing blast furnace gas, comprising the steps of:
a. blast furnace gas from a blast furnace enters a dry dedusting unit, and a material flow I is formed after dedusting;
b. the material flow I enters an organic sulfur conversion device filled with a medium-temperature hydrolysis catalyst, and the material flow I is subjected to catalytic conversion to form a material flow II;
c. the material flow II enters a TRT power generation unit to generate power to form a material flow III;
d. the material flow III enters a desulfurizing tower and forms a material flow IV after being absorbed by a desulfurizing agent, wherein the desulfurizing agent is at least one of ferric oxide, zinc oxide, active carbon or microcrystalline materials;
e. and the material flow IV enters a subsequent blast furnace gas use section.
In the above technical solution, a preferable technical solution is that the microcrystalline material catalyst contains at least one element of group ia, iia, va, ib, iib, iiib, ivb, vb, vib, viib or viii in the periodic table of elements.
In the above technical solution, a preferable technical solution is that the ia element in the catalyst is selected from at least one of magnesium and calcium; the group IB element is selected from at least one of copper and silver; the IIIB group element is selected from at least one of lanthanum, cerium and yttrium, and the VIII group element is selected from at least one of iron, cobalt and nickel.
In the above technical solution, a preferable technical solution is that the group ivb element in the catalyst is selected from at least one of Ti, Zr, or Hf; the VB group element is selected from V, Nb or Ta.
In the above technical solution, a preferable technical solution is that the microcrystalline material in the catalyst is selected from at least one of X-type molecular sieve, Y-type molecular sieve, a-type molecular sieve, ZSM-type molecular sieve, mordenite, β -type zeolite, SAPO-type molecular sieve, ALPO-type molecular sieve, MCM-22 molecular sieve, MCM-49, MCM-56, SSZ-13 molecular sieve, ZSM-5/mordenite, ZSM-5/β zeolite, ZSM-5/Y, MCM-22/mordenite, ZSM-5/Magadiite, ZSM-5/β zeolite/mordenite, ZSM-5/β zeolite/Y zeolite or ZSM-5/Y zeolite/mordenite.
In the above technical scheme, the preferable technical scheme is that the ZSM type microcrystalline material in the catalyst comprises at least one of ZSM-5, ZSM-23, ZSM-11 and ZSM-48, and the molecular ratio of silicon to aluminum of the ZSM type microcrystalline material is 20-10000.
In the above technical solution, a preferable technical solution is that the organic sulfur is at least one of carbon sulfide, thiol, thioether, thiophene, methyl mercaptan, and methyl thioether.
In the above technical scheme, the preferable technical scheme is that the medium-temperature hydrolysis catalyst is used at an airspeed of 100-3000 h-1。
In the technical scheme, the preferable technical scheme is that the medium-temperature hydrolysis catalyst is used at an airspeed of 500-2500 h-1。
In the technical scheme, the preferable technical scheme is that the use temperature of the medium-temperature hydrolysis catalyst is 50-250 ℃, and the pressure is 0-8 MPa.
In the technical scheme, the preferable technical scheme is that the use temperature of the medium-temperature hydrolysis catalyst is 100-250 ℃, and the pressure is 0-6 MPa.
In the above technical solution, the preferred technical solution is that the dry dust removal unit employs a cloth bag for dust removal.
In the above technical solution, the preferred technical solution is that the dry dust removal unit employs at least one of a gravity dust remover, a cyclone dust remover, a bag-type dust remover, an electric dust remover, or a ceramic high-temperature dust remover.
In the above technical solution, a preferable technical solution is that the adsorbent filled in the desulfurization tower in the step d) is a microcrystalline material adsorbent.
In the above technical solution, the preferable technical solution is that the microcrystalline material desulfurizing agent is a honeycomb block type, the appearance of the microcrystalline material desulfurizing agent is a honeycomb block cuboid with a size of 100mm x 500-1000 mm, and the porosity is 20-40%.
In the above technical solution, a preferable technical solution is that the microcrystalline material desulfurizing agent is a honeycomb block-shaped cuboid with an appearance of 100mm x 500-1000 mm.
In the above technical solution, the preferred technical solution is that the medium temperature hydrolysis catalyst is a honeycomb block type, and the porosity is 20-40%. The appearance of the medium-temperature hydrolysis catalyst is a honeycomb block-shaped cuboid with the size of 100mm x 500-1000 mm.
In the above technical scheme, the preferred technical scheme is that the appearance of the medium-temperature hydrolysis catalyst is a honeycomb block-shaped cuboid with the size of 150mm x 500-1000 mm.
Most of the desulfurization processes in the prior art are processes for removing sulfur dioxide from flue gas after combustion of blast furnace gas, which is also called a post-desulfurization process. After the sulfur of the coal gas is removed, the coal gas is combusted, so that the flue gas does not contain sulfur dioxide, and a post-desulfurization process of the flue gas is not needed. The pre-desulfurization process is simple, the occupied area is small, the operation cost is low, byproducts which are difficult to treat are not generated, and the desulfurization cost is greatly reduced.
In the process of blast furnace gas purification, after the blast furnace gas in the dry dedusting system is dedusted and purified, the prior art can remove the hydrogen sulfide in the gas by a wet hydrogen sulfide removing method such as additionally arranging a spray tower and the likeBut the heat value of the gas is lost, the recycling value of the blast furnace gas is reduced, organic sulfur is difficult to remove, and common medium-temperature hydrolysis catalysts need to be additionally provided with anti-poisoning equipment and have complex use process. The method of the invention has the following advantages: (1) the microcrystalline material catalyst is used, so that the organic sulfur can be completely removed, and the problem that the discharged sulfide exceeds the standard is solved. (2) The microcrystalline material catalyst is anti-poisoning and anti-coking, reduces anti-poisoning pretreatment devices, and reduces production cost. (3) Dry removal of H after TRT2S, corrosion to subsequent pipeline equipment is reduced, and the heat value of the coal gas is effectively reserved.
The technical scheme adopted by the invention is as follows: blast furnace gas from the top of the blast furnace enters a dry dedusting unit, trace moisture in the blast furnace gas is utilized after dedusting, the blast furnace gas enters a medium-temperature hydrolysis organic sulfur conversion device, the blast furnace gas after organic sulfur conversion enters a TRT power generation device, the blast furnace gas after TRT power generation is absorbed by activated carbon or ferric oxide in a desulfurization tower, inorganic sulfur in the raw gas and hydrogen sulfide generated after organic sulfur medium-temperature hydrolysis catalysis are removed, and the blast furnace gas enters a subsequent blast furnace gas utilization section. The hydrogen sulfide content at the outlet is less than 1mg/m3The dust content is less than 5mg/m3. Organic sulfur carried in the gas is converted, and the emission of sulfur dioxide in the flue gas of a combustion engine is 10m/m3The device runs stably, and a better technical effect is achieved.
Drawings
FIG. 1 is a schematic view of a blast furnace gas purification process according to the present invention.
In fig. 1, 1 is blast furnace gas from a blast furnace, 2 is a material flow i, which is the blast furnace gas after dry dedusting, and 3 is a material flow ii, which is the blast furnace gas after catalytic conversion by organic sulfur; 4 is material flow III which is blast furnace gas after TRT power generation; 5 is a stream IV for adsorption of H by a desulfurizing tower2S and the blast furnace gas after organic sulfur.
I is a dry dedusting system, II is an organic sulfur conversion device, III is a TRT power generation device, IV is a desulfurizing tower, and V is a subsequent use working section.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
As shown in figure 1, blast furnace gas from a blast furnace enters a cloth bag dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen sulfide in the material flow I is 20mg/m3Organic sulfide content 100mg/m3Dust concentration 10mg/m3. The material flow I enters an organic sulfur conversion device, the gas space velocity is 1000, the reaction temperature is 150 ℃, the organic sulfur conversion device is filled with a potassium modified alumina medium temperature hydrolysis catalyst to convert organic sulfur in blast furnace gas into inorganic sulfur to form a material flow II, and the hydrogen sulfide concentration in the material flow II is 110mg/m3Organic sulfide content 10mg/m3Dust concentration 5mg/m3. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. The material flow III enters a desulfurizing tower and forms a material flow IV after being absorbed by a ZSM-5 molecular sieve adsorbent, and the sulfide content in the material flow IV is less than 10mg/m3The dust concentration is less than 5mg/m3. The material flow IV enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentration of hydrogen sulfide at the outlet of the comprehensive purification tower is stable, subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in the tail gas emission of a combustion engine is less than 10mg/m3。
[ example 2 ]
As shown in the attached figure 1, blast furnace gas from a blast furnace enters a dry dedusting unit, and forms a material flow I after dedusting, wherein the concentration of hydrogen sulfide in the material flow I is 25mg/m3Organic sulfide content 250mg/m3Dust concentration 20mg/m3. The material flow I enters an organic sulfur conversion device, the gas space velocity is 500, the reaction temperature is 170 ℃, the organic sulfur conversion device is filled with a medium temperature hydrolysis catalyst ZSM-5 molecular sieve catalyst to convert organic sulfur in blast furnace gas into inorganic sulfur to form a material flow II, and the hydrogen sulfide concentration in the material flow II is 270mg/m3Organic sulfide content 5mg/m3Dust concentration 10mg/m3. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. The material flow III enters a desulfurizing tower and passes through active carbon and oxygenAfter iron sulfide adsorption, a material flow IV is formed, wherein the sulfide content in the material flow IV is less than 8mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow III enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentration of chlorine hydrogen sulfide at the outlet of the comprehensive purification tower is stable, subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in tail gas emission of a combustion engine is less than 8mg/m3。
[ example 3 ]
As shown in the attached figure 1, blast furnace gas from a blast furnace enters a dry dedusting unit, and forms a material flow I after dedusting, wherein the concentration of hydrogen sulfide in the material flow I is 15mg/m3Organic sulfide content 100mg/m3Dust concentration 8mg/m3. The material flow I enters an organic sulfur conversion device, the gas space velocity is 600, the reaction temperature is 150 ℃, the organic sulfur conversion device is filled with a potassium modified alumina medium temperature hydrolysis catalyst to convert organic sulfur in blast furnace gas into inorganic sulfur to form a material flow II, and the hydrogen sulfide concentration in the material flow II is 100mg/m3Organic sulfide content 5mg/m3Dust concentration 5mg/m3. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. The material flow III enters a desulfurizing tower and forms a material flow IV after being absorbed by a copper modified Y molecular sieve absorbent, and the sulfide content in the material flow IV is less than 8mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow IV enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentration of hydrogen sulfide at the outlet of the comprehensive purification tower is stable, subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in the tail gas emission of a combustion engine is less than 8mg/m3。
[ example 4 ]
As shown in the attached figure 1, blast furnace gas from a blast furnace enters a dry dedusting unit, and forms a material flow I after dedusting, wherein the concentration of hydrogen sulfide in the material flow I is 10mg/m3Organic sulfide content 120mg/m3Dust concentration 10mg/m3. The material flow I enters an organic sulfur conversion device, the organic sulfur conversion device is filled with magnesium modified alumina moderate temperature hydrolysis catalyst and honeycomb block adsorbent with the shape of 150 x 600mm, organic sulfur in blast furnace gas is converted into inorganic sulfur to form a material flow II,the concentration of hydrogen sulfide in the material flow II is 130mg/m3Organic sulfide content 0mg/m3Dust concentration 5mg/m3. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. The material flow III enters a desulfurizing tower and forms a material flow IV after being absorbed by a zinc modified ZSM-5 molecular sieve, and the sulfide content in the material flow IV is less than 10mg/m3The dust concentration is less than 5mg/m3The material flow IV enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentration of hydrogen sulfide at the outlet of the comprehensive purification tower is stable, subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in the tail gas emission of a combustion engine is less than 10mg/m3。
[ example 5 ]
As shown in the attached figure 1, blast furnace gas from a blast furnace enters a dry dedusting unit, and forms a material flow I after dedusting, wherein the concentration of hydrogen sulfide in the material flow I is 30mg/m3Has a content of organic sulfides of 80mg/m3Dust concentration of 5mg/m3. The material flow I enters an organic sulfur conversion device, the organic sulfur conversion device is filled with potassium and cerium modified alumina moderate temperature hydrolysis catalyst, honeycomb block adsorbent with the shape of 150 x 600mm, gas space velocity is 1000, reaction temperature is 180 ℃, organic sulfur in blast furnace gas is converted into inorganic sulfur, a material flow II is formed, and hydrogen sulfide concentration in the material flow II is 50mg/m3Organic sulfide content 10mg/m3Dust concentration 5mg/m3. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. The material flow III enters a desulfurizing tower and forms a material flow IV after being adsorbed by ZSM-5 and a zinc modified Y molecular sieve adsorbent, and the sulfide content in the material flow IV is less than 10mg/m3The dust concentration is less than 5mg/m3. The material flow IV enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentration of hydrogen sulfide at the outlet of the comprehensive purification tower is stable, subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in the tail gas emission of a combustion engine is less than 5mg/m3。
[ example 6 ]
As shown in attached figure 1, blast furnace gas from a blast furnace enters a dry dedusting unit, and forms a material flow I after dedusting, wherein the concentration of hydrogen sulfide in the material flow I is 0-50 mg/m3BetweenThe organic sulfide content is 100 to 200mg/m3Dust concentration of 10-20 mg/m3In the meantime. The material flow I enters an organic sulfur conversion device, the organic sulfur conversion device is filled with a potassium and lanthanum modified alumina medium-temperature hydrolysis catalyst, organic sulfur in blast furnace gas is converted into inorganic sulfur, a material flow II is formed, and the concentration of hydrogen sulfide in the material flow II is 100-250 mg/m3The content of organic sulfide is 0-10 mg/m3Dust concentration of 10-20 mg/m3In the meantime. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. The material flow III enters a desulfurizing tower and forms a material flow IV after being adsorbed by a copper modified ZSM-5 and a zinc modified Y molecular sieve adsorbent, and the sulfide content in the material flow IV is less than 10mg/m3The dust concentration is less than 5mg/m3. The material flow IV enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentration of hydrogen sulfide at the outlet of the comprehensive purification tower is stable, subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in the tail gas emission of a combustion engine is less than 5mg/m3。
[ example 7 ]
As shown in attached figure 1, blast furnace gas from a blast furnace enters a dry dedusting unit, and forms a material flow I after dedusting, wherein the concentration of hydrogen sulfide in the material flow I is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3In the meantime. The material flow I enters an organic sulfur conversion device, the organic sulfur conversion device is filled with a potassium and lanthanum modified alumina medium-temperature hydrolysis catalyst and a honeycomb block adsorbent with the shape of 150 x 600mm, organic sulfur in blast furnace gas is converted into inorganic sulfur to form a material flow II, and the concentration of hydrogen sulfide in the material flow II is 100-250 mg/m3The content of organic sulfide is 0-10 mg/m3Dust concentration of 10-20 mg/m3In the meantime. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. Feeding the material flow III into a desulfurizing tower, adsorbing by using a rare earth lanthanum modified Y molecular sieve adsorbent, and forming a material flow IV by using a honeycomb block adsorbent with the adsorbent shape of 150X 600mm, wherein the sulfide content in the material flow IV is less than 10mg/m3The dust concentration is less than 5mg/m3. The material flow IV enters a power generation device to generate power, and the device is connected withThe operation is continued for more than 3 months, the concentration of the hydrogen sulfide at the outlet of the comprehensive purification tower is stable, the subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in the tail gas emission of the combustion engine is less than 5mg/m3。
[ example 8 ]
As shown in attached figure 1, blast furnace gas from a blast furnace enters a dry dedusting unit, and forms a material flow I after dedusting, wherein the concentration of hydrogen sulfide in the material flow I is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3In the meantime. The material flow I enters an organic sulfur conversion device, a potassium and vanadium modified alumina medium temperature hydrolysis catalyst ZSM and a mordenite molecular sieve catalyst are filled in the organic sulfur conversion device, a honeycomb block adsorbent with the shape of 150 x 600mm is used as the catalyst, the organic sulfur in blast furnace gas is converted into inorganic sulfur, a material flow II is formed, and the concentration of hydrogen sulfide in the material flow II is 100-250 mg/m3The content of organic sulfide is 0-10 mg/m3Dust concentration of 10-20 mg/m3In the meantime. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. Feeding the material flow III into a desulfurizing tower, adsorbing by a rare earth lanthanum modified Y molecular sieve catalyst to obtain a honeycomb block adsorbent with the shape of 150 x 600mm, and forming a material flow IV, wherein the sulfide content in the material flow IV is less than 15mg/m3The dust concentration is less than 5mg/m3. The material flow IV enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentration of hydrogen sulfide at the outlet of the comprehensive purification tower is stable, subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in the tail gas emission of a combustion engine is less than 7mg/m3。
[ example 9 ]
As shown in attached figure 1, blast furnace gas from a blast furnace enters a dry dedusting unit, and forms a material flow I after dedusting, wherein the concentration of hydrogen sulfide in the material flow I is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3In the meantime. The material flow I enters an organic sulfur conversion device, the organic sulfur conversion device is filled with potassium and iron modified alumina medium-temperature hydrolysis catalyst, organic sulfur in blast furnace gas is converted into inorganic sulfur, and material flow is formedAnd II, wherein the organic sulfide is at least one of mercaptan, thioether, thiophene, methyl mercaptan and methyl thioether. The content of organic sulfide in the material flow II is 0-10 mg/m3Dust concentration of 10-20 mg/m3In the meantime. And the material flow II enters a TRT power generation unit to form a material flow III after power generation. The material flow III enters a desulfurizing tower and forms a material flow IV after being absorbed by ZSM and mordenite molecular sieve microcrystalline material absorbent, and the sulfide content in the material flow IV is less than 15mg/m3The dust concentration is less than 5mg/m3. The material flow IV enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentration of hydrogen sulfide at the outlet of the comprehensive purification tower is stable, subsequent pipeline equipment is not obviously corroded, and the concentration of sulfur dioxide in the tail gas emission of a combustion engine is less than 7mg/m3。
Claims (10)
1. A method for desulphurizing blast furnace gas, comprising the steps of:
a. blast furnace gas from a blast furnace enters a dry dedusting unit, and a material flow I is formed after dedusting;
b. the material flow I enters an organic sulfur conversion device filled with a medium-temperature hydrolysis catalyst, and the material flow I is subjected to catalytic conversion to form a material flow II;
c. the material flow II enters a TRT power generation unit to generate power to form a material flow III;
d. the material flow III enters a desulfurizing tower and forms a material flow IV after being absorbed by a desulfurizing agent, wherein the desulfurizing agent is at least one of ferric oxide, zinc oxide, active carbon or microcrystalline materials;
e. and the material flow IV enters a subsequent blast furnace gas use section.
2. The process of claim 1, wherein the medium-temperature hydrolysis catalyst comprises at least one element selected from the group consisting of group IA, group IIA, group VA, group IB, group IIB, group IIIB, group IVB, group VB, group VIB, group VIIB and group VIII of the periodic Table of elements.
3. The method for desulfurizing high-coal gas according to claim 2, wherein the group IIA element in the catalyst is at least one selected from magnesium and calcium; the group IB element is selected from at least one of copper and silver; the IIIB group element is selected from at least one of lanthanum, cerium and yttrium, and the VIII group element is selected from at least one of iron, cobalt and nickel.
4. The method for desulfurizing high-coal gas according to claim 1, wherein the group IVB element in the catalyst is at least one selected from Ti, Zr or Hf; the VB group element is selected from V, Nb or Ta.
5. The method of desulfurizing blast furnace gas according to claim 1, wherein said microcrystalline material is at least one selected from the group consisting of an X-type molecular sieve, a Y-type molecular sieve, an A-type molecular sieve, a ZSM-type molecular sieve, mordenite, β -type zeolite, a SAPO-type molecular sieve, an ALPO-type molecular sieve, an MCM-22 molecular sieve, MCM-49, MCM-56, an SSZ-13 molecular sieve, ZSM-5/mordenite, ZSM-5/β zeolite, ZSM-5/Y, MCM-22/mordenite, ZSM-5/Magadiite, ZSM-5/β zeolite/mordenite, ZSM-5/β zeolite/Y zeolite, and ZSM-5/Y zeolite/mordenite.
6. The blast furnace gas purification method according to claim 5, wherein the catalyst ZSM type microcrystalline material comprises at least one of ZSM-5, ZSM-23, ZSM-11 and ZSM-48, and the ZSM type microcrystalline material has a silicon-aluminum molecular ratio of 20 to 10000.
7. The method for desulfurizing blast furnace gas according to claim 1, wherein the desulfurizing agent is a honeycomb briquette type having a porosity of 20 to 40%.
8. The method for desulfurizing blast furnace gas according to claim 1, wherein the medium temperature hydrolysis catalyst is used at a space velocity of 100-3000 h-1。
9. The method for desulfurizing blast furnace gas according to claim 1, wherein the medium temperature hydrolysis catalyst is used at a temperature of 50 to 250 ℃ and a pressure of 0 to 8 MPa.
10. The method for desulfurizing blast furnace gas according to claim 1, wherein the medium-temperature hydrolysis catalyst is of a honeycomb briquette type and has a porosity of 20 to 40%.
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