CN111334339A - Fine desulfurization method for blast furnace gas - Google Patents
Fine desulfurization method for blast furnace gas Download PDFInfo
- Publication number
- CN111334339A CN111334339A CN202010180544.6A CN202010180544A CN111334339A CN 111334339 A CN111334339 A CN 111334339A CN 202010180544 A CN202010180544 A CN 202010180544A CN 111334339 A CN111334339 A CN 111334339A
- Authority
- CN
- China
- Prior art keywords
- blast furnace
- material flow
- furnace gas
- zsm
- enters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Industrial Gases (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a fine 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 a TRT power generation unit, and a material flow II is formed after power generation; c. the material flow II enters a desulfurizing tower, an organic sulfur conversion device filled with a low-temperature hydrolysis catalyst is arranged at the lower part of the desulfurizing tower, the material flow II is hydrolyzed and catalyzed by the low-temperature catalyst to form a material flow III, and the catalyst is a microcrystalline material catalyst; the upper part of the desulfurizing tower is filled with a fine desulfurizing agent, and the material flow III is absorbed by the fine desulfurizing agent to form a material flow IV; d. 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 in the industrial production of the blast furnace gas fine desulfurization.
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 is easy to be poisoned, an anti-poisoning step (a purifying furnace filled with a protective agent) is required before use, the process is complex, and the temperature after TRT is highThe gas is subjected to wet hydrogen sulfide removal, so that the heat value of the gas is reduced, and subsequent pipeline equipment is corroded.
The desulfurization process in the prior art is mainly a process for removing sulfur dioxide in flue gas after blast furnace gas is combusted, and is also called a post-desulfurization process. 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.
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 the production of heating or power generation by adopting gas and has the advantages of clean purification, simple process, low sulfur emission, difficult corrosion of pipelines 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 purifying blast furnace gas, a method for fine desulfurization of blast furnace gas, comprises 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 a TRT power generation unit, and a material flow II is formed after power generation;
c. the material flow II enters a desulfurizing tower, a low-temperature hydrolysis catalyst is filled at the lower part of the desulfurizing tower, a fine desulfurizing agent is filled at the upper part of the desulfurizing tower, and the material flow II forms a material flow III after being subjected to hydrolysis catalysis by the low-temperature catalyst; adsorbing the material flow III by a fine desulfurization adsorbent to form a material flow IV;
d. and the material flow IV enters a subsequent blast furnace gas use section.
In the above technical solution, the preferred technical solution is that the low-temperature hydrolysis catalyst uses alumina as a carrier, and the 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.
The microcrystal catalyst for treating organic sulfur in blast furnace gas contains at least one element of IA, IIA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII elements in periodic table.
In the above technical solution, a preferable technical solution is that the microcrystalline material in the fine desulfurization adsorbent is at least one selected from 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 or ZSM-5/Y zeolite/mordenite.
In the above technical solution, a preferable technical solution is that the ZSM-type microcrystalline material in the fine desulfurization adsorbent includes at least one of ZSM-5, ZSM-23, ZSM-11 and ZSM-48, and the molecular ratio of the ZSM-type microcrystalline material to silica/alumina is 100 to 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 technical scheme, the preferable technical scheme is that the low-temperature hydrolysis catalyst is used at an airspeed of 100-3000 h-1。
In the technical scheme, the preferable technical scheme is that the low-temperature hydrolysis catalyst is used at an airspeed of 500-2500 h-1。
In the technical scheme, the preferable technical scheme is that the low-temperature hydrolysis catalyst is used at the temperature of 50-140 ℃ and under the pressure of 0-8 MPa.
In the technical scheme, the preferable technical scheme is that the low-temperature hydrolysis catalyst is used at the temperature of 60-100 ℃ and the pressure of 0-6 MPa. The low-temperature hydrolysis catalyst is in a honeycomb block type, and the porosity is 20-40%.
In the above technical solution, the preferable technical solution is that the dry dust removal unit employs a dry 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 fine desulfurization adsorbent filled in the desulfurization tower of step c) is a microcrystalline material adsorbent. The fine desulfurization adsorbent is in a honeycomb block type, and the porosity is 20-40%.
In the above technical solution, a preferred technical solution is that the appearance of the low-temperature hydrolysis catalyst is a honeycomb block-shaped cuboid with a size of 100mm x 500-1000 mm.
In the above technical solution, a preferred technical solution is that the appearance of the low-temperature hydrolysis catalyst is a honeycomb block-shaped cuboid of 150mm x 500-1000 mm.
In the above technical solution, a preferred technical solution is that the fine desulfurization adsorbent is a honeycomb block-shaped cuboid with an appearance of 100mm x 500-1000 mm.
In the above technical solution, a preferred technical solution is that the fine desulfurization adsorbent is a honeycomb block-shaped rectangular parallelepiped of 150mm x 500-1000 mm in appearance.
In the process of blast furnace gas purification, after the blast furnace gas in a dry dedusting system is dedusted and purified, the hydrogen sulfide in the gas can be removed by a wet hydrogen sulfide removal method such as adding a spray tower in the prior art, but the calorific value of the gas is lost, the recycling value of the blast furnace gas is reduced, organic sulfur is difficult to remove, and a general hydrolysis catalyst needs to be added with anti-poisoning equipment, so that the use process is complex. 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.
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.
The technical scheme adopted by the invention is as follows: the blast furnace gas from the top of the blast furnace enters a dry dedusting unit, enters a TRT power generation device after dedusting, utilizes trace moisture in the blast furnace gas after TRT power generation, enters an organic sulfur conversion device with a low-temperature hydrolysis catalyst at the lower part in a desulfurization tower, is adsorbed by activated carbon or ferric oxide at the upper part of the desulfurization tower, removes inorganic sulfur in the raw gas and hydrogen sulfide generated after catalyzing organic sulfur through low-temperature hydrolysis, and then 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 material flow i, which is blast furnace gas after dry dedusting, and 3 is material flow ii, which is blast furnace gas after TRT power generation; 4 is a material flow III, namely blast furnace gas after organic sulfur is catalytically converted through the lower part of the desulfurizing tower; 5 is a stream IV for adsorbing H by passing through the upper part of the desulfurizing tower2And (4) the blast furnace gas after S.
I is a dry dedusting system, II is a TRT power generation device, III is a desulfurizing tower, IV is an organic sulfur conversion device at the lower part of the desulfurizing tower, V is an inorganic sulfur adsorption device at the upper part of the desulfurizing tower, and VI 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 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 20mg/m3Organic sulfide content 100mg/m3Dust concentration 10mg/m3. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. The material flow II enters an organic sulfur conversion device at the lower part of the desulfurizing tower, the organic sulfur conversion device is filled with a potassium modified alumina low-temperature hydrolysis catalyst to convert organic sulfur in blast furnace gas into inorganic sulfur to form a material flow III, and the concentration of hydrogen sulfide in the material flow III is 110mg/m3Organic sulfide content 10mg/m3Dust concentration 5mg/m3. Adsorbing the material flow III by a ZSM-5 molecular sieve adsorbent at the upper part of the desulfurizing tower to form a material flow IV, wherein the sulfide content of 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 tail gas emission of a combustion engine is twoThe concentration of sulfur oxide is less than 10mg/m3。
[ example 2 ]
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 25mg/m3Organic sulfide content 250mg/m3Dust concentration 20mg/m3. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. The material flow II enters an organic sulfur conversion device at the lower part of the desulfurization tower, the organic sulfur conversion device is filled with a potassium modified silicon oxide low-temperature hydrolysis catalyst, the catalyst is in a honeycomb block shape of 150 x 600mm, organic sulfur in blast furnace gas is converted into inorganic sulfur to form a material flow III, and the concentration of hydrogen sulfide in the material flow III is 270mg/m3Organic sulfide content 5mg/m3Dust concentration 10mg/m3. Adsorbing the material flow III with ZSM-5 molecular sieve to form material flow IV with honeycomb block shape of 150 × 600mm and sulfide content less than 8mg/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 8mg/m3。
[ example 3 ]
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 15mg/m, and the content of organic sulfide is 100mg/m3Dust concentration 8mg/m3. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. The material flow II enters an organic sulfur conversion device at the lower part of the desulfurization tower, the organic sulfur conversion device is filled with a potassium modified alumina low-temperature hydrolysis catalyst, the catalyst is in a honeycomb block shape of 150 x 600mm, organic sulfur in blast furnace gas is converted into inorganic sulfur to form a material flow III, and the concentration of hydrogen sulfide in the material flow III is 100mg/m3Organic sulfide content 5mg/m3Dust concentration 5mg/m3. The material flow III is adsorbed by a copper modified Y molecular sieve catalyst at the upper part of the desulfurizing towerThe adsorbent is in the shape of a honeycomb block adsorbent of 150 x 600mm, forming a stream IV, the sulphide content of which is less than 8mg/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 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. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. The material flow II enters an organic sulfur conversion device at the lower part of the desulfurizing tower, the organic sulfur conversion device is filled with a potassium and lanthanum modified alumina low-temperature hydrolysis catalyst to convert organic sulfur in blast furnace gas into inorganic sulfur to form a material flow III, and the concentration of hydrogen sulfide in the material flow III is 130mg/m3Organic sulfide content 0mg/m3Dust concentration 5mg/m3. The material flow III is absorbed by a zinc modified ZSM-5 molecular sieve adsorbent at the upper part of the desulfurizing tower to form a material flow IV, and the sulfide content of 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 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/m3Organic sulfide content 80mg/m3Dust concentration 5mg/m3. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. The material flow II enters an organic sulfur conversion device at the lower part of the desulfurizing tower, and the organic sulfur conversion device is filled with a potassium and lanthanum modified alumina low-temperature hydrolysis catalyst and a gas airspeed500 ℃ and 60 ℃ to convert organic sulfur in blast furnace gas into inorganic sulfur to form a material flow III, wherein the concentration of hydrogen sulfide in the material flow III is 50mg/m3Organic sulfide content 10mg/m3Dust concentration 5mg/m3. After the material flow III is absorbed by ZSM-5 at the upper part of the desulfurizing tower and a honeycomb block adsorbent with a zinc modified Y molecular sieve shape of 150 x 600mm, the gas space velocity is 500, the reaction temperature is 60 ℃, and a material flow IV is formed, 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 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/m3The content of organic sulfides is 100-200 mg/m3The dust concentration is 10-20 mg/m3In the meantime. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. The material flow II enters an organic sulfur conversion device at the lower part of the desulfurization tower, the gas space velocity is 1500, the reaction temperature is 80 ℃, the organic sulfur conversion device is filled with a magnesium and cerium modified alumina low-temperature hydrolysis catalyst to convert organic sulfur in blast furnace gas into inorganic sulfur to form a material flow III, and the concentration of hydrogen sulfide in the material flow III is 100-250 mg/m3Organic sulfide content of 0-10 mg/m3The dust concentration is 10-20 mg/m3In the meantime. Adsorbing the material flow III with copper modified ZSM-5 and zinc modified Y molecular sieve at the upper part of the desulfurizing tower and honeycomb block adsorbent with the shape of 150 x 600mm to form a material flow IV, 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 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/m3The content of organic sulfides is 100-200 mg/m3The dust concentration is 10-20 mg/m3In the meantime. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. The material flow II enters an organic sulfur conversion device at the lower part of the desulfurization tower, the gas space velocity is 600, the reaction temperature is 100 ℃, the organic sulfur conversion device is filled with a low-temperature hydrolysis catalyst, namely a rare earth lanthanum modified Y molecular sieve catalyst, the catalyst is 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 III, and the concentration of hydrogen sulfide in the material flow III is 100-250 mg/m3Organic sulfide content of 0-10 mg/m3The dust concentration is 10-20 mg/m3In the meantime. Adsorbing the material flow III with copper modified ZSM-5 and zinc modified Y molecular sieve to form material flow IV, wherein the adsorbent is 150 × 600mm honeycomb block 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 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/m3The content of organic sulfides is 100-200 mg/m3The dust concentration is 10-20 mg/m3In the meantime. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. The material flow II enters an organic sulfur conversion device at the lower part of the desulfurizing tower, a low-temperature hydrolysis catalyst ZSM and a mordenite molecular sieve catalyst are filled in the organic sulfur conversion device, organic sulfur in blast furnace gas is converted into inorganic sulfur to form a material flow III, the gas space velocity is 1000, the reaction temperature is 70 ℃, and the material flow III is formedThe concentration of hydrogen sulfide in III is 100-250 mg/m3Organic sulfide content of 0-10 mg/m3The dust concentration is 10-20 mg/m3In the meantime. Adsorbing the material flow III by a copper modified ZSM-5 and a zinc modified Y molecular sieve at the upper part of the desulfurizing tower to form 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/m3The content of organic sulfides is 100-200 mg/m3The dust concentration is 10-20 mg/m3In the meantime. And the material flow I enters a TRT power generation unit to form a material flow II after power generation. And the material flow II enters an organic sulfur conversion device at the lower part of the desulfurization tower, a low-temperature hydrolysis catalyst ZSM and a mordenite molecular sieve catalyst are filled in the organic sulfur conversion device, the organic sulfur in the blast furnace gas is converted into inorganic sulfur, and a material flow III is formed, wherein the organic sulfide is at least one of mercaptan, thioether, thiophene, methyl mercaptan and methyl sulfide. The content of organic sulfide in the material flow III is 0-10 mg/m3The dust concentration is 10-20 mg/m3In the meantime. Adsorbing the material flow III by a copper modified ZSM-5 and a zinc modified Y molecular sieve at the upper part of the desulfurizing tower to form 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。
Claims (10)
1. A fine desulfurization method for blast furnace gas comprises 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 a TRT power generation unit, and a material flow II is formed after power generation;
c. the material flow II enters a desulfurizing tower, a low-temperature hydrolysis catalyst is filled at the lower part of the desulfurizing tower, a fine desulfurizing agent is filled at the upper part of the desulfurizing tower, and the material flow II forms a material flow III after being subjected to hydrolysis catalysis by the low-temperature catalyst; adsorbing the material flow III by a fine desulfurization adsorbent to form a material flow IV;
d. and the material flow IV enters a subsequent blast furnace gas use section.
2. The fine desulfurization method for blast furnace gas according to claim 1, characterized in that the low-temperature hydrolysis catalyst is a metal-supported oxide catalyst; the fine desulfurization adsorbent is at least one of activated carbon, ferric oxide or microcrystalline material adsorbent.
3. The process of fine desulfurization of blast furnace gas according to claim 2, characterized in that the low-temperature hydrolysis catalyst comprises at least one element selected from the group consisting of IA, IIA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII elements of the periodic Table of elements on an alumina support.
4. The fine desulfurization method for blast furnace gas according to claim 3, characterized in that the group IIA element in the catalyst is at least one selected from the group consisting 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.
5. The fine desulfurization method for blast furnace gas according to claim 3, characterized in 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.
6. The fine desulfurization method for blast furnace gas according to claim 2, characterized in that the microcrystalline material in the fine desulfurization adsorbent is selected from the group consisting 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
At least one of molecular sieves, 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/zeolite Y or ZSM-5/zeolite Y/mordenite.
7. The fine desulfurization method for blast furnace gas according to claim 1, characterized in 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 ZSM-type microcrystalline material has a silicon-aluminum molecular ratio of 20 to 10000.
8. The fine desulfurization method for blast furnace gas according to claim 1, characterized in that the space velocity of the low-temperature hydrolysis catalyst is 100-3000 h-1。
9. The fine desulfurization method for blast furnace gas according to claim 1, characterized in that the low-temperature hydrolysis catalyst is used at a temperature of 50 to 140 ℃ and a pressure of 0 to 8 MPa.
10. The fine desulfurization method for blast furnace gas according to claim 1, characterized in that the low-temperature hydrolysis catalyst is of a honeycomb briquette type, and the porosity is 20-40%; the fine desulfurization adsorbent is in a honeycomb block type, and the porosity is 20-40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010180544.6A CN111334339A (en) | 2020-03-16 | 2020-03-16 | Fine desulfurization method for blast furnace gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010180544.6A CN111334339A (en) | 2020-03-16 | 2020-03-16 | Fine desulfurization method for blast furnace gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111334339A true CN111334339A (en) | 2020-06-26 |
Family
ID=71180102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010180544.6A Pending CN111334339A (en) | 2020-03-16 | 2020-03-16 | Fine desulfurization method for blast furnace gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111334339A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111876206A (en) * | 2020-08-07 | 2020-11-03 | 北京北科环境工程有限公司 | Blast furnace gas fine desulfurization combined process method |
| CN111944564A (en) * | 2020-08-07 | 2020-11-17 | 北京北科环境工程有限公司 | Blast furnace gas dust removal and hydrolysis integrated desulfurization system |
| CN113122340A (en) * | 2021-04-20 | 2021-07-16 | 唐山奥博环保科技有限公司 | Blast furnace gas purification method |
| CN113797709A (en) * | 2021-10-28 | 2021-12-17 | 江西省杰夫环保科技有限公司 | Microcrystalline rotating wheel zeolite molecular sieve for efficiently removing VOCs (volatile organic compounds) and preparation method thereof |
| CN113813988A (en) * | 2021-10-27 | 2021-12-21 | 江西省杰夫环保科技有限公司 | Preparation method of high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization |
| CN113996345A (en) * | 2021-10-19 | 2022-02-01 | 山东师范大学 | Desulfurization catalyst, blast furnace gas desulfurization system and desulfurization method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609202A (en) * | 2019-01-17 | 2019-04-12 | 武汉禾谷环保有限公司 | A kind of blast furnace gas desulfurizing and purifying method |
| CN110252068A (en) * | 2019-07-15 | 2019-09-20 | 湖北申昙环保新材料有限公司 | The desulfurizing and purifying method of blast furnace gas |
-
2020
- 2020-03-16 CN CN202010180544.6A patent/CN111334339A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609202A (en) * | 2019-01-17 | 2019-04-12 | 武汉禾谷环保有限公司 | A kind of blast furnace gas desulfurizing and purifying method |
| CN110252068A (en) * | 2019-07-15 | 2019-09-20 | 湖北申昙环保新材料有限公司 | The desulfurizing and purifying method of blast furnace gas |
Non-Patent Citations (2)
| Title |
|---|
| 王驰: "《典型有毒有害气体净化技术》", 31 March 2019, 北京冶金工业出版社 * |
| 肖俊军: ""高炉煤气脱硫技术措施探讨"", 《2019年全国高炉炼铁学术年会摘要集》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111876206A (en) * | 2020-08-07 | 2020-11-03 | 北京北科环境工程有限公司 | Blast furnace gas fine desulfurization combined process method |
| CN111944564A (en) * | 2020-08-07 | 2020-11-17 | 北京北科环境工程有限公司 | Blast furnace gas dust removal and hydrolysis integrated desulfurization system |
| CN113122340A (en) * | 2021-04-20 | 2021-07-16 | 唐山奥博环保科技有限公司 | Blast furnace gas purification method |
| CN113122340B (en) * | 2021-04-20 | 2023-02-21 | 唐山奥博环保科技有限公司 | Blast furnace gas purification method |
| CN113996345A (en) * | 2021-10-19 | 2022-02-01 | 山东师范大学 | Desulfurization catalyst, blast furnace gas desulfurization system and desulfurization method |
| CN113996345B (en) * | 2021-10-19 | 2024-02-09 | 山东师范大学 | Desulfurization catalyst, blast furnace gas desulfurization system and desulfurization method |
| CN113813988A (en) * | 2021-10-27 | 2021-12-21 | 江西省杰夫环保科技有限公司 | Preparation method of high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization |
| CN113797709A (en) * | 2021-10-28 | 2021-12-17 | 江西省杰夫环保科技有限公司 | Microcrystalline rotating wheel zeolite molecular sieve for efficiently removing VOCs (volatile organic compounds) and preparation method thereof |
| CN113797709B (en) * | 2021-10-28 | 2024-06-25 | 江西省杰夫环保科技有限公司 | Microcrystalline rotating wheel zeolite molecular sieve for efficiently removing VOCs and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111334339A (en) | Fine desulfurization method for blast furnace gas | |
| CN111334341A (en) | Method for desulfurizing blast furnace gas | |
| CN1880412B (en) | Process for cleaning gases from gasification units | |
| CN110819393A (en) | Method and device for fine desulfurization and purification of blast furnace gas | |
| TWI482656B (en) | Process and system with multiple fixed-fluidized beds for contaminant removal | |
| JP5479812B2 (en) | Method and system for impurity reduction from a gas stream | |
| CN108165322A (en) | The purification method of coke-stove gas | |
| CN100411709C (en) | A method for purifying flue gas by use of powdered activated coke | |
| CN112915777A (en) | Blast furnace gas dechlorination, desulfurization and purification process | |
| CN102642810B (en) | Combined process for preparing Fischer-Tropsch synthetic oil raw material gas by utilizing coke-oven gas | |
| CN113122340B (en) | Blast furnace gas purification method | |
| CN110252068A (en) | The desulfurizing and purifying method of blast furnace gas | |
| BRPI0923954B1 (en) | PROCESS FOR THE DISPOSAL OF SULFURTED, NITROGEN AND HALOGENATED IMPURSENTS CONTAINED IN SYNTHESIS GAS | |
| CN111286368A (en) | Method and device for adsorption desulfurization of blast furnace gas | |
| CN108970328B (en) | Device and process for treating high-sulfur waste gas in chemical industry and recovering sulfur | |
| CN111334340A (en) | Method for purifying blast furnace gas | |
| CN208082173U (en) | The processing system of activated coke method coke oven flue gas desulphurization denitration acid vapour is handled with system for preparing sulfuric acid | |
| CN108102727A (en) | For the method for coke oven gas purification recycling aromatic hydrocarbons | |
| CN110252069A (en) | The sulfur method of blast furnace gas | |
| CN110252070A (en) | The purification method of blast furnace gas | |
| CN215250669U (en) | Feed gas purification system for hydrogen production from coke oven gas | |
| CN115770469A (en) | Method for purifying blast furnace gas and collecting hot blast furnace carbon | |
| JPH03238019A (en) | Purification of high temperature reductive gas | |
| CN107236576A (en) | Coke oven gas purification method for fuel engine power generation | |
| CN111334338A (en) | Method for desulfurizing and purifying blast furnace gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200626 |
|
| RJ01 | Rejection of invention patent application after publication |