CN111334340A - Method for purifying blast furnace gas - Google Patents
Method for purifying blast furnace gas Download PDFInfo
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- CN111334340A CN111334340A CN202010180549.9A CN202010180549A CN111334340A CN 111334340 A CN111334340 A CN 111334340A CN 202010180549 A CN202010180549 A CN 202010180549A CN 111334340 A CN111334340 A CN 111334340A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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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
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/205—Methods and apparatus for treating the purifying masses without their regeneration
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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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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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
- C10K1/024—Dust removal by filtration
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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
- C10K1/026—Dust removal by centrifugal forces
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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
- C10K1/028—Dust removal by electrostatic precipitation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to a blast furnace gas purification method, which mainly solves the technical problems that in the prior art, chloride, sulfide, oil and dust are not completely removed in blast furnace gas purification, a gas pipeline is easy to corrode, and the emission of sulfur dioxide after blast furnace gas combustion exceeds the standard. The invention adopts the following steps: a. blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal; b. the material flow I enters a comprehensive adsorption tower to form a material flow II, and the comprehensive purification tower contains a microcrystalline material adsorbent; c. the material flow II 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 purifying blast furnace gas used for heating or power generation.
Background
The blast furnace gas is a byproduct of iron and steel enterprises in the iron-making process, and contains carbon monoxide, carbon dioxide, nitrogen and hydrogen with low calorific valueAnd (3) combusting the gas. The blast furnace gas which is not purified contains a large amount of dust, the dust-containing gas can block a gas pipeline and a burner of a combustion device, and the gas unit can be abraded, so that the pressure loss is increased. Therefore, the dust removal treatment is carried out before the utilization, and the dust removal is divided into coarse dust removal and fine dust removal. In the process of blast furnace coal injection, bituminous coal or anthracite can be injected to different degrees, and during coal injection, sulfur element generates SO through high-temperature chemical reaction2，SO3Etc.; the imported ore, especially the Austenite, contained a large amount of Cl-. Saturated vapor in the coal gas is gradually separated out along with the reduction of the temperature of the coal gas, chlorine and sulfur in the saturated vapor are dissolved in water, coal gas condensate water is easy to have stronger acidity and corrode a coal gas pipeline, and the safety operation of a blast furnace gas pipe network is influenced by serious people. The existence of chlorine and sulfide in blast furnace gas can corrode the blades of the gas turbine, and the service life of the gas turbine is shortened. Removing H from sulfide in coal gas2S, organic sulfur is also contained, and sulfur dioxide in the flue gas exceeds the standard after untreated combustion. Organic matter such as heavy oil contained in blast furnace gas also blocks the nozzle of the combustion engine. Therefore, the blast furnace gas needs to be purified before combustion and power generation, and dust, chloride, sulfide, heavy oil and the like carried in the gas are removed.
In the existing blast furnace gas purification process, the dust removal link is a dry dust removal process which replaces the traditional wet process. The corrosion problem of the gas pipeline after purification treatment is found to be very prominent in the dry dust removal operation. Most of chloride and sulfide in the gas are removed by adopting a blast furnace gas alkali spraying method, so that the corrosion of a gas pipeline is reduced, but because a large amount of alkali spraying and water spraying are circularly washed, the heat value of the gas is reduced, the utilization value of the gas is influenced, a large amount of water resources are consumed, and a large amount of high-salinity and high-chlorine wastewater is generated to be treated.
Document CN201710404777.8 discloses a blast furnace gas deacidification method, which comprises the following steps: set up blast furnace gas deacidification device on current blast furnace gas dry process dust pelletizing system's basis, blast furnace gas deacidification device includes: powder spray gun, jetting jar and air supply source, powder spray gun includes: spray irrigation through the gas pipeline and a nozzle arranged on the spray pipe; the nozzle is positioned in the gas pipeline; the injection tank is fixedly connected with the powder spray gun through a powder spray pipeline; the injection tank is provided with a vulcanization nozzle; the air supply source is connected with the fluidization nozzle through an organ; and the injection carrier enters the injection tank through the fluidization nozzle to fluidize lime powder in the injection tank, the fluidized lime powder flows into the powder spray gun through the powder injection pipeline and finally flows into the gas pipeline, the strong water absorption of the lime powder absorbs partial water in the blast furnace gas to generate calcium hydroxide, and then the calcium hydroxide and acid gases in the gas, such as HCl, SO2, SO3, H2S, CO2 and the like, are subjected to chemical reaction to generate substances such as CaCl2, CaS, CaSO3, CaSO4, CaCO3 and the like, and finally the substances are recovered to the ash storage bin to reduce the content of the acid gases in the gas.
Document CN201220070822.3 relates to a blast furnace gas dry dedusting and dechlorinating compound device, which comprises a power generation device and a pressure reducing valve bank connected in parallel behind a blast furnace through a pipeline, wherein a particle bed deduster is connected in series in front of the power generation device and the pressure reducing valve bank, and the particle bed deduster contains dechlorinating particles, desulfurization particles, deamination particles and moisture absorption particles. A coarse dust removal device is arranged in front of the particle bed dust remover, and a dry fine dust removal device is arranged behind the particle bed dust remover. And simultaneously removing chlorine, sulfur and ammonia in the blast furnace gas.
The invention discloses a gas purification method, which can completely remove hydrogen chloride and hydrogen sulfide and remove heavy oil and dust after fine dust removal in blast furnace gas. The technical problem that the blast furnace gas is not purified completely at present is solved in a targeted manner.
Disclosure of Invention
The invention aims to solve the technical problems that a gas pipeline is easy to corrode due to the incomplete removal of chloride, sulfide, dust and heavy oil in blast furnace gas, the chloride and the sulfide corrode blades of a combustion engine, and the emission of sulfur dioxide exceeds the standard. The method is used for production by adopting coal gas for heating or power generation, and has the advantages of clean purification, 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, comprising the steps of:
a. blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal;
b. the material flow I enters a comprehensive adsorption tower to form a material flow II, and the comprehensive adsorption tower contains a microcrystalline material adsorbent;
c. the material flow II enters a subsequent blast furnace gas use section;
d. after the adsorbent in the comprehensive adsorption tower is adsorbed and saturated, taking out 1000-10000 m from the material flow II3Heating purified blast furnace gas to 150-300 ℃ to serve as desorption gas, regenerating the comprehensive adsorption tower, marking the regenerated desorption gas as a material flow III, and enabling the material flow III to enter a boiler for combustion to form boiler flue gas, and marking the material flow IV;
e. and enabling the material flow IV to enter a flue gas desulfurization and denitrification unit, removing nitrogen oxides and sulfur dioxide to form flue gas, and emptying a material flow V.
In the above technical solution, a preferable technical solution is that the microcrystalline material adsorbent contains at least one element of group ia, iia, va, ib, iib, iiib, ivb, vb, vib, viib or viii elements in the periodic table of elements.
In the above technical solution, a preferable technical solution is that the ia element in the microcrystalline material adsorbent 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 microcrystalline material in the microcrystalline material adsorbent is selected from at least one 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 or ZSM-5/Y zeolite/mordenite.
In the above technical scheme, the preferable technical scheme is that the ZSM type microcrystalline material in the microcrystalline material adsorbent comprises at least one of ZSM-5, ZSM-23, ZSM-11 and ZSM-48, and the silicon-aluminum molecular ratio of the ZSM type microcrystalline material is 100-10000.
In the above technical solution, a preferable technical solution is that the microcrystalline material is a hydrophobic adsorbent. The ZSM type microcrystalline material has a silicon-aluminum molecular ratio of 20-10000.
In the above technical scheme, the preferable technical scheme is that the ZSM type microcrystalline material has a silicon-aluminum molecular ratio of 100-3000.
In the above technical solution, the preferable technical solution is that the microcrystalline material adsorbent simultaneously removes oil, dust, ammonia gas, organic sulfur and inorganic sulfur in blast furnace gas.
In the above technical solution, a preferable technical solution is that the sulfide is at least one of hydrogen sulfide, sulfur dioxide, carbon disulfide, mercaptan, thioether, thiophene, methyl mercaptan, and methyl sulfide.
In the above technical solution, a preferable technical solution is that the microcrystalline material adsorbent is a recyclable adsorbent.
In the above technical scheme, the preferable technical scheme is that the dust removal unit adopts 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 microcrystalline material adsorbent is a regenerable adsorbent.
In the above technical scheme, the preferable technical scheme is that the microcrystalline material adsorbent is regenerated for more than 3 hours in nitrogen or blast furnace gas at 100-200 ℃ after being adsorbed and saturated, and is reused after being regenerated.
In the above technical scheme, the preferred technical scheme is that the molecular sieve adsorbent is regenerated for 10-100 hours in blast furnace gas at 150-200 ℃ after adsorption saturation, and the molecular sieve adsorbent is reused after regeneration is completed.
In the above technical scheme, the preferred technical scheme is that the molecular sieve adsorbent is cooled to 30-80 ℃ after being regenerated and then put into use.
In the above technical scheme, the preferable technical scheme is that after the microcrystalline material adsorbent is subjected to adsorption saturation, the microcrystalline material adsorbent is used for adsorbing the saturated microcrystalline material with the adsorption quantity of 2000-6000 m3Regenerating the purified coke oven gas or blast furnace gas with the temperature of 150-250 ℃.
In the above technical scheme, the preferable technical scheme is that the microcrystalline material adsorbent is regenerated in nitrogen at 150-250 ℃ after being saturated by adsorption.
In the above technical scheme, the preferable technical scheme is that the material flow IV enters a flue gas desulfurization and denitration unit of sintering flue gas, or enters a flue gas desulfurization and denitration unit of a boiler, or enters a flue gas desulfurization and denitration unit of a coke oven, or enters a flue gas desulfurization and denitration unit of a heating furnace.
In the above technical solution, a preferred technical solution is that the 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; the comprehensive adsorption tower runs in a mode that 2-20 adsorption towers are connected in parallel, when one adsorption tower A is saturated in adsorption, the adsorption tower A is switched to enter a regeneration procedure, part of material flow I enters the other standby adsorption tower B to form a material flow II, and the comprehensive purification tower A, B contains the microcrystalline material adsorbent.
In the process of blast furnace gas purification technology, after the blast furnace gas in the dry dedusting system is dedusted and purified, the hydrogen chloride in the gas can be removed by wet hydrogen chloride removal methods such as adding an alkali spraying tower in the prior art, but the calorific value of the gas is lost, and the recycling value of the blast furnace gas is reduced. The method of the invention has the following advantages: (1) the microcrystalline material adsorbent can thoroughly remove hydrogen chloride, hydrogen sulfide and organic sulfur, and solves the problems of easy corrosion of gas pipelines, corrosion of gas turbine blades and standard exceeding of sulfide emission. (2) The adsorbent is multifunctional, can simultaneously perform dechlorination, desulfurization, deoiling and dust removal, and can simultaneously perform a comprehensive purification process in one adsorption tower, so that devices for respectively dechlorinating and desulfurizing are reduced, and the production cost is reduced. (3) The pressure and the temperature of the blast furnace gas after dechlorination, desulfurization and purification can not be greatly reduced, and the heat value of the gas is effectively reserved.
The technical scheme adopted by the invention is as follows: the blast furnace gas from the top of the blast furnace enters a dust removal unit, the blast furnace gas after dust removal enters a comprehensive purification tower, the purification tower contains microcrystalline material adsorbents, and chlorides and sulfides in the gas are removed at the same time and then enter the subsequent blast furnace gas power generation section. And (3) regenerating after the adsorbent in the comprehensive adsorption tower is saturated, feeding concentrated regenerated desorption gas into a boiler for combustion, feeding boiler flue gas and sintering flue gas into a flue gas desulfurization and denitrification unit together, and exhausting flue gas subjected to nitrogen oxide and sulfur removal.
The content of hydrogen sulfide at the outlet of the comprehensive purification tower is less than 10mg/m3The content of hydrogen chloride is less than 10mg/m3Oil content of 0 and dust content of less than 5mg/m3. Organic sulfur carried in the gas is also removed, and the emission of sulfur dioxide in the flue gas of a combustion engine is 10mg/m3Hereinafter, the apparatus operates stably. The emission of sulfur dioxide in the flue gas after removing nitrogen oxide and sulfur is 8mg/m3In the following, good technical effects are obtained.
Detailed Description
[ example 1 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen chloride in the material flow I is 200mg/m3The concentration of hydrogen sulfide is 50mg/m3Organic sulfide content 200mg/m3Dust concentration 10mg/m3Oil content 10mg/m3. The material flow I enters a comprehensive purification tower, the comprehensive adsorption tower contains a ZSM-5 microcrystalline material adsorbent, hydrogen chloride and sulfide in the coal gas are removed simultaneously to form a material flow II, and the chloride content in the material flow II is less than 10mg/m3The sulfide content is less than 10mg/m3The oil content is less than 2mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, and pipelines and blades of a gas turbine are not seenObvious corrosion, no nozzle blockage of the combustion engine, and sulfur dioxide concentration in the tail gas emission of the combustion engine less than 10mg/m3。
After the adsorbent in the comprehensive adsorption tower is adsorbed for one week, purified coal gas is adopted for regeneration at 200 ℃, after regeneration, the adsorption performance of the adsorbent is stable, and the chloride content in the material flow II is less than 20mg/m3The sulfide content is less than 10mg/m3The oil content is less than 20mg/m3The dust concentration is less than 5mg/m3. And (3) regenerating the concentrated gas, namely feeding the material flow III into a boiler for combustion to form a material flow IV, feeding the material flow IV into a desulfurization and denitrification unit of the sintering flue gas, and discharging the flue gas subjected to nitrogen oxide and sulfur removal to form a material flow V. The sulfur dioxide content in the material flow V is 10mg/m3Hereinafter, the apparatus operates stably.
[ example 2 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen chloride in the material flow I is 100mg/m3The concentration of hydrogen sulfide is 25-75 mg/m3Organic sulfide content of 100-250 mg/m3Dust concentration of 10-20 mg/m3Oil content of 20-80 mg/m3In the meantime. The material flow I enters a comprehensive purification tower, the comprehensive adsorption tower contains a copper modified ZSM-5 microcrystalline material adsorbent, hydrogen chloride and sulfide in the coal gas are removed simultaneously to form a material flow II, and the chloride content in the material flow II is less than 8mg/m3The sulfide content is less than 8mg/m3The oil content is less than 15mg/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 concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the concentration of sulfur dioxide in the tail gas emission of the gas turbine is less than 8mg/m3。
After the adsorbent in the comprehensive adsorption tower is adsorbed for one week, purified coal gas is regenerated at the temperature of 250 ℃ at 3000 m/h, the adsorption performance of the adsorbent is stable after regeneration, and the chloride content in the material flow II is less than 15mg/m3The sulfide content is less than 10mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3. And (3) the regenerated and concentrated gas enters a boiler to be combusted to form a material flow IV, the material flow IV and sintering flue gas enter a flue gas desulfurization and denitrification unit together, and the flue gas subjected to nitrogen oxide and sulfur removal forms a material flow V to be discharged. The sulfur dioxide content in the material flow V is 8mg/m3Hereinafter, the apparatus operates stably.
[ example 3 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and is subjected to dry cloth bag dust removal to form a material flow I, wherein the concentration of hydrogen chloride in the material flow I is 100-300 mg/m3The concentration of hydrogen sulfide is 25-75 mg/m3Organic sulfide content of 100-250 mg/m3Dust concentration of 10-20 mg/m3Oil content of 20-80 mg/m3In the meantime. The material flow I enters a comprehensive purification tower, the comprehensive purification tower contains a copper modified Y microcrystalline material adsorbent, hydrogen chloride and sulfide in the coal gas are removed simultaneously to form a material flow II, and the chloride content in the material flow III is less than 8mg/m3The sulfide content is less than 8mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the concentration of sulfur dioxide in the tail gas emission of the gas turbine is less than 8mg/m3。
After the adsorbent in the comprehensive adsorption tower is adsorbed for two weeks, purified coal gas is regenerated at 150 ℃, the adsorption performance of the adsorbent is stable after regeneration, and the chloride content in the material flow II is less than 15mg/m3The sulfide content is less than 10mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3. And (3) the regenerated and concentrated gas enters a boiler to be combusted to form a material flow IV, the material flow IV and boiler flue gas enter a flue gas desulfurization and denitrification unit together, and the flue gas subjected to nitrogen oxide and sulfur removal forms a material flow V to be discharged. The sulfur dioxide content in the material flow V is 10mg/m3Hereinafter, the apparatus operates stably.
[ example 4 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dry cloth bag dust removal, wherein the concentration of hydrogen chloride in the material flow I is 50-200 mg/m3The concentration of hydrogen sulfide is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3Oil content of 10-100 mg/m3In the meantime. The material flow I enters a comprehensive purification tower, the comprehensive purification tower contains a zinc modified ZSM-5 adsorbent, hydrogen chloride and sulfide in the coal gas are removed simultaneously to form a material flow II, and the chloride content in the material flow II is less than 10mg/m3The sulfide content is less than 10mg/m3The oil content is less than 20mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the concentration of sulfur dioxide in the tail gas emission of the gas turbine is less than 10mg/m3。
After the adsorbent in the comprehensive adsorption tower is adsorbed for one week, adopting 10000 m/h purified blast furnace gas to regenerate at 180 ℃, wherein after regeneration, the adsorption performance of the adsorbent is stable, and the chloride content in the material flow III is less than 15mg/m3The sulfide content is less than 10mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3. And (3) the regenerated and concentrated gas enters a boiler to be combusted to form a material flow IV, the material flow IV enters a coke oven flue gas desulfurization and denitrification unit, and the flue gas subjected to nitrogen oxide and sulfur removal forms a material flow V to be discharged. The sulfur dioxide content in the material flow V is 10mg/m3Hereinafter, the apparatus operates stably.
[ example 5 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen chloride in the material flow I is 50-200 mg/m3The concentration of hydrogen sulfide is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3Oil content of 10-100 mg/m3In the meantime. The material flow I enters a comprehensive purification tower, the comprehensive purification tower contains a copper modified ZSM-5 microcrystalline material and a zinc modified Y microcrystalline material adsorbent, and hydrogen chloride and sulfide in the coal gas are removed simultaneously to form a material flow II, wherein the chloride content in the material flow II is less than 10mg/m3The sulfide content is less than 10mg/m3The oil content is less than 10mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the concentration of sulfur dioxide in the tail gas emission of the gas turbine is less than 5mg/m3。
After the adsorbent in the comprehensive adsorption tower is adsorbed for one week, the purified coal gas is regenerated at 160 ℃, the adsorption performance of the adsorbent is stable after regeneration, and the chloride content in the material flow II is less than 12mg/m3The sulfide content is less than 10mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3. And (3) the regenerated and concentrated gas enters a boiler to be combusted to form a material flow IV, the material flow IV enters a flue gas desulfurization and denitrification unit of a heating furnace, and the flue gas subjected to nitrogen oxide and sulfur removal forms a material flow V to be discharged. The sulfur dioxide content in the material flow V is 7mg/m3Hereinafter, the apparatus operates stably.
[ example 6 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen chloride in the material flow I is 50-200 mg/m3The concentration of hydrogen sulfide is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3Oil content of 10-100 mg/m3In the meantime. And the material flow I enters a comprehensive purification tower, wherein the comprehensive purification tower contains a copper-modified ZSM-5 microcrystalline material and a zinc-modified Y microcrystalline material adsorbent, the silicon-aluminum molar ratio of the ZSM-5 microcrystalline material is more than 100, and the silicon-aluminum molar ratio of the Y microcrystalline material is more than 20. The adsorbent simultaneously removes hydrogen chloride and sulfide in the coal gas to form a material flow II, and the chloride content in the material flow II is less than 10mg/m3The sulfide content is less than 10mg/m3The oil content is less than 10mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the concentration of sulfur dioxide in the tail gas emission of the gas turbine is less than 5mg/m3。
After the adsorbent in the comprehensive adsorption tower is used for adsorbing for one week, the purified coke oven gas with the speed of 3000 m/h is regenerated at 220 ℃, the adsorption performance of the adsorbent is stable after regeneration, and the chloride content in the material flow II is less than 12mg/m3The sulfide content is less than 10mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3. And (3) the regenerated and concentrated gas enters a boiler to be combusted to form a material flow IV, the material flow IV and sintering flue gas enter a flue gas desulfurization and denitrification unit together, and the flue gas subjected to nitrogen oxide and sulfur removal forms a material flow V to be discharged. The sulfur dioxide content in the material flow V is 7mg/m3Hereinafter, the apparatus operates stably.
[ example 7 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen chloride in the material flow I is 50-200 mg/m3The concentration of hydrogen sulfide is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3Oil content of 10-100 mg/m3In the meantime. The material flow I enters a comprehensive purification tower, the comprehensive purification tower contains a rare earth lanthanum modified Y microcrystal material adsorbent, hydrogen chloride and sulfide in the coal gas are removed at the same time to form a material flow II, and the chloride content in the material flow II is less than 10mg/m3The sulfide content is less than 10mg/m3The oil content is less than 10mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the sulfur dioxide in the tail gas emission of the gas turbine is concentratedThe degree is less than 5mg/m3。
After the adsorbent in the comprehensive adsorption tower is used for adsorbing for one week, the blast furnace gas purified at 6000 m/h is regenerated at 190 ℃, the adsorption performance of the adsorbent is stable after regeneration, and the chloride content in the material flow II is less than 20mg/m3The sulfide content is less than 10mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3. And the gas obtained by regeneration and concentration enters a boiler to be combusted to form boiler flue gas, the boiler flue gas and the sintering flue gas enter a flue gas desulfurization and denitrification unit together, and the flue gas subjected to nitrogen oxide and sulfur removal forms a material flow V to be discharged. The sulfur dioxide content in the material flow V is 8mg/m3Hereinafter, the apparatus operates stably.
[ example 8 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen chloride in the material flow I is 50-200 mg/m3The concentration of hydrogen sulfide is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3Oil content of 10-100 mg/m3In the meantime. The material flow I enters a comprehensive purification tower, the comprehensive purification tower contains a ZSM microcrystalline material and a mordenite adsorbent, and hydrogen chloride and sulfide in the coal gas are removed to form a material flow II, wherein the chloride content in the material flow II is less than 20mg/m3The content of sulfide is less than 15mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the concentration of sulfur dioxide in the tail gas emission of the gas turbine is less than 7mg/m3。
Introducing 3000 m/h nitrogen for regeneration at 190 deg.C after adsorbing for one week, wherein the adsorbent has stable adsorption performance, and chloride content in material flow III is less than 20mg/m3The sulfide content is less than 10mg/m3The oil content is less than 20mg/m3The dust concentration is less than 5mg/m3. And (3) the regenerated and concentrated gas enters a boiler to be combusted to form a material flow IV, the material flow IV and sintering flue gas enter a flue gas desulfurization and denitrification unit together, and the flue gas subjected to nitrogen oxide and sulfur removal forms a material flow V to be discharged. The sulfur dioxide content in the material flow V is 10mg/m3Hereinafter, the apparatus operates stably.
[ example 9 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen chloride in the material flow I is 50-200 mg/m3The concentration of hydrogen sulfide is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3Oil content of 10-100 mg/m3In the meantime. The material flow I enters a comprehensive purification tower, the comprehensive purification tower contains a ZSM microcrystalline material and a mordenite adsorbent, and hydrogen chloride and sulfide in the coal gas are removed to form a material flow II, wherein the chloride content in the material flow II is less than 20mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3The content of sulfide is less than 15mg/m3The sulfide is at least one of hydrogen sulfide, sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan and methyl thioether. The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the concentration of sulfur dioxide in the tail gas emission of the gas turbine is less than 7mg/m3。
After the adsorbent in the comprehensive adsorption tower is adsorbed for one week, the purified coke oven gas is regenerated at the temperature of 200 ℃ at 4000 m/h, the adsorption performance of the adsorbent is stable after regeneration, and the chloride content in the material flow III is less than 20mg/m3The sulfide content is less than 10mg/m3The oil content is less than 18 mg/m3The dust concentration is less than 5mg/m3. And (3) the regenerated and concentrated gas enters a boiler to be combusted to form a material flow IV, the material flow IV and sintering flue gas enter a flue gas desulfurization and denitrification unit together, and the flue gas subjected to nitrogen oxide and sulfur removal forms a material flow V to be discharged. The sulfur dioxide content in the material flow V is 8mg/m3The followingThe device operates stably.
[ example 10 ]
Blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal, wherein the concentration of hydrogen chloride in the material flow I is 50-200 mg/m3The concentration of hydrogen sulfide is 0-50 mg/m3Organic sulfide content of 100-200 mg/m3Dust concentration of 10-20 mg/m3Oil content of 10-100 mg/m3In the meantime. The material flow I enters a comprehensive purification tower, the comprehensive purification tower contains a ZSM-5 microcrystalline material and a mordenite adsorbent, and hydrogen chloride and sulfide in the coal gas are removed to form a material flow II, wherein the chloride content in the material flow II is less than 20mg/m3The content of sulfide is less than 15mg/m3The oil content is less than 15mg/m3The dust concentration is less than 5mg/m3(ii) a The material flow II enters a power generation device for power generation, the device continuously operates for more than 3 months, the concentrations of hydrogen chloride and hydrogen sulfide at the outlet of the comprehensive purification tower are stable, the pipeline and the blades of the gas turbine are not obviously corroded, the nozzle of the gas turbine is not blocked, and the concentration of sulfur dioxide in the tail gas emission of the gas turbine is less than 7mg/m3。
Introducing 3000 m/h nitrogen for regeneration at 200 deg.C after adsorbing for one week, wherein the adsorbent in the comprehensive adsorption tower has stable adsorption performance, and chloride content in stream II is less than 20mg/m3The sulfide content is less than 10mg/m3The oil content is less than 20mg/m3The dust concentration is less than 5mg/m3。
Claims (10)
1. A method for purifying blast furnace gas, comprising the steps of:
a. blast furnace gas from a blast furnace enters a dust removal unit, and forms a material flow I after dust removal;
b. the material flow I enters a comprehensive adsorption tower to form a material flow II, and the comprehensive adsorption tower contains a microcrystalline material adsorbent;
c. the material flow II enters a subsequent blast furnace gas use section;
d. after the adsorbent in the comprehensive adsorption tower is adsorbed and saturated, taking out 1000-10000 m from the material flow II3H ofHeating the purified blast furnace gas to 150-300 ℃ to be used as desorption gas, regenerating the comprehensive adsorption tower, marking the regenerated desorption gas as a material flow III, and enabling the material flow III to enter a boiler for combustion to form boiler flue gas, and marking the material flow IV;
e. and enabling the material flow IV to enter a flue gas desulfurization and denitrification unit, removing nitrogen oxides and sulfur dioxide to form flue gas, and emptying a material flow V.
2. The method according to claim 1, characterized in that the adsorbent based on a microcrystalline material contains at least one element from group IA, IIA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII of the periodic Table of elements.
3. The method according to claim 1, wherein the IIA element in the periodic Table 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 blast furnace gas purification method according to claim 1, wherein the microcrystalline material in the microcrystalline material type 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.
5. The blast furnace gas purification method according to claim 4, wherein the ZSM type microcrystalline material in the microcrystalline material adsorbent 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.
6. The blast furnace gas purification method according to claim 1, wherein the microcrystalline material type adsorbent simultaneously removes oil, dust, ammonia gas, organic sulfur and inorganic sulfur from the blast furnace gas; the sulfide is at least one of hydrogen sulfide, sulfur dioxide, carbon disulfide, mercaptan, thioether, thiophene, methyl mercaptan and methyl thioether.
7. The blast furnace gas purification method according to claim 1, wherein the microcrystalline material adsorbent is used for 2000-6000 m after adsorption saturation3Regenerating the purified coke oven gas or blast furnace gas with the temperature of 150-250 ℃.
8. The method for purifying blast furnace gas according to claim 1, wherein the microcrystalline material adsorbent is regenerated in nitrogen at 150 to 250 ℃ after being saturated by adsorption.
9. The blast furnace gas purification method according to claim 1, wherein the stream IV is introduced into a flue gas desulfurization and denitrification unit for sintering flue gas, or into a flue gas desulfurization and denitrification unit for boiler flue gas, or into a flue gas desulfurization and denitrification unit for coke oven flue gas, or into a flue gas desulfurization and denitrification unit for heating furnace flue gas.
10. The blast furnace gas purification method according to claim 1, wherein the dust removal unit employs at least one of a gravity dust remover, a cyclone dust remover, a cloth bag dust remover, an electric dust remover, or a ceramic high temperature dust remover; the comprehensive adsorption tower runs in a mode that 2-20 adsorption towers are connected in parallel, when one adsorption tower A is saturated in adsorption, the adsorption tower A is switched to enter a regeneration procedure, part of material flow I enters the other standby adsorption tower B to form a material flow II, and the comprehensive purification tower A, B contains the microcrystalline material adsorbent.
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