CN112961710A - Novel blast furnace gas desulfurization method - Google Patents
Novel blast furnace gas desulfurization method Download PDFInfo
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- CN112961710A CN112961710A CN202110274965.XA CN202110274965A CN112961710A CN 112961710 A CN112961710 A CN 112961710A CN 202110274965 A CN202110274965 A CN 202110274965A CN 112961710 A CN112961710 A CN 112961710A
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- sulfide
- blast furnace
- carbonate
- absorbent
- furnace gas
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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
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
- C10K1/122—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing only carbonates, bicarbonates, hydroxides or oxides of alkali-metals (including Mg)
Abstract
The invention discloses a novel blast furnace gas desulfurization method, and belongs to the technical field of atmospheric pollution control. The main steps are absorption of carbonyl sulfide by a desulfurizing tower, reduction of an absorbent by a regeneration tank, reutilization and supplement of the absorbent and treatment of a sulfide product. Wherein the mass concentration of alkali in the alkaline aqueous solution absorbent is 0.1-20%, the reaction temperature is 20-200 ℃, the contact time of coal gas and alkali liquor is more than 1 second, and the carbonyl sulfide and hydrogen sulfide content in the absorbed gas is more than 1mg/m3. The desulfurization treatment of the invention has wide application temperature, the absorbent can be recycled, the invention is economical and applicable, the process flow is simple, and the invention can remove the chlorine in the blast furnace gas and reduce the corrosion to the subsequent use procedures. Can play a great role in actual production.
Description
Technical Field
The invention relates to a method for removing carbonyl sulfide in blast furnace gas of a factory, belongs to the technical field of air pollution control, and particularly relates to a novel blast furnace gas desulfurization method.
Background
Carbonyl sulfide (COS) is a flammable and toxic gas, and is very common in industrial production. Carbonyl sulfide and other sulfur-containing substances may exist in the exhaust gas discharged from the factory, which can cause serious pollution to the global atmosphere and even soil, and further affect the human body. Due to the environmental issues in recent years and the improvement of the production conditions and waste emission standards of factories, the control of the sulfur content in the waste gas of factories is urgent. And the existence of carbonyl sulfide can also corrode devices and devices to a certain extent, thereby bringing economic loss to industrial production. At present, methods for removing carbonyl sulfide comprise wet desulfurization and dry desulfurization, and the wet desulfurization process comprises a gypsum method, a seawater method, a double alkali method, an ammonia method and the like; the dry desulfurization method has an adsorbent method, high desulfurization precision, simple equipment and the like, but has limited capacity and slow reaction. At present, wet desulphurization technology and solid adsorption method are relatively mature and are applied to various large industrial production fields.
Patent application 201810264976.8 discloses a method for removing carbonyl sulfide by using an ionic liquid compound agent, which utilizes alcohol amine solution, ionic liquid, absorption enhancer and water to be mixed and then absorbed by sulfur-containing gas, and the method has high desulfurization efficiency, but the production process is complicated, the preparation requirement of the ionic liquid compound agent is high, and the method is not beneficial to industrial production; in patent application 201910517554.1, "a device and a method for removing carbonyl sulfide in blast furnace gas and improving the combustion heat value of blast furnace gas" can obviously improve the combustion heat value of blast furnace gas by removing carbonyl sulfide in blast furnace gas through membrane separation and pressure swing adsorption, but the membrane manufacturing cost is high and the technology is extremely strong; patent application 201810147532.6 discloses a method for removing carbonyl sulfide with nanometer layered solid alkali, which comprises hydrolyzing carbonyl sulfide with water at 40-80 deg.C under the catalysis of nanometer layered solid alkali, and oxidizing to obtain elemental sulfur and sulfate, thereby removing carbonyl sulfide. The method has high removal rate and simple production process of the solid alkali, but has narrow applicable temperature range and is not suitable for the desulfurization treatment of the industrial blast furnace gas; the invention patent 201610928220.X 'a method and a device for simultaneously removing carbonyl sulfide and carbon disulfide' for firstly generating H by catalytic hydrogenation2S, catalyzing to generate sulfuric acid, and designing a matching device. The method has high removal efficiency, can utilize the self heat of gas, but has complex operation and larger investment of the catalyst and raw materials thereof.
Various methods exist in the past, and different problems exist, and in order to better desulfurize, efforts are still needed to meet national requirements and maximize industrial production benefits.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
Aiming at the defects of the prior method, the invention provides a novel blast furnace gas desulfurization method, which has the advantages of wide desulfurization treatment application temperature, renewable utilization of an absorbent, economy and applicability, simple process flow, removal of chlorine in blast furnace gas and reduction of corrosion to subsequent use procedures.
In order to solve the technical problems, the invention adopts the following technical scheme:
a novel blast furnace gas desulfurization method comprises the following steps:
(1) absorbing sulfur by the desulfurizing tower: blast furnace gas is introduced into a desulfurizing tower, and alkaline aqueous solution is sprayed by the desulfurizing tower to be used as a sulfur absorbent to absorb sulfur-containing compounds in the blast furnace gas. Generating water solution of sulfide, carbonate and chloride dissolved in water, which is called recovery solution for short;
(2) reducing the absorbent in the regeneration tank: introducing the recovered liquid obtained in the step (1) into a regeneration tank, and regenerating the recovered liquid by using metal hydroxide or metal oxide to obtain regenerated sulfur absorbent, sulfide 2 and alkali carbonate 2;
(3) and (3) treating the vulcanization product: separating the sulfide 2 and the alkali carbonate 2 in the step (2) by one of pressure filtration, vacuum filtration, centrifugal separation and the like for additional use; and obtaining the regenerated absorbent.
(4) Recycling and replenishing of the absorbent: adding the regenerated sulfur absorbent in the step (3) into the step (1) for recycling;
further, the sulfur-containing compound in the step (1) is the sum of carbonyl sulfide, hydrogen sulfide and other forms of sulfides contained in the blast furnace gas.
Further, the absorbent in the step (1) is one or a combination of more of ammonia, magnesium hydroxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, strontium hydroxide or barium hydroxide aqueous solution.
Further, the desulfurization tower in the step (1) is one or more of a spray tower, a bubble tower, a plate tower, a venturi or other gas-liquid contact devices, wherein one or more desulfurization towers are adopted.
Further, the sulfide in the step (1) is one or more of magnesium sulfide, calcium sulfide, sodium sulfide, potassium sulfide, cesium sulfide, strontium sulfide and barium sulfide; the sulphides in step (1) also include other forms of sulphur-containing compounds formed during desulphurisation.
Further, the alkali carbonate in the step (1) is one or more of magnesium carbonate, calcium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, strontium carbonate or barium carbonate.
Further, the spraying of the alkaline aqueous solution by the desulfurization tower in the step (1) is not limited to one spraying tower for spraying the alkaline aqueous solution by passing the blast furnace gas once, but also comprises multiple times of passing through a plurality of desulfurization spraying towers; the total time for the blast furnace gas to pass through the aqueous alkaline solution is more than 1 second, i.e. the total time for one or more contacts with the aqueous alkaline solution is more than 1 second.
Further, the metal hydroxide in the step (2) is one or more of calcium hydroxide and magnesium hydroxide; the metal oxide is calcium oxide, barium oxide, and magnesium oxide.
Further, the sulfide 2 in the step (2) is calcium sulfide, barium sulfide and magnesium sulfide, and the alkali carbonate 2 is calcium carbonate, barium carbonate and/or magnesium carbonate.
Further, the reaction conditions in the step (1) are that the mass concentration of the absorbent is 0.1-20%, and the sulfur content of the blast furnace gas is more than 1mg/m3The reaction temperature is 20-200 ℃, and the reaction time is more than 1 second.
Preferably, a certain amount of alkaline water is additionally supplemented to the step (1) to ensure the normal operation of the process.
The invention has the following beneficial effects: the desulfurizing agent with good desulfurizing effect is replaced by more economic raw materials under certain conditions to obtain the desulfurizing agent again, so that the cost of industrial waste gas purification is greatly reduced, the content of carbonyl sulfide can be effectively reduced, and the national standard is met. And no new pollutants are generated in the removal process, and the desulfurization products are carbonate and sodium sulfide, which can also create additional economic benefits. Economic and environment-friendly, simple process and wide applicable temperature range, and is suitable for the desulfurization process of blast furnace gas in various industrial productions.
Detailed Description
The method is further described below with reference to specific embodiments, but is not limited to this case.
Example 1
A method for removing carbonyl sulfide in blast furnace gas specifically comprises the following steps:
(1) in this case, sodium hydroxide solution is used as an absorbent, and the sodium hydroxide solution with a mass concentration of 8% is sprayed from the upper part of the spray tower to the lower part of the spray tower, and 100mg/m of carbonyl sulfide and hydrogen sulfide are introduced from the lower part of the spray tower3The spraying speed and the gas flow rate can be adjusted in time according to production requirements, and the total time of the blast furnace gas passing through the spraying tower is more than 1 second; the temperature of the blast furnace gas inlet is 60-180 degrees.
(2) The purified gas absorbed in the step (1) is discharged from the upper end of the spray tower, dried and then enters the next process, and the sodium hydroxide solution is converted into sodium sulfide, sodium chloride and sodium carbonate (containing a small amount of sodium bicarbonate) and flows into a regeneration tank filled with an excessive saturated calcium hydroxide solution along with the liquid;
(3) rapidly stirring for 30min by a stirrer in a regeneration tank, standing and filtering, and filtering out calcium sulfide and calcium carbonate by adopting filter pressing, wherein the filtrate is a regenerated sulfur absorbent- - -sodium hydroxide (containing a small amount of calcium hydroxide) solution;
(4) and (3) introducing the filtrate sodium hydroxide (containing a small amount of calcium hydroxide) into the spray tower to recycle the alkaline water absorption liquid, and timely cleaning the filter residue and then discharging.
After the treatment by the method for removing carbonyl sulfide in blast furnace gas, the content of carbonyl sulfide in the purified blast furnace gas can be reduced to 2-20 mg/m3。
Example 2
A novel method for removing carbonyl sulfide in blast furnace gas specifically comprises the following steps:
(1) introducing blast furnace gas containing carbonyl sulfide and hydrogen sulfide at the temperature of 20-220 ℃ into an absorption tower filled with a sodium hydroxide solution with the mass concentration of 12.5% in a bubbling manner by using a bubbling tower, wherein different bubble speeds can be adjusted according to the concentration of the carbonyl sulfide, and an instrument for detecting the sulfur concentration is arranged on the absorption tower.
(2) Sodium hydroxide solution is properly supplemented in the absorption tower, and when the concentration of the sodium hydroxide solution in the absorption tower is detected to be too low to absorb the sulfur content in the blast furnace gas to exceed the standard, the contact time of the blast furnace gas can be shortened or the concentration of the sodium hydroxide can be increased to improve the desulfurization degree. And (4) leading the desulfurization waste liquid out to a sedimentation tank, and adding a proper amount of quicklime into the sedimentation tank to regenerate the desulfurization alkaline water.
(3) Quickly stirring by a stirrer in the regeneration tank for 10-50min, standing, and press-filtering to obtain filtrate, i.e. regenerated sodium hydroxide (containing calcium hydroxide) solution. And introducing the filtrate into the spray tower to recycle the alkaline water absorption liquid, and discharging the filter residue after timely cleaning.
Wherein the content of carbonyl sulfide in the purified blast furnace gas can be reduced to 1-10 mg/m3。
The above are merely preferred test cases of the present invention, and are not intended to limit the scope of the present invention; obviously, various modifications and improvements can be made to achieve better removal results according to the embodiments described in the present specification. The application is limited only by the claims and their full scope and equivalents.
Claims (10)
1. The novel blast furnace gas desulfurization method is characterized by comprising the following steps of:
(1) absorbing sulfur by the desulfurizing tower: introducing blast furnace gas into a desulfurizing tower, spraying an alkaline aqueous solution as a sulfur absorbent by the desulfurizing tower, and absorbing sulfur-containing compounds in the blast furnace gas to generate an aqueous solution of water-soluble sulfides, carbonates and chlorides, which is called recovery solution for short;
(2) reducing the absorbent in the regeneration tank: introducing the recovered liquid obtained in the step (1) into a regeneration tank, and regenerating the recovered liquid by using metal hydroxide or metal oxide to obtain regenerated sulfur absorbent, sulfide 2 and alkali carbonate 2;
(3) and (3) treating the vulcanization product: separating the sulfide 2 and the alkali carbonate 2 in the step (2) through pressure filtration, vacuum filtration or centrifugal separation for further use; meanwhile, the regenerated sulfur absorbent is obtained;
(4) recycling of the absorbent: and (4) adding the regenerated sulfur absorbent in the step (3) into the step (1) for recycling.
2. The method according to claim 1, characterized in that the sulfur-containing compounds in step (1) are the sum of carbonyl sulfide, hydrogen sulfide and other forms of sulfides contained in blast furnace gas.
3. The method according to claim 1, wherein the absorbent in step (1) is one or more of ammonia, magnesium hydroxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, strontium hydroxide and barium hydroxide aqueous solution.
4. The method of claim 1, wherein the desulfurization tower in step (1) is one or more of a spray tower, a bubble tower, a tray tower, a venturi or other gas-liquid contact device, and one or more desulfurization towers are adopted.
5. The method according to claim 1, wherein the sulfide in step (1) is one or more of magnesium sulfide, calcium sulfide, sodium sulfide, potassium sulfide, cesium sulfide, strontium sulfide, and barium sulfide; the sulphides in step (1) also include other forms of sulphur-containing compounds formed during desulphurisation.
6. The method of claim 1, wherein the base carbonate in step (1) is one or more of magnesium carbonate, calcium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, strontium carbonate, or barium carbonate.
7. The method according to claim 1, wherein the spraying of the alkaline aqueous solution by the desulfurization tower in the step (1) is not limited to the one-time blast furnace gas passing through the one-time spraying tower spraying the alkaline aqueous solution, but also comprises multiple passes through a plurality of desulfurization spraying towers; the total time for the blast furnace gas to pass through the aqueous alkaline solution is more than 1 second, i.e. the total time for one or more contacts with the aqueous alkaline solution is more than 1 second.
8. The method according to claim 1, wherein the metal hydroxide in the step (2) is one or more of calcium hydroxide and magnesium hydroxide; the metal oxide is calcium oxide; the sulfide 2 is calcium sulfide and magnesium sulfide, and the alkali carbonate 2 is calcium carbonate and/or magnesium carbonate.
9. The method according to claim 1, wherein the reaction conditions in the step (1) are that the mass concentration of the absorbent is 0.1-20%, and the sulfur content of the blast furnace gas is more than 1mg/m3The reaction temperature is 20-200 ℃, and the reaction time is more than 1 second.
10. The method of claim 1, wherein step (1) is additionally supplemented with an amount of alkaline water to ensure proper operation of the process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276841A (en) * | 2021-12-30 | 2022-04-05 | 新兴铸管股份有限公司 | Desulfurization method of blast furnace gas |
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2021
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114276841A (en) * | 2021-12-30 | 2022-04-05 | 新兴铸管股份有限公司 | Desulfurization method of blast furnace gas |
| CN114276841B (en) * | 2021-12-30 | 2023-10-24 | 新兴铸管股份有限公司 | Desulfurization method for blast furnace gas |
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