CN114836246A - Process for purifying and recycling coke oven gas to recover high-quality concentrated ammonia water and sulfur - Google Patents
Process for purifying and recycling coke oven gas to recover high-quality concentrated ammonia water and sulfur Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/05—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by wet processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/006—Hydrogen cyanide
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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
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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
- C10K1/121—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 NH3 only (possibly in combination with NH4 salts)
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention relates to a process for purifying and recycling coke oven gas to recover high-quality concentrated ammonia water and sulfur, wherein the coke oven gas enters a desulfurizing tower to remove hydrogen sulfide in the gas, hydrogen cyanide and part of ammonia enter an ammonia absorption tower to remove most of ammonia in the gas, a desulfurization rich solution is regenerated through a pressurization, decyanation and deacidification process, and an ammonia absorption rich solution enters a desorption tower to be regenerated, so that 10-25% of high-quality concentrated ammonia water can be recovered through the process. Compared with the prior art, in the process, the coke oven gasThe hydrogen sulfide and the ammonia in the process are utilized most effectively, the concentration of the recovered high-quality strong ammonia water is adjustable, and the high-quality strong ammonia water can be directly used for desulfurization and denitrification or for preparing anhydrous ammonia products; the content of hydrogen sulfide in the purified coal gas is not more than 200mg/m 3 Ammonia is not more than 50mg/m 3 The total ammonia in the ammonia distillation wastewater is not more than 150 mg/L; the whole process has the characteristics of high deacidification and deamination efficiency, high resource utilization rate, reduction of material grade of process equipment, low engineering investment, low energy consumption and the like.
Description
Technical Field
The invention relates to a novel process for gas desulfurization, deamination and decyanation, belongs to the chemical engineering technology, and particularly relates to a process for purifying and recycling high-quality concentrated ammonia water and sulfur from coke oven gas.
Background
At present, most domestic gas desulfurization processes adopt wet oxidation desulfurization and wet absorption desulfurization, wherein the wet oxidation desulfurization is popular to be carried out by an HPF method which takes ammonia AS an alkali source, and the wet absorption desulfurization is popular to be carried out by an ammonia-sulfur method (AS) circulating desulfurization and a vacuum carbonate method. However, each of these running processes has advantages and disadvantages, among which HPF desulfurization is good, but desulfurization waste liquid and low-quality sulfur paste are difficult to handle. The vacuum carbonate method also has the problem that the desulfurization waste liquid is difficult to treat. Although the AS process does not have the problems of solid waste and liquid waste, the sulfur content of the desulfurized coal gas is more than 500mg/m 3 And the process does not meet the coking index requirements, and has the problems of high equipment investment, high operation technical requirements, easy equipment blockage, easy corrosion and the like.
Some domestic scholars and engineering technicians improve the existing AS process, Chinese patent CN201611249990.8 discloses a process for preparing ammonia water by desulfurization and deamination of coke oven gas in 2017, 05.17.A pressure operation is carried out on a desulfurization pregnant solution desorption tower on the basis of AS, so that the desulfurization efficiency is improved, the ammonia water is prepared by deacidifying and steaming the residual ammonia water at low pressure, but the whole process still has the problem of improvement; and secondly, residual ammonia water is subjected to low-pressure deacidification and ammonia distillation, about 30% of acid gas can be removed from the tower top, most of the acid gas still enters ammonia gas at the side line, the purity of the ammonia gas is further influenced, and when the ammonia gas is sent to be used for flue gas desulfurization and denitrification, the ammonium sulfate mother liquor is darkened to generate precipitate. Therefore, it is necessary to develop a process which can be stably operated and can produce high-quality concentrated aqueous ammonia.
Disclosure of Invention
Aiming at the defects in the prior art, according to the embodiment of the invention, the process for purifying and recycling the high-quality concentrated ammonia water and the sulfur from the coke oven gas is expected to meet the requirements of relevant national environmental regulations, has high desulfurization efficiency, low process energy consumption, capability of recovering the high-quality concentrated ammonia water, equipment integration and wide application range.
According to the embodiment, the process for purifying and recycling the high-quality concentrated ammonia water and the sulfur from the coke oven gas comprises the following steps:
(1) and (4) desulfurization by a desulfurization unit: the method comprises the following steps that coal gas containing hydrogen sulfide, hydrogen cyanide and ammonia enters a desulfurizing tower from the bottom of the desulfurizing tower, the desulfurizing tower is sequentially provided with a final cooling section, a desulfurizing section and an alkaline washing section from bottom to top, the desulfurizing section and the alkaline washing section are respectively provided with a tower breaking disc, the coal gas is circularly washed and cooled to 20-22 ℃ in the final cooling section and then enters the desulfurizing section, deacidified barren solution from an deacidification tower passes through a barren solution heat exchanger, a barren solution first-stage cooler and a barren solution second-stage cooler and then is mixed with strong ammonia water for concentration adjustment, then enters the desulfurizing section for washing and removing the hydrogen sulfide and the hydrogen cyanide in the coal gas, the washed coal gas enters the alkaline washing section, is further washed by circulating alkali liquor to remove the hydrogen sulfide, and then enters an ammonia absorption tower;
(2) Ammonia absorption by the ammonia absorption unit: the coal gas from the desulfurizing tower enters an ammonia absorption tower and is in countercurrent contact with ammonium phosphate barren solution sprayed on the top of the tower, the ammonia absorption tower is provided with an upper section and a lower section which are independently and circularly washed, the lower section is circularly washed by a 2# ammonia absorption tower circulating pump, the upper section is circularly washed by a 1# ammonia absorption tower circulating pump, and a certain amount of ammonium phosphate rich solution is continuously extracted from the lower section circulating solution and sent to a desorption unit;
(3) the desulfurization rich solution decyanation deacidification ammonia distillation unit is characterized in that desulfurization rich solution absorbed by a desulfurization unit is automatically fed into a rich solution tank, simultaneously coking residual ammonia water is fed into the rich solution tank, the two are mixed and then fed to a ceramic filter under pressure by a rich solution pump to remove impurities such as tar, the primarily purified desulfurization rich solution passes through a lean and rich solution heat exchanger and then enters a decomposition tower to be decomposed by cyanide, the decomposed rich solution fully flows into the middle upper part of a deacidification tower, deacidification lean solution extracted from the bottom of the tower is subjected to heat exchange by the lean and rich solution heat exchanger, most of the deacidification is carried out, one part of the deacidification lean solution is fed to a fixed ammonium tower to be used as discharged wastewater, the other part of the deacidification lean solution is fed into the top of the deacidification tower through a reflux lean solution cooler to adjust the temperature of the top of the tower, and acid gas at the top of the deacidification tower is fed into a Laplace furnace to produce sulfur; fixing the ammonia tower to be normal pressure ammonia distillation, feeding ammonia gas at the tower top into a coal gas inlet pipeline of the ammonia absorption tower, and feeding waste water at the tower bottom to biochemistry;
(4) The ammonium phosphate rich liquid desorption unit is characterized in that ammonium phosphate rich liquid absorbing ammonia flows into a solution tank after impurities such as tar and naphthalene are removed through a tar remover, then the ammonium phosphate rich liquid is sent to an ammonium phosphate lean rich liquid heat exchanger through a pressure boosting pump, acidic gas is removed through flash evaporation in a contactor after heat exchange, the ammonium phosphate rich liquid with the acidic gas removed is sent to a No. 1 dephlegmator at the top of a desorption tower through a feeding pump of the desorption tower, the No. 1 dephlegmator is arranged in an upper section and a lower section, the ammonium phosphate rich liquid enters the lower section and enters the desorption tower after heat exchange with hot ammonia gas at the top of the tower, the hot ammonia gas and circulating water exchange heat in the upper section, and the concentration of concentrated ammonia water products at the top of the tower can be adjusted by changing the amount of circulating water.
Preferably, in the process for purifying and recycling the coke oven gas to recover the high-quality concentrated ammonia water and the sulfur, the deacidification tower is operated under the pressure of 0.3-0.6MPaG, and the operation temperature at the top of the tower is 35-40 ℃.
Preferably, in the process for purifying and recycling the coke oven gas to recover the high-quality concentrated ammonia water and the sulfur, one part of the concentrated ammonia water produced at the top of the desorption tower is sent to the desulfurization unit to adjust the ammonia-sulfur ratio of the deacidified lean solution, and the other part of the concentrated ammonia water is used as a product, wherein the concentration of the concentrated ammonia water is 10-25%, and the content of hydrogen sulfide is not more than 0.1 wt%.
Preferably, in the process for purifying and recycling the coke oven gas to recover the high-quality concentrated ammonia water and the sulfur, the deacidification tower, the desorption tower and the fixed ammonium tower are indirectly heated by steam through the reboiler.
Compared with the prior art, the invention has the following characteristics:
(1) on the basis of the AS process, ammonia in the gas is removed by adopting an ammonium phosphate ammonia washing mode, so that the influence of the quality of ammonia washing water on deamination in the AS desulfurization process can be avoided, and the stability of the gas deamination effect is ensured;
(2) the residual ammonia water and the desulfurization rich solution are simultaneously decyanated and deacidified, so that on one hand, the corrosion of a system is reduced, the material requirements of a deacidification tower and a fixed ammonium tower are low, on the other hand, the content of cyanide in the biochemical wastewater is not more than 10mg/L, and the biochemical treatment cost is greatly reduced;
(3) the ammonia source in the coal gas and the residual ammonia water of the whole system finally enters the ammonium phosphate rich solution, the concentrated ammonia water is produced by desorption in the desorption tower, the resource is utilized to the maximum extent, and the top of the desorption tower is additionally provided with the dephlegmator, so that the concentration of the concentrated ammonia water can be adjusted, and the requirements of different productions are met;
(4) as the ammonium phosphate barren solution hardly absorbs acid gas in the ammonia absorption process, the strong ammonia water produced by the desorption tower has low content of acid gas, high-quality strong ammonia water for desulfurization and denitrification can be produced, the strong ammonia water can be used for producing anhydrous ammonia by rectification, and the product scheme is adjustable.
In conclusion, the invention has the advantages of high efficiency of gas desulfurization and deamination, stable system operation, capability of recycling high-quality concentrated ammonia water to the maximum extent, low investment and capability of meeting the requirements of green chemical production by reasonably arranging process equipment.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further illustrated with reference to the following figures and specific examples. These examples are to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. After reading the description of the invention, one skilled in the art can make various changes and modifications to the invention, and such equivalent changes and modifications also fall into the scope of the invention defined by the claims.
As shown in fig. 1, it is a flow chart of a special process for purifying and recycling high-quality concentrated ammonia water and sulfur from coke oven gas according to a preferred embodiment of the present invention.
As shown in FIG. 1, the gas (containing H) is compressed by a blower 2 S:5-9g/m 3 ，NH 3 :3-7g/m 3 ) Firstly enters the final cooling section at the lower part of the desulfurizing tower and is sprayed and cooled to about 23 ℃ by the final cooling water to ensure that H is absorbed 2 The operating temperature of S. The final cooling water is cooled to about 22 ℃ by low-temperature water through a final cooling cooler for recycling. In order to prevent the accumulation of the final cooling circulation impurities and the possible naphthalene deposition, proper amount of ammonia water is continuously injected into a final cooling circulation water system,meanwhile, a certain amount of water discharged sewage is controlled by the liquid level at the bottom of the tower and is sent to a tar-ammonia water separator. The finally cooled coal gas is in countercurrent contact with washing liquid from top to bottom in a desulfurization section in the tower, and cooled deacidified lean solution (containing NH at 21-22 ℃) is sprayed 3 :10-12g/L，H 2 S is-0.1 g/L) and strong ammonia water mixed liquor are sprayed, and most of H in coal gas is sprayed and washed 2 The S is removed. The desulfurization rich solution generated by washing automatically flows into a rich solution tank. In the alkaline washing section at the upper part of the desulfurizing tower, alkaline liquor is used for further absorbing H in the coal gas 2 And the S and HCN gas escapes from the top of the desulfurizing tower. Part of the waste alkali liquor is cut out at the outlet of the alkali liquor circulating pump and sent to the fixed ammonium tower to decompose and fix ammonium salt.
And (3) feeding the coal gas from the desulfurizing tower into an ammonia absorption tower, wherein the ammonia absorption tower is an upper section and a lower section of air injection towers, the coal gas enters from the bottom of the ammonia absorption tower, phosphoric acid lean solution is in countercurrent contact with the coal gas, the upper section and the lower section are respectively provided with a circulating pump for circulating washing, and ammonium phosphate rich solution is continuously pumped from the circulating solution of the lower section to a desorption tower for regeneration.
After the coke oven gas is desulfurized and ammonia-absorbed, purifying H in the gas 2 S content is not more than 200mg/m 3 ，NH 3 Not more than 50mg/m 3 。
The mixed liquid of the desulfurization rich liquid and the residual ammonia water from the rich liquid tank enters a ceramic filter after being boosted by a rich liquid pump, the filtered desulfurization rich liquid exchanges heat with the barren liquid through a barren rich liquid heat exchanger, the temperature of the rich liquid after heat exchange is 125-140 ℃, and the mixture enters a decomposition tower for decomposing cyanide. The decomposed rich liquid (the cyanide decomposition rate is 95-99%) flows from the top of the decomposition tower to the middle upper part of the deacidification tower (the operation pressure is 0.3-0.6 MPaG). The rectifying section of the deacidification tower is a packed tower, and acid gas extracted from the tower top is sent to a sulfur recovery unit. The stripping section of the deacidification tower is a plate tower (15-30 blocks), and barren liquor extracted from the bottom of the deacidification tower is sent to a barren and rich liquor heat exchanger to exchange heat with rich liquor after passing through a barren liquor pump. The barren solution after heat exchange of the barren solution and rich solution heat exchanger is divided into two parts, and one part is sent to a barren solution first-stage cooler; the other portion was sent to the waste water heat exchanger as feed to the stationary ammonium column. The barren liquor cooled by the barren liquor first-stage cooler is divided into two parts, and one part is sent to the desulfurizing tower; the other part is cooled to 25-30 ℃ by a reflux barren liquor cooler and then is sent to the upper part of the deacidification tower as a cold material.
The barren liquor which is heat exchanged by the waste water heat exchanger to 90-95 ℃ is sent to the upper part of a fixed ammonium tower (normal pressure operation), in the fixed ammonium tower, waste alkali liquor cut out by a desulfurization tower alkali washing section decomposes fixed ammonium salt, and ammonia steam escaping from the tower top of the fixed ammonium tower is sent to an ammonia absorption tower. The ammonia distillation wastewater from the bottom of the fixed ammonium tower is cooled to about 40 ℃ by a wastewater heat exchanger and a wastewater cooler in sequence and is sent to biochemistry, the total ammonia content of the ammonia distillation wastewater is-150 mg/L, and the cyanide content is-10 mg/L.
In the system, coke oven gas and ammonia in residual ammonia water enter an ammonia absorption tower and are absorbed by ammonium phosphate lean solution to obtain ammonium phosphate rich solution, the ammonium phosphate rich solution firstly enters a tar remover to remove impurities such as tar and naphthalene and then flows into a solution tank, then the ammonium phosphate rich solution is sent to an ammonium phosphate lean solution heat exchanger through an ammonium phosphate rich solution boosting pump, the ammonium phosphate rich solution enters a contactor to be subjected to flash evaporation to remove acid gas after heat exchange, the ammonium phosphate rich solution from which the acid gas is removed is firstly sent to a No. 1 dephlegmator at the top of a desorption tower through a feeding pump of the desorption tower, the No. 1 dephlegmator is arranged in an upper section and a lower section, the ammonium phosphate rich solution enters a desorption tower after heat exchange with hot ammonia gas at the top of the tower in the lower section, the hot ammonia gas and circulating water exchange heat in the upper section, and the concentration of concentrated ammonia water at the top of the tower can be adjusted by changing the circulating water amount. One part of the produced strong ammonia water is sent to a desulfurizing tower to be used for adjusting the ammonia-sulfur ratio in deacidification barren solution, the desulfurizing efficiency of the desulfurizing tower is ensured, the other part of the produced strong ammonia water is sent out as a product, the concentration of the strong ammonia water is 10-25 percent and can be adjusted as required, the acid-containing gas is not more than 0.1 percent by weight, and the produced strong ammonia water can be used as a desulfurizing and denitrifying ammonia water raw material.
The deacidification tower and the fixed ammonium tower can avoid using titanium materials, and adopt 316L composite boards, thereby reducing the investment.
In conclusion, the main body of the invention is improved on the AS process, the improved process has strong independence and simple process operation, the ammonia absorption mode introduces the ammonium phosphate barren solution absorption method, the ammonium phosphate barren solution absorption method has high selectivity and hardly absorbs acid gas, so that high-purity strong ammonia water can be prepared, and the concentration of the strong ammonia water can be flexibly adjusted by arranging the partial condenser on the upper part of the desorption tower; the deacidification tower adopts pressurization operation, and the ammonia content in the acid gas at the tower top is not more than 1 wt%, so that the problem that an acid gas pipeline is easy to block in the conventional AS process is solved; the whole system can ensure the stability of long-term operation, is flexible and adjustable, can utilize the ammonia source in the system to the maximum extent, and meets the requirements of green chemical industry.
Claims (4)
1. A process for purifying and recycling high-quality concentrated ammonia water and sulfur from coke oven gas is characterized by comprising the following steps:
(1) and (4) desulfurization by a desulfurization unit: the method comprises the following steps that coal gas containing hydrogen sulfide, hydrogen cyanide and ammonia enters a desulfurizing tower from the bottom of the desulfurizing tower, the desulfurizing tower is sequentially provided with a final cooling section, a desulfurizing section and an alkaline washing section from bottom to top, the desulfurizing section and the alkaline washing section are respectively provided with a tower breaking disc, the coal gas is circularly washed and cooled to 20-22 ℃ in the final cooling section and then enters the desulfurizing section, deacidified barren solution from an deacidification tower passes through a barren solution heat exchanger, a barren solution first-stage cooler and a barren solution second-stage cooler and then is mixed with strong ammonia water for concentration adjustment, then enters the desulfurizing section for washing and removing the hydrogen sulfide and the hydrogen cyanide in the coal gas, the washed coal gas enters the alkaline washing section, is further washed by circulating alkali liquor to remove the hydrogen sulfide, and then enters an ammonia absorption tower;
(2) Ammonia absorption by the ammonia absorption unit: the coal gas from the desulfurizing tower enters an ammonia absorption tower and is in countercurrent contact with ammonium phosphate barren solution sprayed on the top of the tower, the ammonia absorption tower is provided with an upper section and a lower section which are independently and circularly washed, the lower section is circularly washed by a 2# ammonia absorption tower circulating pump, the upper section is circularly washed by a 1# ammonia absorption tower circulating pump, and a certain amount of ammonium phosphate rich solution is continuously extracted from the lower section circulating solution and sent to a desorption unit;
(3) a desulfurization rich solution decyanation deacidification ammonia distillation unit: the desulfurization rich solution absorbed by the desulfurization unit is automatically fed into a rich solution tank, simultaneously coking residual ammonia water is fed into the rich solution tank, the two are mixed and then fed to a ceramic filter under pressure by a rich solution pump to remove impurities such as tar, the primarily purified desulfurization rich solution passes through a lean-rich solution heat exchanger and then enters a decomposition tower to be decomposed by cyanide, the decomposed rich solution is fully fed into the middle upper part of a deacidification tower, most of deacidification lean solution extracted from the bottom of the tower is carried out after heat exchange by the lean-rich solution heat exchanger, one part of deacidification lean solution is fed to a fixed ammonium tower to be used as discharged wastewater, the other part of deacidification rich solution enters the top of the deacidification tower through a reflux lean solution cooler to adjust the temperature of the top of the tower, and acid gas at the top of the deacidification tower is fed into a Claus furnace to produce sulfur; fixing the ammonia tower to be normal pressure ammonia distillation, introducing ammonia gas at the tower top into a coal gas inlet pipeline of the ammonia absorption tower, and conveying waste water at the tower bottom to biochemistry;
(4) Ammonium phosphate rich solution desorption unit: the ammonium phosphate rich solution absorbing ammonia flows into a solution tank after tar, naphthalene and other impurities are removed by a decoking device, then the ammonium phosphate rich solution is sent to an ammonium phosphate lean and rich solution heat exchanger by an ammonium phosphate rich solution boosting pump, the ammonium phosphate rich solution enters a contactor to be subjected to flash evaporation to remove acid gas after heat exchange, the ammonium phosphate rich solution from which the acid gas is removed is sent to a No. 1 dephlegmator at the top of a desorption tower by a desorption tower feeding pump, the No. 1 dephlegmator is arranged in an upper section and a lower section, the ammonium phosphate rich solution enters the desorption tower after heat exchange with hot ammonia gas at the top of the tower in the lower section, the hot ammonia gas exchanges heat with circulating water in the upper section, and the concentration of the concentrated ammonia water product at the top of the tower can be adjusted by changing the amount of circulating water.
2. The process for purifying and recycling the high-quality concentrated ammonia water and the sulfur from the coke oven gas as claimed in claim 1, wherein the operating pressure of the deacidification tower is 0.3-0.6MPaG, and the operating temperature at the top of the tower is 35-40 ℃.
3. The process for purifying and recycling coke oven gas as claimed in claim 1, wherein a part of the concentrated ammonia water produced at the top of the desorption tower is sent to a desulfurization unit to adjust the ammonia-sulfur ratio of the deacidified barren solution, and the other part is used as a product, wherein the concentration of the concentrated ammonia water is 10-25%, and the content of hydrogen sulfide is not more than 0.1 wt%.
4. The process for purifying and recycling the high-quality concentrated ammonia water and the sulfur from the coke oven gas as claimed in claim 1, wherein the deacidification tower, the desorption tower and the fixed ammonium tower are indirectly heated by steam in a reboiler.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196809A (en) * | 2022-08-04 | 2022-10-18 | 广西钢铁集团有限公司 | Method for removing hydrogen cyanide in rich solution by using pressurization type AS (acrylonitrile-styrene) desulfurization process in coking plant |
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| CN114836246B (en) | 2023-09-19 |
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