CN115196809A - Method for removing hydrogen cyanide in rich solution by using pressurization type AS (acrylonitrile-styrene) desulfurization process in coking plant - Google Patents
Method for removing hydrogen cyanide in rich solution by using pressurization type AS (acrylonitrile-styrene) desulfurization process in coking plant Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/16—Treatment of water, waste water, or sewage by heating by distillation or evaporation using waste heat from other processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/066—Overpressure, high pressure
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Abstract
The invention provides a method for removing hydrogen cyanide in a rich solution by a pressurized AS desulfurization process of a coke-oven plant, which comprises the following process steps: the pregnant solution from the washing desulfurizing tower enters a pregnant solution tank, one part of the filtered pregnant solution passes through a lean pregnant solution heat exchanger, the other part of the filtered pregnant solution passes through a deamination water pregnant solution heat exchanger, two parts of pregnant solution after heat exchange are mixed and enter a decyanation tower through a pregnant solution heater, and cyanide in the desulfurizing solution is effectively removed, equipment corrosion is reduced, and the production running cost is reduced through high-temperature pressurization decyanation treatment of the pregnant solution.
Description
Technical Field
The invention relates to the technical field of coal gas purification of a coking plant, in particular to a method for removing hydrogen cyanide in a pregnant solution by a pressurized AS (acrylonitrile-styrene) desulfurization process of the coking plant.
Background
The coke oven gas generally contains H 2 S (mass concentration 4-10 g/m) 3 ) And HCN (mass concentration 1-2.5 g/m) 3 ) The coal gas purification process has corrosion hazard to process equipment, and the environment is polluted after combustion, so the coal gas needs to be subjected to desulfurization, decyanation and purification treatment. At present, the wet desulphurization and decyanation technology is mainly adopted at home, corrosion is a great problem in the pressurization type AS desulphurization process of the wet desulphurization and decyanation, and according to the introduction of data, when the content of hydrogen cyanide in the desulphurization solution is low, the cast iron tower body has enough corrosion resistance even at higher temperature. When desulfurization is carried outWhen the hydrogen sulfide content in the liquid exceeds 6g/L and the hydrogen cyanide content exceeds 0.3-0.4g/L, the cast iron can not be used. Particularly, in the pressure deacidification, the corrosion of the evaporated acid gas is stronger, and the corrosion rate can be greatly reduced only when the hydrogen cyanide in the desulfurization solution is reduced to 0.2 g/L. Therefore, cyanide in the desulfurization solution is effectively removed, equipment corrosion is reduced, and the method has great significance for reducing production and operation cost.
In summary, the following problems exist in the prior art: in the pressurized AS desulfurization process of wet desulfurization and decyanation, the concentration of hydrogen cyanide in the desulfurization solution is high, equipment is corroded, and the production running cost is increased.
Disclosure of Invention
The invention provides a method for removing hydrogen cyanide in pregnant solution by a pressurized AS desulfurization process in a coke-oven plant, which aims to solve the problems of high concentration of hydrogen cyanide in desulfurization solution, equipment corrosion and production and operation cost increase in the pressurized AS desulfurization process of wet desulfurization and decyanation.
Therefore, the invention provides a method for removing hydrogen cyanide in pregnant solution by using a pressurized AS (acrylonitrile-styrene) desulfurization process in a coke-oven plant.
AS is a method for removing hydrogen sulfide in coke oven gas by adopting an ammonia sulfur circulating washing process.
The method for removing hydrogen cyanide in the pregnant solution by using the pressurized AS desulfurization process of the coke-oven plant comprises the following process steps which are carried out in sequence:
the method comprises the following steps: the rich solution from the washing desulfurizing tower 1 enters a rich solution tank 6, and is pumped into a ceramic filter 7 through a rich solution pump 9 for filtering, removing oil and impurities;
step two: the filtered rich solution is divided into two parts, one part exchanges heat with the lean solution through a lean rich solution heat exchanger 14, the other part exchanges heat with the deamination water through a deamination water rich solution heat exchanger 13, the mixed temperature of the two parts of rich solution is about 110 ℃ after heat exchange, and the mixed solution enters a decyanation tower 2 after being exchanged heat to 125-128 ℃ through a rich solution heater 8;
step three: in the operation process of the decyanation tower 2, the high-temperature state and the high-pressure state of the pregnant solution in the tower are kept, the temperature and the pressure of the tower top are controlled, and the residence time of the pregnant solution in the decyanation tower is ensured;
step four: the decyanated pregnant solution is sent to a deacidification tower 3 for deacidification;
step five: acid gas in the rich solution is removed by the deacidification tower 3 to obtain barren solution, the barren solution extracted from the bottom of the deacidification tower 3 passes through a barren solution pump 10 and then is divided into two parts, one part is sent to the ammonia volatilization tower 4 to be recycled as a heat source, and the other part is sent to a barren and rich solution heat exchanger 14 to exchange heat with the rich solution; the barren solution after heat exchange is divided into two parts, wherein one part is sent to a barren solution first-stage cooler 16, and the other part is sent to a fixed ammonia tower feeding heat exchanger 15 to be used as the feeding material of a fixed ammonia tower 5; the barren liquor after passing through the barren liquor first-stage cooler 16 is divided into two parts, one part is sent to a barren liquor second-stage cooler 18, and the other part is sent to the upper part of the deacidification tower 3 for rectification as a cold material after being cooled by a backflow barren liquor cooler 17.
Further, according to the method for removing hydrogen cyanide in the rich solution by using the pressurized AS desulfurization process in the coke-oven plant, the tower top temperature in the third step is controlled to be 125-128 ℃.
Further, the method for removing hydrogen cyanide in the pregnant solution by the pressurized AS desulfurization process in the coke-oven plant comprises the step three, wherein the tower pressure is controlled to be 0.35-0.4MPa.
Further, according to the method for removing hydrogen cyanide in the pregnant solution by using the pressurized AS desulfurization process in the coke-oven plant, the residence time of the pregnant solution in the decyanation tower in the third step is more than 1.2 hours.
Further, the method for removing hydrogen cyanide in the pregnant solution by the pressurized AS desulfurization process in the coke-oven plant also comprises the following six steps: the acid gas extracted from the tower top is fed into gas-liquid separator, pressure regulated and fed into ammonia decomposing Claus furnace to be partially oxidized, one third of the gas is fed into burner in the upper part of Claus furnace, and H 2 S and oxygen are combusted to generate SO 2 The other two thirds of the gas directly enter a Claus furnace, wherein H 2 S and SO formed by combustion 2 The claus reaction is carried out to produce elemental sulphur.
Further, the method for removing hydrogen cyanide in the pregnant solution by using the pressurized AS desulfurization process in the coke-oven plant comprises the following step E: decomposing acid gas to ammonia and recovering sulfur to prepare sulfur.
According to the invention, through the high-temperature pressurization and decyanation treatment of the pregnant solution, cyanide content in the pregnant solution can be reduced to 10mg/l, corrosion of the desulfurization solution and acidic gas evaporated by pressure deacidification on equipment pipelines is greatly reduced, the technical defect in the pressurization type AS desulfurization process of wet desulfurization and decyanation is overcome, cyanide in the desulfurization solution is effectively removed, and the subsequent equipment type selection and maintenance cost is saved.
Drawings
FIG. 1 is a schematic view of the present invention;
wherein, 1, a desulfurizing tower; 2. a decyanation tower; 3. a deacidification tower; 4. an ammonia volatilization tower; 5. fixing an ammonia tower; 6. a pregnant solution tank; 7. a ceramic filter; 8. a rich liquid heater; 9. a rich liquor pump; 10. a barren liquor pump; 11. a deamination water pump; 12. ammonia distillation wastewater pump; 13. a ammonia water removal rich liquid heat exchanger; 14. a lean-rich liquid heat exchanger; 15. fixing a feeding heat exchanger of the ammonia tower; 16. a lean solution first-stage cooler; 17. a reflux lean liquor cooler; 18. barren liquor two-stage cooler
Detailed Description
In order to clearly understand the technical features, purposes and effects of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the drawings in the embodiments of the present invention.
Example 1:
the method comprises the following steps: the rich solution from the washing desulfurizing tower 1 enters a rich solution tank 6, and is pumped into a ceramic filter 7 through a rich solution pump 9 for filtering, removing oil and impurities.
The rich solution is an ammonia solution for absorbing acid gases such as hydrogen sulfide in a washing process. The barren solution is an ammonia water solution obtained by resolving acid gases such as hydrogen sulfide in the rich solution in a deacidification process; the preparation of sulfur by ammonia decomposition and sulfur recovery is a reaction in a complex furnace.
Step two: the filtered pregnant solution is divided into two parts, one part exchanges heat with the barren solution through a barren pregnant solution heat exchanger 14, the other part exchanges heat with the deamination water through a deamination water pregnant solution heat exchanger 13, the mixed temperature of the two parts of pregnant solution after heat exchange is about 110 ℃, and the pregnant solution enters a decyanation tower 2 after exchanging heat to 125-128 ℃ through a pregnant solution heater 8.
Step three: in the operation process of the decyanation tower 2, the high temperature state of the rich liquid in the tower is kept, and the temperature of the tower top is controlled to be 125-128 ℃.
Step four: in the operation process of the decyanation tower 2, the high-pressure state of rich liquid in the tower is kept, and the tower pressure is controlled to be 0.35-0.4MPa;
step five: the residence time of the pregnant solution in the decyanation tower is more than 1.2 hours.
Step six: the rich solution after decyanation is sent to a deacidification tower 3 for deacidification to generate acid gas, one part of the barren solution is sent to a volatile ammonia tower 4 for recycling as a heat source, the other part of the barren solution is sent to a fixed ammonia tower 5 for feeding after serial heat exchange and cooling, the desulfurized barren solution is used for washing hydrogen sulfide and refluxing the barren solution to the upper part of the deacidification tower for rectification, the acid gas is used for decomposing ammonia and recycling sulfur to prepare sulfur, and the acid gas comes from the rich solution.
Example 2:
AS shown in fig. 1, an embodiment of the present invention provides a method for removing hydrogen cyanide in a rich solution by a pressurized AS desulfurization process in a coke-oven plant, which comprises the following specific steps:
the method comprises the following steps: the rich solution from the washing desulfurization tower 1 enters a rich solution tank 6 and is pumped into a ceramic filter 7 through a rich solution pump 9.
Step two: the rich solution after being filtered and deoiled is divided into two parts, one part exchanges heat with the lean solution through a lean rich solution heat exchanger 14, the other part exchanges heat with the deamination water through a deamination water rich solution heat exchanger 13, and the mixing temperature of the two parts of rich solution after heat exchange is about 110 ℃.
Step three: then the cyanide is decomposed in a decyanation tower 2 after the heat exchange of the pregnant solution heater 8 is carried out to 125-128 ℃.
The coil heater is arranged at the bottom of the decyanation tower, and hydrogen cyanide is decomposed under the high pressure of about 0.35MPa in the decyanation tower according to the following principle:
HCN+2H 2 O→NH 4 COOH；
step four: the enriched liquid after decyanation fully flows into the middle upper part of the deacidification tower 3 from the top of the decyanation tower 2.
Step five: acid gas in the rich solution is removed by the deacidification tower 3, the deacidification lean solution is divided into two parts after passing through a lean solution pump 10, and one part is sent to the ammonia volatilization tower 4 to be recycled as a heat source.
Step six: the other part is sent to a lean-rich liquid heat exchanger 14 to exchange heat with rich liquid; the barren solution after heat exchange is divided into two parts, wherein one part is sent to a barren solution first-stage cooler 16, and the other part is sent to a fixed ammonia tower feeding heat exchanger 15 to be used as the feeding material of a fixed ammonia tower 5; the barren liquor after passing through the barren liquor first-stage cooler 16 is divided into two parts, one part is sent to a barren liquor second-stage cooler 18, and the other part is sent to the upper part of the deacidification tower 3 for rectification to generate acid gas after being cooled by a reflux barren liquor cooler 17.
In fig. 1, the function of the related device is:
fixing the ammonia tower 5: after heat exchange, a part of barren solution enters the fixed ammonia tower through a fixed ammonia tower feeding heat exchanger 15; deamination water pump 11: the ammonia water removed from the bottom of the volatile ammonia tower is sent to an ammonia washing tower in a washing procedure, so that the system forms liquid phase circulation; ammonia distillation wastewater pump 12: after the redundant barren liquor in the system enters the fixed ammonia tower 5, the ammonia distillation wastewater pump sends the redundant liquid of the fixed ammonia tower 5, namely the ammonia distillation wastewater to a biochemical system; fixed ammonia tower feed heat exchanger 15: heating up barren liquor which is about to enter a fixed ammonia tower 5, and simultaneously cooling down ammonia distillation wastewater going to biochemistry; lean liquid first-stage cooler 16: using circulating water at about 32 ℃ to cool the barren solution; lean solution secondary cooler 18: cooling the barren solution again by using low-temperature water at about 18 ℃; the return lean liquid cooler 17: the barren liquor is cooled by low-temperature water at about 18 ℃ and then is sent to an acid removal tower.
Preferably, the sixth step also comprises decomposing the acid gas into ammonia and recovering sulfur to prepare sulfur.
Step seven: the acid gas extracted from the tower top is fed into gas-liquid separator, pressure regulated and fed into ammonia decomposing Claus furnace to be partially oxidized, one third of the gas is fed into burner in the upper part of Claus furnace, and H 2 S and oxygen are combusted to generate SO 2 (ii) a The remaining two thirds are directed to a Claus furnace, wherein H 2 S and SO formed by combustion 2 The claus reaction is carried out to produce elemental sulphur.
According to the invention, through the high-temperature pressurization and decyanation treatment of the pregnant solution, the cyanide content of the pregnant solution can be reduced to 10mg/l, the corrosion of the desulfurization solution and the acidic gas evaporated by pressure deacidification to the equipment pipeline is greatly reduced, the technical defects in the pressurization type AS desulfurization process of wet desulfurization and decyanation are overcome, the cyanide in the desulfurization solution is effectively removed, and the subsequent equipment type selection and maintenance cost is saved.
The above description is only an exemplary embodiment of the present invention, and is not intended to limit the scope of the present invention. In order that the components of the present invention may be combined without conflict, it should be understood that equivalent changes and modifications made by those skilled in the art without departing from the spirit and principle of the present invention are within the scope of the present invention.
Claims (5)
1. A method for removing hydrogen cyanide in a pregnant solution by a pressurized AS desulfurization process in a coke-oven plant is characterized by comprising the following specific process steps:
a, rich liquor from a washing desulfurizing tower (1) enters a rich liquor tank (6), and is pumped into a ceramic filter (7) through a rich liquor pump (9) to be filtered, deoiled and decontaminated;
b, dividing the filtered rich solution into two parts, wherein one part exchanges heat with the lean solution through a lean rich solution heat exchanger (14), the other part exchanges heat with the deamination water through a deamination water rich solution heat exchanger (13), the mixed temperature of the two parts of rich solution is 110 ℃ after heat exchange, and the mixed temperature is changed to 125-128 ℃ through a rich solution heater (8) and then enters a decyanation tower (2);
step C, in the operation process of the decyanation tower (2), keeping the high-temperature state and the high-pressure state of the pregnant solution in the tower, controlling the temperature and the pressure of the tower top, and ensuring the residence time of the pregnant solution in the decyanation tower;
d, delivering the decyanated pregnant solution to a deacidification tower (3) for deacidification;
step E, removing acid gas in the rich solution by the deacidification tower (3) to obtain barren solution, dividing the barren solution extracted from the bottom of the deacidification tower (3) into two parts after passing through a barren solution pump (10), wherein one part is sent to the volatile ammonia tower (4) to be recycled as a heat source, and the other part is sent to a barren and rich solution heat exchanger (14) to exchange heat with the rich solution; the barren solution after heat exchange is divided into two parts, one part is sent to a barren solution first-stage cooler (16), and the other part is sent to a fixed ammonia tower feeding heat exchanger (15) to be used as the feeding of a fixed ammonia tower (5); the barren liquor after passing through the barren liquor first-stage cooler (16) is divided into two parts, one part is sent to a barren liquor second-stage cooler (18), and the other part is sent to the upper part of the deacidification tower (3) for rectification as a cold material after being cooled by the backflow barren liquor cooler (17).
2. The method for removing hydrogen cyanide from the pregnant solution by the pressurized AS desulfurization process in the coke-oven plant AS claimed in claim 1, wherein the temperature of the top of the tower in the step C is controlled to be 125-128 ℃.
The method for removing hydrogen cyanide from a pregnant solution by using the pressurized AS desulfurization process in a coke-oven plant AS claimed in claim 1, wherein the column pressure in the step C is controlled to be 0.35-0.4MPa.
3. The method for removing hydrogen cyanide from the pregnant solution by the pressurized AS desulfurization process in the coke-oven plant AS claimed in claim 1, wherein the residence time of the pregnant solution in the decyanation tower in step C is more than 1.2 hours.
4. The method for removing hydrocyanic acid from a pregnant solution through a pressurized AS desulfurization process of a coke-oven plant AS claimed in claim 1, further comprising the step F: the acid gas extracted from the tower top is fed into gas-liquid separator, pressure regulated and fed into ammonia decomposing Claus furnace to adopt partial oxidation process, one third of the gas is fed into burner in the upper portion of Claus furnace, and H 2 S and oxygen are combusted to generate SO 2 The other two thirds of the gas directly enter a Claus furnace, wherein H 2 S and SO formed by combustion 2 The claus reaction proceeds to elemental sulphur.
5. The method for removing hydrogen cyanide from a pregnant solution by using a pressurized AS desulfurization process in a coke-oven plant AS claimed in claim 1, wherein the step E further comprises: decomposing acid gas into ammonia and recovering sulfur to prepare sulfur.
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| CN202210932288.0A CN115196809A (en) | 2022-08-04 | 2022-08-04 | Method for removing hydrogen cyanide in rich solution by using pressurization type AS (acrylonitrile-styrene) desulfurization process in coking plant |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210932288.0A CN115196809A (en) | 2022-08-04 | 2022-08-04 | Method for removing hydrogen cyanide in rich solution by using pressurization type AS (acrylonitrile-styrene) desulfurization process in coking plant |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333464A (en) * | 2008-08-04 | 2008-12-31 | 马永伟 | Desulphurization process by vacuum ammonia method |
| CN101457162A (en) * | 2007-12-12 | 2009-06-17 | 鞍山立信焦耐工程技术有限公司 | Wet-type absorption coke oven gas desulphurization and decyanation process using ammine as alkali source |
| CN105985814A (en) * | 2015-02-09 | 2016-10-05 | 上海同特化工科技有限公司 | Treatment technology for removing hydrogen sulfide, hydrogen cyanide and ammonia in coal gas |
| CN114836246A (en) * | 2022-04-04 | 2022-08-02 | 上海圣升化工科技有限公司 | Process for purifying and recycling coke oven gas to recover high-quality concentrated ammonia water and sulfur |
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- 2022-08-04 CN CN202210932288.0A patent/CN115196809A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457162A (en) * | 2007-12-12 | 2009-06-17 | 鞍山立信焦耐工程技术有限公司 | Wet-type absorption coke oven gas desulphurization and decyanation process using ammine as alkali source |
| CN101333464A (en) * | 2008-08-04 | 2008-12-31 | 马永伟 | Desulphurization process by vacuum ammonia method |
| CN105985814A (en) * | 2015-02-09 | 2016-10-05 | 上海同特化工科技有限公司 | Treatment technology for removing hydrogen sulfide, hydrogen cyanide and ammonia in coal gas |
| CN114836246A (en) * | 2022-04-04 | 2022-08-02 | 上海圣升化工科技有限公司 | Process for purifying and recycling coke oven gas to recover high-quality concentrated ammonia water and sulfur |
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