CN112093778A - Treatment process for by-product low-quality sulfur in coke oven gas desulfurization process - Google Patents
Treatment process for by-product low-quality sulfur in coke oven gas desulfurization process Download PDFInfo
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
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Abstract
The invention relates to a treatment process of a byproduct low-quality sulfur in a coke oven gas desulfurization process. The beneficial effects are as follows: the process removes metal salts in the low-quality sulfur through separation and washing, so that the metal salts become raw materials of the process for preparing acid from sulfur, the problem that the low-quality sulfur as a byproduct of a sodium wet oxidation desulfurization process is difficult to treat can be effectively solved, the recycling of sulfur resources is realized, and the environment is protected.
Description
Technical Field
The invention relates to the technical field of coke oven gas purification, in particular to a treatment process of by-product low-quality sulfur in a coke oven gas desulfurization process.
Background
The wet oxidation desulfurization process for the coke oven gas has the outstanding advantages of high desulfurization and decyanation efficiency, simple process flow and the like, so the wet oxidation desulfurization process is widely applied to the coking industry in China. The desulfurization process is divided into an ammonia wet oxidation desulfurization process (such as HPF desulfurization and PDS desulfurization) which takes ammonia contained in the coke oven gas as an alkali source and a sodium wet oxidation desulfurization process (such as improved ADA desulfurization and tannin extract desulfurization) which takes sodium carbonate added as an alkali source according to different alkali sources. No matter what alkali source is adopted, the coke oven gas wet oxidation desulfurization process can produce low-quality sulfur and desulfurization waste liquid as byproducts, and the low-quality sulfur and the desulfurization waste liquid need to be subjected to harmless treatment.
The by-products of the ammonia wet oxidation desulfurization process, namely the low-quality sulfur and the desulfurization waste liquid, contain ammonium thiocyanate, ammonium thiosulfate, ammonium sulfate and other sulfur-containing ammonium salts, and the process for preparing acid by burning the low-quality sulfur and the desulfurization waste liquid can be adopted to fundamentally solve the process problems of recycling the low-quality sulfur and harmlessly post-treating the desulfurization byproduct salt waste liquid. However, both the low-quality sulfur and the desulfurization waste liquid, which are by-products of the sodium wet oxidation desulfurization process, contain metal salts such as sodium carbonate, sodium thiocyanate, sodium thiosulfate, sodium sulfate, and the like, and cannot be treated by the incineration acid-making process of the low-quality sulfur and the desulfurization waste liquid. The metal salts contained in the waste heat boiler can cause the burned flue gas to contain a large amount of fused salt, the fused salt can be adhered to a heat exchange tube after encountering the heat exchange tube with lower temperature in the waste heat boiler, the adhesion amount is rapidly increased along with the flow of the flue gas, the ash deposition and slagging speed is very high, the heat exchange and the blockage of a flue gas channel are seriously influenced, the slag removal is very difficult, the boiler is required to be stopped for ash removal and slag removal, the overhaul frequency is high, the time is long, and the labor intensity is high.
At present, the byproduct desulfurization waste liquid of the sodium wet oxidation desulfurization process is generally treated by a salt extraction process, and an effective treatment process for the byproduct low-quality sulfur is still lacking. In order to avoid the formation of coking solid waste and influence on environment, low-quality sulfur is mostly sold at low price or even given away for free to solid waste recycling manufacturers for treatment, so that sulfur resources cannot be effectively and reasonably utilized, and the due value of the sulfur resources is not exerted. In certain areas of China, even because no solid waste recovery manufacturers are willing to accept, a large amount of low-quality sulfur can only be accumulated in a coking plant to form new coking solid waste, so that the environment is polluted, and the problem is urgently solved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention solves the technical problem of providing the treatment process of the byproduct low-quality sulfur of the coke oven gas desulfurization process, which removes metal salts in the low-quality sulfur through separation and washing to enable the low-quality sulfur to become the raw material of the process for preparing acid from sulfur, can effectively solve the problem of difficult treatment of the low-quality sulfur byproduct of the wet oxidation desulfurization process by a sodium method, realizes the recycling of sulfur resources and protects the environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a treatment process of a low-quality sulfur byproduct in a coke oven gas desulfurization process comprises the following steps:
1) solid-liquid separation: separating sulfur foam sent by the desulfurization unit to obtain salt-containing filtrate (liquid phase) and salt-containing sulfur (solid phase), wherein the salt-containing filtrate flows into a filtrate tank and is sent back to the desulfurization unit or a salt extraction device by a filtrate pump;
2) washing and desalting: washing the salt-containing sulfur to obtain salt-containing washing water and desalted sulfur, wherein the salt-containing washing water flows into a filtrate tank and is sent back to a desulfurization unit or a salt extraction device by a filtrate pump;
3) and (3) molten sulfur recovery: the desalted sulfur is heated and melted into liquid sulfur through a sulfur melting tank, the liquid sulfur flows to a liquid sulfur buffer tank, and is pressurized by a liquid sulfur pump and then is sent to a sulfur acid preparation device to be used as a raw material for preparing sulfuric acid.
A treatment process of low-quality sulfur as a byproduct of a coke oven gas desulfurization process is disclosed, wherein the device comprises a separation/washing device, a filtrate tank, a sulfur melting tank, a liquid sulfur buffer tank, a filtrate pump and a liquid sulfur pump, and is characterized in that the separation/washing device is provided with a sulfur foam inlet and a washing water inlet, and is also provided with a salt-containing filtrate outlet, a salt-containing washing water outlet and a desalted sulfur outlet which are connected with the filtrate tank, and is provided with a desalted sulfur outlet and a sulfur melting tank; the filtrate tank is connected with a filtrate pump; the sulfur melting tank is connected with the liquid sulfur buffer tank; and a liquid sulfur pump is arranged in the liquid sulfur buffer tank.
The separation/washing device is a plate-and-frame filter press or a combination of a centrifugal machine, a stirring tank and a sulfur slurry pump, wherein the plate-and-frame filter press is provided with a compressed air inlet; the centrifuge is two, and one centrifuge's entry is sulphur foam entry, contains the salt filtrating export and is connected with the filtrate groove, contains salt sulphur export and is connected with the stirred tank, and the stirred tank is equipped with the washing water entry and passes through the entry linkage of sulphur stuff pump with another centrifuge, and another centrifuge contains salt washing water export and is connected with the filtrate groove, and the sulphur export of desalination is connected with the sulphur melting tank.
Further, the separating/washing device can also be one or a combination of a plurality of rotary drum filters, microporous filters and leaf filters.
The washing water is one or a combination of more of desalted water, distilled water, steam condensate water and industrial fresh water.
Compared with the prior art, the invention has the beneficial effects that:
1) the problem that the low-quality sulfur as a byproduct of a sodium wet oxidation desulfurization process is difficult to treat can be effectively solved;
2) metal salts in low-quality sulfur can be effectively removed to be used as raw materials of a sulfur acid-making device, so that the sulfur resource is recycled, and the due economic value is generated;
3) effectively avoids the low-quality sulfur from becoming new coking solid waste and protects the environment.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention (example 1);
FIG. 2 is a schematic diagram of the process flow of the present invention (example 2).
In the figure: 1-separation/washing device 11-plate and frame filter press 12-centrifuge 13-stirring tank 14-sulfur pump 2-filtrate tank 3-sulfur melting tank 4-liquid sulfur buffer tank 5-filtrate pump 6-liquid sulfur pump
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
as shown in the figures 1 and 2, the treatment process of the byproduct low-quality sulfur of the coke oven gas desulfurization process comprises the following steps:
1) solid-liquid separation: the sulfur foam sent by the desulfurization unit is subjected to solid-liquid two-phase separation by a separation device 1 to obtain salt-containing filtrate (liquid phase) and salt-containing sulfur (solid phase), wherein the salt-containing filtrate flows into a filtrate tank 2 and is sent back to the desulfurization unit or a salt extraction device by a filtrate pump 5;
2) washing and desalting: washing the sulfur containing salt by a washing device 1 to obtain salt-containing washing water and desalted sulfur, wherein the salt-containing washing water flows into a filtrate tank 2 and is sent back to a desulfurization unit or a salt extraction device by a filtrate pump 5;
3) and (3) molten sulfur recovery: the desalted sulfur is heated and melted into liquid sulfur through a sulfur melting tank 3, the liquid sulfur flows to a liquid sulfur buffer tank 4, and the liquid sulfur is pressurized through a liquid sulfur pump 6 and then is sent to a sulfur acid preparation device to be used as a raw material for preparing sulfuric acid.
A treatment process of low-quality sulfur as a byproduct of a coke oven gas desulfurization process comprises a separation/washing device 1, a filtrate tank 2, a sulfur melting tank 3, a liquid sulfur buffer tank 4, a filtrate pump 5 and a liquid sulfur pump 6, wherein the separation/washing device 1 is provided with a sulfur foam inlet and a washing water inlet, and is also provided with a salt-containing filtrate outlet, a salt-containing washing water outlet connected with the filtrate tank 2, and a desalted sulfur outlet connected with the sulfur melting tank 3; the filtrate tank 2 is connected with a filtrate pump 5; the sulfur melting tank 3 is connected with the liquid sulfur buffer tank 4; and a liquid sulfur pump 6 is arranged in the liquid sulfur buffer tank 4.
The separation/washing device 1 is a combination of a plate and frame filter press 11 or a centrifuge 12, a stirring tank 13 and a slurry pump 14, wherein the plate and frame filter press 11 is provided with a compressed air inlet (see figure 1); the centrifuge 12 is two, and the entry of a centrifuge is sulphur foam entry, contains salt filtrating export and is connected with filtrate groove 2, contains salt sulphur export and is connected with stirred tank 3, and stirred tank 3 is equipped with the washing water entry and passes through sulphur stuff pump 14 and another centrifuge's entry linkage, and another centrifuge contains salt washing water export and is connected with filtrate groove 2, and the sulphur export of desalination is connected with sulphur melting tank 3 (see figure 2).
Further, the separation/washing device 1 can also be one or a combination of a plurality of rotary drum filters, microporous filters and leaf filters.
The washing water is one or a combination of more of desalted water, distilled water, steam condensate water and industrial fresh water.
[ example 1 ]
The separation/washing device 1 is a plate and frame filter press 11.
As shown in fig. 1, the sulfur foam sent from the desulfurization unit is sent to a plate-and-frame filter press 11 for filtration and separation, the salt-containing filtrate flowing out through the filter plate enters a filtrate tank 2, and is pressurized by a filtrate pump 5 and then sent back to the desulfurization unit or sent to a salt extraction device for salt extraction; the sulfur particles in the sulfur foam are squeezed and retained in each filter chamber, and salt-containing sulfur is automatically formed. And after the filtering and separating operation is finished, starting washing water, washing the sulfur containing salt, and dissolving metal salts in the washing water. And after the washing operation is finished, starting compressed air, drying the desalted sulfur, and reducing the water content to obtain the desalted sulfur dry cake. And after the drying operation is finished, loosening the compressed filter plate, unloading the desalted sulfur dry cakes, automatically unloading the desalted sulfur dry cakes to the sulfur melting tank 3 for sulfur melting operation, and melting the desalted sulfur dry cakes into liquid sulfur.
The liquid sulfur in the sulfur melting tank 3 flows to the liquid sulfur buffer tank 4 fully, is pressurized by the liquid sulfur pump 6 and then is sent to a sulfur acid-making device to be used as a raw material for preparing sulfuric acid.
[ example 2 ]
The separation/washing apparatus 1 is a combination of a centrifuge 12, an agitation tank 13 and a slurry pump 14.
As shown in FIG. 2, the sulfur foam from the desulfurization unit is sent to a centrifuge 12 for solid-liquid two-phase centrifugal separation to obtain a salt-containing filtrate and salt-containing sulfur. Salt-containing filtrate enters a filtrate tank 2, is pressurized by a filtrate pump 5 and then is sent back to a desulfurization unit or a salt extraction device; the sulfur containing salt is sent into the stirring tank 3 and is fully mixed with the added washing water under forced stirring. In the stirring tank 3, the sulfur containing salt and the washing water are fully and uniformly mixed to form a suspension solution, namely sulfur slurry, wherein metal salts are dissolved in the washing water. The sulfur slurry in the stirring tank 3 is pressurized by a sulfur slurry pump 14, and then sent to another centrifuge 12 for solid-liquid two-phase separation again, so that salt-containing washing water and desalted sulfur are obtained. The salt-containing washing water enters a filtrate tank 2; the desalted sulfur enters a sulfur melting tank 3 and is melted into liquid sulfur by heating.
The liquid sulfur in the sulfur melting tank 3 flows to the liquid sulfur buffer tank 4 fully, is pressurized by the liquid sulfur pump 6 and then is sent to a sulfur acid-making device to be used as a raw material for preparing sulfuric acid.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A treatment process of a low-quality sulfur byproduct in a coke oven gas desulfurization process comprises the following steps:
1) solid-liquid separation: separating sulfur foam sent by the desulfurization unit to obtain salt-containing filtrate (liquid phase) and salt-containing sulfur (solid phase), wherein the salt-containing filtrate flows into a filtrate tank and is sent back to the desulfurization unit or a salt extraction device by a filtrate pump;
2) washing and desalting: washing the salt-containing sulfur to obtain salt-containing washing water and desalted sulfur, wherein the salt-containing washing water flows into a filtrate tank and is sent back to a desulfurization unit or a salt extraction device by a filtrate pump;
3) and (3) molten sulfur recovery: the desalted sulfur is heated and melted into liquid sulfur through a sulfur melting tank, the liquid sulfur flows to a liquid sulfur buffer tank, and is pressurized by a liquid sulfur pump and then is sent to a sulfur acid preparation device to be used as a raw material for preparing sulfuric acid.
2. The device for realizing the treatment process of the byproduct low-quality sulfur in the coke oven gas desulfurization process of claim 1 comprises a separation/washing device, a filtrate tank, a sulfur melting tank, a liquid sulfur buffer tank, a filtrate pump and a liquid sulfur pump, and is characterized in that the separation/washing device is provided with a sulfur foam inlet and a washing water inlet, and is also provided with a salt-containing filtrate outlet, a salt-containing washing water outlet connected with the filtrate tank, and a desalted sulfur outlet connected with the sulfur melting tank; the filtrate tank is connected with a filtrate pump; the sulfur melting tank is connected with the liquid sulfur buffer tank; and a liquid sulfur pump is arranged in the liquid sulfur buffer tank.
3. The treatment process of the byproduct low-quality sulfur in the coke oven gas desulfurization process according to claim 1 or 2, characterized in that the separation/washing device is a plate-and-frame filter press or a combination of a centrifuge, a stirring tank and a sulfur slurry pump, wherein the plate-and-frame filter press is provided with a compressed air inlet; the centrifuge is two, and one centrifuge's entry is sulphur foam entry, contains the salt filtrating export and is connected with the filtrate groove, contains salt sulphur export and is connected with the stirred tank, and the stirred tank is equipped with the washing water entry and passes through the entry linkage of sulphur stuff pump with another centrifuge, and another centrifuge contains salt washing water export and is connected with the filtrate groove, and the sulphur export of desalination is connected with the sulphur melting tank.
4. The treatment process of the low-quality sulfur byproduct of the coke oven gas desulfurization process according to claim 1 or 2, wherein the separation/washing device can also be one or a combination of a rotary drum filter, a microporous filter and a leaf filter.
5. The treatment process of the low-quality sulfur byproduct of the coke oven gas desulfurization process according to claim 1 or 2, wherein the washing water is one or a combination of more of desalted water, distilled water, steam condensate water and industrial fresh water.
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| CN202011102846.8A CN112093778A (en) | 2020-10-15 | 2020-10-15 | Treatment process for by-product low-quality sulfur in coke oven gas desulfurization process |
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| CN202011102846.8A CN112093778A (en) | 2020-10-15 | 2020-10-15 | Treatment process for by-product low-quality sulfur in coke oven gas desulfurization process |
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Cited By (2)
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| CN112794291A (en) * | 2021-02-26 | 2021-05-14 | 中冶焦耐(大连)工程技术有限公司 | Pretreatment process and system for low-quality sulfur and secondary salt waste liquid produced by coke oven gas desulfurization |
| CN112794290A (en) * | 2021-02-26 | 2021-05-14 | 中冶焦耐(大连)工程技术有限公司 | Process and system for treating low-quality sulfur and secondary salt waste liquid produced by coke oven gas desulfurization |
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