CN104208992A - Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur - Google Patents
Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur Download PDFInfo
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- CN104208992A CN104208992A CN201410482673.5A CN201410482673A CN104208992A CN 104208992 A CN104208992 A CN 104208992A CN 201410482673 A CN201410482673 A CN 201410482673A CN 104208992 A CN104208992 A CN 104208992A
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Abstract
The invention discloses a method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur. The method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur sequentially comprises the following steps: introducing the acid gas into a combustion furnace to be mixed with air introduced by the other pipeline so as to carry out a combustion reaction; introducing the gas reacted in the combustion furnace into a cooler to be cooled to 230-250 DEG C, after cooling, separating the cooled liquid sulfur at a liquid outlet, introducing mixed gas in the combustion furnace into a catalyst reactor, enabling hydrogen sulfide to react with sulfur dioxide in the catalyst reactor so as to generate sulfur and water, and separating the generated liquid sulfur at the liquid outlet of the catalyst reactor; introducing the mixed gas in the catalyst reactor into a hydrogenation reactor and enabling the sulfur dioxide to react with hydrogen in the hydrogenation reactor; introducing the gas in the hydrogenation reactor into a hydrogen sulfide absorption device and preparing the hydrogen sulfide into elemental sulfur under the action of an alkaline solution, a complex catalyst and the introduced air. The method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur has the advantages of short process route, high quality of produced sulfur and low energy consumption, is capable of fully removing SO2 gas and is green and environmentally friendly.
Description
Technical field
The present invention relates to industrial waste gas processing technology field, especially a kind ofly desulfurization is carried out to the sour gas containing hydrogen sulfide and reclaims the method for sulphur.
Background technology
Along with China's rapid economic development, the Raw Material Demand amounts such as coal, oil, natural gas are constantly increased, due to China's oil and amount of natural gas less, major part depends on from external import.Along with national market demand strengthens, good quality raw material import difficulty is large, price competition excitation, and for reducing costs, the most sulfur content of import raw material is higher.For reaching subsequent clients and the market demand, must remove sulphur.Sulfur recovery technology was introduced and development through nearly 40 years at home, presented domestic free technology and international technology parallel development trend.1883, first British scientist Crouse proposed from H
2s gas Recovered sulphur process, through 100 years development, technology obtains significant improvement.According to statistics, 2000-2003, China Sulfur retracting device increases to 100 from 62 covers more and overlaps, and has again the large and medium-sized device of nearly 50 cover to go into operation to 2014.Though economical fast-developing, environmental pollution is in recent years serious, and particularly haze weather causes significant damage to environment, and SO
2comparatively large to haze weather " contribution ", SO in gas, in order to Environment control, discharges in country
2content will be reduced to 50mg/m in 2015
3below.SO in domestic present all sulfur recovery units
2discharge 95% is not up to standard.For many years, though sulfur recovery technology is through repeatedly changing and improving, and add vent gas treatment measure, but technological principle does not become, the technology of present use is many on improvement Crouse basis, developed in basic theory, technological process, catalyst preparation, device structure and material, automatic control schemes and the many-side such as chain and improved, but finally thoroughly not realized zero release of pollutant.It is " a kind of containing H that existing a kind of application number CN96102799.1 name is called
2extract the method for elemental sulfur in the mist of S " Chinese invention patent disclose a kind of from one containing H
2extract the method for elemental sulfur in the mist of S, wherein, first this mist is desulfurized and produces elemental sulfur simultaneously in a claus plant, and secondly, the sulphur compound still contained in Crouse's waste gas is transformed into H by hydrogenation
2s, next, Crouse's waste gas of hydrogenation carries out H
2the Direct Catalytic Oxidation of S also generates elemental sulfur.But this invention can not remove SO completely
2, gas purging, and H
2the absorption process energy consumption of S is comparatively large, therefore, is necessary to improve further the method.
Summary of the invention
Technical problem to be solved by this invention provides a kind of desulfurization can to reclaim sulphur and the complete removed desulfurization of sulfuration Hydrogen Energy in sour gas reclaim the method for sulphur for above-mentioned prior art present situation.
The present invention solves the problems of the technologies described above adopted technical scheme: this carries out desulfurization to the sour gas containing hydrogen sulfide and reclaims the method for sulphur, it is characterized in that: in turn include the following steps:
Step one, pass in combustion furnace by the sour gas containing hydrogen sulfide, mix with the air passing into combustion furnace from another pipeline and carry out combustion reaction, the admission pressure of the sour gas passed in described combustion furnace remains 20 ~ 100KPa; Reaction equation equation is: 2H
2s+O
2→ 2S ↓+2H
2o; 2H
2s+3O
2→ 2SO
2+ 2H
2o;
Step 2, in combustion furnace, reacted gas enters into cooler and is cooled to 230 ~ 250 DEG C, after cooling, liquid sulfur is isolated from liquid outlet, and the hydrogen sulfide gas of after-flame and the mist of the rear sulfur dioxide gas generated of burning do not enter hydrogen-catalyst reactor completely in combustion furnace, in hydrogen-catalyst reactor base catalyst effect under to make between hydrogen sulfide and sulfur dioxide reaction generate sulphur and water, the liquid sulfur generated is separated from the liquid outlet of hydrogen-catalyst reactor, and reaction equation is: 2H
2s+SO
2→ 3S ↓+2H
2o;
Step 3, by unreacted in hydrogen-catalyst reactor, hydrogen sulfide and sulfur dioxide mixture gas enter to pressure and remain in the hydrogenation reactor of 20 ~ 100KPa completely, in hydrogenation reactor, sulphur dioxide reduction is become hydrogen sulfide with H-H reaction by the sulfur dioxide of mist, and reaction equation is: SO
2+ 3H
2→ H
2s+2H
2o;
Step 4, by the hydrogen sulfide in hydrogenation reactor and sulfur dioxide by hydrogen reduction become the gas of hydrogen sulfide to enter into hydrogen sulfide absorption device that it is built-in with alkaline solution and complex compound catalyst, by hydrogen sulfide alkaline solution, complex compound catalyst and pass into air effect under generate elemental sulfur, reaction equation is:
·CO
3 2-+CO
2+H
2O→2HCO
3 -
·H
2S+OH
-→HS
-+H
2O
Fe
3+(complex state)+HS
-→ Fe
2+(complex state)+S+H
+
Net reaction is: Fe
3+(complex state)+H
2s+OH
-→ Fe
2+(complex state)+S ↓+H
2o
Namely complete desulfurization and reclaim sulphur step.
As improvement, the hydrogen sulfide absorption device in step 4 passes into air with interval, until no longer produce precipitation.
As further improvement, the time at every turn passing into air is 0.2 ~ 3 second.
As improvement, in the combustion furnace of step one, reacted gas enters into pressure is that the cooler of 20 ~ 100KPa is cooled to 230 ~ 250 DEG C.
As improvement, in step 3, by unreacted in hydrogen-catalyst reactor, hydrogen sulfide and sulfur dioxide mixture gas enter to pressure and remain in the hydrogenation reactor of 20 ~ 100KPa completely.
As improvement, the hydrogen sulfide absorption device interior reaction temperature in described step 4 remains on 50 ~ 60 DEG C.
As improvement, in described combustion furnace, the reaction temperature of gas combustion remains on 980 ~ 1370 DEG C, and the reaction time is 0.5 ~ 3 second.
As improvement, in described hydrogen-catalyst reactor, reaction temperature remains 265 ~ 275 DEG C, and the reaction time is 3 ~ 10 seconds.
As improvement, the liquid sulfur that described combustion furnace and hydrogen-catalyst reactor reaction generate is collected in sulphur pond respectively by pipeline is unified, and the liquid sulfur in described sulphur pond is delivered to sulfur granulator by sulfur pump and produces solid sulfur.
As improvement, described catalyst is complex compound catalyst, and described base catalyst is Al
2o
3, described alkaline solution is Na
2cO
3solution.
Compared with prior art, of the present inventionly desulfurization is carried out to the sour gas containing hydrogen sulfide and the method tool reclaiming sulphur has the following advantages: process route is short, and device therefor manufacture processing is simple, production domesticization can be realized completely, good catalyst activity, produce sulphur quality better, energy consumption is low, and it is convenient to control.After this technique desulfurization operations, more than 95% H in gas
2s is converted into elemental sulfur, SO in residual gas
2be converted into H completely
2s, the gas going out the 3rd reactor contains a small amount of H
2s, by hydrogen sulfide absorption device, absorbs most H
2s, makes H
2s gas is at O
2be converted into elemental sulfur with under catalyst action, gas reaches and removes H
2s object, H in final gas
2s content is less than 1ppM, SO
2content is zero.Catalyst adopts the complex compound of variable valency metal iron, and be the composite complex system of two kinds of metallic irons, for stable performance during sulphur-containing solution, desulfuration efficiency is high, and power of regeneration is strong, and effective Sulfur capacity can reach 0.60g/L (with H
2s content≤1500mg/Nm
3calculate) more than, H after desulfurization
2s content can reach 5mg/Nm
3below, and be furnished with several functions auxiliary agent in catalyst, the stability of catalyst can be improved, reduce degradation rate, improve the surface property of sulphur particle, make sulphur particle growth, measuring most of sulfur granules particle diameter through material institute of Chinese Academy of Sciences laser granulometry is 11 μm, sulphur foaming abundancy is stablized, and is easy to remove; Regenerative response is complete, forms binary catalyst oxidation system, accelerates regenerative response speed, to improve after absorbing HS-oxidation rate in solution, makes to leave HS in the solution of hydrogen sulfide absorption device
-concentration drops to minimum; Containing ionic surfactant material in solution, can reduce the surface tension of solution, make the relative enrichment of simple substance sulphur, be very easy to separate out from sulphur liquid, content of suspension sulfur is low, not easily accumulated plugging.Hydrogen sulfide absorption unit temp remains on 50 ~ 60 DEG C, and when temperature is 50-60 DEG C, solution is to CO
2uptake little, be conducive to H
2s removes.High temperature absorbs can accelerate HCO3
-desorb, generate CO3
2-, stabilizing solution acid-base value, reduces alkaline consumption.
Accompanying drawing explanation
Fig. 1 is the structural representation applying device of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
As shown in Figure 1, of the present inventionly desulfurization carried out to the sour gas containing hydrogen sulfide and reclaim the method for sulphur, in turn including the following steps:
Step one, pass in combustion furnace 1 by the sour gas containing hydrogen sulfide, mix with the air passing into combustion furnace 1 from another pipeline and carry out combustion reaction, the admission pressure of the sour gas passed in described combustion furnace 1 remains 20 ~ 100KPa; Reaction equation equation is: 2H
2s+O
2→ 2S ↓+2H
2o; 2H
2s+3O
2→ 2SO
2+ 2H
2o;
Step 2, in combustion furnace 1, reacted gas enters into cooler 2 and is cooled to 230 ~ 250 DEG C, after cooling, liquid sulfur is isolated from liquid outlet, and the hydrogen sulfide gas of after-flame and the mist of the rear sulfur dioxide gas generated of burning do not enter hydrogen-catalyst reactor 3 completely in combustion furnace 1, in hydrogen-catalyst reactor 3 base catalyst effect under to make between hydrogen sulfide and sulfur dioxide reaction generate sulphur and water, the liquid sulfur generated is separated from the liquid outlet of hydrogen-catalyst reactor 3, and reaction equation is: 2H
2s+SO
2→ 3S ↓+2H
2o;
Step 3, by unreacted in hydrogen-catalyst reactor 3, hydrogen sulfide and sulfur dioxide mixture gas enter to pressure and remain in the hydrogenation reactor 4 of 20 ~ 100KPa completely, in hydrogenation reactor 4, sulphur dioxide reduction is become hydrogen sulfide with H-H reaction by the sulfur dioxide of mist, and reaction equation is: SO
2+ 3H
2→ H
2s+2H
2o;
Step 4, by the hydrogen sulfide in hydrogenation reactor 4 and sulfur dioxide by hydrogen reduction become the gas of hydrogen sulfide to enter into hydrogen sulfide absorption device 5 that it is built-in with alkaline solution and complex compound catalyst, by hydrogen sulfide alkaline solution, complex compound catalyst and pass into air effect under generate elemental sulfur, reaction equation is:
·CO
3 2-+CO
2+H
2O→2HCO
3 -
·H
2S+OH
-→HS
-+H
2O
Fe
3+complex state+HS
-→ Fe
2+complex state+S+H
+
Net reaction is: Fe
3+complex state+H
2s+OH
-→ Fe
2+complex state+S ↓+H
2o
Namely complete desulfurization and reclaim sulphur step.
Hydrogen sulfide absorption device 5 in step 4 passes into air with interval, until no longer produce precipitation.The time at every turn passing into air is 0.2 ~ 3 second.In the combustion furnace 1 of step one, reacted gas enters into pressure is that the cooler 2 of 20 ~ 100KPa is cooled to 230 ~ 250 DEG C.In step 3, by unreacted in hydrogen-catalyst reactor 3, hydrogen sulfide and sulfur dioxide mixture gas enter to pressure and remain in the hydrogenation reactor 4 of 20 ~ 100KPa completely.Hydrogen sulfide absorption device 5 interior reaction temperature in described step 4 remains on 50 ~ 60 DEG C.In described combustion furnace 1, the reaction temperature of gas combustion remains on 980 ~ 1370 DEG C, and the reaction time is 0.5 ~ 3 second.In described hydrogen-catalyst reactor 3, reaction temperature remains 265 ~ 275 DEG C, and the reaction time is 3 ~ 10 seconds.Described combustion furnace 1 and hydrogen-catalyst reactor 3 react the liquid sulfur generated and collect in sulphur pond 6 respectively by pipeline is unified, and the liquid sulfur in described sulphur pond 6 is delivered to sulfur granulator by sulfur pump and produces solid sulfur.Described catalyst is complex compound catalyst, and described base catalyst is Al
2o
3, described alkaline solution is Na
2cO
3solution.
Claims (10)
1. desulfurization carried out to the sour gas containing hydrogen sulfide and reclaim a method for sulphur, it is characterized in that: in turn include the following steps:
Step one, the sour gas containing hydrogen sulfide is passed in combustion furnace (1), mix with the air passing into combustion furnace (1) from another pipeline and carry out combustion reaction, the admission pressure of the sour gas passed in described combustion furnace (1) remains 20 ~ 100KPa; Reaction equation equation is: 2H
2s+O
2→ 2S ↓+2H
2o; 2H
2s+3O
2→ 2SO
2+ 2H
2o;
Step 2, in combustion furnace (1), reacted gas enters into cooler (2) and is cooled to 230 ~ 250 DEG C, after cooling, liquid sulfur is isolated from liquid outlet, and the hydrogen sulfide gas of after-flame and the mist of the rear sulfur dioxide gas generated of burning do not enter hydrogen-catalyst reactor (3) completely in combustion furnace (1), under the effect of the middle base catalyst of hydrogen-catalyst reactor (3), make reaction between hydrogen sulfide and sulfur dioxide generate sulphur and water, the liquid sulfur generated is separated from the liquid outlet of hydrogen-catalyst reactor (3), and reaction equation is: 2H
2s+SO
2→ 3S ↓+2H
2o;
Step 3, by unreacted in hydrogen-catalyst reactor (3), hydrogen sulfide and sulfur dioxide mixture gas enter to pressure and remain in the hydrogenation reactor (4) of 20 ~ 100KPa completely, in the hydrogenation reactor (4) mist sulfur dioxide and H-H reaction and sulphur dioxide reduction is become hydrogen sulfide, reaction equation is: SO
2+ 3H
2→ H
2s+2H
2o;
Step 4, by the hydrogen sulfide in hydrogenation reactor (4) and sulfur dioxide by hydrogen reduction become the gas of hydrogen sulfide to enter into hydrogen sulfide absorption device (5) that it is built-in with alkaline solution and complex compound catalyst, by hydrogen sulfide alkaline solution, complex compound catalyst and pass into air effect under generate elemental sulfur, reaction equation is:
·CO
3 2-+CO
2+H
2O→2HCO
3 -
·H
2S+OH
-→HS
-+H
2O
Fe
3+(complex state)+HS
-→ Fe
2+(complex state)+S+H
+
Net reaction is: Fe
3+(complex state)+H
2s+OH
-→ Fe
2+(complex state)+S ↓+H
2o
Namely complete desulfurization and reclaim sulphur step.
2. method according to claim 1, is characterized in that: the hydrogen sulfide absorption device (5) in step 4 passes into air, with interval until no longer produce precipitation.
3. method according to claim 2, is characterized in that: the time at every turn passing into air is 0.2 ~ 3 second.
4., according to described method arbitrary in claims 1 to 3, it is characterized in that: in the combustion furnace (1) of step one, reacted gas enters into the cooler (2) that pressure is 20 ~ 100KPa and is cooled to 230 ~ 250 DEG C.
5. according to described method arbitrary in claims 1 to 3, it is characterized in that: in step 3, by unreacted in hydrogen-catalyst reactor (3), hydrogen sulfide and sulfur dioxide mixture gas enter to pressure and remain in the hydrogenation reactor (4) of 20 ~ 100KPa completely.
6., according to described method arbitrary in claims 1 to 3, it is characterized in that: hydrogen sulfide absorption device (5) interior reaction temperature in described step 4 remains on 50 ~ 60 DEG C.
7., according to described method arbitrary in claims 1 to 3, it is characterized in that: in described combustion furnace (1), the reaction temperature of gas combustion remains on 980 ~ 1370 DEG C, and the reaction time is 0.5 ~ 3 second.
8., according to described method arbitrary in claims 1 to 3, it is characterized in that: in described hydrogen-catalyst reactor (3), reaction temperature remains 265 ~ 275 DEG C, and the reaction time is 3 ~ 10 seconds.
9. according to described method arbitrary in claims 1 to 3; it is characterized in that: the liquid sulfur that described combustion furnace (1) and hydrogen-catalyst reactor (3) reaction generate is collected in sulphur pond (6) respectively by pipeline is unified, and the liquid sulfur in described sulphur pond (6) is delivered to sulfur granulator by sulfur pump and produces solid sulfur.
10., according to described method arbitrary in claims 1 to 3, it is characterized in that: described catalyst is complex compound catalyst, described base catalyst is Al
2o
3, described alkaline solution is Na
2cO
3solution.
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| US10357741B2 (en) | 2017-09-07 | 2019-07-23 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US10369517B2 (en) | 2017-09-07 | 2019-08-06 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US10449488B2 (en) | 2017-09-07 | 2019-10-22 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US11027234B2 (en) | 2018-04-13 | 2021-06-08 | Jiangnan Environmental Protection Group Inc. | Oxidization of ammonia desulfurization solution |
| US10953365B2 (en) | 2018-07-20 | 2021-03-23 | Jiangnan Environmental Protection Group Inc. | Acid gas treatment |
| US11529584B2 (en) | 2018-07-20 | 2022-12-20 | Jiangnan Environmental Protection Group Inc. | Acid gas treatment |
| US11224838B2 (en) | 2019-12-26 | 2022-01-18 | Jiangnan Environmental Protection Group Inc. | Controlling aerosol production during absorption in ammonia-based desulfurization |
| CN112516765A (en) * | 2020-11-12 | 2021-03-19 | 衡阳丰联精细化工有限公司 | Sulfur dioxide gas mixture purifier containing hydrogen sulfide |
| CN114920386A (en) * | 2022-05-17 | 2022-08-19 | 四川省银河化学股份有限公司 | Method for desulfurizing hot spring water and co-producing sulfur soap |
| CN114920386B (en) * | 2022-05-17 | 2023-04-07 | 四川省银河化学股份有限公司 | Method for desulfurizing hot spring water and co-producing sulfur soap |
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