CN103112831B - Liquid sulphur degassing device and liquid sulphur degassing method - Google Patents
Liquid sulphur degassing device and liquid sulphur degassing method Download PDFInfo
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- CN103112831B CN103112831B CN201310060097.0A CN201310060097A CN103112831B CN 103112831 B CN103112831 B CN 103112831B CN 201310060097 A CN201310060097 A CN 201310060097A CN 103112831 B CN103112831 B CN 103112831B
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Abstract
The invention relates to a liquid sulphur degassing device and a liquid sulphur degassing method. The liquid sulphur degassing device comprises a liquid sulphur tank communicated with a liquid sulphur pipeline, wherein the liquid sulphur tank is internally provided with gas stripping equipment which can strip hydrogen sulphide gas in liquid sulphur, and the upper part of the liquid sulphur tank is provided with gas pumping equipment which can pump the hydrogen sulphide gas with other gases in the liquid sulphur tank out of the liquid sulphur tank; and the liquid sulphur degassing device is characterized in that the liquid sulphur tank comprises a gas stripping tank and a finished product tank, wherein an overflow dam is arranged between the gas stripping tank and the finished product tank; the liquid sulphur pipeline is communicated with the gas stripping tank; the suction inlet of the liquid sulphur pump is connected with the bottom of the finished product tank; the outlet of the gas pumping equipment is connected with the material inlet of an absorption tower; and the top of the absorption tower is provided with a waste gas outlet, the upper part of the absorption tower is provided with an absorption liquid inlet, a liquid outlet arranged at the bottom of the absorption tower is connected with a main pipeline, and the main pipeline is provided with a pressure pump which pumps out, pressurizes and conveys the liquid in the absorption tower. The liquid sulphur degassing device provided by the invention is simple in process, low in equipment investment and good in degassing effect.
Description
Technical field
The present invention relates to sulphur recovery field, specifically refer to a kind of liquid sulfur degassing device and method of recyclable sulphur.
Background technology
The general H containing 300ppm in the molten sulfur that sulfur recovery facility is produced
2s, if dispatch from the factory with molten sulfur form, H in course of conveying
2s easily causes knot poly-, as H in air
2s content reaches 3.4% and namely reaches H
2the limits of explosion of S, and steel container itself is containing holding ignitable material FeS, has at this moment possessed the condition of blasting, has thus had potential safety hazard; If dispatch from the factory with solid sulphur form, then in moulding process, along with the reduction of temperature, H
2s will overflow, contaminate environment, the H do not overflowed
2s remains in solid sulfur, in user's use procedure, will cause secondary pollution.Thus no matter sulphur is dispatch from the factory with solid-state or liquid form, must by the H in molten sulfur
2s removes.
Current molten sulfur degasification method mainly contains: molten sulfur circulating degasification, low-pressure air bubbling are degassed, high-pressure air bubbling is degassed, molten sulfur stirring+additive etc.
Wherein, the technological process of molten sulfur circulating degasification is: smoke the molten sulfur in sulphur pond with pump, returns to sulphur pond again by pipeline, so constantly circulation, until the H in molten sulfur
2s is taken off to meeting the requirements, the H released in degasification process
2s is evacuated to tail gas burning furnace with the injected system of sulphur pool gas and burns.The method is simple, but sweetening effectiveness is not ideal, does not reach the requirement being less than 10ppm (w), and the method desulfurization, do not reclaim sulphur.
The degassed technological process of air bubbling is: air is injected continuously two bubblers be arranged in sulphur pond, play air lift H
2the effect of S.Containing H in degassed rear molten sulfur
2s amount≤10ppm, the H released in degasification process
2s is evacuated to sulfur reclaimer tail gas incinerator with the injected system of sulphur pool gas and burns.The method flow process is comparatively simple, H in molten sulfur
2s can be less than the requirement of 10ppm (w), but de-rear gas does not reclaim sulphur.
The degassed technological process of high-pressure air bubbling is: its with liquid sulfur pump the molten sulfur pressurization in molten sulfur pond, molten sulfur enters in thionizer again after cooling, this thionizer bottom passes into pressurized air, and thionizer is built with catalyzer or filler, and from thionizer top, tail gas out enters roasting kiln and reclaims sulphur.H in the molten sulfur of the method
2s can be less than the requirement of 10ppm (w), and after de-, tail gas can reclaim sulphur, but flow process is complicated, investment large, operation easier is large, and the tail gas burning furnace that the tail gas in molten sulfur pond also needs injected system to be evacuated to sulfur recovery facility burns.
Molten sulfur stirring+additive method technique is simple, but quality product is by the impact of additive, and site work environment is poor, and equipment failure is many, and also add the consumption of additive.
Summary of the invention
Technical problem to be solved by this invention is the liquid sulfur degassing device providing that a kind of technique is simple, facility investment is low for the present situation of prior art and can reclaim sulphur.
Another technical problem to be solved by this invention is to provide that a kind of technique is simple, facility investment is low and can reclaims the liquid stream degas method of sulphur.
The present invention solves the problems of the technologies described above adopted technical scheme: this liquid sulfur degassing device, comprise the molten sulfur pond be connected with molten sulfur pipeline, the air lift equipment that stink damp in molten sulfur can be put forward is provided with in this molten sulfur pond, the top in described molten sulfur pond is provided with the extraction equipment that hydrogen sulfide air lift gone out extracts described molten sulfur pond out together with other gas in molten sulfur pond, it is characterized in that: described molten sulfur pond comprises air lift pond and end product pool, be provided with between described air lift pond and end product pool for limit molten sulfur in described air lift pond to enter in described end product pool and height lower than the overfall dike of described air lift pond height, the described air lift pond described in molten sulfur pipeline communication, and the outlet of molten sulfur pipeline is positioned at the bottom position of described gas cell, molten sulfur pump intake for being extracted out by the finished product molten sulfur in end product pool connects the bottom of described end product pool,
The outlet of described extraction equipment connects the material inlet on absorption tower; The top on described absorption tower is provided with outlet port, the top on described absorption tower is provided with absorption liquid entrance, the liquid exit be arranged on bottom described absorption tower connects main pipeline, and described main pipeline is provided with to be extracted out liquid in described absorption tower and the force (forcing) pump of positive delivery; The outlet of described main pipeline is divided into the first lateral and the second lateral, wherein the first lateral connects regeneration of absorption solution system, second lateral connects the absorption liquid entrance on described absorption tower, further, described second lateral is provided with the interchanger for cooling the liquid extracted out in described absorption tower.
Because in air lift process, the speed of bubbling is larger, therefore a small amount of sulphur in molten sulfur also can with hydrogen sulfide by air lift out, in order to can this part sulphur of efficient recovery, the structure of preferred version to absorption tower of the application have also been made special design, top, described absorption tower is tower plate structure, for washing the hydrogen sulfide in mixed gas, the bottom on described absorption tower is vacant, and is provided with filtration unit in bottom, described absorption tower near liquid exit position; For increasing the residence time of the absorption liquid dissolving hydrogen sulfide in absorption tower, get off with the sulfur deposition making a small amount of air lift go out, and the length ratio of described top and described bottom is 1:2; Described material inlet is arranged on 1/3 At The Height on described absorption tower.
The height of described overfall dike needs to determine according to the residence time of molten sulfur in air lift pond, and preferably, the height of described overfall dike is 2-2.5 rice.
In such scheme, described air lift equipment can be bubbler, and described extraction equipment can be steam injector.
Can settle down as soon as possible in air lift pond to make the sulphur in molten sulfur, the bottom surface in described air lift pond is downward-sloping by side, end product pool direction described in lateral, like this, the solid sulfur settled down in molten sulfur can be assembled along the bottom surface in air lift pond to lower, to reduce the amount proposed with stink damp.
Use above-mentioned liquid sulfur degassing device to carry out the method for molten sulfur degasification, it is characterized in that comprising the steps:
Molten sulfur enters described air lift pond with certain speed from molten sulfur pipeline, under the effect of air lift equipment, air injects the molten sulfur in air lift pond continuously, the weight rate of molten sulfur is 10 ~ 15:1 with the ratio of the injection weight rate of air, controlling the residence time of molten sulfur in described gas cell is 8-12 hour, and air lift goes out the hydrogen sulfide in molten sulfur; The hydrogen sulfide that air lift goes out by described extraction equipment is extracted out and is pressurizeed from material inlet and enters in described absorption tower together with the mixed gas of other gas in molten sulfur pond, and the pressure that control mixed gas enters described absorption tower is 0.005 ~ 0.010MPa (G);
The mixed gas entering described absorption tower is up, with enter absorption liquid descending in absorption tower from described absorption liquid entrance and meet, hydrogen sulfide in mixed gas is dissolved in described absorption liquid, is extracted out together with absorption liquid from the bottom on absorption tower by described force (forcing) pump; The temperature controlling the absorption liquid entered in described absorption tower is 40 ~ 45 DEG C, and the weight ratio of described mixed gas and described absorption liquid is 1:6 ~ 10; Described absorption liquid adopts reproducible basic solvent;
Obtaining temperature at the top on absorption tower is 45 ~ 50 DEG C, H
2gas after the desulfurization of S content≤10ppm, by chimney high altitude discharge after this portion gas feeding incineration system burns; Two-way is divided into after the absorption liquid having dissolved hydrogen sulfide extracted out through described force (forcing) pump enters main pipeline, wherein the first via sends into regeneration of absorption solution system through the first branch line, and the top that the second tunnel returns to absorption tower from the second branch line after described interchanger cooling enters from top, described absorption tower together with fresh absorption liquid; The weight of described fresh absorption liquid is 0.2 ~ 0.5 times of described mixed gas weight.
The conveniently recycling of absorption liquid, preferably, described absorption liquid can select mass concentration to be the ammoniacal liquor of 2-6% or mass concentration to be the amine liquid of 20-40%.
Compared with prior art; the present invention reclaims air lift hydrogen sulfide out from molten sulfur by arranging absorption tower; make the chilling of air lift hydrogen sulfide mixed gas out and be absorbed in same equipment to complete; such facility investment is low; technique is simple; production efficiency is high; and the yield of sulphur can be improved; and can significantly reduce the emission concentration of smoke stack emission sulfur dioxide in flue gas and be conducive to environment protection; adopt the basic solvent of regeneration simultaneously; after regenerating unit regeneration, make the basic solvent after regenerating drop into again in absorption tower on the one hand, what receive on the other hand contains H
2s gas can send sulfur recovery facility back to as acid material, thus can reduce the outer row of sulfide further, improves sulfur recovery rate.Especially the present invention is applied in the molten sulfur that gas volume is little, temperature is high, concentration of hydrogen sulfide is high, and above-mentioned advantage is then more obvious.
Accompanying drawing explanation
Fig. 1 is the two dimensional structure schematic diagram of the embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
This liquid sulfur degassing device comprises:
Molten sulfur pipeline 1, for carrying pending molten sulfur, its one end connects the molten sulfur outlet end of sulfur recovery facility, and the other end inserts in air lift pond 21 bottom making 1 its outlet near air lift pond 21.
Molten sulfur pond 2, comprises air lift pond 21 and end product pool 22.The degree of depth in the air lift pond 21 in the present embodiment is less than the degree of depth of end product pool 22, and the bottom surface in air lift pond 21 is incline structure, namely downward-sloping by lateral end product pool 22 direction in air lift pond 21, to facilitate the deposition of solid-state sulphur in molten sulfur.Be provided with overfall dike 23 between air lift pond 21 and end product pool 22, in the present embodiment, the height of overfall dike 23 is 2.5 meters.Be provided with bubbler 3 in air lift pond, bubbler can according to the size of power and use need arrange multiple, be generally 2 ~ 3; The bleeding point of steam injector 4 is arranged on the top in air lift pond 21, and the suction port of liquid sulfur pump 5 is arranged on the bottom of end product pool 22.
The material inlet on the connection absorption tower, air outlet 6 of steam injector 4.In the present embodiment, absorption tower is divided into upper and lower two portions, and the top on absorption tower accounts for 2/3 of absorption tower total height, and material inlet is positioned at 1/3 place of absorption tower height, namely between bottom and top.The top on absorption tower is provided with pneumatic outlet, and the top on absorption tower is provided with absorption liquid entrance, and the bottom on absorption tower is provided with liquid exit.Top, absorption tower is conventional tower plate structure; The bottom on absorption tower is vacant, and is provided with the filtering net (not shown) for filter solid sulphur in the position near liquid exit.Liquid exit connects main pipeline 61, force (forcing) pump 7 is arranged on main pipeline 61, the outlet of main pipeline 61 is divided into the first lateral 62 and the second lateral 63, wherein the first lateral 62 connects regeneration of absorption solution system (not shown), second lateral 63 connects absorption liquid entrance, further, the second lateral is provided with interchanger 64.
The sulfur recovery facility of supporting for above-mentioned liquid sulfur degassing device 60,000 tons/year of scales is used.
Be that the molten sulfur of 300ppm (W) enters air lift pond 21 with the speed of 12 tons/hour from molten sulfur pipeline by concentration of hydrogen sulfide, under the effect of bubbler 3, air injects the molten sulfur in air lift pond continuously with the speed of 1000 kgs/hour, the residence time of molten sulfur in air lift pond is 10 hours, and air lift goes out the hydrogen sulfide in molten sulfur.The hydrogen sulfide that air lift goes out is extracted out together with other gas in molten sulfur pond, enters in absorption tower 6 after steam injector 4 pressurizes from material inlet, controls that the pressure that mixed gas enters absorption tower is 0.005 ~ 0.010MPa, temperature is 110 ~ 120 DEG C.Temperature is that the absorption liquid of 40 ~ 45 DEG C enters absorption tower 6 from absorption liquid entrance.The weight ratio controlling mixed gas and absorption liquid is 1:8; Absorption liquid in the present embodiment adopts mass concentration to be the ammonia solution of 5%.
The mixed gas entered in absorption tower 6 is up, meets with descending absorption liquid, and the hydrogen sulfide in mixed gas is dissolved in absorption liquid.Dissolved the bottom of absorption liquid through absorption tower of hydrogen sulfide, wherein a small amount of sulfur deposition gets off, and net filtration is out after filtration.The pressurized pump 7 of absorption liquid being stripped of sulphur is extracted out from the liquid exit bottom absorption tower.Obtaining temperature at the top on absorption tower is 45 ~ 50 DEG C, H
2gas after the desulfurization of S content≤10ppm, this portion gas sends into incineration system burning, by chimney high altitude discharge after the pneumatic outlet at top, absorption tower is discharged.
The absorption liquid having dissolved hydrogen sulfide extracted out bottom absorption tower through force (forcing) pump 7 is divided into two-way after main pipeline 61, wherein the first via sends into regeneration of absorption solution system (not shown) through the first branch line 62, second tunnel enters in absorption tower 6 from absorption liquid entrance after interchanger 64 is cooled to 40 ~ 45 DEG C together with fresh absorption liquid, continues mixed gas up in washing absorption tower.The flow of fresh absorption liquid is 0.3 times of the mixed gas flow entered in absorption tower, and that is, the absorption liquid of sent for regeneration system is 0.3 times of mixed gas flow.
After above-mentioned molten sulfur degasification process, in finished product molten sulfur, the concentration of hydrogen sulfide is less than or equal to 10ppm (W), removes 17.4 tons/year, hydrogen sulfide year.If adopt former low-pressure air bubbling degasification technique, the gas removed directly enters incinerator and burns, and add the sulfur dioxide emissions of 34.8 tons/year, device aiutage sulfur dioxide emissioning concentration adds 155mg/nm
3.The present embodiment then can reclaim the sulphur of 17.4 tons/year more, and aiutage sulfur dioxide emissioning concentration is by 465mg/nm
3be down to 310mg/nm
3, quantity discharged declines greatly, reaches the bumper harvests of economic benefit and social benefit simultaneously.
Claims (4)
1. a molten sulfur degasification method, comprise the molten sulfur pond be connected with molten sulfur pipeline, the air lift equipment that stink damp in molten sulfur can be put forward is provided with in this molten sulfur pond, the top in described molten sulfur pond is provided with the extraction equipment that hydrogen sulfide air lift gone out extracts described molten sulfur pond out together with other gas in molten sulfur pond, it is characterized in that: described molten sulfur pond comprises air lift pond and end product pool, be provided with between described air lift pond and end product pool for limit molten sulfur in described air lift pond to enter in described end product pool and height lower than the overfall dike of described air lift pond height; The described air lift pond described in molten sulfur pipeline communication, and the outlet of molten sulfur pipeline is positioned at the bottom position of described gas cell; Molten sulfur pump intake for being extracted out by the finished product molten sulfur in end product pool connects the bottom of described end product pool;
The outlet of described extraction equipment connects the material inlet on absorption tower; The top on described absorption tower is provided with outlet port, the top on described absorption tower is provided with absorption liquid entrance, the liquid exit be arranged on bottom described absorption tower connects main pipeline, and described main pipeline is provided with to be extracted out liquid in described absorption tower and the force (forcing) pump of positive delivery; The outlet of described main pipeline is divided into the first lateral and the second lateral, wherein the first lateral connects regeneration of absorption solution system, second lateral connects the absorption liquid entrance on described absorption tower, further, described second lateral is provided with the interchanger for cooling the liquid extracted out in described absorption tower;
Top, described absorption tower is tower plate structure, and the bottom on described absorption tower is vacant, and, and be provided with the filtration unit for filtering sulphur near liquid exit position in bottom, described absorption tower; The length ratio of described top and described bottom is 1:2; Described material inlet is arranged on 1/3 At The Height on described absorption tower;
The bottom surface in described air lift pond is downward-sloping by side, end product pool direction described in lateral;
Molten sulfur degasification method comprises the steps:
Molten sulfur enters described air lift pond with certain speed from molten sulfur pipeline, under the effect of air lift equipment, air injects the molten sulfur in air lift pond continuously, the weight rate of molten sulfur is 10 ~ 15:1 with the ratio of the injection weight rate of air, controlling the residence time of molten sulfur in described gas cell is 8-12 hour, and air lift goes out the hydrogen sulfide in molten sulfur; The hydrogen sulfide that air lift goes out by described extraction equipment is extracted out and is pressurizeed from material inlet and enters in described absorption tower together with the mixed gas of other gas in molten sulfur pond, and the pressure that control mixed gas enters described absorption tower is 0.005 ~ 0.010MPa;
The mixed gas entering described absorption tower is up, with enter absorption liquid descending in absorption tower from described absorption liquid entrance and meet, hydrogen sulfide in mixed gas is dissolved in described absorption liquid, is extracted out together with absorption liquid from the bottom on absorption tower by described force (forcing) pump; The temperature controlling the absorption liquid entered in described absorption tower is 40 ~ 45 DEG C, and the weight ratio of described mixed gas and described absorption liquid is 1:6 ~ 10; Described absorption liquid adopts reproducible basic solvent;
Obtaining temperature at the top on absorption tower is 45 ~ 50 DEG C, H
2gas after the desulfurization of S content≤10ppm, by chimney high altitude discharge after this portion gas feeding incineration system burns; Two-way is divided into after the absorption liquid having dissolved hydrogen sulfide extracted out through described force (forcing) pump enters main pipeline, wherein the first via sends into regeneration of absorption solution system through the first branch line, and the top that the second tunnel returns to absorption tower from the second branch line after described interchanger cooling enters from top, described absorption tower together with fresh absorption liquid; The weight of described fresh absorption liquid is 0.2 ~ 0.5 times of described mixed gas weight.
2. molten sulfur degasification method according to claim 1, is characterized in that the height of described overfall dike is 2-2.5 rice.
3. molten sulfur degasification method according to claim 2, it is characterized in that described air lift equipment is bubbler, described extraction equipment is steam injector.
4. molten sulfur degasification method according to claim 1, is characterized in that described absorption liquid to be mass concentration is that the ammoniacal liquor of 2-6% or mass concentration are the amine liquid of 20-40%.
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| US5080695A (en) * | 1990-10-12 | 1992-01-14 | Marathon Oil Company | Method of removing hydrogen sulfide from liquid sulfur |
| CN101274196B (en) * | 2007-12-11 | 2010-12-08 | 镇海石化工程有限责任公司 | Desulphurization method of amine liquid with high removal rate of hydrogen sulfide |
| CN102381685A (en) * | 2010-08-25 | 2012-03-21 | 中国石油化工股份有限公司 | Degassing technique for liquid sulfur |
| CN102923671B (en) * | 2012-10-19 | 2014-08-20 | 中国石油化工股份有限公司 | Novel liquid sulfur degassing and storing equipment and liquid sulfur degassing method |
| CN203159222U (en) * | 2013-02-26 | 2013-08-28 | 镇海石化工程股份有限公司 | Liquid sulfur degassing device |
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| US10207220B2 (en) | 2017-03-15 | 2019-02-19 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
| US10016721B1 (en) | 2017-05-25 | 2018-07-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desufurization process and apparatus |
| US10092877B1 (en) | 2017-05-25 | 2018-10-09 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10213739B2 (en) | 2017-05-25 | 2019-02-26 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10099170B1 (en) | 2017-06-14 | 2018-10-16 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US10159929B1 (en) | 2017-06-14 | 2018-12-25 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US20190001267A1 (en) | 2017-07-03 | 2019-01-03 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10112145B1 (en) | 2017-09-07 | 2018-10-30 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
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