CN105314606A - Liquid sulfur degassing technology - Google Patents
Liquid sulfur degassing technology Download PDFInfo
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- CN105314606A CN105314606A CN201410247976.9A CN201410247976A CN105314606A CN 105314606 A CN105314606 A CN 105314606A CN 201410247976 A CN201410247976 A CN 201410247976A CN 105314606 A CN105314606 A CN 105314606A
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Abstract
The invention belongs to the technical field of sulphur recovery and relates to a liquid sulfur degassing technology. Air is used as a gas source, liquid sulfur separated exhaust gas is injected into a condenser by a steam injector, a temperature of a last-stage sulfur condenser is controlled in a range of 127-135 DEG C, and sulfur steam is further condensed and recovered. The liquid sulfur separated exhaust gas and third-stage reactor tail gas are mixed and then are fed into a forth-stage condenser and the sulfur steam is recovered, or the mixed gas and forth-stage reactor tail gas are mixed and then are fed into a fifth-stage condenser and the sulfur steam is recovered, or the mixed gas simultaneously enters into the forth-stage condenser and the fifth-stage condenser so that the sulfur steam is recovered. The treated process gas is introduced into a tail gas incinerator, is burned and then is discharged so that a flue gas SO2 emission concentration of a sulphur recovery device is reduced by 100-300g/m<3>. The liquid sulfur degassing technology has the characteristics of simple structure, low investment and good feasibility.
Description
Technical field
The invention belongs to technical field of sulfur recovery, be specifically related to a kind of liquid sulphur degasification technique.
Background technology
Sulphur unit, as the end equipment of Gas Purification Factory, Petrochemical Enterprises and coal chemical industry enterprises, governs the normal operation of other upstream device, has become the standard configuration device of such enterprise at present.Sulfur recovery facility generally adopts the mode recovery sulphur of two-stage Crouse+absorption reducing process combination, and for local refinery or the less more use of sulphur unit three grades of scale, level Four claus process recovery sulphur.Along with the increasingly stringent of domestic emission standards for sulfur dioxide, in " 12 " period, domestic sulphur unit SO
2emission concentration limit value will by 960mg/m
3under be adjusted to 400mg/m
3, special discharge value is 200mg/m
3, Shandong Province will put into effect sulphur unit SO
2emission concentration is not more than 300mg/m
3regulation, this is comparatively test for the sulfur recovery facility of three grades or level Four claus process to sulphur unit especially.Molten sulfur deviates from waste gas as affecting sulphur unit flue gas SO
2one of principal element of emission concentration, most incinerator of being delivered to by this waste gas burns both at home and abroad, increases sulfur recovery facility flue gas SO
2emission concentration 100 ~ 300mg/m
3.
Sulfide in molten sulfur is with H
2s and H
2s
xform exists, along with the rising of temperature, and total H
2s solubleness and H
2s
xsolubleness increases, H
2s solubleness reduces, H in first-stage condenser molten sulfur
2s
xcontent is 500 ~ 700ppm, H in secondary condenser molten sulfur
2s
xcontent is 180 ~ 280ppm, H in three grades of condenser molten sulfurs
2s
xcontent is 70 ~ 110ppm.If do not removed molten sulfur medium sulphide content, in molten sulfur transportation, easily in molten sulfur tank car, there is H
2s gathers, and there is explosion hazard; Do not remove H
2it is shaping that the molten sulfur of S delivers to sulfur forming machine, can discharge H in conveying and moulding process
2, there is the potential safety hazard that personnel are poisoning in S gas, cause larger impact to environment simultaneously.The ultimate principle of molten sulfur degasification is the H that release is dissolved
2s gas, and allow polysulfide be rapidly decomposed into H
2s, with sweeping gas the H in molten sulfur
2s blows away.The sweep gas of molten sulfur degasification is generally air, steam, Claus tail gas and nitrogen, and steam easily causes pipeline and equipment corrosion; H contained by Claus tail gas
2s can make molten sulfur dissociate H
2s convergence balances, and is unfavorable for H in molten sulfur
2s removes; The usual oxygen level of nitrogen is lower, is unfavorable for the oxidation of sulfocompound.Therefore, usually use air as the sweep gas of molten sulfur degasification.
The main method of molten sulfur degasification has the degassed and circulating degasification of bubbling, bubbling is degassed is adopt the form of bubbling waste gas in molten sulfur to be deviate from rear introducing incinerator to burn, circulating degasification then adopts injecting catalyst in molten sulfur pond, impels polysulphide decomposition, through degassed pump circulation, spray make H
2s overflows, and volley through steam injector and burn to tail gas burning furnace, molten sulfur is all deviate from waste gas and directly caused tail gas burning furnace process by two kinds of methods, and sulfur dioxide emissioning concentration is higher.
Summary of the invention
The object of this invention is to provide a kind of liquid sulphur degasification technique, its less investment, implementation are strong, process cost is low, effectively reduce sulfur recovery facility SO
2emission concentration, improves sulphur recovery transformation efficiency.
Liquid sulphur degasification technique of the present invention is that to carry out bubbling using air as source of the gas to molten sulfur in molten sulfur pond degassed, and molten sulfur is deviate from waste gas and entered one of following condenser, and sulphur steam is reclaimed in further condensation; Reclaim after the Process Gas after sulphur steam introduces tail gas burning furnace burning and discharge;
1) when described condenser progression is level Four, molten sulfur is deviate from waste gas and is entered level Four condenser;
2) when described condenser progression is Pyatyi, molten sulfur is deviate from waste gas and is entered Pyatyi condenser;
3) when described condenser progression is Pyatyi, molten sulfur is deviate from waste gas and is entered level Four condenser and Pyatyi condenser simultaneously.
The present invention is mainly applicable to the sulfur recovery facility of three grades or level Four claus process.
Wherein, preferred technical scheme is as follows:
It is degassed that the present invention carries out bubbling using air as source of the gas to molten sulfur in molten sulfur pond, and not only oxidable molten sulfur deviates from the H in waste gas
2s, and the decomposition being conducive to polysulfide in molten sulfur pond, under atmospheric pressure, the tolerance of air source of the gas and the mass ratio of molten sulfur are 0.02 ~ 0.1:1, preferably 0.04 ~ 0.06:1.Time degassed, make source of the gas with air, degassed to molten sulfur bubbling in molten sulfur pond through gas blower, the waste gas that molten sulfur is deviate from is power with steam, volleys to condenser through steam injector.The temperature of application claims final stage sulfur condenser controls at 127 ~ 135 DEG C, and sulphur steam is reclaimed in further condensation, guarantees to cool sulphur steam to greatest extent.
Described liquid sulphur degasification technique, is divided into three kinds of situations:
(1) when condenser progression is level Four, molten sulfur is deviate to enter level Four condenser after waste gas mixes with the three reactor tail gas with elementary sulfur and reclaim sulphur steam.Level Four condenser is final stage sulfur condenser.
The present invention is for reducing the SO of sulfur recovery facility
2during emission concentration, step is as follows:
1. containing H
2partial combustion in Reaktionsofen after the sour gas of S and air mixed, H
2s and SO
2there is the Reaktionsofen tail gas of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after first-stage condenser cooling;
2. the Reaktionsofen tail gas after reclaiming elementary sulfur enters A reactor, generates the A reactor tail gas with elementary sulfur under catalyst action after Claus catalyzed conversion, and elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after secondary condenser cooling;
3. the A reactor tail gas after reclaiming elementary sulfur enters second reactor, under catalyst action, generate the second reactor tail gas with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after three grades of condenser coolings;
4. the second reactor tail gas after reclaiming elementary sulfur enters three reactor, generates the three reactor tail gas with elementary sulfur under catalyst action after Claus catalyzed conversion;
5. the three reactor tail gas with elementary sulfur is deviate from after waste gas mixes to enter level Four condenser with molten sulfur, and elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after the cooling of level Four condenser;
6. reclaim the Process Gas after elementary sulfur enter incinerator burn after through smoke stack emission.
(2), when described condenser progression is Pyatyi, molten sulfur is deviate to enter Pyatyi condenser after waste gas mixes with the fourth-order reaction device tail gas with elementary sulfur and reclaim sulphur steam.Pyatyi condenser is final stage sulfur condenser.
The present invention is for reducing the SO of sulfur recovery facility
2during emission concentration, step is as follows:
1. containing H
2partial combustion in Reaktionsofen after the sour gas of S and air mixed, H
2s and SO
2there is the Reaktionsofen tail gas of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after first-stage condenser cooling;
2. the Reaktionsofen tail gas after reclaiming elementary sulfur enters A reactor, generates the A reactor tail gas with elementary sulfur under catalyst action after Claus catalyzed conversion, and elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after secondary condenser cooling;
3. the A reactor tail gas after reclaiming elementary sulfur enters second reactor, under catalyst action, generate the second reactor tail gas with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after three grades of condenser coolings;
4. the second reactor tail gas after reclaiming elementary sulfur enters three reactor, under catalyst action, generate the three reactor tail gas with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after the cooling of level Four condenser;
5. the three reactor tail gas after reclaiming elementary sulfur enters fourth-order reaction device, generates the fourth-order reaction device tail gas with elementary sulfur under catalyst action after Claus catalyzed conversion;
6. the fourth-order reaction device tail gas with elementary sulfur is deviate from after waste gas mixes to enter Pyatyi condenser with molten sulfur, and elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after the cooling of Pyatyi condenser;
7. reclaim the Process Gas after elementary sulfur enter incinerator burn after through smoke stack emission.
(3) described condenser progression is Pyatyi, and molten sulfur is deviate from waste gas and entered level Four condenser and Pyatyi condenser simultaneously;
Molten sulfur is deviate to enter level Four condenser after waste gas mixes with the three reactor tail gas with elementary sulfur and reclaim sulphur steam;
Molten sulfur is deviate to enter Pyatyi condenser after waste gas mixes with the fourth-order reaction device tail gas with elementary sulfur and reclaim sulphur steam.
Pyatyi condenser is final stage sulfur condenser.
The present invention is for reducing the SO of sulfur recovery facility
2during emission concentration, step is as follows:
1. containing H
2partial combustion in Reaktionsofen after the sour gas of S and air mixed, H
2s and SO
2there is the Reaktionsofen tail gas of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after first-stage condenser cooling;
2. the Reaktionsofen tail gas after reclaiming elementary sulfur enters A reactor, generates the A reactor tail gas with elementary sulfur under catalyst action after Claus catalyzed conversion, and elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after secondary condenser cooling;
3. the A reactor tail gas after reclaiming elementary sulfur enters second reactor, under catalyst action, generate the second reactor tail gas with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after three grades of condenser coolings;
4. the second reactor tail gas after reclaiming elementary sulfur enters three reactor, generates the three reactor tail gas with elementary sulfur under catalyst action after Claus catalyzed conversion;
5. the three reactor tail gas with elementary sulfur is deviate from after waste gas mixes to enter level Four condenser with molten sulfur, and elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after the cooling of level Four condenser;
6. the three reactor tail gas after reclaiming elementary sulfur enters fourth-order reaction device, generates the fourth-order reaction device tail gas with elementary sulfur under catalyst action after Claus catalyzed conversion;
7. the fourth-order reaction device tail gas with elementary sulfur is deviate from after waste gas mixes to enter Pyatyi condenser with molten sulfur, and elementary sulfur wherein enters molten sulfur pond and obtains Molten sulphur after the cooling of Pyatyi condenser;
8. reclaim the Process Gas after elementary sulfur enter incinerator burn after through smoke stack emission.
As known from the above, the present invention also provides simultaneously and a kind ofly invests low, that implementation is strong, process cost is few reduction sulfur recovery facility SO
2the method of emission concentration.
The present invention:
In operating process, adjustment general mood ratio, makes sour gas and air generating portion in Reaktionsofen burn, control combustion temperature 900 ~ 1400 DEG C, the H of about 65% (v) in stove
2there is Claus reaction and be converted into sulphur, remaining H in S
2s has 1/3 to be converted into SO
2.
2H
2S+3O
2→2SO
2+2H
2O(1)
SO
2+2H
2S→2H
2O+3S(2)
A reactor, second reactor, three reactor, fourth-order reaction device, according to certain grading distribution scheme filling Claus conversion catalyst, under the effect of catalyzer, occur to react as follows:
SO
2+2H
2S→2H
2O+3S(2)
COS+H
2O→H
2S+CO
2(3)
CS
2+2H
2O→2H
2S+CO
2(4)
The sulphur generated enters molten sulfur pond through condenser at different levels, and adopt air to carry out degassed to molten sulfur, not only oxidable molten sulfur deviates from the H in waste gas
2s, and the decomposition being conducive to polysulfide in molten sulfur pond, concrete degasification process is as follows:
H
2S
X→H
2S+S
X-1(5)
Be used as power molten sulfur is deviate from waste gas to volley through steam injector with steam, volley the molten sulfur to deviate from waste gas and mix laggard level Four condenser with three reactor tail gas and reclaim sulphur steam, or mix laggard Pyatyi condenser with fourth-order reaction device tail gas and reclaim sulphur steam, or enter level Four and Pyatyi condenser reclaims sulphur steam simultaneously.
The catalyzer of the present invention's reactor charge at different levels loads according to specific grading distribution scheme:
A reactor and final stage reactor top filling 1/1 to two/3rd highly have the multi-functional sulfur recovery catalyst of omitted oxygen function, bottom filling 1/2 to two/3rd height bigger serface alumina base sulfur recovery catalyst, effectively avoid oxygen in waste gas to cause damage to catalyst performance, all the other each stage reactors all load bigger serface alumina base sulfur recovery catalyst.
Above-mentioned grading distribution scheme effectively avoids the oxygen in waste gas to cause damage to catalyst performance.Process Gas after process is introduced after tail gas burning furnace burns and is discharged, and reduces sulfur recovery facility flue gas SO
2emission concentration 100 ~ 300mg/m
3.The present invention has the advantages that investment is low, implementation is strong, process cost is few.
The multi-functional sulfur recovery catalyst of LS-981 of described research institute of asphalt in Shenli Refinery of omitted oxygen function sulfur recovery catalyst preferred China Petrochemical Industry exploitation, external without like product.LS-981 multifunctional sulfur recovery catalyst adopts the preparation technology of Alumina-titanium oxide composite carrier and uniqueness, overcomes common aluminum oxide or titania-based catalyst sulfate radical content is high, and pore volume, specific surface area is little, intensity is low, wear away high shortcoming.With the addition of deoxy activity component, improve catalyzer de-oxygen function, there is good deoxy activity.This catalyzer has good hydrothermal stability, coking resistivity, sulfuric-resisting salinization ability simultaneously, Crouse is active, tempreture organic sulphur hydrolysis is active.Be applicable to the oxygen containing sulfur recovery facility for the treatment of processes gas.
Described bigger serface alumina base sulfur recovery catalyst specific surface area should higher than 350m
2/ g, the LS-02 catalyzer of research institute of asphalt in Shenli Refinery of preferred China Petrochemical Industry development.LS-02 catalyzer is the novel oxidized aluminium base catalyst for sulphur that a kind of specific surface area is larger, pore volume is higher developed on LS-300 basis, this catalyzer Claus activity is high, resistant to thermal aging and hydrothermal aging ability strong, and uniform particles, abrasion are little, crushing strength is high, thus ensure that the long-term operation of catalyzer; More reasonably pore structure, macropore is more, and pore structure be bimodal distribution, and the sulphur that reaction is generated speeds away catalyzer duct, improves Claus activity and the tempreture organic sulphur hydrolysis activity of catalyzer further.
Described catalyzer is commercially available prod, and its physico-chemical property and technical indicator are in table 1.
Table 1 catalyzer physico-chemical property and technical indicator table
Beneficial effect of the present invention is as follows:
Technique of the present invention is using air as source of the gas, molten sulfur is deviate from waste gas and is volleyed to condenser through steam injector, the temperature of final stage sulfur condenser controls at 127 ~ 135 DEG C, sulphur steam is reclaimed in further condensation, molten sulfur is deviate from waste gas and is mixed laggard level Four condenser with three reactor tail gas and reclaim sulphur steam, or mix laggard Pyatyi condenser with fourth-order reaction device tail gas and reclaim sulphur steam, or enter level Four and Pyatyi condenser recovery sulphur steam simultaneously, Process Gas after process is introduced after tail gas burning furnace burns and is discharged, and reduces sulfur recovery facility flue gas SO
2emission concentration 100 ~ 300mg/m
3.The present invention utilizes the feature that last condenser stage temperature is low, molten sulfur is deviate from waste gas and causes last condenser stage recovery sulphur steam, eliminate SO further
2the impact of emission concentration.The present invention have structure simple, invest low, that implementation is strong feature.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that molten sulfur deviates from that waste gas enters level Four condenser and Pyatyi condenser simultaneously;
Fig. 2 is the process flow sheet that molten sulfur deviates from that waste gas enters level Four condenser;
Fig. 3 is the process flow sheet that molten sulfur deviates from that waste gas enters Pyatyi condenser;
Fig. 4 is comparative example 1-6 process flow sheet;
Fig. 5 is comparative example 7-12 process flow sheet;
In figure: 1, sour gas; 2, air; 3, Reaktionsofen; 4, waste heat boiler; 5, Reaktionsofen tail gas; 6, first-stage condenser; 7, A reactor; 8, A reactor tail gas; 9, secondary condenser; 10, second reactor; 11, second reactor tail gas; 12, three grades of condensers; 13, three reactor; 14, three reactor tail gas; 15, level Four condenser; 16, air; 17, gas blower; 18, under meter; 19, degassed pond; 20, molten sulfur pond; 21, steam; 22, steam injector; 23, incinerator; 24, chimney; 25, fourth-order reaction device; 26, fourth-order reaction device tail gas; 27, Pyatyi condenser; 28, molten sulfur deviates from waste gas.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Carry out according to following three kinds of situations in embodiment:
(1) when condenser progression is level Four, molten sulfur is deviate to enter level Four condenser 15 after waste gas 28 mixes with the three reactor tail gas 14 with elementary sulfur and reclaim sulphur steam.Level Four condenser 15 is final stage sulfur condenser.As shown in Figure 2.
The present invention is for reducing the SO of sulfur recovery facility
2during emission concentration, step is as follows:
1. containing H
2partial combustion in Reaktionsofen 3 after the sour gas 1 of S mixes with air 2, H
2s and SO
2there is the Reaktionsofen tail gas 5 of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after first-stage condenser 6 cools;
2. the Reaktionsofen tail gas 5 after reclaiming elementary sulfur enters A reactor 7, under catalyst action, generate the A reactor tail gas 8 with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after secondary condenser 9 cools;
3. the A reactor tail gas 8 after reclaiming elementary sulfur enters second reactor 10, under catalyst action, generate the second reactor tail gas 11 with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after three grades of condensers 12 cool;
4. the second reactor tail gas 11 after reclaiming elementary sulfur enters three reactor 13, generates the three reactor tail gas 14 with elementary sulfur under catalyst action after Claus catalyzed conversion;
5. the three reactor tail gas 14 with elementary sulfur is deviate from after waste gas 28 mixes to enter level Four condenser 15 with molten sulfur, and elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after level Four condenser 15 cools;
6. the Process Gas after reclaiming elementary sulfur enters after incinerator 23 burns and discharges through chimney 24.
(2), when described condenser progression is Pyatyi, molten sulfur is deviate to enter Pyatyi condenser 27 after waste gas 28 mixes with the fourth-order reaction device tail gas 26 with elementary sulfur and reclaim sulphur steam.Pyatyi condenser 27 is final stage sulfur condenser.As shown in Figure 3.
The present invention is for reducing the SO of sulfur recovery facility
2during emission concentration, step is as follows:
1. containing H
2partial combustion in Reaktionsofen 3 after the sour gas 1 of S mixes with air 2, H
2s and SO
2there is the Reaktionsofen tail gas 5 of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after first-stage condenser 6 cools;
2. the Reaktionsofen tail gas 5 after reclaiming elementary sulfur enters A reactor 7, under catalyst action, generate the A reactor tail gas 8 with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after secondary condenser 9 cools;
3. the A reactor tail gas 8 after reclaiming elementary sulfur enters second reactor 10, under catalyst action, generate the second reactor tail gas 11 with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after three grades of condensers 12 cool;
4. the second reactor tail gas 11 after reclaiming elementary sulfur enters three reactor 13, under catalyst action, generate the three reactor tail gas 14 with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after level Four condenser 15 cools;
5. the three reactor tail gas 14 after reclaiming elementary sulfur enters fourth-order reaction device 25, generates the fourth-order reaction device tail gas 26 with elementary sulfur under catalyst action after Claus catalyzed conversion;
6. the fourth-order reaction device tail gas 26 with elementary sulfur is deviate from after waste gas 28 mixes to enter Pyatyi condenser 27 with molten sulfur, and elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after Pyatyi condenser 27 cools;
7. the Process Gas after reclaiming elementary sulfur enters after incinerator 23 burns and discharges through chimney 24.
(3) described condenser progression is Pyatyi, and molten sulfur is deviate from waste gas 28 and entered level Four condenser 15 and Pyatyi condenser 27 simultaneously;
Molten sulfur is deviate to enter level Four condenser 15 after waste gas 28 mixes with the three reactor tail gas 14 with elementary sulfur and reclaim sulphur steam;
Molten sulfur is deviate to enter Pyatyi condenser 27 after waste gas 28 mixes with the fourth-order reaction device tail gas 26 with elementary sulfur and reclaim sulphur steam.
Pyatyi condenser is final stage sulfur condenser.As shown in Figure 1.
The present invention is for reducing the SO of sulfur recovery facility
2during emission concentration, step is as follows:
1. containing H
2partial combustion in Reaktionsofen 3 after the sour gas 1 of S mixes with air 2, H
2s and SO
2there is the Reaktionsofen tail gas 5 of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after first-stage condenser 6 cools;
2. the Reaktionsofen tail gas 5 after reclaiming elementary sulfur enters A reactor 7, under catalyst action, generate the A reactor tail gas 8 with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after secondary condenser 9 cools;
3. the A reactor tail gas 8 after reclaiming elementary sulfur enters second reactor 10, under catalyst action, generate the second reactor tail gas 11 with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after three grades of condensers 12 cool;
4. the second reactor tail gas 11 after reclaiming elementary sulfur enters three reactor 13, generates the three reactor tail gas 14 with elementary sulfur under catalyst action after Claus catalyzed conversion;
5. the three reactor tail gas 14 with elementary sulfur is deviate from after waste gas 28 mixes to enter level Four condenser 15 with molten sulfur, and elementary sulfur wherein enters molten sulfur pond 20 and obtains Molten sulphur after level Four condenser 15 cools;
6. the three reactor tail gas 14 after reclaiming elementary sulfur enters fourth-order reaction device 25, generates the fourth-order reaction device tail gas 26 with elementary sulfur under catalyst action after Claus catalyzed conversion;
7. with fourth-order reaction device tail gas 26 sulphur of elementary sulfur deviate from waste gas 28 mix after the elementary sulfur entered in Pyatyi condenser 27 after Pyatyi condenser 27, enter molten sulfur pond 20 Molten sulphur;
8. reclaim the Process Gas after elementary sulfur to enter after incinerator 23 through chimney 24.
Embodiment 1
Certain sulphur unit adopts three grades of Claus unit sulfur recovery units, and present invention process schema is shown in Fig. 2, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.02kg.Molten sulfur is deviate from waste gas 28 and is volleyed to level Four (final stage) condenser 15 through steam injector 22, the temperature of level Four condenser 15 controls at 135 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 97.20%.
Comparative example 1
Adopt three grades of Crouse's recovery sulphur techniques, process flow sheet is shown in Fig. 4, identical with the technique of embodiment 1, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 1 compared with comparative example 1, sulfur recovery facility flue gas SO
2emission concentration reduces 185mg/m
3.
Embodiment 2
Certain sulphur unit adopts three grades of Claus unit sulfur recovery units, and present invention process schema is shown in Fig. 2, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.02kg.Molten sulfur is deviate from waste gas 28 and is volleyed to level Four (final stage) condenser 15 through steam injector 22, the temperature of level Four condenser 15 controls at 130 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 97.31%.
Comparative example 2
Adopt three grades of Crouse's recovery sulphur techniques, process flow sheet is shown in Fig. 4, identical with the technique of embodiment 2, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 2 compared with comparative example 2, sulfur recovery facility flue gas SO
2emission concentration reduces 245mg/m
3.
Embodiment 3
Certain sulphur unit adopts three grades of Claus unit sulfur recovery units, and present invention process schema is shown in Fig. 2, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.03kg.Molten sulfur is deviate from waste gas 28 and is volleyed to level Four (final stage) condenser 15 through steam injector 22, the temperature of level Four condenser 15 controls at 129 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 97.76%.
Comparative example 3
Adopt three grades of Crouse's recovery sulphur techniques, process flow sheet is shown in Fig. 4, identical with the technique of embodiment 3, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 3 compared with comparative example 3, sulfur recovery facility flue gas SO
2emission concentration reduces 285mg/m
3.
Embodiment 4
Certain sulphur unit adopts three grades of Claus unit sulfur recovery units, and present invention process schema is shown in Fig. 2, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.04kg.Molten sulfur is deviate from waste gas 28 and is volleyed to level Four (final stage) condenser 15 through steam injector 22, the temperature of level Four sulfur condenser 15 controls at 133 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced after tail gas burning furnace burns 23 and discharged, and sulfur recovery rate is 97.57%.
Comparative example 4
Adopt three grades of Crouse's recovery sulphur techniques, process flow sheet is shown in Fig. 4, identical with the technique of embodiment 4, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 4 compared with comparative example 4, sulfur recovery facility flue gas SO
2emission concentration reduces 213mg/m
3.
Embodiment 5
Certain sulphur unit adopts three grades of Claus unit sulfur recovery units, and present invention process schema is shown in Fig. 2, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.05kg.Molten sulfur is deviate from waste gas 28 and is volleyed to level Four (final stage) condenser 15 through steam injector 22, the temperature of level Four condenser 15 controls at 127 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 97.91%.
Comparative example 5
Adopt three grades of Crouse's recovery sulphur techniques, process flow sheet is shown in Fig. 4, identical with the technique of embodiment 5, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 5 compared with comparative example 5, sulfur recovery facility flue gas SO
2emission concentration reduces 290mg/m
3.
Embodiment 6
Certain sulphur unit adopts three grades of Claus unit sulfur recovery units, and present invention process schema is shown in Fig. 2, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.04kg.Molten sulfur is deviate from waste gas 28 and is volleyed to level Four (final stage) condenser 15 through steam injector 22, the temperature of level Four condenser 15 controls at 127 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 97.90%.
Comparative example 6
Adopt three grades of Crouse's recovery sulphur techniques, process flow sheet is shown in Fig. 4, identical with the technique of embodiment 6, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 6 compared with comparative example 6, sulfur recovery facility flue gas SO
2emission concentration reduces 278mg/m
3.
Embodiment 7
Certain sulphur unit adopts level Four Claus unit sulfur recovery unit, and present invention process schema is shown in Fig. 3, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.06kg.Molten sulfur is deviate from waste gas 28 and is volleyed to Pyatyi (final stage) condenser 27 through steam injector 22, the temperature of Pyatyi condenser 27 controls at 130 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 98.34%.
Comparative example 7
Adopt level Four Crouse recovery sulphur technique, process flow sheet is shown in Fig. 5, identical with the technique of embodiment 7, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 7 compared with comparative example 7, sulfur recovery facility flue gas SO
2emission concentration reduces 300mg/m
3.
Embodiment 8
Certain sulphur unit adopts level Four Claus unit sulfur recovery unit, and present invention process schema is shown in Fig. 3, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.04kg.Molten sulfur is deviate from waste gas 28 and is volleyed to Pyatyi (final stage) condenser 27 through steam injector 22, the temperature of Pyatyi condenser 27 controls at 134 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 98.17%.
Comparative example 8
Adopt level Four Crouse recovery sulphur technique, process flow sheet is shown in Fig. 5, identical with the technique of embodiment 8, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 8 compared with comparative example 8, sulfur recovery facility flue gas SO
2emission concentration reduces 273mg/m
3.
Embodiment 9
Certain sulphur unit adopts level Four Claus unit sulfur recovery unit, and present invention process schema is shown in Fig. 3, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.08kg.Molten sulfur is deviate from waste gas 28 and is volleyed to Pyatyi (final stage) condenser 27 through steam injector 22, the temperature of Pyatyi condenser 27 controls at 133 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 98.23%.
Comparative example 9
Adopt level Four Crouse recovery sulphur technique, process flow sheet is shown in Fig. 5, identical with the technique of embodiment 9, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 9 compared with comparative example 9, sulfur recovery facility flue gas SO
2emission concentration reduces 287mg/m
3.
Embodiment 10
Certain sulphur unit adopts level Four Claus unit sulfur recovery unit, and present invention process schema is shown in Fig. 3, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.08kg.Molten sulfur is deviate from waste gas 28 and is volleyed to Pyatyi (final stage) condenser 27 through steam injector 22, the temperature of Pyatyi condenser 27 controls at 128 DEG C, sulphur steam is reclaimed in further condensation, and the Process Gas after process is introduced tail gas burning furnace 23 and burned rear discharge, and sulfur recovery rate is 98.33%.
Comparative example 10
Adopt level Four Crouse recovery sulphur technique, process flow sheet is shown in Fig. 5, identical with the technique of embodiment 10, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 10 compared with comparative example 10, sulfur recovery facility flue gas SO
2emission concentration reduces 293mg/m
3.
Embodiment 11
Certain sulphur unit adopts level Four Claus unit sulfur recovery unit, and present invention process schema is shown in Fig. 1, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.04kg.Molten sulfur is deviate from waste gas 28 and is entered level Four condenser 15 and Pyatyi condenser 27 reclaims sulphur steam simultaneously, the temperature of Pyatyi (final stage) condenser 27 controls at 135 DEG C, sulphur steam is reclaimed in further condensation, Process Gas after process is introduced tail gas burning furnace 23 and is burned rear discharge, and sulfur recovery rate is 98.07%.
Comparative example 11
Adopt level Four Crouse recovery sulphur technique, process flow sheet is shown in Fig. 5, identical with the technique of embodiment 11, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 11 compared with comparative example 11, sulfur recovery facility flue gas SO
2emission concentration reduces 250mg/m
3.
Embodiment 12
Certain sulphur unit adopts level Four Claus unit sulfur recovery unit, and present invention process schema is shown in Fig. 1, and it is degassed that the present invention carries out bubbling using air 16 as source of the gas to molten sulfur in molten sulfur pond 20, and under atmospheric pressure, the tolerance of gas is equivalent to the gas of per kilogram molten sulfur 0.10kg.Molten sulfur is deviate from waste gas 28 and is entered level Four condenser 15 and Pyatyi condenser 27 reclaims sulphur steam simultaneously, the temperature of Pyatyi (final stage) condenser 27 controls at 126 DEG C, sulphur steam is reclaimed in further condensation, Process Gas after process is introduced tail gas burning furnace 23 and is burned rear discharge, and sulfur recovery rate is 98.16%.
Comparative example 12
Adopt level Four Crouse recovery sulphur technique, process flow sheet is shown in Fig. 5, identical with the technique of embodiment 12, and unique difference is that molten sulfur is deviate from waste gas and directly entered tail gas burning furnace 23 and burn rear discharge.
Embodiment 12 compared with comparative example 12, sulfur recovery facility flue gas SO
2emission concentration reduces 295mg/m
3.
Table 2 embodiment and comparative example result table
Claims (10)
1. a liquid sulphur degasification technique, is characterized in that: carry out bubbling using air (16) as source of the gas to molten sulfur in molten sulfur pond (20) degassed, and molten sulfur is deviate from waste gas and entered one of following condenser, and sulphur steam is reclaimed in further condensation; Reclaim after the Process Gas after sulphur steam introduces tail gas burning furnace (23) burning and discharge;
1) described condenser progression is level Four, and molten sulfur is deviate from waste gas (28) and entered level Four condenser (15);
2) described condenser progression is Pyatyi, and molten sulfur is deviate from waste gas (28) and entered Pyatyi condenser (27);
3) described condenser progression is Pyatyi, and molten sulfur is deviate from waste gas (28) and entered level Four condenser (15) and Pyatyi condenser (27) simultaneously.
2. liquid sulphur degasification technique according to claim 1, is characterized in that: under atmospheric pressure, and the tolerance of air source of the gas and the mass ratio of molten sulfur are 0.02 ~ 0.1:1.
3. liquid sulphur degasification technique according to claim 1, is characterized in that: the temperature of last condenser stage controls at 127 ~ 135 DEG C.
4. the liquid sulphur degasification technique according to claim 1,2 or 3, it is characterized in that: described condenser progression is level Four, molten sulfur is deviate to enter level Four condenser (15) after waste gas (28) mixes with the three reactor tail gas (14) with elementary sulfur and reclaim sulphur steam.
5. liquid sulphur degasification technique according to claim 4, is characterized in that: for reducing the SO of sulfur recovery facility
2emission concentration, step is as follows:
Containing H
2partial combustion in Reaktionsofen (3) after the sour gas (1) of S mixes with air (2), H
2s and SO
2there is the Reaktionsofen tail gas (5) of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after first-stage condenser (6) cooling;
The Reaktionsofen tail gas (5) reclaimed after elementary sulfur enters A reactor (7), under catalyst action, generate the A reactor tail gas (8) with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after secondary condenser (9) cooling;
The A reactor tail gas (8) reclaimed after elementary sulfur enters second reactor (10), under catalyst action, generate the second reactor tail gas (11) with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after three grades of condenser (12) coolings;
The second reactor tail gas (11) reclaimed after elementary sulfur enters three reactor (13), generates the three reactor tail gas (14) with elementary sulfur under catalyst action after Claus catalyzed conversion;
Three reactor tail gas (14) with elementary sulfur is deviate from after waste gas (28) mixes to enter level Four condenser (15) with molten sulfur, and elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after level Four condenser (15) cooling;
The Process Gas reclaimed after elementary sulfur enters after incinerator (23) burns and discharges through chimney (24).
6. the liquid sulphur degasification technique according to claim 1,2 or 3, it is characterized in that: described condenser progression is Pyatyi, molten sulfur is deviate to enter Pyatyi condenser (27) after waste gas (28) mixes with the fourth-order reaction device tail gas (26) with elementary sulfur and reclaim sulphur steam.
7. liquid sulphur degasification technique according to claim 6, is characterized in that: for reducing the SO of sulfur recovery facility
2emission concentration, step is as follows:
Containing H
2partial combustion in Reaktionsofen (3) after the sour gas (1) of S mixes with air (2), H
2s and SO
2there is the Reaktionsofen tail gas (5) of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after first-stage condenser (6) cooling;
The Reaktionsofen tail gas (5) reclaimed after elementary sulfur enters A reactor (7), under catalyst action, generate the A reactor tail gas (8) with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after secondary condenser (9) cooling;
The A reactor tail gas (8) reclaimed after elementary sulfur enters second reactor (10), under catalyst action, generate the second reactor tail gas (11) with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after three grades of condenser (12) coolings;
The second reactor tail gas (11) reclaimed after elementary sulfur enters three reactor (13), under catalyst action, generate the three reactor tail gas (14) with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after level Four condenser (15) cooling;
The three reactor tail gas (14) reclaimed after elementary sulfur enters fourth-order reaction device (25), generates the fourth-order reaction device tail gas (26) with elementary sulfur under catalyst action after Claus catalyzed conversion;
Fourth-order reaction device tail gas (26) with elementary sulfur is deviate from after waste gas (28) mixes to enter Pyatyi condenser (27) with molten sulfur, and elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after Pyatyi condenser (27) cooling;
The Process Gas reclaimed after elementary sulfur enters after incinerator (23) burns and discharges through chimney (24).
8. the liquid sulphur degasification technique according to claim 1,2 or 3, is characterized in that: described condenser progression is Pyatyi, and molten sulfur is deviate from waste gas (28) and entered level Four condenser (15) and Pyatyi condenser (27) simultaneously;
Molten sulfur is deviate to enter level Four condenser (15) after waste gas (28) mixes with the three reactor tail gas (14) with elementary sulfur and reclaim sulphur steam;
Molten sulfur is deviate to enter Pyatyi condenser (27) after waste gas (28) mixes with the fourth-order reaction device tail gas (26) with elementary sulfur and reclaim sulphur steam.
9. liquid sulphur degasification technique according to claim 8, is characterized in that: for reducing the SO of sulfur recovery facility
2emission concentration, step is as follows:
Containing H
2partial combustion in Reaktionsofen (3) after the sour gas (1) of S mixes with air (2), H
2s and SO
2there is the Reaktionsofen tail gas (5) of Claus reaction generation with elementary sulfur; Elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after first-stage condenser (6) cooling;
The Reaktionsofen tail gas (5) reclaimed after elementary sulfur enters A reactor (7), under catalyst action, generate the A reactor tail gas (8) with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after secondary condenser (9) cooling;
The A reactor tail gas (8) reclaimed after elementary sulfur enters second reactor (10), under catalyst action, generate the second reactor tail gas (11) with elementary sulfur after Claus catalyzed conversion, elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after three grades of condenser (12) coolings;
The second reactor tail gas (11) reclaimed after elementary sulfur enters three reactor (13), generates the three reactor tail gas (14) with elementary sulfur under catalyst action after Claus catalyzed conversion;
Three reactor tail gas (14) with elementary sulfur is deviate from after waste gas (28) mixes to enter level Four condenser (15) with molten sulfur, and elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after level Four condenser (15) cooling;
The three reactor tail gas (14) reclaimed after elementary sulfur enters fourth-order reaction device (25), generates the fourth-order reaction device tail gas (26) with elementary sulfur under catalyst action after Claus catalyzed conversion;
Fourth-order reaction device tail gas (26) with elementary sulfur is deviate from after waste gas (28) mixes to enter Pyatyi condenser (27) with molten sulfur, and elementary sulfur wherein enters molten sulfur pond (20) and obtains Molten sulphur after Pyatyi condenser (27) cooling;
The Process Gas reclaimed after elementary sulfur enters after incinerator (23) burns and discharges through chimney (24).
10. the liquid sulphur degasification technique according to claim 1,2 or 3, it is characterized in that: A reactor and final stage reactor top filling 1/1 to two/3rd highly have the multi-functional sulfur recovery catalyst LS-981 of omitted oxygen function, bottom filling 1/2 to two/3rd height bigger serface alumina base sulfur recovery catalyst LS-02.
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| Publication number | Priority date | Publication date | Assignee | Title |
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