Prior art:
At present, the recovery sulphur technology has conventional Kraus process, Crouse to extend class method and conventional Crouse+reduction absorption class vent gas treatment method from hydrogen sulfide containing acid gas, and their basic skills and shortcoming are described below:
1, conventional Kraus process: conventional Kraus process proposed in about 1890, industrialization in 1938,
The main chemical reactions formula of this method has two kinds, and the one, the chemical reaction in main burning furnace, reaction formula has: 2H
2S+3O
2→ 2H
2O+2SO
22H
2S+SO
2→ 2H
2O+3S
e/ e; CH
4+ SO
2→ COS+H
2O+H
2CO+S → COS; CO
2+ H
2S → COS+H
2O; CH
4+ 2S
2→ CS
2+ 2H
2S; 2CO+S
2→ CO
2+ CS
2The 2nd, the chemical reaction in catalyticreactor: 2H
2S+SO
2→ 2H
2O+3S
e/ e; COS+H
2O → CO
2+ 2H
2S; CS
2+ 2H
2O → CO
2+ 2H
2S, above-mentioned reaction is thermopositive reaction;
The shortcoming of conventional Kraus process is: according to a large amount of facts have proved, the sulfur recovery rate of conventional Cross unit can only reach 94%~97% usually, and sulfur recovery rate has been restricted following reason:
(1) because claus reaction is subjected to thermodynamic (al) restriction, the conversion reaction of sulphur can not still have a spot of H fully in the process gas
2S, SO
2, limited the transformation efficiency of sulphur;
(2) claus reaction will produce a certain amount of steam, along with the increase of moisture content, and corresponding reduction H
2S, SO
2Concentration, influenced the balance of claus reaction, hindered the generation of sulphur, limited the transformation efficiency of sulphur;
(3) owing to CO in the acid gas
2With the existence of hydro carbons, then can form COS and CS in the process gas
2, must make it to take place hydrolysis reaction, for this reason, the temperature of first reactor must be controlled at 300 ~ 340 ℃, though high temperature helps hydrolysis reaction, is unfavorable for the carrying out of claus reaction, has then limited the transformation efficiency of sulphur;
(4) transformation efficiency of conventional claus process sulphur is not normal very responsive to the proportioning of air and sour gas, if can not keep H
2S: SO
2=2: 1 optimum proportion will cause the transformation efficiency of sulphur to reduce;
Because of being subjected to the restriction of thermodynamic(al)equilibrium and kinetic factor, with H in the feeding gas
2The difference of S content and convertor progression, sulfur recovery rate are all below 97%, for the sulfur recovery facility tail gas SO after burning more than the 100t/d
2Quantity discharged up to 250kg/h, big for environment pollution;
2, conventional Crouse+reduction absorbs class vent gas treatment method: conventional Crouse+reduction absorption class vent gas treatment method is that sulphur and the sulfide with various forms in the Claus tail gases is reduced to H
2S absorbs then, and the total sulfur yield of these class methods can reach 99.8%, SO in the incineration tail gas
2Be 300ppm or lower; Wherein most widely used is SCOT method and BSRP method, this class device flow process complexity, and equipment is many, initial cost and operation working cost are all quite high, the sulphur that is reclaimed far can not compensate for process cost, and is general only being on a grand scale of sulfur recovery facility, or just use under the very tight situation of environmental requirement;
3, Crouse extends the class method: Crouse extends the super Kraus process that the class method has MCRC Kraus process, CBA Kraus process, Clinsulf method and direct oxidation class, is described below respectively:
(1), MCRC Kraus process: the MCRC Kraus process has 1 conventional claus reaction device+1 height of bed temperature regeneration convertor+1 cryogenic absorption attitude convertor, be called for short " three flow processs ", high temperature regeneration convertor and 2 blocked operations of cryogenic absorption attitude convertor, or 1 conventional claus reaction device+1 height of bed temperature regeneration convertor+2 cryogenic absorption attitude convertor, be called for short " four flow processs " high temperature regeneration convertor and 3 blocked operations of cryogenic absorption attitude convertor; Cryogenic absorption attitude convertor is operated under process gas sulphur dew point, and this helps chemical reaction and carries out raising sulphur transformation efficiency towards the direction that generates sulphur; Because the temperature in the cryogenic absorption attitude convertor is low, near the sulphur dew point, the catalyst surface in the cryogenic absorption attitude convertor constantly adheres to solid sulfur, catalyst activity progressively scatters and disappears, must improve cryogenic absorption attitude convertor temperature, the sulphur of catching up with catalyst surface to adhere to, regenerated catalyst; Regenerate completely that the high temperature regeneration convertor enters ADSORPTION STATE immediately, the cryogenic absorption attitude convertor of the saturated sulphur of corresponding absorption enters ecological immediately again, and cryogenic absorption and high temperature regeneration change operation; A conventional claus reaction device adds two about 99.0%, conventional claus reaction devices of the total sulphur rate of recovery of cryogenic absorption attitude convertor flow process and adds three total sulphur rate of recovery about 99.2% of cryogenic absorption attitude convertor flow process;
The shortcoming of this method: because the cryogenic absorption attitude convertor after the regeneration does not have precooling process, switching to the cryogenic absorption attitude convertor after regeneration of switching point in the ADSORPTION STATE process progressively is cooled in the transitional period of normal low temp adsorption temp by high temperature, two cryogenic absorption attitude convertor temperature in three flow processs all are not in the sulphur dew point, also only there is 1 cryogenic absorption attitude convertor temperature to be in the sulphur dew point in four flow processs, transformation efficiency is low, total sulphur rate of recovery is lower than normal value, causes the sulfur recovery rate fluctuation;
(2), CBA Kraus process: the CBA Kraus process is a kind of improvement to the MCRC Kraus process; The same with the MCRC Kraus process, the MCRC Kraus process has 1 conventional claus reaction device+1 height of bed temperature regeneration convertor+1 cryogenic absorption attitude convertor, be called for short " three flow processs ", high temperature regeneration convertor and 2 blocked operations of cryogenic absorption attitude convertor) or 1 conventional claus reaction device+1 height of bed temperature regeneration convertor+2 cryogenic absorption attitude convertor, be called for short " four flow processs " high temperature regeneration convertor and 3 blocked operations of cryogenic absorption attitude convertor; Cryogenic absorption attitude convertor is operated under process gas sulphur dew point, and this helps chemical reaction and carries out raising sulphur transformation efficiency towards the direction that generates sulphur; Because the temperature in the cryogenic absorption attitude convertor is low, near the sulphur dew point, the catalyst surface in the cryogenic absorption attitude convertor constantly adheres to solid sulfur, catalyst activity progressively scatters and disappears, must improve cryogenic absorption attitude convertor temperature, the sulphur of catching up with catalyst surface to adhere to, regenerated catalyst; Regenerating completely, the high temperature regeneration convertor begins precooling process, process gas progressively reacts transition to low-temperature Claus in second reactor, at this moment, be about to enter that catalyzer does not adsorb saturated as yet in the more ecological cryogenic absorption attitude convertor, keep the cryogenic absorption attitude, better controlled is waited to be about to enter in the ecological again cryogenic absorption attitude convertor catalyzer and is adsorbed when saturated in reactor capacity design, regenerating completely, the high temperature regeneration convertor carries out the transition to cold state fully, at this moment, adsorb saturated cryogenic absorption attitude convertor switching and just switch to high temperature regeneration, realize high temperature regeneration, the low temperature precooling, the blocked operation of cryogenic absorption, guarantee to have at least in the handoff procedure 2 to be cryogenic absorption attitude convertor, effectively overcome the fluctuation of sulfur recovery rate when switching.A conventional claus reaction device adds two about 99.0%, conventional claus reaction devices of the total sulphur rate of recovery of cryogenic absorption attitude convertor flow process and adds three total sulphur rate of recovery about 99.2% of cryogenic absorption attitude convertor flow process;
The shortcoming of this method: because at regeneration period, the process gas that enters the high temperature regeneration convertor is the pyroprocess gas of conventional claus reaction device outlet without condensation refrigerated separation overwhelming majority sulphur steam, sulphur steam content height in this process gas, reaction has reached balance, in the high temperature regeneration convertor, almost there is not the conversion of generting element sulphur direction, this reactor does not play the effect of conversion, and total transformation efficiency reduces.Simultaneously, the H in the high temperature regeneration convertor exit procedure gas
2S and SO
2Etc. unconverted sulfide content height, enter the H in the process gas of cryogenic absorption attitude convertor
2S and SO
2Etc. unconverted sulfide content height, cryogenic absorption attitude convertor interior element sulfur content is big, and catalyzer just loses activity at short notice;
(3), Clinsulf method: the Clinsulf method by the exploitation of German Linde company can be divided into two kinds of Clinsulf-Do and Clinsulf-SDP substantially.Clinsulf-Do is a kind of with H
2The direct catalyzed oxidation of S is the sulfur recovery method of sulphur, its core is a Linde isothermal reactor, reactor is divided into two sections, cooling coil was an adiabatic reaction section in epimere was unkitted, can make the rapid rising of temperature of reaction and improve speed of response, the hypomere of catalytic bed is equipped with spiral coil cooling tube, and heat-eliminating medium is taken heat away makes the reactor outlet temperature low to the dew point near sulphur, this helps chemical reaction and carries out towards the direction that generates sulphur, thereby a reactor has reached two purposes simultaneously; Clinsulf-SDP carries out improved a kind of inferior dew point method to conventional Claus, its basic thought is a reaction heat of directly taking the Claus reaction from beds rather than the sulfur condenser in downstream away, thereby can make whole bed keep temperature of reaction constant, the carrying out that helps claus reaction, total sulphur rate of recovery about 99.2%;
The shortcoming of this method: Clinsulf-Do no matter, or Clinsulf-SDP all exists shortcomings such as the inner-cooled reactor assembly is too huge, operational stability difference, its suitability is restricted;
(4), super Kraus process: add a Super-claus reactor and form by having two or three conventional claus reaction devices by the Superclaus method of SEC company exploitation, in the Super-claus reactor, load catalyst for selective oxidation.Acid gas the heating power section in due order equivalent control air amount carry out combustion reactions so that leave the H in the process gas of the conventional Crouse's catalytic section of last step
2S concentration is 0.6~1.0% (V), SO
2Content is very low, helps transforming to the direction of generting element sulphur; Claus tail gases through reheat to about 220 ℃ and with air mixed after enter the Super-claus reactor, the H in the tail gas
2S direct oxidation on the selective oxidation beds is an elementary sulfur, the transformation efficiency about 85% in this reactor.Conventional claus reaction device adds the total sulphur rate of recovery about 99.2% behind the Super-claus reactor;
The shortcoming of this method: this method is because the temperature of reactor height, equally with conventional Kraus process receives thermodynamic (al) restriction, and the conversion reaction of sulphur is incomplete equally.
Specific implementation method: provide embodiments of the invention: hydrogen sulfide containing acid gas and air mixed in main burning furnace below in conjunction with accompanying drawing, carry out claus reaction, the process gas of waste heat boiler first tube side is as the thermal source again that enters A reactor process gas, A reactor exit procedure gas enters in the secondary sulphur condensate cooler and cools off, and tells the molten sulfur of condensation; The present invention is provided with a cover gas/gas interchanger, with the heat of 600 ℃ of flue gases on the process gas of sulfur recovery facility waste heat boiler first tube side or the incinerator exhaust pass regeneration thermal source as subsequent reactor; Secondary, three grades, fourth-order reaction device and three grades, level Four, Pyatyi sulphur condensate cooler are by seven switching valve time variable control, blocked operation.In a switching cycle, all have two bed bioreactors to be in the cryogenic absorption attitude, and a bed bioreactor experience progressively ramp regeneration, stable regeneration, progressively precooling, stable cooling several stages; Processing step is as follows:
The first step: isolate sour water from the acid gas that desulfurization unit comes through the acid gas separator, again after the heating of acid gas preheater, enter the air thorough mixing after the air preheater heating that main burning furnace 1 and main air blower send here and in stove, carry out claus reaction; Second step: the high temperature gas flow that is come out by main burning furnace 1 is divided into two partly after the first tube side temperature of waste heat boiler 2 is reduced to 650 ℃, first partly 650 ℃ of process gas of 30~50% blend to 280 ℃ of thermals source with 160 ℃ of process gas that one-level sulphur condensate cooler 3 comes out as A reactor, the process gas of A reactor 4 outlets enters secondary sulphur condensate cooler 5 and is cooled to 127 ℃ of first part; Another partly continues to be cooled to 316 ℃ by second tube side of waste heat boiler 2, and then is cooled to 160 ℃ through one-level sulphur condensate cooler 3; The 3rd step: when second reactor 8 is in regeneration, pre-cold state, at the regeneration initial stage, the process gas that is cooled to 127 ℃ from secondary sulphur condensate cooler 5 passes through gas/gas interchanger 7 backs and 650 ℃ of process gas heat exchange of extracting 70%~50% from first tube side of waste heat boiler 2 out, enters second reactor 8 after temperature rises to 340 ℃; After 650 ℃ of process gas heat exchange of first tube side extraction 70%~50% of waste heat boiler 2, return in the import process gas of one-level sulphur condensate cooler 3, after the regeneration fully, the process gas that is cooled to 127 ℃ from B-grade condensation water cooler 5 does not need heat just directly to enter second reactor 8 beginning precooling process by three-way switch valve 9 again; The 4th step: the process gas that goes out second reactor 8 enters three grades of sulphur condensate coolers 6 and is cooled to 127 ℃, and wherein the molten sulfur of condensation is told and flowed to the molten sulfur pipeline, and gas enters three reactor 19 and carries out the low-temperature Claus reaction; The 5th step: the process gas that goes out three reactor 19 enters level Four sulphur condensate cooler 10 and is cooled to 127 ℃, and wherein the molten sulfur of condensation is told and flowed to the molten sulfur pipeline, and gas enters fourth-order reaction device 11 and carries out low-temperature Claus reaction then; The 6th step: the process gas that goes out the fourth-order reaction device enters Pyatyi sulphur condensate cooler 12 and is cooled to 127 ℃, wherein the molten sulfur of condensation is told and is flowed to the molten sulfur pipeline, gas enters and enters tail gas burning furnace 14 after sulphur drop that molten sulfur trap 13 will wherein carry and sulphur mist capture then, the waste gas after the burning through flue by chimney 23 dischargings; This device secondary, three grades, 8,19,11 and three grades of fourth-order reaction devices, level Four, Pyatyi sulphur condensate cooler 6,10,12 carry out the time variable control operation by seven switching valves;
Embodiment one:
Step 0: original state
When the on off sequence initialize, air communication is crossed the unitary approach of sulphur recovery and is entered recycling step of the present invention, when step 0, air communication is crossed one-level sulphur condensate cooler 3, A reactor 4, secondary sulphur condensate cooler 5, second reactor 8, three grades of sulphur condensate coolers 6, three reactor 19, level Four sulphur condensate cooler 10, fourth-order reaction device 11, Pyatyi sulphur condensate cooler 12, arrive tail gas burning furnace 14 then, when two, three, fourth- order reaction device 8,19,11 when being in adsorbed state, and sulfur recovery rate is the maximum in this cycle, and this mode lasts till when the sulphur adsorptive capacity is near 0.75 kilogram of sulphur of per kilogram catalyzer absorption in second reactor 8 always just to be finished;
Step 1: switch three-way valve 9
Switch three-way valve 9, the process gas that secondary sulphur condensate cooler 5 is exported enters gas/gas interchanger 7 and is warming up to 340 ℃, enters second reactor 8 then; Step 1 will continue 1 minute;
Step 2: second reactor 8 heating
Along with 340 ℃ process air-flows arrive second reactor 8, just begin heating, temperature is 340 ℃ when the beds top, and arriving the bed bottom is 300 ℃, and this step continues 4 hours;
Step 3: 8 regeneration or steady stages of second reactor
When second reactor 8 temperature outs reach 300 ℃, sulphur begins to separate sucking-off from catalyzer, this will continue 3 hours, when this step will finish, the temperature of second reactor 8 exit gass will rise to 340 ℃ rapidly, whole reaction bed temperature also is 340 ℃, and does not almost have sulphur in the catalyzer;
Step 4: second reactor 8 regeneration or endothermic phases
Finish the regeneration of second reactor 8, process gas need continue to flow through beds 30 minutes can guarantee that so all sulphur parses fully from catalyst bed;
Step 5: switch three-way valve 9 again
During this step, switch three-way valve 9 again, and the process gas that 5 outlets of secondary sulphur condensate cooler are 127 ℃ does not enter gas/gas interchanger 7 and just directly enters second reactor 8;
Step 6: second reactor 8 precoolings
Because secondary sulphur condensate cooler 5 just directly leads to second reactor 8 without hot again, so the temperature of beds begins to descend, head temperature is cooled to about 127 ℃ from 340 ℃, about 240 ℃ of bottom, stop when second reactor 8 Outlet Gas Temperatures arrive 240 ℃, this step continues 3 hours;
Step 7: switch three-way valve 17, open two-port valve 18
During this step, open two-port valve 18, switch three-way valve 17 is transferred to angled position simultaneously; Air-flow will be by second reactor 8 and three reactor 19; Tail gas forwards tail gas burning furnace 14 to from three grades of sulphur condensate coolers 6;
Step 8: switch three-way valve 22, close two-port valve 16
When the mid-way of two-port valve 18, begin to close two-port valve 16 to switch; When T-valve 17 arrived the mid-way, T-valve 22 began to switch to dc state; Air communication is crossed secondary sulphur condensate cooler 5, three reactor 19, and level Four sulphur condensate cooler 10, fourth-order reaction device 11, Pyatyi sulphur condensate cooler 12,8, three grades of sulphur condensate coolers 6 of second reactor arrive tail gas burning furnace 14 then;
Step 9: second reactor absorption and last cooling
At this moment, three reactor 19 is first reactor 4 and the process gas of absorption from secondary sulphur condensate cooler 5.This step continues about 3 hours, adsorbs 0.75 kilogram of sulphur up to sulphur adsorptive capacity in three reactor 9 near about per kilogram catalyzer;
Step in the remaining cycle is a step 1 to 9 repetition, with different reactor sequences;
Step 10-switch three-way valve 9
Switch three-way valve 9, the process gas of secondary sulphur condensate cooler 5 enters gas/gas interchanger 7, and temperature is risen to 340 ℃.This step continues about 1 minute;
The heating of step 11-three reactor
The process gas that enters 7,340 ℃ in gas/gas interchanger along with the process gas of secondary sulphur condensate cooler 5 flows to three reactor 19, just begins heating.Before this step, temperature will be that about 340 ℃ and temperature will be about 300 ℃ in the bed bottom on beds.This step continues about 4 hours;
Step 12-three reactor 19 regeneration plateaus
When three reactor 19 temperature outs reach 296 ℃, sulphur begins to separate sucking-off from catalyzer.To produce 6 tonnes of sulphur during this step, it will continue about 3 hours.When this step will finish, three reactor 19 Outlet Gas Temperatures will rise to about 340 ℃ rapidly, almost not have sulphur in the catalyzer;
19 regeneration heat absorption or the thermal treatments of step 13-three reactor
Finish the regeneration of three reactor 19, the process gas of heat about 30 minutes of the beds that continues to flow through.This guarantees that all sulphur desorb from catalyst bed fully;
Step 14-switch three-way valve 9
During this step, switch three-way valve 9, the process gas that 5 outlets of secondary sulphur condensate cooler are 127 ℃ does not enter gas/gas interchanger 7 and directly enters three reactor 19;
19 precoolings of step 15-three reactor
Because refrigerative is handled gas from secondary sulphur condensate cooler 5 three reactor 19 of flowing through, beds is cooled at the top about 127 ℃ and in the bottom about 240 ℃ from 340 ℃, stop when three reactor 19 Outlet Gas Temperatures arrive 240 ℃, this step continues about 3 hours;
Step 16-switch three-way valve 20 is opened two-port valve 21
Two-port valve 21 is opened during this step, and T-valve 20 is transferred to angled position simultaneously.Air-flow will be by three reactor 19 and fourth-order reaction device 11, and tail gas will begin to forward to tail gas burning furnace 14 from level Four sulphur condensate cooler 10;
Step 17-switch three-way valve 17 is closed two-port valve 18
When two-port valve 21 semi-open mid-ways to switch, two-port valve 18 begins to cut out.When T-valve 20 confirm to arrive its mid-way by the mid-way switch, T-valve 17 will begin to switch to dc state.Air-flow is by secondary sulphur condensate cooler 5 now, fourth-order reaction device 11, and Pyatyi sulphur condensate cooler 12,8, three grades of sulphur condensate coolers 6 of second reactor, three reactor 19, level Four sulphur condensate cooler 10 arrives tail gas burning furnace 14 then;
19 absorption of step 18-three reactor and last cooling
At this moment, fourth-order reaction device 11 is A reactor 4 and the process gas of absorption from secondary sulphur condensate cooler 5, and second reactor 8 is that second after reaction device is because it finishes its last cooling step for the absorption preparation.This step continues about 3 hours, adsorbs 0.75 kilogram of sulphur up to sulphur adsorptive capacity in fourth-order reaction device 11 near about per kilogram catalyzer;
Step 19-switch three-way valve 9
Switch three-way valve 9, the process gas of secondary sulphur condensate cooler 5 enters gas/gas interchanger 7, and temperature is risen to 340 ℃.This step continues about 1 minute;
11 heating of step 20-fourth-order reaction device
The process gas that enters 7,340 ℃ in gas/gas interchanger along with the process gas of secondary sulphur condensate cooler 5 flows to fourth-order reaction device 11, just begins heating.Before this step, temperature will be that about 344 ℃ and temperature will be about 300 ℃ in the bed bottom on beds.This step continues about 4 hours;
Step 21-fourth-order reaction device 11 regeneration plateaus
When fourth-order reaction device 11 temperature outs reach 296 ℃, sulphur begins to separate sucking-off from catalyzer, will produce 6 tonnes of sulphur during this step, and it will continue about 2.8 hours.When this step will finish, fourth-order reaction device 11 Outlet Gas Temperatures will rise to about 340 ℃ rapidly, and in the end in this step, whole reaction bed temperature is at 340 ℃, and almost not have sulphur in the catalyzer;
Step 22-fourth-order reaction device 11 regeneration (heat absorption or thermal treatment)
Finish the regeneration of fourth-order reaction device 11, the process gas of heat about 30 minutes of the beds that continues to flow through, this guarantees that all sulphur desorb from catalyst bed fully;
Step 23-switch three-way valve 9
During this step, switch three-way valve 9, the process gas that 5 outlets of secondary sulphur condensate cooler are 127 ℃ does not enter gas/gas interchanger 7 and directly enters fourth-order reaction device 11;
11 precoolings of step 24-fourth-order reaction device
Because refrigerative is handled gas from the secondary sulphur condensate cooler 5 fourth-order reaction device 11 of flowing through, beds is cooled at the top about 127 ℃ and in the bottom about 240 ℃ from 344 ℃, and this step continued about 3 hours and termination when fourth-order reaction device 11 Outlet Gas Temperatures arrive 241 ℃;
Step 25-switch three-way valve 22 is opened two-port valve 16
Two-port valve 16 is opened during this step, and T-valve 22 is transferred to angled position simultaneously.Air-flow will be by fourth-order reaction device 11 and second reactor 8, and tail gas will begin to forward to tail gas burning furnace 14 from Pyatyi sulphur condensate cooler 12;
Step 26-switch three-way valve 20 is closed two-port valve 21
When two-port valve 16 semi-open mid-ways to switch, two-port valve 21 begins to cut out.Confirm to arrive its mid-way by the mid-way switch when T-valve 22, T-valve 20 will begin to switch to dc state, air-flow is by secondary sulphur condensate cooler 5 now, 8, three grades of sulphur condensate coolers 6 of second reactor, three reactor 19, level Four sulphur condensate cooler 10, fourth-order reaction device 11, Pyatyi sulphur condensate cooler 12 arrives tail gas burning furnace 14 then;
Step 25 and 26 order be must guarantee the there always an open access to tail gas burning furnace 14;
11 absorption of step 27-fourth-order reaction device and last cooling
At this moment, second reactor 8 is first reactor and the process gas of absorption from one-level sulphur condensate cooler 3, and fourth-order reaction device 11 is that second after reaction device is because it finishes its last cooling step for the absorption preparation.This step continues about 3 hours, adsorbs 0.75 kilogram of sulphur up to sulphur adsorptive capacity in second reactor 8 near about per kilogram catalyzer;
Step 28-switch three-way valve 9
Switch three-way valve 9, the process gas of secondary sulphur condensate cooler 5 enters gas/gas interchanger 7, and temperature is risen to 340 ℃.This step continues about 1 minute, gets back to step 2 then;
Embodiment two:
One step: isolate sour water from the acid gas that desulfurization unit comes through the acid gas separator, again after the heating of acid gas preheater, enter the air thorough mixing after the air preheater heating that main burning furnace 1 and main air blower send here and in stove, carry out claus reaction; Two steps: the high temperature gas flow that is come out by main burning furnace 1 is divided into two partly after the first tube side temperature of waste heat boiler 2 is reduced to 650 ℃, first partly high temperature gas flow tell the process gas fusion that 30%~50% process gas is used for coming out with one-level sulphur condensate cooler 3 and heat up, another partly remaining high temperature gas flow continues to be cooled to 316 ℃ by second tube side of waste heat boiler 2, and then be cooled to 160 ℃ through one-level sulphur condensate cooler 3, here, most sulphur steam is condensed; Three steps: 650 ℃ of process gas of 70%~50% that process gas that comes out from one-level sulphur condensate cooler 3 and waste heat boiler 2 come out are mixed to 280 ℃, enter A reactor, H2S in the air-flow and SO2 react generting element sulphur on beds, the process gas of A reactor outlet enters secondary sulphur condensate cooler 5 and is cooled to 127 ℃, most sulphur vapor condensations are wherein become molten sulfur, and tell the molten sulfur of condensation, reduce the sulphur content in the process gas that enters the downstream greatly; Four steps: if second reactor 8 is in regeneration, pre-cold conditions, and three reactor 19, fourth-order reaction device 11 are in the state of absorption, so:
The regeneration initial stage, be cooled to 600 ℃ of flue gases that 127 ℃ of process gas extract out on by gas/gas interchanger and incinerator exhaust pass from secondary sulphur condensate cooler and carry out heat exchange, temperature enters second reactor after rising to 340 ℃, the molten sulfur that adsorbs on the beds is progressively vaporized, after rising to 340 ℃, temperature enters second reactor 8, the molten sulfur that adsorbs on the beds is progressively vaporized, after the regeneration fully, the process gas that is cooled to 127 ℃ from secondary sulphur condensate cooler 5 does not need heat just directly to enter second reactor 8 by three-way switch valve again, regenerating completely, second reactor 8 begins precooling process, process gas progressively reacts transition to low-temperature Claus in second reactor 8, at this moment, the catalyzer that is about to enter reproduced state in three reactor 19 does not adsorb saturated as yet, keep the cryogenic absorption attitude, catalyzer absorption in reactor 19 is saturated, when being about to enter reproduced state, regenerating completely, second reactor 8 carries out the transition to cold state fully, at this moment, the saturated cryogenic absorption attitude reactor of absorption switches to high temperature regeneration; Four steps: the process gas that goes out second reactor 8 enters three grades of sulphur condensate coolers 6 and is cooled to 127 ℃, and wherein the molten sulfur of condensation is told and flowed to the molten sulfur pipeline, and gas enters three reactor 19, carries out the low-temperature Claus reaction therein; Five steps: the process gas that goes out three reactor 19 enters level Four sulphur condensate cooler 10 and is cooled to 127 ℃, and wherein the molten sulfur of condensation is told and flowed to the molten sulfur pipeline, and gas enters fourth-order reaction device 11, carries out the low-temperature Claus reaction therein; Six steps: the process gas that goes out the fourth-order reaction device enters Pyatyi sulphur condensate cooler 12 and is cooled to 127 ℃, wherein the molten sulfur of condensation is told and is flowed to the molten sulfur pipeline, gas enters and enters tail gas burning furnace 14 after sulphur drop that molten sulfur trap 13 will wherein carry and sulphur mist capture, the waste gas after the burning through flue by chimney 23 dischargings; This device secondary, three grades, 8,19,11 and three grades of fourth-order reaction devices, level Four, Pyatyi sulphur condensate cooler 6,10,12 carry out the time variable control operation by seven switching valves; The detail operations step is as follows:
Step 0: original state
When the on off sequence initialize, air communication is crossed the unitary approach of sulphur recovery and is entered recycling step of the present invention, when step 0, air communication is crossed one-level sulphur condensate cooler 3, A reactor 4, secondary sulphur condensate cooler 5, second reactor 8, three grades of sulphur condensate coolers 6, three reactor 19, level Four sulphur condensate cooler 10, fourth-order reaction device 11, Pyatyi sulphur condensate cooler 12, arrive tail gas burning furnace 14 then, when two, three, fourth- order reaction device 8,19,11 when being in adsorbed state, and sulfur recovery rate is the maximum in this cycle, and this mode lasts till when the sulphur adsorptive capacity is near 0.75 kilogram of sulphur of per kilogram catalyzer absorption in second reactor 7 always just to be finished;
Step 1: switch three-way valve 9
Switch three-way valve 9, the process gas that secondary sulphur condensate cooler 5 is exported enters gas/gas interchanger 7 and is warming up to 340 ℃, enters second reactor 8 then; Step 1 will continue 1 minute;
Step 2: second reactor 8 heating
Along with 340 ℃ process air-flows arrive second reactor 8, just begin heating, temperature is 340 ℃ when the beds top, and arriving the bed bottom is 300 ℃, and this step continues 4 hours;
Step 3: 8 regeneration or steady stages of second reactor
When second reactor 8 temperature outs reach 300 ℃, sulphur begins to separate sucking-off from catalyzer, this will continue 3 hours, when this step will finish, the temperature of second reactor 8 exit gass will rise to 340 ℃ rapidly, whole reaction bed temperature also is 340 ℃, and does not almost have sulphur in the catalyzer;
Step 4: second reactor 8 regeneration or endothermic phases
Finish the regeneration of second reactor 8, process gas need continue to flow through beds 30 minutes can guarantee that so all sulphur parses fully from catalyst bed;
Step 5: switch three-way valve 9 again
During this step, switch three-way valve 9 again, and the process gas that 5 outlets of secondary sulphur condensate cooler are 127 ℃ does not enter gas/gas interchanger 7 and just directly enters second reactor 8;
Step 6: second reactor 8 precoolings
Because secondary sulphur condensate cooler 5 just directly leads to second reactor 8 without hot again, so the temperature of beds begins to descend, head temperature is cooled to about 127 ℃ from 340 ℃, about 240 ℃ of bottom, stop when second reactor 8 Outlet Gas Temperatures arrive 240 ℃, this step continues 3 hours;
Step 7: switch three-way valve 17, open two-port valve 18
During this step, open two-port valve 18, switch three-way valve 17 is transferred to angled position simultaneously; Air-flow will be by second reactor 8 and three reactor 19; Tail gas forwards tail gas burning furnace 14 to from three grades of sulphur condensate coolers 6;
Step 8: switch three-way valve 22, close two-port valve 16
When the mid-way of two-port valve 18, begin to close two-port valve 16 to switch; When T-valve 17 arrived the mid-way, T-valve 22 began to switch to dc state; Air communication is crossed secondary sulphur condensate cooler 5, three reactor 19, and level Four sulphur condensate cooler 10, fourth-order reaction device 11, Pyatyi sulphur condensate cooler 12,8, three grades of sulphur condensate coolers 6 of second reactor arrive tail gas burning furnace 14 then;
Step 9: second reactor absorption and last cooling
At this moment, three reactor 19 is first reactor 4 and the process gas of absorption from secondary sulphur condensate cooler 5, and this step continues 3 hours, up to 0.75 kilogram of sulphur of the approaching about per kilogram catalyzer absorption of sulphur adsorptive capacity in three reactor 9.
Annotate: the step in the remaining cycle is a step 1 to 9 repetition, with different reactor sequences.This part is remaining to have integrity.
Step 10-switch three-way valve 9
Switch three-way valve 9, the process gas of secondary sulphur condensate cooler 5 enters gas/gas interchanger 7, and temperature is risen to 340 ℃.This step continues about 1 minute;
The heating of step 11-three reactor
Along with the process gas of secondary sulphur condensate cooler 5 enters gas/gas interchanger 7,340 ℃ process gas flows to three reactor 19, just begin heating, before this step, temperature will be that about 340 ℃ and temperature will be about 300 ℃ in the bed bottom on beds, and this step continues about 4 hours;
19 regeneration (plateau) of step 12-three reactor
When three reactor 19 temperature outs reach 296 ℃, sulphur begins to separate sucking-off from catalyzer, during this step, will produce 6 tonnes of sulphur, it will continue about 3 hours, when this step will finish, three reactor 19 Outlet Gas Temperatures will rise to about 340 ℃ rapidly, almost not have sulphur in the catalyzer;
Step 13-three reactor 19 regeneration (heat absorption or thermal treatment)
Finish the regeneration of three reactor, the process gas of heat about 30 minutes of the beds that continues to flow through, this guarantees that all sulphur parse from catalyst bed fully;
Step 14-switch three-way valve 9
During this step, switch three-way valve 9, the process gas that 5 outlets of secondary sulphur condensate cooler are 127 ℃ does not enter gas/gas interchanger 7 and directly enters three reactor 19;
19 precoolings of step 15-three reactor
Because refrigerative is handled gas from secondary sulphur condensate cooler 5 three reactor 19 of flowing through, beds from 340 ℃ be cooled at the top about 127 ℃ with in the bottom about 240 ℃ (different devices is difference slightly), stop when three reactor 19 Outlet Gas Temperatures arrive 240 ℃, this step continues about 3 hours;
Step 16-switch three-way valve 20 is opened two-port valve 21
Two-port valve 21 is opened during this step, and T-valve 20 is transferred to angled position simultaneously.Air-flow will be by three reactor 19 and fourth-order reaction device 11, and tail gas will begin to forward to tail gas burning furnace 14 from level Four sulphur condensate cooler 10;
Step 17-switch three-way valve 17 is closed two-port valve 18
When two-port valve 21 semi-open mid-ways to switch, two-port valve 18 begins to cut out.Confirm to arrive its mid-way by the mid-way switch when T-valve 20, T-valve 17 will begin to switch to dc state, air-flow is by secondary sulphur condensate cooler 5 now, fourth-order reaction device 11, Pyatyi sulphur condensate cooler 12, second reactor 8, three grades of sulphur condensate coolers 6, three reactor 19, level Four sulphur condensate cooler 10 arrives tail gas burning furnace 14 then;
19 absorption of step 18-three reactor and last cooling
At this moment, fourth-order reaction device 11 is A reactor 4 and the process gas of absorption from secondary sulphur condensate cooler 5, and second reactor 8 is that second after reaction device is because it finishes its last cooling step for the absorption preparation.This step continues about 3 hours, adsorbs 0.75 kilogram of sulphur up to sulphur adsorptive capacity in fourth-order reaction device 11 near about per kilogram catalyzer;
Step 19-switch three-way valve 9
Switch three-way valve 9, the process gas of secondary sulphur condensate cooler 5 enters gas/gas interchanger 7, and temperature is risen to 340 ℃, and this step continues about 1 minute;
11 heating of step 20-fourth-order reaction device
Along with the process gas of secondary sulphur condensate cooler 5 enters gas/gas interchanger 7,340 ℃ process gas flows to fourth-order reaction device 11, just begin heating, before this step, temperature will be that about 344 ℃ and temperature will be about 300 ℃ in the bed bottom on beds.This step continues about 4 hours;
11 regeneration (plateau) of step 21-fourth-order reaction device
When fourth-order reaction device 11 temperature outs reach 296 ℃, sulphur begins to separate sucking-off from catalyzer.To produce 6 tonnes of sulphur during this step, it will continue about 2.8 hours, when this step will finish, fourth-order reaction device 11 Outlet Gas Temperatures will rise to about 340 ℃ rapidly, in the end in this step, whole reaction bed temperature is at 340 ℃, and does not almost have sulphur in the catalyzer;
Step 22-fourth-order reaction device 11 regeneration (heat absorption or thermal treatment)
Finish the regeneration of fourth-order reaction device 11, the process gas of heat about 30 minutes of the beds that continues to flow through, this guarantees that all sulphur parse from catalyst bed fully;
Step 23-switch three-way valve 9
During this step, switch three-way valve 9, the process gas that 5 outlets of secondary sulphur condensate cooler are 127 ℃ does not enter gas/gas interchanger 7 and directly enters fourth-order reaction device 11;
11 precoolings of step 24-fourth-order reaction device
Because refrigerative is handled gas from the secondary sulphur condensate cooler 5 fourth-order reaction device 11 of flowing through, beds from 344 ℃ be cooled at the top about 127 ℃ with in the bottom about 240 ℃ (different devices is difference slightly).This step continued about 3 hours and stopped when fourth-order reaction device 11 Outlet Gas Temperatures arrive 241 ℃;
Step 25-switch three-way valve 22 is opened two-port valve 16
Two-port valve 16 is opened during this step.T-valve 22 is transferred to angled position simultaneously.Air-flow will be by fourth-order reaction device 11 and second reactor 8.Tail gas will begin to forward to tail gas burning furnace 14 from Pyatyi sulphur condensate cooler 12;
Step 26-switch three-way valve 20 is closed two-port valve 21
When two-port valve 16 semi-open mid-ways to switch, two-port valve 21 begins to cut out.When T-valve 22 confirm to arrive its mid-way by the mid-way switch, T-valve 20 will begin to switch to dc state.Air-flow is by secondary sulphur condensate cooler 5 now, 8, three grades of sulphur condensate coolers 6 of second reactor, and three reactor 19, level Four sulphur condensate cooler 10, fourth-order reaction device 11, Pyatyi sulphur condensate cooler 12 arrives tail gas burning furnace 14 then;
Step 25 and 26 order be must guarantee the there always an open access to tail gas burning furnace 14;
11 absorption of step 27-fourth-order reaction device and last cooling
At this moment, second reactor 8 is first reactor and the process gas of absorption from one-level sulphur condensate cooler 3, and fourth-order reaction device 11 is that second after reaction device is because it finishes its last cooling step for the absorption preparation.This step continues about 3 hours, adsorbs 0.75 kilogram of sulphur up to sulphur adsorptive capacity in second reactor 8 near about per kilogram catalyzer;
Step 28-switch three-way valve 9
Switch three-way valve 9, the process gas of secondary sulphur condensate cooler 5 enters gas/gas interchanger 7, and temperature is risen to 340 ℃, and this step continues about 1 minute, gets back to step 2 then.