CN104986740A - Claus tail gas treatment system and treatment method - Google Patents
Claus tail gas treatment system and treatment method Download PDFInfo
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- CN104986740A CN104986740A CN201510461344.7A CN201510461344A CN104986740A CN 104986740 A CN104986740 A CN 104986740A CN 201510461344 A CN201510461344 A CN 201510461344A CN 104986740 A CN104986740 A CN 104986740A
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Abstract
The invention provides a Claus tail gas treatment system. The system comprises a hydrogenation unit, a fast cooling unit, a desulfurization unit, an optional hydrolysis unit and an optional liquid sulfur degassing gas supply unit. The invention further provides a Claus tail gas treatment method. According to the tail gas treatment system and treatment method provided by the invention, the sulfur removal rate can be greater than 99.99%; H2S concentration of exhaust gas emitted into the atmosphere is less than 10 ppm, and is, when converted into the SO2 concentration, less than 50 mg/m3; the removal rate and emission concentration can meet the current highest emission limit standard. Furthermore, the system and method have the advantages of: being environmentally-friendly, stable and reliable, less in investment and low in operating cost.
Description
Technical field
The present invention relates to sulfur-containing tail gas process field, be specifically related to a kind for the treatment of system of claus sulphur recovery units tail gas, and adopt the exhaust gas treating method of described treatment system.
Background technology
In the production process such as petrochemical complex, Coal Chemical Industry, the sulphur in raw material finally changes into hydrogen sulfide containing sour gas in the course of processing, must carry out processing or reclaiming.Usually adopt Crouse's recovery technology of sulfur that hydrogen sulfide is changed into sulphur at present.
Crouse's recovery technology of sulfur is made up of a thermal response section and several catalyst reaction section, namely containing H
2the sour gas of S carries out incomplete combustion with air in roasting kiln, strictly controls air quantity, makes H
2the SO generated after S burning
2amount meets H
2s/SO
2molecular ratio equals or close to 2, H
2s and SO
2at high temperature react generting element sulphur, by the restriction of thermodynamic condition, remaining H
2s and SO
2enter catalyst reaction section under the effect of catalyzer, proceed the reaction of generting element sulphur.All arrange sulfur condenser in thermal response section and each catalyst reaction section downstream, elemental sulphur condenses reaction generated is separated, and condensed liquid-state sulfur enters the wait of liquid stream storage tank and directly transports outward or be molded into solid sulfur outward transport with molten sulfur.
In the reaction that thermal response section occurs, the chemical equation of main reaction is as follows:
H
2S+3/2O
2---SO
2+H
2O
2H
2S+SO
2---3/2S
2+2H
2O
The chemical equation of side reaction is as follows:
C
nH
(2n+2)+(3n+1)/2O
2---(n+1)H
2O+n CO
2
H
2S+CO
2---COS+H
2O
CH
4+2S
2---CS
2+2H
2S
2NH
3+3/2O
2---3H
2O+N
2
CO
2+3/2S
2---CS
2+SO
2
In the reaction that catalyst reaction section occurs, the chemical equation of main reaction is as follows:
2H
2S+SO
2---3/xS
x+2H
2O
Side reaction (mainly COS and CS
2hydrolysis reaction) chemical equation as follows:
COS+H
2O---CO
2+H
2S
CS
2+2H
2O---CO
2+2H
2S
In Crouse's recovery technology of sulfur, due to the restriction by chemical equilibrium under temperature of reaction and reversible reaction, even if when equipment and operational condition good, use active good catalyzer and three grades of claus process, sulfur recovery rate is the highest also can only reach 95% ~ 97%, needs to adopt sulfur recovery tail gas treatment process to carry out further emissions reduction.
So far nearly 20 kinds more than of industrialized tail gas clean-up technique has been realized.Mainly be divided into the three major types such as low temperature Claus process, selective oxidation method, reducing absorping method.
Low temperature Claus process is when lower than sulphur dew point, H on solid catalyst
2s and SO
2proceed claus reaction, because temperature is lower, after the condensation of the sulphur of gaseous state, be conducive to molecular balance and move towards the direction generating sulphur, increase sulfur recovery rate, the sulfur recovery rate adopting this technique to make the sulfur recovery unit of vent gas treatment total reaches as high as 99%.This method comparatively speaking simple, the facility investment of flow process and process cost lower.Because temperature is lower, thus COS, CS
2cannot transform decomposition Deng organic sulfide in tail gas, the method is to front end sulphur technique H simultaneously
2s/SO
2proportion requirement strict.
Selective oxidation method is after Crouse's sulphur recovery, increase the reactor that is equipped with catalyst for selective oxidation, and this catalyzer is by H
2the direct selective oxidation of S becomes elementary sulfur, in order to make substantially not contain SO in the final stage claus reaction device outlet of upstream sulfur recovery facility
2, now sulphur recovery must be made to adopt the excessive operation of hydrogen sulfide, instead of conventional control H
2s/SO
2the operation measure of=2, makes the hydrogen sulfide containing 0.8% ~ 1.5% (v) in the tail gas of the final stage reactor leaving sulphur recovery.The sulfur recovery rate adopting this technique to make the sulfur recovery unit of vent gas treatment total is about 99%.
Reducing absorping method is mixed by the reducing gas such as Claus tail gases and hydrogen and after being heated to about 220 DEG C, entering hydrogenator, under hydrogenation catalyst effect, make the sulphur in tail gas and sulfide (S
6, S
8, COS, CS
2) being almost all transformed into hydrogen sulfide, this Process Gas enters desulfuration absorbing tower after cooling, and most hydrogen sulfide and partial CO 2, by hydramine solvent absorbing, make total sulfur in tail gas be less than 300ppm, discharge after tail gas burns.Absorb hydrogen sulfide, the rich solution of carbonic acid gas enters regenerator column, regeneration overhead sour gas delivers to sulfur recovery as raw material, and the lean solution after regeneration returns to absorption tower and recycles.This technique utilizes the sulphur in tail gas of sulphur and sulfide hydrogenating reduction or is hydrolyzed into hydrogen sulfide, and through hydramine solvent absorbing to reach the object of cleaning of off-gas, the total sulfur in tail gas can be reduced to below 300ppm, and the total yield of sulphur can reach 99.8%.This method technical process is more complicated, operation and working cost very high.
Generally speaking, in this three classes treatment process, though selective oxidation processes and low-temperature Claus technique have the advantages such as technical process is simple, less investment, process cost are low, sulfur recovery rate is low, can only 99% be reached, can not meet in existing national source of atmospheric pollution emission standard SO
2emission concentration is less than 550mg/m
3requirement.Reduction-absorption process flow process is complicated, it is high to invest, process cost is high, though the requirement of existing national discharge standard of air pollutants can be met, but desulfurization degree can only reach 99.8%, higher environmental protection standard can not be met, such as, even if adopt special formulation alcohol amine solvent, strengthen solvent cycle amount and the regeneration degree of depth, also cannot meet major area SO in petroleum refining industry pollutant emission standard
2<100mg/m
3, general regional SO in petrochemical industry pollutant emission standard
2<100mg/m
3requirement, more cannot reach major area SO in petrochemical industry pollutant emission standard
2<50mg/m
3standard.
In recent years, due to the restriction of environmental capacity, the requirement of local governments at all levels to the emission concentration of sulfur recovery rate and sulphur is higher, and drug in some provinces requires SO
2emission concentration is less than 50mg/m
3, this has higher requirement to sulfur recovery tail gas treatment process.
In addition, be pooled to the molten sulfur of molten sulfur storage tank from every grade of sulfur condenser and be generally dissolved with a small amount of H
2s, in order to ensure safe processing or transport, first must remove the H be dissolved in wherein from molten sulfur
2s, general adopts circulation spray processing or stripping process, utilizes the sprinkling of molten sulfur to stir or pass into hydrogen sulfide content gas that is extremely low or not sulfur-bearing to carry out the means such as stripping and remove hydrogen sulfide, removes H at these
2can be formed containing H in the process of S
2the waste gas of S, is called molten sulfur degasification gas, and the sulfide in usual molten sulfur degasification gas is to SO in exhaust emissions
2contribution reach 100 ~ 200mg/m
3, therefore, also need to process this gas.
Summary of the invention
In view of the above-mentioned defect existed in current Crouse's sulfur recovery tail gas treatment process, an object of the present invention is to provide a kind of claus tail-gas clean-up system both at home and abroad.
Another object of the present invention is to provide a kind of claus tail-gas clean-up method.
A kind of claus tail-gas clean-up system provided by the invention, comprises following processing unit:
Hydrogenation unit, for pending Claus tail gases and reducing gas being reacted, makes wherein sulfur-bearing composition change H into
2s;
Hydrolysis unit, for COS, CS of will remaining in the tail gas of described hydrogenation unit
2h is changed into by hydrolysis reaction
2s;
Quenching unit, for cooling the tail gas of described hydrolysis unit; And
Desulfurization unit, for the tail gas of described quenching unit is carried out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into.
In claus tail-gas clean-up system provided by the invention, described treatment system also comprises the molten sulfur degasification gas feed unit for providing described molten sulfur degasification gas to carry out oxidation sweetening process, and it is connected with described desulfurization unit.
In claus tail-gas clean-up system provided by the invention, described molten sulfur degasification gas feed unit comprises sulphur mist washing device and jet apparatus, described sulphur mist washing device washes away sulphur in described molten sulfur degasification gas for using spray water, and described jet apparatus is used for desulfurization unit described in the described molten sulfur degasification gas suction after by washing.
In claus tail-gas clean-up system provided by the invention, described hydrolysis unit comprises desuperheating device and hydrolysis reaction device, wherein, described desuperheating device is used for the tail gas of described hydrogenation unit to carry out desuperheating process, its heat-eliminating medium is water vapor, described hydrolysis reaction device is used for the tail gas of the described hydrogenation unit after desuperheating process to be hydrolyzed reaction, is wherein filled with hydrolyst.
Another kind of claus tail-gas clean-up system provided by the invention, comprises following processing unit:
Hydrogenation unit, for pending Claus tail gases and reducing gas being reacted, makes wherein sulfur-bearing composition change H into
2s;
Quenching unit, for cooling the tail gas of described hydrogenation unit;
Desulfurization unit, for the tail gas of described quenching unit is carried out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into; And
Molten sulfur degasification gas feed unit, it is connected with described desulfurization unit, states molten sulfur degasification gas carry out oxidation sweetening process for providing.
In claus tail-gas clean-up system provided by the invention, described treatment system also comprises hydrolysis unit, and it is between described hydrogenation unit and described quenching unit, for COS, CS of will remaining in the tail gas of described hydrogenation unit
2h is changed into by hydrolysis reaction
2s.
In claus tail-gas clean-up system provided by the invention, described hydrolysis unit comprises desuperheating device and hydrolysis reaction device, wherein, described desuperheating device is used for the tail gas of described hydrogenation unit to carry out desuperheating process, its heat-eliminating medium is water vapor, described hydrolysis reaction device is used for the tail gas of the described hydrogenation unit after desuperheating process to be hydrolyzed reaction, is wherein filled with hydrolyst.
In claus tail-gas clean-up system provided by the invention, described molten sulfur degasification gas feed unit comprises sulphur mist washing device and jet apparatus, described sulphur mist washing device washes away sulphur in described molten sulfur degasification gas for using spray water, and described jet apparatus is used for desulfurization unit described in the described molten sulfur degasification gas suction after by washing.
In above-mentioned claus tail-gas clean-up system, described hydrogenation unit comprises primary heater unit and hydrogenation reaction device, and wherein, described primary heater unit is used for Claus tail gases pending described in preheating, described hydrogenation reaction device is used for carrying out hydrogenation reaction, is wherein filled with hydrogenation catalyst.
In above-mentioned claus tail-gas clean-up system, described hydrogenation reaction device is also connected with reducing gas air supply unit, for providing reducing gas to described hydrogenation reaction device.
In above-mentioned claus tail-gas clean-up system, described quenching unit comprises quenching apparatus, recycle pump and refrigerating unit, the liquid distributor for spraying quenched water is provided with in described quenching apparatus, the quenched water of spray carries out chilling with the tail gas counter current contact of from bottom to top carrying, described recycle pump is connected with the bottom of described quenching apparatus, and described refrigerating unit is connected with the liquid distributor of described recycle pump and described quenching apparatus respectively.
In above-mentioned claus tail-gas clean-up system, described recycle pump is also connected with described sulphur mist washing device, for described sulphur mist washing device supplementary feed.
In above-mentioned claus tail-gas clean-up system, described desulfurization unit comprises desulphurization reactor containing catalyst solution and sulphur filtration unit, the tail gas of described quenching unit and/or described molten sulfur degasification gas oxidized generation elemental sulfur in described desulphurization reactor, is discharged after then being filtered by described elemental sulfur by described sulphur filtration unit.
In above-mentioned claus tail-gas clean-up system, described desulfurization unit also comprises connected liquid distributing device and supercharging device, described liquid distributing device is connected with described quenching unit, for removing the moisture in the tail gas of described quenching unit, described supercharging device is connected with described desulphurization reactor, after the tail gas of described quenching unit is carried out supercharging, pass into described desulphurization reactor.
A kind of claus tail-gas clean-up method provided by the invention comprises the following steps:
S1: pending Claus tail gases and reducing gas are reacted, makes wherein sulfur-bearing composition change H into
2s;
S2: be hydrolyzed the tail gas of described S1 step reaction, makes COS, CS of remaining
2change H into
2s;
S3: by tail gas quenching to 30 ~ 90 DEG C of described S2 step;
S4: the tail gas of described S3 step is carried out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into.
Wherein, by tail gas quenching to 40 ~ 80 DEG C of described S2 step in described S3 step, 50 ~ 70 DEG C are preferably chilled to.
Wherein, described S4 step also comprises: carry out oxidation sweetening process by from the molten sulfur degasification gas of Cross unit and the tail gas of described S3 step simultaneously.
Another kind of claus tail-gas clean-up method provided by the invention comprises the following steps:
S1: pending Claus tail gases and reducing gas are reacted, makes wherein sulfur-bearing composition change H into
2s;
S2: by tail gas quenching to 30 ~ 90 DEG C of described S1 step;
S3: carry out oxidation sweetening process by the tail gas of described S2 step and from the molten sulfur degasification gas of Cross unit, make H wherein
2s changes elemental sulfur into.
Wherein, by tail gas quenching to 40 ~ 80 DEG C of described S1 step in described S2 step, 50 ~ 70 DEG C are preferably chilled to.
Wherein, after described S1 step also comprises and pending Claus tail gases and reducing gas to be reacted, then the reaction that is hydrolyzed, make COS, CS of remaining
2change H into
2s.
Claus tail-gas clean-up system provided by the invention and treatment process have the following advantages:
(1) exhaust treatment system of the present invention and treatment process are by process such as hydrogenation, hydrolysis, oxidation sweetenings, and the sulfur-bearing composition in Claus tail gases can be made farthest to change H into
2s, then change solid-state elemental sulfur into and reclaim, the sulphur in waste gas can be made substantially to be removed and reclaim, and sulfur removal rate can reach more than 99.99%, is discharged into H in the tail gas of air
2s concentration is less than 10ppm, is converted to SO
2concentration <50mg/m
3, this decreasing ratio and emission concentration can meet current maximum emission limitation standard.
(2) exhaust treatment system of the present invention and treatment process are while process Claus tail gases, the molten sulfur degasification gas from molten sulfur storage tank can be made to carry out desulfurization process in the lump, further increase the quality of claus process exhaust gas emission, alleviate environmental pollution.
(3), in exhaust treatment system of the present invention and treatment process, the waste water produced for system can be used again, not only reduces the consumption of extraneous water resource, decreases the discharge of waste water, thus further mitigate environmental stress.
(4) treatment system of the present invention is reliable and stable, less investment, process cost are low, have a extensive future.
Accompanying drawing explanation
Fig. 1 is the structural representation of claus tail-gas clean-up system of the present invention;
Wherein, description of reference numerals is as follows: 11, primary heater unit; 12, hydrogenation reaction device; 21, desuperheating device; 22, hydrolysis reaction device; 31, quenching apparatus; 32, recycle pump; 33, refrigerating unit; 34, level control valve; 41, desulphurization reactor; 42, sulphur filtration unit; 43, liquid distributing device; 44, supercharging device; 51, sulphur mist washing device; 511, sulphur mist washer; 512, cleaning circulation pump; 52, jet apparatus; 521, injector; 522, squirt pump; A, Claus tail gases; B, reducing gas; The tail gas of C, hydrogenation unit; The tail gas of D, hydrolysis unit; The tail gas of E, quenching unit; F, elemental sulfur; The tail gas of G, desulfurization unit; H, molten sulfur degasification gas; I, low pressure water vapor; J, oxygen-containing gas.
Embodiment
Below, the present invention will be described in detail by reference to the accompanying drawings.
One aspect of the present invention provides a kind of claus tail-gas clean-up system, it comprises hydrogenation unit, hydrolysis unit, quenching unit and desulfurization unit successively according to treatment scheme, wherein, hydrogenation unit is used for pending Claus tail gases and reducing gas to react to make wherein sulfur-bearing composition change H into
2s, hydrolysis unit is used for COS, CS residual in the tail gas of hydrogenation unit
2h is changed into further by hydrolysis reaction
2s, quenching unit is used for the tail gas quenching of hydrolysis unit to lower the temperature, and desulfurization unit is used for the tail gas of quenching unit to carry out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into, completes the treating processes of Claus tail gases thus.
During above-mentioned claus tail-gas clean-up system works, first the tail gas A from Crouse's treatment unit enters hydrogenation unit, the SO in tail gas
2, COS, CS
2(H is mainly Deng sulfur-bearing composition and reducing gas B
2) reaction, generate H
2s, CO
2and H
2o.
SO
2+3H
2---H
2S+2H
2O
S+H
2---H
2S
Usually also comprise CO in reducing gas B, it participates in following reaction occurs:
SO
2+CO---COS+O
2
S+CO---COS
Meanwhile, also can there is following reaction in the tail gas A of Crouse's treatment unit:
COS+H
2O---H
2S+CO
2
CS
2+2H
2O---2H
2S+CO
2
In the tail gas C of hydrogenation unit, most of sulfur-bearing composition changes H into
2s form, but still a small amount of COS and CS may be remained
2, total amount is less than 100ppm usually, then enters hydrolysis unit and converts it into H further
2s, in hydrolysis unit, occurs to react as follows:
COS+H
2O---H
2S+CO
2
CS
2+2H
2O---2H
2S+CO
2
The tail gas typical temperature of hydrolysis unit is higher, and carry out desulfurization process again after need carrying out cooling process, therefore the tail gas D of hydrolysis unit enters quenching unit and carries out cooling process.The temperature of the tail gas E after quenching unit process can be 30 ~ 90 DEG C, is preferably 40 ~ 80 DEG C, most preferably is 50 ~ 70 DEG C.In Claus tail gases amine absorption technique conventional at present, exhaust temperature is generally 35 ~ 40 DEG C, its main purpose is that (such as 35 ~ 40 DEG C time) amine liquid has good assimilation effect to hydrogen sulfide when temperature is lower, and the present invention is due to without the need to carrying out amine absorption technique, therefore without the need to strictly controlling exhaust temperature, can regulate according to production status, be conducive to the usage quantity reducing heat-eliminating medium.
Tail gas E after quenching unit process sends in desulfurization unit, by the oxide treatment of desulfurization unit, by H
2s changes elemental sulfur F into, and solid elemental sulfur F can be used as byproduct and collects recycling, and the tail gas G of desulfurization unit directly discharges or burning disposal.
In an embodiment of claus tail-gas clean-up system according to the present invention, claus tail-gas clean-up system of the present invention also comprises molten sulfur degasification gas feed unit, it is connected with desulfurization unit, the molten sulfur degasification gas H produced can be delivered to desulfurization unit removing H wherein in Cross unit
2s.
In an embodiment of claus tail-gas clean-up system according to the present invention, as shown in Figure 1, molten sulfur degasification gas feed unit comprises the sulphur mist washing device 51 and jet apparatus 52 that connect successively, spray water is provided with in sulphur mist washing device 51, for washing away the sulphur in molten sulfur degasification gas H, jet apparatus 52 for by washing after molten sulfur degasification gas suction desulfurization unit.
In one preferred embodiment, as shown in Figure 1, sulphur mist washing device 51 comprises sulphur mist washer 511 and cleaning circulation pump 512, top in sulphur mist washer 511 is provided with spray thrower, from top to bottom spray washing water, and molten sulfur degasification gas H washs with its counter current contact from bottom to top, by spray, sulfur vapor contained in molten sulfur degasification gas H is removed, and making the temperature of molten sulfur degasification gas H be reduced to less than 120 DEG C, sulphur becomes solid-state by liquid conversion, is stored in bottom sulphur mist washer 511.Cleaning circulation pump 512 for by bottom sulphur mist washer 511 washing water extract out, and be delivered to spray thrower circulation spray.While molten sulfur degasification temperature degree reduces, sour water vaporization after portion washes enters in molten sulfur degasification gas, and therefore must supplement washing water, described washing water can from the supply outside treatment system, also the waste water of other unit for the treatment of system can be adopted, as the water coolant of quenching unit.The present invention is not particularly limited for sulphur mist washer, this area can be used to possess arbitrarily the equipment of same or similar function, such as washing tower etc.
In one preferred embodiment, as shown in Figure 1, jet apparatus 52 comprises injector 521 and squirt pump 522, and among the tail gas H suction desulfurization unit after sulphur mist washing device 51 can wash by injector 521, squirt pump 522 is for providing suction power for injector 521.The present invention is not particularly limited for injector, squirt pump, and this area can be used to possess arbitrarily the equipment of same or similar function.
In an embodiment of claus tail-gas clean-up system according to the present invention, as shown in Figure 1, hydrogenation unit comprises primary heater unit 11 and hydrogenation reaction device 12.Primary heater unit 11 is for the pending Claus tail gases A of preheating to suitable temperature of reaction, and primary heater unit 11 can possess arbitrarily the equipment of same or similar function, as interchanger etc. for this area.Hydrogenation reaction device 12 is for reacting the Claus tail gases A after preheating and reducing gas B, and hydrogenation reaction device 12 can be the equipment that this area possesses arbitrarily same or similar function, as hydrogenator etc.Hydrogenation catalyst is filled with in hydrogenation reaction device 12, hydrogenation catalyst is wherein not particularly limited, such as can select with aluminum oxide is the cobalt, molybdenum catalyst etc. of carrier, preferred low temperature hydrogenation catalyzer, it can run in the inlet temperature of 200 DEG C to 220 DEG C, thus steam heating reactor can be adopted, save facility investment.
In one preferred embodiment, hydrogenation reaction device 12 is also connected with reducing gas air supply unit, for providing reducing gas B to hydrogenation reaction device 12.
In an embodiment of claus tail-gas clean-up system according to the present invention, as shown in Figure 1, hydrolysis unit comprises the hydrolysis reaction device 22 in desuperheating device 21 and desuperheating device 21 downstream.Adopt low pressure water vapor I as heat-eliminating medium in desuperheating device 21, water can be provided as reaction raw materials to follow-up hydrolysis reaction simultaneously.Hydrolyst is filled with in hydrolysis reaction device 22, hydrolyst is not particularly limited, such as can select loading type organic sulfur hydrolyst or titanium base hydrolyst, preferably adopt titanium base hydrolyst, titanium base hydrolyst can keep very high tempreture organic sulphur hydrolysis transformation efficiency for a long time.First the tail gas C of hydrogenation unit enters desuperheating device 21 and lowers the temperature, so that follow-up hydrolysis reaction occurs at desirable temperature, the gas entrainment water after cooling enters in hydrolysis reaction device 22, and be hydrolyzed reaction under hydrolyst catalysis.The present invention is not particularly limited for desuperheating device, hydrolysis reaction device, this area can be used to possess arbitrarily the equipment of same or similar function, as usual heat exchanger, reactor.
In an embodiment of claus tail-gas clean-up system according to the present invention, as shown in Figure 1, quenching unit mainly comprises quenching apparatus 31, and it comprises bottom inlet mouth, air outlet, top, top water-in and bottom discharge mouth, and inside is provided with the liquid distributor for spraying quenched water.The tail gas D of hydrolysis unit enters in quenching apparatus 31 by bottom inlet mouth, quenched water is entered in quenching apparatus 31 by top water-in and is sprayed by liquid distributor, tail gas D carries out chilling with the quenched water counter current contact of spray in uphill process, tail gas E after chilling is discharged by air outlet, top, quenched water temperature after chilling raises, and is drawn out of by bottom discharge mouth.Quenching unit also comprises the recycle pump 32 and refrigerating unit 33 that are connected, recycle pump 32 is connected with the bottom discharge mouth of quenching apparatus 31, quenched water bottom quenching apparatus 31 is extracted out, in order to maintain the temperature of quenched water, it is carried out cooling process by refrigerating unit 33, refrigerating unit 33 is connected with liquid distributor by the top water-in of quenching apparatus 31, cooled quenched water can be used again.The present invention is not particularly limited for quenching apparatus, recycle pump, refrigerating unit, and this area can be used to possess arbitrarily the equipment of same or similar function, as quench tower, interchanger etc.As used quench tower, wherein can in-built filler, also can be empty spray tower.
In one preferred embodiment, as shown in Figure 1, recycle pump 32 can be connected with the sulphur mist washer 511 of molten sulfur degasification gas feed unit, and quenched water is used for the washing of sulphur mist as supplementary feed.In quenching unit, along with the cooling of the tail gas D of hydrolysis unit, wherein contained water-cooled is congealed into liquid, the bottom of quenching apparatus 31 is gathered in together with quenched water, the liquid level of quenched water progressively raises, need too much water to discharge quenching apparatus 31, now part quenched water can be used for supply sulphur mist washer 511.Level control valve 34 can be set in recycle pump 32 outlet, be regulated the flow of the quenched water being transported to sulphur mist washer 511 by level control valve 34, thus control the liquid level of quenching apparatus 31, the water consumption for the treatment of system can also be saved.
In an embodiment of claus tail-gas clean-up system according to the present invention, as shown in Figure 1, desulfurization unit comprises desulphurization reactor 41 containing catalyst solution and sulphur filtration unit 42, the tail gas E of quenching unit is oxidized to elemental sulfur F in desulphurization reactor 41, in order to prevent the elemental sulfur F excessive accumulation in desulphurization reactor 41 generated, sulphur filtration unit 42 is adopted to filter the catalyst solution containing elemental sulfur F, elemental sulfur F is separated with catalyst solution, elemental sulfur F discharges treatment system as byproduct, filtrate returns desulphurization reactor 41 and continues to recycle.In desulphurization reactor 41, the catalyst solution of filling can by H
2s is oxidized to elemental sulfur, and reacted catalyst solution can with oxygen-containing gas J oxidation regeneration to recycle.Catalyst solution indefinite, can adopt this area to possess any kind of same or similar function, as long as can by H
2s is oxidized to elemental sulfur, and the Complexing Iron catalyzer such as can commonly used for this area can also be vanadium series catalyst etc.
In one preferred embodiment, as shown in Figure 1, desulphurization reactor 41 is also connected with the squirt pump 522 of molten sulfur degasification gas feed unit, can extract the working fluid of solution as squirt pump 522 from desulphurization reactor 41.
In one preferred embodiment, as shown in Figure 1, desulfurization unit also comprises the liquid distributing device 43 and supercharging device 44 that are connected, liquid distributing device 43 is connected with quenching unit, for removing the moisture carried secretly in the tail gas E of quenching unit, supercharging device 44 is connected with desulphurization reactor 41, for the tail gas E of quenching unit is carried out supercharging, then injects desulphurization reactor 41 and reacts.
The present invention is not particularly limited for the desulphurization reactor in desulfurization unit, sulphur filtration unit, liquid distributing device, supercharging device, and this area can be used to possess arbitrarily the equipment of same or similar function.Such as desulphurization reactor can adopt bubbling reactor, also can adopt the spray tower reactor of in-built filler.
In above-mentioned claus tail-gas clean-up system, as H after hydrogenation unit process
2when S transformation efficiency is higher, also hydrolysis unit can not be comprised, therefore, present invention also offers another kind of claus tail-gas clean-up system, it comprises hydrogenation unit, quenching unit, desulfurization unit and molten sulfur degasification gas feed unit according to treatment scheme, wherein, hydrogenation unit is used for pending Claus tail gases and reducing gas to react to make wherein sulfur-bearing composition change H into
2s, quenching unit is used for the tail gas quenching of hydrolysis unit to lower the temperature, and desulfurization unit is used for the tail gas of quenching unit to carry out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into, and molten sulfur degasification gas feed unit is connected with desulfurization unit, states molten sulfur degasification gas carry out oxidation sweetening process for providing together with the tail gas of quenching unit.
Each embodiment of above-mentioned claus tail-gas clean-up system can see Fig. 1 and aforementioned description.
Second aspect of the present invention provides a kind of claus tail-gas clean-up method, adopts treatment system of the present invention, comprises the following steps:
S1: pending Claus tail gases and reducing gas are reacted, makes wherein sulfur-bearing composition change H into
2s;
S2: be hydrolyzed the tail gas of S1 step reaction, makes COS, CS of remaining
2change H into
2s;
S3: by the tail gas quenching to 30 of S2 step ~ 90 DEG C;
S4: the tail gas of S3 step is carried out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into.
In one preferred embodiment, in S3 step by the tail gas quenching to 40 of S2 step ~ 80 DEG C.In a preferred embodiment, by the tail gas quenching to 50 of S2 step ~ 70 DEG C.
In one preferred embodiment, S4 step also comprises: the molten sulfur degasification gas from Cross unit is carried out oxidation sweetening process simultaneously.
Claus tail-gas clean-up method of the present invention also comprises another kind of embodiment, specifically, comprises the following steps:
S1: pending Claus tail gases and reducing gas are reacted, makes wherein sulfur-bearing composition change H into
2s;
S2: by the tail gas quenching to 30 of S1 step ~ 90 DEG C;
S3: carry out oxidation sweetening process by the tail gas of S2 step and from the molten sulfur degasification gas of Cross unit, make H wherein
2s changes elemental sulfur into.
In one preferred embodiment, in S2 step by the tail gas quenching to 40 of S1 step ~ 80 DEG C.In a preferred embodiment, by the tail gas quenching to 50 of S1 step ~ 70 DEG C.
In one preferred embodiment, after S1 step also comprises and pending Claus tail gases and reducing gas to be reacted, then the reaction that is hydrolyzed, make COS, CS of remaining
2change H into
2s.
Treatment in accordance with the present invention system and/or treatment process, can reach more than 99.9% to the decreasing ratio of the hydrogen sulfide in Claus tail gases, and the molten sulfur degasification gas of Cross unit also can obtain process simultaneously, is discharged into the H in the tail gas of air
2s concentration is less than 10ppm, is converted to SO
2concentration <50mg/m
3, this transformation efficiency and emission concentration can meet current maximum emission limitation standard, and drastically reduce the area the acid water yield needing outer row's process.
Below, the present invention is further described by embodiment.
Embodiment
According to following step process Claus tail gases and molten sulfur degasification gas.
A, unstripped gas comprise the molten sulfur degasification gas of Claus tail gases and Cross unit, and Claus tail gases comes from the third stage sulfur condenser of two-stage Cross unit, and its component and character are: H
2s content 1.36% (V), SO
2content 0.34%, H
2content 1.59%, COS content 0.08% (V), CO content 5.05%, CO
2content 44.45% (V), N
2content 10.72% (V), H
2o content 36.3%, S
xcontent 0.1%, temperature is 160 DEG C, and pressure is 114Kpa; Molten sulfur degasification gas comes from liquid sulfur pit, and its component and character are: H
2s content 0.844% (V), H
2o content 3.74% (V), N
2content 75.4% (V), O
2content 20.0%, S
xcontent 0.01%, temperature is 138 DEG C, and pressure is 90KPa.
First b, Claus tail gases enter preheater, adopt middle pressure steam that gas temperature is elevated to 238 DEG C, then hydrogenator is entered, low temperature Co-Mo hydrogenation catalyst TG-107 (Axens Products) has been loaded in hydrogenator, in hydrogenator, under the effect of catalyzer, the SO in Claus tail gases
2, COS, CS
2with H
2, CO reaction, generate H
2s, CO
2and H
2o.These reactions are thermopositive reaction, and therefore, hydrogenator temperature out reaches 308 DEG C.
C, hydrogenator tail gas enter desuperheater, by spraying into low-pressure saturated steam, exhaust temperature are reduced to about 180 DEG C, and provide extra water for hydrolysis reaction simultaneously, then enter hydrolysis reactor, are filled with TiO hydrolysis reactor is in-built
2base hydrolyst CRS31 (Axens Products), under catalyst action, COS and the H in hydrogenation tail gas
2there is hydrolysis reaction in O, generates H further
2s and CO
2.
D, hydrolysis reactor tail gas enter quench tower, in quench tower, tail gas and the quenched water counter current contact recycled, temperature is reduced to about 50 DEG C, recycle pump extracts quenched water and delivers among the liquid distributor on quench tower top bottom quench tower, excessive heat is taken out by quenched water water cooler, recirculated cooling water is adopted to cool to quenched water, the excess acid water cooled down is transported in sulphur mist washer, its flow is by Liquid level valve regulation, and cooled tail gas enters subsequent cell.
E, enter sulphur mist washer from the molten sulfur degasification gas of liquid sulfur pit, cleaning circulation pump extracts sour water and delivers among the nozzle on sulphur mist washer top bottom sulphur mist washer, spray washing is carried out to molten sulfur degasification gas, the temperature of molten sulfur degasification gas is made to be reduced to about 90 DEG C, the sulphur carried secretly in molten sulfur degasification gas becomes solid-state by liquid conversion, and the excessive quenched water coming from quench tower supplements and maintains the sour water liquid level bottom sulphur mist washer.
F, after chilling, tail gas enters point flow container and isolates the drop carried secretly, then 65KPa (G) is boosted to by booster fan, then desulphurization reactor is entered by the gas distributor bottom desulphurization reactor, enter bottom desulphurization reactor after sulphur mist washer molten sulfur degasification gas out mixes with catalyst solution under the suction of injector, these two strands of gases contact with iron catalyst solution with the network loaded in desulphurization reactor, hydrogen sulfide in gas and network and ferrous solution react and generate elemental sulfur, elemental sulfur is suspended in catalyst solution, sulphur filter is adopted to be filtered out from catalyst solution by elemental sulfur.Used network and ferrous solution adopt atmospheric oxidation regeneration, desulphurization reaction actuator temperature about 50 DEG C.
G, the waste gas flowed out from desulphurization reactor top enter incinerator burning, and after testing, in desulphurization reactor tail gas, hydrogen sulfide content is 2ppm, SO after burning
2content 10mg/m
3.
Although with reference to exemplary embodiment describing the present invention, should be appreciated that term used illustrates and exemplary and nonrestrictive term.Spirit of the present invention or essence is not departed from because the present invention can specifically implement in a variety of forms, so it should also be understood that, above-described embodiment is not limited to any aforesaid details, and should explain widely in the spirit and scope that claims limit, therefore fall into whole change in claim or its equivalent scope and remodeling and all should be claims and contained.
Claims (20)
1. a claus tail-gas clean-up system, is characterized in that, comprises following processing unit:
Hydrogenation unit, for pending Claus tail gases and reducing gas being reacted, makes wherein sulfur-bearing composition change H into
2s;
Hydrolysis unit, for COS, CS of will remaining in the tail gas of described hydrogenation unit
2h is changed into by hydrolysis reaction
2s;
Quenching unit, for cooling the tail gas of described hydrolysis unit; And
Desulfurization unit, for the tail gas of described quenching unit is carried out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into.
2. claus tail-gas clean-up system according to claim 1, is characterized in that, described treatment system also comprises the molten sulfur degasification gas feed unit for providing described molten sulfur degasification gas to carry out oxidation sweetening process, and it is connected with described desulfurization unit.
3. claus tail-gas clean-up system according to claim 2, it is characterized in that, described molten sulfur degasification gas feed unit comprises sulphur mist washing device and jet apparatus, described sulphur mist washing device washes away sulphur in described molten sulfur degasification gas for using spray water, and described jet apparatus is used for desulfurization unit described in the described molten sulfur degasification gas suction after by washing.
4. the claus tail-gas clean-up system according to any one of claim 1-3, it is characterized in that, described hydrolysis unit comprises desuperheating device and hydrolysis reaction device, wherein, described desuperheating device is used for the tail gas of described hydrogenation unit to carry out desuperheating process, its heat-eliminating medium is water vapor, and described hydrolysis reaction device is used for the tail gas of the described hydrogenation unit after desuperheating process to be hydrolyzed reaction, is wherein filled with hydrolyst.
5. a claus tail-gas clean-up system, is characterized in that, comprises following processing unit:
Hydrogenation unit, for pending Claus tail gases and reducing gas being reacted, makes wherein sulfur-bearing composition change H into
2s;
Quenching unit, for cooling the tail gas of described hydrogenation unit;
Desulfurization unit, for the tail gas of described quenching unit is carried out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into; And
Molten sulfur degasification gas feed unit, it is connected with described desulfurization unit, states molten sulfur degasification gas carry out oxidation sweetening process for providing.
6. claus tail-gas clean-up system according to claim 5, is characterized in that, described treatment system also comprises hydrolysis unit, and it is between described hydrogenation unit and described quenching unit, for COS, CS of will remaining in the tail gas of described hydrogenation unit
2h is changed into by hydrolysis reaction
2s.
7. claus tail-gas clean-up system according to claim 6, it is characterized in that, described hydrolysis unit comprises desuperheating device and hydrolysis reaction device, wherein, described desuperheating device is used for the tail gas of described hydrogenation unit to carry out desuperheating process, its heat-eliminating medium is water vapor, and described hydrolysis reaction device is used for the tail gas of the described hydrogenation unit after desuperheating process to be hydrolyzed reaction, is wherein filled with hydrolyst.
8. the claus tail-gas clean-up system according to any one of claim 5-7, it is characterized in that, described molten sulfur degasification gas feed unit comprises sulphur mist washing device and jet apparatus, described sulphur mist washing device washes away sulphur in described molten sulfur degasification gas for using spray water, and described jet apparatus is used for desulfurization unit described in the described molten sulfur degasification gas suction after by washing.
9. the claus tail-gas clean-up system according to any one of claim 1-8, it is characterized in that, described hydrogenation unit comprises primary heater unit and hydrogenation reaction device, wherein, described primary heater unit is used for Claus tail gases pending described in preheating, described hydrogenation reaction device is used for carrying out hydrogenation reaction, is wherein filled with hydrogenation catalyst.
10. claus tail-gas clean-up system according to claim 9, is characterized in that, described hydrogenation reaction device is also connected with reducing gas air supply unit, for providing reducing gas to described hydrogenation reaction device.
11. claus tail-gas clean-up systems according to any one of claim 1-8, it is characterized in that, described quenching unit comprises quenching apparatus, recycle pump and refrigerating unit, the liquid distributor for spraying quenched water is provided with in described quenching apparatus, the quenched water of spray carries out chilling with the tail gas counter current contact of from bottom to top carrying, described recycle pump is connected with the bottom of described quenching apparatus, and described refrigerating unit is connected with the liquid distributor of described recycle pump and described quenching apparatus respectively.
12. claus tail-gas clean-up systems according to claim 11, is characterized in that, described recycle pump is also connected with described sulphur mist washing device, for described sulphur mist washing device supplementary feed.
13. claus tail-gas clean-up systems according to any one of claim 1-8, it is characterized in that, described desulfurization unit comprises desulphurization reactor containing catalyst solution and sulphur filtration unit, the tail gas of described quenching unit and/or described molten sulfur degasification gas oxidized generation elemental sulfur in described desulphurization reactor, is discharged after then being filtered by described elemental sulfur by described sulphur filtration unit.
14. claus tail-gas clean-up systems according to claim 13, it is characterized in that, described desulfurization unit also comprises connected liquid distributing device and supercharging device, described liquid distributing device is connected with described quenching unit, for removing the moisture in the tail gas of described quenching unit, described supercharging device is connected with described desulphurization reactor, after the tail gas of described quenching unit is carried out supercharging, pass into described desulphurization reactor.
15. 1 kinds of claus tail-gas clean-up methods, is characterized in that, comprise the following steps:
S1: pending Claus tail gases and reducing gas are reacted, makes wherein sulfur-bearing composition change H into
2s;
S2: be hydrolyzed the tail gas of described S1 step reaction, makes COS, CS of remaining
2change H into
2s;
S3: by tail gas quenching to 30 ~ 90 DEG C of described S2 step;
S4: the tail gas of described S3 step is carried out oxidation sweetening process, makes H wherein
2s changes elemental sulfur into.
16. claus tail-gas clean-up methods according to claim 15, is characterized in that, by tail gas quenching to 40 ~ 80 DEG C of described S2 step in described S3 step, are preferably chilled to 50 ~ 70 DEG C.
17. claus tail-gas clean-up methods according to claim 15 or 16, it is characterized in that, described S4 step also comprises: carry out oxidation sweetening process by from the molten sulfur degasification gas of Cross unit and the tail gas of described S3 step simultaneously.
18. 1 kinds of claus tail-gas clean-up methods, is characterized in that, comprise the following steps:
S1: pending Claus tail gases and reducing gas are reacted, makes wherein sulfur-bearing composition change H into
2s;
S2: by tail gas quenching to 30 ~ 90 DEG C of described S1 step;
S3: carry out oxidation sweetening process by the tail gas of described S2 step and from the molten sulfur degasification gas of Cross unit, make H wherein
2s changes elemental sulfur into.
19. claus tail-gas clean-up methods according to claim 18, is characterized in that, by tail gas quenching to 40 ~ 80 DEG C of described S1 step in described S2 step, are preferably chilled to 50 ~ 70 DEG C.
20. claus tail-gas clean-up methods according to claim 18 or 19, is characterized in that, after described S1 step also comprises and pending Claus tail gases and reducing gas to be reacted, then the reaction that is hydrolyzed, make COS, CS of remaining
2change H into
2s.
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| CN106829875A (en) * | 2017-03-08 | 2017-06-13 | 安徽宣城金宏化工有限公司 | A kind of handling process and equipment for carbon disulphide production Process Gas |
| CN106853323A (en) * | 2016-12-19 | 2017-06-16 | 宁波市化工研究设计院有限公司 | The sulfur recovery tail gas absorption system of minimum discharge |
| CN109071226A (en) * | 2016-03-23 | 2018-12-21 | 埃克森美孚研究工程公司 | The Claus unit processing of parking tail gas |
| CN109181784A (en) * | 2018-09-27 | 2019-01-11 | 中国成达工程有限公司 | It is a kind of by multi-component complex organic sulfur conversion in crude synthesis gas be hydrogen sulfide device and technique |
| CN110732238A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | sulfur-containing tail gas treatment method and system |
| CN110817809A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Claus tail gas treatment method and treatment system |
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| CN109071226A (en) * | 2016-03-23 | 2018-12-21 | 埃克森美孚研究工程公司 | The Claus unit processing of parking tail gas |
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| CN110732238A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | sulfur-containing tail gas treatment method and system |
| CN110817809A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Claus tail gas treatment method and treatment system |
| CN110817809B (en) * | 2018-08-14 | 2023-09-15 | 中国石油化工股份有限公司 | Claus tail gas treatment method and treatment system |
| CN109181784A (en) * | 2018-09-27 | 2019-01-11 | 中国成达工程有限公司 | It is a kind of by multi-component complex organic sulfur conversion in crude synthesis gas be hydrogen sulfide device and technique |
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