CN105293445A - Low sulfur emission sulphur recovery process - Google Patents
Low sulfur emission sulphur recovery process Download PDFInfo
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Abstract
The present invention provides a low sulfur emission sulphur recovery process, which comprises a burning furnace, a first stage Claus reactor, a second stage Claus reactor, a selective hydrogenation reduction reactor, a selective oxidation reactor, and two adsorption desulfurization towers capable of being connected in a series parallel connection manner, wherein the burning furnace, the first stage Claus reactor and the second stage Claus reactor are sequentially connected in series. According to the present invention, with the appropriate selection of each catalyst, the appropriate selection of the desulfurization agent, and the accurate control of each step process condition, the total standard sulfur in the process emission gas is that SO2 is less than or equal to 10 mg/m<3>; after the desulfurization agent penetrates, 250-300 DEG C inert gas is used to perform in-situ thermal regeneration, the regeneration outlet gas returns to the burning furnace, the condenser after the burning furnace, the condenser after the first stage Claus reactor, the condenser after the second stage Claus reactor, the condenser after the selective hydrogenation reduction reactor, or the condenser after the selective oxidation reactor to recover elemental sulfur, H2S, SO2 and other sulfides in the regeneration gas, and the total standard sulfur in the evacuation tail gas during the desulfurization tower regeneration process is that SO2 is less than or equal to 10 mg/m<3>; and the low sulfur emission sulphur recovery process has advantages of low sulfur emission, long desulfurization agent operating, high desulfurization capacity, less replacement frequency, low cost and the like.
Description
Technical field
The present invention relates to a kind of recovery technology of sulfur, be specifically related to a kind of recovery technology of sulfur of low sulphur emissions.
Background technology
In petrochemical complex, Coal Chemical Industry, coal gasification course, a part of sulphur contained by raw material can change into H usually
2s, forms H through being separated
2the sour gas that S content is higher, this sour gas generally processes through recovery technology of sulfur, by H
2s is converted into elemental sulfur as much as possible.Some high H
2in the decontamination process of S content Sweet natural gas, be separated H
2the sour gas that S is formed, also will be converted into elemental sulfur through recovery technology of sulfur as much as possible.
, in operation process, also there is emptying tail gas and solid waste two problems in described sulfur recovery facility.Through the tail gas that chimney is emptying, wherein, SO
2concentration is continuous monitoring project, although the higher limit of existing discharge standard of air pollutants GB16297-1996 is as 700mg/m
3be not difficult to reach, but also may there is more strict emission standard in place industry or location; H
2s is one of odor pollution material included by emission standard for odor pollutants GB14554-93, and emission limit is more strict, the accurate higher limit of factory's boundary mark as three grades be 0.45/0.80mg/m
3, 100 meters of smoke stack emission amount higher limits are 14kg/h.
The useless agent that mainly multiple catalysts used, sorbent material drew off after losing efficacy in sulfur recovery facility of described solid waste, due to kind, the complicated component of this kind of useless agent, not only intractability is large, also exist scrap, transport, a series of environmental pollution of processing and legal risk.
Chinese patent 200910018803.9 discloses a kind of catalyst combination process of sulfur recovery facility, comprise the roasting kiln, one-level claus reaction device, the secondary claus reaction device that are connected in series successively, selective hydrogenation reduction reactor, selective oxidation reaction device and two catalyzed oxidation adsorption desulfurize towers in parallel; One-level claus reaction device top filling de-oxygen type catalyst for recovering sulfur, bottom filling TiO
2catalyst for recovering sulfur, secondary claus reaction device filling auxiliary agent type catalyst for recovering sulfur, by the SO of the overwhelming majority
2, H
2s reaction is converted into elemental sulfur; Selective hydrogenation reduction reactor filling SO
2selective reduction catalyst, by remaining a small amount of SO
2selective reduction is elemental sulfur; Selective oxidation reaction device filling H
2s catalyst for selective oxidation, by remaining H
2s major part selective oxidation is elemental sulfur; Catalyzed oxidation adsorption desulfurize tower filling H
2s catalytic oxidation adsorption desulfurizer, by the H of remnants
2s catalyzed oxidation is elemental sulfur, makes the tail gas after desulfurization reach GB16297-1996 country emission request, but there are following three defects:
A, described technique do not give full play to the desulfurization precision of catalytic oxidation adsorption desulfurizer
Conventional catalytic oxidation adsorption desulfurizer is as Na
2cO
3/ gac, NaOH/ gac, K
2cO
3/ gac, KOH/ gac, Fe
2o
3/ gac, Na
2cO
3/ aluminum oxide, K
2cO
3/ aluminum oxide etc., at not too high, the appropriate O of temperature
2with under the condition of moisture, can by a small amount of SO in process gas
2with excessive H
2s reaction is converted into elemental sulfur, by remaining H
2s catalyzed oxidation is elemental sulfur, thus has very high desulfurization precision, as lower than 10mg/m
3and even, lower than 5mg/m
3, 2mg/m
3, 1mg/m
3;
But the operating procedure condition given by this technique is concrete not, if catalyzed oxidation adsorption desulfurize tower enters implication SO
2/ H
2the concentration ratio of S is higher than the 1:2 generated required for elemental sulfur, the SO that thionizer is worked off one's feeling vent one's spleen
2concentration just may higher than 10mg/m
3, this point is at selective oxidation reaction device entrance O
2too high levels, temperature easily occur time too high, because of SO
2h
2s Selective Oxidation is generated as the side reaction product of elemental sulfur; Or selective hydrogenation reduction reactor enters, and the temperature of implication is not high enough, H
2quantity not sufficient, cause SO
2cannot Restore All, this part SO
2also can enter catalyzed oxidation adsorption desulfurize tower, thionizer may be caused to work off one's feeling vent one's spleen the SO of established technology tail gas
2content is far above 10mg/m
3, the desulfurization precision of catalytic oxidation adsorption desulfurizer can not be played;
B, described technique do not play the renewable performance of catalytic oxidation adsorption desulfurizer
Conventional catalytic oxidation adsorption desulfurizer is as Na
2cO
3/ gac, NaOH/ gac, K
2cO
3/ gac, KOH/ gac, Fe
2o
3/ gac, Na
2cO
3/ aluminum oxide, K
2cO
3/ aluminum oxide etc., purge through 180-300 DEG C of indifferent gas after cryogenic absorption sulphur, and sulphur can evaporative removal, and the catalyzed oxidation adsorption desulfurize performance of sweetening agent can be recovered largely; Under the operating condition that this technique is normal, because thionizer enters the material not containing in implication and obviously may reduce above-mentioned catalytic oxidation adsorption desulfurizer regenerability, need the S-contained substance mainly H of sweetening agent catalyzed oxidation adsorption treatment
2s, and a small amount of SO
2with micro-elemental sulfur, thus through 180-300 DEG C of indifferent gas hot recycling, good regeneration effect may be reached, if by manipulation of regeneration, reach total desulfurization amount that single Sulfur capacity 2-3 is doubly above, just have industrial value;
In C, described technique, the repeatedly replacing of catalytic oxidation adsorption desulfurizer brings more safety and environment pollution hidden trouble
The catalytic oxidation adsorption desulfurizer loaded in described adsorption desulfurize tower is saturated or after penetrating, and needs to unload agent and the catalytic oxidation adsorption desulfurizer more renewed, thus exist number of times more regularly change agent problem; When unloading agent, top sweetening agent bed often has caking, more difficultly draws off, the H of top sweetening agent bed physical adsorption
2s releases, and there is obvious peculiar smell, unloads agent site environment poor, if suitably do not process, still can distribute H in storage, transportation
2s, SO
2peculiar smell, contaminate environment, also affects the safety of operator; Institute draws off containing more than sulphur 20% (quality) in waste desulfurizing agent, and have inflammable danger in storage, transportation, SO is released in burning
2environmental pollution can be caused again; Process producer, in useless agent treating processes, often because small scale, facility are limited, easily causes serious environmental pollution, and in useless agent, contained sulphur also can not be effectively utilized substantially.
Thus, be necessary to do above-mentioned technique perfect further.
Summary of the invention
For overcoming above-mentioned technological deficiency, the invention provides a kind of recovery technology of sulfur of low sulphur emissions, comprise the roasting kiln, one-level claus reaction device, the secondary claus reaction device that are connected in series successively, selective hydrogenation reduction reactor, selective oxidation reaction device and two can series-parallel adsorption desulfurize towers;
Wherein, one-level claus reaction device top filling Fe
2o
3/ Al
2o
3de-oxygen type catalyst for recovering sulfur, bottom filling TiO
2catalyst for recovering sulfur; Described de-oxygen type catalyst for recovering sulfur is active except having good claus reaction, also by the O in Process Gas
2by with H
2s reaction generates elemental sulfur and removes; Described TiO
2catalyst for recovering sulfur is active except having good claus reaction, also by COS, the CS in Process Gas
2, mercaptan, the organosulfur such as thioether be all converted into elemental sulfur or H
2s;
Secondary claus reaction device filling catalyst for recovering sulfur, under lower slightly temperature condition, make claus reaction reach the good degree of depth, described catalyst for recovering sulfur is Fe
2o
3/ Al
2o
3de-oxygen type catalyst for recovering sulfur, TiO
2catalyst for recovering sulfur, TiO
2/ Al
2o
3catalyst for recovering sulfur and common Al
2o
3one or both in catalyst for recovering sulfur; H in this secondary claus reaction device exit procedure gas
2volume content≤1.0% of S, SO
2volume content≤0.60%;
Selective hydrogenation reduction reactor filling SO
2selective reduction catalyst, utilizes the H generated in roasting kiln
2by SO
2restore All, primary product is elemental sulfur, and by product is H
2s; H in this selective hydrogenation reduction reactor exit procedure gas
2volume content 0.5-1.5%, H
2volume content≤1.1% of S;
Selective oxidation reaction device filling H
2s catalyst for selective oxidation, the O filled into by introducing air before utilizing this reactor inlet
2by most H
2s selective oxidation is elemental sulfur, and by product is minute quantity SO
2; H in this selective oxidation reaction device exit procedure gas
2volume content≤0.10% of S, and be SO
2more than three times of volume content;
The filling of adsorption desulfurize tower can the catalytic oxidation adsorption desulfurizer of hot recycling, by micro-elemental sulfur absorption contained by Process Gas under 10-50 DEG C of condition, by the SO of contained minute quantity
2with contained H
2s is converted into elemental sulfur and adsorbs, by the H of remnants
2s is oxidized to elemental sulfur and adsorbs; The desulfurization precision folding of described catalytic oxidation adsorption desulfurizer is SO
2≤ 10mg/m
3, in thionizer entirety, the Sulfur capacity when this desulfurization precision>=100g sulphur/1000g sweetening agent; Purge with 200-300 DEG C of indifferent gas during hot recycling, after sulphur evaporative removal, catalyzed oxidation adsorption desulfurize performance is recovered substantially, is SO at guarantee desulfurization precision folding
2≤ 10mg/m
3condition under, through repeatedly hot recycling reach first Sulfur capacity 3-5 doubly more than total desulfurization amount;
Described recovery technology of sulfur comprises the steps:
1) containing H
2enter roasting kiln after the sour gas of S and air mixed to burn, the temperature of roasting kiln controls at 1150-1350 DEG C, 340-350 DEG C is cooled to after the Process Gas produced after burning enters waste heat boiler, Process Gas enters the first condensate cooler from waste heat boiler outlet and is cooled to 140-160 DEG C, is separated enters Molten sulphur groove in roasting kiln after the elemental sulfur condensation generated with Process Gas;
2) 240-270 DEG C is heated to from the first condenser overhead Process Gas out, enter one-level claus reaction device and proceed claus reaction, exit procedure gas enters the second condenser and is cooled to 140-160 DEG C, enters Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas;
3) carry out claus reaction generate elemental sulfur further from entering secondary claus reaction device after the second condenser overhead Process Gas is out heated to 210-230 DEG C, exit procedure gas enters the 3rd condenser and is cooled to 140-160 DEG C, enters Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas;
4) be heated to 200-210 DEG C from the 3rd condenser overhead Process Gas out, enter Chemoselective reduction device, SO
2selective reduction is elemental sulfur, enters the 4th condenser be cooled to 140-160 DEG C from Chemoselective reduction device Process Gas out, enters Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas;
5) be preheating to 180-210 DEG C of laggard selectable oxidation reactor from the 4th condenser overhead Process Gas out, fill into appropriate air, H
2s selective oxidation is elemental sulfur, suitably controls the air amount of filling into and bed temperature, makes the remaining H in working off one's feeling vent one's spleen
2s content is by-product SO
2more than three times, enter the 5th condenser from selective oxidation reaction device Process Gas out and be cooled to 140-160 DEG C, Molten sulphur groove is entered after the elemental sulfur generated is separated with Process Gas, Process Gas is cooled to 10-50 DEG C through the 6th condenser again, makes most water, residue elemental sulfur condensation removing;
6) enter adsorption desulfurize tower from the 6th condenser overhead Process Gas out, the catalytic oxidation adsorption desulfurizer loaded at 10-50 DEG C by SO
2and H
2s reaction is converted into elemental sulfur, by the H of remnants
2s is oxidized to elemental sulfur, can fill into appropriate air if desired, and the elemental sulfur of generation is deposited in the endoporus of sweetening agent, and adsorption desulfurize tower exit procedure gas total sulfur folding is SO
2≤ 10mg/m
3, emptying through chimney from adsorption desulfurize tower Process Gas out;
7) when adsorption desulfurize tower exit procedure gas total sulfur folding is SO
2soon more than 10mg/m
3time, this adsorption desulfurize tower cuts out, and carries out in-situ heat regeneration with 250-300 DEG C of indifferent gas, after hot recycling completes, be cooled to less than 80 DEG C for subsequent use, or without cooling immediately incision carry out desulfurization; Reactivation outlet gas gets back to roasting kiln, the condenser after roasting kiln, the condenser after one-level claus reaction device, condenser after secondary claus reaction device, condenser after selective hydrogenation reduction reactor, or the condenser after selective oxidation reaction device, by the elemental sulfur in resurgent gases and H
2s, SO
2sulfides reclaims, and the emptying tail gas total sulfur folding of thionizer regeneration period is SO
2≤ 10mg/m
3.
In low sulphur emissions recovery technology of sulfur of the present invention, catalytic oxidation adsorption desulfurizer can adopt Na
2cO
3/ gac, NaOH/ gac, K
2cO
3/ gac, KOH/ gac, Fe
2o
3/ gac, Na
2cO
3/ aluminum oxide, K
2cO
3/ aluminum oxide, Fe
2o
3/ aluminum oxide, Fe
2o
3one or more in/silicon oxide and ferric oxide desulfurizer, all can reach total sulfur folding is SO
2≤ 10mg/m
3desulfurization precision.Wherein, load Na
2cO
3, NaOH, K
2cO
3, KOH sweetening agent to SO
2processing power comparatively large, load Fe
2o
3sweetening agent or Fe
2o
3sweetening agent is to H
2the processing power of S is larger.Fill whole sweetening agent in thionizer, when this desulfurization precision, the first Sulfur capacity of these sweetening agents can >=100g sulphur/1000g sweetening agent, through 250-300 DEG C of indifferent gas repeatedly hot recycling can reach first Sulfur capacity 3-5 doubly more than total desulfurization amount.
In low sulphur emissions recovery technology of sulfur of the present invention, catalytic oxidation adsorption desulfurizer used is SO at total sulfur folding
2≤ 10mg/m
3first Sulfur capacity before penetrating, preferably>=200g sulphur/1000g sweetening agent, preferably>=300g sulphur/1000g sweetening agent, more preferably>=400g sulphur/1000g sweetening agent, and through repeatedly hot recycling can reach first Sulfur capacity 3-5 doubly more than total desulfurization amount.
In low sulphur emissions recovery technology of sulfur of the present invention, desulfurization precision folding is adopted to be SO
2≤ 5mg/m
3catalytic oxidation adsorption desulfurizer, the total sulfur of emptying tail gas can be low to moderate folding for SO
2≤ 5mg/m
3, fill whole sweetening agent in thionizer, when this desulfurization precision, first Sulfur capacity preferably>=100g sulphur/1000g sweetening agent, preferably>=200g sulphur/1000g sweetening agent, more preferably>=300g sulphur/1000g sweetening agent, and through repeatedly hot recycling can reach first Sulfur capacity 3-5 doubly more than total desulfurization amount.
In low sulphur emissions recovery technology of sulfur of the present invention, desulfurization precision folding is adopted to be SO
2≤ 2mg/m
3catalytic oxidation adsorption desulfurizer, the total sulfur of emptying tail gas can be low to moderate folding for SO
2≤ 2mg/m
3, fill whole sweetening agent in thionizer, when this desulfurization precision, first Sulfur capacity>=100g sulphur/1000g sweetening agent, preferably>=200g sulphur/1000g sweetening agent, preferably>=300g sulphur/1000g sweetening agent, and through repeatedly hot recycling can reach first Sulfur capacity 3-5 doubly more than total desulfurization amount.
In low sulphur emissions recovery technology of sulfur of the present invention, catalytic oxidation adsorption desulfurizer used, preferred suitably prepd Na
2cO
3the Na of the 5-10% of charge capacity
2cO
3/ gac, Fe
2o
3the Fe of charge capacity 5-20%
2o
3/ gac, or with Fe
2o
3for the ferric oxide desulfurizer of main component, filling whole sweetening agent in thionizer, is SO at desulfurization precision folding
2≤ 10mg/m
3, SO
2≤ 5mg/m
3, SO
2≤ 2mg/m
3condition under, the first Sulfur capacity of these three kinds of sweetening agents can reach>=200g sulphur/1000g sweetening agent, and even>=300g sulphur/1000g sweetening agent, 400g sulphur/1000g sweetening agent, 500g sulphur/1000g sweetening agent, the Sulfur capacity of first Sulfur capacity more than 95% can be reached after first hot recycling, the Sulfur capacity of first Sulfur capacity more than 80% can be reached after five hot recycling, ten times regeneration after can reach first Sulfur capacity more than 65% Sulfur capacity, namely five hot recycling can reach total desulfurization amount of first Sulfur capacity more than 4 times, ten hot recycling can reach total desulfurization amount of first Sulfur capacity more than 7 times.
In low sulphur emissions recovery technology of sulfur of the present invention, preferably work off one's feeling vent one's spleen with thionizer and do resurgent gases, after reactivation outlet gas preferably gets back to selective oxidation reaction device, the 5th condenser is mixed into from selective oxidation reaction device Process Gas out, be cooled to 140-160 DEG C, elemental sulfur condensation separation in gas mixture enters Molten sulphur groove, removes the gas mixture of elemental sulfur again after the 6th condenser, the second online adsorption desulfurize tower process, more emptying through chimney; Before reactivation outlet gas also can get back to Chemoselective reduction device, the 3rd condenser is mixed into from secondary claus reaction device Process Gas out, be cooled to 140-160 DEG C, elemental sulfur condensation separation in gas mixture enters Molten sulphur groove, the gas mixture of removing elemental sulfur is again after selective reduction, selective oxidation, the second online adsorption desulfurize tower process, emptying through chimney again, now can allow in reactivation outlet gas containing slightly many SO
2, namely allow in resurgent gases containing slightly many O
2.
In the low sulphur emissions recovery technology of sulfur of the present invention, elected when being the sweetening agent of carrier in order to gac, the O of resurgent gases
2content should control within 100ppm, and to avoid the scaling loss of absorbent charcoal carrier, reactivation outlet gas now can be introduced into the 5th condenser again through online adsorption desulfurize tower process.When selecting the sweetening agent of charcoal non activated carrier, the O of resurgent gases
2content controls within 2000ppm, if O
2content is lower, and reactivation outlet gas can be introduced into the 5th condenser again through online adsorption desulfurize tower process; If O
2content is higher, should be introduced into the 3rd condenser again through selective reduction device treatment S O
2.By the suitable control to processing condition, the emptying tail gas total sulfur of i.e. this technique of working off one's feeling vent one's spleen of regeneration period on-line adsorption thionizer, can reach conversion for SO
2≤ 10mg/m
3,≤5mg/m
3,≤2mg/m
3level.
With thionizer work off one's feeling vent one's spleen do resurgent gases time, suitably should control the air amount of filling into of selective oxidation reaction device entrance, the second online adsorption desulfurize tower entrance, make the O that the second online adsorption desulfurize tower is worked off one's feeling vent one's spleen in i.e. resurgent gases
2content≤100ppm, or≤2000ppm.
In low sulphur emissions recovery technology of sulfur of the present invention, the superheated vapour of 250-300 DEG C can also be adopted as resurgent gases and thermal source, after reactivation outlet gas preferably gets back to selective oxidation reaction device, the 5th condenser is mixed into from selective oxidation reaction device Process Gas out, be cooled to 140-160 DEG C, elemental sulfur condensation separation in gas mixture enters Molten sulphur groove, and the gas mixture of removing elemental sulfur is again through the 6th condenser, the second online adsorption desulfurize tower process, emptying.By the suitable control to processing condition, the emptying tail gas total sulfur of i.e. this technique of working off one's feeling vent one's spleen of regeneration period on-line adsorption thionizer, can reach conversion for SO
2≤ 10mg/m
3,≤5mg/m
3,≤2mg/m
3level.The advantage of superheated vapour is not containing O
2, not ablation absorbent charcoal carrier in regenerative process, does not produce the SO that may need to consider process yet
2, all collect after the elemental sulfur in reactivation outlet gas (with from the Process Gas mixing out of selective oxidation reaction device) and steam (water) cooling, adsorption desulfurize tower enter the flow of implication, composition do not change substantially.
In low sulphur emissions recovery technology of sulfur of the present invention, H in described selective oxidation reaction device exit procedure gas
2the volume content of S preferably controls as SO
2the 3-5 of volume content doubly.
In the low sulphur emissions recovery technology of sulfur of the present invention, separately can establish heater element in catalyzed oxidation adsorption desulfurize tower, to improve reproduction speed.
In the low sulphur emissions recovery technology of sulfur of the present invention, in thionizer non-renewable period, preferably two adsorption desulfurize tower parallel operations as far as possible, to alleviate bed resistance; Use before also preferably the thionizer soon regenerated being serially connected in another thionizer, to improve the desulfurization amount in a front desulfurization cycle of tower sweetening agent, thus extend regeneration period and the work-ing life of sweetening agent; Certainly, all will under the prerequisite arranging regeneration opportunity properly, when namely ensureing that a tower regenerates, another tower still can ensure desulfurization precision.
Low sulphur emissions recovery technology of sulfur of the present invention, has the following advantages:
1) low sulphur emissions is maintained
In above-mentioned low sulphur emissions recovery technology of sulfur of the present invention, sour gas is through roasting kiln, one-level claus reaction device, secondary claus reaction device, after the process of selective hydrogenation reduction reactor, selective oxidation reaction device, adsorption desulfurize tower, air-discharging total sulfur folding is SO
2≤ 10mg/m
3.Because this technique entirety is comparatively perfect, it is stable, simple that thionizer enters implication main component, only comprises N
2, H
2o, a small amount of O
2, a small amount of H
2s, minute quantity SO
2with micro-elemental sulfur, sometimes also CO may be contained
2not containing the material that obviously can reduce above-mentioned catalytic oxidation adsorption desulfurizer regenerability, catalytic oxidation adsorption desulfurizer only carries out the reaction generating elemental sulfur, and deposit, be adsorbed in the endoporus of sweetening agent, and the high performance of the catalytic oxidation adsorption desulfurizer desulfurization precision loaded in thionizer and feature, its put into operation after long period in, i.e. sulfur recovery facility worked off one's feeling vent one's spleen by thionizer will through the emptying tail gas of chimney, it is very low containing sulphur concentration, rolls over for SO
2as lower than 10mg/m
3and even, lower than 5mg/m
3, 2mg/m
3, 1mg/m
3, until emptying tail gas containing sulphur concentration close to or switch immediately after reaching this concentration value or cut out regeneration, thus continue to ensure that air-discharging total sulfur folding is SO
2≤ 10mg/m
3.Two thionizers can come into operation in turn, also can be used together, and when the used time needs guarantee one to regenerate, another can normally desulfurization.
2) sulfur recovery rate is bordering on 100%
In above-mentioned low sulphur emissions recovery technology of sulfur of the present invention, the H of the elemental sulfur deposited in catalytic oxidation adsorption desulfurizer in regenerative sulfur binding tower, top sweetening agent bed adsorption
2the evaporation of S, blow to the 5th condenser, mix with from selective oxidation reaction device Process Gas out, elemental sulfur condensation separation is entered Molten sulphur groove, and the gas mixture of removing elemental sulfur, again through the 6th condenser, the second online adsorption desulfurize tower process, regenerates the H of desorption
2s is oxidized to elemental sulfur and deposits in the second thionizer, and tail gas is emptying through chimney.Such circulation is gone down, and in sweetening agent, comprises the elemental sulfur deposited in the sweetening agent through repeatedly regenerating, will scrapping, the H adsorbed
2s finally can be converted into sulphur, enters Molten sulphur groove, and maintains low sulphur emissions.Because air-discharging total sulfur folding is SO
2≤ 10mg/m
3and even, lower than 5mg/m
3, 2mg/m
3, 1mg/m
3, and in sour gas more than 20% H
2s concentration is compared, and the sulfur recovery rate of this technique is bordering on 100%, and the sulphur especially reclaimed all enters Molten sulphur groove.
3) life-span of sweetening agent is long, desulfurization amount is large, and change number of times few, expense is low
In above-mentioned low sulphur emissions recovery technology of sulfur of the present invention, sour gas is through roasting kiln, one-level claus reaction device, secondary claus reaction device, after the process of selective hydrogenation reduction reactor, selective oxidation reaction device, it is comparatively stable, simple that adsorption desulfurize tower enters implication main component, only comprises N
2, H
2o, a small amount of H
2s, minute quantity SO
2with micro-elemental sulfur, sometimes also containing CO
2, not containing the material that obviously may reduce above-mentioned catalytic oxidation adsorption desulfurizer regenerability, thus catalytic oxidation adsorption desulfurizer only carries out the reaction generating elemental sulfur, the elemental sulfur generated also deposits, be adsorbed in the endoporus of sweetening agent, thus after 250-300 DEG C of indifferent gas hot recycling, deposition, the evaporation of absorption elemental sulfur, blow away, and the active ingredient of sweetening agent, pore structure is recovered as newly substantially, desulfurization process can be continued on for, through repeatedly hot recycling reach first Sulfur capacity 3-5 doubly more than total desulfurization amount, and even more than 10 times, thus the life-span of sweetening agent is long, desulfurization amount is large, replacing number of times is few, expense is low.
4) turndown ratio is large on the whole for this technique
In above-mentioned low sulphur emissions recovery technology of sulfur of the present invention, due to perfect technology, and the sweetening agent filled in thionizer can carry out in-situ heat regeneration, desulfurization precision is high, desulfurization amount is comparatively large, expense is lower, so roasting kiln, one-level claus reaction device, secondary claus reaction device, the operation leeway that selective hydrogenation reduction reactor, selective oxidation reaction device allow is comparatively large, and Acidic Gas Treating amount also can be larger.
5) sweetening agent unloads agent, scraps that treatment condition are good, safety
In above-mentioned low sulphur emissions recovery technology of sulfur of the present invention, before described catalytic oxidation adsorption desulfurizer unloads agent, by manipulation of regeneration, by the elemental sulfur of deposition, the H of absorption
2a S 250-300 DEG C indifferent gas blows off, no longer containing sulphur and H
2, thus there is not obvious peculiar smell in S, sweetening agent mobility of bed is without caking, and unload agent easily, site environment is better, and safe operating conditions is better; Institute draws off not containing sulphur in waste desulfurizing agent, nonflammable in storage, transportation, can not burn and release SO
2cause environmental pollution, useless agent process is much relatively easy, and it is also comparatively simple to scrap formality.
Accompanying drawing explanation
Accompanying drawing 1,2 is the concise and to the point flow process of the present invention's low sulphur emissions recovery technology of sulfur, and wherein Fig. 1 thionizer is worked off one's feeling vent one's spleen and done resurgent gases, and Fig. 2 superheated vapour does resurgent gases.
Device numbering is followed successively by 1 roasting kiln, 2 waste heat boilers, 3 first condensers, 4 well heaters, 5 one-level claus reaction devices, 6 second condensers, 7 secondary claus reaction devices, 8 the 3rd condensers, 9 selective hydrogenation reduction reactors, 10 the 4th condensers, 11 selective oxidation reaction devices, 12 the 5th condensers, 13 the 6th condensers, 14 adsorption desulfurize towers, 15 Molten sulphur grooves, 16 regeneration blower fans, 17 chimneys.
Embodiment
Embodiment 1
The sulfur recovery facility that refinery is a set of 50,000 tons/year, comprise the roasting kiln, one-level claus reaction device, the secondary claus reaction device that are connected in series successively, selective hydrogenation reduction reactor, selective oxidation reaction device and two can series-parallel adsorption desulfurize towers, one-level claus reaction device top filling Fe
2o
3/ Al
2o de-oxygen type catalyst for recovering sulfur 15m
3, bottom filling TiO
2catalyst for recovering sulfur 25m
3; Secondary claus reaction device top filling Fe
2o
3/ Al
2o
3de-oxygen type catalyst for recovering sulfur 15m
3, bottom filling TiO
2/ Al
2o
3catalyst for recovering sulfur 25m
3; Selective hydrogenation reduction reactor filling CoO-MoO
3/ Al
2o
3selective reduction SO
2catalyzer 20m
3, selective oxidation reaction device filling Fe
2o
3/ SiO
2selective oxidation H
2s catalyzer 30m
3, two adsorption desulfurize towers load Na respectively
2cO
3/ activated carbon catalysis oxidation-adsorption sweetening agent 150m
3; The elementary operation condition of this device is:
1) sour gas 15000m
3/ hr, H
2s volume content 30-40%, all the other are CO mainly
2, join appropriate air (12500m
3about/hr) enter roasting kiln and burn, the temperature of roasting kiln controls at about 1200 DEG C, 350 DEG C are cooled to after the Process Gas produced after burning enters waste heat boiler, Process Gas enters the first condensate cooler from waste heat boiler outlet and is cooled to 150 DEG C, is separated enters Molten sulphur groove in roasting kiln after the elemental sulfur condensation generated with Process Gas;
2) 250 DEG C are heated to from the first condenser overhead Process Gas out, enter one-level claus reaction device and proceed claus reaction, exit procedure gas enters the second condenser and is cooled to 150 DEG C, enter Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas, the second condenser overhead Process Gas is not out containing COS, CS
2, mercaptan, the organosulfur such as thioether;
3) carry out claus reaction generate elemental sulfur further from entering secondary claus reaction device after the second condenser overhead Process Gas is out heated to 220 DEG C, exit procedure gas enters the 3rd condenser and is cooled to 150 DEG C, Molten sulphur groove is entered, the 3rd condenser overhead Process Gas H out after the elemental sulfur of generation is separated with Process Gas
2the volume content 0.8%, SO of S
2volume content 0.6%;
4) be heated to 200 DEG C from the 3rd condenser overhead Process Gas out, enter Chemoselective reduction device, SO
2selective reduction is elemental sulfur, enters the 4th condenser be cooled to 150 DEG C from Chemoselective reduction device Process Gas out, enters Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas; H in 4th condensator outlet Process Gas
2the volume content 0.83% of S, not containing SO
2;
5) be preheating to 210 DEG C of laggard selectable oxidation reactors from the 4th condenser overhead Process Gas out, fill into appropriate air, H
2s selective oxidation is elemental sulfur, enter the 5th condenser from selective oxidation reaction device Process Gas out and be cooled to 150 DEG C, Molten sulphur groove is entered after the elemental sulfur generated is separated with Process Gas, Process Gas is cooled to 40 DEG C through the 6th condenser again, make most water, residue elemental sulfur condensation removing, the H in the 6th condensator outlet gas
2s volume content 0.06%, SO
2volume content 0.02%, not containing COS, CS
2, mercaptan, the organosulfur such as thioether;
6) enter an adsorption desulfurize tower (another does not put into operation) from the 6th condenser overhead Process Gas out, the catalytic oxidation adsorption desulfurizer loaded is by SO
2and H
2s reaction is converted into elemental sulfur, by remaining H
2s is oxidized to elemental sulfur, and the elemental sulfur of generation is deposited in the endoporus of sweetening agent; Adsorption desulfurize tower exit procedure gas total sulfur folding is SO
2≤ 10mg/m
3, emptying through chimney.
This sulfur recovery facility, before operation in 1200hr, adsorption desulfurize tower can't detect H in giving vent to anger
2s and SO
2, start afterwards to detect, during 1500hr, total sulfur folding is SO
21mg/m
3, during 1700hr, total sulfur folding is SO
22mg/m
3, during 1900hr, total sulfur folding is SO
23mg/m
3, during 2100hr, total sulfur folding is SO
25mg/m
3, during 2450hr, total sulfur folding is SO
210mg/m
3, this adsorption desulfurize tower is cut out regeneration, and another incision puts into operation.In plant running process, adsorption desulfurize tower can't detect H in giving vent to anger
2s, SO
2other S-contained substance in addition.
During the regeneration of adsorption desulfurize tower, by online adsorption desulfurize tower exit procedure gas O
2content controls to below 100ppm, as regeneration source of the gas, starts regeneration blower fan and interchanger, resurgent gases is heated to 250 DEG C, carries out in-situ heat regeneration to sweetening agent, controls regeneration tolerance and is about 10000m
3/ hr, reactivation outlet gas is mixed into the 5th condenser with from selective oxidation reaction device Process Gas out, be cooled to 150 DEG C, elemental sulfur condensation separation in gas mixture enters Molten sulphur groove, the gas mixture of removing elemental sulfur is again after the 6th condenser, online adsorption desulfurize tower process, a part recycles as resurgent gases, and another part is emptying through chimney; Namely be regenerated to that temperature of working off one's feeling vent one's spleen is identical with temperature in continues regeneration 20 hours after 250 DEG C, stop interchanger cooling, regenerated to when being cooled to 80 DEG C, the about 100hr of regenerative process.Regeneration period, online thionizer is worked off one's feeling vent one's spleen, and namely emptying tail gas total sulfur folding is SO
2lower than 2mg/m
3.
After having regenerated, thionizer incision after regeneration put into operation immediately, another cuts out for subsequent use, carries out 5 runnings and 4 regeneration continuously by above-mentioned elementary operation condition.
Following table 1 lists the total sulfur of working off one's feeling vent one's spleen of thionizer in these 5 operation process and reaches the runtime of different concns and corresponding desulfurization amount.
In table 1 operation process, thionizer total sulfur of working off one's feeling vent one's spleen reaches runtime and the desulfurization amount of different concns
After the 5th running terminates, carry out manipulation of regeneration, take out about 100L sweetening agent check from thionizer top, find that sweetening agent very easily takes out, not caking, the difference of outward appearance and new sweetening agent is not obvious, free from extraneous odour, and without efflorescence, calcination is without sulfur burning smell.Can inference, when scrapping after re-using for some time, unload agent after manipulation of regeneration, can not there is obvious peculiar smell, it is little to unload agent difficulty, and site environment is better, and safe operating conditions is better.
Embodiment 2
The sulfur recovery facility that Methanol Plant is a set of 30,000 tons/year, comprise the roasting kiln, one-level claus reaction device, the secondary claus reaction device that are connected in series successively, selective hydrogenation reduction reactor, selective oxidation reaction device and two can series-parallel adsorption desulfurize towers, one-level claus reaction device top filling Fe
2o
3/ Al
2o de-oxygen type catalyst for recovering sulfur 12m
3, bottom filling TiO
2catalyst for recovering sulfur 20m
3; Secondary claus reaction device top filling Fe
2o
3/ Al
2o
3de-oxygen type catalyst for recovering sulfur 12m
3, bottom filling TiO
2catalyst for recovering sulfur 20m
3; Selective hydrogenation reduction reactor filling CoO-MoO
3/ Al
2o
3selective reduction SO
2catalyzer 15m
3, selective oxidation reaction device filling Fe
2o
3/ SiO
2selective oxidation H
2s catalyzer 25m
3, two adsorption desulfurize towers load Fe respectively
2o
3/ activated carbon catalysis oxidation-adsorption sweetening agent 150m
3; The elementary operation condition of this device is:
1) sour gas 16000m
3/ hr, H
2s volume content about 20%, CO
2about 50%, join appropriate air (10000m
3about/hr) enter roasting kiln and burn, the temperature of roasting kiln controls at about 1250 DEG C, 350 DEG C are cooled to after the Process Gas produced after burning enters waste heat boiler, Process Gas enters the first condensate cooler from waste heat boiler outlet and is cooled to 150 DEG C, is separated enters Molten sulphur groove in roasting kiln after the elemental sulfur condensation generated with Process Gas;
2) 250 DEG C are heated to from the first condenser overhead Process Gas out, enter one-level claus reaction device and proceed claus reaction, exit procedure gas enters the second condenser and is cooled to 150 DEG C, enter Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas, the second condenser overhead Process Gas is not out containing COS, CS
2, mercaptan, the organosulfur such as thioether;
3) carry out claus reaction generate elemental sulfur further from entering secondary claus reaction device after the second condenser overhead Process Gas is out heated to 220 DEG C, exit procedure gas enters the 3rd condenser and is cooled to 150 DEG C, Molten sulphur groove is entered, the 3rd condenser overhead Process Gas H out after the elemental sulfur of generation is separated with Process Gas
2the volume content 1.0%, SO of S
2volume content 0.5%;
4) be heated to 200 DEG C from the 3rd condenser overhead Process Gas out, enter Chemoselective reduction device, SO
2selective reduction is elemental sulfur, enters the 4th condenser be cooled to 150 DEG C from Chemoselective reduction device Process Gas out, enters Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas; H in 4th condensator outlet Process Gas
2the volume content 1.03% of S, not containing SO
2;
5) be preheating to 210 DEG C of laggard selectable oxidation reactors from the 4th condenser overhead Process Gas out, fill into appropriate air, H
2s selective oxidation is elemental sulfur, enter the 5th condenser from selective oxidation reaction device Process Gas out and be cooled to 150 DEG C, Molten sulphur groove is entered after the elemental sulfur generated is separated with Process Gas, Process Gas is cooled to 40 DEG C through the 6th condenser again, make most water, residue elemental sulfur condensation removing, the H in the 6th condensator outlet gas
2s volume content 0.08%, SO
2volume content 0.02%, not containing COS, CS
2, mercaptan, the organosulfur such as thioether;
6) enter an adsorption desulfurize tower (another does not put into operation) from the 6th condenser overhead Process Gas out, the catalytic oxidation adsorption desulfurizer loaded is by SO
2and H
2s reaction is converted into elemental sulfur, by remaining H
2s is oxidized to elemental sulfur, and the elemental sulfur of generation is deposited in the endoporus of sweetening agent; Adsorption desulfurize tower exit procedure gas total sulfur folding is SO
2≤ 10mg/m
3, emptying through chimney.
This sulfur recovery facility, before operation in 1700hr, adsorption desulfurize tower can't detect H in giving vent to anger
2s and SO
2, start afterwards to detect, during 1800hr, total sulfur folding is SO
21mg/m
3, during 1900hr, total sulfur folding is SO
22mg/m
3, during 2050hr, total sulfur folding is SO
23mg/m
3, during 2200hr, total sulfur folding is SO
25mg/m
3, during 2300hr, total sulfur folding is SO
210mg/m
3, this adsorption desulfurize tower is cut out regeneration, and another incision puts into operation.In plant running process, adsorption desulfurize tower can't detect H in giving vent to anger
2s, SO
2other S-contained substance in addition.
During the regeneration of adsorption desulfurize tower, with superheated vapour as regeneration source of the gas, be heated to 280 DEG C, in-situ heat regeneration is carried out to sweetening agent, control quantity of steam and be about 10000m
3/ hr, reactivation outlet gas is mixed into the 5th condenser with from selective oxidation reaction device Process Gas out, be cooled to 150 DEG C, elemental sulfur condensation separation in gas mixture enters Molten sulphur groove, the gas mixture of removing elemental sulfur is again after the 6th condenser, online adsorption desulfurize tower process, emptying through chimney; Namely be regenerated to that temperature of working off one's feeling vent one's spleen is identical with temperature in continues regeneration 20 hours after 280 DEG C, stop steam and heating, regeneration completes, the about 90hr of regenerative process.Regeneration period, online thionizer is worked off one's feeling vent one's spleen, and namely emptying tail gas total sulfur folding is SO
2lower than 2mg/m
3.
After having regenerated, without cooling, thionizer incision after regeneration put into operation immediately, another cuts out for subsequent use, carries out 8 runnings and 7 regeneration continuously by above-mentioned elementary operation condition.
Following table 2 lists the total sulfur of working off one's feeling vent one's spleen of thionizer in these 8 operation process and reaches the runtime of each concentration and corresponding desulfurization amount.
In table 2 operation process, thionizer total sulfur of working off one's feeling vent one's spleen reaches the runtime of different concns and corresponding desulfurization amount
After 8th running terminates, carry out manipulation of regeneration, take out about 100L sweetening agent check from thionizer top, find that sweetening agent very easily takes out, not caking, the difference of outward appearance and new sweetening agent is not obvious, free from extraneous odour, and without efflorescence, calcination is without sulfur burning smell.Can inference, when scrapping after re-using for some time, unload agent after manipulation of regeneration, can not there is obvious peculiar smell, it is little to unload agent difficulty, and site environment is better, and safe operating conditions is better.
Claims (7)
1. a recovery technology of sulfur for low sulphur emissions, comprises the roasting kiln, one-level claus reaction device, the secondary claus reaction device that are connected in series successively, and selective hydrogenation reduction reactor, selective oxidation reaction device and two can series-parallel adsorption desulfurize towers;
Wherein, one-level claus reaction device top filling Fe
2o
3/ Al
2o
3de-oxygen type catalyst for recovering sulfur, bottom filling TiO
2catalyst for recovering sulfur; Described de-oxygen type catalyst for recovering sulfur is active except having good claus reaction, also by the O in Process Gas
2by with H
2s reaction generates elemental sulfur and removes; Described TiO
2catalyst for recovering sulfur is active except having good claus reaction, also by COS, the CS in Process Gas
2, mercaptan, the organosulfur such as thioether be all converted into elemental sulfur or H
2s;
Secondary claus reaction device filling catalyst for recovering sulfur, under lower slightly temperature condition, make claus reaction reach the good degree of depth, described catalyst for recovering sulfur is Fe
2o
3/ Al
2o
3de-oxygen type catalyst for recovering sulfur, TiO
2catalyst for recovering sulfur, TiO
2/ Al
2o
3catalyst for recovering sulfur and common Al
2o
3one or both in catalyst for recovering sulfur; H in this secondary claus reaction device exit procedure gas
2volume content≤1.0% of S, SO
2volume content≤0.60%;
Selective hydrogenation reduction reactor filling SO
2selective reduction catalyst, utilizes the H generated in roasting kiln
2by SO
2restore All, primary product is elemental sulfur, and by product is H
2s; H in this selective hydrogenation reduction reactor exit procedure gas
2volume content 0.5-1.5%, H
2volume content≤1.1% of S;
Selective oxidation reaction device filling H
2s catalyst for selective oxidation, the O filled into by introducing air before utilizing this reactor inlet
2by most H
2s selective oxidation is elemental sulfur, and by product is minute quantity SO
2; H in this selective oxidation reaction device exit procedure gas
2volume content≤0.10% of S, and be SO
2more than three times of volume content;
The filling of adsorption desulfurize tower can the catalytic oxidation adsorption desulfurizer of hot recycling, by micro-elemental sulfur absorption contained by Process Gas under 50-150 DEG C of condition, by the SO of contained minute quantity
2with contained H
2s is converted into elemental sulfur and adsorbs, by the H of remnants
2s is oxidized to elemental sulfur and adsorbs; The desulfurization precision folding of described catalytic oxidation adsorption desulfurizer is SO
2≤ 10mg/m
3, in thionizer entirety, the Sulfur capacity when this desulfurization precision>=100g sulphur/1000g sweetening agent; Purge with 200-300 DEG C of indifferent gas during hot recycling, after sulphur evaporative removal, catalyzed oxidation adsorption desulfurize performance is recovered substantially, is SO at guarantee desulfurization precision folding
2≤ 10mg/m
3condition under, through repeatedly hot recycling reach first Sulfur capacity 3-5 doubly more than total desulfurization amount;
Described recovery technology of sulfur comprises the steps:
1) containing H
2enter roasting kiln after the sour gas of S and air mixed to burn, the temperature of roasting kiln controls at 1150-1350 DEG C, 340-350 DEG C is cooled to after the Process Gas produced after burning enters waste heat boiler, Process Gas enters the first condensate cooler from waste heat boiler outlet and is cooled to 140-160 DEG C, is separated enters Molten sulphur groove in roasting kiln after the elemental sulfur condensation generated with Process Gas;
2) 240-270 DEG C is heated to from the first condenser overhead Process Gas out, enter one-level claus reaction device and proceed claus reaction, exit procedure gas enters the second condenser and is cooled to 140-160 DEG C, enters Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas;
3) carry out claus reaction generate elemental sulfur further from entering secondary claus reaction device after the second condenser overhead Process Gas is out heated to 210-230 DEG C, exit procedure gas enters the 3rd condenser and is cooled to 140-160 DEG C, enters Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas;
4) be heated to 200-210 DEG C from the 3rd condenser overhead Process Gas out, enter Chemoselective reduction device, SO
2selective reduction is elemental sulfur, enters the 4th condenser be cooled to 140-160 DEG C from Chemoselective reduction device Process Gas out, enters Molten sulphur groove after the elemental sulfur of generation is separated with Process Gas;
5) be preheating to 180-210 DEG C of laggard selectable oxidation reactor from the 4th condenser overhead Process Gas out, fill into appropriate air, H
2s selective oxidation is elemental sulfur, suitably controls the air amount of filling into and bed temperature, makes the remaining H in working off one's feeling vent one's spleen
2s content is by-product SO
2more than three times, enter the 5th condenser from selective oxidation reaction device Process Gas out and be cooled to 140-160 DEG C, enter Molten sulphur groove after the elemental sulfur generated is separated with Process Gas, Process Gas is cooled to 50-150 DEG C through the 6th condenser again, makes the further condensation removing of water, residue elemental sulfur;
6) enter adsorption desulfurize tower from the 6th condenser overhead Process Gas out, the catalytic oxidation adsorption desulfurizer loaded at 50-150 DEG C by SO
2and H
2s reaction is converted into elemental sulfur, by the H of remnants
2s is oxidized to elemental sulfur, can fill into appropriate air if desired, and the elemental sulfur of generation is deposited in the endoporus of sweetening agent, and adsorption desulfurize tower exit procedure gas total sulfur folding is SO
2≤ 10mg/m
3, emptying through chimney from adsorption desulfurize tower Process Gas out;
7) when adsorption desulfurize tower exit procedure gas total sulfur folding is SO
2soon more than 10mg/m
3time, this adsorption desulfurize tower cuts out, and carries out in-situ heat regeneration with 250-300 DEG C of indifferent gas, after hot recycling completes, lowers the temperature for subsequent use, or carries out desulfurization without cooling incision immediately; Reactivation outlet gas gets back to roasting kiln, the condenser after roasting kiln, the condenser after one-level claus reaction device, condenser after secondary claus reaction device, condenser after selective hydrogenation reduction reactor, or the condenser after selective oxidation reaction device, by the elemental sulfur in resurgent gases and H
2s, SO
2sulfides reclaims, and the emptying tail gas total sulfur folding of thionizer regeneration period is SO
2≤ 10mg/m
3.
2. low sulphur emissions recovery technology of sulfur as claimed in claim 1, is characterized in that, described catalytic oxidation adsorption desulfurizer is Fe
2o
3/ gac, Fe
2o
3/ aluminum oxide, Fe
2o
3one or more in/silicon oxide and ferric oxide desulfurizer.
3. low sulphur emissions recovery technology of sulfur as claimed in claim 2, is characterized in that, described catalytic oxidation adsorption desulfurizer is the Fe of charge capacity 5-20%
2o
3/ gac, or with Fe
2o
3for the ferric oxide desulfurizer of main component.
4. the arbitrary low sulphur emissions recovery technology of sulfur as described in claim 1-3, is characterized in that, H in described selective oxidation reaction device exit procedure gas
2the volume content of S controls as SO
2the 3-5 of volume content doubly.
5. the arbitrary low sulphur emissions recovery technology of sulfur as described in claim 1-3, is characterized in that, in thionizer non-renewable period, the parallel operation of two adsorption desulfurize towers, changes into before thionizer soon regenerates before being serially connected in another thionizer and using.
6. the arbitrary low sulphur emissions recovery technology of sulfur as described in claim 1-3, it is characterized in that, to work off one's feeling vent one's spleen with thionizer or superheated vapour does resurgent gases, after reactivation outlet gas gets back to selective oxidation reaction device, the 5th condenser is mixed into from selective oxidation reaction device Process Gas out, be cooled to 140-160 DEG C, elemental sulfur condensation separation in gas mixture enters Molten sulphur groove, remove the gas mixture of elemental sulfur again after the 6th condenser, the second online adsorption desulfurize tower process, more emptying through chimney.
7. the arbitrary low sulphur emissions recovery technology of sulfur as described in claim 1-3, it is characterized in that, work off one's feeling vent one's spleen with thionizer and do resurgent gases, before reactivation outlet gas gets back to Chemoselective reduction device, the 3rd condenser is mixed into from secondary claus reaction device Process Gas out, be cooled to 140-160 DEG C, elemental sulfur condensation separation in gas mixture enters Molten sulphur groove, remove the gas mixture of elemental sulfur again after selective reduction, selective oxidation, the second online adsorption desulfurize tower process, more emptying through chimney.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107572483A (en) * | 2017-01-16 | 2018-01-12 | 赵西营 | Technique that is a kind of while producing carbon disulfide, sulphur and insoluble sulfur |
| CN108910831A (en) * | 2018-08-30 | 2018-11-30 | 山东迅达化工集团有限公司 | A kind of recovery technology of sulfur of high-concentration acidic wastewater gas |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659400A (en) * | 2009-09-11 | 2010-03-03 | 山东迅达化工集团有限公司 | Catalyst combination process of sulfur recovering device |
| CN103480252A (en) * | 2012-06-13 | 2014-01-01 | 中国石油天然气股份有限公司 | Hydrogen sulfide-containing acid gas treatment method |
-
2015
- 2015-11-18 CN CN201510794600.4A patent/CN105293445B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659400A (en) * | 2009-09-11 | 2010-03-03 | 山东迅达化工集团有限公司 | Catalyst combination process of sulfur recovering device |
| CN103480252A (en) * | 2012-06-13 | 2014-01-01 | 中国石油天然气股份有限公司 | Hydrogen sulfide-containing acid gas treatment method |
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| CN107572483B (en) * | 2017-01-16 | 2020-04-21 | 赵西营 | Process for simultaneously producing carbon disulfide, sulfur and insoluble sulfur |
| CN108910831A (en) * | 2018-08-30 | 2018-11-30 | 山东迅达化工集团有限公司 | A kind of recovery technology of sulfur of high-concentration acidic wastewater gas |
| CN109019523A (en) * | 2018-08-30 | 2018-12-18 | 山东迅达化工集团有限公司 | A kind of sour gas recovery technology of sulfur of ultralow sulphur emissions |
| CN109133012A (en) * | 2018-08-30 | 2019-01-04 | 山东迅达化工集团有限公司 | The recovery technology of sulfur of high-concentration acidic wastewater gas |
| CN109179339A (en) * | 2018-08-30 | 2019-01-11 | 山东迅达化工集团有限公司 | The recovery technology of sulfur of middle low concentration sour gas |
| CN109019523B (en) * | 2018-08-30 | 2020-10-23 | 山东迅达化工集团有限公司 | Acid gas sulfur recovery process with ultralow sulfur emission |
| CN109179339B (en) * | 2018-08-30 | 2020-10-23 | 山东迅达化工集团有限公司 | Sulfur recovery process for acid gas with medium and low concentration |
| CN113786811A (en) * | 2021-10-13 | 2021-12-14 | 山东迅达催化剂有限公司 | Adsorption desulfurizing agent capable of being thermally regenerated and having COS hydrolysis function, preparation method and application thereof |
| CN113800478A (en) * | 2021-10-13 | 2021-12-17 | 山东迅达催化剂有限公司 | Low-carbon and ultralow-sulfur-emission acid gas sulfur recovery process |
| CN113800478B (en) * | 2021-10-13 | 2023-12-15 | 山东迅达催化剂有限公司 | Low-carbon and ultralow-sulfur emission acid gas sulfur recovery process |
| CN113786811B (en) * | 2021-10-13 | 2024-04-30 | 山东迅达催化剂有限公司 | Adsorption desulfurizing agent capable of being thermally regenerated and having COS hydrolysis function, preparation method and application thereof |
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