CN105293444A - Low sulfur emission sulphur recovery process - Google Patents
Low sulfur emission sulphur recovery process Download PDFInfo
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- CN105293444A CN105293444A CN201510793850.6A CN201510793850A CN105293444A CN 105293444 A CN105293444 A CN 105293444A CN 201510793850 A CN201510793850 A CN 201510793850A CN 105293444 A CN105293444 A CN 105293444A
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- sulfur
- process gas
- elemental sulfur
- reaction device
- catalyst
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 226
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 96
- 239000011593 sulfur Substances 0.000 title claims abstract description 94
- 239000005864 Sulphur Substances 0.000 title claims abstract description 59
- 238000011084 recovery Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 112
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 68
- 238000001179 sorption measurement Methods 0.000 claims abstract description 57
- 230000003647 oxidation Effects 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 20
- 230000023556 desulfurization Effects 0.000 claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 103
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000006722 reduction reaction Methods 0.000 claims description 26
- 239000003765 sweetening agent Substances 0.000 claims description 25
- 238000005516 engineering process Methods 0.000 claims description 24
- 235000003599 food sweetener Nutrition 0.000 claims description 24
- 230000003197 catalytic effect Effects 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 239000002918 waste heat Substances 0.000 claims description 9
- 238000011944 chemoselective reduction Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 210000000952 spleen Anatomy 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 150000003568 thioethers Chemical class 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Treating Waste Gases (AREA)
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>; and the low sulfur emission sulphur recovery process has advantages of low sulfur emission, long desulfurization agent service life, 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.
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, make the tail gas after desulfurization reach GB16297-1996 country emission request, but this technique does not relate to and provides the technical scheme of low sulphur emissions, does not play 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, ferric oxide desulfurizer 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, if total sulfur folding is SO
2lower than 10mg/m
3and even, lower than 5mg/m
3, 2mg/m
3, 1mg/m
3.
But this technique does not specifically provide the concrete operations processing condition that can play catalytic oxidation adsorption desulfurizer desulfurization precision.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, can not remove completely at 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.
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 CoO-MoO
3/ Al
2o
3selective reduction SO
2catalyzer, 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 Fe
2o
3/ SiO
2selective oxidation H
2s catalyzer, 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;
Adsorption desulfurize tower filling catalytic oxidation adsorption desulfurizer, by elemental sulfur absorption micro-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>=300g sulphur/1000g sweetening agent;
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) from the 6th condenser overhead Process Gas out, fill into appropriate air, enter adsorption desulfurize tower, 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, 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.
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
3one or more in/gac 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, Fe
2o
3/ gac 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 Sulfur capacity of these sweetening agents can >=300g sulphur/1000g sweetening agent.
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
3sulfur capacity before penetrating, preferably>=400g sulphur/1000g sweetening agent, has longer running period, 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.
Low sulphur emissions recovery technology of sulfur start of run of the present invention, the work off one's feeling vent one's spleen total sulfur of the i.e. emptying tail gas of this technique of thionizer is usually lower or can't detect, and improves gradually afterwards; Roll over for SO to total sulfur
22mg/m
3time sulphur adsorptive capacity can reach 200g sulphur/1000g sweetening agent, and even>=300g sulphur/1000g sweetening agent; Roll over for SO to total sulfur
25mg/m
3time sulphur adsorptive capacity can reach 300g sulphur/1000g sweetening agent, and even>=400g sulphur/1000g sweetening agent; Roll over for SO to total sulfur
210mg/m
3time sulphur adsorptive capacity can reach 400g sulphur/1000g sweetening agent, and even>=450g sulphur/1000g.
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, two adsorption desulfurize towers can parallel operation, to alleviate bed resistance; Use before preferably the thionizer soon penetrated being serially connected in another thionizer, to improve the desulfurization amount of front tower sweetening agent, thus extend the work-ing life of sweetening agent.
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 performance, 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
21mg/m
3as lower than 10mg/m
3and even, lower than 5mg/m
3, 2mg/m
3, until emptying tail gas containing sulphur concentration close to or switch immediately after reaching this concentration value or cut out, thus continue to ensure that emptying tail gas total sulfur folding is SO
2≤ 10mg/m
3.
2) 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
2not containing the material that obviously may reduce above-mentioned catalytic oxidation adsorption desulfurizer performance, thus catalytic oxidation adsorption desulfurizer only carries out the reaction generating elemental sulfur, the elemental sulfur generated also deposits, is adsorbed in the endoporus of sweetening agent, thus the life-span of sweetening agent is long, desulfurization amount is large, replacing number of times is few, and expense is low.
Accompanying drawing explanation
Accompanying drawing is the concise and to the point flow process of the present invention's low sulphur emissions recovery technology of sulfur, and 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 chimneys
Embodiment
Embodiment 1
The sulfur recovery facility of 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, 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, cut out by this adsorption desulfurize tower, 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.
Embodiment 2
The sulfur recovery facility of 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 2500hr, total sulfur folding is SO
210mg/m
3, cut out by this adsorption desulfurize tower, 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.
Following table 1 lists in embodiment 1,2 device operation process, and thionizer total sulfur of working off one's feeling vent one's spleen 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
Claims (5)
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 CoO-MoO
3/ Al
2o
3selective reduction SO
2catalyzer, 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 Fe
2o
3/ SiO
2selective oxidation H
2s catalyzer, 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 3 times of volume content;
Adsorption desulfurize tower filling catalytic oxidation adsorption desulfurizer, by elemental sulfur absorption micro-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>=300g sulphur/1000g sweetening agent;
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 3 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 10-50 DEG C through the 6th condenser again, makes most water, residue elemental sulfur condensation removing;
6) from the 6th condenser overhead Process Gas out, fill into appropriate air, enter adsorption desulfurize tower, 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, 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.
2. low sulphur emissions recovery technology of sulfur as claimed in claim 1, is characterized in that, described catalytic oxidation adsorption desulfurizer is Na
2cO
3/ gac, NaOH/ gac, K
2cO
3/ gac, KOH/ gac, Fe
2o
3one or more in/gac 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 Na of charge capacity 5-10%
2cO
3the Fe of/gac, 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, uses before the thionizer soon penetrated is serially connected in another thionizer.
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| CN106698361A (en) * | 2016-12-14 | 2017-05-24 | 山东迅达化工集团有限公司 | Sulfur recycling process for acid gas |
| CN106914103A (en) * | 2017-04-11 | 2017-07-04 | 德阳劲达节能科技有限责任公司 | A kind of Claus tail gases low-temp desulfurization system and technique |
| CN108178132A (en) * | 2018-02-24 | 2018-06-19 | 洛阳瑞昌石油化工设备有限公司 | Sulfur recovery method and equipment in a kind of carbon disulphide production |
| CN109019524A (en) * | 2018-08-30 | 2018-12-18 | 山东迅达化工集团有限公司 | A kind of recovery technology of sulfur of middle low concentration sour 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 |
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| CN106914103A (en) * | 2017-04-11 | 2017-07-04 | 德阳劲达节能科技有限责任公司 | A kind of Claus tail gases low-temp desulfurization system and technique |
| CN108178132A (en) * | 2018-02-24 | 2018-06-19 | 洛阳瑞昌石油化工设备有限公司 | Sulfur recovery method and equipment in a kind of carbon disulphide production |
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| CN109019524A (en) * | 2018-08-30 | 2018-12-18 | 山东迅达化工集团有限公司 | A kind of recovery technology of sulfur of middle low concentration sour gas |
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| CN112546851A (en) * | 2020-11-13 | 2021-03-26 | 中国科学院过程工程研究所 | Activated carbon, preparation method thereof and application thereof in desulfurization |
| CN112546851B (en) * | 2020-11-13 | 2022-04-26 | 中国科学院过程工程研究所 | Activated carbon, preparation method thereof and application thereof in desulfurization |
| CN116036785A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Low-emission sulfur recovery process and sulfur recovery system |
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