CN105293444B - The recovery technology of sulfur of low-sulfur discharge - Google Patents
The recovery technology of sulfur of low-sulfur discharge Download PDFInfo
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- CN105293444B CN105293444B CN201510793850.6A CN201510793850A CN105293444B CN 105293444 B CN105293444 B CN 105293444B CN 201510793850 A CN201510793850 A CN 201510793850A CN 105293444 B CN105293444 B CN 105293444B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 108
- 239000011593 sulfur Substances 0.000 title claims abstract description 108
- 238000011084 recovery Methods 0.000 title claims abstract description 33
- 238000005516 engineering process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 105
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 73
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 238000010521 absorption reaction Methods 0.000 claims abstract description 29
- 238000002485 combustion reaction Methods 0.000 claims abstract description 23
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 21
- 230000023556 desulfurization Effects 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 102
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 57
- 239000005864 Sulphur Substances 0.000 claims description 54
- 230000003647 oxidation Effects 0.000 claims description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 238000006722 reduction reaction Methods 0.000 claims description 22
- 238000001179 sorption measurement Methods 0.000 claims description 21
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 238000011944 chemoselective reduction Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000002918 waste heat Substances 0.000 claims description 8
- 125000001741 organic sulfur group Chemical group 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 210000000952 spleen Anatomy 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 235000001508 sulfur Nutrition 0.000 claims 17
- -1 mercaptan thioether Chemical class 0.000 claims 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 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
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- Treating Waste Gases (AREA)
Abstract
The present invention provides a kind of recovery technology of sulfur of low-sulfur discharge, including the combustion furnace one-level claus reaction two grades of claus reaction devices of device being sequentially connected in series, and selective hydrogenation reduction reactor selective oxidation reaction device and two can series-parallel absorption desulfurizing towers；It is SO by each catalyst, the appropriate selection of desulfurizing agent, the accurate control to each process condition, making technique discharge gas total sulfur folding2 ≤10mg/m3.The low-sulfur discharge recovery technology of sulfur of the present invention, with low-sulfur discharge, desulfurizing agent long lifespan desulfurization amount is big, and replacing number of times is few, the low advantage of expense.
Description
Technical field
The present invention relates to a kind of recovery technology of sulfur, and in particular to a kind of recovery technology of sulfur of low-sulfur discharge.
Background technology
In petrochemical industry, coal chemical industry, coal gasification course, a part of sulphur contained by raw material would generally change into H2S, through separation
Form H2The higher sour gas of S contents, the sour gas is typically handled through recovery technology of sulfur, by H2S is converted as much as possible
For elemental sulfur.Some high H2In the decontamination process of S content natural gases, H is separated2The sour gas of S formation, will also be returned through sulphur
Skill of knocking off is converted into elemental sulfur as much as possible.
, during operation, also there is emptying tail gas and solid waste two in the sulfur recovery facility.Through chimney
The tail gas of emptying, wherein, SO2Concentration is continuous monitoring project, although existing discharge standard of air pollutants GB16297-
1996 higher limit such as 700mg/m3It is not difficult to reach, but place industry or location there is likely to be more strict discharge mark
It is accurate；H2S is one of odor pollution material included by emission standard for odor pollutants GB14554-93, and emission limit is more tight
Lattice, the quasi- higher limit of factory's boundary mark such as three-level is 0.45/0.80mg/m3, 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, including successively
Combustion furnace, one-level claus reaction device, the two grades of claus reaction devices of concatenation, selective hydrogenation reduction reactor, selective oxygen
Change reactor and two catalysis oxidation absorption desulfurizing towers in parallel；Load de-oxygen type sulphur in one-level claus reaction device top
Reclaim catalyst, bottom filling TiO2Catalyst for recovering sulfur, two grades of claus reaction device filling auxiliary agent type sulphur recovery catalysis
Agent, by the SO of the overwhelming majority2、H2S reactions are converted into elemental sulfur；Selective hydrogenation reduction reactor loads SO2Selective reduction is urged
Agent, by remaining a small amount of SO2Selective reduction is elemental sulfur；Selective oxidation reaction device loads H2S selective oxidations are catalyzed
Agent, by remaining H2S major part selective oxidations are elemental sulfur；Catalysis oxidation absorption desulfurizing tower filling H2The absorption of S catalysis oxidations is de-
Sulphur agent, by remaining H2S catalysis oxidations are elemental sulfur, the tail gas after desulfurization is reached the national emission requests of GB16297-1996,
But the technique is without reference to the technical scheme for providing low-sulfur discharge, and the desulfurization for not playing catalytic oxidation adsorption desulfurizer is smart
Degree.
Conventional catalytic oxidation adsorption desulfurizer such as Na2CO3/ activated carbon, NaOH/ activated carbons, K2CO3/ activated carbon, KOH/
Activated carbon, Fe2O3/ activated carbon, ferric oxide desulfurizer etc., temperature is less high, appropriate O2, can be by work under conditions of moisture
A small amount of SO in skill gas2With excessive H2S reactions are converted into elemental sulfur, by remaining H2S catalysis oxidations are elemental sulfur, so as to have
Very high desulfurization precision, such as total sulfur folding are SO2Less than 10mg/m3, even below 5mg/m3、2mg/m3、1mg/m3。
But the technique, which does not specifically give, can play the concrete operations technique bar of catalytic oxidation adsorption desulfurizer desulfurization precision
Part.If catalysis oxidation absorption desulfurizing tower enters implication SO2/H2S concentration ratio is higher than 1 required for generation elemental sulfur:2, desulfurization
The SO that tower is worked off one's feeling vent one's spleen2Concentration may be higher than 10mg/m3, this point is in selective oxidation reaction device entrance O2Too high levels, temperature
Easily occur when too high, because of SO2It is H2S Selective Oxidations are generated as the side reaction product of elemental sulfur；Or selective hydrogenation is also
The temperature of former reactor inlet gas is not high enough, H2Amount it is not enough, cause SO2Can not Restore All, this part SO2Also it can enter and urge
Change oxidation-adsorption desulfurizing tower, it is impossible to removed completely in catalysis oxidation absorption desulfurizing tower, be likely to result in desulfurizing tower and work off one's feeling vent one's spleen i.e. technique
The SO of tail gas2Content is far above 10mg/m3。
Thus, it is necessary to further perfect is done to above-mentioned technique.
The content of the invention
To overcome above-mentioned technological deficiency, the present invention provides a kind of recovery technology of sulfur of low-sulfur discharge, including is sequentially connected in series
Combustion furnace, one-level claus reaction device, two grades of claus reaction devices, selective hydrogenation reduction reactor, selective oxidation are anti-
Answer device and two can series-parallel absorption desulfurizing tower；
Wherein, one-level claus reaction device top filling Fe2O3/Al2O3De-oxygen type catalyst for recovering sulfur, bottom
Load TiO2Catalyst for recovering sulfur；The de-oxygen type catalyst for recovering sulfur with preferable claus reaction except living
Property, also by the O in Process Gas2By with H2S reactions generate elemental sulfur and removed；The TiO2Catalyst for recovering sulfur is except tool
There is preferable claus reaction activity, also by COS, CS in Process Gas2, mercaptan, the organic sulfur such as thioether be completely converted into simple substance
Sulphur or H2S；
Two grades of claus reaction devices load catalyst for recovering sulfur, under lower slightly temperature conditionss, reach claus reaction
To preferable depth, the catalyst for recovering sulfur is Fe2O3/Al2O3De-oxygen type catalyst for recovering sulfur, TiO2Sulphur is returned
Receive catalyst, TiO2/Al2O3Catalyst for recovering sulfur and common Al2O3One or both of catalyst for recovering sulfur；Should
H in two grades of claus reaction device exit procedure gas2S volume content≤1.0%, SO2Volume content≤0.60%；
Selective hydrogenation reduction reactor loads CoO-MoO3/Al2O3Selective reduction SO2Catalyst, using in combustion furnace
The H of generation2By SO2Restore All, primary product is elemental sulfur, and accessory substance is H2S；The selective hydrogenation reduction reactor is exported
H in Process Gas2Volume content 0.5-1.5%, H2S volume content≤1.1%；
Selective oxidation reaction device loads Fe2O3/SiO2Selective oxidation H2S catalyst, leads to using before the reactor inlet
Cross and introduce the O that air is filled into2By most H2S selective oxidations are elemental sulfur, and accessory substance is very small amount SO2；The selective oxygen
Change H in reactor outlet Process Gas2S volume content≤0.10%, and be SO2It is more than the three times of volume content；
Desulfurizing tower filling catalytic oxidation adsorption desulfurizer is adsorbed, by micro simple substance contained by Process Gas under the conditions of 10-50 DEG C
Sulphur is adsorbed, will contained minimal amount of SO2With contained H2S is converted into elemental sulfur and adsorbed, by remaining H2S is oxidized to elemental sulfur simultaneously
Absorption；The desulfurization precision folding of the catalytic oxidation adsorption desulfurizer is SO2≤10mg/m3, by desulfurizing tower integrally in terms of, in the desulfurization
Sulfur capacity >=300g sulphur/1000g desulfurizing agents during precision；
The recovery technology of sulfur comprises the following steps:
1) H is contained2S sour gas is burnt after being mixed with air into combustion furnace, and the temperature control of combustion furnace exists
1150-1350 DEG C, the Process Gas produced after burning is cooled to 340-350 DEG C after entering waste heat boiler, and Process Gas is from waste heat boiler
Outlet is cooled to 140-160 DEG C into the first condensate cooler, with process qi leel after the elemental sulfur condensation generated in combustion furnace
From entrance Molten sulphur groove；
2) Process Gas come out from the first condenser overhead is heated to 240-270 DEG C, into one-level claus reaction device after
Continuous to carry out claus reaction, exit procedure gas is cooled to 140-160 DEG C into the second condenser, makes the elemental sulfur and process of generation
Qi leel is from rear entrance Molten sulphur groove；
3) Process Gas come out from the second condenser overhead is heated to after 210-230 DEG C enter into two grades of claus reaction devices
Row claus reaction further generates elemental sulfur, and exit procedure gas is cooled to 140-160 DEG C into the 3rd condenser, makes generation
Elemental sulfur enters Molten sulphur groove after being separated with Process Gas；
4) Process Gas come out from the 3rd condenser overhead is heated to 200-210 DEG C, into Chemoselective reduction device,
SO2Selective reduction is elemental sulfur, and the Process Gas come out from Chemoselective reduction device is cooled to 140- into the 4th condenser
160 DEG C, the elemental sulfur of generation enters Molten sulphur groove after being separated with Process Gas；
5) Process Gas come out from the 4th condenser overhead is preheating to 180-210 DEG C of laggard selectable oxidation reactor,
Fill into appropriate air, H2S selective oxidations are elemental sulfur, the suitable control air amount of filling into and bed temperature, are made in working off one's feeling vent one's spleen
Remaining H2S contents are by-product SO2Three times more than, it is cold that the Process Gas come out from selective oxidation reaction device enters the 5th condenser
But 140-160 DEG C is arrived, the elemental sulfur of generation enters Molten sulphur groove after being separated with Process Gas, and Process Gas is cold through the 6th condenser again
But to 10-50 DEG C, remove most water, remaining elemental sulfur condensation；
6) Process Gas come out from the 6th condenser overhead, fills into appropriate air, and into absorption desulfurizing tower, that is loaded urges
Change oxidation-adsorption desulfurizing agent at 10-50 DEG C by SO2And H2S reactions are converted into elemental sulfur, by remaining H2S is oxidized to elemental sulfur, raw
Into elemental sulfur be deposited in the endoporus of desulfurizing agent, absorption desulfurizing tower exit procedure gas total sulfur folding is SO2≤10mg/m3, from absorption
The Process Gas that desulfurizing tower comes out is emptied through chimney.
In the low-sulfur discharge recovery technology of sulfur of the present invention, catalytic oxidation adsorption desulfurizer can use Na2CO3/ activated carbon,
NaOH/ activated carbons, K2CO3/ activated carbon, KOH/ activated carbons, Fe2O3One kind or many in/activated carbon and ferric oxide desulfurizer
Kind, it is SO to be all up total sulfur folding2≤10mg/m3Desulfurization precision.Wherein, Na is loaded2CO3、NaOH、K2CO3, KOH desulfurization
Agent is to SO2Disposal ability it is larger, Fe2O3/ activated carbon or Fe2O3Desulfurizing agent is to H2S disposal ability is larger.Filled with desulfurizing tower
Whole desulfurizing agent meters, in the desulfurization precision, the Sulfur capacity of these desulfurizing agents can >=300g sulphur/1000g desulfurizing agents.
In the low-sulfur discharge recovery technology of sulfur of the present invention, catalytic oxidation adsorption desulfurizer used is SO in total sulfur folding2
≤10mg/m3Sulfur capacity before penetrating, preferably >=400g sulphur/1000g desulfurizing agents, with longer service cycle, preferably appropriate system
Standby Na2CO3The 5-10% of load capacity Na2CO3/ activated carbon, Fe2O3Load capacity 5-20% Fe2O3/ activated carbon, or with
Fe2O3For the ferric oxide desulfurizer of main component.
The low-sulfur discharge recovery technology of sulfur start of run of the present invention, desulfurizing tower is worked off one's feeling vent one's spleen the emptying tail gas of i.e. this technique
Total sulfur is generally relatively low or can't detect, and gradually steps up afterwards；It is SO to total sulfur folding2 2mg/m3When sulphur adsorbance can reach
200g sulphur/1000g desulfurizing agents, or even >=300g sulphur/1000g desulfurizing agents；It is SO to total sulfur folding2 5mg/m3When sulphur adsorbance can
To reach 300g sulphur/1000g desulfurizing agents, or even >=400g sulphur/1000g desulfurizing agents；It is SO to total sulfur folding2 10mg/m3When sulphur
Adsorbance can reach 400g sulphur/1000g desulfurizing agents, or even >=450g sulphur/1000g.
In the low-sulfur discharge recovery technology of sulfur of the present invention, H in the selective oxidation reaction device exit procedure gas2S's
Volume content is preferably controlled to SO23-5 times of volume content.
In low-sulfur discharge recovery technology of sulfur of the present invention, two absorption desulfurizing towers can be operated in parallel, to mitigate bed resistance
Power；It is preferred that used before the desulfurizing tower soon penetrated is serially connected in another desulfurizing tower, to improve the desulfurization amount of preceding tower desulfurizing agent, from
And extend the service life of desulfurizing agent.
The low-sulfur discharge recovery technology of sulfur of the present invention, with advantages below:
1) low-sulfur discharge is maintained
The present invention above-mentioned low-sulfur discharge recovery technology of sulfur in, sour gas by combustion furnace, one-level claus reaction device,
Two grades of claus reaction devices, after selective hydrogenation reduction reactor, selective oxidation reaction device, the processing of absorption desulfurizing tower, row
Air total sulfur folding is SO2≤10mg/m3.Because this technique is integrally more perfect, desulfurizing tower enters implication main component and stablized, simply,
Only include N2、H2O, a small amount of O2, a small amount of H2S, very small amount SO2With micro elemental sulfur, it is also possible to sometimes containing CO2, it is obvious without meeting
The material of above-mentioned catalytic oxidation adsorption desulfurizer performance is reduced, generation elemental sulfur is only carried out on catalytic oxidation adsorption desulfurizer
Reaction, and deposit, adsorb in the endoporus of desulfurizing agent, and the catalytic oxidation adsorption desulfurizer desulfurization precision loaded in desulfurizing tower
High performance and feature, in its long period after putting into operation, desulfurizing tower works off one's feeling vent one's spleen what i.e. sulfur recovery facility will be emptied through chimney
Tail gas, it is very low containing sulphur concentration, rolls over for SO21mg/m3Such as it is less than 10mg/m3, even below 5mg/m3、2mg/m3, until emptying
Tail gas containing sulphur concentration switches or cut out immediately close to or up after this concentration value, so as to persistently ensure that emptying tail gas total sulfur folding is
SO2≤10mg/m3。
2) long lifespan of desulfurizing agent, desulfurization amount are big, and replacing number of times is few, and expense is low
The present invention above-mentioned low-sulfur discharge recovery technology of sulfur in, sour gas by combustion furnace, one-level claus reaction device,
Two grades of claus reaction devices, after selective hydrogenation reduction reactor, the processing of selective oxidation reaction device, adsorb desulfurizing tower entrance
Gas main component is relatively stable, simple, only including N2、H2O, a small amount of H2S, very small amount SO2With micro elemental sulfur, also contain sometimes
CO2, without may substantially reduce the material of above-mentioned catalytic oxidation adsorption desulfurizer performance, thus on catalytic oxidation adsorption desulfurizer
The reaction of generation elemental sulfur is only carried out, the elemental sulfur of generation is also deposited, adsorbed in the endoporus of desulfurizing agent, thus the longevity of desulfurizing agent
Life is long, desulfurization amount is big, and replacing number of times is few, and expense is low.
Brief description of the drawings
Accompanying drawing is the brief flow that low-sulfur of the present invention discharges recovery technology of sulfur, and device numbering is followed successively by 1 combustion furnace, and 2 give up
Heat boiler, 3 first condensers, 4 heaters, 5 one-level claus reaction devices, 6 second condensers, 7 two grades of claus reaction devices, 8
3rd condenser, 9 selective hydrogenation reduction reactors, 10 the 4th condensers, 11 selective oxidation reaction devices, 12 the 5th condensations
Device, 13 the 6th condensers, 14 absorption desulfurizing towers, 15 Molten sulphur grooves, 16 chimneys
Embodiment
Embodiment 1
A set of 50,000 tons/year of sulfur recovery facility, including be sequentially connected in series combustion furnace, one-level claus reaction device, two grades
Claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device and two can series-parallel absorption desulfurizing tower,
Load Fe in one-level claus reaction device top2O3/Al2O de-oxygen type catalyst for recovering sulfur 15m3, bottom filling TiO2Sulphur
Reclaim catalyst 25m3；Load Fe in two grades of claus reaction device tops2O3/Al2O3De-oxygen type catalyst for recovering sulfur 15m3,
Load TiO in bottom2/Al2O3Catalyst for recovering sulfur 25m3；Selective hydrogenation reduction reactor loads CoO-MoO3/Al2O3Selection
Property reduction SO2Catalyst 20m3, selective oxidation reaction device filling Fe2O3/SiO2Selective oxidation H2S catalyst 30m3, two
Absorption desulfurizing tower loads Na respectively2CO3/ activated carbon catalysis oxidation-adsorption desulfurizing agent 150m3；The basic operation condition of the device is:
1) sour gas 15000m3/ hr, H2S volume content 30-40%, remaining is mainly CO2, with appropriate air
(12500m3/ hr or so) to enter combustion furnace and burnt, the temperature control of combustion furnace is in 1200 DEG C or so, the mistake produced after burning
Journey gas, which enters, is cooled to 350 DEG C after waste heat boiler, Process Gas exports into the first condensate cooler from waste heat boiler and is cooled to 150
DEG C, it is segregated into Molten sulphur groove with Process Gas after the elemental sulfur condensation generated in combustion furnace；
2) Process Gas come out from the first condenser overhead is heated to 250 DEG C, into one-level claus reaction device continue into
Row claus reaction, exit procedure gas is cooled to 150 DEG C into the second condenser, makes after the elemental sulfur of generation separates with Process Gas
Into Molten sulphur groove, the Process Gas that the second condenser overhead comes out is free of COS, CS2, mercaptan, the organic sulfur such as thioether；
3) Process Gas come out from the second condenser overhead is heated to enter two grades of claus reaction devices progress gram after 220 DEG C
The further generation elemental sulfur of Louth reaction, exit procedure gas is cooled to 150 DEG C into the 3rd condenser, make generation elemental sulfur and
Enter Molten sulphur groove, the Process Gas H that the 3rd condenser overhead comes out after Process Gas separation2S volume content 0.8%, SO2's
Volume content 0.6%；
4) Process Gas come out from the 3rd condenser overhead is heated to 200 DEG C, into Chemoselective reduction device, SO2Choosing
Selecting property is reduced to elemental sulfur, and the Process Gas come out from Chemoselective reduction device is cooled to 150 DEG C, generation into the 4th condenser
Elemental sulfur separated with Process Gas after enter Molten sulphur groove；H in 4th condensator outlet Process Gas2S volume content
0.83%, without SO2；
5) Process Gas come out from the 4th condenser overhead is preheating to 210 DEG C of laggard selectable oxidation reactors, fills into
Appropriate air, H2S selective oxidations are elemental sulfur, and it is cold that the Process Gas come out from selective oxidation reaction device enters the 5th condenser
But to 150 DEG C, the elemental sulfur of generation enters Molten sulphur groove after being separated with Process Gas, and Process Gas is cooled to through the 6th condenser again
40 DEG C, remove most water, remaining elemental sulfur condensation, the H in the 6th condensator outlet gas2S volume contents 0.06%, SO2
Volume content 0.02%, without COS, CS2, mercaptan, the organic sulfur such as thioether；
6) Process Gas come out from the 6th condenser overhead enters an absorption desulfurizing tower (another is not put into operation), is filled
The catalytic oxidation adsorption desulfurizer filled out is by SO2And H2S reactions are converted into elemental sulfur, by remaining H2S is oxidized to elemental sulfur, generation
Elemental sulfur be deposited in the endoporus of desulfurizing agent；It is SO to adsorb desulfurizing tower exit procedure gas total sulfur folding2≤10mg/m3, arranged through chimney
It is empty.
The sulfur recovery facility, in the preceding 1200hr of operation, H is can't detect in absorption desulfurizing tower outlet2S、SO2,
Start detection afterwards, total sulfur folding is SO during 1500hr2 1mg/m3, total sulfur folding is SO during 1700hr2 2mg/m3, it is total during 1900hr
Sulphur folding is SO2 3mg/m3, total sulfur folding is SO during 2100hr2 5mg/m3, total sulfur folding is SO during 2450hr2 10mg/m3, by this
Absorption desulfurizing tower is cut out, and another incision puts into operation.During plant running, H is can't detect in absorption desulfurizing tower outlet2S、SO2With
Outer other sulphur-containing substances.
Embodiment 2
A set of 30,000 tons/year of sulfur recovery facility, including be sequentially connected in series combustion furnace, one-level claus reaction device, two grades
Claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device and two can series-parallel absorption desulfurizing tower,
Load Fe in one-level claus reaction device top2O3/Al2O de-oxygen type catalyst for recovering sulfur 12m3, bottom filling TiO2Sulphur
Reclaim catalyst 20m3；Load Fe in two grades of claus reaction device tops2O3/Al2O3De-oxygen type catalyst for recovering sulfur 12m3,
Load TiO in bottom2Catalyst for recovering sulfur 20m3；Selective hydrogenation reduction reactor loads CoO-MoO3/Al2O3Selective reduction
SO2Catalyst 15m3, selective oxidation reaction device filling Fe2O3/SiO2Selective oxidation H2S catalyst 25m3, two adsorb de-
Sulphur tower loads Fe respectively2O3/ activated carbon catalysis oxidation-adsorption desulfurizing agent 150m3；The basic operation condition of the device is:
1) sour gas 16000m3/ hr, H2S volume contents about 20%, CO2About 50%, with appropriate air (10000m3/ hr is left
It is right) to enter combustion furnace and burnt, the temperature control of combustion furnace is at 1250 DEG C or so, and the Process Gas produced after burning enters waste heat boiler
350 DEG C are cooled to after stove, Process Gas exports into the first condensate cooler from waste heat boiler and is cooled to 150 DEG C, in combustion furnace
After the elemental sulfur condensation of generation Molten sulphur groove is segregated into Process Gas；
2) Process Gas come out from the first condenser overhead is heated to 250 DEG C, into one-level claus reaction device continue into
Row claus reaction, exit procedure gas is cooled to 150 DEG C into the second condenser, makes after the elemental sulfur of generation separates with Process Gas
Into Molten sulphur groove, the Process Gas that the second condenser overhead comes out is free of COS, CS2, mercaptan, the organic sulfur such as thioether；
3) Process Gas come out from the second condenser overhead is heated to enter two grades of claus reaction devices progress gram after 220 DEG C
The further generation elemental sulfur of Louth reaction, exit procedure gas is cooled to 150 DEG C into the 3rd condenser, make generation elemental sulfur and
Enter Molten sulphur groove, the Process Gas H that the 3rd condenser overhead comes out after Process Gas separation2S volume content 1.0%, SO2's
Volume content 0.5%；
4) Process Gas come out from the 3rd condenser overhead is heated to 200 DEG C, into Chemoselective reduction device, SO2Choosing
Selecting property is reduced to elemental sulfur, and the Process Gas come out from Chemoselective reduction device is cooled to 150 DEG C, generation into the 4th condenser
Elemental sulfur separated with Process Gas after enter Molten sulphur groove；H in 4th condensator outlet Process Gas2S volume content
1.03%, without SO2；
5) Process Gas come out from the 4th condenser overhead is preheating to 210 DEG C of laggard selectable oxidation reactors, fills into
Appropriate air, H2S selective oxidations are elemental sulfur, and it is cold that the Process Gas come out from selective oxidation reaction device enters the 5th condenser
But to 150 DEG C, the elemental sulfur of generation enters Molten sulphur groove after being separated with Process Gas, and Process Gas is cooled to through the 6th condenser again
40 DEG C, remove most water, remaining elemental sulfur condensation, the H in the 6th condensator outlet gas2S volume contents 0.08%, SO2
Volume content 0.02%, without COS, CS2, mercaptan, the organic sulfur such as thioether；
6) Process Gas come out from the 6th condenser overhead enters an absorption desulfurizing tower (another is not put into operation), is filled
The catalytic oxidation adsorption desulfurizer filled out is by SO2And H2S reactions are converted into elemental sulfur, by remaining H2S is oxidized to elemental sulfur, generation
Elemental sulfur be deposited in the endoporus of desulfurizing agent；It is SO to adsorb desulfurizing tower exit procedure gas total sulfur folding2≤10mg/m3, arranged through chimney
It is empty.
The sulfur recovery facility, in the preceding 1700hr of operation, H is can't detect in absorption desulfurizing tower outlet2S and
SO2, start detection afterwards, total sulfur folding is SO during 1800hr2 1mg/m3, total sulfur folding is SO during 1900hr2 2mg/m3, during 2050hr
Total sulfur folding is SO2 3mg/m3, total sulfur folding is SO during 2200hr2 5mg/m3, total sulfur folding is SO during 2500hr2 10mg/m3, by this
Platform absorption desulfurizing tower is cut out, and another incision puts into operation.During plant running, H is can't detect in absorption desulfurizing tower outlet2S、SO2
Other sulphur-containing substances in addition.
Table 1 below is listed in embodiment 1,2 device operation process, and desulfurizing tower total sulfur of working off one's feeling vent one's spleen reaches the operatings of various concentrations
Time and corresponding desulfurization amount.
Desulfurizing tower total sulfur of working off one's feeling vent one's spleen reaches the duration of runs and the desulfurization amount of various concentrations in the operation process of table 1
Claims (5)
1. a kind of recovery technology of sulfur of low-sulfur discharge, including two grades grams of combustion furnace one-level claus reaction device being sequentially connected in series
Louth reactor, selective hydrogenation reduction reactor selective oxidation reaction device and two can series-parallel absorption desulfurizing towers；
Wherein, one-level claus reaction device top filling Fe2O3/Al2O3De-oxygen type catalyst for recovering sulfur, bottom filling
TiO2 catalyst for recovering sulfur；The de-oxygen type catalyst for recovering sulfur except with preferable claus reaction activity,
Also by the O in Process Gas2By with H2S reactions generate elemental sulfur and removed；The TiO2 Catalyst for recovering sulfur except with
Preferable claus reaction activity, also by the COS CS in Process Gas2The organic sulfurs such as mercaptan thioether are completely converted into elemental sulfur
Or H2S；
Two grades of claus reaction devices load catalyst for recovering sulfur, under lower slightly temperature conditionss, make claus reaction reach compared with
Good depth, the catalyst for recovering sulfur is Fe2O3/Al2O3De-oxygen type catalyst for recovering sulfur TiO2Sulphur recovery
Catalyst TiO2 /Al2O3Catalyst for recovering sulfur and common Al2O3One or both of catalyst for recovering sulfur；Should
H in two grades of claus reaction device exit procedure gas2S volume content≤1.0%, SO2Volume content≤0.60%；
Selective hydrogenation reduction reactor loads CoO-MoO3/Al2O3Selective reduction SO2Catalyst, is generated using in combustion furnace
H2By SO2Restore All, primary product is elemental sulfur, and accessory substance is H2S；The selective hydrogenation reduction reactor exit procedure
H in gas2Volume content 0.5-1.5%, H2S volume content≤1.1%；
Selective oxidation reaction device loads Fe2O3/SiO2Selective oxidation H2S catalyst, using before the reactor inlet by drawing
Enter the O that air is filled into2By most H2S selective oxidations are elemental sulfur, and accessory substance is very small amount SO2；The selective oxidation
H in reactor outlet Process Gas2S volume content≤0.10%, and be SO2More than 3 times of volume content, without COS CS2
The organic sulfurs such as mercaptan thioether；
Desulfurizing tower filling catalytic oxidation adsorption desulfurizer is adsorbed, micro elemental sulfur contained by Process Gas is inhaled under the conditions of 10-50 DEG C
It is attached, will contained minimal amount of SO2With contained H2S is converted into elemental sulfur and adsorbed, by remaining H2S is oxidized to elemental sulfur and inhaled
It is attached；The desulfurization precision folding of the catalytic oxidation adsorption desulfurizer is SO2 ≤10mg/m3, by desulfurizing tower integrally in terms of, the desulfurization essence
Sulfur capacity >=300g sulphur/1000g desulfurizing agents when spending；
The recovery technology of sulfur comprises the following steps:
1) H is contained2S sour gas is burnt after being mixed with air into combustion furnace, and the temperature control of combustion furnace is in 1150-
1350 DEG C, the Process Gas produced after burning is cooled to 340-350 DEG C after entering waste heat boiler, Process Gas from waste heat boiler export into
Enter the first condensate cooler and be cooled to 140-160 DEG C, be segregated into after the elemental sulfur condensation generated in combustion furnace with Process Gas
Molten sulphur groove；
2) Process Gas come out from the first condenser overhead is heated to 240-270 DEG C, into one-level claus reaction device continue into
Row claus reaction, exit procedure gas is cooled to 140-160 DEG C into the second condenser, makes the elemental sulfur and process qi leel of generation
From rear entrance Molten sulphur groove；
3) Process Gas come out from the second condenser overhead is heated to enter two grades of claus reaction devices progress gram after 210-230 DEG C
Louth reaction further generates elemental sulfur, and exit procedure gas is cooled to 140-160 DEG C into the 3rd condenser, makes the simple substance of generation
Sulphur enters Molten sulphur groove after being separated with Process Gas；
4) Process Gas come out from the 3rd condenser overhead is heated to 200-210 DEG C, into Chemoselective reduction device, SO2Choosing
Selecting property is reduced to elemental sulfur, and the Process Gas come out from Chemoselective reduction device is cooled to 140-160 DEG C into the 4th condenser,
The elemental sulfur of generation enters Molten sulphur groove after being separated with Process Gas；
5) Process Gas come out from the 4th condenser overhead is preheating to 180-210 DEG C of laggard selectable oxidation reactor, fills into
Appropriate air, H2S selective oxidations are elemental sulfur, the suitable control air amount of filling into and bed temperature, make the remnants in working off one's feeling vent one's spleen
H2S contents are by-product SO2More than 3 times, the Process Gas come out from selective oxidation reaction device is cooled into the 5th condenser
140-160 DEG C, the elemental sulfur of generation enters Molten sulphur groove after being separated with Process Gas, and Process Gas is cooled to through the 6th condenser again
10-50 DEG C, remove the remaining elemental sulfur condensation of most water；
6) Process Gas come out from the 6th condenser overhead, fills into appropriate air, into absorption desulfurizing tower, the catalysis oxygen loaded
Change adsorption desulfurizing agent at 10-50 DEG C by SO2And H2S reactions are converted into elemental sulfur, by remaining H2S is oxidized to elemental sulfur, generation
Elemental sulfur be deposited in the endoporus of desulfurizing agent, absorption desulfurizing tower exit procedure gas total sulfur folding is SO2 ≤10mg/m3, from absorption
The Process Gas that desulfurizing tower comes out is emptied through chimney
2. the low-sulfur discharge recovery technology of sulfur as described in claim 1, it is characterised in that the catalysis oxidation adsorbs desulfurization
Agent is Na2CO3/ activated carbon NaOH/ activated carbons K2CO3/ activated carbon KOH/ activated carbons Fe2O3/ activated carbon and iron oxide are de-
One or more in sulphur agent
3. the low-sulfur discharge recovery technology of sulfur as described in claim 2, it is characterised in that the catalysis oxidation adsorbs desulfurization
Agent is load capacity 5-10% Na2CO3/ activated carbon supported amount 5-20% Fe2O3/ activated carbon, or with Fe2O3For main component
Ferric oxide desulfurizer.
4. any low-sulfur discharge recovery technology of sulfur as described in claim 1-3, it is characterised in that the selective oxidation
H in reactor outlet Process Gas2S volume content control is SO23-5 times of volume content.
5. any low-sulfur discharge recovery technology of sulfur as described in claim 1-3, it is characterised in that de- what is soon penetrated
Sulphur tower is used before being serially connected in another desulfurizing tower.
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| CN106698361B (en) * | 2016-12-14 | 2019-04-05 | 山东迅达化工集团有限公司 | The recovery technology of sulfur of sour 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 |
| CN108178132B (en) * | 2018-02-24 | 2021-08-06 | 洛阳瑞昌环境工程有限公司 | Sulfur recovery method and equipment in carbon disulfide production |
| CN109019524B (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 |
| 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 |
| 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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