CN105314607B - The low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas - Google Patents

The low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas Download PDF

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CN105314607B
CN105314607B CN201510865912.XA CN201510865912A CN105314607B CN 105314607 B CN105314607 B CN 105314607B CN 201510865912 A CN201510865912 A CN 201510865912A CN 105314607 B CN105314607 B CN 105314607B
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sulfur
desulfurizing tower
desulfurization
air
desulfurizing
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CN201510865912.XA
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CN105314607A (en
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胡文宾
崔国栋
王强
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山东迅达化工集团有限公司
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

The present invention provides a kind of low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas, H2The low concentration sour gas of S contents 5 20%, the absorption desulfurizing tower that can and connect through a direct oxidation reactor, a selective oxidation reaction device and two are handled, and reach desulfurization purpose;TiO is loaded in direct oxidation reactor2Catalyst for recovering sulfur, loads H in selective oxidation reaction device2Catalyst point multilayer is loaded in S catalyst for selective oxidation, direct oxidation reactor and selective oxidation reaction device, and interlayer sets air intake and temperature-reducing coil, the filling of absorption desulfurizing tower can hot recycling catalytic oxidation adsorption desulfurizer;By the appropriate selection to catalyst, desulfurizing agent, the accurate control to each process condition, it is SO to make technique discharge gas total sulfur folding2≤10mg/m3.By hot recycling, service life, the desulfurization amount of catalytic oxidation adsorption desulfurizer greatly increase.This technique, has low-sulfur discharge, and sulfur recovery rate is bordering on 100%, and long lifespan, the desulfurization amount of desulfurizing agent are big, replace that number is few, expense is low, and desulfurizing agent unloads agent, scraps the advantages that treatment conditions are good, safe.

Description

The low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas

Technical field

The present invention relates to a kind of recovery technology of sulfur, and in particular to a kind of low-sulfur discharge sulphur of intermediate concentration sour gas returns Knock off skill.

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 Formation contains H2The sour gas of S, the sour gas are generally handled through recovery technology of sulfur, by H2S is converted into simple substance as much as possible Sulphur.

The recovery technology of sulfur device, during operation, also there are problems that emptying tail gas and solid waste two.Through The tail gas of chimney emptying, wherein, SO2Concentration is continuous monitoring project, although existing discharge standard of air pollutants The upper limit value of GB16297-1996 such as 700mg/m3Be not difficult to reach, but place industry or location there is likely to be it is more stringent Discharge standard;H2S is one of odor pollution material included by emission standard for odor pollutants GB14554-93, emission limit More stringent, the quasi- upper limit value of factory's boundary mark such as three-level is 0.45/0.80mg/m3, 100 meters of smoke stack emission amount upper limit values are 14kg/h. The solid waste is mainly multiple catalysts used in sulfur recovery facility, the useless agent drawn off after adsorbent failure, due to this Class is given up agent kind, complicated component, and not only intractability is big, also there is a series of environmental pollutions for scrapping, transport, handling and law Risk.

Industrially to H2The intermediate concentration sour gas of S contents 5-20%, can by including direct oxidation, selective oxidation, The combination sulfur removal technology of oxidation-adsorption is handled, H2S is converted into sulphur, its key reaction is:

Also generate SO2Side reaction:

S+O2→SO2 (3)

In the technique, direct oxidation reactor by the overwhelming majority H2S is converted into elemental sulfur, and selective oxidation reaction device will Remaining most H2S is converted into elemental sulfur, and catalysis oxidation adsorbs desulfurizing tower by remaining H2S is converted into elemental sulfur, by suitably controlling The operating conditions such as oxygen-supplying amount and the temperature of each reactor are made, the tail gas total sulfur content after desulfurization can be made to reach GB16297-1996 states Family's emission request, is emptied by chimney.

But in putting into practice, limited by catalyst reaction performance and technology controlling and process level, the emptying tail gas of the technique, although can To reach GB16297-1996 to SO2The requirement of upper limit of concentration value, GB14554-93 are to H2S upper limit of concentration value and discharge capacity etc. will Ask, but differ and surely reach the requirement of place industry or the existing more stringent discharge standard in location, for example reach emptying Tail gas total sulfur folding is SO2≤10mg/m3Requirement, its main cause is direct oxidation reactor, selective oxidation reaction device and urges The change tectonic sieving of oxidation-adsorption desulfurizing tower, the performance of catalyst and desulfurizing agent, process regulation presence need improvements.

The content of the invention

To overcome above-mentioned technological deficiency, the present invention provides a kind of low-sulfur discharge sulphur recovery work of intermediate concentration sour gas Skill, H2The intermediate concentration sour gas of S contents 5-20%, through a direct oxidation reactor, a selective oxidation reaction device and Two absorption desulfurizing tower processing that can and connect, reach desulfurization purpose;

Wherein, direct oxidation reactor filling TiO2Catalyst for recovering sulfur, catalyst reactor point multilayer are loaded, layer Between set air intake and temperature-reducing coil, which utilizes the introduced O of air2By most of H in sour gas2S selectivity oxygen Elemental sulfur is turned to, accessory substance is a small amount of SO2

Selective oxidation reaction device loads Fe2O3/ silicon oxide selectivity aoxidizes H2S catalyst, catalyst reactor point are more Layer filling, interlayer sets air intake and temperature-reducing coil, and the catalyst is by part SO2And H2S reactions are converted into elemental sulfur, and utilize The introduced O of air2By most of H in Process Gas2S selective oxidations are elemental sulfur;

Adsorb desulfurizing tower filling can hot recycling catalytic oxidation adsorption desulfurizer, entrance is incorporated appropriate air, by Process Gas Contained micro elemental sulfur absorption, by contained minimal amount of SO2With contained H2S is converted into elemental sulfur and adsorbs, by remaining H2S oxygen Turn to elemental sulfur and adsorb in endoporus;The desulfurization precision folding of the catalytic oxidation adsorption desulfurizer is SO2≤10mg/m3, with de- Sulphur tower is integrally counted, the Sulfur capacity in the desulfurization precision >=100g sulphur/1000g desulfurizing agents;With 250-300 DEG C of indifferent gas during hot recycling Purge, catalysis oxidation absorption desulfurization performance recovers substantially after sulphur evaporative removal, is ensureing that desulfurization precision folding is SO2≤10mg/m3 Under conditions of, total desulfurization amount of more than 3-5 times of first Sulfur capacity is reached through multiple hot recycling;

The recovery technology of sulfur includes the following steps:

1) sour gas and and metering supplying air, mixing after, heated device is preheating to 180~200 DEG C, is entered by top Direct oxidation reactor, entrance sprays into the air of metering between catalyst layer;The air capacity and coil pipe cooling degree of each bed are adjusted, Control 200-300 DEG C of top half bed temperature, 300-350 DEG C of the latter half bed temperature;Control air total amount and respectively entering The amount of allocating of mouth, makes the middle H that works off one's feeling vent one's spleen2The volume content 1.0-2.0%, SO of S2Volume content≤0.20%, without COS, CS2、 The organic sulfurs such as mercaptan, thioether;Work off one's feeling vent one's spleen and enter the first condenser, be cooled to 140-160 DEG C, the elemental sulfur of generation is segregated into liquid Body sulphur groove;

2) the first condenser overhead is worked off one's feeling vent one's spleen, and the air mixing of metering supplying, heated device are preheating to 180~210 DEG C Afterwards, selective oxidation reaction device is entered by top, entrance sprays into the air measured between catalyst layer;Adjust the air capacity of each bed With coil pipe cooling degree, 200-230 DEG C of bed temperature is controlled, by most of H2S selective oxidations are elemental sulfur, are made in working off one's feeling vent one's spleen H2The volume content 0.10-0.20%, SO of S2Volume content≤0.04%;Work off one's feeling vent one's spleen and enter the second condenser, be cooled to 140- 160 DEG C, the elemental sulfur of generation is segregated into Molten sulphur groove;

3) the second condenser overhead is worked off one's feeling vent one's spleen, then is cooled to 40-60 DEG C through the 3rd condenser and is removed part water and residue list After the condensation of matter sulphur, and the air mixing of metering supplying, absorption desulfurizing tower is entered by top, carries out desulfurization process;Adsorb desulfurizing tower Total sulfur of working off one's feeling vent one's spleen folding is SO2≤10mg/m3, emptied through chimney;

4) when absorption desulfurizing tower exit procedure gas total sulfur folding is SO2Soon more than 10mg/m3When, which cuts out, Carry out hot recycling in situ with 250-300 DEG C of indifferent gas, after the completion of hot recycling, be cooled to less than 80 DEG C it is spare, or be without cooling Incision carries out desulfurization;Regenerate implication and work off one's feeling vent one's spleen from selective oxidation reaction device and be mixed into the second condenser, be cooled to 140-160 DEG C, the elemental sulfur condensation separation in gaseous mixture enters Molten sulphur groove, and the gaseous mixture for removing elemental sulfur is cold through the 3rd again Condenser, empty after the second absorption desulfurizing tower processing of line, then through chimney, and desulfurizing tower empties tail gas total sulfur folding and is during regenerating SO2≤10mg/m3

In the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas of the present invention, catalytic oxidation adsorption desulfurizer can use Na2CO3/ activated carbon, NaOH/ activated carbons, K2CO3/ activated carbon, KOH/ activated carbons, Fe2O3/ activated carbon, Na2CO3/ aluminium oxide, K2CO3/ aluminium oxide, Fe2O3/ aluminium oxide, Fe2O3One or more in/silica and ferric oxide desulfurizer, are all up total The desulfurization precision of sulphur≤10ppm.In terms of whole desulfurizing agents are filled by desulfurizing tower, first Sulfur capacity >=100g in the desulfurization precision Sulphur/1000g desulfurizing agents, total desulfurization amount of more than 3-5 times of first Sulfur capacity is can reach through the multiple hot recycling of 250-300 DEG C of indifferent gas. In the low-sulfur discharge recovery technology of sulfur of the present invention, catalytic oxidation adsorption desulfurizer used, before total sulfur≤10ppm is penetrated First Sulfur capacity, preferably >=200g sulphur/1000g desulfurizing agents, preferably >=300g sulphur/1000g desulfurizing agents, more preferably >=400g sulphur/ 1000g desulfurizing agents, and can reach through multiple hot recycling total desulfurization amount of more than 3-5 times of first Sulfur capacity.

In the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas of the present invention, using the catalysis of desulfurization precision≤5ppm Oxidation-adsorption desulfurizing agent, empty tail gas total sulfur can as low as≤5ppm, whole desulfurizing agents are filled by desulfurizing tower in terms of, in the desulfurization During precision, first Sulfur capacity preferably >=100g sulphur/1000g desulfurizing agents, preferably >=200g sulphur/1000g desulfurizing agents, more preferably >=300g Sulphur/1000g desulfurizing agents, and can reach through multiple hot recycling total desulfurization amount of more than 3-5 times of first Sulfur capacity.

In the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas of the present invention, using the catalysis of desulfurization precision≤2ppm Oxidation-adsorption desulfurizing agent, empty tail gas total sulfur can as low as≤2ppm, whole desulfurizing agents are filled by desulfurizing tower in terms of, in the desulfurization During precision, first Sulfur capacity >=100g sulphur/1000g desulfurizing agents, preferably >=200g sulphur/1000g desulfurizing agents, preferably >=300g sulphur/ 1000g desulfurizing agents, and can reach through multiple hot recycling total desulfurization amount of more than 3-5 times of first Sulfur capacity.

In the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas of the present invention, catalysis oxidation used absorption desulfurization Agent, preferably suitably prepd Na2CO3The Na of the 5-10% of load capacity2CO3/ activated carbon, Fe2O3The Fe of load capacity 5-15%2O3/ living Property charcoal, or with Fe2O3For the ferric oxide desulfurizer of main component, whole desulfurizing agents are filled by desulfurizing tower in terms of, desulfurization precision≤ 10ppm、SO2≤5ppm、SO2Under conditions of≤2ppm, the first Sulfur capacity of these three desulfurizing agents can reach >=and 200g sulphur/ 1000g desulfurizing agents, or even >=300g sulphur/1000g desulfurizing agents, 400g sulphur/1000g desulfurizing agents, 500g sulphur/1000g desulfurizing agents, just The Sulfur capacity of first Sulfur capacity more than 95% can be reached after secondary hot recycling, first Sulfur capacity 80% can be reached after five hot recyclings Sulfur capacity above, can reach the Sulfur capacity of first Sulfur capacity more than 65% after ten regeneration, i.e. five hot recyclings can reach just Total desulfurization amount that more than 4 times of secondary Sulfur capacity, ten hot recyclings can reach total desulfurization amount of more than 7 times of first Sulfur capacity.

In the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas of the present invention, catalytic oxidation adsorption desulfurizer is in desulfurization In-situ regeneration in tower, regeneration gas can use nitrogen or superheated steam, preferably be worked off one's feeling vent one's spleen with desulfurizing tower and do regeneration gas, heated with heater To 250-300 DEG C, regenerate implication and return to after selective oxidation reaction device, with the process come out from selective oxidation reaction device Gas is mixed into the second condenser, is cooled to 140-160 DEG C, and the elemental sulfur condensation separation in gaseous mixture enters Molten sulphur groove, The gaseous mixture of elemental sulfur is removed again through the 3rd condenser, the online second absorption desulfurizing tower processing, emptying.Inhaled online during regeneration The emptying tail gas total sulfur of i.e. this technique of working off one's feeling vent one's spleen of attached desulfurizing tower, can reach conversion is SO2≤10mg/m3、≤5mg/m3、≤ 2mg/m3Level.The advantages of superheated steam, is free from O2, not ablation absorbent charcoal carrier in regenerative process, also not producing to need Consider the SO of processing2, all collected after regenerating the elemental sulfur in implication and steam (water) cooling, absorption desulfurizing tower enters implication Flow, component do not change substantially.

Worked off one's feeling vent one's spleen with desulfurizing tower when doing regeneration gas, answer suitable control selective oxidation reaction device, the online second absorption de- The air mass flow of sulphur tower, makes desulfurizing tower work off one's feeling vent one's spleen the O of i.e. regeneration gas2Content is controlled within 200ppm, otherwise O2It is anti-with elemental sulfur The SO that should be generated2Excessive concentration, can exceed the disposal ability of the second online absorption desulfurizing tower;It is carrier to be elected to activated carbon Desulfurizing agent when, the O of regeneration gas2Content should be controlled within 100ppm, to avoid the scaling loss of absorbent charcoal carrier.

, can be another in catalysis oxidation absorption desulfurizing tower in the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas of the present invention If heater element, to improve reproduction speed.

In the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas of the present invention, in desulfurizing tower non-renewable period, preferably Two absorption desulfurizing tower parallel operations, to mitigate bed resistance;Soon regenerated desulfurizing tower is further preferably serially connected in another desulfurization Use before tower, with the desulfurization amount in one desulfurization cycle of tower desulfurizing agent before raising so that extend desulfurizing agent regeneration period and Service life;Certainly, it will ensure that another tower still ensures that desulfurization during tower regeneration on the premise of regeneration opportunity is arranged properly Precision.

The low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas of the present invention, has the following advantages:

1) low-sulfur discharge is maintained

In common sour gas, contained H2Sulfide outside S, is generally only possible to micro COS, SO2, basic detection Less than CS difficult to deal with2, the TiO of micro COS in direct oxidation reactor2All hydrolyzed on catalyst for recovering sulfur, because And in the low-sulfur discharge recovery technology of sulfur of the present invention, by direct oxidation reactor, selective oxidation reaction device, absorption desulfurization The processing after cure thing of tower removes substantially, air-discharging total sulfur≤10mg/m3.Desulfurizing tower, which enters implication main component, only includes N2、CO2、 H2O, a small amount of O2, a small amount of H2S, very small amount SO2With micro elemental sulfur, without can substantially reduce above-mentioned catalytic oxidation adsorption desulfurizer The material of regenerability, only carries out the reaction of generation elemental sulfur on catalytic oxidation adsorption desulfurizer, and deposits, adsorbs in desulfurization In the endoporus of agent, and the performance and feature that the catalytic oxidation adsorption desulfurizer desulfurization precision that is loaded in desulfurizing tower is high, it puts into operation In long period afterwards, desulfurizing tower is worked off one's feeling vent one's spleen the tail gas that i.e. sulfur recovery facility will be emptied through chimney, it is very low containing sulphur concentration, such as Less than 10mg/m3, even below 5mg/m3、2mg/m3、1mg/m3, until emptying tail gas to be close to or up to this containing sulphur concentration dense Switch immediately after angle value or cut out regeneration, so as to persistently ensure air-discharging total sulfur≤10ppm.If contain a small amount of NH in sour gas3, Then finally substantially can be with (NH4)2SO3Or (NH4)2SO4Mode be deposited in the catalytic oxidation adsorption desulfurizer of desulfurizing tower, only meeting Shorten the service life of desulfurizing agent.

2) sulfur recovery rate is bordering on 100%

In the above-mentioned low-sulfur discharge recovery technology of sulfur of the present invention, institute in catalytic oxidation adsorption desulfurizer in regenerative sulfur binding tower Elemental sulfur, the H of top desulfurizing agent bed adsorption of deposition2The evaporation of S, be blown to the second condenser, and from selective oxidation reaction The Process Gas mixing that device comes out, enters Molten sulphur groove by elemental sulfur condensation separation, removes the gaseous mixture of elemental sulfur again through the 3rd Condenser, the online second absorption desulfurizing tower processing, regenerate the H of desorption2S is oxidized to elemental sulfur and sinks in the second desulfurizing tower Product, tail gas are emptied through chimney.So circulation is gone down, and in desulfurizing agent, including is sunk in the desulfurizing agent by repeatedly regenerating, to be scrapped Long-pending elemental sulfur, the H adsorbed2S finally can be converted into sulphur, into Molten sulphur groove, and maintain low-sulfur to discharge.Due to row Air total sulfur folding is SO2≤10mg/m3, even below 5mg/m3、2mg/m3、1mg/m3, and in sour gas 3-5% H2S concentration Compare, the sulfur recovery rate of this technique is bordering on 100%, and the sulphur especially recycled has fully entered Molten sulphur groove.

3) long lifespan of desulfurizing agent, desulfurization amount are big, and replacement number is few, and expense is low

In the above-mentioned low-sulfur discharge recovery technology of sulfur of the present invention, as long as sour gas raw material, catalysis oxidation adsorb desulfurizing tower Entrance, which is free of, may substantially reduce the material of above-mentioned catalytic oxidation adsorption desulfurizer regenerability, on catalytic oxidation adsorption desulfurizer Reaction with regard to only carrying out generation elemental sulfur, the elemental sulfur of generation are also deposited, adsorbed in the endoporus of desulfurizing agent, thus through 250- After 300 DEG C of indifferent gas hot recyclings, deposition, the evaporation of absorption elemental sulfur, blow away, and the active component of desulfurizing agent, pore structure are substantially extensive It is multiple to continue on for desulfurization process as new, total desulfurization amount of more than 3-5 times of first Sulfur capacity, or even 10 are reached through multiple hot recycling More than times, thus the long lifespan of desulfurizing agent, desulfurization amount are big, and replacement number is few, and expense is low.

4) desulfurizing agent unload agent, scrap treatment conditions it is good, safety

In the above-mentioned low-sulfur discharge recovery technology of sulfur of the present invention, before the catalytic oxidation adsorption desulfurizer unloads agent, pass through Regeneration treatment, by the elemental sulfur of deposition, the H of absorption2S is blown off with 250-300 DEG C of indifferent gas, no longer containing sulphur and H2S, thus There is no obvious peculiar smell, desulfurizing agent mobility of bed unloads that agent is easy, and site environment is preferable without caking, and safe operating conditions are preferable; Sulphur is free of in drawn off waste desulfurizing agent, stores, is nonflammable in transportational process, will not burn and release SO2Environmental pollution is caused, is given up Agent processing is much relatively easy, and it is also relatively simple to scrap formality.

Brief description of the drawings

Attached drawing 1,2 discharges the brief flow of recovery technology of sulfur for low-sulfur of the present invention, and wherein Fig. 1 is worked off one's feeling vent one's spleen with desulfurizing tower and done Regeneration gas, Fig. 2 do regeneration gas with superheated steam.

Device numbering is followed successively by 1 direct oxidation reactor, 2 first condensers, 3 selective oxidation reaction devices, 4 second condensations Device, 5 the 3rd condensers, 6 Molten sulphur grooves, 7 absorption desulfurizing towers, 8 heaters, 9 regeneration wind turbines, 10 chimneys.

Embodiment

Embodiment 1

A set of 10,000 tons/year of sulfur recovery facility, including a direct oxidation reactor, a selective oxidation reaction Device and two can series-parallel absorption desulfurizing towers;Wherein direct oxidation reactor filling TiO2Catalyst for recovering sulfur 60m3, catalysis 6 layers of filling of agent point, interlayer set air intake and temperature-reducing coil;Selective oxidation reaction device loads Fe2O3/SiO2Selective oxidation H2S catalyst 60m3, points of 6 layers filling of catalyst, interlayer sets air intake and temperature-reducing coil;Two absorption desulfurizing towers load respectively Na2CO3/ activated carbon catalysis oxidation-adsorption desulfurizing agent 200m3;The basic operation condition of the device is:

1) sour gas 20000m3/ hr, H2S volume contents 5.0%, remaining is mainly CO2, COS≤20mg/m3, SO2≤ 100mg/m3, no CS2, in direct oxidation reactor and supplying air 2200m3/ hr or so reacts;Sour gas is incorporated 1000m3The air of/hr or so, enters direct oxidation reactor, remaining 1200m after being preheating to 200 DEG C by top3/ hr's or so Air is distributed by entrance between catalyst layer, and metering sprays into;The air capacity and coil pipe cooling degree of each bed are adjusted, controls the first half Divide 260-300 DEG C of bed temperature, 300-350 DEG C of the latter half bed temperature, makes the middle H that works off one's feeling vent one's spleen2The volume content 1.0% of S, SO2 Volume content 0.10%, without COS, CS2, mercaptan, the organic sulfur such as thioether;Work off one's feeling vent one's spleen and enter the first condenser, be cooled to 150 DEG C, the elemental sulfur of generation is segregated into Molten sulphur groove;

2) the first condenser overhead is worked off one's feeling vent one's spleen, the air total amount 180m of supplying3/ hr or so, in selective oxidation reaction device Reacted;The air mixing of supplying is worked off one's feeling vent one's spleen and measured to first condenser overhead, after heated device is preheating to 180 DEG C, by pushing up Portion enters selective oxidation reaction device, adjusts the air capacity and coil pipe cooling degree of each bed, controls 210 DEG C of bed temperature, will Most of H2S selective oxidations are elemental sulfur, and work off one's feeling vent one's spleen middle H2The volume content 0.10% of S, SO2Volume content 0.04%;Go out Implication enters the second condenser, is cooled to 150 DEG C, the elemental sulfur of generation is segregated into Molten sulphur groove;

3) the second condenser overhead is worked off one's feeling vent one's spleen, then is cooled to 40 DEG C through the 3rd condenser and is removed part water and remaining elemental sulfur After condensation, and metering supplying 25m3The air mixing of/hr or so, entering an absorption desulfurizing tower by top, (another is not thrown Fortune), desulfurization process is carried out, the catalytic oxidation adsorption desulfurizer loaded is by SO2And H2S reactions are converted into elemental sulfur, by remaining H2S is oxidized to elemental sulfur, and the elemental sulfur of generation is deposited in the endoporus of desulfurizing agent;Absorption desulfurizing tower work off one's feeling vent one's spleen total sulfur folding be SO2≤ 10mg/m3, emptied through chimney.In device operational process, adsorb in desulfurizing tower outlet and can't detect H2S、SO2In addition other contain Sulfur material.

The sulfur recovery facility, in the preceding 1200hr of operation, adsorbs in desulfurizing tower outlet and can't detect H2S and SO2, start to detect afterwards, total sulfur folding is SO during 1300hr21mg/m3, total sulfur folding is SO during 1400hr22mg/m3, when 1520hr is total Sulphur folding is SO25mg/m3, total sulfur folding is SO during 1700hr210mg/m3, this absorption desulfurizing tower is cut out into regeneration, another incision Put into operation.

When adsorbing desulfurizing tower regeneration, start regeneration wind turbine and heat exchanger, online absorption desulfurizing tower exit procedure gas is added Heat carries out desulfurizing agent hot recycling in situ, control regeneration tolerance is about 13000m to 250 DEG C3/ hr, regenerate implication with from choosing The Process Gas that selecting property oxidation reactor comes out is mixed into the second condenser, is cooled to 150 DEG C, the elemental sulfur condensation in gaseous mixture Molten sulphur groove is segregated into, removes the gaseous mixture of elemental sulfur again through the 3rd condenser, after the absorption desulfurizing tower processing of line, one Part is recycled as regeneration gas, and another part is emptied through chimney;It is regenerated to temperature of working off one's feeling vent one's spleen identical with inlet temperature i.e. 250 Continue 20hr after DEG C, stop heat exchanger cooling, completed to regeneration when being cooled to 150 DEG C, regenerative process about 100hr.During regeneration, Online desulfurizing tower is worked off one's feeling vent one's spleen, that is, it is SO to empty tail gas total sulfur folding2Less than 10mg/m3, O2Content 100ppm.

After the completion of regeneration, immediately by after regeneration desulfurizing tower incision put into operation, another cut out it is spare, by above-mentioned basic operation bar Part is carried out continuously 8 operatings and 7 regeneration.

Table 1 below lists the total sulfur of working off one's feeling vent one's spleen of desulfurizing tower in this 8 operation process and reaches duration of runs of each concentration and corresponding Desulfurization amount

Desulfurizing tower total sulfur of working off one's feeling vent one's spleen reaches the duration of runs of various concentrations and corresponding desulfurization amount in 1 operation process of table

After 8th operating, regeneration treatment is carried out, about 100L desulfurizing agents is taken out from desulfurizing tower top and checks, find de- Sulphur agent is easily taken out, and is not lumpd, and appearance and the difference unobvious of new desulfurizing agent, free from extraneous odour, no dusting, calcination is without sulfur burning Smell.It can reuse when scrapping after a period of time with inference, unload agent after regeneration treatment, be not in obvious peculiar smell, unload agent Difficulty is small, and site environment is preferable, and safe operating conditions are preferable.

Embodiment 2

A set of 10,000 tons/year of sulfur recovery facility, including a direct oxidation reactor, a selective oxidation reaction Device and two can series-parallel absorption desulfurizing towers;Wherein direct oxidation reactor filling TiO2Catalyst for recovering sulfur 40m3, catalysis 6 layers of filling of agent point, interlayer set air intake and temperature-reducing coil;Selective oxidation reaction device loads Fe2O3/SiO2Selective oxidation H2S catalyst 40m3, points of 6 layers filling of catalyst, interlayer sets air intake and temperature-reducing coil;Two absorption desulfurizing towers load respectively Fe2O3/ activated carbon catalysis oxidation-adsorption desulfurizing agent 125m3;The basic operation condition of the device is:

1) sour gas 5000m3/ hr, H2S volume contents 20%, remaining is mainly CO2, SO2≤100mg/m3, without COS, CS2, mercaptan, the organic sulfur such as thioether, in direct oxidation reactor and supplying air 2200m3/ hr or so reacts;Sour gas is matched somebody with somebody Enter 1000m3The air of/hr or so, enters direct oxidation reactor, remaining 1200m after being preheating to 180 DEG C by top3/ hr or so Air distributed by entrance between catalyst layer, metering spray into;The air capacity and coil pipe cooling degree of each bed are adjusted, controls upper half 260-300 DEG C of part bed temperature, 300-350 DEG C of the latter half bed temperature, makes the middle H that works off one's feeling vent one's spleen2The volume content 2.0% of S, SO2Volume content 0.20%, without COS, CS2, mercaptan, the organic sulfur such as thioether;Work off one's feeling vent one's spleen and enter the first condenser, be cooled to 150 DEG C, the elemental sulfur of generation is segregated into Molten sulphur groove;

2) the first condenser overhead is worked off one's feeling vent one's spleen, the air total amount 285m of supplying3/ hr or so, in selective oxidation reaction device Reacted;The air mixing of supplying is worked off one's feeling vent one's spleen and measured to first condenser overhead, after heated device is preheating to 180 DEG C, by pushing up Portion enters selective oxidation reaction device, adjusts the air capacity and coil pipe cooling degree of each bed, controls 210 DEG C of bed temperature, will Most of H2S selective oxidations are elemental sulfur, and work off one's feeling vent one's spleen middle H2The volume content 0.15% of S, SO2Volume content 0.03%;Go out Implication enters the second condenser, is cooled to 150 DEG C, the elemental sulfur of generation is segregated into Molten sulphur groove;

3) the second condenser overhead is worked off one's feeling vent one's spleen, then is cooled to 40 DEG C through the 3rd condenser and is removed part water and remaining elemental sulfur After condensation, and metering supplying 17m3The air mixing of/hr or so, entering an absorption desulfurizing tower by top, (another is not thrown Fortune), desulfurization process is carried out, the catalytic oxidation adsorption desulfurizer loaded is by SO2And H2S reactions are converted into elemental sulfur, by remaining H2S is oxidized to elemental sulfur, and the elemental sulfur of generation is deposited in the endoporus of desulfurizing agent;Absorption desulfurizing tower work off one's feeling vent one's spleen total sulfur folding be SO2 ≤10mg/m3, emptied through chimney.In device operational process, adsorb in desulfurizing tower outlet and can't detect H2S、SO2In addition other Sulphur-containing substance.

The sulfur recovery facility, in the preceding 1400hr of operation, adsorbs in desulfurizing tower outlet and can't detect H2S and SO2, start to detect afterwards, total sulfur folding is SO during 1550hr21mg/m3, total sulfur folding is SO during 1700hr22mg/m3, when 1900hr is total Sulphur folding is SO25mg/m3, total sulfur folding is SO during 2050hr210mg/m3, this absorption desulfurizing tower is cut out into regeneration, another incision Put into operation.In device operational process, adsorb in desulfurizing tower outlet and can't detect H2S、SO2Other sulphur-containing substances in addition.

When adsorbing desulfurizing tower regeneration, by the use of steam as regeneration source of the gas, 280 DEG C are heated to, in-situ heat is carried out again to desulfurizing agent Raw, control quantity of steam is about 10000m3/ hr, regenerates implication and is mixed into the Process Gas come out from selective oxidation reaction device Enter the second condenser, be cooled to 150 DEG C, the elemental sulfur condensation separation in gaseous mixture enters Molten sulphur groove, removes elemental sulfur Gaseous mixture empties after the 3rd condenser, the processing of online absorption desulfurizing tower through chimney again;After being regenerated to 280 DEG C of temperature of working off one's feeling vent one's spleen Continue 20hr, stop steam and regenerative heater, regeneration is completed, regenerative process about 90hr.During regeneration, online desulfurizing tower goes out Implication, that is, it is SO to empty tail gas total sulfur folding2Less than 2mg/m3

After the completion of regeneration, immediately by after regeneration desulfurizing tower incision put into operation, another cut out it is spare, by above-mentioned basic operation bar Part is carried out continuously 10 operatings and 9 regeneration.

Table 2 below lists the total sulfur of working off one's feeling vent one's spleen of desulfurizing tower in this 10 operation process and reaches duration of runs of each concentration and corresponding Desulfurization amount

After 10th operating, regeneration treatment is carried out, about 100L desulfurizing agents is taken out from desulfurizing tower top and checks, find de- Sulphur agent is easily taken out, and is not lumpd, and appearance and the difference unobvious of new desulfurizing agent, free from extraneous odour, no dusting, calcination is without sulfur burning Smell.It can reuse when scrapping after a period of time with inference, unload agent after regeneration treatment, be not in obvious peculiar smell, unload agent Difficulty is small, and site environment is preferable, and safe operating conditions are preferable.

Desulfurizing tower total sulfur of working off one's feeling vent one's spleen reaches the duration of runs of various concentrations and corresponding desulfurization amount in 2 operation process of table

Claims (6)

1. a kind of low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas, H2The intermediate concentration sour gas of S contents 5-20%, The absorption desulfurizing tower that can and connect through a direct oxidation reactor, a selective oxidation reaction device and two is handled, and is reached Desulfurization purpose;
Wherein, direct oxidation reactor filling TiO2Catalyst for recovering sulfur, catalyst reactor point multilayer are loaded, and interlayer is set Air intake and temperature-reducing coil, the catalyst utilize the introduced O of air2By most of H in sour gas2S selective oxidations are Elemental sulfur, accessory substance are a small amount of SO2
Selective oxidation reaction device loads Fe2O3/ silicon oxide selectivity aoxidizes H2S catalyst, catalyst reactor point multilayer fill Fill out, interlayer sets air intake and temperature-reducing coil, and the catalyst is by part SO2And H2S reactions are converted into elemental sulfur, and utilize air Introduced O2By most of H in Process Gas2S selective oxidations are elemental sulfur;
Adsorb desulfurizing tower filling can hot recycling catalytic oxidation adsorption desulfurizer, entrance supplying metering air, by Process Gas institute Adsorbed containing micro elemental sulfur, by contained minimal amount of SO2With contained H2S is converted into elemental sulfur and adsorbs, by remaining H2S is aoxidized For elemental sulfur and adsorb in endoporus;The desulfurization precision folding of the catalytic oxidation adsorption desulfurizer is SO2≤10mg/m3 , with de- Sulphur tower is integrally counted, the Sulfur capacity in the desulfurization precision >=100g sulphur/1000g desulfurizing agents;With 250-300 DEG C of indifferent gas during hot recycling Purge, catalysis oxidation absorption desulfurization performance recovers substantially after sulphur evaporative removal, is ensureing that desulfurization precision folding is SO2≤10mg/m3 Under conditions of, total desulfurization amount of more than 3 times of first Sulfur capacity is reached through multiple hot recycling;
The recovery technology of sulfur includes the following steps:
1) sour gas and metering supplying air, mixing after, heated device is preheating to 180~200 DEG C, enters direct oxygen by top Change reactor, entrance sprays into the air measured between catalyst layer;The air capacity and coil pipe cooling degree of each bed are adjusted, in control 200-300 DEG C of half part bed temperature, 300-350 DEG C of the latter half bed temperature;Control air total amount and matching somebody with somebody in each entrance Enter amount, make the middle H that works off one's feeling vent one's spleen2The volume content 1.0-2.0%, SO of S2Volume content≤0.20%, without COS, CS2, mercaptan, Thioether;Work off one's feeling vent one's spleen and enter the first condenser, be cooled to 140-160 DEG C, the elemental sulfur of generation is segregated into Molten sulphur groove;
2) the first condenser overhead is worked off one's feeling vent one's spleen, and the air mixing of metering supplying, after heated device is preheating to 180~210 DEG C, by Top enters selective oxidation reaction device, and entrance sprays into the air measured between catalyst layer;Adjust the air capacity and disk of each bed Pipe cooling degree, controls 200-230 DEG C of bed temperature, by most of H2S selective oxidations are elemental sulfur, make the middle H that works off one's feeling vent one's spleen2S's Volume content 0.10-0.20%, SO2Volume content≤0.04%;Work off one's feeling vent one's spleen and enter the second condenser, be cooled to 140-160 DEG C, the elemental sulfur of generation is segregated into Molten sulphur groove;
3) the second condenser overhead is worked off one's feeling vent one's spleen, then is cooled to 40-60 DEG C through the 3rd condenser and is removed part water and remaining elemental sulfur After condensation, and the air mixing of metering supplying, absorption desulfurizing tower is entered by top, carries out desulfurization process;Adsorb desulfurizing tower outlet Gas total sulfur folding is SO2≤10mg/m3, emptied through chimney;
4) when an absorption desulfurizing tower exit procedure gas total sulfur folding is SO2Soon more than 10mg/m3When, which cuts out, Carry out hot recycling in situ with 250-300 DEG C of indifferent gas, after the completion of hot recycling, be cooled to less than 80 DEG C it is spare, or be without cooling Incision carries out desulfurization;Regenerate implication and work off one's feeling vent one's spleen from selective oxidation reaction device and be mixed into the second condenser, be cooled to 140-160 DEG C, the elemental sulfur condensation separation in gaseous mixture enters Molten sulphur groove, and the gaseous mixture for removing elemental sulfur is cold through the 3rd again After another desulfurizing tower processing in condenser, absorption desulfurization operation, then empty through chimney, it is total that desulfurizing tower empties tail gas during regenerating Sulphur folding is SO2≤10mg/m3
2. the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas as claimed in claim 1, it is characterised in that described to urge It is Na to change oxidation-adsorption desulfurizing agent2CO3/ activated carbon, NaOH/ activated carbons, K2CO3/ activated carbon, KOH/ activated carbons, Fe2O3/ activity One or more in charcoal and ferric oxide desulfurizer.
3. the low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas as claimed in claim 2, it is characterised in that described to urge Change the Na that oxidation-adsorption desulfurizing agent is load capacity 5-10%2CO3The Fe of/activated carbon, load capacity 5-20%2O3/ activated carbon, or With Fe2O3For the ferric oxide desulfurizer of main component.
4. the low-sulfur discharge recovery technology of sulfur of any intermediate concentration sour gas as described in claim 1-3, it is characterised in that In desulfurizing tower non-renewable period, two absorption desulfurizing tower parallel operations.
5. the low-sulfur discharge recovery technology of sulfur of any intermediate concentration sour gas as described in claim 1-3, it is characterised in that In desulfurizing tower non-renewable period, used before the desulfurizing tower soon penetrated is serially connected in another desulfurizing tower.
6. the low-sulfur discharge recovery technology of sulfur of any intermediate concentration sour gas as described in claim 1-3, it is characterised in that Heater element is separately set in catalysis oxidation absorption desulfurizing tower.
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