CN106629625B - Handle the recovery technology of sulfur of low concentration sour gas - Google Patents

Handle the recovery technology of sulfur of low concentration sour gas Download PDF

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CN106629625B
CN106629625B CN201611149100.6A CN201611149100A CN106629625B CN 106629625 B CN106629625 B CN 106629625B CN 201611149100 A CN201611149100 A CN 201611149100A CN 106629625 B CN106629625 B CN 106629625B
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sulfur
bed
catalyst
temperature
reactor
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CN106629625A (en
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胡文宾
杨金帅
崔国栋
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SHANDONG XUNDA CHEMICAL GROUP CO Ltd
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SHANDONG XUNDA CHEMICAL GROUP CO Ltd
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The present invention provides a kind of recovery technology of sulfur for handling low concentration sour gas, for containing H2The sour gas of S 1-3% (volume), capital equipment is along acid gas stream to including heater, H2S direct oxidation reactor, medium temperature condenser, heater, H2S selective oxidation reaction device, medium temperature condenser, low-temperature condenser, medium temperature condenser, low-temperature condenser bottom connect liquid sulfur pit；Wherein, direct oxidation reactor is water cooling self limiting temperature reactor, loads TiO2Base H2S direct oxidation catalyst for recovering sulfur utilizes the introduced O of air2By in sour gas 95% or more H2S is converted into elemental sulfur, and catalyst bed removes the warming-up section of reaction gas entrance, remaining is samming bed, and the temperature difference in samming bed is limited within 10 DEG C certainly；Selective oxidation reaction device is adiabatic reactor, loads Fe2O3/ silica H2S catalyst for selective oxidation, utilizes O contained in Process Gas by 230-250 DEG C of bed temperature2By H2S conversion, mainly generates elemental sulfur and SO2, work off one's feeling vent one's spleen H2S≤20 mg/m3, SO2≤400 mg/m3。

Description

Handle the recovery technology of sulfur of low concentration sour gas
Technical field
The present invention relates to a kind of recovery technology of sulfur, and in particular to a kind of sulphur recovery work for handling low concentration sour gas Skill.
Background technique
During petrochemical industry, coal chemical industry, coal gas, most of sulphur contained by raw material would generally be converted to H2S, through separating It is formed and contains H2The sour gas of S；Also often separation is formed containing H in sour gas decontamination process2The sour gas of S.These sour gas are general It is handled through recovery technology of sulfur, by H2S is converted into elemental sulfur as much as possible.
Sour gas sulfur recovery facility, during operation, the tail gas emptied through chimney, SO2Concentration is continuous monitoring Project, emission request is more stringent in recent years, and such as " petroleum refining industry pollutant emission standard " (GB31570-2015) is provided SO in general area2Concentration of emission limit value is 400mg/m3(total sulfur is converted into SO2).Because of H2S is main odor pollution substance One of, concentration of emission should reduce as far as possible.
To H2The low concentration sour gas of S content 1-3%, past are anti-through a direct oxidation reactor, a selective oxidation It answers device to carry out sulphur recovery, empties the SO of tail gas2Concentration can achieve≤900mg/m3(total sulfur is converted into SO2), meet at that time Emission request, but be not easy to reach existing general area SO2≤400mg/m3Emission request.Thus, it is sometimes desirable to it is anti-by reequiping It answers device or improves process conditions, reach existing emission request.And absorption desulfurization or wet desulphurization is used to be further processed tail gas, In some occasions and improper.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of recovery technology of sulfur for handling low concentration sour gas, it is used for Containing H2The sour gas of S 1-3% (volume), capital equipment is along acid gas stream to including heater, H2S direct oxidation reactor, medium temperature Condenser, heater, H2S selective oxidation reaction device, medium temperature condenser, low-temperature condenser, wherein medium temperature condenser, low temperature Condenser bottom connects liquid sulfur pit；
Direct oxidation reactor is water cooling self limiting temperature reactor, loads TiO2Base H2S direct oxidation catalyst for recovering sulfur, Utilize the introduced O of air2By in sour gas 95% or more H2S is converted into elemental sulfur, and makes the middle SO that works off one's feeling vent one's spleen2≤100 mg/ m3；Catalyst bed removes the warming-up section of reaction gas entrance, remaining is samming bed；The temperature of the samming bed can be according to anti- It should require, high low adjustment is carried out within the scope of 200-230 DEG C；The temperature difference in the samming bed is limited within 10 DEG C certainly；
Selective oxidation reaction device is adiabatic reactor, loads Fe2O3/ silica H2S catalyst for selective oxidation, bed 230-250 DEG C of temperature, utilize O contained in Process Gas2By H2S conversion, mainly generates elemental sulfur and SO2, work off one's feeling vent one's spleen H2S≤20 mg/m3, SO2≤400 mg/m3；
Wherein, sour gas is incorporated the desired amount of air and is mixed well, and first heated device is preheating to 180~200 DEG C, enters Direct oxidation reactor reaction；Direct oxidation reactor outlet gas is cooled to 140-160 DEG C through medium temperature condenser, the simple substance of generation Sulphur, which condenses and separates, enters liquid sulfur pit, and the Process Gas for separating molten sulfur is incorporated appropriate air and is mixed well, and heated device is preheating to 230 It~240 DEG C, is reacted into selective oxidation reaction device；Selective oxidation reaction device, which is worked off one's feeling vent one's spleen, is cooled to 140- through medium temperature condenser 160 DEG C, the elemental sulfur of generation, which condenses and separates, enters liquid sulfur pit, separate the Process Gas of molten sulfur through low-temperature condenser be cooled to 60 DEG C with Under further catch sulphur after emptied by chimney.
In the recovery technology of sulfur of low concentration sour gas of the present invention, the water cooling self limiting temperature direct oxidation reactor can be solved Temperature brought by direct oxidation reaction is strongly exothermic controls problem, by that will remove the reaction bed temperature control after entrance warming-up section The level close to samming is made, advantageous reaction bed temperature condition is formed, can will work off one's feeling vent one's spleen H2S concentration, SO2Concentration Lower level is arrived in control simultaneously, and the self limiting temperature reactor is appropriate using the pressure for being slightly below the equal temperature section temperature of catalyst bed Boiling water-vapour mixture make cooling medium, heat exchange area is sufficiently large, can reach the equal temperature section catalyst bed temperature difference≤10 DEG C or even Lower level；The TiO of reactor filling2Base H2S direct oxidation catalyst for recovering sulfur is usually sensitive to steam, but studies hair It is existing, under the conditions of 250 DEG C of following temperature, when the vapour concentration in moisture, that is, Process Gas generated is controlled in reduced levels Such as 10%(volume) within when will not cause claus reaction substantially, to guarantee H2The conversion ratio of S and the selectivity of elemental sulfur, The SO of generation2It is less.
If such as COS, CS containing organic sulfur in sour gas2It is higher, it is desirable alternatively to by most COS, CS2It disposes, then may be used With along airflow direction in H2S direct oxidation reactor TiO2TiO is set after base catalyst for recovering sulfur bed2Base medium temperature is organic Sulfide hydrolysis bed, or in TiO2The outlet section of base catalyst for recovering sulfur bed loads in mixture TiO2Base medium temperature organic sulfur water Solve catalyst；It can also be in H2S selective oxidation reaction device Fe2O3Before/silicon oxide catalyst, TiO is set2Base medium temperature is organic Sulfide hydrolysis bed, or in H2The Fe of S selective oxidation reaction device2O3/ silicon oxide catalyst bed inlet section loads in mixture TiO2Base medium temperature organic sulfur hydrolyst；It can also be along airflow direction in H2TiO is arranged in the outlet section of S direct oxidation reactor2 Base medium temperature organic sulfur hydrolyst bed and TiO2The mixing bed of base catalyst for recovering sulfur, and in H2S selective oxidation is anti- Answer device entrance that TiO is set2Base medium temperature organic sulfur hydrolyst bed and Fe2O3The mixing bed of/silicon oxide catalyst. (TiO2Base catalyst for recovering sulfur+Fe2O3/ silicon oxide catalyst) and TiO2The volume ratio of base medium temperature organic sulfur hydrolyst (0.7-0.9): (0.3-0.1).The TiO2The main component of base medium temperature organic sulfur hydrolyst is TiO2And choosing From salt or oxide one or more in alkali metal, alkaline-earth metal, rare earth element, using not having the active bonding of Crouse Agent, is not susceptible to sulfation or speed is slower, tempreture organic sulphur hydrolysis ability with higher, but does not cause claus reaction.? Under the normal operating condition of desulfurization purification process of the present invention, TiO2Base medium temperature organic sulfur hydrolyst can be by major part COS、CS2It is hydrolyzed to H2S, percent hydrolysis >=95% can usually make reactor outlet organic sulfur content COS+CS2≤20 mg/m3, have Help control absorption desulfurizing tower treated chimney air-discharging total S≤50 mg/m3。
The water cooling self limiting temperature direct oxidation reactor, it is preferred to use vertical pipes water cooling self limiting temperature direct oxidation reaction Device moves heat system including reactor body, positioned at the water vapor heat-tranferring system on reactor body top, reactor body and water vapor System is not connected to；
Reactor body includes shell, catalyst reaction bed, input and output material pipeline and interface, catalyst loading and unloading structure；
Water vapor heat-tranferring system includes the metal heat-exchange casing of carbonated drink room, sufficient amount and heat exchange area, heat exchange sleeve by Inner and outer tubes nesting forms, outer tube upward opening in carbonated drink room bottom plate, extend downwardly into catalyst bed bottom or bottom It sets and in lower end closure；Inner tube lower end extends to outer pipe bottom, and upper end extends to except outer tube upper port；Inner tube to down-flow water, Outer tube is to upper steam water interface；Sleeve upper end mouth have can guarantee inner tube only intake, flow into water and substantially not into the knot of vapour Structure is influenced smaller or completely unaffected by the outer tube or other outer tubes steam water interface be discharged of this casing；The water Vaporization heat-tranferring system heat exchange sleeve gos deep into the height 0.5-20m, tube spacing 0.02-0.10m, heat exchange area 10- of catalyst bed 50m2/m3Catalyst.
The upper end formation of the water vapor heat-tranferring system heat exchange sleeve wants to guarantee inner tube to down-flow water, and outer tube is upward Steam water interface is flowed, can be that inner tube upwardly extends opening and outer tube is open to side or extends to upper side and is open, or is outer Pipe upwardly extends opening, inner tube lateral bending pass through outer tube wall be open to side or to side-lower extend opening or inner tube from Outer tube upper opening is to being bent under side.The carbonated drink liquid level of suitable control carbonated drink room is answered, to guarantee that it is sufficient that inner tube supplies water.
The present invention has in the radial reactor in height self limiting temperature area, and the upper end of water vapor heat-tranferring system heat exchange sleeve is tied Structure, in place of can also be that inner tube upper port extends to above outer tube upper port, inner tube is suitable for reading and outer tube difference in height suitable for reading, can be 1-3 times of outer tube diameter；Outer tube upper end can also have internal diameter expanding reach or oared segrne pii, and internal diameter expands segment length can be in outer tube 1-2 times of diameter, internal diameter can be 0.9-1.1 times of outer pipe outside diameter, oared segrne pii loudspeaker angle 10-20 degree, although the stream that inner tube is downward Water can suck a small amount of steam bubble, but the flow direction of carbonated drink will not change in inner and outer pipes, and the shifting thermal energy power range of decrease is little, and effect equally may be used It leans on.
The upper end formation of the water vapor heat-tranferring system heat exchange sleeve can set water chamber, heat exchange sleeve on carbonated drink room Inner tube upwardly extend and be open in water chamber bottom plate, control water chamber liquid level, it is ensured that inner tube supplies water sufficient, water chamber, carbonated drink room point Not She Zhi the advantages of further include that reactor is directly preheating to reaction temperature by the Shi Ketong high steam that goes into operation；It can also be by carbonated drink room If siphunculus connects water chamber, the steam water interface of carbonated drink room fully enters water chamber, and steam is discharged from water chamber, its advantage is that by abundant Steam mixing can accomplish that water chamber water temperature is consistent with saturated vapor, to obtain the smaller catalyst bed temperature difference.
In the vertical pipes water cooling self limiting temperature direct oxidation reactor, carbonated drink room, water chamber can also be connected high-order vapour Packet improves the flow velocity and shifting heat, equal thermal energy power of water, carbonated drink in heat exchange sleeve to obtain bigger inner and outer pipes pressure difference.
In the vertical pipes water cooling self limiting temperature direct oxidation reactor, the structure of catalyst bed is flowed to according to Process Gas It can be axially or radially, wherein the axial arrangement of Process Gas upper entering and lower leaving is preferable, the reason is that H2S and O2Reaction speed quickly, instead Region is answered to concentrate, each casing can play limit temperature effect simultaneously in the axial arrangement bed of Process Gas upper entering and lower leaving；Diameter It is that bed resistance is smaller, but only some casing has played shifting heat effect to the advantages of structure.
In the vertical pipes water cooling self limiting temperature direct oxidation reactor, the bottom of catalyst bed can use orifice plate sieve Stacking support, can also load inert ceramic balls since reactor bottom from large to small and be supported, wherein latter arrangement is convenient for Drawing off when catalyst change.It is preferred that the upper plane of inert ceramic balls filling is higher than the lower end plane of water cold sleeve, to prevent from being catalyzed Overtemperature, temperature runaway occur for agent bed lower part.
In the vertical pipes water cooling self limiting temperature direct oxidation reactor, the equal temperature section heat exchange sleeve of water vapor heat-tranferring system Inner tube water to flow down, outer tube carbonated drink is to upper power, it is mixed that there are carbonated drinks in the vertical vaporization space between outer tube Object is closed, density is lower than liquid water, this feature makes the heat-tranferring system be provided with stronger automatic bidirectional temperature adjustment ability-should be certainly Dynamic bidirectional temp regulation ability is more obvious when vertical water cold sleeve is longer, so that the temperature of the equal temperature section of catalyst bed be made to protect substantially It holds constant, reduces the temperature difference between the fluctuating range and different location of the equal temperature section temperature of catalyst bed: if outside temperature section casing Bed temperature increase, then the vaporization aggravation between water cold sleeve inner and outer pipes, the density of steam water interface further decreases, water/ The dynamic motive force of steam flow increases, and the water of sleeve pipe increases, and evaporating capacity, that is, cooling capacity improves, to limit catalyst bed The increasing degree of layer temperature section temperature；On the contrary, if the bed temperature outside temperature section casing slightly reduces, water cold sleeve inner and outer pipes it Between vaporization weaken, the density of steam water interface can increase, and the dynamic motive force of water/steam flow reduces, the water of sleeve pipe Reduce, evaporating capacity moves thermal energy power and reduces, to limit the range of decrease of catalyst bed samming temperature；This rugged catalyst bed The automatic bidirectional regulating power of layer temperature section temperature had both been present in the different height position of a certain casing of equal temperature section, existed in In each casing of equal temperature section.Thus the heat-removing way can make the temperature difference of the equal temperature section of catalyst bed different parts up and down Smaller, temperature fluctuation is smaller and more constant.This water cold sleeve structure, additional automatic double of vertical usage mode bring To temperature adjustment ability, no longer have when it is changed to horizontally arranged and use and it is most of horizontally arranged and use Cooling component be not readily reachable by and have.
The vertical pipes water cooling self limiting temperature direct oxidation reactor, the efficiency for vaporizing shifting heat by boiling water is very high, from limit Temperature is very capable, and the temperature difference of equal temperature section bed is can be controlled within 10 DEG C, as long as the shifting heat area of water vapor heat-tranferring system is enough The setting of big and casing is reasonably distributed, and equal temperature section bed temperature depends primarily on the pressure of saturated vapor, by controlling or adjusting steaming Steam pressure can guarantee or adjustment reaction bed temperature, and temperature section bed temperature, the temperature difference are fed by catalyst bed entrance The influence of conditional fluctuation is little, and the bulk temperature level of catalyst bed can preferably be controlled by controlling main Control point temperature.Such as Fruit reactor inlet temperature is identical with equal temperature section temperature, then does not just have warming-up section in reactor, temperature is consistent on the whole, can be described as Uniform-temperature reactor or isothermal reactor, at this time reactor converts H2The ability of S is larger.
But usual reactor inlet temperature is more lower than equal temperature section temperature, thus catalyst bed entrance is a heating Section.In radial reactor, vertical pipes inner and outer pipes substantially only have water flow in warming-up section, and heating efficiency is smaller, and heating is main By exothermic heat of reaction, unless by boiling water forced circulation.In axial flow reactor, if entrance on the top of catalyst bed, In entrance vapour condensation occurs for the steam water interface that equal temperature section flows back to from casing middle and lower part and heat release, this heating efficiency are very big, It is very big to the effect of heating；If entrance in the lower part of catalyst bed, at this in casing only have water flow, heating efficiency compared with It is small, it heats up also mainly by exothermic heat of reaction.Boundary between warming-up section and equal temperature section, automatically forms, and casing is arranged in warming-up section, can Avoid overtemperature, temperature runaway.
In pipeline between direct oxidation reactor and before heater and selective oxidation reaction device and heater before Between pipeline in, static mixer is preferably respectively set, to improve sour gas, Process Gas and the degree of mixedness of air, realizes more Good reaction effect.
Medium temperature condenser, low-temperature condenser outlet section can set the condensation sulphur trap made by stainless steel mesh, to reduce Elemental sulfur enters the quantity of rear process.H can be reduced into selective oxidation reaction device2The conversion ratio of S, emptying will also result in environment Pollution.
Low-temperature condenser should constantly or periodically melt sulphur, desulphurization.After its temperature of working off one's feeling vent one's spleen is increased to such as 80 DEG C of certain value, stop Cooling water, Process Gas are gradually heated up heating, until 140 DEG C or so and being kept for a period of time, the condensation elemental sulfur of accumulation melts, Liquid sulfur pit is flowed into, condensing capacity is restored, and is opened cooling water later and is restored normal.
The vertical pipes water cooling self limiting temperature direct oxidation reactor, in addition to self limiting temperature ability, when catalyst is scrapped It easily draws off, can also be handled by blocking, being welded leakage casing when a small number of casings leak.
In the present invention, the operation temperature of direct oxidation reactor, selective oxidation reaction device and heater is no greater than 250 DEG C, content of organics is very low, because without generating organic sulfur, and the TiO of direct oxidation reactor filling2The catalysis of base sulphur recovery Agent has certain COS hydrolysis ability, also using TiO2Base medium temperature organic sulfur hydrolyst is by COS, CS2It is substantially transitioned to H2S is simultaneously further oxidized to elemental sulfur.Since most low concentration sour gas such as low-temp methanol washing process are made in sour gas, sulphur The organic sulfur content that alcohol, thioether, thiophene etc. are difficult to handle is very low, thus the present invention can be used for handling most of low concentration sour gas Sulphur recovery processing.
As long as the content of the ingredients such as organic sulfur such as mercaptan, thioether, thiophene is not high in sour gas, sulphur recovery work of the invention Skill is easy to reach emptying tail gas H2S≤10mg/m3, total sulfur folding is SO2≤400 mg/m3, reach the discharge in existing general area It is horizontal.
Detailed description of the invention
Fig. 1, the recovery technology of sulfur general flow chart of low concentration sour gas；
Fig. 2-3, radial flow vertical pipes water cooling self limiting temperature direct oxidation reactor；
Fig. 4-5, axial flow type vertical pipes water cooling self limiting temperature direct oxidation reactor；
Several upper end formations of Fig. 6-11, Fig. 3, the vertical water cold sleeve of 5 reactors.
Legend: 1 direct oxidation reactor shell, 2 direct oxidation catalyst beds, 3 Catalyst packing pipes, 4 carbonated drink rooms/water Room, 5 heat exchange sleeve inner tubes, 6 heat exchange sleeve outer tubes, 7 partitions, radial reaction bed container of 8 side walls with venthole, 9 band ventilations The radial reaction bed inner tube in hole, 10 vertical water cooling heat exchange sleeves, 11 support porcelain balls, the outlet of 12 boiling water-saturated vapor, 13 boiling water Or cold water inlet, 14 catalyst unloading mouths, 15 sour gas import or exports, 21 carbonated drink rooms.
Specific embodiment
Embodiment
The sulfur recovery facility of a set of low concentration sour gas, process flow is as shown in Fig. 1, contains H for handling2S 1- The sour gas of 3% (volume), capital equipment is along acid gas stream to including heater, H2S direct oxidation reactor, medium temperature condenser, Heater, H2S selective oxidation reaction device, medium temperature condenser, two can series-parallel operation low-temperature condenser；Wherein, low temperature Condensator outlet end sets and catches sulphur net made of multilayer stainless (steel) wire, and bottom connects liquid sulfur pit；
Direct oxidation reactor is vertical pipes water cooling self limiting temperature reactor, loads A988G TiO2Base H2S direct oxidation sulphur Sulphur recycles 38 m of catalyst3, 0.7 m of porcelain ball is loaded in bottom3；Selective oxidation reaction device is adiabatic reactor, loads A888G Fe2O3/ silica H2S catalyst for selective oxidation 15m3, catalyst bed middle and upper part mixed packing A921G TiO2Base medium temperature has Machine sulfide hydrolysis 5m3；The catalyst, the product grade that desulfurizing agent is Shandong Xunda Chemical Industrial Group Co., Ltd.；
Wherein vertical pipes water cooling self limiting temperature direct oxidation reactor, primary structure is as shown in Fig. 2, including reactor master Body, water vapor heat-tranferring system, reactor body are not connected to water vapor heat-tranferring system；Reactor body includes shell 1, catalyst Reaction bed 2, feed inlet and outlet 15, Catalyst packing pipe 3, catalyst unloading mouth 14；Catalyst bed bottom is supported by porcelain ball 11； Water vapor heat-tranferring system includes water chamber 4, carbonated drink room 21, vertical water cooling shifting thermal sleeve 10, and it is embedding by inner tube 5 and outer tube 6 to move thermal sleeve It covers, outer tube upward opening extends downwardly under catalyst bed position and in lower end closure in carbonated drink room bottom plate；Inner tube Lower end extends to outer pipe bottom, and upper end opening is in water chamber bottom plate；The height 10m of catalyst bed；The spacing 56mm of thermal sleeve is moved, Casing inner tube Φ 19x2mm, outer tube Φ 38x3mm, casing radical 538,643 m of heat exchange area3；Reactor diameter Φ 2700mm, Total high 17900mm.
The main operating process conditions of one kind of this sour gas sulfur recovery facility are as follows:
Basic composition (volume content) and the flow of sour gas: H2S2.8%, COS0.02%, H2O 1.0%, flow 10000N m3/h；Air is incorporated to O21.5%；
180 DEG C of direct oxidation reactor inlet temperature, when the gauge pressure 2.0MPa of carbonated drink room, 219 DEG C of reaction bed temperature, 8 DEG C of the temperature difference of warm area different height and diameter key position；142 DEG C of degree of medium temperature condensator outlet temperature, H2S 1300 mg/m3, SO2≤100 mg/m3, the mg/m of COS≤1003, O20.18%(volume)；
H2Medium temperature condensator outlet gas is incorporated a small amount of air to O after S direct oxidation reactor20.38%；Selective reaction device 230 DEG C of inlet temperature, 240 DEG C of reaction bed temperature；143 DEG C of degree of medium temperature condensator outlet temperature；Low-temperature condenser is worked off one's feeling vent one's spleen 40 DEG C of temperature, H2S≤10mg/m3, SO2≤350 mg/m3, the mg/m of COS≤103, O20.25%(volume).
Another main operating process conditions are as follows:
Basic composition (volume content) and the flow of sour gas: H2S1.5%, COS0.01%, H2O 1.0%, flow 10000N m3/h；Air is incorporated to O20.98%；
180 DEG C of direct oxidation reactor inlet temperature, when the gauge pressure 2.0MPa of carbonated drink room, 215 DEG C of reaction bed temperature, 6 DEG C of the temperature difference of warm area different height and diameter key position；142 DEG C of degree of medium temperature condensator outlet temperature, H2S 600 mg/m3, SO2≤100 mg/m3, the mg/m of COS≤503, O20.25%(volume)；
232 DEG C of selective reaction device inlet temperature, 240 DEG C of reaction bed temperature；Medium temperature condensator outlet temperature degree 143 ℃；Low-temperature condenser is worked off one's feeling vent one's spleen 40 DEG C of temperature, is worked off one's feeling vent one's spleen and is formed H2S ≤10mg/m3, SO2≤200 mg/m3, the mg/ of COS≤10 m3, O20.20%(volume).
In this sour gas sulfur recovery facility operation process, two low-temperature condensers are used in series, and change series connection per hour Order once arranges a molten sulfur, and preceding condenser is discharged trap solid-state sulphur fusing into cooling water heating, and post-condenser is into cold But water catches sulphur.
In this sour gas sulfur recovery facility operation process, 99.8% or more gained sulfur product purity reaches industrial level-one The requirement of standard.
In this sour gas sulfur recovery facility, the catalyst bed temperature of vertical pipes water cooling self limiting temperature direct oxidation reactor Degree depends primarily on the pressure of saturated vapor, can guarantee or adjust catalyst bed temperature by controlling or adjusting steam pressure i.e. Degree, and each position temperature difference of bed is smaller, is influenced by the fluctuation of catalyst bed entrance feed conditions little, controls main Control point The bulk temperature that temperature can preferably control catalyst bed is horizontal, not overtemperature, not temperature runaway, is not easy to tie carbon, catalyst uses Service life or period are longer.

Claims (10)

1. a kind of recovery technology of sulfur for handling low concentration sour gas, for containing H2The sour gas of S volumetric concentration 1-3%, mainly sets It is standby along acid gas stream to including primary heater, H2S direct oxidation reactor, the first medium temperature condenser, secondary heater, H2S choosing Selecting property oxidation reactor, the second medium temperature condenser, low-temperature condenser, wherein the first medium temperature condenser, the second medium temperature condenser, Low-temperature condenser bottom connects liquid sulfur pit；
H2S direct oxidation reactor is water cooling self limiting temperature reactor, loads TiO2Base H2S direct oxidation catalyst for recovering sulfur, benefit With the introduced O of air2By in sour gas 95% or more H2S is converted into elemental sulfur, and makes the middle SO that works off one's feeling vent one's spleen2≤100 mg/m3； Catalyst bed removes the warming-up section of reaction gas entrance, remaining is samming bed；The temperature of the samming bed is wanted according to reaction It asks, high low adjustment is carried out within the scope of 200-230 DEG C；The temperature difference in the samming bed is limited within 10 DEG C certainly；
H2S selective oxidation reaction device is adiabatic reactor, loads Fe2O3/ silica H2S catalyst for selective oxidation, bed temperature 230-250 DEG C of degree, utilizes O contained in Process Gas2By H2S conversion, mainly generates elemental sulfur and SO2, work off one's feeling vent one's spleen H2S≤20 mg/m3, SO2≤400 mg/m3；
Wherein, sour gas is incorporated the desired amount of air and is mixed well, and first heated device is preheating to 180-200 DEG C, into H2S is straight Connect oxidation reactor reaction；H2S direct oxidation reactor outlet gas is cooled to 140-160 DEG C through the first medium temperature condenser, generates Elemental sulfur condense and separate and enter liquid sulfur pit, the Process Gas supplying for separating molten sulfur and mixes well air, pre- through secondary heater Heat arrives 220-235 DEG C, into H2The reaction of S selective oxidation reaction device；H2S selective oxidation reaction device is worked off one's feeling vent one's spleen through the second medium temperature Condenser is cooled to 140-160 DEG C, and the elemental sulfur of generation, which condenses and separates, enters liquid sulfur pit, separates the Process Gas of molten sulfur through low temperature cold Condenser be cooled to 60 DEG C catch sulphur further below after emptied by chimney.
2. the recovery technology of sulfur of sour gas as described in claim 1, which is characterized in that along airflow direction in H2S direct oxidation is anti- Answer device TiO2TiO is set after base catalyst for recovering sulfur bed2Base medium temperature organic sulfur hydrolyst bed, or in TiO2Base The outlet section of catalyst for recovering sulfur bed loads in mixture TiO2Base medium temperature organic sulfur hydrolyst；Or in H2S selective oxidation is anti- Answer device Fe2O3Before/silicon oxide catalyst, TiO is set2Base medium temperature organic sulfur hydrolyst bed, or in H2S selectivity The Fe of oxidation reactor2O3/ silicon oxide catalyst bed inlet section loads in mixture TiO2Base medium temperature organic sulfur hydrolyst；Or edge Airflow direction is in H2TiO is arranged in the outlet section of S direct oxidation reactor2Base medium temperature organic sulfur hydrolyst bed and TiO2Base The mixing bed of catalyst for recovering sulfur, and in H2TiO is arranged in S selective oxidation reaction device entrance2Base medium temperature tempreture organic sulphur hydrolysis Catalyst bed and Fe2O3The mixing bed of/silicon oxide catalyst； TiO2Base catalyst for recovering sulfur and Fe2O3/ silica is urged The total volume of agent, with TiO2The ratio of base medium temperature organic sulfur hydrolyst volume is (0.7-0.9): (0.3-0.1).
3. the recovery technology of sulfur of sour gas as described in claim 1, which is characterized in that TiO2Base catalyst for recovering sulfur be containing TiO285-90%, remaining ingredient are CaSO4Titania-based catalyst for recovering sulfur, or contain TiO299% titanium dioxide sulphur Sulphur recycles catalyst；TiO2The ingredient of base medium temperature organic sulfur hydrolyst is TiO2And selected from alkali metal, alkaline-earth metal, One or more salt or oxide in rare earth element, using not having the active binder of Crouse.
4. the recovery technology of sulfur of sour gas as described in claim 1, which is characterized in that the water cooling self limiting temperature reactor is Vertical pipes water cooling self limiting temperature reactor, including reactor body, positioned at the water vapor heat-tranferring system on reactor body top, instead Device main body is answered not to be connected to water vapor heat-tranferring system；
Reactor body includes shell, catalyst reaction bed, input and output material pipeline and interface, catalyst loading and unloading structure；
Water vapor heat-tranferring system includes the metal heat-exchange casing of carbonated drink room, sufficient amount and heat exchange area, and heat exchange sleeve is by inner tube It is nested with outer tube to form, outer tube upward opening in carbonated drink room bottom plate, extend downwardly into catalyst bed bottom or under position simultaneously In lower end closure；Inner tube lower end extends to outer pipe bottom, and upper end extends to except outer tube upper port；Inner tube is to down-flow water, outer tube To upper steam water interface；Sleeve upper end mouth have can guarantee that inner tube only intakes, flows into water without the structure into vapour, by this set The influence of the outer tube of pipe or other outer tubes steam water interface be discharged is smaller or completely unaffected.
5. the recovery technology of sulfur of sour gas as claimed in claim 4, which is characterized in that vertical pipes water cooling self limiting temperature reactor Water vapor heat-tranferring system heat exchange sleeve go deep into the height 0.5-20m of catalyst bed, tube spacing 0.02-0.10m, heat exchange area 10-50m2/m3Catalyst.
6. the recovery technology of sulfur of sour gas as claimed in claim 4, which is characterized in that vertical pipes water cooling self limiting temperature reactor The upper end formation of water vapor heat-tranferring system heat exchange sleeve, is that inner tube upwardly extends opening and outer tube is open to side or to upper side Extend opening or outer tube upwardly extends opening, inner tube lateral bending passes through outer tube wall and is open to side or extends to side-lower Opening or inner tube from outer tube upper opening to side under be bent；It is interior in place of either inner tube upper port extends to above outer tube upper port Suitable for reading and outer tube difference in height suitable for reading is managed, is 1-3 times of outer tube diameter；Or there is internal diameter expanding reach or oared segrne pii, internal diameter Expand 1-2 times that segment length is outer tube diameter, internal diameter is 0.9-1.1 times of outer pipe outside diameter, oared segrne pii loudspeaker angle 10-20 degree.
7. the recovery technology of sulfur of sour gas as claimed in claim 4, which is characterized in that vertical pipes water cooling self limiting temperature reactor The upper end formation of water vapor heat-tranferring system heat exchange sleeve, sets water chamber on carbonated drink room, and the inner tube of heat exchange sleeve upwardly extends simultaneously Opening is in water chamber bottom plate；Or siphunculus connection water chamber is set by carbonated drink room, the steam water interface of carbonated drink room fully enters water chamber, from water Steam is discharged in room；Or carbonated drink room, water chamber connect high-order drum.
8. the recovery technology of sulfur of sour gas as claimed in claim 4, which is characterized in that vertical pipes water cooling self limiting temperature reactor In, the structure of catalyst bed is axially or radially.
9. the recovery technology of sulfur of sour gas as described in claim 1, which is characterized in that medium temperature condenser, low-temperature condenser go out Mouth section, if the condensation sulphur trap made by stainless steel mesh.
10. the recovery technology of sulfur of sour gas as described in claim 1, which is characterized in that H2S direct oxidation reactor and before In pipeline between primary heater and H2In pipeline between S selective oxidation reaction device and before secondary heater, set respectively Set static mixer.
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CN101810998A (en) * 2010-02-22 2010-08-25 李红 Method for treating low-concentration sulfur dioxide waste gas
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