CN106629625A - Sulfur recovery process for treating low-concentration acidic gases - Google Patents

Sulfur recovery process for treating low-concentration acidic gases Download PDF

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Publication number
CN106629625A
CN106629625A CN201611149100.6A CN201611149100A CN106629625A CN 106629625 A CN106629625 A CN 106629625A CN 201611149100 A CN201611149100 A CN 201611149100A CN 106629625 A CN106629625 A CN 106629625A
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sulfur
temperature
reactor
catalyst
bed
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CN201611149100.6A
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CN106629625B (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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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
    • C01B17/0434—Catalyst compositions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
    • C01B17/043—Catalytic converters
    • 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 invention provides a sulfur recovery process for treating low-concentration acidic gases, for the acidic gases containing 1-3% by volume of H2S. Main equipment comprises a heater, an H2S direct oxidation reactor, a medium temperature condenser, a heater, an H2S selective oxidation reactor, a medium temperature condenser and a low temperature condenser in an acidic gas flowing direction, wherein bottoms of the medium temperature condenser and the low temperature condenser are connected with a liquid sulfur tank; the direct oxidation reactor is a water cooled temperature self-limiting reactor, and is filled with TiO2 based H2S for direct oxidation of a sulfur recovery catalyst; O2 introduced from air is used for converting 95% or more of H2S in the acidic gases into elemental sulfur; except a heating section at a reaction gas inlet, the rest of a catalyst bed layer is a uniform temperature bed layer; a temperature difference in the uniform temperature bed layer is self-limited within 10 DEG C; the selective oxidation reactor is an adiabatic reactor, and is filled with Fe2O3/silica H2S selective oxidation catalyst; the bed temperature is 230-250 DEG C; O2 contained in the process gas is used for converting H2S to mainly generate elemental sulfur and SO2; the outlet gas contains H2S less than or equal to 20 mg/m<3>, and SO2 less than or equal to 400 mg/m<3>.

Description

Process 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 of process low concentration sour gas Skill.
Background technology
During petrochemical industry, Coal Chemical Industry, coal gas, the most of sulphur contained by raw material would generally change into H2S, it is separated Formed and contain H2The sour gas of S；Also often separate to be formed in sour gas decontamination process and contain H2The sour gas of S.These sour gas are general Jing recovery technology of sulfur is processed, by H2S is converted into as much as possible elemental sulfur.
Sour gas sulfur recovery facility, during operation, the tail gas of Jing chimneys emptying, its SO2Concentration is continuous monitoring Project, in recent years emission request is more strict, such as《Petroleum refining industry pollutant emission standard》(GB31570-2015) specify In the SO in general area2Concentration of emission limit value is 400mg/m3（Total sulfur is converted into SO2）.Because of H2S is main odor pollution material One of, concentration of emission should try one's best reduction.
To H2The low concentration sour gas of S contents 1-3%, mono- direct oxidation reactor of past Jing, a selective oxidation are anti- Answer device to carry out sulphur recovery, empty the SO of tail gas2Concentration can reach≤900mg/m3（Total sulfur is converted into SO2）, meet at that time Emission request, but be difficult to reach existing general regional SO2≤400mg/m3Emission request.Thus, it is sometimes desirable to it is anti-by repacking Answer device or improve process conditions, reach existing emission request.And absorption desulfurization or wet desulphurization are adopted to the further process of tail gas, It is in some occasions and improper.
The content of the invention
To solve above-mentioned technical problem, the present invention provides a kind of recovery technology of sulfur for processing low concentration sour gas, 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 reactors, middle temperature Condenser, heater, H2S selective oxidation reaction devices, middle temperature condenser, low-temperature condenser, wherein, middle temperature condenser, low temperature Condenser bottom connects liquid sulfur pit；
Direct oxidation reactor is water-cooled self limiting temperature reactor, loads TiO2Base H2S direct oxidation catalyst for recovering sulfur, utilizes The introduced O of air2By in sour gas more than 95% H2S is converted into elemental sulfur, and makes the middle SO that works off one's feeling vent one's spleen2≤100 mg/m3；Urge Agent bed removes the warming-up section of reaction gas entrance, and remaining is samming bed；The temperature of the samming bed can be wanted according to reaction Ask, high high adjustment is carried out in the range 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 temperature 230-250 DEG C, using O contained in Process Gas2By H2S is converted, and 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 allocated the desired amount of air into and is fully mixed, and first heated device is preheating to 180～200 DEG C, enters direct Oxidation reactor reacts；The middle temperature condensers of direct oxidation reactor outlet gas Jing are cooled to 140-160 DEG C, and the elemental sulfur of generation is cold Solidifying to be segregated into liquid sulfur pit, the Process Gas for separating molten sulfur are allocated appropriate air into and are fully mixed, and heated device is preheating to 230～ 240 DEG C, into the reaction of selective oxidation reaction device；Selective oxidation reaction device middle temperature condensers of Jing of working off one's feeling vent one's spleen are cooled to 140- 160 DEG C, the elemental sulfur condensation separation of generation enters liquid sulfur pit, separate molten sulfur Process Gas Jing low-temperature condensers be cooled to 60 DEG C with Under further catch after sulphur by chimney empty.
In the recovery technology of sulfur of low concentration sour gas of the present invention, the water-cooled self limiting temperature direct oxidation reactor can be solved Strongly exothermic brought a temperature control difficult problem is reacted in direct oxidation, by by except the reaction bed temperature control after entrance warming-up section The level close to samming is made, favourable reaction bed temperature condition is formed, can be by the H that works off one's feeling vent one's spleen2S concentration, SO2Concentration Relatively low level is arrived in control simultaneously, and the self limiting temperature reactor is appropriate using the pressure of the slightly below equal temperature section temperature of beds Boiling water-vapour mixture make cooling medium, heat exchange area is sufficiently large, can reach the equal temperature section beds temperature difference≤10 DEG C or even Lower level；The TiO of reactor filling2Base H2S direct oxidations catalyst for recovering sulfur is generally sensitive to steam, but research is sent out It is existing, under the conditions of 250 DEG C of temperature below, when the vapour concentration in the moisture for being generated i.e. Process Gas is controlled in reduced levels Such as 10%（Volume）Within when will not cause claus reaction substantially, so as to ensure 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, CS2Dispose, then may be used With along airflow direction in H2S direct oxidation reactor TiO2TiO is set after base catalyst for recovering sulfur bed2The middle temperature of base is organic Sulfide hydrolysis bed, or in TiO2The outlet section of base catalyst for recovering sulfur bed loads in mixture TiO2The middle temperature organic sulfur water of base Solution catalyst；Can also be in H2S selective oxidation reaction device Fe2O3Before/silicon oxide catalyst, TiO is set2The middle temperature of base is organic Sulfide hydrolysis bed, or in H2The Fe of S selective oxidation reaction devices2O3/ silicon oxide catalyst bed inlet section is loaded in mixture TiO2The middle temperature organic sulfur hydrolyst of base；Can with along airflow direction in H2The outlet section of S direct oxidation reactors arranges TiO2 The middle temperature organic sulfur hydrolyst bed of base and TiO2The mixing bed of base catalyst for recovering sulfur, and in H2S selective oxidations are anti- Answer device entrance that TiO is set2The middle temperature organic sulfur hydrolyst bed of base and Fe2O3The mixing bed of/silicon oxide catalyst. （TiO2Base catalyst for recovering sulfur+Fe2O3/ silicon oxide catalyst）With TiO2The volume ratio of the middle temperature organic sulfur hydrolyst of base (0.7-0.9)：(0.3-0.1).The TiO2The main component of the middle temperature organic sulfur hydrolyst of base is TiO2And choosing From one or more of salt or oxide in alkali metal, alkaline-earth metal, rare earth element, using the bonding for not having Crouse's activity Agent, is not susceptible to sulfation or speed is slower, with higher tempreture organic sulphur hydrolysis ability, but does not cause claus reaction. Under the normal operating condition of desulfurization purification technique of the present invention, TiO2The middle temperature organic sulfur hydrolyst of base can be by major part COS、CS2It is hydrolyzed to H2S, percent hydrolysis >=95% can generally make reactor outlet organic sulfur content COS+CS2≤20 mg/m3, have Help control total S≤50 mg/m of chimney air-discharging after absorption desulfurizing tower is processed3。
The water-cooled self limiting temperature direct oxidation reactor, it is preferred to use the direct oxidation of vertical pipes water-cooled self limiting temperature is reacted Device, including reactor body, positioned at the water vapor heat-tranferring system on reactor body top, reactor body and water vapor move heat system System is not connected；
Reactor body includes housing, 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 sleeve pipe 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 base plate, extend downwardly into beds bottom or under position simultaneously In lower end closure；Inner tube lower end extends to outer pipe bottom, and upper end is extended to outside outer tube upper port；Inner tube is to down-flow water, outer tube To upper steam water interface；Sleeve upper end mouth is received with ensure that the structure that inner tube is only intake, flows into water and do not enter vapour substantially The impact that the outer tube of this sleeve pipe or other outer tubes discharge steam water interface is less or completely unaffected；The water vapor is moved Hot systems heat exchange sleeve gos deep into the height 0.5-20m of beds, tube pitch 0.02-0.10m, heat exchange area 10-50m2/m3 Catalyst.
The upper end formation of the water vapor heat-tranferring system heat exchange sleeve, will ensure that inner tube to down-flow water, and outer tube is upwards Stream steam water interface, can be that inner tube upwardly extends opening and outer tube extends opening to lateral opening or to side top, or outward Pipe upwardly extends opening, and inner tube lateral thrust is open through outer tube wall to lateral opening or extend to side-lower, or inner tube from Outer tube upper shed bends under side.The carbonated drink liquid level of suitable control carbonated drink room is answered, to ensure that it is sufficient that inner tube supplies water.
In radial reactor of the present invention with height self limiting temperature area, the upper end knot of water vapor heat-tranferring system heat exchange sleeve Structure, can also be that inner tube upper port extends to above outer tube upper port part, and 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 footpath, internal diameter can be 0.9-1.1 times of outer tube external diameter, oared segrne pii loudspeaker angle 10-20 degree, although the downward stream of inner tube Water can suck a small amount of steam bubble, but the flow direction of carbonated drink will not change in inner and outer pipes, move the heat energy power range of decrease less, and effect equally may be used Lean on.
The upper end formation of the water vapor heat-tranferring system heat exchange sleeve, can set hydroecium, heat exchange sleeve on carbonated drink room Inner tube upwardly extend and be open in hydroecium base plate, control hydroecium liquid level, it is ensured that inner tube supplies water sufficient, hydroecium, carbonated drink room point The advantage not arranged also includes that can lead to high steam when going into operation directly is preheating to reaction temperature by reactor；Can be with by carbonated drink room If siphunculus connects hydroecium, the steam water interface of carbonated drink room fully enters hydroecium, and from hydroecium steam is discharged, and its advantage is by abundant Steam mixing can accomplish that hydroecium water temperature is consistent with saturated vapor, with the less beds temperature difference of acquisition.
In the vertical pipes water-cooled self limiting temperature direct oxidation reactor, can also be by carbonated drink room, the high-order vapour of hydroecium connection Bag, to obtain bigger inner and outer pipes pressure reduction, improves the flow velocity and shifting heat, soaking ability of water, carbonated drink in heat exchange sleeve.
In the vertical pipes water-cooled self limiting temperature direct oxidation reactor, the structure of beds is flowed to according to Process Gas Can be that axially or radially, wherein preferably, reason is H to the axial arrangement of Process Gas upper entering and lower leaving2S and O2Reaction speed quickly, instead In answering set of regions, each sleeve pipe can simultaneously play limit temperature effect in the axial arrangement bed of Process Gas upper entering and lower leaving；Footpath It is that bed resistance is less to the advantage of structure, but only some sleeve pipe has played shifting heat effect.
In the vertical pipes water-cooled self limiting temperature direct oxidation reactor, the bottom of beds can use orifice plate screen cloth Stacking is supported, it is also possible to is started to load inert ceramic balls from large to small from reactor bottom and is supported, and wherein latter arrangement is easy to Drawing off during catalyst change.It is preferred that lower end plane of the upper plane of inert ceramic balls filling higher than water cold sleeve, to prevent catalysis There is overtemperature, temperature runaway in agent bed bottom.
In the vertical pipes water-cooled self limiting temperature direct oxidation reactor, the equal temperature section heat exchange sleeve of water vapor heat-tranferring system Inner tube water to dirty, outer tube carbonated drink to upper power, there is carbonated drink in the vertical vaporization space between outer tube and mix Compound, its density is less than aqueous water, and this feature makes the heat-tranferring system be provided with stronger automatic bidirectional temperature adjustment ability-should be from Dynamic bidirectional temp regulation ability becomes apparent from when vertical water cold sleeve is longer, so that the temperature of the equal temperature section of beds is protected substantially Hold constant, reduce the temperature difference between the fluctuating range and diverse location of the equal temperature section temperature of beds：If outside temperature section sleeve pipe Bed temperature raise, then the vaporization aggravation between water cold sleeve inner and outer pipes, the density of steam water interface further reduces, water/ The dynamic motive force increase of steam flow, the water yield increase of sleeve pipe, evaporating capacity is that cooling capacity is improved, so as to limit catalyst bed The increasing degree of layer temperature section temperature；On the contrary, if the bed temperature outside temperature section sleeve pipe is slightly reduced, 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 yield of sleeve pipe Reduce, evaporating capacity moves the reduction of heat energy power, so as to limit the range of decrease of beds samming temperature；This rugged catalyst bed The automatic bidirectional regulating power of layer temperature section temperature had both been present in the differing heights position of a certain sleeve pipe of equal temperature section, existed in In each sleeve pipe of temperature section.Thus the heat-removing way can make the temperature difference of the equal temperature section of beds different parts up and down Less, temperature fluctuation is less and more constant.This water cold sleeve structure, extra automatic pair that its vertical occupation mode is brought To temperature adjustment ability, it is changed to horizontally arranged at it and no longer has when using, is also most of horizontally arranged and uses Cooling component was not readily reachable by and had.
The vertical pipes water-cooled 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 hot area of the shifting of water vapor heat-tranferring system is enough Big and sleeve pipe is arranged, is reasonably distributed, and equal temperature section bed temperature depends primarily on the pressure of saturated vapor, is steamed by controlling or adjusting Steam pressure can ensure or adjust reaction bed temperature, and temperature section bed temperature, the temperature difference are fed by beds entrance The impact of conditional fluctuation less, preferably controls the bulk temperature level of beds by controlling main Control point temperature.Such as Fruit reactor inlet temperature is identical with equal temperature section temperature, then just without warming-up section in reactor, on the whole temperature is consistent, can be described as Uniform-temperature reactor or isothermal reactor, at this time reactor conversion H2The ability of S is larger.
But generally reactor inlet temperature is more lower than equal temperature section temperature, thus beds entrance is an intensification Section.In radial reactor, vertical pipes inner and outer pipes substantially only have current in warming-up section, and heating efficiency is less, heat up main By exothermic heat of reaction, unless by boiling water forced circulation.In axial flow reactor, if entrance is on the top of beds, There is vapour and condense and heat release in the steam water interface flowed back to from the equal temperature section in sleeve pipe middle and lower part, this heating efficiency is very big in entrance, Effect to heating up is very big；If entrance is in the bottom of beds, at this in sleeve pipe only have current, heating efficiency compared with It is little, heat up also mainly by exothermic heat of reaction.The intersegmental boundary of warming-up section and samming, automatically forms, and warming-up section arranges sleeve pipe, can Avoid overtemperature, temperature runaway.
In direct oxidation reactor and the before pipeline between heater, and selective oxidation reaction device and heater before Between pipeline in, be preferably respectively provided with static mixer, to improve sour gas, Process Gas and the degree of mixedness of air, realize more Good reaction effect.
Middle 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 operation.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 certain value such as 80 DEG C, stop Cooling water, Process Gas are gradually heated up heating up, and to 140 DEG C or so and are kept for a period of time, and the condensation elemental sulfur of accumulation melts, Liquid sulfur pit is flowed into, condensing capacity is recovered, cooling water is opened afterwards and recovers normal.
The vertical pipes water-cooled self limiting temperature direct oxidation reactor, except with self limiting temperature ability, when catalyst is scrapped Easily draw off, can also be processed by blocking, being welded leakage sleeve pipe when minority sleeve pipe is leaked.
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, thus does not generate organic sulfur, and the TiO of direct oxidation reactor filling2Base sulphur recovery is catalyzed Agent has certain COS hydrolysis abilities, also using TiO2The middle temperature organic sulfur hydrolyst of base is by COS, CS2It is substantially transitioned to H2S is simultaneously further oxidized to elemental sulfur.Because most low concentration sour gas such as low-temp methanol washing process are obtained in sour gas, sulphur The organic sulfur content that alcohol, thioether, thiophene etc. are difficult to process is very low, thus the present invention can be used to process most of low concentration sour gas Sulphur recovery process.
As long as the content of the organic sulfur such as composition such as mercaptan, thioether, thiophene is not high in sour gas, the sulphur recovery work of the present invention Skill, easily reaches emptying tail gas H2S≤10mg/m3, total sulfur folding is SO2≤400 mg/m3, reach the discharge in existing general area Level.
Description of the drawings
Fig. 1, the recovery technology of sulfur general flow chart of low concentration sour gas；
Fig. 2-3, radial flow vertical pipes water-cooled self limiting temperature direct oxidation reactor；
Fig. 4-5, axial flow type vertical pipes water-cooled self limiting temperature direct oxidation reactor；
Fig. 6-11, Fig. 3, several upper end formations of the vertical water cold sleeve of 5 reactors.
Legend：1 direct oxidation reactor shell, 2 direct oxidation beds, 3 Catalyst packing pipes, 4 carbonated drink rooms/water Room, 5 heat exchange sleeve inner tubes, 6 heat exchange sleeve outer tubes, 7 dividing plates, the radial direction reaction bed container of 8 side cornice passages, 9 band ventilations The radial direction reaction bed inner tube in hole, 10 vertical water-cooled heat exchange sleeves, 11 support porcelain ball, 12 boiling water-saturated vapor outlet, 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, technological process as shown in Figure 1, for processing H is contained2S 1- The sour gas of 3% (volume), capital equipment is along acid gas stream to including heater, H2S direct oxidation reactors, middle temperature condenser, Heater, H2S selective oxidation reaction devices, middle temperature condenser, two can series-parallel operation low-temperature condenser；Wherein, low temperature Condensator outlet end sets and catch by made by multilayer stainless (steel) wire sulphur net, bottom connection liquid sulfur pit；
Direct oxidation reactor is vertical pipes water-cooled self limiting temperature reactor, loads A988G TiO2Base H2S direct oxidation sulphur Reclaim the m of catalyst 383, the m of porcelain ball 0.7 is loaded in bottom3；Selective oxidation reaction device is adiabatic reactor, loads A888G Fe2O3/ silica H2S catalyst for selective oxidation 15m3, beds middle and upper part mixed packing A921G TiO2The middle temperature of base has Machine sulfide hydrolysis 5m3；The catalyst, desulfurizing agent are the product grade of Shandong Xunda Chemical Industrial Group Co., Ltd.；
Wherein vertical pipes water-cooled self limiting temperature direct oxidation reactor, primary structure as shown in Figure 2, including reactor body, Water vapor heat-tranferring system, reactor body is not connected with water vapor heat-tranferring system；Reactor body includes that housing 1, catalyst is anti- Answer bed 2, feed inlet and outlet 15, Catalyst packing pipe 3, catalyst unloading mouth 14；Beds bottom is supported by porcelain ball 11；Water Vaporization heat-tranferring system includes that hydroecium 4, carbonated drink room 21, vertical water-cooled move thermal sleeve 10, moves thermal sleeve nested with outer tube 6 by inner tube 5 Form, outer tube upward opening extends downwardly under beds position and in lower end closure in carbonated drink room base plate；Under inner tube End extends to outer pipe bottom, and upper end open is in hydroecium base plate；The height 10m of beds；Move spacing 56mm of thermal sleeve, set Pipe inner tube Φ 19x2mm, outer tube Φ 38x3mm, sleeve pipe radical 538, the m of heat exchange area 6433；Reactor diameter Φ 2700mm, always High 17900mm.
Mainly operating process conditions are one kind of this sour gas sulfur recovery facility：
The basic composition of sour gas（Volume content）And flow：H2S2.8%, COS0.02%, H2O 1.0%, flow 10000N m3/h；Air is allocated into O21.5%；
180 DEG C of direct oxidation reactor inlet temperature, during gauge pressure 2.0MPa of carbonated drink room, 219 DEG C of reaction bed temperature, uniform temperature zone 8 DEG C of the temperature difference of differing heights and diameter key position；Middle 142 DEG C of temperature condensator outlet temperature degree, H2S 1300 mg/m3, SO2≤ 100 mg/m3, COS≤100 mg/m3, O20.18%（Volume）；
H2Middle temperature condensator outlet gas allocates a small amount of air into O after S direct oxidation reactors20.38%；Selective reaction device enters 230 DEG C of temperature of mouth, 240 DEG C of reaction bed temperature；Middle 143 DEG C of temperature condensator outlet temperature degree；Low-temperature condenser outlet air temperature 40 DEG C of degree, H2S≤10mg/m3, SO2≤350 mg/m3, COS≤10 mg/m3, O20.25%（Volume）.
Mainly operating process conditions are another kind：
The basic composition of sour gas（Volume content）And flow：H2S1.5%, COS0.01%, H2O 1.0%, flow 10000N m3/h；Air is allocated into O20.98%；
180 DEG C of direct oxidation reactor inlet temperature, during gauge pressure 2.0MPa of carbonated drink room, 215 DEG C of reaction bed temperature, uniform temperature zone 6 DEG C of the temperature difference of differing heights and diameter key position；Middle 142 DEG C of temperature condensator outlet temperature degree, H2S 600 mg/m3, SO2≤ 100 mg/m3, COS≤50 mg/m3, O20.25%（Volume）；
232 DEG C of selective reaction device inlet temperature, 240 DEG C of reaction bed temperature；Middle 143 DEG C of temperature condensator outlet temperature degree； Low-temperature condenser is worked off one's feeling vent one's spleen 40 DEG C of temperature, and work off one's feeling vent one's spleen composition H2S ≤10mg/m3, SO2≤200 mg/m3, COS≤10 mg/m3, O20.20%（Volume）.
In this sour gas sulfur recovery facility operation process, two low-temperature condensers are used in series, and series connection is changed per hour Order once arranges a molten sulfur, and front condenser does not enter cooling water intensification discharges trapped solid-state sulphur fusing, and post-condenser enters cold But water catches sulphur.
In this sour gas sulfur recovery facility operation process, gained sulfur product purity more than 99.8% reaches industrial one-level The requirement of standard.
In this sour gas sulfur recovery facility, the beds temperature of vertical pipes water-cooled self limiting temperature direct oxidation reactor Degree depends primarily on the pressure of saturated vapor, and by controlling or adjusting steam pressure beds temperature can be ensured or adjust Degree, and each position temperature difference of bed is less, is affected less, to control main Control point by the fluctuation of beds entrance feed conditions Temperature can preferably control the bulk temperature level of beds, not overtemperature, not temperature runaway, be difficult to tie carbon, and catalyst is used Life-span or cycle are longer.

Claims (10)

1. a kind of recovery technology of sulfur for processing low concentration sour gas, for containing H2The sour gas of S 1-3% (volume), capital equipment Along acid gas stream to including heater, H2S direct oxidation reactors, middle temperature condenser, heater, H2S selective oxidation reactions Device, middle temperature condenser, low-temperature condenser, wherein, middle temperature condenser, low-temperature condenser bottom connection liquid sulfur pit；
Direct oxidation reactor is water-cooled self limiting temperature reactor, loads TiO2Base H2S direct oxidation catalyst for recovering sulfur, utilizes The introduced O of air2By in sour gas more than 95% H2S is converted into elemental sulfur, and makes the middle SO that works off one's feeling vent one's spleen2≤100 mg/m3；Urge Agent bed removes the warming-up section of reaction gas entrance, and remaining is samming bed；The temperature of the samming bed can be wanted according to reaction Ask, high high adjustment is carried out in the range 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 temperature 230-250 DEG C, using O contained in Process Gas2By H2S is converted, and 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 allocated the desired amount of air into and is fully mixed, and first heated device is preheating to 180～200 DEG C, enters direct Oxidation reactor reacts；The middle temperature condensers of direct oxidation reactor outlet gas Jing are cooled to 140-160 DEG C, and the elemental sulfur of generation is cold Solidifying to be segregated into liquid sulfur pit, the Process Gas for separating molten sulfur are allocated appropriate air into and are fully mixed, and heated device is preheating to 220～ 235 DEG C, into the reaction of selective oxidation reaction device；Selective oxidation reaction device middle temperature condensers of Jing of working off one's feeling vent one's spleen are cooled to 140- 160 DEG C, the elemental sulfur condensation separation of generation enters liquid sulfur pit, separate molten sulfur Process Gas Jing low-temperature condensers be cooled to 60 DEG C with Under further catch after sulphur by chimney empty.
2. the recovery technology of sulfur of sour gas as claimed in claim 1, it is characterised in that along airflow direction in H2S direct oxidations are anti- Answer device TiO2TiO is set after base catalyst for recovering sulfur bed2The middle temperature organic sulfur hydrolyst bed of base, or in TiO2Base The outlet section of catalyst for recovering sulfur bed loads in mixture TiO2The middle temperature organic sulfur hydrolyst of base；Can also be in H2S selective oxidations Reactor Fe2O3Before/silicon oxide catalyst, TiO is set2The middle temperature organic sulfur hydrolyst bed of base, or in H2S is selected The Fe of property oxidation reactor2O3/ silicon oxide catalyst bed inlet section loads in mixture TiO2The middle temperature organic sulfur hydrolyst of base；May be used also With along airflow direction in H2The outlet section of S direct oxidation reactors arranges TiO2The middle temperature organic sulfur hydrolyst bed of base with TiO2The mixing bed of base catalyst for recovering sulfur, and in H2S selective oxidation reaction devices entrance arranges TiO2The middle temperature of base is organic Sulfide hydrolysis bed and Fe2O3The mixing bed of/silicon oxide catalyst；（TiO2Base catalyst for recovering sulfur+Fe2O3/ oxidation Si catalyst）With TiO2The volume ratio (0.7-0.9) of the middle temperature organic sulfur hydrolyst of base：(0.3-0.1).
3. the recovery technology of sulfur of sour gas as claimed in claim 1, it is characterised in that TiO2Base catalyst for recovering sulfur be containing TiO285-90%, remaining composition is mainly CaSO4Titania-based catalyst for recovering sulfur, it is or purer containing TiO299% is left Right titanium dioxide catalyst for recovering sulfur；TiO2The main component of the middle temperature organic sulfur hydrolyst of base is TiO2And be selected from One or more of salt or oxide in alkali metal, alkaline-earth metal, rare earth element, using the bonding for not having Crouse's activity Agent.
4. the recovery technology of sulfur of sour gas as claimed in claim 1, it is characterised in that the water-cooled self limiting temperature direct oxidation is anti- Answer device, be vertical pipes water-cooled self limiting temperature direct oxidation reactor, including reactor body, positioned at the water on reactor body top Vaporization heat-tranferring system, reactor body is not connected with water vapor heat-tranferring system；
Reactor body includes housing, 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 sleeve pipe 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 base plate, extend downwardly into beds bottom or under position simultaneously In lower end closure；Inner tube lower end extends to outer pipe bottom, and upper end is extended to outside outer tube upper port；Inner tube is to down-flow water, outer tube To upper steam water interface；Sleeve upper end mouth is received with ensure that the structure that inner tube is only intake, flows into water and do not enter vapour substantially The impact that the outer tube of this sleeve pipe or other outer tubes discharge steam water interface is less or completely unaffected.
5. the recovery technology of sulfur of sour gas as claimed in claim 4, it is characterised in that the direct oxygen of vertical pipes water-cooled self limiting temperature The water vapor heat-tranferring system heat exchange sleeve for changing reactor gos deep into the height 0.5-20m of beds, tube pitch 0.02-0.10m, Heat exchange area 10-50m2/m3Catalyst.
6. the recovery technology of sulfur of sour gas as claimed in claim 4, it is characterised in that the direct oxygen of vertical pipes water-cooled self limiting temperature Change the upper end formation that reactor water vaporizes heat-tranferring system heat exchange sleeve, be inner tube upwardly extend opening and outer tube to lateral opening or Extend opening to side top, or outer tube upwardly extends opening, and inner tube lateral thrust is through outer tube wall to lateral opening or to side Lower section bends under extending opening, or inner tube from outer tube upper shed to side；Can also be that inner tube upper port is extended to above on outer tube Port part, inner tube is suitable for reading and outer tube difference in height suitable for reading, is 1-3 times of outer tube diameter；Can also have internal diameter expanding reach or loudspeaker Mouth section, internal diameter expands 1-2 times that segment length can be outer tube diameter, and internal diameter can be 0.9-1.1 times of outer tube external diameter, oared segrne pii Loudspeaker angle 10-20 degree.
7. the recovery technology of sulfur of sour gas as claimed in claim 4, it is characterised in that the direct oxygen of vertical pipes water-cooled self limiting temperature Change the upper end formation that reactor water vaporizes heat-tranferring system heat exchange sleeve, can set hydroecium on carbonated drink room, heat exchange sleeve it is interior Pipe is upwardly extended and is open in hydroecium base plate；Can be to set siphunculus connection hydroecium by carbonated drink room, the steam water interface of carbonated drink room is complete Portion enters hydroecium, and from hydroecium steam is discharged；Carbonated drink room, hydroecium can connect high-order drum.
8. the recovery technology of sulfur of sour gas as claimed in claim 4, it is characterised in that the direct oxygen of vertical pipes water-cooled self limiting temperature In changing reactor, the structure of beds is for axially or radially.
9. the recovery technology of sulfur of sour gas as claimed in claim 1, it is characterised in that middle 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 claimed in claim 1, it is characterised in that direct oxidation reactor and before plus In pipeline between hot device, and selective oxidation reaction device and before in the pipeline between heater, it is respectively provided with static mixer.
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