CN104190221A - Desulphurization method, device and system for acid gas containing H2S, COS, CS2 and other gases - Google Patents
Desulphurization method, device and system for acid gas containing H2S, COS, CS2 and other gases Download PDFInfo
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- CN104190221A CN104190221A CN201410462558.1A CN201410462558A CN104190221A CN 104190221 A CN104190221 A CN 104190221A CN 201410462558 A CN201410462558 A CN 201410462558A CN 104190221 A CN104190221 A CN 104190221A
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Abstract
The invention provides a desulphurization method for an acid gas containing H2S, COS, CS2 and other gases. The desulphurization method comprises the following desulphurization and transformation processes: carrying out hydrolysis reaction on the acid gas under the catalytic action of MnO; oxidizing the H2S in the acid gas after hydrolysis reaction by an oxygen-containing gas under the catalytic action of a liquid-phase Fe<3+> complexing agent, and transforming the H2S into sulphur to discharge. The invention also provides a desulphurization device for an acid gas containing gases such as H2S, COS and CS2, and a desulphurization system comprising the desulphurization device. According to the desulphurization method provided by the invention, two steps of reaction can be carried out in the same reaction device, so that the method is short in elapsed time and high in efficiency. The desulphurization device and the desulphurization system provided by the invention are high in desulphurization efficiency, low in manufacturing cost, low in probability of blockage, and stable in operation, and have an industrial application value.
Description
Technical field
The present invention relates to industrial Acidic Gas Treating field, be specifically related to a kind of H of containing
2s, COS, CS
2deng sulfur method, the desulfurizer of the sour gas of gas and the desulphurization system that comprises described desulfurizer.
Background technology
Coal Chemical Industry industry is prevailing in recent years, and coal liquefaction, coal preparing natural gas become the major industry of Coal Chemical Industry industry.As everyone knows, in coal, the content of sulphur is higher, causes containing in tail gas more H
2s, SO
2deng sulphur-containing exhaust gas, environment is caused to serious pollution, Coal Chemical Industry tail gas desulfur technology has become study hotspot.
Current desulfur technology can be divided into several classes substantially:
(1) Claus method desulfurization: Claus method flexible and convenient operation, sulfur recovery rate are high, device strong adaptability, investment and operating cost few, be therefore widely used in chemical plant installations.But because Crouse's reaction is more complicated, be reversible reaction, conversion ratio is subject to the restriction of thermodynamical equilibrium under reaction temperature, and the large quantity of moisture generating in course of reaction is difficult to from Process Gas separatedly, makes H
2s concentration constantly declines, and has so more limited balance and has moved to the direction that generates sulphur.Due to the problems of Claus method self existence, and the raising day by day of current environmental requirement, the discharge standard of Claus method can not meet present environmental requirement, therefore will certainly be replaced by novel sulfur removal technology energy-conservation, convenient, that the rate of recovery is high.
(2) biological desulphurization: be to utilize microorganism or its contained enzymatic sulfur-containing compound, the process that its contained sulphur is discharged.Substantially can be divided into Shell-Paques technique, Bio-SR technique and biochemical iron-alkali solution catalyzing.Biological desulphurization has the advantages such as safe non-environmental-pollution, construction cost and operating cost are low, good in economic efficiency, the efficiency of purified gas is high, accommodation is extensive.But because biology reaction speed in sweetening process is slower, and biological inoculum is more loaded down with trivial details in the process of selecting, and in the device running of being everlasting, occurs the desulfuration efficiency decline phenomenon of unknown cause, becomes the obstruction that limits its spread.
(3) wet oxidation process depriving hydrogen sulphide: these class methods are chemical reaction desulfurization, comprises ammoniacal liquor liquid catalytic, tannin extract method, KCA method, complex iron etc., and wherein of greatest concern with complex iron, it not only has good catalytic oxidation ability, and cheap.
Patent US 5126118 has proposed a kind of employing Fe
3+, V
5+circulating sulfur removal technology and the device of ionic catalyst, but for technological parameter index, do not give optimization.
Patent CN 200310112779.8 has proposed a kind of method of using removing sulfide from CO 2 enriched gas by complex iron, but the injection that it is taked absorbs string fluidized-bed process, device is comparatively complicated.
Patent CN 201310472099.0 has proposed a kind of claus tail-gas clean-up technique for sulfur dioxide, hydrogen sulfide and organic sulfur, and it adopts complex iron treatment process, and sulfur recovery rate reaches more than 99.95%, and in tail gas, sulfur content reaches 1.0mg/m
3below.But it adopts hydrogen is hydrogen sulfide by organic sulfur and sulphur dioxide reduction, need extra hydrogenation reactor, processing cost is higher, and hydrogenation step needs 200 ℃ of above high temperature, and energy consumption is large, and its technological parameter index is not given optimization yet.In addition, in the Complexing Iron liquid phase oxidation reduction and desulfurization device that this patent is used, reverse taper discharge device and the cylindrical shell reactor of bottom are concentric structure, and the discharge gate (degas zone) of common Complexing Iron liquid phase oxidation reduction and desulfurization device is not positioned at the center of described devulcanizer, therefore the discharge gate (tap web position) of reverse taper discharge device is not under devulcanizer discharge gate, in addition volume is too huge, when the sulphur slurries in devulcanizer are discharged, inwall landslide by reverse taper discharge device easily forms whirlpool, thereby can cause sulfur plug discharge device, cause whole sweetening process to lose efficacy.
Summary of the invention
For overcoming the defect existing in existing desulfurization process, an object of the present invention is to provide a kind of H of containing
2s, COS, CS
2sulfur method Deng the sour gas of gas.
Another object of the present invention is to provide a kind of H of containing
2s, COS, CS
2desulfurizer Deng the sour gas of gas.
An also object of the present invention is to provide a kind of H of containing
2s, COS, CS
2desulphurization system Deng the sour gas of gas.
The H that contains provided by the invention
2s, COS, CS
2deng the sulfur method of the sour gas of gas, its desulfurization conversion process is: first under MnO catalytic action, make described sour gas generation hydrolysis, the sour gas after hydrolysis is again at liquid phase Fe
3+under complexing agent catalytic action, make H wherein
2s is that sulphur is discharged through oxygen-containing gas oxidation transformation.
In above-mentioned sulfur method, the reaction temperature of described desulfurization conversion process is 40～60 ℃, is preferably 47～53 ℃.
In above-mentioned sulfur method, the time of described desulfurization conversion process is 5～10 seconds.
In above-mentioned sulfur method, in described oxygen-containing gas, the percent by volume of oxygen is 10～100%.
The H that contains provided by the invention
2s, COS, CS
2desulfurizer Deng the sour gas of gas, comprise cylindrical shell reaction unit and the reverse taper discharge device that is arranged at described cylindrical shell reaction unit bottom, described cylindrical shell reaction unit inside is divided into fan-shaped uptake zone, reaction zone and degas zone successively, described uptake zone is for the hydrolysis of described sour gas, described reaction zone is for the oxidation reaction of described sour gas, and described degas zone is for discharging the tail gas after gained sulphur slurries and desulfurization; Wherein, described uptake zone is provided with MnO catalyst bed, described reverse taper discharge device is arranged on below, described degas zone, its end face circumference is inscribed within the bottom surface circumference of described cylindrical shell reaction unit, and the end face radius of described reverse taper discharge device and the bottom surface radius ratio of described cylindrical shell reaction unit are 0.65～0.85:1.
In above-mentioned desulfurizer, the end face radius of described reverse taper discharge device and the bottom surface radius ratio of described cylindrical shell reaction unit are 0.73～0.78:1.
In above-mentioned desulfurizer, described desulfurizer also comprises that pulsed multilayer becomes flexible system, and it comprises:
Peripheral air feed system, in order to provide compressed air;
Multi-layer air coil pipe, be connected with described peripheral air feed system in order to pass into compressed air in described reverse taper discharge device, described multi-layer air coil pipe is 6～9 layers, and every layer of air coil pipe comprises around the supervisor and the some described supervisor arms upper and that extend to described reverse taper discharge device inside that is connected to that are arranged in described reverse taper discharge device internal side wall; And
Control system passes into compressed air in order to control described multi-layer air coil pipe in described reverse taper discharge device, comprises the sequence switch valve that is arranged on described supervisor and in order to control the time schedule controller of described sequence switch valve.
In above-mentioned desulfurizer, the confession wind pressure of described peripheral air feed system is 0.8～1.0MPa.
In above-mentioned desulfurizer, described supervisor is set in qually spaced in the internal side wall of described reverse taper discharge device.
In above-mentioned desulfurizer, described time schedule controller is controlled described multi-layer air coil pipe and in described reverse taper discharge device, is passed into compressed air successively, and the time interval of adjacent vacant gas coil pipe ventilation is 20～60s, and pass into the compressed-air actuated time is 1～4s at every turn.
The H that contains provided by the invention
2s, COS, CS
2desulphurization system Deng the sour gas of gas comprises desulfurizer, and this desulfurizer adopts the desulfurizer described in above technical scheme any one.
In above-mentioned desulphurization system, also comprise the equipment for separating liquid from solid for separating of solid sulfur, the charging aperture of described equipment for separating liquid from solid is connected with the reverse taper discharge device of described desulfurizer, and the liquid outlet opening of described equipment for separating liquid from solid is connected with the cylindrical shell reaction unit of described desulfurizer.
Sulfur method provided by the invention has the following advantages:
(1) adopt the course of reaction of hydrolysis+oxidation, can effectively remove wherein contained H
2s, COS, CS
2deng major impurity, the gas after desulfurization meets environmental requirement, can directly discharge, and the sulphur in sour gas can effectively be reclaimed with solid sulfur form.
(2) adopt the hydrolysis of MnO catalysis sour gas, without extra reaction unit, can in same reactor, complete with oxidation reaction, save reaction unit and shortened the bulk devulcanization reaction time, this hydrolysis is without high temperature, energy consumption is low, security good, and catalyst can Reusability, and desulphurization cost reduces greatly.
Desulfurizer provided by the invention has the following advantages:
(1) hydrolysis can carry out with oxidation reaction in same reactor, has shortened the bulk devulcanization reaction time, and the time of staying of 5-10 second can complete whole sweetening process.
(2) in desulfurizer provided by the invention, reverse taper discharge device is arranged at below, degas zone, the discharge route of sulphur slurries shortens, avoided it in discharge device, to form whirlpool, being conducive to material discharges smoothly, and reverse taper discharge device of the present invention has reduced device volume, has further saved the manufacturing cost of desulfurizer.
(3) in desulfurizer provided by the invention, reverse taper discharge device also has the loosening system of controlled pulsed multilayer, by passing into wherein compressed air, can further avoid the accumulation of sulphur slurries, it is discharged smoothly, thereby further guaranteed the smooth running of whole desulfurizer.
Sulfur method provided by the invention, desulfurizer and desulphurization system desulfuration efficiency are high, low cost of manufacture, have very much industrial applications and are worth.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of desulphurization system of the present invention, wherein, and the profile that desulfurizer cylindrical shell reaction unit is fanning;
Fig. 2 is the top plan view of desulfurizer of the present invention;
Fig. 3 is the profile that comprises the reverse taper discharge device of the loosening system of pulsed multilayer of the present invention;
Wherein, description of reference numerals is as follows:
1, cylindrical shell reaction unit; 101, uptake zone; 102 (comprising 102-1～102-4), reaction zone; 103, degas zone; 2, reverse taper discharge device; 201, peripheral air feed system; 202, multi-layer air coil pipe; 203, supervisor; 204, arm; 205, sequence switch valve; 206, time schedule controller; 3, MnO catalyst bed; 4, overflow plate; 5, deflection plate; 6, the loosening system of pulsed multilayer; 7, equipment for separating liquid from solid.
The specific embodiment
First aspect of the present invention provides a kind of H of containing
2s, COS, CS
2deng the sulfur method of the sour gas of gas, its desulfurization conversion process is: first under MnO catalyst exists, make sour gas generation hydrolysis to be desulfurization, the sour gas after hydrolysis is again at liquid phase Fe
3+under the catalytic action of complexing agent, make H wherein
2s is that sulphur is discharged through oxygen-containing gas oxidation conversion, completes thus the desulfurization of described sour gas.
Sulfur method provided by the invention adopts following reaction mechanism: first, sour gas first under MnO catalyst action by the COS containing in sour gas, CS
2deng organic sulfur composition, be hydrolyzed to H
2s, the H of generation
2contained H in S and sour gas
2s is again at liquid phase Fe
3+under complexing agent catalytic action, be oxidized-reduce conversion reaction and change simple substance sulphur into, removed H
2s, COS, CS
2tail gas can directly discharge, simple substance sulphur recoverable.
Wherein, shown in the following equation of course of reaction:
(1) COS, CS in sour gas
2hydrolysis (in the situation that catalyst exists) Deng organic sulfur:
COS (gas)+H
2o (liquid) ← → CO
2(gas)+H
2s (gas)
CS
2(gas)+2H
2o (liquid) ← → 2H
2s (gas)+CO
2(gas)
(2) H in sour gas
2the oxidation reaction of S:
H
2s (gas)+H
2o (liquid) ← → H
2s (solution)+H
2o (solution)
H
2s (solution) ← → H
++ HS
-
HS
-+2Fe
3+→2Fe
2++H
++S
0
H
2s (gas)+2Fe
3+→ 2H
++ S
0+ 2Fe
2+
Fe
3+the regenerative response of complexing agent is:
1/2O
2(gas)+H
2o → 1/2O
2(liquid)+H
2o
1/2O
2(liquid)+H
2o+2Fe
2+→ 2OH-+2Fe
3+
Overall reaction equation is:
H
2S+1/2O
2→H
2O+S
0
At present, in Coal Chemical Industry sour gas, mainly comprise H
2s, COS, CS
2deng sulfurous gas, in addition, also contain micro-SO
2, NH
3, CO
2and micromolecular saturated alkane, as CH
4deng.While adopting sulfur method of the present invention, in hydrolysing step, little molecule saturated alkane can also be reduced to the CO of suitable discharge
2, removed little molecule saturated alkane impurity simultaneously.
According in sulfur method of the present invention embodiment, the reaction temperature of desulfurization conversion process is 40～60 ℃.Inventor finds under study for action, and hydrolysis under this reaction temperature, oxidation reaction effect are best, also can not make the water in reaction unit unbalance, and energy consumption is low, at the temperature of too high or height, all cannot reach this effect.One preferred embodiment in, the reaction temperature of sweetening process is 47～53 ℃.In sulfur method of the present invention, hydrolysis and H
2the oxidation reaction of S can be carried out under same temperature, without high temperature, has significantly reduced energy consumption.
According in sulfur method of the present invention embodiment, the time of desulfurization conversion process is 5～10 seconds.In sulfur method of the present invention, hydrolysis and H
2the oxidation reaction of S can be carried out in integrated reactor, and hydrolysis efficiency is higher, therefore can obviously shorten material in the reaction time of reactor, has effectively improved desulfuration efficiency.
According in sulfur method of the present invention embodiment, for being oxidized H
2in the oxygen-containing gas of S, the percent by volume of oxygen is 10～100%, can be for any content, for cost consideration, one preferred embodiment in, oxygen-containing gas can be selected air.
Second aspect of the present invention provides a kind of H of containing
2s, COS, CS
2desulfurizer Deng the sour gas of gas, as depicted in figs. 1 and 2, this desulfurizer comprises cylindrical shell reaction unit 1 and the reverse taper discharge device 2 that is arranged at described cylindrical shell reaction unit 1 bottom, and described cylindrical shell reaction unit 1 inside is divided into fan-shaped uptake zone 101, reaction zone 102 (region of 102-1 to 102-4 in figure) and degas zone 103 successively.Described uptake zone 101 is for the hydrolysis of described sour gas, and described reaction zone 102 is for the oxidation reaction of described sour gas, and described degas zone 103 is for discharging the tail gas after gained sulphur slurries and desulfurization; Wherein, described uptake zone 101 is provided with MnO catalyst bed 3, described reverse taper discharge device 2 is arranged on 103 belows, described degas zone, its end face circumference is inscribed within the bottom surface circumference of described cylindrical shell reaction unit 1, and the end face radius of described reverse taper discharge device 2 and the bottom surface radius ratio of described cylindrical shell reaction unit 1 are 0.65～0.85:1.
Specifically, as shown in Figure 2, cylindrical shell reaction unit 1 is divided into uptake zone 101 for sour gas hydrolysis, for the reaction zone 102 of sour gas oxidation reaction and for discharging the degas zone 103 of tail gas after gained sulphur slurries and desulfurization.Because reaction zone 102 relates to H
2the oxidation of S, Fe
3+a plurality of reactions steps such as regeneration of complexing agent catalyst, therefore can further be divided into H by reaction zone 102
2s oxidation reaction zone is if 102-1 and complexing agent renewing zone are as 102-2 to 102-4, and the division of reaction zone is not limited to this, can be adjusted arbitrarily by those skilled in the art.Cylindrical shell reaction unit can adopt existing device, as the circulating desulfurizer of patent US 5126118 records.As shown in Figure 1, different conversion zones is separated by overflow plate 4 and deflection plate 5, and in Fig. 2, straight arrow represents that solution is at reaction unit deflection plate bottom advection, and curved arrow represents that solution is by the top overflow of reaction unit overflow plate.Wherein, uptake zone 101 is provided with one deck MnO catalyst bed 3, and sour gas is by rear generation hydrolysis.Cylindrical shell reaction unit 1 of the present invention is by increasing therein the MnO catalyst bed of uptake zone, the hydrolysis of sour gas, oxidation two-step reaction can be placed in to same reaction unit and complete, reduced chemical industry equipment quantity, and Reaction time shorten greatly, 5-10 can complete the desulfurization conversion process of sour gas second, and desulfuration efficiency obviously improves.
As shown in Figure 1, different from existing reverse taper discharge device, the reverse taper discharge device 2 of desulfurizer of the present invention is not " concentric circles " structure with cylindrical shell reaction unit 1, reverse taper discharge device 2 is arranged on the below of degas zone 103, as shown in Figure 2, its end face circumference is inscribed within the bottom surface circumference of cylindrical shell reaction unit 1, and radius is less than the bottom surface radius of cylindrical shell reaction unit, can reduce thus reverse taper discharge device volume.In addition, the tap web of reverse taper discharge device 2 is under degas zone 103, and sulphur slurries are from degas zone 103 flows down, and discharge the bottom that can flow directly into reverse taper discharge device 2, reduce or avoided the generation of whirlpool, thereby be difficult for occurring the obstruction of discharge device.According in desulfurizer of the present invention embodiment, the end face radius of reverse taper discharge device 2 and the bottom surface radius ratio of cylindrical shell reaction unit 1 are 0.65～0.85:1; In this radius proportion, can make the tap web of reverse taper discharge device 2 not depart from the scope of degas zone 103, also can not make the volume of reverse taper discharge device 2 greatly to making sulphur slurries form whirlpool.One preferred embodiment in, the end face radius of reverse taper discharge device 2 and the bottom surface radius ratio of cylindrical shell reaction unit 2 are 0.73～0.78:1.
As shown in Figure 1, during above-mentioned desulfurizer work, sour gas to be desulfurization enters 101 bottoms, uptake zone with bubbling form, with Fe
3+enveloping agent solution mixes rapidly backward upper flowing, when through MnO beds 3, and the COS in gas, CS
2deng the catalyzed H that is hydrolyzed to of sour gas
2s, also can discharge a small amount of CO after the little molecule saturated alkane hydrolysis in sour gas
2, therefore can increase the content of gas in liquid, strengthen the buoyancy of gas to liquid, be conducive to the solution circulation in reaction unit 1.Sour gas after hydrolysis enters reaction zone 102, and H occurs therein
2the oxidation of S and Fe
2+after the series reaction such as the regeneration of complexing agent, the sulphur generating forms sulphur slurries and 103 via reverse taper discharge device 2, discharges from degas zone together with enveloping agent solution, tail gas after desulfurization can directly discharge owing to meeting discharge standard, has completed thus the sweetening process of sour gas.
According in desulfurizer of the present invention embodiment, above-mentioned desulfurizer also comprises that pulsed multilayer becomes flexible system 6, and as shown in Figure 3, the loosening system of this pulsed multilayer comprises:
Peripheral air feed system 201, in order to provide compressed air;
Multi-layer air coil pipe 202, be connected with peripheral air feed system in order to pass into compressed air in reverse taper discharge device, multi-layer air coil pipe can be divided into 6～9 layers, and every layer of air coil pipe comprises around the supervisor 203 and the some supervisor's arms 204 upper and that extend to reverse taper discharge device inside that is connected to that are arranged in reverse taper discharge device internal side wall; And
Control system passes into compressed air in order to control multi-layer air coil pipe in reverse taper discharge device, comprises the sequence switch valve 205 that is arranged on supervisor and in order to control the time schedule controller 206 of described sequence switch valve.
During the loosening system works of above-mentioned pulsed multilayer, can be by time schedule controller 206 by controlling the sequence switch valve 205 on each layer of air pipe dish, thereby with pulsed, pass into compressed air in supervisor 203, compressed air sprays compressed air by each arm 204 again in reverse taper discharge device, because compressed air can produce loosening effect to the slurries that contain solid sulfur, thereby can further avoid sulphur in reverse taper discharge device, pile up and stop up.
According in desulfurizer of the present invention embodiment, peripheral air feed system for wind pressure, can be 0.8～1.0MPa.
According in desulfurizer of the present invention embodiment, be responsible for 203 and be set in qually spaced in the internal side wall of reverse taper discharge device.
According in desulfurizer of the present invention embodiment, arm 204 is uniformly set on supervisor 203, and the quantity of arm can be adjusted according to actual needs.
The loosening system of pulsed multilayer can arrange compressed-air actuated mode and the time of passing into according to actual needs, to guarantee that sulphur slurries do not pile up, stop up discharge gate.According in desulfurizer of the present invention embodiment, time schedule controller 206 can be controlled multi-layer air coil pipe and in reverse taper discharge device, pass into compressed air successively, the time interval of adjacent vacant gas coil pipe ventilation can be 20～60s, and passing into the compressed-air actuated time can be 1～4s at every turn.According to common Acidic Gas Treating, need, pass into compressed air can to continue to pass into 30～60min be one-period at every turn.
Time schedule controller in the loosening system of above-mentioned pulsed multilayer, sequence switch valve etc. can adopt existing control technology, and the present invention does not limit.
The 3rd aspect of the present invention provides a kind of H of containing
2s, COS, CS
2deng the desulphurization system of the sour gas of gas, this desulphurization system at least comprises any desulfurizer provided by the invention.
According in desulphurization system of the present invention embodiment, as shown in Figure 1, desulphurization system also comprises the equipment for separating liquid from solid 7 for separating of solid sulfur, the charging aperture of equipment for separating liquid from solid 7 is connected with the reverse taper discharge device of desulfurizer, liquid outlet opening is connected with the cylindrical shell reaction unit of desulfurizer, isolated Fe
3+enveloping agent solution returns to cylindrical shell reaction unit 1 and recycles.One preferred embodiment in, equipment for separating liquid from solid 7 can be selected filter press.
Desulfurizer provided by the invention is not limited to said system, applicable to any desulphurization system of same domain, as the process system of patent CN 201310472099.0 records.
For making the object, technical solutions and advantages of the present invention clearer, will be further described below the technical scheme of exemplary embodiment of the present invention.
In following examples, Fe
3+complexing agent is selected commercially available EDTA and polysaccharide Composite Double component ligand.
The desulphurization system of using in following examples can be with reference to Chinese patent CN 201310472099.0, specifically, desulphurization system according to acid gas stream to comprising successively a minute flow container, heat exchanger, desulfurizer of the present invention and filter press.Divide flow container for carrying out gas-liquid separation containing the high sour gas of amount of liquid, separated liquid is discharged, and gas enters next step flow process, if sour gas is lower through other PROCESS FOR TREATMENT or content liquid own, also can omit this step, a minute flow container can adopt the normally used any kind in this area.Heat exchanger is for heating sour gas, and to guarantee to enter the sour gas temperature in desulfurizer, by heat exchanger heat exchange, sour gas intake air temperature need be controlled between 40-60 ℃, and too high or too low intake air temperature can make the water in reaction unit unbalance.Filter press carries out separation for the sulphur slurries that desulfurizer is discharged, and obtains dry sulfur product, and catalyst liquid circulation is returned in reaction unit and recycled.Desulfurizer is also connected with for passing into the air blast of oxygen-containing gas, and for mending and add Fe in course of reaction
3+the chemicals storage tank of enveloping agent solution, by measuring pump by the Fe in chemicals storage tank
3+enveloping agent solution is delivered in desulfurizer, to maintain Fe in desulfurizer
3+the amount of complexing agent.Between desulfurizer and filter press, also include two circulating pumps in parallel for the convey materials that circulates.For guaranteeing the temperature in reaction unit in desulfurizer, the reaction unit part of desulfurizer is also connected with auto-converting type heat exchanger, by circulating pump, the solution in cylindrical shell reaction unit is circulated to regulate temperature.
Embodiment 1
Adopt above-mentioned desulphurization system to process certain company's sour gas, sour gas flow is 731.58Nm
3/ h, its component by volume percentage is H
2s content 18.26%, COS content is 2.67%, CS
2content is 1.28%, and other components are water and CO
2.
First this sour gas is passed into minute flow container carries out separatory and isolates water wherein, gas after separatory passes into and in heat exchanger, carries out heat exchange, making Outlet Gas Temperature is 47 ℃, meets the temperature range of solution in desulfurizer, and is passed in the reaction unit of desulfurizer and Fe
3+redox reaction is carried out in enveloping agent solution mixing.Sour gas enters the bottom of reaction unit uptake zone with the form of bubbling, and upwards flows with solution, first passes through reducing catalyst bed (MnO) and carries out COS, CS
2deng hydrolysis, H
2s is absorbed by solution rapidly and transforms, and the time of staying of sour gas in reaction unit is about 6s.The sulphur generating forms slurries together with liquid catalyst and is entered in reverse taper discharge device by degas zone.
In course of reaction, utilize continuously measuring pump in reaction unit, to add Fe from chemicals storage tank simultaneously
3+complexing agent, addition is 44.69kg/h.Meanwhile, utilize air blast to blast containing oxygen 42% gas in reaction unit, and the air inlet ratio of oxygen-containing gas and sour gas is 4.4:1.In order to maintain the temperature of solution in reaction unit, reaction unit is also connected with circulating pump and auto-converting type heat exchanger, and the internal circulating load of circulating pump is 418.18m
3/ h, the heat exchange amount of auto-converting type heat exchanger is 82.45kw, the temperature that maintains solution in reaction unit of take is 52 ℃.
The end face radius of the reverse taper discharge device of desulfurizer and the bottom surface radius ratio of reaction unit are 0.75:1, reverse taper discharge device is also provided with the loosening system of pulsed multilayer, be provided with 6 layer of air pipe dishes, loosening medium adopts 0.8MPa (g) compressed air, and by time schedule controller, control compressed air and pass into, the time interval of adjacent vacant gas coil pipe ventilation is about 50s, every layer of air coil pipe passes into the compressed-air actuated time at every turn and is about 3s, continue to pass into 30min is one-period at every turn, controls ventilation cycle interval so that reverse taper discharge device discharge is smooth and easy, nothing is piled up.Sulphur slurries flow out from reverse taper discharge device, by two circulating pumps in parallel, to slurries, provide power, slurries are flowed in filter press and carry out Separation of Solid and Liquid, separated complete solid sulfur is collected, filtrate is back in reaction unit and recycles, and so far sulfur removal technology circular response completes.
Tail gas after desulfurization is processed can directly discharge, H in emission
2the content of S is 10.06ppm, COS and CS
2content all below 10ppm, meet the requirement of < < GB 14554-93 emission standard for odor pollutants > >, sulfur recovery rate is 99.96%.And the running of this desulphurization system is stable, can continuous and steady operation 2 years, without sulphur solid accumulation.
Embodiment 2
Adopt above-mentioned desulphurization system to process certain Coal Chemical Industry sour gas, sour gas flow is 1497.14Nm
3/ h, its component by volume percentage is H
2s content 42.22%, COS content is 2.92%, CS
2content is 1.58%, and other components are water and CO
2.
First this sour gas is passed into minute flow container and carry out separatory, the gas after separatory passes in heat exchanger and carries out heat exchange, and Outlet Gas Temperature is 45 ℃, meets the temperature range of solution in desulfurizer, and is passed in the reaction unit of desulfurizer and Fe
3+redox reaction is carried out in enveloping agent solution mixing.Sour gas enters the bottom of reaction unit uptake zone with the form of bubbling, and upwards flows with solution, first passes through reducing catalyst bed (MnO) and carries out COS, CS
2deng hydrolysis, H
2s is absorbed by solution rapidly and transforms, and the time of staying of sour gas in reaction unit 1 is about 8s.The sulphur generating forms slurries together with liquid catalyst and is entered in reverse taper discharge device by degas zone.
In course of reaction, utilize continuously measuring pump to add Fe from chemicals storage tank 10 simultaneously
3+complexing agent, addition is 54.11kg/h.Meanwhile, utilize air blast to blast air in reaction unit, and the air inlet ratio of air and sour gas is 8.8:1.In order to maintain the temperature of solution in reaction unit, reaction unit is also connected with circulating pump and auto-converting type heat exchanger, and the internal circulating load of circulating pump is 148m
3/ h, the heat exchange amount of auto-converting type heat exchanger is 126.98kw, the temperature that maintains solution in reaction unit of take is 49 ℃.
The end face radius of the reverse taper discharge device of desulfurizer and the bottom surface radius ratio of reaction unit are 0.76:1, reverse taper discharge device is also provided with the loosening system of pulsed multilayer, be provided with 6 layer of air pipe dishes, loosening medium adopts 0.9MPa (g) compressed air, and by time schedule controller, control compressed air and pass into, the time interval of adjacent vacant gas coil pipe ventilation is about 30s, every layer of air coil pipe passes into the compressed-air actuated time at every turn and is about 4s, continue to pass into 50min is one-period at every turn, controls ventilation cycle interval so that reverse taper discharge device discharge is smooth and easy, nothing is piled up.Sulphur slurries flow out from reverse taper discharge device, by two circulating pumps in parallel, to slurries, provide power, slurries are flowed in filter press and carry out Separation of Solid and Liquid, separated complete solid sulfur is collected, filtrate is back in reaction unit and recycles, and so far sulfur removal technology circular response completes.
Tail gas after desulfurization is processed can directly discharge, H in emission
2the content of S is 9.91ppm, COS and CS
2content all below 10ppm, meet the requirement of < < GB 14554-93 emission standard for odor pollutants > >, sulfur recovery rate is 99.99%.And the running of this desulphurization system is stable, can continuous and steady operation 2 years, without sulphur solid accumulation.
As can be seen from the above-described embodiment: by sulfur method provided by the invention and desulphurization system, sour gas is carried out after desulfurization processing, gas meets existing discharge standard requirement, and can effectively reclaim sulphur wherein, and system run all right, efficiency is high, cost is low, is suitable for large-scale application.
Although for the present invention is described, the preferred embodiments of the invention are disclosed, but it will be understood by those of skill in the art that in the situation that do not depart from design of the present invention and the scope that claims limit, can make various modifications, interpolation and replacement to the present invention.
Claims (12)
1. one kind contains H
2s, COS, CS
2deng the sulfur method of the sour gas of gas, its desulfurization conversion process is: first under MnO catalytic action, make described sour gas generation hydrolysis, the sour gas after hydrolysis is again at liquid phase Fe
3+under complexing agent catalytic action, make H wherein
2s is that sulphur is discharged through oxygen-containing gas oxidation transformation.
2. sulfur method according to claim 1, is characterized in that, the reaction temperature of described desulfurization conversion process is 40～60 ℃, is preferably 47～53 ℃.
3. sulfur method according to claim 1 and 2, is characterized in that, the time of described desulfurization conversion process is 5～10 seconds.
4. according to the sulfur method described in claim 1-3 any one, it is characterized in that, in described oxygen-containing gas, the percent by volume of oxygen is 10～100%.
5. one kind contains H
2s, COS, CS
2desulfurizer Deng the sour gas of gas, comprise cylindrical shell reaction unit and the reverse taper discharge device that is arranged at described cylindrical shell reaction unit bottom, it is characterized in that, described cylindrical shell reaction unit inside is divided into fan-shaped uptake zone, reaction zone and degas zone successively, described uptake zone is for the hydrolysis of described sour gas, described reaction zone is for the oxidation reaction of described sour gas, and described degas zone is for discharging the tail gas after gained sulphur slurries and desulfurization; Wherein, described uptake zone is provided with MnO catalyst bed, described reverse taper discharge device is arranged on below, described degas zone, its end face circumference is inscribed within the bottom surface circumference of described cylindrical shell reaction unit, and the end face radius of described reverse taper discharge device and the bottom surface radius ratio of described cylindrical shell reaction unit are 0.65～0.85:1.
6. desulfurizer according to claim 5, is characterized in that, the end face radius of described reverse taper discharge device and the bottom surface radius ratio of described cylindrical shell reaction unit are 0.73～0.78:1.
7. according to the desulfurizer described in claim 5 or 6, it is characterized in that, described desulfurizer also comprises that pulsed multilayer becomes flexible system, and it comprises:
Peripheral air feed system, in order to provide compressed air;
Multi-layer air coil pipe, be connected with described peripheral air feed system in order to pass into compressed air in described reverse taper discharge device, described multi-layer air coil pipe is 6～9 layers, and every layer of air coil pipe comprises around the supervisor and the some described supervisor arms upper and that extend to described reverse taper discharge device inside that is connected to that are arranged in described reverse taper discharge device internal side wall; And
Control system passes into compressed air in order to control described multi-layer air coil pipe in described reverse taper discharge device, comprises the sequence switch valve that is arranged on described supervisor and in order to control the time schedule controller of described sequence switch valve.
8. desulfurizer according to claim 7, is characterized in that, the confession wind pressure of described peripheral air feed system is 0.8～1.0MPa.
9. desulfurizer according to claim 7, is characterized in that, described supervisor is set in qually spaced in the internal side wall of described reverse taper discharge device.
10. desulfurizer according to claim 7, it is characterized in that, described time schedule controller is controlled described multi-layer air coil pipe and in described reverse taper discharge device, is passed into compressed air successively, the time interval of adjacent vacant gas coil pipe ventilation is 20～60s, and pass into the compressed-air actuated time is 1～4s at every turn.
11. 1 kinds contain H
2s, COS, CS
2desulphurization system Deng the sour gas of gas, is characterized in that, adopts the desulfurizer described in claim 5-10 any one in described desulphurization system.
12. desulphurization systems according to claim 11, it is characterized in that, described desulphurization system also comprises the equipment for separating liquid from solid for separating of solid sulfur, the charging aperture of described equipment for separating liquid from solid is connected with the reverse taper discharge device of described desulfurizer, and the liquid outlet opening of described equipment for separating liquid from solid is connected with the cylindrical shell reaction unit of described desulfurizer.
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| CN106621764A (en) * | 2016-11-25 | 2017-05-10 | 中南大学 | Device for purifying COS in aluminum electrolysis flue gas |
| CN108970380A (en) * | 2018-09-07 | 2018-12-11 | 宜宾丝丽雅股份有限公司 | A kind of method and device removing hydrogen sulfide in exhaust gas with continuous oxidation |
| CN110835556A (en) * | 2019-11-29 | 2020-02-25 | 中冶南方都市环保工程技术股份有限公司 | Blast furnace gas wet desulphurization system and method |
| CN112457889A (en) * | 2020-11-04 | 2021-03-09 | 新兴河北工程技术有限公司 | Blast furnace coal hydroxy sulphur catalytic conversion tower |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106621764A (en) * | 2016-11-25 | 2017-05-10 | 中南大学 | Device for purifying COS in aluminum electrolysis flue gas |
| CN108970380A (en) * | 2018-09-07 | 2018-12-11 | 宜宾丝丽雅股份有限公司 | A kind of method and device removing hydrogen sulfide in exhaust gas with continuous oxidation |
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| CN110835556A (en) * | 2019-11-29 | 2020-02-25 | 中冶南方都市环保工程技术股份有限公司 | Blast furnace gas wet desulphurization system and method |
| CN112457889A (en) * | 2020-11-04 | 2021-03-09 | 新兴河北工程技术有限公司 | Blast furnace coal hydroxy sulphur catalytic conversion tower |
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|---|---|
| CN104190221B (en) | 2016-03-30 |
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