CN104190221B - Containing H 2s, COS, CS 2deng sulfur method, the Apparatus and system of the sour gas of gas - Google Patents
Containing H 2s, COS, CS 2deng sulfur method, the Apparatus and system of the sour gas of gas Download PDFInfo
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Abstract
The invention provides a kind of containing 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 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.Present invention also offers a kind of containing H
2s, COS, CS
2deng the sour gas of gas desulfurizer and comprise the desulphurization system of this desulfurizer.Two-step reaction can be placed in same reaction unit by sulfur method provided by the invention to carry out, consuming time short, efficiency is high, desulfurizer provided by the invention and desulphurization system desulfuration efficiency is high, low cost of manufacture, and not easily block, stable, there is industrial applications and be worth.
Description
Technical field
The present invention relates to commercial acid gas disposal field, be specifically related to a kind of containing H
2s, COS, CS
2deng the sulfur method of the sour gas of gas, desulfurizer and the desulphurization system comprising described desulfurizer.
Background technology
Coal chemical industry is prevailing in recent years, and coal liquifaction, coal preparing natural gas become the major industry of coal chemical industry.As everyone knows, in coal, the content of sulphur is higher, causes in tail gas containing more H
2s, SO
2deng sulphur-containing exhaust gas, cause serious pollution to environment, Coal Chemical Industry tail gas desulfurization technology becomes study hotspot.
Current desulfur technology can be divided into a few class 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 the reaction of Crouse is more complicated, be reversible reaction, conversion ratio is by the restriction of thermodynamical equilibrium under reaction temperature, and the large quantity of moisture generated in course of reaction is difficult to be separated from Process Gas, makes H
2s concentration constantly declines, and so more limits balance and moves to the direction generating sulphur.Due to the problems that Claus method self exists, and the raising day by day of current environmental requirement, the discharge standard of Claus method can not meet present environmental requirement, thus will certainly replace by novel energy-conservation, convenient, sulfur removal technology that the rate of recovery is high.
(2) biological desulphurization: be utilize microorganism or the enzymatic sulfur-containing compound contained by it, make the process that the sulphur contained by it discharges.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 comparatively slow, and biological inoculum is more loaded down with trivial details in the process selected, and in plant running process of being everlasting, occurs the desulfuration efficiency decline phenomenon of unknown cause, becomes the obstruction limiting its spread.
(3) wet oxidation desulfurization hydrogen: these class methods are chemical reaction desulfurization, comprise ammoniacal liquor liquid catalytic, tannin process, KCA method, complex iron etc., wherein of greatest concern with complex iron, it not only has excellent catalytic oxidation ability, and cheap.
Patent US5126118 proposes a kind of employing Fe
3+, V
5+the circulating sulfur removal technology of ionic catalyst and device, but optimization is not given for technological parameter index.
Patent CN200310112779.8 proposes a kind of method using removing sulfide from CO 2 enriched gas by complex iron, but its injection taked absorbs string fluidized-bed process, and device is comparatively complicated.
Patent CN201310472099.0 proposes 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 to be hydrogen sulfide by organic sulfur and sulphur dioxide reduction, need extra hydrogenation reactor, processing cost is higher, and hydrogenation step needs the high temperature of more than 200 DEG C, and energy consumption is large, and its technological parameter index does not give optimization yet.In addition, in the Complexing Iron liquid phase oxidation reduction and desulfurization device that this patent uses, reverse taper discharge device and the cylindrical shell reactor of bottom are concentric structure, and the discharge gate (degas zone) of Complexing Iron liquid phase oxidation reduction and desulfurization device is not positioned at the center of described devulcanizer usually, therefore the discharge gate (tap web position) of reverse taper discharge device is not immediately below devulcanizer discharge gate, in addition volume is too huge, when sulphur slurries in devulcanizer are discharged, easily whirlpool is formed by the inwall landslide of reverse taper discharge device, thus sulfur plug discharge device can be caused, whole sweetening process is caused to lose efficacy.
Summary of the invention
For overcoming the defect existed in existing desulfurization process, an object of the present invention is to provide a kind of containing H
2s, COS, CS
2deng the sulfur method of the sour gas of gas.
Another object of the present invention is to provide a kind of containing H
2s, COS, CS
2deng the desulfurizer of the sour gas of gas.
An also object of the present invention is to provide a kind of containing H
2s, COS, CS
2deng the desulphurization system of the sour gas of gas.
Provided by the invention containing H
2s, COS, CS
2deng the sulfur method of the sour gas of gas, its desulfurization conversion process is: under MnO catalytic action, first 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 DEG C, is preferably 47 ~ 53 DEG C.
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%.
Provided by the invention containing H
2s, COS, CS
2deng the desulfurizer of the sour gas of gas, comprise cylindrical shell reaction unit and the reverse taper discharge device being 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 used for the hydrolysis of described sour gas, described reaction zone is used 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 top circumferential is inscribed within the base 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 pulsed multilayer and loosens 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 be arranged in described reverse taper discharge device internal side wall and some arms being connected to described supervisor and above and to described reverse taper discharge device inside extending; And
Control system, passes into compressed air in order to control described multi-layer air coil pipe, comprises and be arranged on the sequence switch valve on described supervisor and the time schedule controller in order to control described sequence switch valve in described reverse taper discharge device.
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 controls described multi-layer air coil pipe and in described reverse taper discharge device, passes 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.
Provided by the invention containing H
2s, COS, CS
2desulphurization system Deng the sour gas of gas comprises desulfurizer, and this desulfurizer adopts the desulfurizer described in above any one of technical scheme.
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, effectively can 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 effectively can be reclaimed with solid sulfur form.
(2) hydrolysis of MnO catalysis sour gas is adopted, without the need to extra reaction unit, can complete in same reactor with oxidation reaction, save reaction unit and shorten the bulk devulcanization reaction time, this hydrolysis is without the need to 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 in same reactor with oxidation reaction, shortens 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, avoid it and form whirlpool in discharge device, be conducive to material to discharge smoothly, and reverse taper discharge device of the present invention reduces device volume, further saves the manufacturing cost of desulfurizer.
(3) in desulfurizer provided by the invention, reverse taper discharge device also has controlled pulsed multilayer and loosens system, by passing into compressed air wherein, the accumulation of sulphur slurries can be avoided further, make it discharge smoothly, thus further ensure the smooth operation 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, and wherein, desulfurizer cylindrical shell reaction unit is the profile of fanning;
Fig. 2 is the top plan view of desulfurizer of the present invention;
Fig. 3 of the present inventionly comprises the profile that pulsed multilayer loosens the reverse taper discharge device of system;
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, be responsible for; 204, arm; 205, sequence switch valve; 206, time schedule controller; 3, MnO catalyst bed; 4, overflow plate; 5, deflection plate; 6, pulsed multilayer loosens system; 7, equipment for separating liquid from solid.
Detailed description of the invention
First aspect of the present invention provides a kind of containing H
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 the desulfurization of described sour gas thus.
Sulfur method provided by the invention adopts following reaction mechanism: first, COS, CS that sour gas first will contain in sour gas under MnO catalyst action
2h is hydrolyzed to Deng organic sulphur components
2s, the H of generation
2h contained in S and sour gas
2s is again at liquid phase Fe
3+carry out oxidationreduction conversion reaction under complexing agent catalytic action and change simple substance sulphur into, eliminate 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 presence of a catalyst) 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 H is comprised
2s, COS, CS
2deng sulfurous gas, in addition, the SO also containing trace
2, NH
3, CO
2and micromolecular saturated alkane, as CH
4deng.When adopting sulfur method of the present invention, in hydrolysing step, Small molecular saturated alkane can also be reduced to the CO of suitable discharge
2, eliminate Small molecular saturated alkane impurity simultaneously.
In an embodiment of sulfur method according to the present invention, the reaction temperature of desulfurization conversion process is 40 ~ 60 DEG C.Inventor finds under study for action, and be hydrolyzed under this reaction temperature, oxidation reaction effect is best, the water in reaction unit also can not be made unbalance, and energy consumption is low, all cannot reach this effect at the temperature of too high or height.In one preferred embodiment, the reaction temperature of sweetening process is 47 ~ 53 DEG C.In inventive desulfurization method, hydrolysis and H
2the oxidation reaction of S can be carried out at the same temperature, without the need to high temperature, significantly decreases energy consumption.
In an embodiment of sulfur method according to the present invention, the time of desulfurization conversion process is 5 ~ 10 seconds.In inventive desulfurization method, hydrolysis and H
2the oxidation reaction of S can be carried out in integrated reactor, and hydrolysis efficiency is higher, therefore obviously can shorten the reaction time of material at reactor, effectively improve desulfuration efficiency.
In an embodiment of sulfur method according to the present invention, for being oxidized H
2in the oxygen-containing gas of S, the percent by volume of oxygen is 10 ~ 100%, can be any content, and for cost consideration, in one preferred embodiment, oxygen-containing gas can select air.
Second aspect of the present invention provides a kind of containing H
2s, COS, CS
2deng the desulfurizer of the sour gas of gas, as depicted in figs. 1 and 2, this desulfurizer comprises cylindrical shell reaction unit 1 and is arranged at the reverse taper discharge device 2 of 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 the 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 below described degas zone 103, its top circumferential is inscribed within the base 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 the uptake zone 101 for sour gas hydrolysis, the reaction zone 102 for sour gas oxidation reaction and the degas zone 103 for discharging tail gas after gained sulphur slurries and desulfurization.Because reaction zone 102 relates to H
2the oxidation of S, Fe
3+multiple reactions steps such as the regeneration of complexing agent catalyst, therefore can be divided into H by reaction zone 102 further
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 thereto, and can be adjusted arbitrarily by those skilled in the art.Cylindrical shell reaction unit can adopt existing device, as the circulating desulfurizer that patent US5126118 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 solution advection bottom reaction unit deflection plate, 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 the MnO catalyst bed of uptake zone wherein, the hydrolysis of sour gas, oxidation two-step reaction can be placed in same reaction unit and complete, decrease chemical industry equipment quantity, and can Reaction time shorten greatly, 5-10 can complete the desulfurization conversion process of sour gas second, and desulfuration efficiency significantly improves.
As shown in Figure 1, different from existing reverse taper discharge device, reverse taper discharge device 2 and the cylindrical shell reaction unit 1 of inventive desulfurization device are not " concentric circles " structure, reverse taper discharge device 2 is arranged on the below of degas zone 103, as shown in Figure 2, its top circumferential is inscribed within the base circumference of cylindrical shell reaction unit 1, and radius is less than the bottom surface radius of cylindrical shell reaction unit, can reduce reverse taper discharge device volume thus.In addition, the tap web of reverse taper discharge device 2 is immediately below degas zone 103, and after sulphur slurries flow down from degas zone 103, the bottom that can flow directly into reverse taper discharge device 2 is discharged, reduce or avoid the generation of whirlpool, thus the blocking of discharge device not easily occurs.In an embodiment of desulfurizer according to the present invention, 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; Within the scope of this radius scale, the tap web of reverse taper discharge device 2 can being made not depart from the scope of degas zone 103, also can not making the volume of reverse taper discharge device 2 greatly to making sulphur slurries form whirlpool.In one preferred embodiment, 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 bottom uptake zone 101, with Fe with bubbling form
3+enveloping agent solution mixes rapidly backward upper flowing, when through MnO beds 3, and COS, CS in gas
2be hydrolyzed to H Deng sour gas is catalyzed
2s, also can discharge a small amount of CO after the Small molecular saturated alkane hydrolysis in sour gas
2, therefore can increase the content of gas in liquid, strengthen gas to the buoyancy of liquid, be conducive to the solution circulation in reaction unit 1.Sour gas after hydrolysis enters reaction zone 102, H occurs wherein
2the oxidation of S and Fe
2+after the series reaction such as the regeneration of complexing agent, the sulphur generated forms sulphur slurries and discharges via reverse taper discharge device 2 from degas zone 103 together with enveloping agent solution, tail gas after desulfurization can directly discharge owing to meeting discharge standard, this completes the sweetening process of sour gas.
In an embodiment of desulfurizer according to the present invention, above-mentioned desulfurizer also comprises pulsed multilayer and loosens system 6, and as shown in Figure 3, this pulsed multilayer loosens system and 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 be arranged in reverse taper discharge device internal side wall and some arms 204 being connected to supervisor and above and to reverse taper discharge device inside extending; And
Control system, passes into compressed air in order to control multi-layer air coil pipe in reverse taper discharge device, comprises and is arranged on the sequence switch valve 205 on supervisor and the time schedule controller 206 in order to control described sequence switch valve.
When above-mentioned pulsed multilayer loosens system works, can by time schedule controller 206 by controlling the sequence switch valve 205 on each layer of air pipe dish, thus compressed air is passed into pulsed in supervisor 203, compressed air sprays compressed air by each arm 204 again in reverse taper discharge device, because compressed air can produce to the slurries containing solid sulfur the effect of loosening, thus can avoid sulphur in reverse taper discharge device, pile sum blocking further.
In an embodiment of desulfurizer according to the present invention, the confession wind pressure of peripheral air feed system can be 0.8 ~ 1.0MPa.
In an embodiment of desulfurizer according to the present invention, supervisor 203 is set in qually spaced in the internal side wall of reverse taper discharge device.
In an embodiment of desulfurizer according to the present invention, arm 204 is uniformly set on supervisor 203, and the quantity of arm can adjust according to actual needs.
Pulsed multilayer loosens system and can arrange according to actual needs and pass into compressed-air actuated mode and time, to ensure that sulphur slurries are not piled up, blocked discharge gate.In an embodiment of desulfurizer according to the present invention, time schedule controller 206 can control 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.Need according to common Acidic Gas Treating, pass into that compressed air can continue to pass into 30 ~ 60min is one-period at every turn.
Time schedule controller, sequence switch valve etc. that above-mentioned pulsed multilayer loosens in system can adopt existing control technology, and the present invention does not limit.
3rd aspect of the present invention provides a kind of containing H
2s, COS, CS
2deng the desulphurization system of the sour gas of gas, this desulphurization system at least comprises any one desulfurizer provided by the invention.
In an embodiment of desulphurization system according to the present invention, 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 cylindrical shell reaction unit 1 and recycles.In one preferred embodiment, equipment for separating liquid from solid 7 can select filter press.
Desulfurizer provided by the invention is not limited to said system, is applicable to any desulphurization system of same domain, as the process system that patent CN201310472099.0 records.
For making the object, technical solutions and advantages of the present invention clearly, will be further described below the technical scheme of exemplary embodiment of the present invention.
In following examples, Fe
3+complexing agent selects commercially available EDTA and polysaccharide Composite Double component ligand.
The desulphurization system used in following examples can refer to Chinese patent CN201310472099.0, specifically, desulphurization system according to acid gas stream to comprising a point flow container, heat exchanger, desulfurizer of the present invention and filter press successively.Flow container is divided to be used for the sour gas high containing amount of liquid to carry out gas-liquid separation, the liquid be separated is discharged, and gas enters next step flow process, if sour gas passes through other PROCESS FOR TREATMENT or content liquid own is lower, also can omit this step, a point flow container can adopt the normally used any kind in this area.Heat exchanger is used for sour gas to heat, and to ensure the sour gas temperature entered in desulfurizer, by heat exchanger heat exchange, sour gas intake air temperature need control between 40-60 DEG C, and too high or too low intake air temperature can make the water in reaction unit unbalance.The sulphur slurries that filter press is used for desulfurizer is discharged are separated, and obtain dry sulfur product, and catalyst liquid circulation returns in reaction unit and recycles.Desulfurizer is also connected with the air blast for passing into oxygen-containing gas, and adds Fe for mending in course of reaction
3+the chemical drum of enveloping agent solution, by measuring pump by the Fe in chemical drum
3+enveloping agent solution is delivered in desulfurizer, to maintain Fe in desulfurizer
3+the amount of complexing agent.Two circulating pumps in parallel are also included for the convey materials that circulates between desulfurizer and filter press.For ensureing the temperature in desulfurizer in reaction unit, the reaction unit part of desulfurizer is also connected with auto-converting type heat exchanger, circulates to regulate temperature to the solution in cylindrical shell reaction unit by circulating pump.
Embodiment 1
Adopt above-mentioned desulphurization system process company 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 point flow container to carry out separatory and isolate water wherein, gas after separatory passes in heat exchanger and carries out heat exchange, make Outlet Gas Temperature be 47 DEG C, meet the temperature range of solution in desulfurizer, and passed in the reaction unit of desulfurizer with 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 carries out COS, CS through reducing catalyst bed (MnO)
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 generated forms slurries together with liquid catalyst and is entered in reverse taper discharge device by degas zone.
In course of reaction, utilize measuring pump chemically in reaction unit, to add Fe in product storage tank continuously simultaneously
3+complexing agent, addition is 44.69kg/h.Meanwhile, utilize air blast to blast in reaction unit containing oxygen 42% gas, and the aeration 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, is 52 DEG C to maintain the temperature of solution in reaction unit.
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 pulsed multilayer and loosens system, be provided with 6 layer of air pipe dishes, loosen medium and adopt 0.8MPa (g) compressed air, and passed into by time schedule controller control compressed air, 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, control ventilatory cycle interval to make reverse taper discharge device discharge smooth and easy, without piling up.Sulphur slurries flow out from reverse taper discharge device, there is provided power by two circulating pumps in parallel to slurries, slurries are flowed in filter press and carries out Separation of Solid and Liquid, the solid sulfur be separated is collected, filtrate is back in reaction unit and recycles, and so far sulfur removal technology circular response completes.
Tail gas after desulfurization process can directly discharge, H in emission
2the content of S is 10.06ppm, COS and CS
2content all at below 10ppm, meet the requirement of " GB14554-93 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 process 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 point flow container and carries out separatory, the gas after separatory passes in heat exchanger and carries out heat exchange, and Outlet Gas Temperature is 45 DEG C, meets the temperature range of solution in desulfurizer, and passed in the reaction unit of desulfurizer with 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 carries out COS, CS through reducing catalyst bed (MnO)
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 generated forms slurries together with liquid catalyst and is entered in reverse taper discharge device by degas zone.
In course of reaction, utilize measuring pump chemically to add Fe in product storage tank 10 continuously simultaneously
3+complexing agent, addition is 54.11kg/h.Meanwhile, utilize air blast to blast air in reaction unit, and the aeration 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, is 49 DEG C to maintain the temperature of solution in reaction unit.
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 pulsed multilayer and loosens system, be provided with 6 layer of air pipe dishes, loosen medium and adopt 0.9MPa (g) compressed air, and passed into by time schedule controller control compressed air, 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, control ventilatory cycle interval to make reverse taper discharge device discharge smooth and easy, without piling up.Sulphur slurries flow out from reverse taper discharge device, there is provided power by two circulating pumps in parallel to slurries, slurries are flowed in filter press and carries out Separation of Solid and Liquid, the solid sulfur be separated is collected, filtrate is back in reaction unit and recycles, and so far sulfur removal technology circular response completes.
Tail gas after desulfurization process can directly discharge, H in emission
2the content of S is 9.91ppm, COS and CS
2content all at below 10ppm, meet the requirement of " GB14554-93 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: after desulfurization process being carried out to sour gas by sulfur method provided by the invention and desulphurization system, gas meets existing discharge standard requirement, and the sulphur that can effectively reclaim wherein, and system run all right, efficiency is high, cost is low, is suitable for large-scale application.
Although in order to the present invention is described, disclose the preferred embodiments of the invention, but it will be understood by those of skill in the art that when not departing from the design of the present invention and scope that claims limit, various amendment, interpolation and replacement can be made to the present invention.
Claims (13)
1. one kind contains H
2s, COS, CS
2the sulfur method of the sour gas of gas, its desulfurization conversion process is: under MnO catalytic action, first 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, and said process completes in same reactor; Described reactor comprises cylindrical shell reaction unit and is arranged at the reverse taper discharge device of 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 used for the hydrolysis of described sour gas, described reaction zone is used for the oxidation reaction of described sour gas, described degas zone is for discharging the tail gas after gained sulphur slurries and desulfurization, and described reverse taper discharge device is arranged on below described degas zone.
2. sulfur method according to claim 1, is characterized in that, the reaction temperature of described desulfurization conversion process is 40 ~ 60 DEG C.
3. sulfur method according to claim 2, is characterized in that, the reaction temperature of described desulfurization conversion process is 47 ~ 53 DEG C.
4. the sulfur method according to any one of claim 1-3, is characterized in that, the time of described desulfurization conversion process is 5 ~ 10 seconds.
5. sulfur method according to claim 1, is characterized in that, in described oxygen-containing gas, the percent by volume of oxygen is 10 ~ 100%.
6. one kind contains H
2s, COS, CS
2the desulfurizer of the sour gas of gas, comprise cylindrical shell reaction unit and the reverse taper discharge device being 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 used for the hydrolysis of described sour gas, described reaction zone is used 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 top circumferential is inscribed within the base 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.
7. desulfurizer according to claim 6, 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.
8. the desulfurizer according to claim 6 or 7, is characterized in that, described desulfurizer also comprises pulsed multilayer and loosens 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 be arranged in described reverse taper discharge device internal side wall and some arms being connected to described supervisor and above and to described reverse taper discharge device inside extending; And
Control system, passes into compressed air in order to control described multi-layer air coil pipe, comprises and be arranged on the sequence switch valve on described supervisor and the time schedule controller in order to control described sequence switch valve in described reverse taper discharge device.
9. desulfurizer according to claim 8, is characterized in that, the confession wind pressure of described peripheral air feed system is 0.8 ~ 1.0MPa.
10. desulfurizer according to claim 8, is characterized in that, described supervisor is set in qually spaced in the internal side wall of described reverse taper discharge device.
11. desulfurizers according to claim 8, it is characterized in that, described time schedule controller controls described multi-layer air coil pipe and in described reverse taper discharge device, passes 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.
12. 1 kinds containing H
2s, COS, CS
2the desulphurization system of the sour gas of gas, is characterized in that, adopts the desulfurizer described in any one of claim 6-11 in described desulphurization system.
13. desulphurization systems according to claim 12, 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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| CN106621764B (en) * | 2016-11-25 | 2019-05-24 | 中南大学 | COS purification device in a kind of aluminium electrolytic flue |
| CN108970380B (en) * | 2018-09-07 | 2023-07-21 | 宜宾丝丽雅股份有限公司 | Method and device for removing hydrogen sulfide in waste gas by 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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|---|---|---|---|---|
| CN1246518A (en) * | 1998-09-02 | 2000-03-08 | 中国科学院大连化学物理研究所 | Hydrorefining catalyst without presulfurizing treatment |
| CN101942562A (en) * | 2010-04-26 | 2011-01-12 | 张夫道 | Harmless treatment technology of main metal tailings |
| CN103495333A (en) * | 2013-10-11 | 2014-01-08 | 陕西延长石油（集团）有限责任公司炼化公司 | Treatment technology for Claus tail gas containing sulfur dioxide, hydrogen sulfide and organic sulfur |
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| US20020159939A1 (en) * | 2001-04-27 | 2002-10-31 | Plug Power Inc. | Gas purification system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246518A (en) * | 1998-09-02 | 2000-03-08 | 中国科学院大连化学物理研究所 | Hydrorefining catalyst without presulfurizing treatment |
| CN101942562A (en) * | 2010-04-26 | 2011-01-12 | 张夫道 | Harmless treatment technology of main metal tailings |
| CN103495333A (en) * | 2013-10-11 | 2014-01-08 | 陕西延长石油（集团）有限责任公司炼化公司 | Treatment technology for Claus tail gas containing sulfur dioxide, hydrogen sulfide and organic sulfur |
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