CN105084322A - Method for reducing SO2 discharge concentration of hydrogenation reduction catalyst in hydrogenation presulfurization period - Google Patents
Method for reducing SO2 discharge concentration of hydrogenation reduction catalyst in hydrogenation presulfurization period Download PDFInfo
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- CN105084322A CN105084322A CN201410213226.XA CN201410213226A CN105084322A CN 105084322 A CN105084322 A CN 105084322A CN 201410213226 A CN201410213226 A CN 201410213226A CN 105084322 A CN105084322 A CN 105084322A
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Abstract
The invention discloses a method for reducing SO2 discharge concentration of a hydrogenation reduction catalyst in a hydrogenation presulfurization period, the method comprises the following steps:1)introducing H2S-containing acidic gas in a hydrogenation reactor, contacting H2S and the hydrogenation reaction catalyst under hydrogenation presulfurization condition for a hydrogenation presulfurization reaction to obtain hydrogenation presulfurization tail gas; wherein, sulphur in the hydrogenation presulfurization tail gas exists in forms of H2S by the hydrogenation presulfurization condition; and 2) cooling the hydrogenation presulfurization tail gas and contacting with an amine liquor-containing absorption liquid to obtain residual gas and the amine liquor-containing absorption liquid which absorbs H2S, and burning the residual gas and then discharging. The method can greatly reduce the SO2 concentration in discharged flue gas, effectively solve the problems of high SO2 discharge concentration and polluted atmospheric environment of a sulfur recovery facility during a hydrogenation presulfurization process, and can effectively use massive sulfur resource and reduce the waste of the sulfur resource.
Description
Technical field
The present invention relates to petrochemical complex, Coal Chemical Industry and gas conditioning field, particularly, relate to a kind of sulfur recovery facility hydrogenating reduction catalyzer that reduces at hydrogenation prevulcanized period SO
2the method of emission concentration.
Background technology
Active metal component cobalt/molybdenum in sulfur recovery facility hydrogenating reduction catalyzer, all in oxidation state, just need play katalysis to hydrogenation reduction in hydrogenation reduction device after hydrogenation prevulcanized is treated as sulphided state.Introduce according in " Claus sulfur recovery Technology " (petroleum industry press), hydrogenation method for pre-sulphuration is: hydrogenation reduction device reaction bed temperature is warming up to 200 DEG C, in Process Gas, oxygen level is no more than 0.4 volume %, and online roasting kiln (tail gas clean-up stove) air equivalent is down to 85%-90%.As H in Process Gas
2when+CO content is about 3%, introduce containing H in Process Gas
2the sour gas of S, and by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to about 1 volume % and carries out hydrogenation prevulcanized reaction.As H in hydrogenation reduction device exit flow
2when S content and inlet air flow are substantially suitable, hydrogenation reduction device reaction bed temperature are warming up to 250 DEG C and proceed hydrogenation prevulcanized.As H in hydrogenation reduction device exit flow
2s content again with inlet air flow basic quite time, hydrogenation pre-vulcanization process terminates.At present, after each refinery's sulfur recovery facility hydrogenation prevulcanized flow process is prevulcanized, tail gas enters quench tower, is put to incinerator burn by the drop-out line that goes into operation above quench tower.Aforesaid method is adopted to carry out hydrogenation prevulcanized, time long (general needs 48 hours), and hydrogenation prevulcanized tail gas cannot carry out desulfurizing and purifying but directly by high altitude discharge after incinerator thermal incineration, sulfur dioxide emissioning concentration is high (up to 20000-25000mg/m
3), the waste of the pollution of atmospheric environment and a large amount of Sulphur ressource can be caused.
SO in the flue gas of hydrogenation prevulcanized tail gas of the prior art discharge after burning
2concentration up to 20000-25000mg/m
3, and SO in the flue gas of the residual gas adopting method of the present invention to obtain (gas that hydrogenation prevulcanized tail gas obtains after the absorption liquid containing amine liquid absorbs) discharge after burning
2concentration can be down to 700-1000mg/m
3.Method of the present invention has good industrial application value, can be widely used in the sulfur recovery method in petrochemical complex, Coal Chemical Industry, gas conditioning field.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Summary of the invention
The object of the invention is to overcome above-mentioned defect of the prior art, providing a kind of hydrogenating reduction catalyzer that reduces at hydrogenation prevulcanized period SO
2the method of emission concentration.
The present inventor finds under study for action, makes sulphur in hydrogenation prevulcanized tail gas all with H by controlling hydrogenation prevulcanized condition
2the form of S exists, and will contact with to H in hydrogenation prevulcanized tail gas after the cooling of hydrogenation prevulcanized tail gas with the absorption liquid containing amine liquid
2s absorbs, then gas discharge after burning after absorbing, and can greatly reduce SO in the flue gas of discharge
2concentration (be low to moderate 700-1000mg/m
3), substantially reach " discharge standard of air pollutants " (GB16297-1996) requirement, namely method of the present invention not only efficiently solves sulfur recovery facility hydrogenating reduction catalyzer at hydrogenation prevulcanized period SO
2emission concentration is high, the problem of pollutant atmosphere, and makes sulphur in hydrogenation prevulcanized tail gas all with H by controlling hydrogenation prevulcanized condition
2the form of S exists, and each equipment of hydrogenation absorptive unit can be avoided not to be subject to polluting and corrosion.
To achieve these goals, the invention provides a kind of hydrogenating reduction catalyzer that reduces at hydrogenation prevulcanized period SO
2the method of emission concentration, the method comprises the steps:
(1) will containing H
2the sour gas of S is introduced in hydrogenation reduction device, by H under hydrogenation prevulcanized condition
2s and hydrogenating reduction catalyst exposure carry out hydrogenation prevulcanized reaction, obtain hydrogenation prevulcanized tail gas; Wherein, described hydrogenation prevulcanized condition makes sulphur in hydrogenation prevulcanized tail gas all with H
2the form of S exists;
(2) contact after described hydrogenation prevulcanized tail gas cooling with the absorption liquid containing amine liquid, obtain residual gas and absorb H
2the absorption liquid containing amine liquid of S, described residual gas is discharge after burning.
The present invention shifts to an earlier date prevulcanized exhaust gas flow path to existing hydrogenating reduction catalyzer and improves, and makes sulphur in hydrogenation prevulcanized tail gas all with H by controlling hydrogenation prevulcanized condition
2the form of S exists, and desulfurization is again carried out on hydrogenation prevulcanized tail gas feeding solvent systems/absorption tower, utilizes the absorption liquid containing amine liquid to H in hydrogenation prevulcanized tail gas
2s absorbs, and obtains residual gas and absorbs H
2the absorption liquid containing amine liquid of S, residual gas can greatly reduce SO in the flue gas of discharge after burning
2concentration (is low to moderate 700-1000mg/m
3), substantially reach " discharge standard of air pollutants " (GB16297-1996) requirement, namely method of the present invention efficiently solves sulfur recovery facility at hydrogenation prevulcanized stage SO
2emission concentration is high, the problem of pollutant atmosphere.And method of the present invention makes sulphur in hydrogenation prevulcanized tail gas all with H by controlling hydrogenation prevulcanized condition
2the form of S exists (namely in hydrogenation pre-vulcanization process without the material of incomplete reaction as (S
x, SO
2, SO
3deng generation)), can avoid each equipment of hydrogenation absorptive unit be not subject to pollute with corrosion.One of the present invention preferred embodiment in, will H be absorbed
2s regenerates containing the absorption liquid of amine liquid, and regeneration is obtained containing H
2the sour gas of S is fed through low pressure gas system recoveries, can effectively utilize a large amount of Sulphur ressource, reduces the waste of Sulphur ressource.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of hydrogenating reduction catalyzer that reduces at hydrogenation prevulcanized period SO
2the method of emission concentration, the method comprises the steps:
(1) will containing H
2the sour gas of S is introduced in hydrogenation reduction device, by H under hydrogenation prevulcanized condition
2s and hydrogenating reduction catalyst exposure carry out hydrogenation prevulcanized reaction, obtain hydrogenation prevulcanized tail gas; Wherein, hydrogenation prevulcanized condition makes sulphur in hydrogenation prevulcanized tail gas all with H
2the form of S exists;
(2) contact after the cooling of hydrogenation prevulcanized tail gas with the absorption liquid containing amine liquid, obtain residual gas (after also can be described as the absorption liquid purification containing amine liquid tail gas) and absorb H
2the absorption liquid containing amine liquid of S, residual gas is discharge after burning.
According to method of the present invention, introduce in hydrogenation reduction device containing H
2the sour gas of S contains the H of 90-97 volume %
2the CO of S, 3-10 volume %
2, the hydrocarbon of 0.01-0.03 volume % and the ammonia of 0.01-0.05 volume %.Wherein, containing H
2the various hydrocarbon that hydrocarbon in the sour gas of S can be commonly used for this area, are preferably CH
4.
According to method of the present invention, for hydrogenation reduction device, there is no particular limitation, and the various hydrogenation reduction devices can commonly used for this area can be such as the hydrogenation reduction device of Claus tail-gas hydrogenation absorptive unit.
According to method of the present invention, the range of choices of the kind of hydrogenating reduction catalyzer is wider, can be the various hydrogenating reduction catalyzer that this area routine uses, the hydrogenating reduction catalyzer be namely usually used in the hydrogenation reduction device of Claus tail-gas hydrogenation absorptive unit all can be used for the present invention.For the present invention, under preferable case, hydrogenating reduction catalyzer contains active ingredient Co and Mo, and with the gross weight of hydrogenating reduction catalyzer for benchmark, with oxide basis, the content of Co is more than 2 % by weight, is preferably 3-5 % by weight; The content of Mo is more than 12 % by weight, is preferably 13-16 % by weight.Further preferably, the tap density of hydrogenating reduction catalyzer is 0.75-0.85 ton/m
3.Those skilled in the art should be known, and in hydrogenating reduction catalyzer, the oxide compound of Co is the oxide compound of CoO, Mo is MoO
3.Those skilled in the art can according to apparatus design processing power determination hydrogenating reduction catalyzer with containing H
2the amount of the sour gas of S.
According to method of the present invention, in order to effectively ensure that sulphur in hydrogenation prevulcanized tail gas is all with H
2the form of S exists, and under preferable case, hydrogenation prevulcanized condition comprises: hydrogenation reduction device reaction bed temperature is 180-300 DEG C; Hydrogenation reduction device inlet pressure is 0.002-0.020MPa, is preferably 0.008-0.015MPa; H in hydrogenation reduction device inlet air flow
2s content is 0.5-4 volume %; In hydrogenation reduction device exit flow, hydrogen richness is 2-6 volume %, is preferably 3-5 volume %.Further preferably, hydrogenation prevulcanized condition comprises: control the H in hydrogenation reduction device inlet air flow
2s content is 0.5-1 volume %, and controlling hydrogenation reduction device reaction bed temperature is 180-200 DEG C, starts to carry out hydrogenation prevulcanized reaction; As H in hydrogenation reduction device exit flow
2when S content and inlet air flow are substantially suitable, improve the H in hydrogenation reduction device inlet air flow
2s content, and raise hydrogenation reduction device reaction bed temperature proceed hydrogenation prevulcanized reaction, so carry out the repetitive operation of more than 2 times, until the H in hydrogenation reduction device inlet air flow
2s content is 3-4 volume %, hydrogenation reduction device reaction bed temperature is 250-300 DEG C and as H in hydrogenation reduction device exit flow
2s content again with inlet air flow basic quite time, terminate hydrogenation prevulcanized reaction.
According to method of the present invention, in the hydrogenation prevulcanized tail gas obtained, hydrogen richness is 2-6 volume %, is preferably 3-5 volume %; In the hydrogenation prevulcanized tail gas obtained, oxygen level is 0-50ppm, is preferably 0-20ppm.
According to method of the present invention, for the not special requirement of the method that hydrogenation prevulcanized tail gas is carried out cooling, the various methods can be able to expected for those skilled in the art, can be such as: by hydrogenation prevulcanized tail gas first by vapour generator and then the quench tower entering hydrogenating reduction unit that the hydrogenation prevulcanized tail gas of discharging from quench tower top is cooled hydrogenation prevulcanized tail gas.In order to make the absorption liquid containing amine liquid more abundant to the absorption of hydrogenation prevulcanized tail gas, under preferable case, the temperature of cooled hydrogenation prevulcanized tail gas is 35-45 DEG C.Wherein, the operational condition of quench tower can adjust according to concrete needs, as long as the operational condition controlling quench tower makes the temperature of cooled hydrogenation prevulcanized tail gas be 35-45 DEG C.Such as, the operational condition of quench tower can comprise: working pressure is 15-20kPa, circulating cooling water flow is 200-300t/h, quench tower base level control is 50-60% place.
According to method of the present invention, cooled hydrogenation prevulcanized tail gas is sent in the absorption tower of Claus tail-gas hydrogenation absorptive unit, utilize the absorption liquid containing amine liquid in absorption tower to absorb H in hydrogenation prevulcanized tail gas
2s, so can realize the most of H in hydrogenation prevulcanized tail gas
2s gas is absorbed by the absorption liquid containing amine liquid.The operational condition on absorption tower can be the routine selection of this area, and it can adjust according to practical situation, and under preferable case, the tower top working pressure on absorption tower controls at 7-20kPa; The temperature that absorption liquid containing amine liquid enters absorption tower controls at 20-50 DEG C, is preferably 25-35 DEG C; The absorption liquid Liquid level containing amine liquid in absorption tower is at 50-60% place.
According to method of the present invention, for the absorption liquid containing amine liquid, there is no particular limitation, can absorb H for can be used in this area
2the various absorption liquids containing amine liquid of S.Wherein, amine liquid can be one or more in Monoethanolamine MEA BASF, diethanolamine, diisopropanolamine (DIPA) and N methyldiethanol amine.It will be understood by those skilled in the art that absorption liquid containing amine liquid is except containing except amine liquid, remaining as water.In absorption liquid containing amine liquid, the mass concentration of amine liquid can be 25-40%.H in hydrogenation prevulcanized tail gas is absorbed more fully in order to make the absorption liquid containing amine liquid
2s, under preferable case, the absorption liquid containing amine liquid is the absorption liquid containing N methyldiethanol amine.In like manner, it will be understood by those skilled in the art that absorption liquid containing N methyldiethanol amine is except containing except N methyldiethanol amine, remaining as water.Further preferably, be 25-40% (namely the mass concentration of water is 60-75%) containing the mass concentration of N methyldiethanol amine in the absorption liquid of N methyldiethanol amine.
According to method of the present invention, residual gas is fed through in incinerator and burns, then through smoke stack emission.Due to according to method of the present invention, the sulphur in the hydrogenation prevulcanized tail gas of drawing from hydrogenation reduction device is all with H
2the form of S exists, and hydrogenation prevulcanized tail gas absorbs through the absorption liquid containing amine liquid, and in the residual gas therefore obtained, sulfur content is very micro-, therefore after incinerator burning in the flue gas of smoke stack emission SO
2concentration lowly (be low to moderate 700-1000mg/m
3), and go into operation the hydrogenating reduction presulfiding of catalyst stage at existing sulfur recovery facility, SO in the flue gas of discharge
2concentration up to 20000-25000mg/m
3namely method of the present invention makes sulfur dioxide emissioning concentration greatly reduce, substantially reach " discharge standard of air pollutants " (GB16297-1996) requirement, method of the present invention efficiently solves sulfur recovery facility and to go into operation hydrogenating reduction catalyst hydrogenation prevulcanized stage SO
2emission concentration is high, the problem of pollutant atmosphere.
According to method of the present invention, in order to more effectively utilize the absorption liquid containing amine liquid, method of the present invention also comprises: will absorb H
2carry out regenerating the absorption liquid containing amine liquid obtaining low sulfur content in absorption liquid containing the amine liquid feeding regenerator column of S and contain H
2the sour gas of S is (herein containing H
2the sour gas of S is usually also referred to as resurgent gases).Wherein, low sulfur content can be 0.2-0.5 grams per liter containing sulphur content in the absorption liquid of amine liquid.
According to method of the present invention, the range of choices of regeneration condition is wider, can be that the routine of this area is selected, for the present invention, in order to make to absorb H
2the absorption liquid containing amine liquid of S is better regenerated, and under preferable case, the operational condition in regenerator column comprises: column bottom temperature controls at 115-122 DEG C, and tower top temperature controls at 100 DEG C-110 DEG C, and tower top working pressure controls at 60-70kPa.
In addition, method of the present invention also comprise regeneration is obtained containing H
2the sour gas (resurgent gases) of S is fed through low pressure gas system recoveries.Method of the present invention also comprises and will regenerate partly or entirely returning in step (2) (namely to return in absorption tower) containing the absorption liquid of amine liquid and contacting for H with cooled hydrogenation prevulcanized tail gas of the low sulfur content that obtains
2the absorption of S.
According to method of the present invention, method of the present invention not only efficiently solves sulfur recovery facility hydrogenating reduction catalyzer at hydrogenation prevulcanized stage SO
2emission concentration is high, the problem of pollutant atmosphere, and because the sulphur in hydrogenation prevulcanized tail gas is all with H
2the form of S exists, and therefore, what regeneration can be obtained after absorption and regeneration contains H
2the sour gas of S is fed through low pressure gas system recoveries, makes method of the present invention effectively make use of a large amount of Sulphur ressource thus, decreases the waste of Sulphur ressource.
According to method of the present invention, for the various equipment used in each detailed process all without particular requirement, all can adopt the relevant device that this area is conventional, the present invention is no longer described in detail at this.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In following examples, hydrogenating reduction catalyzer is purchased from Beijing Sanju New Environmental Protection Materials Co., Ltd, and the trade mark is TG-107.
Introduce in hydrogenation reduction device containing H
2the sour gas of S contains the H of 95 volume %
2the CO of S, 4.95 volume %
2, 0.02 volume % CH
4with the ammonia of 0.03 volume %.
EMERSON uv analyzer is adopted to carry out SO in on-line determination flue gas
2concentration, condition determination comprises that temperature is 260 DEG C, pressure is normal pressure.
Embodiment 1
The present embodiment for illustration of reduction hydrogenating reduction catalyzer of the present invention at hydrogenation prevulcanized period SO
2the method of emission concentration.
The hydrogenation reduction device reaction bed temperature of Claus tail-gas hydrogenation absorptive unit is warming up to 200 DEG C, hydrogenation reduction device is inlet pressure control is 0.010MPa, in Process Gas, Control for Oxygen Content is 0.3 volume %, and online burner air equivalent is down to 88%.As H in Process Gas
2+ CO content is 3 volume %, introduces containing H in Process Gas
2the sour gas of S, and by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 1 volume %, by H
2(tap density of hydrogenating reduction catalyzer is 0.8 ton/m for S and hydrogenating reduction catalyzer
3) contact and carry out hydrogenation prevulcanized reaction.As H in hydrogenation reduction device exit flow
2when S content and inlet air flow are substantially suitable, by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 2 volume %, hydrogenation reduction device reaction bed temperature is warming up to 220 DEG C and proceeds hydrogenation prevulcanized reaction; As H in hydrogenation reduction device exit flow
2when S content and inlet air flow are substantially suitable, by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 3 volume %, hydrogenation reduction device reaction bed temperature is warming up to 250 DEG C and proceeds hydrogenation prevulcanized reaction, as H in hydrogenation reduction device exit flow
2s content again with inlet air flow basic quite time, hydrogenation pre-vulcanization process terminates, and obtains hydrogenation prevulcanized tail gas, and wherein, in the hydrogenation prevulcanized tail gas obtained, hydrogen richness is 3 volume %, and oxygen level is 10ppm.
The hydrogenation prevulcanized tail gas obtained is cooled by the quench tower entering hydrogenating reduction unit after vapour generator again, wherein, the operational condition of quench tower comprises: working pressure is 18kPa, circulating cooling water flow is 250t/h, chilling base level control is at 55% place.The temperature of cooled hydrogenation prevulcanized tail gas is 35 DEG C, cooled hydrogenation prevulcanized tail gas is sent in the absorption tower of Claus tail-gas hydrogenation absorptive unit and contact with the absorption liquid (in absorption liquid, the mass concentration of N methyldiethanol amine is 30%) containing N methyldiethanol amine, obtain residual gas and absorb H
2the absorption liquid containing N methyldiethanol amine of S.Wherein, controlled by the tower top working pressure on absorption tower as 15kPa, the temperature that the absorption liquid containing N methyldiethanol amine enters absorption tower controls to be 35 DEG C, and the absorption liquid Liquid level containing N methyldiethanol amine is at 55% place.Residual gas is fed through in incinerator and burns, then through smoke stack emission, SO in the flue gas of discharge
2concentration be 786mg/m
3.
H will be absorbed
2the absorption liquid containing N methyldiethanol amine of S is sent in regenerator column to carry out regenerating and is obtained the absorption liquid containing N methyldiethanol amine that sulphur content is 0.3 grams per liter and containing H
2the sour gas of S, wherein, the operational condition in regenerator column comprises: it is 120 DEG C that column bottom temperature controls, and it is 105 DEG C that tower top temperature controls, and tower top working pressure controls as 65kPa.What regeneration obtained contains H
2the sour gas of S is fed through low pressure gas system recoveries, and is that the absorption liquid containing N methyldiethanol amine of 0.3 grams per liter all returns to absorption tower and is used for H by regenerating the sulphur content that obtains
2the absorption of S.
Embodiment 2
The present embodiment for illustration of reduction hydrogenating reduction catalyzer of the present invention at hydrogenation prevulcanized period SO
2the method of emission concentration.
The hydrogenation reduction device reaction bed temperature of Claus tail-gas hydrogenation absorptive unit is warming up to 180 DEG C, hydrogenation reduction device is inlet pressure control is 0.008MPa, in Process Gas, Control for Oxygen Content is 0.3 volume %, and online burner air equivalent is down to 85%.As H in Process Gas
2+ CO content is 4 volume %, introduces containing H in Process Gas
2the sour gas of S, and by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 0.5 volume %, by H
2(tap density of hydrogenating reduction catalyzer is 0.75 ton/m for S and hydrogenating reduction catalyzer
3) contact and carry out hydrogenation prevulcanized reaction.As H in hydrogenation reduction device exit flow
2when S content first time and inlet air flow are substantially suitable, by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 1.5 volume %, hydrogenation reduction device reaction bed temperature is warming up to 215 DEG C and proceeds hydrogenation prevulcanized reaction; As H in hydrogenation reduction device exit flow
2when S content second time and inlet air flow are substantially suitable, by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 2.5 volume %, hydrogenation reduction device reaction bed temperature is warming up to 235 DEG C and proceeds hydrogenation prevulcanized reaction; As H in hydrogenation reduction device exit flow
2when S content third time and inlet air flow are substantially suitable, by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 3.5 volume %, hydrogenation reduction device reaction bed temperature is warming up to 265 DEG C and proceeds hydrogenation prevulcanized reaction, as H in hydrogenation reduction device exit flow
2s content again with inlet air flow basic quite time, hydrogenation pre-vulcanization process terminates, and obtains hydrogenation prevulcanized tail gas, and wherein, in the hydrogenation prevulcanized tail gas obtained, hydrogen richness is 4 volume %, and oxygen level is 5ppm.
The hydrogenation prevulcanized tail gas obtained is cooled by the quench tower entering hydrogenating reduction unit after vapour generator again, wherein, the operational condition of quench tower comprises: working pressure is 15kPa, circulating cooling water flow is 300t/h, chilling base level control is at 50% place.The temperature of cooled hydrogenation prevulcanized tail gas is 45 DEG C, cooled hydrogenation prevulcanized tail gas is sent in the absorption tower of Claus tail-gas hydrogenation absorptive unit and contact with the absorption liquid (in absorption liquid, the mass concentration of N methyldiethanol amine is 25%) containing N methyldiethanol amine, obtain residual gas and absorb H
2the absorption liquid containing N methyldiethanol amine of S.Wherein, controlled by the tower top working pressure on absorption tower as 20kPa, the temperature that the absorption liquid containing N methyldiethanol amine enters absorption tower controls to be 30 DEG C, and the absorption liquid Liquid level containing N methyldiethanol amine is at 50% place.Residual gas is fed through in incinerator and burns, then through smoke stack emission, SO in the flue gas of discharge
2concentration be 814mg/m
3.
H will be absorbed
2the absorption liquid containing N methyldiethanol amine of S is sent in regenerator column to carry out regenerating and is obtained the absorption liquid containing N methyldiethanol amine that sulphur content is 0.2 grams per liter and containing H
2the sour gas of S, wherein, the operational condition in regenerator column comprises: it is 115 DEG C that column bottom temperature controls, and it is 100 DEG C that tower top temperature controls, and tower top working pressure controls as 60kPa.What regeneration obtained contains H
2the sour gas of S is fed through low pressure gas system recoveries, and is that 80% of the absorption liquid containing N methyldiethanol amine of 0.2 grams per liter returns to absorption tower and is used for H by regenerating the sulphur content that obtains
2the absorption of S.
Embodiment 3
The present embodiment for illustration of reduction hydrogenating reduction catalyzer of the present invention at hydrogenation prevulcanized period SO
2the method of emission concentration.
The hydrogenation reduction device reaction bed temperature of Claus tail-gas hydrogenation absorptive unit is warming up to 190 DEG C, hydrogenation reduction device is inlet pressure control is 0.015MPa, in Process Gas, Control for Oxygen Content is 0.3 volume %, and online burner air equivalent is down to 90%.As H in Process Gas
2+ CO content is 5 volume %, introduces containing H in Process Gas
2the sour gas of S, and by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 0.8 volume %, by H
2(tap density of hydrogenating reduction catalyzer is 0.85 ton/m for S and hydrogenating reduction catalyzer
3) contact and carry out hydrogenation prevulcanized reaction.As H in hydrogenation reduction device exit flow
2when S content and inlet air flow are substantially suitable, by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 2.5 volume %, hydrogenation reduction device reaction bed temperature is warming up to 235 DEG C and proceeds hydrogenation prevulcanized reaction; As H in hydrogenation reduction device exit flow
2s content again with inlet air flow basic quite time, by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 4 volume %, hydrogenation reduction device reaction bed temperature is warming up to 300 DEG C and proceeds hydrogenation prevulcanized reaction; As H in hydrogenation reduction device exit flow
2s content again with inlet air flow basic quite time, hydrogenation pre-vulcanization process terminates, and obtains hydrogenation prevulcanized tail gas, and wherein, in the hydrogenation prevulcanized tail gas obtained, hydrogen richness is 5 volume %, and oxygen level is 2ppm.
The hydrogenation prevulcanized tail gas obtained is cooled by the quench tower entering hydrogenating reduction unit after vapour generator again, wherein, the operational condition of quench tower comprises: working pressure is 20kPa, circulating cooling water flow is 200t/h, chilling base level control is at 60% place.The temperature of cooled hydrogenation prevulcanized tail gas is 40 DEG C, cooled hydrogenation prevulcanized tail gas is sent in the absorption tower of Claus tail-gas hydrogenation absorptive unit and contact with the absorption liquid (in absorption liquid, the mass concentration of N methyldiethanol amine is 40%) containing N methyldiethanol amine, obtain residual gas and absorb H
2the absorption liquid containing N methyldiethanol amine of S.Wherein, controlled by the tower top working pressure on absorption tower as 7kPa, the temperature that the absorption liquid containing N methyldiethanol amine enters absorption tower controls to be 25 DEG C, and the absorption liquid Liquid level containing N methyldiethanol amine is at 60% place.Residual gas is fed through in incinerator and burns, then through smoke stack emission, SO in the flue gas of discharge
2concentration be 796mg/m
3.
H will be absorbed
2the absorption liquid containing N methyldiethanol amine of S is sent in regenerator column to carry out regenerating and is obtained the absorption liquid containing N methyldiethanol amine that sulphur content is 0.5 grams per liter and containing H
2the sour gas of S, wherein, the operational condition in regenerator column comprises: it is 122 DEG C that column bottom temperature controls, and it is 110 DEG C that tower top temperature controls, and tower top working pressure controls as 70kPa.What regeneration obtained contains H
2the sour gas of S is fed through low pressure gas system recoveries, and is that the absorption liquid containing N methyldiethanol amine of 0.5 grams per liter all returns to absorption tower and is used for H by regenerating the sulphur content that obtains
2the absorption of S.
Embodiment 4
According to the method for embodiment 1, unlike, be 15% containing the mass concentration of N methyldiethanol amine in the absorption liquid of N methyldiethanol amine, SO in the flue gas of discharge after residual gas is burned
2concentration be 4000mg/m
3.
Embodiment 5
According to the method for embodiment 1, unlike, be 50% containing the mass concentration of N methyldiethanol amine in the absorption liquid of N methyldiethanol amine, SO in the flue gas of discharge after residual gas is burned
2concentration be 3500mg/m
3.
Embodiment 6
According to the method for embodiment 1, unlike, the absorption liquid (in absorption liquid the mass concentration of Monoethanolamine MEA BASF be 25%) of absorption liquid containing amine liquid containing Monoethanolamine MEA BASF replaces the absorption liquid containing N methyldiethanol amine, SO in the flue gas of discharge after being burned by residual gas
2concentration be 3800mg/m
3.
Comparative example 1
According to the method for embodiment 1, unlike, the hydrogenation prevulcanized tail gas obtained directly is fed through in incinerator burns without cooling and absorbing process, then through smoke stack emission, SO in the flue gas of discharge
2concentration be 20000mg/m
3.
Comparative example 2
The hydrogenation reduction device reaction bed temperature of Claus tail-gas hydrogenation absorptive unit is warming up to 200 DEG C, and in Process Gas, Control for Oxygen Content is 0.3 volume %, and online burner air equivalent is down to 88%.As H in Process Gas
2+ CO content is 3 volume %, introduces containing H in Process Gas
2the sour gas of S, and by the H in hydrogenation reduction device inlet air flow
2s content is adjusted to 1 volume %, by H
2(tap density of hydrogenating reduction catalyzer is 0.8 ton/m for S and hydrogenating reduction catalyzer
3) contact and carry out hydrogenation prevulcanized reaction.As H in hydrogenation reduction device exit flow
2when S content and inlet air flow are substantially suitable, hydrogenation reduction device reaction bed temperature are warming up to 250 DEG C and proceed hydrogenation prevulcanized reaction.As H in hydrogenation reduction device exit flow
2s content again with inlet air flow basic quite time, hydrogenation pre-vulcanization process terminates, and obtains hydrogenation prevulcanized tail gas, and wherein, in the hydrogenation prevulcanized tail gas obtained, hydrogen richness is 3 volume %, and oxygen level is 0.2 volume %.The hydrogenation prevulcanized tail gas obtained is fed through in incinerator and burns, then through smoke stack emission, SO in the flue gas of discharge
2concentration be 25000mg/m
3.
Embodiment 1-6 is known compared with comparative example 1, and method of the present invention greatly reduces SO in the flue gas of discharge
2concentration, not only efficiently solves sulfur recovery facility hydrogenating reduction catalyzer at hydrogenation prevulcanized stage SO
2emission concentration is high, the problem of pollutant atmosphere, and can effectively utilize a large amount of Sulphur ressource, reduces the waste of Sulphur ressource.
Embodiment 1 is known compared with embodiment 4-6 respectively, adopt containing N methyldiethanol amine absorption liquid and in absorption liquid, the mass concentration of N methyldiethanol amine is 25-40% time, the H in hydrogenation prevulcanized tail gas can be absorbed more fully
2s, reduces SO in the flue gas of discharge further
2concentration.
By comparative example 1 and comparative example 2 more known, hydrogenation prevulcanized condition of the present invention can reduce SO in the flue gas of discharge further
2concentration.And it should be noted that, due in the hydrogenation prevulcanized tail gas that obtains in comparative example 2 containing more oxygen, the existence of oxygen easily makes the absorption liquid containing N methyldiethanol amine be oxidized, thus loses sorption, therefore, cannot carry out desulfurizing and purifying.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. one kind is reduced hydrogenating reduction catalyzer at hydrogenation prevulcanized period SO
2the method of emission concentration, is characterized in that, the method comprises the steps:
(1) will containing H
2the sour gas of S is introduced in hydrogenation reduction device, by H under hydrogenation prevulcanized condition
2s and hydrogenating reduction catalyst exposure carry out hydrogenation prevulcanized reaction, obtain hydrogenation prevulcanized tail gas; Wherein, described hydrogenation prevulcanized condition makes sulphur in hydrogenation prevulcanized tail gas all with H
2the form of S exists;
(2) contact after described hydrogenation prevulcanized tail gas cooling with the absorption liquid containing amine liquid, obtain residual gas and absorb H
2the absorption liquid containing amine liquid of S, described residual gas is discharge after burning.
2. method according to claim 1, wherein, described hydrogenation prevulcanized condition comprises: hydrogenation reduction device reaction bed temperature is 180-300 DEG C, and hydrogenation reduction device inlet pressure is 0.002-0.020MPa, H in hydrogenation reduction device inlet air flow
2s content is 0.5-4 volume %, and in hydrogenation reduction device exit flow, hydrogen richness is 2-6 volume %.
3. method according to claim 2, wherein, described hydrogenation prevulcanized condition comprises: control the H in hydrogenation reduction device inlet air flow
2s content is 0.5-1 volume %, and controlling hydrogenation reduction device reaction bed temperature is 180-200 DEG C, starts to carry out hydrogenation prevulcanized reaction; As H in hydrogenation reduction device exit flow
2when S content and inlet air flow are substantially suitable, improve the H in hydrogenation reduction device inlet air flow
2s content, and raise hydrogenation reduction device reaction bed temperature proceed hydrogenation prevulcanized reaction, so carry out the repetitive operation of more than 2 times, until the H in hydrogenation reduction device inlet air flow
2s content is 3-4 volume %, hydrogenation reduction device reaction bed temperature is 250-300 DEG C and as H in hydrogenation reduction device exit flow
2s content again with inlet air flow basic quite time, terminate hydrogenation prevulcanized reaction.
4. method according to claim 1, wherein, the temperature of cooled hydrogenation prevulcanized tail gas is 35-45 DEG C.
5. method according to claim 1, wherein, the temperature of the absorption liquid containing amine liquid is 20-50 DEG C, is preferably 25-35 DEG C.
6. method according to claim 1, wherein, described amine liquid is one or more in Monoethanolamine MEA BASF, diethanolamine, diisopropanolamine (DIPA) and N methyldiethanol amine.
7. method according to claim 6, wherein, the described absorption liquid containing amine liquid is the absorption liquid containing N methyldiethanol amine, and described is 25-40% containing the mass concentration of N methyldiethanol amine in the absorption liquid of N methyldiethanol amine.
8. method according to claim 1, wherein, described method also comprises: will absorb H
2s carries out regenerating containing the absorption liquid of amine liquid the absorption liquid containing amine liquid and resurgent gases that obtain low sulfur content, described low sulfur content be 0.2-0.5 grams per liter containing sulphur content in the absorption liquid of amine liquid.
9. method according to claim 8, wherein, described method also comprises: described resurgent gases is fed through low pressure gas system recoveries.
10. method according to claim 8, wherein, described method also comprises: partly or entirely returned in step (2) by the absorption liquid containing amine liquid regenerating the low sulfur content obtained and contact with cooled hydrogenation prevulcanized tail gas.
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| CN103566730A (en) * | 2012-08-06 | 2014-02-12 | 中国石油化工股份有限公司 | Method for treating sulfur removal sweeping tail gas produced in shutdown process of sulfur recovery device |
| CN103663386A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Method for reducing SO2 emission concentration of sulfur device |
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| CN103663386A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Method for reducing SO2 emission concentration of sulfur device |
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