CN103170223A - Rotational flow strengthening method and device for purifying sulfur production tail gases by Claus method - Google Patents

Rotational flow strengthening method and device for purifying sulfur production tail gases by Claus method Download PDF

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CN103170223A
CN103170223A CN201310125233XA CN201310125233A CN103170223A CN 103170223 A CN103170223 A CN 103170223A CN 201310125233X A CN201310125233X A CN 201310125233XA CN 201310125233 A CN201310125233 A CN 201310125233A CN 103170223 A CN103170223 A CN 103170223A
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gas
tail
tower
chw
cooling
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CN103170223B (en
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白兆圆
汪华林
钱鹏
范轶
吴瑞豪
陈建琦
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Shanghai Huachang Environmental Protection Co Ltd
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Abstract

The invention relates to a rotational flow strengthening method and device for purifying sulfur production tail gases by the Claus method, and provides a rotational flow strengthening method for purifying sulfur production tail gases by the Claus method. The method comprises the following steps of: (i) after heat exchange treatment for sulfur production tail gases by the Claus method, mixing the treated tail gases with hydrogen for hydrogenation reaction so as to reduce and hydrolyze elemental sulfur, SO2, COS and CS2 carried in tail gases to H2S; (ii) primarily cooling gases obtained in step (i) and absorbing H2S by countercurrent to remove waterdrops entrained in the gases while performing secondary cooling; (iii) absorbing H2S by countercurrent from the gases obtained in step (ii) for rotational flow separation so as to further remove H2S, and meanwhile rotationally separating amine liquid entrained; and (iv) burning the purified tail gases obtained in step (iii), and cooling to be discharged to atmosphere. The invention further provides a rotational flow strengthening device for purifying sulfur production tail gases by the Claus method.

Description

Eddy flow intensifying method and the device of Clause method sulfur production tail gas clean-up
Technical field
The invention belongs to chemical industry energy environment protection field, relate to a kind of eddy flow intensifying method and device of Clause method sulfur production tail gas clean-up.Specifically, the invention provides method and the device of institute's sulfur-bearing simple substance and sulfide in a kind of high-efficiency desulfurization sulphur tail gas processed.
Background technology
China advocates energy-saving and emission-reduction work always, strictly controls the sulfur dioxide in air discharge capacity.National departments concerned is being fermented the revision discharge standard of air pollutants, requires newly-built sulphur unit sulfur dioxide emissioning concentration less than 400mg/Nm 3(the particular locality concentration of emission is less than 200mg/Nm 3).Sinopec is actively implemented the green low-carbon development strategy, strive for one of world-class important indicator reducing sulphur unit SO 2 from fume concentration of emission as the oil refining plate, require sulfur dioxide emissioning concentration in 2015 (sulfur dioxide emissioning concentration 400mg/Nm that reaches world-class levels 3), Some Enterprises reaches world lead level (sulfur dioxide emissioning concentration 200mg/Nm 3).
In March, 2012, oil refining division department has carried out the letter accent to each enterprise's sulphur unit ruuning situation, and in May, 2012, the experts of unit such as scientific research in organization system, design, production carry out Field Research to 13 cover sulfur recovery facility ruuning situations of 6 oil refining enterprises again.Found that, the sulphur tail gas processed of partly discharging from sulphur recovery still contains a small amount of H 2S, SO 2, COS, S xEtc. harmful substance, the environmental requirement that after directly burning, discharging does not reach national regulation.
The method of gas removal sulfide can be divided into two base class at present: a class claims dry flue gas desulphurization; Another kind of is wet desulphurization.Dry flue gas desulphurization refers to use powdery or granular absorbent, adsorbent or catalyst and removes SO in flue gas 2Its advantage is that technical process is simple, and without sewage, dirty acid treatment problem, energy consumption is low, and after particularly purifying, flue-gas temperature is higher, is conducive to chimney exhaust diffusion, can not produce " white cigarette " phenomenon, and the flue gas after purification does not need post bake, and corrosivity is little; Its shortcoming is that desulfuration efficiency is lower, and equipment is huge, investment is large, floor space is large, and operating technology requires high.Wet desulphurization refers to utilize the liquid-absorbant washing gas, to remove the hydrogen sulfide in gas.Though the desulfurized effect of this technique is not as dry desulfurization, it has continued operation, flow process is simple, treating capacity is large, investment and the advantage such as operating cost is lower, thereby is widely used in gas sweetening.Wherein, hydramine method desulfurization and decarburization process characteristic is CO in unstripped gas 2/ H 2S can optionally remove H than under very high condition 2S, and CO that will be quite a large amount of 2Be retained in purified gas, therefore not only energy-saving effect is obvious, also greatly improved the quality of Cross unit raw material acid gas.Due to a series of superiority of MDEA solvent, growth momentum is swift and violent during the nearly last ten years.Natural gas and the refinery gas purifier overwhelming majority of China have all adopted this solvent at present.But due to the limitation of its technology itself, after desulfurization, tail gas still is entrained with the H of higher concentration 2S, thus by the tail-gas combustion stove processing of burning, cause a large amount of sulfur dioxide to drain in atmosphere outward, the environment around having polluted.
In sum, analyzing influence sulphur unit SO 2 from fume concentration of emission factor, and for its this a series of problem that exists in refinery unit, innovation proposes a kind of new process, adopt simultaneously less more effective absorption equipment, when optionally removing hydrogen sulfide gas, make amine liquid separated from the gas, obtain purer gas imperative.
Chinese patent application No.200720078359.6, a kind of sulphur recovery and exhaust gas processing device are disclosed, this device utilizes reheater hydrogen manufacturing, by thermal response section, catalyst reaction section and Reducing and absorption section apparatus, carry out burning conversion in the thermal response section respectively, and at high temperature hydrogen sulfide and sulfur dioxide generation claus reaction generate elemental sulfur; Carry out catalytic reaction and refrigerated separation obtains Molten sulphur in catalyst reaction section; Process Gas enters hydrogenation reactor through the steam heater heating and carries out reduction reaction, the remaining hydrogen sulfide gas of absorption of residual, then discharge after burning disposal.This processing method and the effectively Recovered sulphur end of line gas disposal of going forward side by side of device, but the SO 2 from fume concentration of emission is higher, and (200mg/Nm can not reach world-class levels 3), and the plant area area is large, and equipment is complicated, invests higher.
Chinese patent application No.200810022175.7 discloses the technique of a kind of inside and outside water-cooled Claus tail gases Recovered sulphur and qualified discharge, after technological process is mainly Claus tail gases and enters the cooling of water-cooled cooling bed collector, enter reactor generation chemical reaction, tail gas up to standard is through smoke stack emission, the cold bed collector adopts the cross-flow mode to spray cold water, simultaneously, tower body outside spray cold water makes the high-temperature tail gas cooling.This invented technology is simple, invests littlely, and energy consumption is low, non-secondary pollution, but that it absorbs sulfur-containing compound effect is general.
From above-mentioned Sinopec finding and retrospect analysis from documents result, most of enterprise sulphur unit SO 2 from fume concentration of emission (sulfur dioxide emissioning concentration 400mg/Nm that can't reach world-class levels 3), more can not reach world lead level index (sulfur dioxide emissioning concentration 200mg/Nm 3).
Therefore, for improving the element sulphur absorption efficiency, further reduce the concentration of outlet sulfur dioxide in flue gas, reach advanced world standards, be necessary to propose improvement project, develop the process program of a kind of high accuracy, high efficiency desulfurization processing, tail gas clean-up, that is, this area is in the urgent need to developing sulfur dioxide emissioning concentration lower than 200mg/Nm 3Method and apparatus.
Summary of the invention
The invention provides a kind of eddy flow intensifying method and device of Clause method sulfur production tail gas clean-up of novelty, thereby solved problems of the prior art.
On the one hand, the invention provides a kind of eddy flow intensifying method of Clause method sulfur production tail gas clean-up, the method comprises:
(i) Clause method sulfur production tail gas carries out rear the mixing with hydrogen of heat exchange processing and carries out hydrogenation reaction, with elemental sulfur, the SO that will carry in tail gas 2, COS, CS 2Reduce, be hydrolyzed to H 2S;
(ii) the gas that obtains in step (i) is carried out the cooling rear counter-current absorption H of one-level 2S is with the water droplet that is carrying out secondary and carry secretly in removing gas in cooling;
The back flow of gas that (iii) step is obtained in (ii) absorbs H 2S, and then carry out cyclonic separation, further to remove H 2S, the amine liquid that the while cyclonic separation is carried secretly; And
The cleaning of off-gas that (iv) step is obtained in (iii) burns, and enters atmosphere after cooling.
One preferred embodiment in, in step (i), at the tail-gas combustion stove back segment with tail gas heating to 300 ℃; In hydrogenation reactor, utilize hydrogenation catalyst that the sulfur-containing compound in tail gas is carried out hydrogenation and hydrolysis, sulphur is converted into H 2S。
Another preferred embodiment in, enter the H of hydrogenation reactor 2The H that tolerance provides according to online hydrogen analyzer 2Concentration signal is regulated; Described hydrogenation catalyst is cobalt, molybdenum catalyst.
Another preferred embodiment in, step (ii) in, the 0.4MPa saturated vapor occurs in steam generator, with the gas cooled to 170 after hydrogenation reaction ℃, thereby it is cooling to carry out one-level; Tail gas enters in quench tower and absorbs H with the chilled water (chw) counter current contacting 2S, washing is cooled to 33-42 ℃, and the pH value scope of controlling chilled water (chw) is between 6.5-9, thus the water droplet that is carrying out secondary and carry secretly in removing gas in cooling.
Another preferred embodiment in, the chilled water (chw) that uses in quench tower is extracted out from the quench tower bottom with the chilled water (chw) circulating pump, after the chilled water (chw) cooler is cooled to 33-42 ℃, returns quench tower and recycles.
Another preferred embodiment in, step (iii) in, tail gas enters in a grade formula-eddy flow absorption tower with poor amine liquid counter current contacting to absorb H 2S gas, and then further remove contained H via little cyclone 2S gas makes the H in the tail gas after desulfurization 2S concentration is less than 50mg/Nm 3, the amine liquid droplet cyclonic separation of simultaneously cleaning of off-gas being carried secretly out makes in cleaning of off-gas the amine liquid hold-up less than 1ppm.
Another preferred embodiment in, the poor amine liquid of using in level formula-eddy flow absorption tower is the poor amine liquid of N-Propylene Glycol amine of the 35-45% that comes of solvent reclamation device; Absorbed H 2The N-Propylene Glycol amine rich solution of S returns to the solvent reclamation device after rich amine liquid pump boosts.
Another preferred embodiment in, step (iv) in, cleaning of off-gas enters tail-gas combustion stove, under 600 ℃ with cleaning of off-gas in residual sulfide, H 2Burn respectively with hydro carbons and be SO 2, H 2O and CO 2After being cooled to 375 ℃ after incinerator flue gas out reduces phlegm and internal heat through the tail gas heat exchanger of the steam superheater in tail-gas combustion stove stage casing and tail-gas combustion stove back segment respectively, then mix cold air hybrid cooling to 300 ℃, enter atmosphere by the chimney high-altitudes of 80 meters high, wherein, SO in discharged gas fume 2Concentration less than 200mg/Nm 3
On the other hand, the invention provides a kind of eddy flow intensifying device of Clause method sulfur production tail gas clean-up, this device comprises:
Tail-gas combustion stove is used for that Clause method sulfur production tail gas is carried out heat exchange and processes;
The hydrogenation reactor that is connected with tail-gas combustion stove is used for making gas from tail-gas combustion stove to mix with hydrogen and carries out hydrogenation reaction, with elemental sulfur, the SO that will carry in tail gas 2, COS, CS 2Reduce, be hydrolyzed to H 2S;
The steam generator that is connected with hydrogenation reactor, cooling the gas from hydrogenation reactor is carried out one-level;
The quench tower that is connected with steam generator, wherein built-in little cyclone, be used for making gas and chilled water (chw) counter current contacting from steam generator to absorb H 2S, thus remove the water droplet that gas is carried secretly in cooling carrying out secondary;
The level formula that is connected with quench tower-eddy flow absorption tower, the built-in little cyclone of its tower top is used for making from the gas of quench tower counter-current absorption H at first 2S, and then carry out cyclonic separation, further to remove H 2S, the amine liquid that the while cyclonic separation is carried secretly;
The tail-gas combustion stove that is connected with level formula-eddy flow absorption tower is used for and will burns from the cleaning of off-gas of level formula-eddy flow absorption tower tower top, and tail-gas combustion stove flue gas out enters atmosphere after cooling.
One preferred embodiment in, the operating pressure of described hydrogenation reactor is 0.02-0.03MPa; Amine liquid atomizes by atomizer in level formula-eddy flow absorption tower, at absorption tower part counter-current absorption H 2S; This device also comprises: the chilled water (chw) circulating pump that is connected with quench tower, be used for chilled water (chw) from quench tower bottom extraction, and the chilled water (chw) cooler that is connected with the chilled water (chw) circulating pump, after being used for being cooled to 33-42 ℃ from the chilled water (chw) that extract out the quench tower bottom, returning quench tower and recycle.
Description of drawings
Fig. 1 is the Sulphur tail gas desulfurization process chart according to one embodiment of the present invention.
Fig. 2 is the Sulphur tail gas desulfurization process chart of another embodiment according to the present invention.
The specific embodiment
The present inventor finds after having passed through extensive and deep research, in existing Sulphur tail gas desulfurization technique, still there is the higher problem of sulfur dioxide emissioning concentration, and solution-air two-phase haptoreaction also is in a very large yardstick and carries out, absorption efficiency is low, the methyl diethanolamine utilization rate is low, and the large investment of equipment volume is large, and fluctuation of service; Therefore, how under small scale, high accuracy, carry out desulfurization expeditiously and process and more and more receive publicity in industrial research; Present extensive employing hydramine methods both at home and abroad etc. still adopt the absorption tower as removing device as sulfur method; Therefore, the absorption reaction rank from how with the hydramine method reduces, thereby improves absorption efficiency, and the angle that reaches the purpose of efficient absorption and low investment is set out, and the present invention proposes and adopts the drop reinforcing desulfuration, absorbs simultaneously to absorb with eddy flow and takes off the method that liquid unites two into one; The present invention utilizes traditional absorption tower to carry out desulfurization and processes, effectively (the gas-liquid mass transferring reaction is mainly to overcome resistance between the gas and liquid phase interface for desulfurization simple substance and sulfur-containing compound, in the present invention, methyl diethanolamine contacts in the absorption tower part fully with sulphur tail gas processed, utilizes filler greatly to increase contact surface area; Reaction speed and absorption efficiency, gas-liquid mixed degree, gas component, to contain the factors such as sulphur concentration and reaction temperature pressure relevant), the gas of entrained drip is carried out the little cyclonic separation of solution-air of low pressure drop in droplet eddy flow part simultaneously, gas-liquid separation efficient can reach more than 90%; So both complete the coupling that desulphurization reaction and eddy flow take off liquid, improved the utilization ratio of methyl diethanolamine, saved cost and subsequent regeneration energy consumption, and made again the volume of industrial equipment reduce, reduced manufacturing cost.Based on above-mentioned discovery, the present invention is accomplished.
Technical conceive of the present invention is as follows:
It is compound that the present invention adopts absorption reaction and eddy flow absorption to take off liquid to MDEA (N-Propylene Glycol amine), in level formula-eddy flow absorbs tower top, little cyclone is set, make the coupling of cyclone separator and traditional absorption tower, contact absorption with the poor amine liquid of MDEA by the level formula at traditional absorption tower part sulfur-containing tail gas, enter the cyclonic separation part after the desulfurization absorption reaction is processed, remove the amine liquid of carrying secretly in gas; In addition, the chilling tower top that the present invention uses is also installed little cyclone, and the water droplet of carrying secretly through Crouse's sulphur tail gas processed of quenching is carried out cyclonic separation, dried tail gas.Like this, one aspect of the present invention can shorten soak time and the absorption efficiency of hydrogen sulfide greatly; On the other hand, desulfurization absorption reaction part is taken off liquid with eddy flow to be integrated, complete absorption reaction and eddy flow and absorbed the coupling of taking off liquid, guarantee the efficient operation of follow up device, make the single unit system volume reduce, save cost of investment, removed simultaneously drop and other impurity particle of carrying secretly in gas, reduced dust pollution.The invention provides a kind of eddy flow intensifying method and device of Clause method sulfur production tail gas clean-up, improved the precision that removes of sulfur-containing compound, realized the green low-carbon development strategy, (sulfur dioxide emissioning concentration is lower than 200mg/Nm to make sulfur dioxide emissioning concentration reach world-class levels 3).
In a first aspect of the present invention, a kind of eddy flow intensifying method of Clause method sulfur production tail gas clean-up is provided, the method comprises:
At first sulfur-containing tail gas carries out heat exchange processes, and carries out hydrogenation reaction, the elemental sulfur that carries in tail gas, SO after mixing with hydrogen under the effect of hydrogenation catalyst 2, COS, CS 2Reduce, be hydrolyzed to H 2S;
After reacted high-temperature gas is cooling through one-level, secondary, absorbs and take off liquid and process, gas is at first through traditional absorption tower counter-current absorption H 2S, and then through the eddy flow absorption and separation, further remove hydrogen sulfide gas, the amine liquid that the while cyclonic separation is carried secretly;
Cleaning of off-gas enters tail-gas combustion stove and burns afterwards, after being cooled to approximately 375 ℃ after tail-gas combustion stove high-temperature flue gas out is cooling, then mixes the cold air hybrid cooling to approximately 300 ℃, enters atmosphere by the chimney high-altitude.
In the present invention, the main source of acid tail gas has: the tail gas that the conventional Claus technique sulphur processed of the pyrolytic conversion of employing one-level, two-stage catalyzed conversion is partly discharged.
In the present invention, the main sulfur content of sulfur-containing tail gas is about 200-400ppm (303.6-607.2mg/Nm 3), wherein sulfur-containing compound mainly comprises H 2S, SO 2, elementary sulfur, organic sulfur etc.
In the present invention, at the tail-gas combustion stove back segment, gas-heated is arrived approximately 300 ℃; In hydrogenation reactor, utilize cobalt, molybdenum (CT6-5B) catalyst that the sulfur-containing compound in tail gas is carried out hydrogenation and hydrolysis, sulphur is converted into hydrogen sulfide gas.
In the present invention, enter the H of hydrogenation reactor 2The H that the online hydrogen analyzer of tolerance after according to tail gas absorber provides 2Concentration signal is regulated.
In the present invention, 0.4MP occurs in steam generator aSaturated vapor is cooled to approximately 170 ℃ with the high-temperature gas after hydrogenation reaction.
In the present invention, tail gas enters in quench tower and the chilled water (chw) counter current contacting, and washing is cooled to 33-42 ℃, and controls chilled water (chw) pH value scope between 6.5-9.
In the present invention, the chilled water (chw) that the tail gas quenching tower uses is extracted out from tower bottom with the chilled water (chw) circulating pump, after the chilled water (chw) cooler is cooled to 33-42 ℃, returns quench tower and recycles.
In the present invention, low temperature exhaust gas enters on level formula-eddy flow absorption tower, with the poor amine liquid of MDEA counter current contacting, absorbs H 2S gas, and then further remove hydrogen sulfide content gas via little cyclone, the amine liquid droplet cyclonic separation of simultaneously cleaning of off-gas being carried secretly is out.
In the present invention, the amine liquid that adopt on the absorption tower is the poor amine liquid of MDEA of the next 35-45% of solvent reclamation device, has absorbed H 2The MDEA rich solution of S returns to the solvent reclamation device after rich amine liquid pump boosts.
In the present invention, from tail gas absorber tower top cleaning of off-gas out, enter tail-gas combustion stove, under the high temperature of 600 ℃, with sulfide residual in cleaning of off-gas, H 2Burn respectively with hydro carbons and be SO 2, H 2O and CO 2After tail-gas combustion stove high-temperature flue gas out passes through respectively and is cooled to approximately 375 ℃ after steam superheater (tail-gas combustion stove stage casing) and tail gas heat exchanger (tail-gas combustion stove back segment) are reduced phlegm and internal heat, mix again the cold air hybrid cooling to approximately 300 ℃, enter atmosphere by the chimney high-altitudes of 80 meters high.
In the present invention, the industrial N-Propylene Glycol of initial formulation amine aqueous solution, concentration is about 35-45%, and the poor amine liquid of MDEA (35-45% solution) that utilizes afterwards the solvent reclamation device gets final product; In amine liquid droplet cyclone bed reactor, the hydrogen sulfide in MDEA drop and tail gas of sulphur fully contacts and carries out reactive absorption under gravitational field; H in the purified gas that obtains 2S content is less than 50mg/Nm 3The regeneration of drop enriching and recovering, recycling.
Method of the present invention has been improved traditional hydramine method sulfur removal technology fully, a series of old-fashioned cumbersome apparatus such as packed tower in former technological process have been cancelled, not only reduced equipment investment, improved hydrogen sulfide absorption efficient, the reactive absorption that has suppressed carbon dioxide, also reduce floor space, reduced operation easier.And, effectively solve amine liquid and run the damage problem, purified gas is used more effectively in lower procedure.
In a second aspect of the present invention, a kind of eddy flow intensifying device of Clause method sulfur production tail gas clean-up is provided, this device comprises:
Tail-gas combustion stove is used for the unstripped gas preheating, and Purge gas is burned, and heat exchange is cooling;
Hydrogenation reactor is used for mixing the sulphur tail gas reduction processed of hydrogen, obtains hydrogen sulfide gas;
Steam generator, cooling for high-temperature gas being carried out one-level;
Quench tower is used for that gas is carried out secondary cooling, and the water droplet carried secretly of cyclonic separation gas;
Level formula-eddy flow absorption tower is used for the hydrogen sulfide of gas is carried out Reducing and absorption, and utilizes little cyclone to the further Absorption Desulfurization of gas, simultaneously the amine liquid droplet carried secretly of cyclonic separation;
Chimney is used for burning and cooled gas is discharged.
In the present invention, the eddy flow intensifying device of described Clause method sulfur production tail gas clean-up also can comprise:
The chilled water (chw) cooler is used for that water is carried out heat exchange and processes, and enters the quench tower utilization after cooling; And
The chilled water (chw) circulating pump is used for chilled water (chw) is extracted out from tower bottom, returns quench tower after being cooled to 33-42 ℃ to recycle.
In the present invention, at the built-in little cyclone of chilling tower top, will carry out through the gas of quench tower chilling little eddy flow and process, the water droplet of being carried secretly to remove gas, dried tail gas.
In the present invention, hydrogenating reduction gas amine absorbs the built-in little cyclone of tower top, low temperature exhaust gas and MDEA solution reaction, generate the decomposable amine salt of high temperature, and then via the further Absorption Desulfurization of little cyclone part, the amine liquid eddy flow of simultaneously gas being carried secretly gets off, and is purified tail gas.
In the present invention, the operating pressure of hydrogenation reactor is 0.02-0.03MPa.
In the present invention, amine liquid atomizes by atomizer in level formula-eddy flow absorption tower, at absorption tower part adverse current absorbing hydrogen sulphide gas.
In the present invention, on amine liquid droplet cyclone bed reactor top, the little cyclone separator group of gas-liquid is set, is used for removing the amine liquid droplet of carrying secretly through reactor lower part and the reacted gas of amine liquid droplet.
In the present invention, the concentration of described MEDA is at 35-45%, and operating temperature is 33-42 ℃.
In the present invention, the operating pressure of described sulphur tail gas processed is about 0.02-0.03MPa.
In the present invention, the quantity of described little cyclone can be adjusted as the case may be.
In the present invention, after described desulfurizing and purifying technique the amine liquid hold-up in tail gas less than 1ppm.
In the present invention, under described operating condition, the Pressure Drop of equipment is not more than 0.0002MPa.
In the present invention, little cyclone part partly unites two into one with amine absorption hydrogen sulfide, has reduced the complexity of equipment, has saved cost of investment, simultaneously high accuracy, the high efficiency hydrogen sulfide gas that removed.
Below referring to accompanying drawing.
Fig. 1 is the Sulphur tail gas desulfurization process chart according to one embodiment of the present invention.As shown in Figure 1, Clause method sulfur production tail gas enters tail-gas combustion stove 1 back segment heat exchange to 300 ℃, carries out hydrogenation reaction in hydrogenation reactor 2 after mixing hydrogen, with elemental sulfur, the SO that carries in tail gas 2, COS, CS 2Reduce, be hydrolyzed to H 2S; The high-temperature gas of gained, together with external deaerated water, entering steam generator 3, interior that high-temperature gas is carried out one-level is cooling, the 0.4MPa saturated vapor occurs in steam generator 3, high-temperature gas after hydrogenation reaction is cooled to approximately 170 ℃, enters afterwards tail gas quenching tower 4, the built-in little cyclone of these quench tower 4 tower tops, tail gas and chilled water (chw) counter current contacting are carried out secondary and are removed the water droplet that gas is carried secretly cooling the time; The tail gas of gained enters a grade formula-eddy flow absorption tower 5, the built-in little cyclone of tower top on this grade formula-eddy flow absorption tower 5, and at first gas absorb H through traditional absorption tower and poor amine liquid counter current contacting 2S, and then the amine liquid carried secretly of cyclonic separation gas, rich solution return to the regeneration of solvent reclamation device; From level formula-eddy flow absorption tower 5 tower tops cleaning of off-gas out, together with external nitrogen and fuel gas, enter in tail-gas combustion stove 1 and burn, out high-temperature flue gas in tail-gas combustion stove 1, together with external 3.5MPa steam, pass through respectively be cooled to approximately 375 ℃ after steam superheater (tail-gas combustion stove 1 stage casing) and tail gas heat exchanger (tail-gas combustion stove 1 back segment) are reduced phlegm and internal heat after, mix again the cold air hybrid cooling to approximately 300 ℃, enter atmosphere by 80 meters high chimney 6 high-altitudes, remaining 3.5MPa steam adds external deaerated water, sends to pipe network.
Fig. 2 is the Sulphur tail gas desulfurization process chart of another embodiment according to the present invention.As shown in Figure 2, Clause method sulfur production tail gas enters tail-gas combustion stove 1 back segment heat exchange to 300 ℃, carries out hydrogenation reaction in hydrogenation reactor 2 after mixing hydrogen, with elemental sulfur, the SO that carries in tail gas 2, COS, CS 2Reduce, be hydrolyzed to H 2S; The high-temperature gas of gained, together with external deaerated water, entering steam generator 3, interior that high-temperature gas is carried out one-level is cooling, the 0.4MPa saturated vapor occurs in steam generator 3, high-temperature gas after hydrogenation reaction is cooled to approximately 170 ℃, enters afterwards tail gas quenching tower 4, the built-in little cyclone of these quench tower 4 tower tops, tail gas and chilled water (chw) counter current contacting are carried out secondary and are removed the water droplet that gas is carried secretly cooling the time; The chilled water (chw) that uses in quench tower,, returns quench tower 4 and recycles after chilled water (chw) cooler 7 is cooled to 33-42 ℃ from quench tower bottom extraction with chilled water (chw) circulating pump 8; The tail gas of gained enters a grade formula-eddy flow absorption tower 5, the built-in little cyclone of tower top on this grade formula-eddy flow absorption tower 5, and at first gas absorb H through traditional absorption tower and poor amine liquid counter current contacting 2S, and then the amine liquid carried secretly of cyclonic separation gas, rich solution return to the regeneration of solvent reclamation device; From level formula-eddy flow absorption tower 5 tower tops cleaning of off-gas out, together with external nitrogen and fuel gas, enter in tail-gas combustion stove 1 and burn, out high-temperature flue gas in tail-gas combustion stove 1, together with external 3.5MPa steam, pass through respectively be cooled to approximately 375 ℃ after steam superheater (tail-gas combustion stove 1 stage casing) and tail gas heat exchanger (tail-gas combustion stove 1 back segment) are reduced phlegm and internal heat after, mix again the cold air hybrid cooling to approximately 300 ℃, enter atmosphere by 80 meters high chimney 6 high-altitudes, remaining 3.5MPa steam adds external deaerated water, sends to pipe network.
Major advantage of the present invention is:
1) method of the present invention has overcome in existing Sulphur tail gas desulfurization technical process and has used the desulfurizing tower equipment such as plate column, packed tower, has greatly increased the problem of the energy charge of the loss of methyl diethanolamine and regeneration of absorption solution system.By absorbing the built-in little eddy flow absorber portion of tower top at hydrogenating reduction gas amine, the rapid haptoreaction of poor amine liquid drop and sulphur tail gas processed is absorbed, the little rotating flow that carries out simultaneously solution-air absorbs and separates, reduced the methyl diethanolamine loss, alleviate the regenerative system energy consumption, reduced sulfur content in exhaust emissions.
2) level of the present invention formula-eddy flow absorption tower device is the key reaction separation equipment, and compact conformation is simple, floor space is little, the operation efficient stable.Have reaction speed fast, selectively absorb precision high, the obvious advantage such as separative efficiency is high, and energy consumption is low.
3) the built-in little cyclone of the chilling tower top of the hydrogenating reduction gas of Clause method sulfur production tail gas of the present invention makes high-temperature gas chilling and dehydration carry out simultaneously, has reduced the consumption of chilled water (chw).
4) built-in cyclone installation and maintenance of the present invention are convenient, and compact equipment is simple, the inner space utilization rate is high, floor space is little, the operation efficient stable.
The present invention adopts the sulfur method of grade formula chemical absorbing and the combination of eddy flow chemical absorbing, the built-in little cyclone of chilling tower top at the hydrogenating reduction gas of Clause method sulfur production tail gas, and hydrogenating reduction gas amine absorbs the built-in little eddy flow absorber portion of tower top, makes concentration of hydrogen sulfide after the hydrogenating reduction gas sweetening less than 50mg/Nm 3, satisfy chimney SO 2Efflux concentration less than 200mg/Nm 3Index has reduced desulfurization solvent loss and energy consumption.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.But, should be understood that these embodiment only are used for explanation the present invention and do not consist of limitation of the scope of the invention.The test method of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Except as otherwise noted, all percentage and umber are by weight.
Embodiment 1:
In 40,000 ton/years of sulfur recovery facilities, the tail gas of sulphur of sulfur-bearing is strengthened with device according to the eddy flow intensifying method of Clause method sulfur production tail gas clean-up of the present invention and separated, reach with high efficiency, high accuracy, low-loss and complete effective absorption and separation to sulfur-containing compound in tail gas of sulphur, (sulfur dioxide emissioning concentration is lower than 200mg/Nm to make the tail gas sulphur dioxide concentration of emission reach world standard 3).Its specific operation process and effect are described below:
1. tail gas of sulphur gas property and operating condition
Tail gas to be processed is mainly the tail gas that the conventional Claus technique sulphur processed that adopts one-level pyrolytic conversion, two-stage catalyzed conversion is partly discharged.Main component is: the composition in sour gas mainly contains H 2S, CO 2, H 2O, hydrocarbon etc.; The tail gas of sulphur treating capacity is 2000Nm 3/ h, meteorological density operation temperature is 40 ℃, operating pressure is 0.02-0.03MPa; The mixed hydrogen amount of hydrogenation reactor is 115.36Nm 3/ h, the steam pressure of steam generator are 0.4MPa; The concentration of N-Propylene Glycol amine aqueous solution (methyl diethanolamine) is 35-45%.
2. implementation process
Clause method sulfur production tail gas is heated to 300 ℃ in tail-gas combustion stove, be mixed into hydrogenation reactor with hydrogen, under the effect of cobalt, molybdenum (CT6-5B) catalyst, and the elemental sulfur that carries in tail gas, SO 2Carry out hydrogenation reaction, COS, CS 2The reaction that is hydrolyzed is converted into hydrogen sulfide gas with sulfur-containing compound; High-temperature gas after hydrogenation reaction is cooled to 160 ℃ through steam generator; Preliminary cooling cryogenic gas enters the tail gas quenching tower, with the chilled water (chw) counter current contacting, continues washing and is cooled to 40 ℃, by little cyclone processed of chilling tower top; Enter a grade formula-eddy flow absorption tower device through the Clause method sulfur production tail gas of over-quenching with this temperature, in the device absorption portion, utilize the MEDA lean solution to absorb H 2S gas, the tail gas that removes hydrogen sulfide enters the little cyclonic separation part of tower top, processes by the further desulfurization of little cyclone, removes simultaneously the amine liquid drop of carrying secretly in gas; Cleaning of off-gas by Absorption Desulfurization and process cyclonic separation enters tail gas burning furnace, under 600 ℃ of high temperature, with sulfide residual in cleaning of off-gas, H 2Burn with hydro carbons and generate SO 2, H 2O and CO 2After incinerator high-temperature flue gas out passes through respectively and is cooled to approximately 375 ℃ after steam superheater (tail-gas combustion stove stage casing) and tail gas heat exchanger (tail-gas combustion stove back segment) are reduced phlegm and internal heat, mix again cold air hybrid cooling to 300 ℃, enter atmosphere by the chimney high-altitudes of 80 meters high.
3. interpretation of result
After using the method separation of amine liquid droplet cyclone bed reactor reinforcing desulfuration, the cleaning of off-gas hydrogen sulfide content that obtains is lower than 50mg/Nm 3, desulfurization degree reaches 90%, and (sulfur dioxide emissioning concentration is lower than 200mg/Nm to reach world's emission level 3).
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.

Claims (10)

1. the eddy flow intensifying method of a Clause method sulfur production tail gas clean-up, the method comprises:
(i) Clause method sulfur production tail gas carries out rear the mixing with hydrogen of heat exchange processing and carries out hydrogenation reaction, with elemental sulfur, the SO that will carry in tail gas 2, COS, CS 2Reduce, be hydrolyzed to H 2S;
(ii) the gas that obtains in step (i) is carried out the cooling rear counter-current absorption H of one-level 2S is with the water droplet that is carrying out secondary and carry secretly in removing gas in cooling;
The back flow of gas that (iii) step is obtained in (ii) absorbs H 2S, and then carry out cyclonic separation, further to remove H 2S, the amine liquid that the while cyclonic separation is carried secretly; And
The cleaning of off-gas that (iv) step is obtained in (iii) burns, and enters atmosphere after cooling.
2. the method for claim 1, is characterized in that, in step (i), at the tail-gas combustion stove back segment with tail gas heating to 300 ℃; In hydrogenation reactor, utilize hydrogenation catalyst that the sulfur-containing compound in tail gas is carried out hydrogenation and hydrolysis, sulphur is converted into H 2S。
3. method as claimed in claim 2, is characterized in that, enters the H of hydrogenation reactor 2The H that tolerance provides according to online hydrogen analyzer 2Concentration signal is regulated; Described hydrogenation catalyst is cobalt, molybdenum catalyst.
4. the method for claim 1, is characterized in that, step (ii) in, the 0.4MPa saturated vapor occurs in steam generator, with the gas cooled to 170 after hydrogenation reaction ℃, thereby it is cooling to carry out one-level; Tail gas enters in quench tower and absorbs H with the chilled water (chw) counter current contacting 2S, washing is cooled to 33-42 ℃, and the pH value scope of controlling chilled water (chw) is between 6.5-9, thus the water droplet that is carrying out secondary and carry secretly in removing gas in cooling.
5. method as claimed in claim 4, is characterized in that, the chilled water (chw) that uses in quench tower,, returns quench tower and recycles after the chilled water (chw) cooler is cooled to 33-42 ℃ from quench tower bottom extraction with the chilled water (chw) circulating pump.
6. the method for claim 1, is characterized in that, step (iii) in, tail gas enters in a grade formula-eddy flow absorption tower with poor amine liquid counter current contacting to absorb H 2S gas, and then further remove contained H via little cyclone 2S gas makes the H in the tail gas after desulfurization 2S concentration is less than 50mg/Nm 3, the amine liquid droplet cyclonic separation of simultaneously cleaning of off-gas being carried secretly out makes in cleaning of off-gas the amine liquid hold-up less than 1ppm.
7. method as claimed in claim 6, is characterized in that, the poor amine liquid of using in level formula-eddy flow absorption tower is the poor amine liquid of N-Propylene Glycol amine of the 35-45% that comes of solvent reclamation device; Absorbed H 2The N-Propylene Glycol amine rich solution of S returns to the solvent reclamation device after rich amine liquid pump boosts.
8. the method for claim 1, is characterized in that, step (iv) in, cleaning of off-gas enters tail-gas combustion stove, under 600 ℃ with cleaning of off-gas in residual sulfide, H 2Burn respectively with hydro carbons and be SO 2, H 2O and CO 2After being cooled to 375 ℃ after incinerator flue gas out reduces phlegm and internal heat through the tail gas heat exchanger of the steam superheater in tail-gas combustion stove stage casing and tail-gas combustion stove back segment respectively, then mix cold air hybrid cooling to 300 ℃, enter atmosphere by the chimney high-altitudes of 80 meters high, wherein, SO in discharged gas fume 2Concentration less than 200mg/Nm 3
9. the eddy flow intensifying device of a Clause method sulfur production tail gas clean-up, this device comprises:
Tail-gas combustion stove (1) is used for that Clause method sulfur production tail gas is carried out heat exchange and processes;
The hydrogenation reactor (2) that is connected with tail-gas combustion stove (1) is used for making gas from tail-gas combustion stove (1) to mix with hydrogen and carries out hydrogenation reaction, with elemental sulfur, the SO that will carry in tail gas 2, COS, CS 2Reduce, be hydrolyzed to H 2S;
The steam generator (3) that is connected with hydrogenation reactor (2), cooling the gas from hydrogenation reactor (2) is carried out one-level;
The quench tower (4) that is connected with steam generator (3), wherein built-in little cyclone, be used for making gas and chilled water (chw) counter current contacting from steam generator (3) to absorb H 2S, thus remove the water droplet that gas is carried secretly in cooling carrying out secondary;
The level formula that is connected with quench tower (4)-eddy flow absorption tower (5), the built-in little cyclone of its tower top is used for making from the gas of quench tower (4) counter-current absorption H at first 2S, and then carry out cyclonic separation, further to remove H 2S, the amine liquid that the while cyclonic separation is carried secretly;
The tail-gas combustion stove (1) that is connected with level formula-eddy flow absorption tower (5) is used for and will burns from the cleaning of off-gas of level formula-eddy flow absorption tower (5) tower top, and tail-gas combustion stove (1) flue gas out enters atmosphere after cooling.
10. device as claimed in claim 9, is characterized in that, the operating pressure of described hydrogenation reactor (2) is 0.02-0.03MPa; Amine liquid atomizes by atomizer in level formula-eddy flow absorption tower (5), at absorption tower part counter-current absorption H 2S; This device also comprises: the chilled water (chw) circulating pump (8) that is connected with quench tower (4), be used for chilled water (chw) from quench tower (4) bottom extraction, and the chilled water (chw) cooler (7) that is connected with chilled water (chw) circulating pump (8), after being used for to be cooled to 33-42 ℃ from the chilled water (chw) that extract out quench tower (4) bottom, returning quench tower and recycle.
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CN106512650A (en) * 2016-11-23 2017-03-22 北京丰汉工程技术有限公司 Method and system for treating Claus process tail gas
CN110013758A (en) * 2018-01-09 2019-07-16 中国石油化工股份有限公司 Hydrogenated tail gas safe reuse and processing method in hydrogenation apparatus
CN110732238A (en) * 2018-07-19 2020-01-31 中国石油天然气股份有限公司 sulfur-containing tail gas treatment method and system

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