CN103170223B - The eddy flow intensifying method of Clause method sulfur production tail gas clean-up and device - Google Patents
The eddy flow intensifying method of Clause method sulfur production tail gas clean-up and device Download PDFInfo
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Abstract
The present invention relates to eddy flow intensifying method and the device of Clause method sulfur production tail gas clean-up, provide a kind of eddy flow intensifying method of Clause method sulfur production tail gas clean-up, the method comprises: (i) mix with hydrogen after Clause method sulfur production tail gas carries out heat exchange process and carry out hydrogenation reaction, with the elemental sulfur will carried in tail gas, SO
2, COS, CS
2reduce, be hydrolyzed to H
2s; By step (i) in the gas that obtains carry out counter-current absorption H after one-level cooling
2s, to remove the water droplet carried secretly in gas while carrying out secondary cooling; By step (ii) in the back flow of gas that obtains absorb H
2s, and then carry out cyclonic separation, to remove H further
2s, simultaneously the amine liquid of cyclonic separation entrained with; And (iv) by step (iii) in the cleaning of off-gas that obtains burn, enter air after cooling.Additionally provide a kind of eddy flow intensifying device of Clause method sulfur production tail gas clean-up.
Description
Technical field
The invention belongs to chemical industry field of energy source environment protection, 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.
Background technology
China advocates energy-saving and emission-reduction work always, strict control sulfur dioxide in air discharge capacity.National departments concerned is fermenting revision discharge standard of air pollutants, requires that newly-built sulphur unit sulfur dioxide emissioning concentration is less than 400mg/Nm
3(particular locality concentration of emission is less than 200mg/Nm
3).Sinopec actively implements green low-carbon development strategy, reduction sulphur unit SO 2 from fume concentration of emission is striven for one of world-class important indicator as oil refining plate, requires that sulfur dioxide emissioning concentration in 2015 reaches world-class levels (sulfur dioxide emissioning concentration 400mg/Nm
3), Some Enterprises reaches world lead level (sulfur dioxide emissioning concentration 200mg/Nm
3).
In March, 2012, oil refining division department has carried out letter tune to each enterprise sulphur unit ruuning situation, in May, 2012, and the 13 cover sulfur recovery facility ruuning situations of the unit expert such as scientific research in organization system, design, production to 6 oil refining enterprise carry out Field Research again.Found that, the sulphur tail gas processed of discharging from sulphur recovery part still contains a small amount of H
2s, SO
2, COS, S
xetc. harmful substance, after directly burning, discharge does not reach the environmental requirement of national regulation.
The method of current gas removal sulfide can be divided into two base class: a class claims dry flue gas desulphurization; Another kind of is wet desulphurization.Dry flue gas desulphurization refers to that application powdery or granular absorbent, adsorbent or catalyst are to remove the SO in flue gas
2.Its advantage is that technical process is simple, and without sewage, dirty acid treatment problem, energy consumption is low, and particularly after purification, flue-gas temperature is higher, and be conducive to chimney exhaust diffusion, can not produce " white cigarette " phenomenon, 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 and utilizes liquid-absorbant washing gas, to remove the hydrogen sulfide in gas.Though the desulfurized effect of this technique is not as dry desulfurization, the advantages such as it has continued operation, flow process is simple, treating capacity is large, invest and operating cost is lower, are thus widely used in gas sweetening.Wherein, hydramine method desulfurization and decarburization process characteristic is CO in unstripped gas
2/ H
2s, than under very high condition, optionally can remove H
2s, and by quite a large amount of CO
2be retained in purified gas, therefore not only energy-saving effect is obvious, also substantially improves 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 current China have adopted this solvent all.But due to the limitation of its technology itself, after desulfurization, tail gas is still entrained with the H of higher concentration
2s, therefore carry out burning process by tail-gas combustion stove, cause outside a large amount of sulfur dioxide and drain in air, pollute the environment of surrounding.
In sum, analyzing influence sulphur unit SO 2 from fume concentration of emission factor, and for this series of problem that it exists in refinery unit, innovation proposes a kind of new process, adopt less more effective absorption equipment simultaneously, while optionally removing hydrogen sulfide gas, make amine liquid separated from the gas, obtain purer gas imperative.
Chinese patent application No.200720078359.6, disclose a kind of sulphur recovery and exhaust gas processing device, this device utilizes reheater hydrogen manufacturing, by thermal response section, catalyst reaction section and Reducing and absorption section apparatus, carry out burning conversion in thermal response section respectively, and at high temperature hydrogen sulfide and sulfur dioxide generation claus reaction generate elemental sulfur; Catalytic reaction is carried out and refrigerated separation obtains Molten sulphur in catalyst reaction section; Process Gas enters hydrogenation reactor through steam heater heating and carries out reduction reaction, hydrogen sulfide gas more than absorption of residual, then discharges after burning disposal.This processing method and device can effectively Recovered sulphur to be gone forward side by side end of line gas disposal, but SO 2 from fume concentration of emission is higher, and can not reach world-class levels (200mg/Nm
3), and plant area area is large, equipment is complicated, invests higher.
Chinese patent application No.200810022175.7 discloses a kind of inside and outside water-cooled Claus tail gases Recovered sulphur and the technique of qualified discharge, technological process be mainly Claus tail gases enter water-cooled cooling bed collector cooling after, enter reactor generation chemical reaction, tail gas up to standard is through smoke stack emission, cold bed collector adopts cross-current flow to spray cold water, meanwhile, spraying cold water outside tower body makes high-temperature tail gas lower the temperature.This invented technology is simple, and invest little, energy consumption is low, non-secondary pollution, but its absorption 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 can't reach world-class levels (sulfur dioxide emissioning concentration 400mg/Nm
3), more can not reach world lead level index (sulfur dioxide emissioning concentration 200mg/Nm
3).
Therefore, for improving element sulphur absorption efficiency, the concentration of sulfur dioxide in further reduction exiting 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 process, 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, thus solve 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) mix with hydrogen after Clause method sulfur production tail gas carries out heat exchange process and carry out hydrogenation reaction, with the elemental sulfur will carried in tail gas, SO
2, COS, CS
2reduce, be hydrolyzed to H
2s;
By step (i) in the gas that obtains carry out counter-current absorption H after one-level cooling
2s, to remove the water droplet carried secretly in gas while carrying out secondary cooling;
By step (ii) in the back flow of gas that obtains absorb H
2s, and then carry out cyclonic separation, to remove H further
2s, simultaneously the amine liquid of cyclonic separation entrained with; And
By step (iii) in the cleaning of off-gas that obtains burn, enter air after cooling.
In one preferred embodiment, in step (i), at tail-gas combustion stove back segment by tail gas heating to 300 DEG C; 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 regulates; Described hydrogenation catalyst is cobalt, molybdenum catalyst.
Another preferred embodiment in, step (ii) in, there is 0.4MPa saturated vapor in a vapor generator, so that the gas after hydrogenation reaction is cooled to 170 DEG C, thus carry out one-level cooling; Tail gas enters in quench tower and absorbs H with chilled water (chw) counter current contacting
2s, washing is cooled to 33-42 DEG C, and the pH value range of control chilled water (chw) is between 6.5-9, thus while carrying out secondary cooling, remove the water droplet carried secretly in gas.
Another preferred embodiment in, the chilled water (chw) chilled water (chw) circulating pump used in quench tower is extracted out bottom quench tower, after chilled water (chw) cooler is cooled to 33-42 DEG C, returns quench tower and recycles.
Another preferred embodiment in, step (iii) in, tail gas to enter in a grade formula-eddy flow absorption tower with poor amine liquid counter current contacting to absorb H
2s gas, and then remove contained H further via micro-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 being carried secretly by cleaning of off-gas out, makes amine liquid hold-up in cleaning of off-gas be less than 1ppm.
Another preferred embodiment in, the poor amine liquid used in level formula-eddy flow absorption tower is the poor amine liquid of N-Propylene Glycol amine of 35-45% that solvent reclamation device comes; Absorb H
2the N-Propylene Glycol amine rich solution of S returns solvent reclamation device after the boosting of rich amine solution pump.
Another preferred embodiment in, step (iv) in, cleaning of off-gas enters tail-gas combustion stove, the sulfide, the H that will remain in cleaning of off-gas at 600 DEG C
2burn respectively as SO with hydro carbons
2, H
2o and CO
2after incinerator flue gas is out cooled to 375 DEG C after reducing phlegm and internal heat respectively through the steam superheater in tail-gas combustion stove stage casing and the tail gas heat exchanger of tail-gas combustion stove back segment, then mix cold air hybrid cooling to 300 DEG C, enter air by the chimney high-altitude of 80 meters high, wherein, SO in discharged gas fume
2concentration be 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, for carrying out heat exchange process to Clause method sulfur production tail gas;
The hydrogenation reactor be connected with tail-gas combustion stove, to mix with hydrogen for making the gas from tail-gas combustion stove and carries out hydrogenation reaction, with the elemental sulfur will carried in tail gas, SO
2, COS, CS
2reduce, be hydrolyzed to H
2s;
The steam generator be connected with hydrogenation reactor, to carry out one-level cooling to the gas from hydrogenation reactor;
The quench tower be connected with steam generator, wherein built-in micro-cyclone, absorb H for making from the gas of steam generator and chilled water (chw) counter current contacting
2s, thus the water droplet removing that while carrying out secondary cooling gas carries secretly;
Level formula-eddy flow the absorption tower be connected with quench tower, the built-in micro-cyclone of its tower top, for making the gas first counter-current absorption H from quench tower
2s, and then carry out cyclonic separation, to remove H further
2s, simultaneously the amine liquid of cyclonic separation entrained with;
The tail-gas combustion stove be connected with level formula-eddy flow absorption tower, for being burned by the cleaning of off-gas from level formula-eddy flow absorption tower tower top, tail-gas combustion stove flue gas out enters air after cooling.
In one preferred embodiment, the operating pressure of described hydrogenation reactor is 0.02-0.03MPa; In level formula-eddy flow absorption tower, amine liquid is atomized by atomizer, at absorption tower part counter-current absorption H
2s; This device also comprises: the chilled water (chw) circulating pump be connected with quench tower, for chilled water (chw) is extracted out bottom quench tower, and the chilled water (chw) cooler to be connected with chilled water (chw) circulating pump, after the chilled water (chw) extracted out bottom quench tower is cooled to 33-42 DEG C, returns quench tower and recycle.
Accompanying drawing explanation
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 according to another embodiment of the present invention.
Detailed description of the invention
The present inventor finds after have passed through extensive and deep research, in existing Sulphur tail gas desulfurization technique, still there is the problem that sulfur dioxide emissioning concentration is higher, and solution-air two-phase haptoreaction is also in a very large yardstick carries out, absorption efficiency is low, 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 process expeditiously and more and more receive publicity in industrial research; Domestic and international extensively employing hydramine method etc. are as sulfur method at present, still adopt absorption tower as removing device; Therefore, from how the absorption reaction rank of hydramine method to be reduced, thus improve absorption efficiency, reach efficient absorption and the angle of the object of Low investment is set out, the present invention proposes and adopt drop reinforcing desulfuration, simultaneously stability and eddy flow absorb the method taking off liquid and unite two into one; The present invention utilizes conventional suction tower to carry out desulfurization process, (gas-liquid mass transferring reaction mainly overcomes resistance between gas and liquid phase interface for effective desulfurization simple substance and sulfur-containing compound, in the present invention, methyl diethanolamine contacts in absorption tower part fully with sulphur tail gas processed, utilizes filler to substantially increase contact surface area; Reaction speed and absorption efficiency, gas-liquid mixed degree, gas component, relevant containing factors such as sulphur concentration and reaction temperature pressure), carry out the solution-air mini-hydrocyclone separation of low pressure drop at droplet swirl component to the gas of entrained drip, gas-liquid separation efficiency can reach more than 90% simultaneously; So both complete the coupling that desulphurization reaction and eddy flow take off liquid, improve the utilization ratio of methyl diethanolamine, saved cost and subsequent regeneration energy consumption, make again the volume of industrial equipment reduce, reduce manufacturing cost.Based on above-mentioned discovery, the present invention is accomplished.
Technical conceive of the present invention is as follows:
The present invention adopts absorption reaction and eddy flow to absorb de-liquid compound to MDEA (N-Propylene Glycol amine), absorb in tower top at level formula-eddy flow and micro-cyclone is set, make cyclone separator and conventional suction tower-coupled, to be contacted by level formula at conventional suction tower section sulfur-containing tail gas and the poor amine liquid of MDEA and absorb, after the process of desulfurization absorption reaction, enter cyclonic separation part, remove the amine liquid carried secretly in gas; In addition, the chilling tower top that the present invention uses also installs micro-cyclone, carries out cyclonic separation, dried tail gas to the water droplet of the Crouse's sulphur tail gas entrained with through quenching.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 and eddy flow are taken off liquid integrate, complete the coupling of absorption reaction and the de-liquid of eddy flow absorption, ensure the Effec-tive Function of follow up device, single unit system volume is reduced, save cost of investment, be stripped of the drop and other impurity particle carried secretly in gas simultaneously, reduce dust pollution.The invention provides a kind of eddy flow intensifying method and device of Clause method sulfur production tail gas clean-up, what improve sulfur-containing compound removes precision, achieve green low-carbon development strategy, sulfur dioxide emissioning concentration is reached world-class levels, and (sulfur dioxide emissioning concentration is lower than 200mg/Nm
3).
In a first aspect of the present invention, provide a kind of eddy flow intensifying method of Clause method sulfur production tail gas clean-up, the method comprises:
First sulfur-containing tail gas carries out heat exchange process, under the effect of hydrogenation catalyst carries out hydrogenation reaction after mixing with hydrogen, the elemental sulfur carried in tail gas, SO
2, COS, CS
2reduce, be hydrolyzed to H
2s;
Reacted high-temperature gas is after one-level, secondary cooling, and carry out absorbing de-liquid process, first gas absorb H through conventional suction tower counter-flow
2s, and then through eddy flow absorption and separation, remove hydrogen sulfide gas further, the amine liquid of cyclonic separation entrained with simultaneously;
Cleaning of off-gas enters tail-gas combustion stove burning afterwards, after being cooled to about 375 DEG C, then mixes cold air hybrid cooling to about 300 DEG C, enter air by chimney high-altitude after tail-gas combustion stove high-temperature flue gas cooling out.
In the present invention, the main source of acid tail gas has: the tail gas of the conventional Claus technique sulphur part discharge of the pyrolytic conversion of employing one-level, two-stage catalyzed conversion.
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 tail-gas combustion stove back segment by gas-heated to about 300 DEG C; In hydrogenation reactor, utilize cobalt, the sulfur-containing compound in tail gas carries out hydrogenation and hydrolysis by molybdenum (CT6-5B) catalyst, sulphur is converted into hydrogen sulfide gas.
In the present invention, the H of hydrogenation reactor is entered
2the H that tolerance provides according to the online hydrogen analyzer after tail gas absorber
2concentration signal regulates.
In the present invention, there is 0.4MP in a vapor generator
asaturated vapor, is cooled to about 170 DEG C by the high-temperature gas after hydrogenation reaction.
In the present invention, tail gas enter in quench tower with chilled water (chw) counter current contacting, washing is cooled to 33-42 DEG C, and controls chilled water (chw) pH value range between 6.5-9.
In the present invention, the chilled water (chw) chilled water (chw) circulating pump that tail gas quenching tower uses is extracted out from tower bottom, after chilled water (chw) cooler is cooled to 33-42 DEG C, returns quench tower and recycles.
In the present invention, low temperature exhaust gas enters on level formula-eddy flow absorption tower, with MDEA poor amine liquid counter current contacting, absorbs H
2s gas, and then remove hydrogen sulfide content gas further via micro-cyclone, the amine liquid droplet cyclonic separation of simultaneously being carried secretly by cleaning of off-gas is out.
In the present invention, the amine liquid that absorption tower adopts is the poor amine liquid of MDEA of the 35-45% that solvent reclamation device comes, and absorbs H
2the MDEA rich solution of S returns solvent reclamation device after the boosting of rich amine solution pump.
In the present invention, from tail gas absorption column overhead cleaning of off-gas out, enter tail-gas combustion stove, under the high temperature of 600 DEG C, by the sulfide, the H that remain in cleaning of off-gas
2burn respectively as SO with hydro carbons
2, H
2o and CO
2after tail-gas combustion stove high-temperature flue gas is out cooled to about 375 DEG C after reducing phlegm and internal heat respectively through steam superheater (tail-gas combustion stove stage casing) and tail gas heat exchanger (tail-gas combustion stove back segment), mix cold air hybrid cooling again to about 300 DEG C, enter air by the chimney high-altitude of 80 meters high.
In the present invention, initial formulation industrial N-Propylene Glycol amine aqueous solution, concentration is about 35-45%, utilizes the poor amine liquid of MDEA (35-45% solution) that solvent reclamation device comes afterwards; In amine liquid droplet cyclone bed reactor, the hydrogen sulfide in MDEA drop and tail gas of sulphur, under gravitational field, fully contacts and carries out reactive absorption; H in the purified gas obtained
2s content is less than 50mg/Nm
3; Drop enriching and recovering regenerates, and recycles.
Method of the present invention improves traditional hydramine method sulfur removal technology completely, eliminate a series of old-fashioned cumbersome apparatus such as packed tower in former technological process, not only reduce equipment investment, improve hydrogen sulfide absorption efficiency, inhibit the reactive absorption of carbon dioxide, also reduce floor space, reduce operation easier.Further, efficiently solve amine liquid and run damage problem, purified gas is used more effectively in lower procedure.
In a second aspect of the present invention, provide a kind of eddy flow intensifying device of Clause method sulfur production tail gas clean-up, this device comprises:
Tail-gas combustion stove, for unstripped gas preheating, Purge gas is burned, and heat exchange cools;
Hydrogenation reactor, for the sulphur tail gas reduction processed by mixed hydrogen, obtains hydrogen sulfide gas;
Steam generator, for carrying out one-level cooling to high-temperature gas;
Quench tower, for carrying out secondary cooling to gas, and the water droplet that cyclonic separation gas is carried secretly;
Level formula-eddy flow absorption tower, for carrying out Reducing and absorption to the hydrogen sulfide in gas, and utilizes micro-cyclone to the further Absorption Desulfurization of gas, simultaneously the amine liquid droplet of cyclonic separation entrained with;
Chimney, for burning and the discharge of cooled gas.
In the present invention, the eddy flow intensifying device of described Clause method sulfur production tail gas clean-up also can comprise:
Chilled water (chw) cooler, for carrying out heat exchange process to water, entering quench tower and utilizing after cooling; And
Chilled water (chw) circulating pump, for being extracted out from tower bottom by chilled water (chw), returning quench tower after being cooled to 33-42 DEG C and recycling.
In the present invention, at the built-in micro-cyclone of chilling tower top, the gas through quench tower chilling is carried out micro-eddy flow process, to remove the water droplet of gas entrained with, dried tail gas.
In the present invention, hydrogenating reduction gas amine absorbs the built-in micro-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 micro-cyclone part, the amine liquid eddy flow carried secretly by gas gets off, and is purified tail gas simultaneously.
In the present invention, the operating pressure of hydrogenation reactor is 0.02-0.03MPa.
In the present invention, in level formula-eddy flow absorption tower, amine liquid is atomized by atomizer, at absorption tower part adverse current absorbing hydrogen sulphide gas.
In the present invention, gas-liquid mini-hydrocyclone separation device group is set on amine liquid droplet cyclone bed reactor top, for removing the amine liquid droplet carried 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 DEG C.
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 micro-cyclone can adjust as the case may be.
In the present invention, the amine liquid hold-up after described desulfurizing and purifying technique in tail gas is 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, micro-cyclone part and amine absorption hydrogen sulfide part unite two into one, and reduce the complexity of equipment, have saved cost of investment, simultaneously high accuracy, be high efficiencyly stripped of hydrogen sulfide gas.
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 the heat exchange to 300 DEG C of tail-gas combustion stove 1 back segment, after mixing hydrogen, carry out hydrogenation reaction, by the elemental sulfur, the SO that carry in tail gas in hydrogenation reactor 2
2, COS, CS
2reduce, be hydrolyzed to H
2s; The high-temperature gas of gained, together with external deaerated water, enter in steam generator 3 and one-level cooling is carried out to high-temperature gas, 0.4MPa saturated vapor is there is in steam generator 3, high-temperature gas after hydrogenation reaction is cooled to about 170 DEG C, enters tail gas quenching tower 4 afterwards, the built-in micro-cyclone of this quench tower 4 tower top, tail gas and chilled water (chw) counter current contacting, remove the water droplet that gas is carried secretly while carrying out secondary cooling; The tail gas of gained enters a grade formula-eddy flow absorption tower 5, the built-in micro-cyclone of tower top on this grade of formula-eddy flow absorption tower 5, and first gas absorb H through conventional suction tower and poor amine liquid counter current contacting
2s, and then the amine liquid of cyclonic separation gas entrained with, rich solution returns the regeneration of solvent reclamation device; From level formula-eddy flow absorption tower 5 tower top cleaning of off-gas out, together with external nitrogen and fuel gas, enter in tail-gas combustion stove 1 and burn, high-temperature flue gas out in tail-gas combustion stove 1, together with external 3.5MPa steam, after being cooled to about 375 DEG C after reducing phlegm and internal heat respectively through steam superheater (tail-gas combustion stove 1 stage casing) and tail gas heat exchanger (tail-gas combustion stove 1 back segment), mix cold air hybrid cooling again to about 300 DEG C, air is entered by chimney 6 high-altitude of 80 meters high, remaining 3.5MPa steam adds external deaerated water, sends to pipe network.
Fig. 2 is the Sulphur tail gas desulfurization process chart according to another embodiment of the present invention.As shown in Figure 2, Clause method sulfur production tail gas enters the heat exchange to 300 DEG C of tail-gas combustion stove 1 back segment, after mixing hydrogen, carry out hydrogenation reaction, by the elemental sulfur, the SO that carry in tail gas in hydrogenation reactor 2
2, COS, CS
2reduce, be hydrolyzed to H
2s; The high-temperature gas of gained, together with external deaerated water, enter in steam generator 3 and one-level cooling is carried out to high-temperature gas, 0.4MPa saturated vapor is there is in steam generator 3, high-temperature gas after hydrogenation reaction is cooled to about 170 DEG C, enters tail gas quenching tower 4 afterwards, the built-in micro-cyclone of this quench tower 4 tower top, tail gas and chilled water (chw) counter current contacting, remove the water droplet that gas is carried secretly while carrying out secondary cooling; The chilled water (chw) chilled water (chw) circulating pump 8 used in quench tower is extracted out bottom quench tower, after chilled water (chw) cooler 7 is cooled to 33-42 DEG C, returns quench tower 4 and recycles; The tail gas of gained enters a grade formula-eddy flow absorption tower 5, the built-in micro-cyclone of tower top on this grade of formula-eddy flow absorption tower 5, and first gas absorb H through conventional suction tower and poor amine liquid counter current contacting
2s, and then the amine liquid of cyclonic separation gas entrained with, rich solution returns the regeneration of solvent reclamation device; From level formula-eddy flow absorption tower 5 tower top cleaning of off-gas out, together with external nitrogen and fuel gas, enter in tail-gas combustion stove 1 and burn, high-temperature flue gas out in tail-gas combustion stove 1, together with external 3.5MPa steam, after being cooled to about 375 DEG C after reducing phlegm and internal heat respectively through steam superheater (tail-gas combustion stove 1 stage casing) and tail gas heat exchanger (tail-gas combustion stove 1 back segment), mix cold air hybrid cooling again to about 300 DEG C, air is entered by chimney 6 high-altitude of 80 meters high, 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 overcomes in existing Sulphur tail gas desulfurization technical process and uses the desulfurizing tower such as plate column, packed tower equipment, substantially increases the problem of the loss of methyl diethanolamine and the energy charge of regeneration of absorption solution system.By absorbing the built-in micro-eddy flow absorber portion of tower top at hydrogenating reduction gas amine, poor amine liquid drop and the rapid haptoreaction of sulphur tail gas processed are absorbed, the micro-rotating flow simultaneously carrying out solution-air absorbs and is separated, decrease methyl diethanolamine loss, alleviate regenerative system energy consumption, reduce sulfur content in exhaust emissions.
2) level formula of the present invention-eddy flow absorption tower device is key reaction separation equipment, and compact conformation is simple, floor space is little, runs efficient stable.Have reaction speed fast, selective absorbing precision is high, and separative efficiency is high, the obvious advantage of the low grade of energy consumption.
3) the built-in micro-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 carry out with dehydration simultaneously, decreases the consumption of chilled water (chw).
4) built-in cyclone installation and maintenance of the present invention are convenient, and compact equipment is simple, inner space utilization rate is high, floor space is little, run efficient stable.
The sulfur method that the present invention adopts grade formula chemical absorbing and eddy flow chemical absorbing to combine, at the built-in micro-cyclone of the chilling tower top of the hydrogenating reduction gas of Clause method sulfur production tail gas, and hydrogenating reduction gas amine absorbs the built-in micro-eddy flow absorber portion of tower top, makes the concentration of hydrogen sulfide after hydrogenating reduction gas sweetening be less than 50mg/Nm
3, meet chimney SO
2outer row's concentration is less than 200mg/Nm
3index, reduces desulfurization solvent loss and energy consumption.
Embodiment
The present invention is set forth further below in conjunction with specific embodiment.But, should be understood that these embodiments only do not form limitation of the scope of the invention for illustration of the present invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Except as otherwise noted, all percentage and number are by weight.
embodiment 1:
In 40,000 tons/year of sulfur recovery facilities, according to the eddy flow intensifying method of Clause method sulfur production tail gas clean-up of the present invention and device, idetified separation is carried out to the tail gas of sulphur of sulfur-bearing, reach and complete effective absorption and separation to sulfur-containing compound in tail gas of sulphur with high efficiency, high accuracy, low-loss, tail gas sulphur dioxide concentration of emission is reached world standard, and (sulfur dioxide emissioning concentration is lower than 200mg/Nm
3).Its specific operation process and effect are described below:
1. tail gas of sulphur gas property and operating condition
The tail gas that tail gas to be processed is mainly and adopts one-level pyrolytic conversion, the conventional Claus technique sulphur part of two-stage catalyzed conversion is discharged.Main component is: the composition in sour gas mainly contains H
2s, CO
2, H
2o, hydrocarbon etc.; Tail gas of sulphur treating capacity is 2000Nm
3/ h, meteorological density operation temperature is 40 DEG C, and operating pressure is 0.02-0.03MPa; It is 115.36Nm that hydrogenation reactor mixes hydrogen amount
3/ h, the steam pressure of steam generator is 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 DEG C in tail-gas combustion stove, is mixed into hydrogenation reactor with hydrogen, under the effect of cobalt, molybdenum (CT6-5B) catalyst, and the elemental sulfur carried in tail gas, SO
2carry out hydrogenation reaction, COS, CS
2be hydrolyzed reaction, and sulfur-containing compound is converted into hydrogen sulfide gas; High-temperature gas after hydrogenation reaction is cooled to 160 DEG C through steam generator; The cryogenic gas of preliminary cooling enters tail gas quenching tower, with chilled water (chw) counter current contacting, continues washing and is cooled to 40 DEG C, by micro-cyclone processed of chilling tower top; Clause method sulfur production tail gas through over-quenching enters a grade formula-eddy flow absorption tower device with this temperature, in device absorption portion, utilizes MEDA lean solution to absorb H
2s gas, the tail gas removing hydrogen sulfide enters tower top mini-hydrocyclone separation part, by the further desulfurization process of micro-cyclone, removes the amine liquid drop carried secretly in gas simultaneously; Tail gas burning furnace is entered, under 600 DEG C of high temperature, by the sulfide, the H that remain in cleaning of off-gas by Absorption Desulfurization and through the cleaning of off-gas of cyclonic separation
2burn with hydro carbons and generate SO
2, H
2o and CO
2after incinerator high-temperature flue gas is out cooled to about 375 DEG C after reducing phlegm and internal heat respectively through steam superheater (tail-gas combustion stove stage casing) and tail gas heat exchanger (tail-gas combustion stove back segment), mix cold air hybrid cooling to 300 DEG C again, enter air by the chimney high-altitude of 80 meters high.
3. interpretation of result
After using the method for amine liquid droplet cyclone bed reactor reinforcing desulfuration to be separated, the cleaning of off-gas hydrogen sulfide content obtained 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).
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (9)
1. an eddy flow intensifying method for Clause method sulfur production tail gas clean-up, the method comprises:
Mix with hydrogen i () Clause method sulfur production tail gas carries out heat exchange process after and carry out hydrogenation reaction, with the elemental sulfur will carried in tail gas, SO
2, COS, CS
2reduce, be hydrolyzed to H
2s;
(ii) gas obtained in step (i) is carried out the rear counter-current absorption H of one-level cooling
2s, to remove the water droplet carried secretly in gas while carrying out secondary cooling;
(iii) back flow of gas obtained in step (ii) is absorbed H
2s, and then carry out cyclonic separation, to remove H further
2s, simultaneously the amine liquid of cyclonic separation entrained with, wherein, tail gas to enter in a grade formula-eddy flow absorption tower with poor amine liquid counter current contacting to absorb H
2s gas, and then remove contained H further via micro-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 being carried secretly by cleaning of off-gas out, makes amine liquid hold-up in cleaning of off-gas be less than 1ppm; And
(iv) cleaning of off-gas obtained in step (iii) is burned, after cooling, enter air.
2. the method for claim 1, is characterized in that, in step (i), at tail-gas combustion stove back segment by tail gas heating to 300 DEG C; 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, enter the H of hydrogenation reactor
2the H that tolerance provides according to online hydrogen analyzer
2concentration signal regulates; Described hydrogenation catalyst is cobalt, molybdenum catalyst.
4. the method for claim 1, is characterized in that, in step (ii), in a vapor generator 0.4MPa saturated vapor occurs, so that the gas after hydrogenation reaction is cooled to 170 DEG C, thus carries out one-level cooling; Tail gas enters in quench tower and absorbs H with chilled water (chw) counter current contacting
2s, washing is cooled to 33-42 DEG C, and the pH value range of control chilled water (chw) is between 6.5-9, thus while carrying out secondary cooling, remove the water droplet carried secretly in gas.
5. method as claimed in claim 4, it is characterized in that, the chilled water (chw) chilled water (chw) circulating pump used in quench tower is extracted out bottom quench tower, after chilled water (chw) cooler is cooled to 33-42 DEG C, returns quench tower and recycles.
6. the method for claim 1, is characterized in that, the poor amine liquid used in level formula-eddy flow absorption tower is the poor amine liquid of N-Propylene Glycol amine of the 35-45% that solvent reclamation device comes; Absorb H
2the N-Propylene Glycol amine rich solution of S returns solvent reclamation device after the boosting of rich amine solution pump.
7. the method for claim 1, is characterized in that, in step (iv), cleaning of off-gas enters tail-gas combustion stove, the sulfide, the H that will remain in cleaning of off-gas at 600 DEG C
2burn respectively as SO with hydro carbons
2, H
2o and CO
2after incinerator flue gas is out cooled to 375 DEG C after reducing phlegm and internal heat respectively through the steam superheater in tail-gas combustion stove stage casing and the tail gas heat exchanger of tail-gas combustion stove back segment, then mix cold air hybrid cooling to 300 DEG C, enter air by the chimney high-altitude of 80 meters high, wherein, SO in discharged gas fume
2concentration be less than 200mg/Nm
3.
8. an eddy flow intensifying device for Clause method sulfur production tail gas clean-up, this device comprises:
Tail-gas combustion stove (1), for carrying out heat exchange process to Clause method sulfur production tail gas;
The hydrogenation reactor (2) be connected with tail-gas combustion stove (1), to mix with hydrogen for making the gas from tail-gas combustion stove (1) and carries out hydrogenation reaction, with the elemental sulfur will carried in tail gas, SO
2, COS, CS
2reduce, be hydrolyzed to H
2s;
The steam generator (3) be connected with hydrogenation reactor (2), to carry out one-level cooling to the gas from hydrogenation reactor (2);
The quench tower (4) be connected with steam generator (3), wherein built-in micro-cyclone, absorb H for making from the gas of steam generator (3) and chilled water (chw) counter current contacting
2s, thus the water droplet removing that while carrying out secondary cooling gas carries secretly;
The level formula be connected with quench tower (4)-eddy flow absorption tower (5), the built-in micro-cyclone of its tower top, for making the gas first counter-current absorption H from quench tower (4)
2s, and then carry out cyclonic separation, to remove H further
2s, simultaneously the amine liquid of cyclonic separation entrained with;
The tail-gas combustion stove (1) be connected with level formula-eddy flow absorption tower (5), for being burned by the cleaning of off-gas from level formula-eddy flow absorption tower (5) tower top, tail-gas combustion stove (1) flue gas out enters air after cooling.
9. device as claimed in claim 8, it is characterized in that, the operating pressure of described hydrogenation reactor (2) is 0.02-0.03MPa; In level formula-eddy flow absorption tower (5), amine liquid is atomized by atomizer, at absorption tower part counter-current absorption H
2s; This device also comprises: the chilled water (chw) circulating pump (8) be connected with quench tower (4), for chilled water (chw) is extracted out from quench tower (4) bottom, and the chilled water (chw) cooler (7) to be connected with chilled water (chw) circulating pump (8), after the chilled water (chw) extracted out from quench tower (4) bottom is cooled to 33-42 DEG C, returns quench tower and recycle.
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| CN105032141A (en) * | 2015-07-20 | 2015-11-11 | 合肥科启环保科技有限公司 | Sulfur-containing tail gas treatment technology |
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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 |
| CN107132175B (en) * | 2017-07-08 | 2024-02-20 | 郑州轻工业大学 | Test platform and test method for evaluating performance of marine diesel engine tail gas desulfurization device based on land-based system |
| CN110013758B (en) * | 2018-01-09 | 2022-05-03 | 中国石油化工股份有限公司 | Safe recycling and treating method for hydrogenation tail gas in hydrogenation reaction device |
| 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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