CN105944499A - Method for removing sulfur dioxide in industrial tail gas by temperature swing adsorption - Google Patents
Method for removing sulfur dioxide in industrial tail gas by temperature swing adsorption Download PDFInfo
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- CN105944499A CN105944499A CN201610461532.4A CN201610461532A CN105944499A CN 105944499 A CN105944499 A CN 105944499A CN 201610461532 A CN201610461532 A CN 201610461532A CN 105944499 A CN105944499 A CN 105944499A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
- B01D53/0438—Cooling or heating systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
Abstract
The invention discloses a method for removing sulfur dioxide in industrial tail gas by temperature swing adsorption. The sulfur dioxide in the industrial tail gas is removed by the temperature swing adsorption through a temperature swing adsorption device; a double-tower process or a multi-tower process is adopted; the temperature of the tail gas containing the sulfur dioxide is reduced to be lower than an adsorption temperature; the adsorption temperature of an adsorption tower is set and is not higher than a flue gas outlet temperature and is not lower than a circulating water temperature; the desorption temperature of the adsorption tower is higher than the adsorption temperature; the adsorption tower is internally filled with an adsorbent for selectively adsorbing the sulfur dioxide; a time sequence of process steps is set and continuous desulfurization of the gas containing the sulfur dioxide is realized through alternative utilization of two towers or a plurality of towers. The method has the characteristics of small investment, low operation energy consumption, simplicity in operation, no adsorbent consumption, high purification depth, strong anti-impact capability and the like, can realize zero emission of SO2 in the industrial tail gas and is particularly suitable for purifying and recycling the SO2 in the tail gas of a sulfuric acid plant or purifying the SO2 in other industrial tail gas of a nearby sulfuric acid plant.
Description
Technical field
The present invention relates to SO in industrial tail gas2Purification, particularly relate to one and utilize in temp.-changing adsorption deep removal industrial tail gas two
Sulfur oxide (SO2) method, can be SO in industrial tail gas2Reclaim the unstripped gas as sulfuric acid plant after enrichment, be especially suitable for sulphuric acid
The tail gas clean-up of factory, or near have the SO of other industrial tail gas of sulfuric acid plant2Purify.
Background technology
SO2It it is one of the nuisance of industrial tail gas discharge.In October, 2013, standard GB/T 26132-2010 sulfuric acid industry is dirty
Dye thing discharge standard is formally implemented, it is desirable in sulfuric acid tail gas, sulfur dioxide concentration drops to 400mg/m3 from original 860mg/m3
Hereinafter, area below the 200mg/m3 to be dropped to of the special limit value of Air Pollutant Emission is performed.Will July 1 in 2017
SO in the air pollution emission standard implemented2Discharge standard be limited to 100mg/m3.
Existing SO2Removing sulfuldioxide can be divided into following three classes by the degree that desulfurization product recycles: first kind SO2After removing not
Recyclable or be difficult by, such as gypsum, carbide slag method etc., such produces substantial amounts of solid waste, brings secondary pollution.The
Two classes are to be aoxidized or be catalyzed oxidation by chemical reagent by SO2It is converted into dilute sulfuric acid or sulfate, such as hydrogen peroxide oxidation method, ammonia oxygen
Change method, activated carbon catalytic wet method, such as patent CN105381699A describes use hydrogen peroxide and takes off SO2, patent
CN101085410 describes a kind of SO in flue gas2The method changing into ammonium sulphate, such technology needs uninterruptedly to consume oxidation
Agent or catalyst, relate to oxidant supply radius and Cost Problems, remote districts in-convenience in use.3rd class is by low concentration
SO2Absorb or after absorption, desorbing obtains high concentration SO again2, return to antacid workshop section extracting sulfuric acid.Mainly there is patent
The activated coke method that CN102743956A records, the method report conversion ratio is 96-97%, can be SO2Exit concentration controls
Below 200mg/m3, such technology needs regenerator thermal regeneration, regeneration to need to consume amount of heat after absorption or absorption,
Use circulation pump or fan ceaselessly cyclic absorption agent, add operating cost.There is also absorbent ceaselessly to consume and more simultaneously
The problems such as raw energy consumption is big.
Patent CN103446861A has been recorded a kind of circulation process method using temp.-changing adsorption desulfurization regeneration to discard gas, the party
The basic process of method and principle are that the high sulfur-bearing regeneration off gases making temp.-changing adsorption sweetening process produce carries out organic sulfur conversion, will wherein
Organic sulfur conversion become H2S.This technique is primarily directed to organic sulfur and H2S.Use fixing currently without document or patent report
SO in bed temp.-changing adsorption method removing industrial tail gas2, especially SO in sulfuric acid plant's tail gas2Removing.
In sum, SO during prior art solves industrial tail gas2Discharge there is the problem that
(1) there are secondary pollution solid waste or the useless generation of liquid；
(2) need to use circulating fan or pump for the circular regeneration of absorbent, need substantial amounts of operation power consumption, also result in
Abrasion or the reaction of absorbent consume；
(3) desulfurization degree is the highest, generally 80-98%, tail gas SO after process2Concentration is with supplied materials gas SO2Fluctuation and fluctuate relatively
Greatly.
(4) for H2S has a patent of ADSORPTION IN A FIXED BED, but SO2ADSORPTION IN A FIXED BED technique and adsorbent is used not to have this side
The report in face.Above-mentioned activated coke is not proper adsorbent, and participation is reacted by it.
(5) regeneration energy consumption is high, there is presently no patent or document report is arranged by sequential and effectively reduces temp.-changing adsorption regeneration
The method of heat.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the present invention provides SO in a kind of temp.-changing adsorption removing industrial tail gas2Method,
Use SO in fixed bed temp.-changing adsorption removing industrial tail gas2, and the higher concentration SO desorbed2Gas reclaims and is used for preparing
The method of sulphuric acid.Achieve SO in industrial tail gas2Zero-emission, be particularly suited for SO in sulfuric acid plant's tail gas2Purify and reclaim；
Avoid de-SO2Produce a large amount of secondary pollution, overcome bigger operation energy consumption, adsorbent/catalyst consumption.
Present invention provide the technical scheme that
SO in a kind of temp.-changing adsorption removing industrial tail gas2Method, by temperature swing absorption unit realize temp.-changing adsorption removing industry
SO in tail gas2, temperature swing absorption unit includes what at least two adsorption tower, heater and multiple circulation for controlling air-flow disconnected
Control valve；Containing SO2The temperature of tail gas drops to below adsorption temp, and with certain pressure by adsorption tower, adsorption temp not higher than contains
Sulfur flue gas is (containing SO2Tail gas) outlet temperature, be not less than circulating water temperature；The desorption temperature of adsorption tower is higher than adsorption temp；Often
Individual adsorption tower is respectively arranged with and can select to adsorb SO2Adsorbent；Regeneration gas is flow to adsorption tower, discharges stripping gas from adsorption tower；Often
Individual adsorption tower can experience five basic steps, including:
(1) air inlet adsorption step A；
(2) high temperature regeneration gas heating steps HW；
(3) heating of high temperature regeneration gas produces height containing SO simultaneously2Gas returns acid accumulator plant step HP；
(4) low-temp recovery air cooling, starts a period of time generation containing SO2High stripping gas returns acid accumulator plant step LP；
(5) cold step LC of low-temp recovery air-blowing；
In above-mentioned five basic steps, the technological process that step is different with the design of the time of step can be selected；Wherein, step HW
Time can be zero；The time of step LP and step LC can not be all zero simultaneously；By controlling the switch of valve, two towers are set
Or the sequential step of multitower processing step, realization is used alternatingly to containing SO by two towers or multitower2The continuous desulfurization of tail gas.
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, further, heating or cooling time, all by with
Process sulfur-bearing (SO2) regeneration gas flows into adsorption tower by direction that tail gas is contrary so that at adsorption column outlet end (regeneration gas entrance point)
Adsorbent keep fresh so that again absorption time outlet tail gas in SO2Concentration is the lowest；
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, further, heat time heating time is set, heats adsorption tower
The port of export (entrance point of regeneration gas), when adsorption tower temperature is heated to a certain degree, adsorption column outlet end has regenerated, absorption
Tower bed leading portion adsorbent accumulation of heat；Stopping heating, the adsorbent utilizing the entrance point of adsorption column outlet end or regeneration gas to heat comes
Heating regeneration gas, the regeneration gas flow forward of heating, the entrance point of heating adsorption tower or the adsorbent of regeneration gas outflow end make it again
Raw.
Adsorption tower temperature is heated to a certain degree of criterion x: set X=(TGo out-TA)/(TDesorbing-TA), TGo outIt is expressed as
The temperature of tower outlet section, T during desorbingDesorbingRepresent the desorption temperature set, TAAdsorption temp；The value being typically chosen x is 0.2
0.95, the span of optimization is 0.4 0.8.
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, further, when the temperature of sulfur-containing tail gas is higher than required
During the adsorption temp wanted, temperature swing absorption unit may also include the cooler for sulfur-containing tail gas is cooled to below adsorption temp.
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, it is possible to further according to the row of user's sulfur-containing tail gas
The power of bleeding off pressure chooses whether to need aerator, when sulfur-containing tail gas pressure (gauge pressure) is not more than adsorption tower pressure drop with piping loss sum,
Temperature swing absorption unit may also include aerator, for passing through filling batch (adsorption tower) to sulfur-containing tail gas supercharging with guarantee tail gas.
When cooler and aerator are required for, order before and after both can being selected to place with unrestricted choice；In sulfur-containing tail gas temperature
Time higher, before cooler should be placed on.
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, further, when process after tail gas pressure be not more than sulfur
When acid workshop inlet pressure, stripping gas can not be passed through sulfuric acid plant smoothly, temperature swing absorption unit may also include for gas boosting
So that the aerator of the entrance of sulphuric acid device is sent back to after passing through desorbing adsorption tower.
The present invention removes SO in sulfuric acid plant's tail gas by temp.-changing adsorption2, can be realized by double tower device as shown in Figure 1, bag
Include: adsorption tower 1, adsorption tower 2, cooler 3, aerator 4, aerator 5 and heater 6；Control valve 7 19 to be used for
Control opening or disconnecting of air-flow；Technique service valve 20 is standard-sized sheet when properly functioning；Wherein valve 16 is to have circulating-heating to need
Will time use, i.e. stripping gas initial a period of time concentration is the lowest, but has certain temperature, can be the stripping gas of this period of time
Loop back continuation heating and as regeneration gas.Regeneration gas regenerates for adsorption tower, is out containing SO from adsorption tower later2
Stripping gas.
Said apparatus operationally, is respectively arranged with in two adsorption towers and can select to adsorb SO2Adsorbent, first containing SO2Tail gas passes through
3 temperature of cooler drop to below adsorption temp, by passing through adsorption tower 1 through valve 7 after aerator 4 supercharging, handle well
Clean gas is discharged into air through valve 11 as discharge gas；Adsorption tower 2 carries out heating desorption and blows cold simultaneously.Desorbing and blow cold making
With the tail gas after air or process, through valve 17 by aerator 5 during heating, through valve after valve 18 is by heater 6
20,14 entering adsorption tower 2, carry out blowing cold after heating desorption, the tail gas after processing when blowing cold adds by getting around after aerator 5
Hot device directly enters adsorption tower 2 by valve 19,14.Stripping gas returns to the entrance unstripped gas as Sulphuric acid of sulphuric acid device.
Two towers are used alternatingly, thus ensure the continuous operation of desulfurization.
When in this processing step, LC step is not zero, the stripping gas of generation can reach atmospheric emission standard, directly can arrange to air
Gas.Further, in order to really realize " zero " discharge, controlling this technique not to airborne release gas Han SO2, LC step is produced
Raw stripping gas directly removes another one adsorption tower.
The adsorption tower quantity that the fixed bed temperature swing adsorption process that the present invention uses is used is 2-32 tower, in order to enable continuous processing, extremely
Need two adsorption towers less.Can be according to processing tolerance size, the stripping gas SO of requirement2Fluctuation of concentration amplitude and heat integration
Utilization power determines selection adsorption tower quantity.
The filled out adsorbent of adsorption tower that the present invention uses has selection absorption SO2Ability, heating time can be SO2Desorb.
The loadings that adsorbent needs determined according to the single adsorptions time.The adsorption time selected needs more than or equal to heating desorption
With sum cool time.Desorption time is 1-40 hour, is typically chosen 0.5 20 hours cool time.
Depending on the selection of the adsorption temp characteristic according to filled out adsorbent, but not above the outlet temperature of sulfur-containing smoke gas, do not want yet
The circulating water temperature that can be provided by less than user.So temperature is chosen as 0 100 DEG C, optimum adsorption temp is 15-60 DEG C.
The desorption temperature of adsorption tower needs higher than adsorption temp, is typically chosen 80-500 DEG C, and optimal choice is 150-350 DEG C.
Adsorption tower regeneration gas consumption is the 0.1-20% processing tolerance, and optimized choice is 0.5 10%.
The operation adsorptive pressure of this technique selects according to sulfur-containing tail gas, and selection pressure is that normal pressure adds 10kpa to sulfur-containing tail gas pressure
Scope, optimize opereating specification be 0 10kpa.Regeneration pressure is chosen as-10 10Kpa, and optimized choice is-5 5Kpa.
Packed bed (adsorption tower) pressure drop that the present invention uses is 1-20Kpa, and optimized choice is 2-8Kpa.
It is little that the present invention needs regeneration to add heat, and the present invention, in order to reduce the heat required for heating, selects energy of adsorption at low concentrations
The adsorbent that power is big so that adsorb same SO2Required adsorbent inventory is few, and it is the fewest that what regeneration needed adds heat.Adopted
The SO brought into more than or equal to sulfur-containing smoke gas in adsorption time is needed with the dynamic adsorbance of adsorbent2Sulfur content, sorbent characteristics requirement
Under adsorption temp, SO2Concentration is less than 1000mg/m3Time, the dynamic adsorption capacity of adsorbent is more than 5mgSO2/ g adsorbent, excellent
Change selected adsorbent dynamic adsorption capacity more than 20mgSO2/ g adsorbent.
Adding, according to regeneration, the requirement that heat is little, the present invention arranges reasonable sequential to make full use of the stripping gas heat of eliminating, is arranging
Stripping gas is considered to be circulated use during sequential.
Adding, according to regeneration, the requirement that heat is little, the most significantly advantage of this technique is: close during heating desorption (HW)
Reason arranges heat time heating time, arranges heating adsorption column outlet end (entrance point of regeneration gas) certain time, when adsorption tower temperature heats
Time to a certain extent, adsorption column outlet end has regenerated, but bed front-end temperature is higher, and adsorbent has stored amount of heat.
At this moment can stop heating, the adsorbent utilizing adsorption column outlet end (i.e. the entrance point of regeneration gas) to heat carrys out heating regeneration gas,
The regeneration gas flow forward of heating removes the adsorbent of the entrance point (i.e. regeneration gas outflow end) of thermal regeneration adsorption tower.On the one hand can
To make full use of the heat within bed, on the other hand can also cool down the port of export of adsorption tower in advance, reduce cool time.
According to above-mentioned requirements, adsorption tower temperature is heated to a certain degree of criterion and is: set X=(TGo out-TA)/(TDesorbing-TA),
X represents regeneration temperatures criterion；TGo outIt is expressed as the temperature of tower outlet section, T during desorbingDesorbingRepresent the desorption temperature set,
TAAdsorption temp；The value being typically chosen x is 0.2 0.95, and the span of optimization is 0.4 0.8.
According to outlet SO2The requirement that concentration is low, when no matter heating or cool down, is required for by the direction contrary with processing sulfur-containing tail gas
Regeneration gas is flowed into adsorption tower, is always ensured that the adsorbent at adsorption column outlet end (regeneration gas entrance point) keeps fresh, again
SO in tail gas is exported during absorption2Concentration can guarantee that the lowest.
According to above-mentioned requirements, regeneration gas needs heating, and the thermal source of heating can be electricity, steam, discarded waste heat, it is also possible to is it
Combination in any mode.Natively having surplus heat in the case of producing steam in factory, optimized choice is to use a part remaining
Heat directly heats regeneration gas, without with waste heat for generating steam, then uses steam heating regeneration gas.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention provides one to utilize SO in temp.-changing adsorption deep removal industrial tail gas2Method, use fixed bed temp.-changing adsorption take off
Except SO in industrial tail gas2, can be the higher concentration SO desorbed2Reclaiming the unstripped gas as sulfuric acid plant after enrichment, recovery is used for
Prepare sulphuric acid, it is achieved that SO in industrial tail gas2Zero-emission, be particularly suited for SO in sulfuric acid plant's tail gas2Purify and reclaim, or
The SO of other industrial tail gas of sulfuric acid plant is had near person2Purify.
The technical scheme that the present invention provides can be avoided removing SO2Produce a large amount of secondary pollution, overcome bigger operation energy consumption, absorption
Agent/catalyst consumption.This invention has small investment, and operation energy consumption is low, simple to operate, without adsorbent consumption, purify the degree of depth high,
The features such as strong shock resistance, purifying rate is more than 99.8%, containing SO in the tail gas after process2Amount is less than 10mg/m3, meansigma methods is less than
2mg/m3。
Accompanying drawing explanation
Fig. 1 is that temp.-changing adsorption of the present invention removes SO in sulfuric acid plant's tail gas2Use the structure drawing of device of two basic tower process；
Fig. 2 is the structure drawing of device that the present invention uses two tower temperature swing adsorption process of simplification；
In Fig. 1～Fig. 2, T1, T2 adsorption tower；3 coolers；4 aerators, 5 aerators；6 heaters；7～19
Control valve；20 technique service valves.
Fig. 3 is that temp.-changing adsorption of the present invention removes SO in sulfuric acid plant's tail gas2Use the structure drawing of device of three tower absorbing process；
In Fig. 3, T1, T2, T3 adsorption tower；3 coolers；4 aerators, 5 aerators；6 heaters；7～26
Control valve；27 technique service valves.
Fig. 4 temp.-changing adsorption of the present invention removes SO in sulfuric acid plant's tail gas2Use the dress of six towers (three absorption two heating one coolings) technique
Put structure chart；
In Fig. 4, T1～T6 adsorption tower；3 coolers；4 aerators, 5a～5c aerator；6a, 6b heater；
7～48 control valve.
Detailed description of the invention
Below in conjunction with the accompanying drawings, further describe the present invention by embodiment, but limit the scope of the present invention never in any form.
The present invention provides one to utilize SO in temp.-changing adsorption deep removal industrial tail gas2Method, use fixed bed temp.-changing adsorption take off
Except SO in industrial tail gas2, can be the higher concentration SO desorbed2Reclaiming the unstripped gas as sulfuric acid plant after enrichment, recovery is used for
Prepare sulphuric acid, it is achieved that SO in industrial tail gas2Zero-emission.
In the specific implementation, temp.-changing adsorption can be realized by basic double tower device as shown in Figure 1 to remove in sulfuric acid plant's tail gas
SO2.Double tower device as shown in Figure 1 includes: adsorption tower 1, adsorption tower 2, cooler 3, aerator 4, aerator 5 and add
Hot device 6；Device number 7 19 is to control valve, for controlling the on/off of air-flow；20 is technique service valve, time properly functioning is
Standard-sized sheet；Wherein valve 16 is to use when there being circulating-heating to need, i.e. stripping gas initial a period of time concentration is the lowest, but has certain
Temperature, can loop back the stripping gas of this period of time continuation heating and as regeneration gas.
During above-mentioned double tower device busy, two adsorption towers are respectively arranged with and can select to adsorb SO2Adsorbent, first containing SO2Tail gas
Below adsorption temp is dropped to, by passing through adsorption tower 1, through valve through valve 7 after aerator 4 supercharging by 3 temperature of cooler
Door 11 is discharged into air as discharge gas.Adsorption tower 2 carries out heating desorption and blows cold simultaneously.Desorbing and blow cold use air or place
Tail gas after reason, through valve 17 by aerator 5 during heating, enters through valve 20,14 after valve 18 is by heater 6
Adsorption tower 2, carries out blowing cold after heating desorption, the tail gas after processing when blowing cold directly leads to by getting around heater after aerator 5
Cross valve 19,14 and enter adsorption tower 2.Stripping gas returns to the entrance unstripped gas as Sulphuric acid of sulphuric acid device.Two towers alternately make
With, thus ensure the continuous operation of desulfurization.
Fig. 2 is the structure drawing of device that the present invention uses two tower temperature swing adsorption process of simplification；The corresponding two tower process steps pair simplified
The sequential step answered is as shown in table 2, simplifies flow process.
The effect of cooler 3 is that sulfur-containing tail gas is cooled to below adsorption temp, can choose whether according to the temperature of sulfur-containing tail gas
Need cooler；Cooler can not be used when the temperature of sulfur-containing tail gas is less than required adsorption temp.
In Fig. 1 and Fig. 2, the effect of aerator 4 is to ensure that tail gas can pass through filling batch to sulfur-containing tail gas supercharging.Permissible
Discharge pressure according to user's sulfur-containing tail gas chooses whether to need aerator；The basis for estimation removing aerator is sulfur-containing tail gas pressure
(gauge pressure) is more than adsorption tower pressure drop and piping loss sum.
When cooler and aerator are required for, order before and after both can being selected to place with unrestricted choice；In sulfur-containing tail gas temperature
Time higher, before cooler should be placed on.
In Fig. 1 and Fig. 2, the effect of aerator 5 is gas boosting to send sulphuric acid back to after passing through desorbing adsorption tower and setting
Standby entrance, if tail gas pressure more than sulfuric acid plant inlet pressure and can guarantee that stripping gas can be passed through sulphuric acid car smoothly after Chu Liing
Between, at this, aerator can omit.
The sequential of basic two Deethanizer design such as table 1.In table 1, A is the air inlet adsorption treatment stage；HW is that high temperature regeneration gas heats rank
Section；HP is that the heating of high temperature regeneration gas returns stripping gas to the acid accumulator plant stage simultaneously；LP is that low-temp recovery air cooling is simultaneously stripping gas
Return acid accumulator plant；LC is that the cold stripping gas of low-temp recovery air-blowing removes another adsorption tower；O represents that valve leaves；C represents that valve closes；Valve 20 by
Then technique maintenance valve, always on time properly functioning.
The valve switch order of 1 liang of tower ten step desulphurization process of table
Table 2 is the sequential step that the two tower process steps simplified are corresponding.
Table 2 simple flow two tower step
In many tower process, can adsorb with multiple towers simultaneously, set total adsorption tower number as n, the tower number simultaneously adsorbed is m.Enter
Gas blower fan can use a blower fan simultaneously to the air inlet simultaneously of m tower, it is also possible to the tower adsorbed each respectively with m blower fan.
When air intake valve selects, valve can be each used to be connected with m blower fan with n tower.So the valve quantity of air inlet be n ×
m.In order to save valve, it is also possible to arrange each blower fan and be fixed to n/m tower air inlet therein.Such as six tower 3 absorbing process,
Can select corresponding 6 valves of each blower fan, air intake valve quantity is 18.Can also the corresponding adsorption tower 1,4 of blower fan 1,
The corresponding adsorption tower 2,5 of blower fan 2, the corresponding adsorption tower 3,6 of blower fan 3, such intake valve just has only to 6.When adsorption tower quantity
When not being the integral multiple of blower fan, it is also possible to the adsorption tower that fan is corresponding is allocated, such as 5 tower 2 absorbing process, blower fan 1
Corresponding adsorption tower 1,2,3, the corresponding absorption 3,4,5 of blower fan 2, such air intake valve is 6, enterprising in the open sequential of valve
Row is arranged, as equally ensureing each tower air inflow.In a word, in multitower technological process, multitower adsorbs air inlet simultaneously
Various changes be all the spirit and scope of present invention.
In many tower process, when heating steps only heats and does not has thermal cycle, it is possible to use a regeneration heating blower and one
Heater.But, when heating steps is more than heating and has situation about coupling with other step, such as, when heating steps
Some adsorption towers heating, some adsorption towers are at circulating-heating, in this case, the quantity of heating blower and heater with adding
The adsorption tower quantity of heat is equal, i.e. has how many adsorption tower heating to be accomplished by mating how many heating blowers and heaters.
Fig. 3 is apparatus structure and the process chart of three tower temp.-changing adsorption desulfurization, and table 3 is that three tower temp.-changing adsorption sulfur removal technologies are corresponding
Each tower work step；Wherein, at each tower step table of the tower carrying out adsorbing the while that table 3a having two in being three towers；Table
3b is each tower step table of the same time only one of which tower for adsorbing in three towers.
Each tower step table of table 3a tri-tower 2 tower absorbing process
Each tower step table of table 3b tri-tower 1 tower absorbing process
Fig. 4 is apparatus structure and the process chart of six tower temp.-changing adsorption desulfurization, and table 4 is corresponding each of six tower temp.-changing adsorption desulfurization
The one of which arrangement mode of the step of tower: 1 cooling process is heated in six tower 3 air inlets 2.HW step desorbing in this table
Gas can go another just to start adsorption step adsorption tower, and the air-flow of LC starts the tower of HP to another.As a example by T1 tower, it
HW the A, its LC of T4 tower can be gone to remove the HP of T3 tower.In this table, HW Step Time can be 0, LP and LC
In one of them Step Time can be 0.
Each tower step table of table 4 six tower (3 absorption 2 heating 1 cooling) technique
The filled out adsorbent of adsorption tower that the present invention uses has selection absorption SO2Ability, heating time can be SO2Desorb.
The loadings that adsorbent needs determined according to the single adsorptions time.The adsorption time selected needs more than or equal to heating desorption
With sum cool time.One step ground, desorption time is 1-40 hour, is typically chosen 0.5 20 hours cool time.
Depending on the selection of the adsorption temp characteristic according to filled out adsorbent, but not above the outlet temperature of sulfur-containing smoke gas, do not want yet
The circulating water temperature that can be provided by less than user.So temperature is chosen as 0 100 DEG C, optimum adsorption temp is 15-60 DEG C.
The desorption temperature of adsorption tower needs higher than adsorption temp, is typically chosen 80-500 DEG C, and optimal choice is 150-350 DEG C.
Adsorption tower regeneration gas consumption is the 0.1-20% processing tolerance, and optimized choice is 0.5 10%.
The operation adsorptive pressure of this technique selects according to sulfur-containing tail gas, and selection pressure is that normal pressure adds 10kpa to sulfur-containing tail gas pressure
Scope, optimize opereating specification be 0 10kpa.Regeneration pressure is chosen as-10 10Kpa, and optimized choice is-5 5Kpa.
The packed bed pressure drop that the present invention uses is 1-20Kpa, and optimized choice is 2-8Kpa.
The present invention disclosure satisfy that operation energy consumption low, regeneration add the requirement that heat is little.Due to the required heat of heating and adsorbent amount
Being directly proportional, the present invention, in order to reduce the heat required for heating, selects the adsorbent that absorbability at low concentrations is big so that inhale
Attached same SO2Required adsorbent inventory is few so that regeneration need to add heat few.Used adsorbent dynamic
Adsorbance needs the SO brought into more than or equal to sulfur-containing smoke gas in adsorption time2Sulfur content, sorbent characteristics requires under adsorption temp,
SO2When concentration is less than 1000mg/m3, the dynamic adsorption capacity of adsorbent is more than 5mgSO2/ g adsorbent, optimized choice adsorbent moves
State adsorption capacity is more than 20mgSO2/ g adsorbent.
The present invention arranges reasonable sequential to make full use of the stripping gas heat of eliminating, considers stripping gas to follow when arranging sequential
Ring uses, and adds, to reach to regenerate, the effect that heat is little.
Adding, according to regeneration, the requirement that heat is little, the most significantly advantage of this technique is: rationally arranges during heating desorption and adds
The heat time, it is set, when adsorption tower temperature is heated to certain journey heating adsorption column outlet end (entrance point of regeneration gas) certain time
When spending, adsorption column outlet end has regenerated, but bed front-end temperature is higher, and adsorbent has stored amount of heat.At this moment may be used
To stop heating, the adsorbent utilizing the port of export (entrance point of regeneration gas) to heat carrys out heating regeneration gas, the regeneration gas of heating
Flow forward removes the adsorbent of the entrance point (regeneration gas outflow end) of thermal regeneration adsorption tower.On the one hand bed can be made full use of
Internal heat, on the other hand can also cool down the port of export of adsorption tower in advance, reduces cool time.
According to above-mentioned requirements, adsorption tower temperature is heated to a certain degree of criterion x and is: set X=(TGo out-TA)/(TDesorbing
-TA), TGo outIt is expressed as the temperature of tower outlet section, T during desorbingDesorbingRepresent the desorption temperature set, TAAdsorption temp；It is typically chosen x
Value be 0.2 0.95, the span of optimization is 0.4 0.8.
According to outlet SO2The requirement that concentration is low, when no matter heating or cool down, is required for by the direction contrary with processing sulfur-containing tail gas
Regeneration gas is flowed into adsorption tower, is always ensured that the adsorbent at adsorption column outlet end (regeneration gas entrance point) keeps fresh, again
SO in tail gas is exported during absorption2Concentration can guarantee that the lowest.
According to above-mentioned requirements, regeneration gas needs heating, and the thermal source of heating can be electricity, steam, discarded waste heat, it is also possible to is it
Combination in any mode.Natively having surplus heat in the case of producing steam in factory, optimized choice is to use a part remaining
Heat directly heats regeneration gas, without with waste heat for generating steam, then uses steam heating regeneration gas.
Although having been presented for process chart and the Ge Ta job step table of four preferred versions, those skilled in the art can recognize
Knowledge is arrived, and there is other embodiments in the spirit and scope of patent requirements.Such as, some step in five steps is can
With omit；Some equipment is dispensed with in varied situations；Adsorption tower number is 2 32, even if selecting adsorption tower number solid
Being set to n, adsorption tower number can be 1 to (n-1) simultaneously, set add circulating-heating, thermal desorption, desorbing while blow cold, individually
Blow cold quantity, all there is various arrangement and combination.Reason due to length, it is impossible to enumerate.But as long as being that this patent is wanted
In the spirit and scope asked, it it is all the summary of the invention of this patent.
Embodiment one:
Process 150000m3/ h, sulfur-containing tail gas forms: SO2Content is at 500 2000mg/m3Fluctuation, meansigma methods 800mg/m3；
Exhaust temperature, 40-65 DEG C；Tail gas pressure, 6Kpa；Cooling temperature of circulating water, 30 DEG C；Select adsorbent: there is SO2Select
The PU-28 of absorbability, adsorption temp is 35-40 DEG C, and under mean concentration, dynamic adsorption capacity is 60mgSO2/ g adsorbent.
Select two tower sequential, flow chart such as Fig. 1, sequential arrangement such as table 1, each Step Time is set to table 5:
The set of time of the two each steps of tower sequential selected by table 5
| Step | A | HR | HP | LP | LC |
| Time/hour | 24 | 3 | THP | 6 | 24-3-THP-6 |
Wherein THPDetermine according to regeneration temperatures criterion X, set stripping gas outlet temperature by X, when temperature reaches
After standard, switch into next step voluntarily by control program.
Adsorbent selects dynamic adsorption capacity to be 20-100mgSO2The adsorbent of/g, it is 104 tons that two towers amount to loading amount.
Adsorption tower design pressure drop 2-4Kpa, piping loss 1.5Kpa；
Owing to tail gas pressure is more than adsorption tower pressure drop and piping loss sum, it is possible to omit aerator 4；
Regeneration gas temperature selects 300 DEG C；3% regulated the flow of vital energy at selection, so being 4500m3/h.Regeneration gas thermal source uses sulfuric acid plant
Waste heat, standby electricity heater；
Regeneration temperatures criterion X takes 0.4；
SO2Average emission concentration is less than 1mg/m3。
Embodiment two:
Processing tail gas situation identical with embodiment one, embodiment two selects three tower process flow processs, and the air inlet simultaneously of two towers, flow chart is such as
Fig. 3, each tower step is as shown in table 3, and each Step Time is set to table 6:
The set of time of the three each steps of tower sequential selected by table 6
| Step | A | HR | HP | LP | LC |
| Time/hour | 26 | 3 | THP | 3 | 13-3-THP-3 |
Owing to two towers adsorb simultaneously, so remaining four step is adsorption time half.Each tower air inflow is 75000m3/h。
Adsorbent selects dynamic adsorption capacity to be 20-100mgSO2The adsorbent of/g, it is 84 tons that three towers amount to loading amount.
Adsorption tower selects radial bed, designs pressure drop 2-4Kpa, piping loss 1.5Kpa；
Owing to tail gas pressure is more than adsorption tower pressure drop and piping loss sum, it is possible to omit aerator 4,
Regeneration gas temperature selects 300 DEG C, selects 2.5% regulated the flow of vital energy at air inlet, so being 150000 × 2.5% equal to 3750m3/h。
The waste heat of regeneration gas thermal source sulfuric acid plant.Standby electricity heater.
Regeneration temperatures criterion X takes 0.5.
SO2Average emission concentration is less than 1mg/m3。
Embodiment three:
Treatment temperature, pressure, composition are identical with embodiment one；The process tolerance of the present embodiment becomes 300000m3/h。
Selecting six tower process, three tower absorption, two tower heating, a tower blows cold.Flow chart such as Fig. 4, each tower step is as shown in table 4,
Each Step Time is set to table 7:
The set of time of the six each steps of tower sequential selected by table
| Step | A | HR | HP | LP | LC |
| Time/hour | 18 | 3 | 9 | 3 | 3 |
Owing to three towers adsorb simultaneously, so remaining four step sum is equal to adsorption time.Each tower air inflow is 100000m3/h。
Adsorbent selects dynamic adsorption capacity to be 20-100mgSO2The adsorbent of/g, it is 153 tons that six towers amount to loading amount.
Adsorption tower design pressure drop 3-4Kpa, piping loss 1.5Kpa；
Owing to tail gas pressure is more than adsorption tower pressure drop and piping loss sum, it is possible to omit aerator 4,
Regeneration gas temperature selects 300 DEG C, selects 2.5% regulated the flow of vital energy at air inlet, so being 300000 × 2.5% equal to 7500m3/h。
Having two towers regenerating, also a tower is using low-temp recovery gas, so each blower fan tolerance is 2500m simultaneously3/h。
The waste heat of regeneration gas thermal source sulfuric acid plant.Standby electricity heater.
SO2Average emission concentration is less than 1mg/m3。
It should be noted that publicizing and implementing the purpose of example is that help is further appreciated by the present invention, but those skilled in the art
It is understood that various substitutions and modifications are all possible without departing from the present invention and spirit and scope of the appended claims.
Therefore, the present invention should not be limited to embodiment disclosure of that, and the scope of protection of present invention defines with claims
Scope is as the criterion.
Claims (11)
1. a method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas, realizes temp.-changing adsorption by temperature swing absorption unit and removes
Sulfur dioxide in industrial tail gas；Described temperature swing absorption unit uses double tower or many tower process, including at least two adsorption tower, one
Individual or multiple heaters and multiple for controlling the control valve that airflow disconnects；Described temp.-changing adsorption removing industrial tail gas in two
The method of sulfur oxide specifically includes following steps:
Temperature containing SO 2 tail gas is dropped to below adsorption temp, passes through adsorption tower with certain pressure；
Set the adsorption temp of adsorption tower, make the adsorption temp of adsorption tower not higher than contain the flue gas exit temperature of SO 2 tail gas,
It is not less than circulating water temperature；Make the desorption temperature of adsorption tower higher than adsorption temp；
Each adsorption tower is respectively arranged with the adsorbent that can select to adsorb sulfur dioxide；By controlling the switch of valve, two towers or are set more
The sequential of tower process step, is used alternatingly realization to the continuous desulfurization containing sulfur dioxide gas by two towers or multitower；
The clean gas handled well is directly discharged to air.
2. during temp.-changing adsorption removes industrial tail gas as claimed in claim 1, the method for sulfur dioxide, is characterized in that, each adsorption tower
In can experience five basic steps, including:
(1) air inlet adsorption step A；
(2) high temperature regeneration gas heating steps HW；
(3) heating of high temperature regeneration gas produces the height gas containing sulfur dioxide simultaneously and returns acid accumulator plant step HP；
(4) low-temp recovery air cooling, starts a period of time generation containing SO2High stripping gas returns acid accumulator plant step LP；
(5) cold step LC of low-temp recovery air-blowing.
3. during temp.-changing adsorption removes industrial tail gas as claimed in claim 2, the method for sulfur dioxide, is characterized in that, described step
The time of HW can be zero；The time of described step LP and step LC can not be all zero simultaneously.
4. during temp.-changing adsorption removes industrial tail gas as claimed in claim 2, the method for sulfur dioxide, is characterized in that, in heating or cold
But time, all by with the direction processed containing SO 2 tail gas is contrary, regeneration gas being flowed into adsorption tower, adsorption column outlet end is regeneration gas
Entrance point so that the adsorbent at adsorption column outlet end keeps fresh；Described regeneration gas consumption is the 0.1-20% processing tolerance,
It is preferably and processes the 0.5 10% of tolerance.
5. during temp.-changing adsorption removes industrial tail gas as claimed in claim 4, the method for sulfur dioxide, is characterized in that, arrange adsorption tower
The heat time heating time of the port of export, when adsorption column outlet end regenerated, adsorption tower bed leading portion adsorbent accumulation of heat time, stop heating,
The adsorbent utilizing adsorption column outlet end to heat carrys out heating regeneration gas, the regeneration gas flow forward after heating, reheats adsorption tower
The adsorbent of entrance point make it regenerate.
6. during temp.-changing adsorption removes industrial tail gas as claimed in claim 1, the method for sulfur dioxide, is characterized in that, when containing titanium dioxide
When the temperature of sulfur tail gas is higher than set adsorption temp, described temperature swing absorption unit also includes for containing SO 2 tail gas cold
But to the cooler below adsorption temp.
7. during temp.-changing adsorption removes industrial tail gas as claimed in claim 1, the method for sulfur dioxide, is characterized in that, when containing titanium dioxide
When the pressure of sulfur tail gas is not more than adsorption tower pressure drop with piping loss sum, described temperature swing absorption unit also includes aerator, is used for
Give containing SO 2 tail gas supercharging to ensure that tail gas can pass through adsorption tower.
8. during temp.-changing adsorption removes industrial tail gas as claimed in claim 1, the method for sulfur dioxide, is characterized in that, tail after processing
When the pressure of gas no more than sulfuric acid plant inlet pressure, stripping gas can not be passed through sulfuric acid plant smoothly, described temperature swing absorption unit is also
Including for gas boosting so that the aerator of the entrance of sulphuric acid device is sent back to after passing through desorbing adsorption tower.
9. during temp.-changing adsorption removes industrial tail gas as claimed in claim 1, the method for sulfur dioxide, is characterized in that, described alternating temperature is inhaled
Adsorption device uses double tower process, including: adsorption tower one, adsorption tower two, cooler, aerator one, aerator two and heater；
Also include multiple valve；Comprise the steps:
By cooler, temperature is dropped to below adsorption temp containing SO 2 tail gas；
By being discharged into greatly as discharge gas through valve by adsorption tower one, the clean gas handled well through valve after aerator one supercharging
Gas；Adsorption tower two carries out heating desorption and blows cold simultaneously；Desorbing and blow cold use air or process after tail gas, pass through during heating
Aerator two, then by entering adsorption tower two after heater, carries out blowing cold after heating desorption, the tail gas after processing when blowing cold leads to
Get around heater after crossing aerator two and be directly entered adsorption tower two；
Stripping gas returns to the entrance unstripped gas as Sulphuric acid of sulphuric acid device；
Two towers are used alternatingly, thus ensure the continuous operation of desulfurization.
10. during temp.-changing adsorption removes industrial tail gas as claimed in claim 1, the method for sulfur dioxide, is characterized in that, described absorption
The quantity of tower is 2～32；Described adsorption temp is 0 100 DEG C, and optimum adsorption temp is 15-60 DEG C；The desorption temperature of adsorption tower
Selecting 80-500 DEG C, optimal choice is 150-350 DEG C.
In 11. temp.-changing adsorption as claimed in claim 1 removing industrial tail gas, the method for sulfur dioxide, is characterized in that, described absorption
Agent is under adsorption temp, when sulfur dioxide concentration is less than 1000mg/m3Time, the dynamic adsorption capacity of adsorbent is more than 5mgSO2/g
Adsorbent；Preferably, adsorbent dynamic adsorption capacity is more than 20mgSO2/ g adsorbent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106693604A (en) * | 2016-11-17 | 2017-05-24 | 北京同方洁净技术有限公司 | Activated carbon air purifier and purification method thereof |
| CN111375273A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Treatment method and device for sulfur dioxide-containing waste gas |
| CN111375274A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Containing SO2Gas treatment method and apparatus |
| CN114307531A (en) * | 2021-12-30 | 2022-04-12 | 四川天采科技有限责任公司 | Refinery VOCs tail gas fluidized moving bed temperature swing adsorption FMBTSA purification process and system |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693604A (en) * | 2016-11-17 | 2017-05-24 | 北京同方洁净技术有限公司 | Activated carbon air purifier and purification method thereof |
| CN106693604B (en) * | 2016-11-17 | 2019-05-03 | 北京同方洁净技术有限公司 | Activated carbon air purifier and its purification method |
| CN111375273A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Treatment method and device for sulfur dioxide-containing waste gas |
| CN111375274A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Containing SO2Gas treatment method and apparatus |
| CN111375273B (en) * | 2018-12-31 | 2022-05-03 | 中国石油化工股份有限公司 | Treatment method and device for sulfur dioxide-containing waste gas |
| CN114307531A (en) * | 2021-12-30 | 2022-04-12 | 四川天采科技有限责任公司 | Refinery VOCs tail gas fluidized moving bed temperature swing adsorption FMBTSA purification process and system |
| CN114307531B (en) * | 2021-12-30 | 2022-11-29 | 四川天采科技有限责任公司 | Refinery VOCs tail gas fluidized moving bed temperature swing adsorption FMBTSA purification process and system |
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