CN105944499B - A kind of method that temp.-changing adsorption removes sulfur dioxide in industrial tail gas - Google Patents
A kind of method that temp.-changing adsorption removes sulfur dioxide in industrial tail gas Download PDFInfo
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- CN105944499B CN105944499B CN201610461532.4A CN201610461532A CN105944499B CN 105944499 B CN105944499 B CN 105944499B CN 201610461532 A CN201610461532 A CN 201610461532A CN 105944499 B CN105944499 B CN 105944499B
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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 the methods of sulfur dioxide in a kind of temp.-changing adsorption removing industrial tail gas, realize that temp.-changing adsorption removes the sulfur dioxide in industrial tail gas by temperature swing absorption unit；Using double tower or multitower technique；Temperature containing SO 2 tail gas is dropped into adsorption temp or less；The adsorption temp for setting adsorption tower is not less than circulating water temperature not higher than flue gas exit temperature；Adsorption tower desorption temperature is set to be higher than adsorption temp；Equipped with the adsorbent that can select absorption sulfur dioxide in adsorption tower；The timing of processing step is set, realization is used alternatingly to the continuous desulfurization containing sulfur dioxide gas by two towers or multitower.The features such as present invention has small investment, and operation energy consumption is low, easy to operate, and no adsorbent consumption, purification depth be high, strong shock resistance is, it can be achieved that SO in industrial tail gas2Zero-emission is particularly suitable for SO in sulfuric acid plant's tail gas2Recovery Purifying, or nearby have other industrial tail gas SO of sulfuric acid plant2Purification.
Description
Technical field
The present invention relates to SO in industrial tail gas2Purification more particularly to a kind of industrial tail is removed in depth using temp.-changing adsorption
Sulfur dioxide (SO in gas2) method, can be SO in industrial tail gas2Unstripped gas of the recycling as sulfuric acid plant after enrichment, is especially suitable for
The tail gas clean-up of sulfuric acid plant, or nearby have the SO of other industrial tail gas of sulfuric acid plant2Purification.
Background technique
SO2It is one of the nuisance of industrial tail gas discharge.In October, 2013, standard GB/T 26132-2010 sulfuric acid work
Industry pollutant emission standard is formally implemented, it is desirable that sulfur dioxide concentration drops to 400mg/ from original 860mg/m3 in sulfuric acid tail gas
M3 is hereinafter, and the area that executes the special limit value of Air Pollutant Emission will drop to 200mg/m3 or less.It will July 1 in 2017
SO in the air pollution emission standard of implementation2Discharge standard be limited to 100mg/m3.
Existing SO2Removing sulfuldioxide can by desulfurization product recycle degree be divided into following three classes: first kind SO2Removing
It not can be recycled or be difficult to be utilized afterwards, such as gypsum, carbide slag method, such generates a large amount of solid waste, brings secondary pollution.
Second class is by chemical reagent oxidation or catalysis oxidation by SO2It is converted into dilute sulfuric acid or sulfate, such as hydrogen peroxide oxidation method, ammonia
Oxidizing process, active carbon catalytic wet method, such as patent CN105381699A are described and are taken off SO using hydrogen peroxide2, patent
CN101085410 describes a kind of SO in flue gas2The method for being converted to sulfate of ammoniac, such technology need uninterrupted consumption oxidation
Agent or catalyst, are related to oxidant supply radius and cost problem, and remote districts are inconvenient to use.Third class is by low concentration
SO2It absorbs or desorbs to obtain high concentration SO again after adsorbing2, return to relieving haperacidity workshop section extracting sulfuric acid.Mainly there is patent CN102743956A
The activated coke method of record, this method report that conversion ratio is 96-97%, can be SO2Exit concentration control is in 200mg/m3 hereinafter, should
Class technology needs regenerator heating regeneration after absorption or absorption, and regeneration needs to consume amount of heat, uses circulating pump or wind
Machine ceaselessly cyclic absorption agent, increases operating cost.Ceaselessly consume and regeneration energy consumption is big etc. asks there is also absorbent simultaneously
Topic.
A kind of circulation process method that gas is discarded using temp.-changing adsorption desulfurization regeneration is described in patent CN103446861A,
The basic process and principle of this method are that the high sulfur-bearing regeneration off gases for generating temp.-changing adsorption sweetening process carry out organic sulfur conversion,
By organic sulfur conversion therein at H2S.The technique is primarily directed to organic sulfur and H2S.It is used currently without document or patent report
Fixed bed temp.-changing adsorption method removes SO in industrial tail gas2, especially SO in sulfuric acid plant's tail gas2Removing.
In conclusion the prior art solves SO in industrial tail gas2Discharge the problem is that:
(1) there are secondary pollution solid waste or the useless generation of liquid；
(2) circular regeneration for needing to be used for absorbent using circulating fan or pump, is needed largely to run power consumption, also can
Lead to the abrasion or reaction consumption of absorbent；
(3) desulfurization degree is not high, generally 80-98%, tail gas SO after processing2Concentration is with supplied materials gas SO2Fluctuation and fluctuate
It is larger.
(4) it is directed to H2S has a patent of ADSORPTION IN A FIXED BED, but SO2Using ADSORPTION IN A FIXED BED technique and adsorbent without this
The report of aspect.Above-mentioned activated coke is not proper adsorbent, it will participate in reacting.
(5) regeneration energy consumption is high, and there is presently no patents or document report, and temp.-changing adsorption is effectively reduced by timing setting
The method of reactivation heat.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides SO in a kind of temp.-changing adsorption removing industrial tail gas2's
Method uses SO in fixed bed temp.-changing adsorption removing industrial tail gas2, and the higher concentration SO desorbed2Gas recycling is used for
The method for preparing sulfuric acid.Realize SO in industrial tail gas2Zero-emission, be particularly suitable for SO in sulfuric acid plant's tail gas2It purifies and returns
It receives；Avoid de- SO2A large amount of secondary pollutions are generated, biggish operation energy consumption, adsorbent/catalyst consumption are overcome.
Present invention provide the technical scheme that
SO in a kind of temp.-changing adsorption removing industrial tail gas2Method, realize that temp.-changing adsorption is de- by temperature swing absorption unit
Except SO in industrial tail gas2, temperature swing absorption unit includes at least two adsorption towers, heater and multiple circulations for being used to control air-flow
The control valve of disconnection；Containing SO2The temperature of tail gas drops to adsorption temp hereinafter, passing through adsorption tower, adsorption temp with certain pressure
(contain SO not higher than sulfur-containing smoke gas2Tail gas) outlet temperature, be not less than circulating water temperature；The desorption temperature of adsorption tower is higher than absorption
Temperature；Absorption SO can be selected by being respectively arranged in each adsorption tower2Adsorbent；By regeneration air stream into adsorption tower, it is discharged from adsorption tower
Stripping gas；Each adsorption tower can undergo five basic steps, comprising:
(1) air inlet adsorption step A；
(2) high temperature regeneration gas heating stepses HW；
(3) high temperature regeneration gas is heated while being generated high containing SO2Gas returns acid accumulator plant step HP；
(4) low-temp recovery air cooling starts a period of time generation and contains SO2High stripping gas returns acid accumulator plant step LP；
(5) the cold step LC of low-temp recovery air-blowing；
In above-mentioned five basic steps, the time that can choose step and step designs different process flows；Wherein, it walks
The time of rapid HW can be zero；The time of step LP and step LC cannot all be simultaneously zero；It is arranged by the switch of control valve
Realization is used alternatingly to containing SO by two towers or multitower in the sequential step of two towers or multitower processing step2The continuous desulfurization of tail gas.
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, further, in heating or cooling,
By with processing sulfur-bearing (SO2) regeneration gas flows into adsorption tower by the opposite direction of tail gas so that adsorption column outlet end (regeneration gas into
Mouthful end) adsorbent keep fresh so that SO when adsorbing again in outlet tail gas2Concentration is very low；
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, further, be arranged heating time, heating inhale
Attached tower outlet end (input end of regeneration gas), when adsorption tower temperature heats to a certain extent, the regeneration of adsorption column outlet end is completed,
Adsorption tower bed leading portion adsorbent accumulation of heat；Stop heating, the suction heated using the input end at adsorption column outlet end or regeneration gas
Attached dose is carried out heating regeneration gas, and the regeneration gas flow forward of heating heats the input end of adsorption tower or the absorption of regeneration air stream outlet
Agent makes its regeneration.
Adsorption tower temperature is heated to a degree of judgment criteria x: setting X=(TOut-TA)/(TDesorption-TA), TOutIt is expressed as
The temperature of tower outlet section, T when desorptionDesorptionIndicate the desorption temperature of setting, TAAdsorption temp；The value for being typically chosen x is 0.2-
0.95, the value range 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
When required adsorption temp, temperature swing absorption unit may also include for sulfur-containing tail gas to be cooled to adsorption temp cooling below
Device.
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, it is possible to further according to user's sulfur-containing tail gas
Discharge pressure choose whether to need air blower, when sulfur-containing tail gas pressure (gauge pressure) no more than adsorption tower pressure drop and piping loss it
And when, temperature swing absorption unit may also include air blower, for being pressurized to sulfur-containing tail gas to guarantee that tail gas can pass through filling batch
(adsorption tower).
When cooler and air blower require, the tandem of the two placement can be selected with unrestricted choice；In sulfur-bearing tail
When temperature degree is higher, cooler should be placed on front.
For SO in above-mentioned temp.-changing adsorption removing industrial tail gas2Method, further, when processing rear molding atmospheric pressure it is little
When sulfuric acid plant inlet pressure, stripping gas smoothly cannot be passed through sulfuric acid plant, temperature swing absorption unit may also include for gas
Body pressurization so as to can pass through desorption adsorption tower after send back to sulphuric acid device entrance air blower.
The present invention removes SO in sulfuric acid plant's tail gas by temp.-changing adsorption2, can be by double tower device as shown in Figure 1 come real
It is existing, comprising: adsorption tower 1, adsorption tower 2, cooler 3, air blower 4, air blower 5 and heater 6；Control valve 7-19 is for controlling
Air-flow processed being opened or disconnecting；Technique service valve 20 is standard-sized sheet when operating normally；Wherein valve 16 is that having circulating-heating needs
When use, i.e. the initial a period of time concentration of stripping gas is very low, but has certain temperature, the stripping gas of this period of time can be followed
Loopback goes to continue heating and as regeneration gas.Regeneration gas is regenerated for adsorption tower, is to contain SO after coming out from adsorption tower2's
Stripping gas.
At work, absorption SO can be selected to above-mentioned apparatus by being respectively arranged in two adsorption towers2Adsorbent, first contain SO2Tail gas
Temperature is dropped to adsorption temp hereinafter, handling well through valve 7 by adsorption tower 1 after being pressurized by air blower 4 by cooler 3
Clean gas through valve 11 as discharge gas be discharged into atmosphere；Adsorption tower 2 carries out heating desorption and blows cold simultaneously.It desorbs and blows cold
Using air or treated tail gas, through valve 17 by air blower 5 when heating, through valve after valve 18 is by heater 6
20,14 enter adsorption tower 2, blow after heating desorption it is cold, when blowing cold will treated tail gas by getting around heating after air blower 5
Device directly passes through valve 19,14 and enters adsorption tower 2.Stripping gas returns to unstripped gas of the entrance as Sulphuric acid of sulphuric acid device.Two
Tower is used alternatingly, to guarantee the continuous operation of desulfurization.
When LC step is not zero in this processing step, the stripping gas of generation can reach atmospheric emission standard, can be to atmosphere
Directly it is vented.Further, it in order to really realize that " zero " discharges, controls this technique and does not discharge gas containing SO2, LC step to atmosphere
The stripping gas of generation directly removes another adsorption tower.
Adsorption tower quantity used by the fixed bed temperature swing adsorption process that the present invention uses is 2-32 tower, in order to continuously locate
Reason, at least needs two adsorption towers.It can be according to processing tolerance size, the stripping gas SO of requirement2Fluctuation of concentration amplitude, Yi Jire
Amount comprehensive utilization situation determines selection adsorption tower quantity.
The filled out adsorbent of the adsorption tower that the present invention uses has selection absorption SO2Ability, when heated can be SO2Solution
It sucks out.
The loadings that adsorbent needs are determined according to the single adsorptions time.The adsorption time of selection, which needs to be more than or equal to, to be added
The sum of thermal desorption and cooling time.Desorption time is 1-40 hours, is typically chosen cooling time 0.5-20 hours.
The selection of adsorption temp is depending on the characteristic of filled out adsorbent, but not above the outlet temperature of sulfur-containing smoke gas,
Also it is not below the circulating water temperature that user can be provided.So temperature is selected as 0-100 DEG C, optimal adsorption temp is 15-60
℃。
The desorption temperature of adsorption tower needs to be higher than adsorption temp, is typically chosen 80-500 DEG C, optimal selection 150-350
℃。
Adsorption tower regeneration gas dosage is the 0.1-20% for handling tolerance, and optimum choice is 0.5-10%.
The operation adsorptive pressure of this technique is selected according to sulfur-containing tail gas, selects pressure for normal pressure to sulfur-containing tail gas pressure
Add the range of 10kpa, optimization opereating specification is 0-10kpa.Regeneration pressure is selected as-10-10Kpa, and optimum choice is-5-
5Kpa。
Packed bed (adsorption tower) pressure drop that the present invention uses is 1-20Kpa, optimum choice 2-8Kpa.
It is small that the present invention needs to regenerate heating amount, the present invention in order to reduce heat required for heat, selection is at low concentrations
The big adsorbent of adsorption capacity, so that adsorbing same SO2Required adsorbent inventory is few, regenerates the heating amount of needs just
It is few.The dynamic adsorbance of used adsorbent needs to be more than or equal to the SO that sulfur-containing smoke gas is brought into adsorption time2Sulfur content, absorption
Agent characteristic requirements are under adsorption temp, SO2Concentration is lower than 1000mg/m3When, the dynamic adsorption capacity of adsorbent is greater than 5mgSO2/g
Adsorbent, optimum choice adsorbent dynamic adsorption capacity are greater than 20mgSO2/ g adsorbent.
According to the small requirement of regeneration heating amount, reasonable timing is arranged to make full use of the stripping gas heat of exclusion in the present invention,
Stripping gas is considered to be recycled when timing is arranged.
According to the small requirement of regeneration heating amount, the advantage the most significant of this technique is: during heating desorption (HW)
Rationally setting heating time, setting heating adsorption column outlet end (input end of regeneration gas) certain time, when adsorption tower temperature adds
Heat to a certain extent when, adsorption column outlet end has regenerated completion, but bed front-end temperature is higher, and adsorbent has stored big calorimetric
Amount.At this moment it can stop heating, be heated again using the adsorbent that adsorption column outlet end (i.e. the input end of regeneration gas) has heated
Anger, the regeneration gas flow forward of heating remove the adsorbent of the input end (i.e. regeneration air stream outlet) of heating regenerative adsorption tower.One
Aspect can make full use of the heat inside bed, on the other hand can also cool down the outlet end of adsorption tower in advance, reduce cooling
Time.
According to above-mentioned requirements, adsorption tower temperature, which is heated to a degree of judgment criteria, is: setting X=(TOut-TA)/
(TDesorption-TA), X indicates regeneration temperatures judgment criteria；TOutIt is expressed as the temperature of tower outlet section when desorption, TDesorptionIndicate setting
Desorption temperature, TAAdsorption temp；The value for being typically chosen x is 0.2-0.95, and the value range of optimization is 0.4-0.8.
According to outlet SO2Concentration low requirement when no matter heating or cooling down, is required by opposite with processing sulfur-containing tail gas
Direction regeneration gas is flowed into adsorption tower, be always ensured that and keep new in the adsorbent of adsorption column outlet end (regeneration gas input end)
It is fresh, SO in outlet tail gas when adsorbing again2Concentration can guarantee very low.
According to above-mentioned requirements, regeneration gas needs to heat, and the heat source of heating can be electricity, steam, discarded waste heat, is also possible to
Their any combination mode.In the case where factory natively has surplus heat for generating steam, optimum choice is using one
Point waste heat directly heats regeneration gas, without with waste heat for generating steam, then with steam heating regeneration gas.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provide it is a kind of using temp.-changing adsorption be removed in depth industrial tail gas in SO2Method, use fixed bed alternating temperature
SO in adsorbing and removing industrial tail gas2, can be the higher concentration SO desorbed2Unstripped gas of the recycling as sulfuric acid plant after enrichment, is returned
Receipts are used to prepare sulfuric acid, realize SO in industrial tail gas2Zero-emission, be particularly suitable for SO in sulfuric acid plant's tail gas2It purifies and returns
It receives, or nearby has the SO of other industrial tail gas of sulfuric acid plant2Purification.
Technical solution provided by the invention can avoid removing SO2A large amount of secondary pollutions are generated, biggish operation energy is overcome
Consumption, adsorbent/catalyst consumption.The invention has small investment, and operation energy consumption is low, easy to operate, and no adsorbent consumption, purification are deep
The features such as degree is high, strong shock resistance, purifying rate is more than 99.8%, containing SO in treated tail gas2Amount is lower than 10mg/m3, average
Value is lower than 2mg/m3。
Detailed description of the invention
Fig. 1 is SO in temp.-changing adsorption removing sulfuric acid plant's tail gas of the present invention2Using the structure drawing of device of two basic tower process；
Fig. 2 is structure drawing of device of the present invention using two simplified tower temperature swing adsorption process；
In FIG. 1 to FIG. 2, T1, T2-adsorption tower；3-coolers；4-air blowers, 5-air blowers；6-heaters；7~
19-control valves；20-technique service valves.
Fig. 3 is SO in temp.-changing adsorption removing sulfuric acid plant's tail gas of the present invention2Using the structure drawing of device of three tower absorbing process；
In Fig. 3, T1, T2, T3-adsorption tower；3-coolers；4-air blowers, 5-air blowers；6-heaters；7~
26-control valves；27-technique service valves.
SO in Fig. 4 temp.-changing adsorption removing sulfuric acid plant's tail gas of the present invention2Using six towers (three absorption, two heating one is cooling) technique
Structure drawing of device；
In Fig. 4, T1~T6-adsorption tower；3-coolers；4-air blowers, 5a~5c-air blower；6a, 6b-heating
Device；7~48-control valves.
Specific embodiment
With reference to the accompanying drawing, the present invention, the model of but do not limit the invention in any way are further described by embodiment
It encloses.
The present invention provide it is a kind of using temp.-changing adsorption be removed in depth industrial tail gas in SO2Method, use fixed bed alternating temperature
SO in adsorbing and removing industrial tail gas2, can be the higher concentration SO desorbed2Unstripped gas of the recycling as sulfuric acid plant after enrichment, is returned
Receipts are used to prepare sulfuric acid, realize SO in industrial tail gas2Zero-emission.
In the specific implementation, it can realize that temp.-changing adsorption removes sulfuric acid plant by basic double tower device as shown in Figure 1
SO in tail gas2.Double tower device as shown in Figure 1 includes: adsorption tower 1, adsorption tower 2, cooler 3, air blower 4, air blower 5 and adds
Hot device 6；Device number 7-19 is control valve, for controlling the on/off of air-flow；20 be technique service valve, and when normal operation is complete
It opens；Wherein valve 16 is used when there is circulating-heating to need, i.e. the initial a period of time concentration of stripping gas is very low, but has certain temperature
Degree can loop back the stripping gas of this period of time and continue heating and as regeneration gas.
At work, absorption SO can be selected to above-mentioned double tower device by being respectively arranged in two adsorption towers2Adsorbent, first contain SO2
Temperature is dropped to adsorption temp hereinafter, passing through adsorption tower 1, warp through valve 7 after being pressurized by air blower 4 by cooler 3 by tail gas
Valve 11 is discharged into atmosphere as discharge gas.Adsorption tower 2 carries out heating desorption and blows cold simultaneously.Desorb and blow it is cold using air or
Treated tail gas is entered through valve 20,14 after valve 18 is by heater 6 and is inhaled by air blower 5 through valve 17 when heating
Attached tower 2, blow after heating desorption it is cold, will treated that tail gas is directly passed through by getting around heater after air blower 5 when blowing cold
Valve 19,14 enters adsorption tower 2.Stripping gas returns to unstripped gas of the entrance as Sulphuric acid of sulphuric acid device.Two towers are used alternatingly,
To guarantee the continuous operation of desulfurization.
Fig. 2 is structure drawing of device of the present invention using two simplified tower temperature swing adsorption process；Corresponding two simplified tower process
The corresponding sequential step of step is as shown in table 2, simplifies process.
The effect of cooler 3 is that sulfur-containing tail gas is cooled to adsorption temp hereinafter, can be selected according to the temperature of sulfur-containing tail gas
It selects and whether needs cooler；Cooler can not be used when the temperature of sulfur-containing tail gas is lower than required adsorption temp.
In Fig. 1 and Fig. 2, the effect of air blower 4 is to be pressurized to sulfur-containing tail gas to guarantee that tail gas can pass through filling batch.It can
To choose whether to need air blower according to the discharge pressure of user's sulfur-containing tail gas；The judgment basis for removing air blower is sulfur-containing tail gas
Pressure (gauge pressure) is greater than the sum of adsorption tower pressure drop and piping loss.
When cooler and air blower require, the tandem of the two placement can be selected with unrestricted choice；In sulfur-bearing tail
When temperature degree is higher, cooler should be placed on front.
In Fig. 1 and Fig. 2, the effect of air blower 5 be gas boosting so as to can pass through desorption adsorption tower after send sulphur back to
The entrance of sour equipment, if processing rear molding atmospheric pressure is greater than sulfuric acid plant inlet pressure and can guarantee that stripping gas can be smoothly passed through
Sulfuric acid plant, air blower can be omitted at this.
The timing of basic two Deethanizer design such as table 1.In table 1, A is the air inlet adsorption treatment stage；HW is the heating of high temperature regeneration gas
Stage；HP is that high temperature regeneration gas heats simultaneously in the stripping gas time acid accumulator plant stage；LP is low-temp recovery air cooling simultaneously solution
Air-breathing returns acid accumulator plant；LC is that the cold stripping gas of low-temp recovery air-blowing removes another adsorption tower；O indicates that valve is opened；C indicates that valve closes；Valve 20
Due to being technique maintenance valve, when normal operation, is always on.
The valve switch order of 1 liang of ten step desulphurization process of tower of table
Table 2 is the simplified corresponding sequential step of two tower process steps.
2 simple flow of table, two tower step
The tower number that in multitower technique, can be adsorbed simultaneously with multiple towers, set total adsorption tower number as n, while adsorbed is m.
Ventilating fan can be used a blower while give the air inlet simultaneously of m tower, can also be with m blower respectively to each absorption
Tower.In air intake valve selection, can each be connect using valve with m blower with n tower.The valve quantity of air inlet is n in this way
×m.In order to save valve, each blower also can be set and be fixed to n/m tower air inlet therein.Such as six towers, 3 absorbing process,
It can choose corresponding 6 valves of each blower, air intake valve quantity is 18.It can also be with the corresponding adsorption tower 1,4 of blower 1, wind
Machine 2 corresponds to adsorption tower 2,5, the corresponding adsorption tower 3,6 of blower 3, and such intake valve just only needs 6.When adsorption tower quantity is not wind
It when the integral multiple of machine, can also be allocated with the corresponding adsorption tower of fan, such as 5 tower, 2 absorbing process, the corresponding absorption of blower 1
Tower 1,2,3, the corresponding absorption 3,4,5 of blower 2, such air intake valve is 6, is configured in the open timing of valve, equally may be used
To guarantee that each tower air inflow is the same.In short, in multitower process flow, the various change that multitower adsorbs air inlet simultaneously is all
The spirit and scope of the content of present invention.
In multitower technique, when heating stepses are only heated without thermal cycle, a regeneration heating blower also can be used
With a heater.But when heating stepses are more than and heat and have the case where coupling with other steps, for example, heating
Some adsorption towers are heating when step, and some adsorption towers are in circulating-heating, in this case, the quantity of heating blower and heater
Equal with the adsorption tower quantity in heating, i.e. how many adsorption tower heating just needs to match how many a heating blowers and heating
Device.
Fig. 3 is the apparatus structure and process flow chart of three tower temp.-changing adsorption desulfurization, and table 3 is three tower temp.-changing adsorption sulfur removal technologies
The step of corresponding each tower works；Wherein, table 3a is that there are two simultaneously in each tower step table of the tower adsorbed in three towers；
Table 3b is each tower step table of only one tower for being used for absorption of same time in three towers.
Each tower step table of tri- tower of table 3a, 2 tower absorbing process
Each tower step table of tri- tower of table 3b, 1 tower absorbing process
Fig. 4 is the apparatus structure and process flow chart of six tower temp.-changing adsorption desulfurization, and table 4 is that six tower temp.-changing adsorption desulfurization are corresponding
Each tower the step of one of arrangement mode: six towers, 3 air inlet 2 heat 1 cooling process.HW step desorption in the 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.By taking T1 tower as an example, it
HW can remove the A of T4 tower, its LC removes the HP of T3 tower.In this table, HW Step Time can be step one of in 0, LP and LC
The rapid time can be 0.
Each tower step table of 4 six tower of table (3 absorption, 2 heating 1 is cooling) technique
The filled out adsorbent of the adsorption tower that the present invention uses has selection absorption SO2Ability, when heated can be SO2Solution
It sucks out.
The loadings that adsorbent needs are determined according to the single adsorptions time.The adsorption time of selection, which needs to be more than or equal to, to be added
The sum of thermal desorption and cooling time.One step, desorption time is 1-40 hours, is typically chosen cooling time 0.5-20 hours.
The selection of adsorption temp is depending on the characteristic of filled out adsorbent, but not above the outlet temperature of sulfur-containing smoke gas,
Also it is not below the circulating water temperature that user can be provided.So temperature is selected as 0-100 DEG C, optimal adsorption temp is 15-60
℃。
The desorption temperature of adsorption tower needs to be higher than adsorption temp, is typically chosen 80-500 DEG C, optimal selection 150-350
℃。
Adsorption tower regeneration gas dosage is the 0.1-20% for handling tolerance, and optimum choice is 0.5-10%.
The operation adsorptive pressure of this technique is selected according to sulfur-containing tail gas, selects pressure for normal pressure to sulfur-containing tail gas pressure
Add the range of 10kpa, optimization opereating specification is 0-10kpa.Regeneration pressure is selected as-10-10Kpa, and optimum choice is-5-
5Kpa。
The packed bed pressure drop that the present invention uses is 1-20Kpa, optimum choice 2-8Kpa.
The present invention can satisfy the requirement that operation energy consumption is low, regeneration heating amount is small.Due to heat and absorption required for heating
Agent dosage is directly proportional, and the present invention heats required heat to reduce, and selects the big adsorbent of adsorption capacity at low concentrations,
So that adsorbing same SO2Required adsorbent inventory is few, so that the heating amount that regeneration needs is few.Use absorption
The dynamic adsorbance of agent needs to be more than or equal to the SO that sulfur-containing smoke gas is brought into adsorption time2Sulfur content, sorbent characteristics require
Under adsorption temp, SO2When concentration is lower than 1000mg/m3, the dynamic adsorption capacity of adsorbent is greater than 5mgSO2/ g adsorbent, optimization
Selected adsorbent dynamic adsorption capacity is greater than 20mgSO2/ g adsorbent.
Reasonable timing is arranged to make full use of the stripping gas heat of exclusion in the present invention, considers when timing is arranged stripping gas
It is recycled, to achieve the effect that regeneration heating amount is small.
According to the small requirement of regeneration heating amount, the advantage the most significant of this technique is: during heating desorption rationally
Heating time, setting heating adsorption column outlet end (input end of regeneration gas) certain time, when adsorption tower temperature is heated to are set
When to a certain degree, adsorption column outlet end has regenerated completion, but bed front-end temperature is higher, and adsorbent has stored amount of heat.
At this moment can stop heating, using the adsorbent that outlet end (input end of regeneration gas) has heated come heating regeneration gas, heating
Regeneration gas flow forward removes the adsorbent of the input end (regeneration air stream outlet) of heating regenerative adsorption tower.It on the one hand can be sufficiently sharp
With the heat inside bed, the outlet end of adsorption tower on the other hand can also be cooled down in advance, reduce cooling time.
According to above-mentioned requirements, adsorption tower temperature, which is heated to a degree of judgment criteria x, is: setting X=(TOut-TA)/
(TDesorption-TA), TOutIt is expressed as the temperature of tower outlet section when desorption, TDesorptionIndicate the desorption temperature of setting, TAAdsorption temp；General choosing
The value for selecting x is 0.2-0.95, and the value range of optimization is 0.4-0.8.
According to outlet SO2Concentration low requirement when no matter heating or cooling down, is required by opposite with processing sulfur-containing tail gas
Direction regeneration gas is flowed into adsorption tower, be always ensured that and keep new in the adsorbent of adsorption column outlet end (regeneration gas input end)
It is fresh, SO in outlet tail gas when adsorbing again2Concentration can guarantee very low.
According to above-mentioned requirements, regeneration gas needs to heat, and the heat source of heating can be electricity, steam, discarded waste heat, is also possible to
Their any combination mode.In the case where factory natively has surplus heat for generating steam, optimum choice is using one
Point waste heat directly heats regeneration gas, without with waste heat for generating steam, then with steam heating regeneration gas.
Although having been presented for the process flow chart and Ge Ta work step table of four preferred embodiments, those skilled in the art
Member is, it will be recognized that there are other embodiments in the spirit and scope of patent requirements.For example, some steps in five steps
Suddenly it is dispensed；Some equipment are dispensed in varied situations；Adsorption tower number is 2-32, even if selection absorption
Tower number is fixed as n, while adsorption tower number can be 1 to (n-1), and setting plus circulating-heating, thermal desorption blow cold while desorbing, is single
Cold quantity is solely blown, there is various arrangements and combination.Due to length, it cannot enumerate.But as long as being this patent
It is required that spirit and scope in, be all the summary of the invention of this patent.
Embodiment one:
Handle 150000m3/ h, sulfur-containing tail gas composition: SO2Content is in 500-2000mg/m3Fluctuation, average value 800mg/
m3；Exhaust temperature, 40-65 DEG C；Tail gas pressure, 6Kpa；Cooling temperature of circulating water, 30 DEG C；It selects adsorbent: there is SO2Selection is inhaled
The PU-28 of attached ability, adsorption temp are 35-40 DEG C, and dynamic adsorption capacity is 60mgSO under mean concentration2/ g adsorbent.
Two tower timing, flow chart such as Fig. 1 are selected, timing arrangement such as table 1, each Step Time are set as table 5:
Table 5 selects the time setting of two each steps of tower timing
| Step | A | HR | HP | LP | LC |
| Time/hour | 24 | 3 | THP | 6 | 24-3-THP-6 |
Wherein THPIt is determined according to regeneration temperatures judgment criteria X, stripping gas outlet temperature is set by X, works as temperature
After reaching standard, next step is voluntarily switched by controlling program.
Adsorbent selects dynamic adsorption capacity for 20-100mgSO2The adsorbent of/g, it is 104 tons that two towers, which amount to loading amount,.
Adsorb Deethanizer design pressure drop 2-4Kpa, piping loss 1.5Kpa；
Since tail gas pressure is greater than the sum of adsorption tower pressure drop and piping loss, it is possible to omit air blower 4；
Regeneration gas temperature selects 300 DEG C；The 3% of selection processing gas, so being 4500m3/h.Regeneration gas heat source uses sulfuric acid
The waste heat in workshop, spare electric heater；
Regeneration temperatures judgment criteria X takes 0.4；
SO2Average emission concentration is less than 1mg/m3。
Embodiment two:
Processing tail gas situation is the same as example 1, and embodiment two selects three tower process processes, the air inlet simultaneously of two towers, process
Figure such as Fig. 3, each tower step is as shown in table 3, and each Step Time is set as table 6:
Table 6 selects the time setting of three each steps of tower timing
| Step | A | HR | HP | LP | LC |
| Time/hour | 26 | 3 | THP | 3 | 13-3-THP-3 |
Since two towers adsorb simultaneously, so remaining four step is adsorption time half.Each tower air inflow is
75000m3/h。
Adsorbent selects dynamic adsorption capacity for 20-100mgSO2The adsorbent of/g, it is 84 tons that three towers, which amount to loading amount,.
Adsorption tower selects radial bed, designs pressure drop 2-4Kpa, piping loss 1.5Kpa；
Since tail gas pressure is greater than the sum of adsorption tower pressure drop and piping loss, it is possible to air blower 4 is omitted,
Regeneration gas temperature selects 300 DEG C, the 2.5% of air inlet processing gas is selected, so being 150000 × 2.5% to be equal to
3750m3/h.The waste heat of regeneration gas heat source sulfuric acid plant.Spare electric heater.
Regeneration temperatures judgment criteria X takes 0.5.
SO2Average emission concentration is less than 1mg/m3。
Embodiment three:
Treatment temperature, pressure, composition are the same as example 1；The processing tolerance of the present embodiment becomes 300000m3/h。
Six tower process are selected, the absorption of three towers, the heating of two towers, a tower blows cold.Flow chart such as Fig. 4, each tower step such as 4 institute of table
Show, each Step Time is set as table 7:
Table selects the time setting of six each steps of tower timing
| Step | A | HR | HP | LP | LC |
| Time/hour | 18 | 3 | 9 | 3 | 3 |
Since three towers adsorb simultaneously, so the sum of remaining four step is equal to adsorption time.Each tower air inflow is
100000m3/h。
Adsorbent selects dynamic adsorption capacity for 20-100mgSO2The adsorbent of/g, it is 153 tons that six towers, which amount to loading amount,.
Adsorb Deethanizer design pressure drop 3-4Kpa, piping loss 1.5Kpa；
Since tail gas pressure is greater than the sum of adsorption tower pressure drop and piping loss, it is possible to air blower 4 is omitted,
Regeneration gas temperature selects 300 DEG C, the 2.5% of air inlet processing gas is selected, so being 300000 × 2.5% to be equal to
7500m3/h.There are two towers to be regenerated simultaneously, and there are one towers to use low-temp recovery gas, so each blower tolerance is
2500m3/h.The waste heat of regeneration gas heat source sulfuric acid plant.Spare electric heater.
SO2Average emission concentration is less than 1mg/m3。
It should be noted that the purpose for publicizing and implementing example is to help to further understand the present invention, but the skill of this field
Art personnel, which are understood that, not to be departed from the present invention and spirit and scope of the appended claims, and various substitutions and modifications are all
It is possible.Therefore, the present invention should not be limited to embodiment disclosure of that, and the scope of protection of present invention is with claim
Subject to the range that book defines.
Claims (9)
1. a kind of method of sulfur dioxide in temp.-changing adsorption removing industrial tail gas, realizes that temp.-changing adsorption is de- by temperature swing absorption unit
Except the sulfur dioxide in industrial tail gas；The temperature swing absorption unit use double tower or multitower technique, including at least two adsorption towers,
One or more heaters and multiple control valves disconnected for controlling airflow；
Following basic step can be undergone in each adsorption tower, comprising:
(1) air inlet adsorption step A；
(2) high temperature regeneration gas heating stepses HW；
(3) high temperature regeneration gas, which heats while generating the high gas containing sulfur dioxide, returns acid accumulator plant step HP；
(4) low-temp recovery air cooling starts a period of time generation and contains SO2High stripping gas returns acid accumulator plant step LP；
(5) the cold step LC of low-temp recovery air-blowing；
The time of the step HW can be zero；The time of the step LP and step LC cannot all be simultaneously zero；
The heating time at adsorption column outlet end is set, and when adsorption column outlet end, regeneration is completed, adsorption tower bed leading portion adsorbent stores
When hot, stop heating, using the adsorbent that adsorption column outlet end has been heated come heating regeneration gas, the regeneration gas after heating flows forward
Dynamic, the adsorbent for reheating the input end of adsorption tower makes its regeneration；
When being heated or cooled, regeneration gas is flowed into adsorption tower by with processing opposite direction containing SO 2 tail gas, is adsorbed
Tower outlet end is regeneration gas input end, so that the adsorbent at adsorption column outlet end keeps fresh；
The method of sulfur dioxide specifically comprises the following steps: in the temp.-changing adsorption removing industrial tail gas
Temperature containing SO 2 tail gas is dropped into adsorption temp hereinafter, passing through adsorption tower with certain pressure；
The adsorption temp for setting adsorption tower makes the adsorption temp of adsorption tower not higher than the exhanst gas outlet temperature containing SO 2 tail gas
Degree is not less than circulating water temperature；The desorption temperature of adsorption tower is set to be higher than adsorption temp；The adsorption temp is 0-100 DEG C；It inhales
The desorption temperature of attached tower is 80-500 DEG C；
The adsorbent that can select absorption sulfur dioxide is respectively arranged in each adsorption tower；By the switch of control valve be arranged two towers or
Realization is used alternatingly to the continuous desulfurization containing sulfur dioxide gas by two towers or multitower in the timing of multitower processing step；Adsorbent
Under adsorption temp, when sulfur dioxide concentration is lower than 1000mg/m3When, the dynamic adsorption capacity of adsorbent is greater than 5mgSO2/ g inhales
Attached dose；
Contain SO in the clean gas handled well2Amount is lower than 10mg/m3, average value is lower than 2mg/m3；It is directly discharged to atmosphere；Purifying rate
More than 99.8%.
2. the method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas as described in claim 1, characterized in that the regeneration gas
Dosage is the 0.1-20% for handling tolerance.
3. the method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas as described in claim 1, characterized in that the regeneration gas
Dosage is preferably handle tolerance 0.5-10%.
4. the method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas as described in claim 1, characterized in that when containing titanium dioxide
When the temperature of sulphur tail gas is higher than set adsorption temp, the temperature swing absorption unit further includes for that will contain SO 2 tail gas
It is cooled to adsorption temp cooler below.
5. the method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas as described in claim 1, characterized in that when containing titanium dioxide
When the pressure of sulphur tail gas is not more than the sum of adsorption tower pressure drop and piping loss, the temperature swing absorption unit further includes air blower, is used
It is pressurized in containing SO 2 tail gas to guarantee that tail gas can pass through adsorption tower.
6. the method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas as described in claim 1, characterized in that when processing rear molding
When the pressure of gas cannot smoothly be passed through sulfuric acid plant no more than sulfuric acid plant inlet pressure, stripping gas, the temperature swing absorption unit
Further include for gas boosting can be passed through desorption adsorption tower after send back to sulphuric acid device entrance air blower.
7. the method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas as described in claim 1, characterized in that the alternating temperature is inhaled
Adsorption device uses double tower process, comprising: adsorption tower one, adsorption tower two, cooler, air blower one, air blower two and heater；Also
Including multiple valves；Include the following steps:
Temperature is dropped to by cooler by adsorption temp or less containing SO 2 tail gas；
Through valve by adsorption tower one after being pressurized by air blower one, the clean gas handled well is discharged into through valve as discharge gas
Atmosphere；Adsorption tower two carries out heating desorption and blows cold simultaneously；It desorbs and blows cold using air or treated tail gas, when heating is logical
Cross air blower two, then by entering adsorption tower two after heater, blow after heating desorption it is cold, will treated tail gas when blowing cold
Adsorption tower two is directly entered by getting around heater after air blower two；
Stripping gas returns to unstripped gas of the entrance as Sulphuric acid of sulphuric acid device；
Two towers are used alternatingly, to guarantee the continuous operation of desulfurization.
8. the method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas as described in claim 1, characterized in that the adsorption tower
Quantity be 2~32；Optimal adsorption temp is 15-60 DEG C；The desorption temperature optimal selection of adsorption tower is 150-350 DEG C.
9. the method for sulfur dioxide in temp.-changing adsorption removing industrial tail gas as described in claim 1, characterized in that preferably, inhale
Attached dose of dynamic adsorption capacity is greater than 20mgSO2/ g adsorbent.
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Address after: 100080 401, Yanyuan resources building, 151 Zhongguancun North Street, Haidian District, Beijing Patentee after: Beijing Beida Pioneer Technology Co.,Ltd. Patentee after: HUADING COPPER DEVELOPMENT Co.,Ltd. Address before: 100080 401, Yanyuan resources building, 151 Zhongguancun North Street, Haidian District, Beijing Patentee before: BEIJING PEKING UNIVERSITY PIONEER TECHNOLOGY Co.,Ltd. Patentee before: HUADING COPPER DEVELOPMENT Co.,Ltd. |