CN102302894A - Renewable flue gas desulphurization process - Google Patents
Renewable flue gas desulphurization process Download PDFInfo
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- CN102302894A CN102302894A CN201110210049A CN201110210049A CN102302894A CN 102302894 A CN102302894 A CN 102302894A CN 201110210049 A CN201110210049 A CN 201110210049A CN 201110210049 A CN201110210049 A CN 201110210049A CN 102302894 A CN102302894 A CN 102302894A
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Abstract
The invention provides a renewable flue gas desulphurization process. The renewable flue gas desulphurization process comprises an absorption process and a desorption process. In the absorption process, the following steps are sequentially carried out according to the flowing direction of flue gas: absorbing oxysulfide in the flue gas by using a half-lean solution to form a first pregnant solution; further absorbing the oxysulfide in the flue gas by using a lean solution to form a second pregnant solution; catching a desulfuration solution carried in the flue gas by using a detergent; and discharging clean flue gas. The desorption process comprises the following steps of: carrying out first desorption on part of the first pregnant solution to form a half-lean solution and desorption gases; simultaneously carrying out second desorption on part of the first pregnant solution and part of the half-lean solution to form a lean solution and desorption gases; condensing and recycling oxysulfide in the desorption gases; and respectively supplying the other part of the half-lean solution and the lean solution for the absorption process so as to realize the circulation of the desulfuration solution between the absorption process and the desorption process. The renewable flue gas desulphurization process is suitable for processing various oxysulfide-contained flue gases or industrial waste gases.
Description
Technical field
The present invention relates to chemical industry, thermoelectricity and metallurgical technology field, more particularly, relate to a kind of renewable flue gas desulfurization technique.
Background technology
At present, the business website of Kang Shifu (cansolv) Co., Ltd (
Http:// www.cansolv.com/cn / so2scrubbingschema.ch2) on but a kind of flue gas desulfurization technique of desorb is disclosed.This technology at first utilizes amine liquid to absorb sulfur in smoke; The sulfur dioxide in the desorb amine liquid at high temperature then; With the sulfur dioxide gas of acquisition higher degree, and the amine liquid of the absorbing sulfur dioxide ability that is restored simultaneously, said amine liquid can recycle.At present, but also have a kind of process of ionic liquid desorb desulfurization, this technical process is similar basically with the process of above-mentioned amine method desulphurization technological process.The difference of the two is that desulfurization absorption liquid component is different, the ability basically identical of its absorbing sulfur dioxide.The one-level absorption that above-mentioned two kinds of sulfur removal technologies all adopt and the desorption technique of one-level desorb; In addition; They have optionally adopted flue gas prewashing technology according to the dustiness situation in the flue gas to be desulfurization, and they all adopt the prior resin desalinating process to the recovery processing of desulfuration solution.
At present, the sulfur removal technology of prior art has many deficiencies, mainly shows as: suspended impurity content is high in the desulfuration solution, system jams is serious, desulfurization degree is low, the desorb energy consumption is big, the desulfuration solution recovery is difficult, strong acid root removal efficiency is low etc.In addition; Highly acid gas contents such as dust content is big because the sinter fume in the metallurgical industry has, sulfur trioxide, chlorine, nitrate anion are than characteristics such as height; So when the sulfur dioxide gas in the sinter fume that the sulfur removal technology that uses prior art removes; Above-mentioned deficiency will be more serious, and defective such as the former thereby resin desalting effect difference that causes such as can further to occur that when under high-load sulfate radical condition, using resin to remove chlorine root, nitrate anion Choice of Resin property is poor, resin is loaded big and desulfuration solution loss be big.Simultaneously, flue gas desulphurization system carries moisture content secretly because of flue gas and resin desalination washings are mended into desulphurization system, causes the increase of the desulphurization system water yield, and how effectively reducing system's water yield is that desulfuration solution concentration keeps certain key.
Summary of the invention
To the above-mentioned deficiency of prior art, the invention provides a kind of renewable flue gas desulfurization technique, to solve one or multinomial deficiency of the prior art.
The invention provides a kind of renewable flue gas desulfurization technique; Said renewable flue gas desulfurization technique comprises through using desulfuration solution to absorb the absorption technique of the oxysulfide that contains in the flue gas and coming desorb to be absorbed with the desorption technique of the desulfuration solution of oxysulfide with the recovery oxysulfide through heating; Wherein, Said absorption technique comprises the following steps of carrying out successively by the flow of flue gas direction: (i) use first desulfuration solution to absorb the oxysulfide in the flue gas, form first rich solution; (ii) use second desulfuration solution further to absorb the oxysulfide in the flue gas, form second rich solution, with second rich solution as second desulfuration solution or as first desulfuration solution; (iii) use washing agent to capture the desulfuration solution of carrying secretly in the flue gas; (iv) discharge clean flue gas; Said desorption technique may further comprise the steps: (a) part of first rich solution is carried out a desorb, form semi lean solution and desorption gas; (b) simultaneously the another part of first rich solution and the part of semi lean solution are carried out the secondary desorb, form lean solution and desorption gas; (c) condensation and reclaim the oxysulfide in the desorption gas; Another part of semi lean solution as first desulfuration solution, and is provided lean solution respectively to absorption technique as second desulfuration solution, to realize the circulation of desulfuration solution between absorption technique and desorption technique; The oxysulfide content of said first rich solution or second rich solution is higher than the oxysulfide content of semi lean solution, and the oxysulfide content of said semi lean solution is higher than the oxysulfide content of lean solution.
Compared with prior art; Renewable flue gas desulfurization technique of the present invention comprises that flue gas washing step, absorption technique, desorption technique, desulfuration solution purify recovery technology; Thereby can improve desulfurized effect, (for example reduce the desorb energy consumption; System of the present invention can reduce reboiler energy consumption about 35%), prevent system jams, reduce the desulfuration solution loss; And can adapt to the absorbent absorption characteristic; And technology of the present invention can be applicable to various flue gas or the industrial waste gases that contain oxysulfide (for example, sulfur dioxide and sulfur trioxide).For example, renewable flue gas desulfurization technique of the present invention can be applied to the field that sintered discharge gas, blast furnace gas, coke-stove gas, coal-fired plant boiler waste gas, heating furnace waste gas etc. need carry out the exhuast gas desulfurization processing and reclaim.
Description of drawings
Through the description of carrying out with reference to the accompanying drawings, above-mentioned and other purposes of the present invention and characteristics will become apparent, in the accompanying drawing:
Figure 1A shows a kind of schematic representation of apparatus that is used to realize the renewable flue gas desulfurization technique of first exemplary embodiment according to the present invention;
Figure 1B illustrates the renewable flue gas desulfurization technique sketch map of first exemplary embodiment according to the present invention;
Fig. 2 A shows a kind of schematic representation of apparatus according to the renewable flue gas desulfurization technique of invention second exemplary embodiment that is used to realize;
Fig. 2 B shows the renewable flue gas desulfurization technique sketch map according to invention second exemplary embodiment.
Main Reference numeral:
100: absorption system 110: semi lean solution absorber portion 111: the semi lean solution inlet
113: the first flue gases of rich solution outlet in 112: the first rise 114: the first packing layers of gas hood
116: the first rich solution grooves 120 of 115: the first liquid distribution troughs: lean solution absorber portion
121: 123: the second flue gases of lean solution inlet rich solution outlet in 122: the second rise gas hood
126: the second rich solution grooves of 125: the second liquid distribution troughs of 124: the second packing layers
130: desulfuration solution captures section 131: cleaning solution inlet 132: the trapping solution outlet
Flue gas rose 135: the three liquid distribution troughs of 134: the three packing layers of gas hood in 133: the three
136: capture liquid bath 137: circulating pump
200: 211: the first rich solution inlets of 210: the first stripping stages of desorption system
212: 213: the first desorption gas of semi lean solution outlet rise 214: the four packing layers of gas hood
Liquid distribution trough 216 in 215: the four: 220: the second stripping stages of semi lean solution storage tank
221: the second rich solution inlets 222: 223: the second desorption gas of lean solution outlet rise gas hood
225: the five liquid distribution troughs 226 of 224: the five packing layers: lean solution storage tank
230: reboiler 230 ': second reboiler 240: desorber demist layer 250: dividing plate
300: desulfuration solution purifies resuscitation system 310: sedimentation filtration system 320: freezing and crystallizing system
330: the resin desalination system
430: the three pipelines of 420: the second pipelines of 410: the first pipelines
413: the second poor rich liquid heat exchangers of 412: the first poor rich liquid heat exchangers
500: the flue gas washing system
600: the desorption gas treatment system
The specific embodiment
In order to understand the present invention better, before embodiment was described in detail, employed part term was simply explained in need describing the present invention.In this manual, sulfur-containing smoke gas to be desulfurization (hereafter is a flue gas) comprises at least a in sinter fume, metallurgical gas, the flue gas in power station boiler etc., and oxysulfide wherein mainly is a sulfur dioxide.The present specification, the term "desulfurization solution" means for the removal of sulfur oxides in the flue gas (including sulfur dioxide and sulfur trioxide, in the following, for example sulfur dioxide) was added, "desulfurization solution rich liquid" (hereinafter referred to as "rich liquid") means the absorption of sulfur dioxide desulfurization solution "desulfurization solution depleted fluid" (hereinafter referred to as "poor liquid") means the absence of absorption of sulfur dioxide in the desulfurization solution or already desorbed of sulfur dioxide absorbed in the desulfurization solution in which, if desulfurization solution through two or more times to the desorption of sulfur dioxide absorbed prolapse, the desorption of the first and the last time after the desulfurization desulfurization desorption solution prior to desulfurization can be called "semi-lean solution desulfurization solution" (hereinafter referred to as "semi-lean solution") , after the last desorption desulfurization desulfurization solution as "poor liquid"; if rich liquid desulfurization solution to emerge only by a desorption of the absorbed sulfur dioxide, then again after desulfurization desulfurization desorption solution can become "lean solution."Therefore, the oxysulfide content of semi lean solution is higher than the oxysulfide content of lean solution, i.e. the ability that the ability force rate semi lean solution of lean solution absorption oxysulfide absorbs oxysulfide is strong.
In this manual, the main absorbent components in the desulfuration solution, the composition that promptly can absorb oxysulfide and oxysulfide is resolved can comprise at least a in organic alkali lye (for example, organic amine liquid) and the various solion.In addition, desulfuration solution also comprises activator, acid and water.Selectively, desulfuration solution also can comprise anti-inefficacy agent, surfactant.
Renewable flue gas desulfurization technique according to the present invention comprises through using desulfuration solution to absorb the absorption technique of the oxysulfide that contains in the flue gas and coming desorb to be absorbed with the desorption technique of the desulfuration solution of oxysulfide with the recovery oxysulfide through heating.
Wherein, said absorption technique comprises the following steps of carrying out successively by the flow of flue gas direction: use first desulfuration solution to absorb the oxysulfide in the flue gas, form first rich solution; Use second desulfuration solution further to absorb the oxysulfide in the flue gas; Form second rich solution; With the part of second rich solution as second desulfuration solution and with another part of second rich solution as first desulfuration solution, perhaps with the second whole rich solutions as second desulfuration solution or as first desulfuration solution; Use washing agent to capture the desulfuration solution of carrying secretly in the flue gas; Discharge clean flue gas.Said desorption technique may further comprise the steps: the part of first rich solution is carried out a desorb, form semi lean solution and desorption gas; Simultaneously the another part of first rich solution and the part of semi lean solution are carried out the secondary desorb, form lean solution and desorption gas; Condensation is also reclaimed the oxysulfide in the desorption gas.Another part of semi lean solution as first desulfuration solution, and is provided lean solution respectively to absorption technique as second desulfuration solution, to realize the circulation of desulfuration solution between absorption technique and desorption technique; The oxysulfide content of said first rich solution or second rich solution is higher than the oxysulfide content of semi lean solution, and the oxysulfide content of said semi lean solution is higher than the oxysulfide content of lean solution.
In one embodiment of the invention; Said renewable flue gas desulfurization technique can comprise that also the oxysulfide content with the oxysulfide content of second rich solution and semi lean solution compares; When the oxysulfide content of second rich solution is higher, the second whole rich solutions is provided to said desorption technique with first rich solution.
In one embodiment of the invention, said absorption technique also can comprise the step of using demister said clean flue gas to be carried out demist.
In one embodiment of the invention, in the capture step of said absorption technique, the trapping solution that contains desulfuration solution can be returned as cleaning solution and use.
In one embodiment of the invention, the capture step of said absorption technique also can comprise through trapping solution being carried out concentration or trapping solution being sent into the step that desorption system reclaims desulfuration solution with rich solution.
In one embodiment of the invention, said cleaning solution can be industrial soft water, desalted water or a part of trapping solution.
In one embodiment of the invention, said desulfuration solution can be organic base solution, organic amine solution or can be low temperature absorption oxysulfide and at least a in the ionic liquid of high temperature desorb oxysulfide.In addition, said desulfuration solution also can comprise activator, acid and water, perhaps also can comprise activator, acid, water and surfactant.
In one embodiment of the invention, the secondary desorb in the said desorption technique can comprise through reboiler coming first rich solution and/or second rich solution of part desorb are carried out desorb.
In one embodiment of the invention; A desorb in the said desorption technique can be the flash distillation desorb for HTHP desorb and secondary desorb; Said HTHP desorb can realize through first stripping stage that the bottom is provided with reboiler; Said flash distillation desorb can realize through second stripping stage that is connected with vacuum extractor, be provided with dividing plate between said first stripping stage and second stripping stage.
In one embodiment of the invention, said renewable flue gas desulfurization technique washs flue gas before also can being included in and getting into said absorption technique, so that flue gas is lowered the temperature and dedusting.Preferably, said washing step can realize that through S shape flue and scrubbing tower wherein, said scrubbing tower can comprise void tower flue gas washing section, filler flue gas washing section and demist layer from the bottom up successively through making pending flue gas.In addition, said washing step can comprise that also the booster fan through being arranged on S shape flue front end makes the flue gas supercharging.
In one embodiment of the invention; Said renewable flue gas desulfurization technique also can comprise and carries out heat exchange to providing to first rich solution of desorption technique and/or second rich solution and lean solution and/or semi lean solution; With the temperature that improves first rich solution and/or second rich solution and reduce lean solution and/or the temperature of semi lean solution; Thereby improved Btu utilization efficient; And because desulfuration solution at low temperatures (for example; 30 ℃～60 ℃) oxysulfide in the flue gas is had better absorption efficiency, so purification heat back lean solution and/or semi lean solution have also reached the temperature requirement of absorption technique.In addition; Said renewable flue gas desulfurization technique also can comprise first rich solution that will carry out a desorb and/or second rich solution and desorption gas are carried out heat exchange; With the temperature of further raising first rich solution and/or second rich solution and reduce the temperature of desorption gas, thereby further improve Btu utilization efficient.
In one embodiment of the invention, said renewable flue gas desulfurization technique also can comprise and purifies recovery to the lean solution of absorption technique and handle providing, to remove suspension, metal cation and the strong acid radical ion that contains in the lean solution.Wherein, said purification recovery treatment step can comprise sedimentation, filtration, freezing and crystallizing and the resin desalination step of carrying out in turn.Said purification recovery treatment step also can only comprise sedimentation, filtration and the freezing and crystallizing that carries out in turn, perhaps only comprises sedimentation, the filtration+resin desalination carried out in turn.In addition, said sedimentation and filtration step can carry out before lean solution is carried out heat exchange, and said freezing and crystallizing and resin desalination step can be carried out after lean solution is carried out heat exchange.In the present invention, said strong acid radical ion can comprise sulfate ion, chlorion and nitrate ion.In addition, said precipitation step also can comprise the step that in the lean solution of treating sedimentation, adds precipitation by metallic ion agent and suspension filter aid.In addition, said purification recovery treatment step also can comprise to adding alkali through sedimentation with filtering in the clear liquid that obtains, with the metal ion in the further removal clear liquid.
In one embodiment of the invention, can carry out the purification recovery identical with foregoing to lean solution and semi lean solution respectively simultaneously handles.Promptly; In one embodiment of the invention; Said renewable flue gas desulfurization technique also can comprise and purifies recovery respectively to the lean solution of absorption technique and semi lean solution and handle providing; Said purification recovery treatment step comprises sedimentation, filtration, freezing and crystallizing and the resin desalination step of carrying out in turn, thereby removes suspension, metal cation and the strong acid radical ion that contains in lean solution and the semi lean solution respectively.In addition, said sedimentation and filtration step can carry out before lean solution or semi lean solution carry out heat exchange, and said freezing and crystallizing and resin desalination step can be carried out after lean solution or semi lean solution carry out heat exchange.
In one embodiment of the invention, said condensation and the step that reclaims the oxysulfide in the desorption gas can may further comprise the steps: desorption gas is carried out condensation to form condensate liquid and the desorption gas of carrying desulfuration solution secretly; The said desorption gas of carrying desulfuration solution secretly is carried out gas-liquid separation oxysulfide gas and liquid phase; Reclaim oxysulfide gas.Further, said condensation and the step that reclaims the oxysulfide in the desorption gas also can comprise to condensate liquid with by the said liquid phase that gas-liquid separation obtains filters, and then filtrating is provided to a desorb or step that filtrating is effluxed.
In one embodiment of the invention; The said step that desorption gas is carried out condensation can comprise multi-stage condensing in sequence; And the condensate liquid that the first order condensation in the said multi-stage condensing forms is discharged to the external world, the condensate liquid that other grade condensation in the said multi-stage condensing forms through with the desorption gas heat exchange after provide to desorption technique.
In one embodiment of the invention; The said step that desorption gas is carried out condensation can comprise one-level condensation and B-grade condensation; The condensate liquid that said one-level condensation forms is discharged to the external world, the condensate liquid that said B-grade condensation forms through with the desorption gas heat exchange after provide to desorption technique.
Now, will describe exemplary embodiment of the present invention in detail.Example of the present invention illustrates in the accompanying drawings, and wherein, identical label is represented components identical all the time.Below will be through describing embodiment, to explain the present invention with reference to accompanying drawing.Yet the present invention can implement with multiple different form, should not be understood that to be confined to the exemplary embodiment in this proposition.It openly will be thorough with completely providing these embodiment to make of the present invention, and scope of the present invention is conveyed to those skilled in the art fully.In the accompanying drawings, for clarity, can exaggerate the layer with the zone size and relative size.
Here but usage space relative terms (for example, " following ", " in ... below ", " top " etc.) is described element or the relative position relation of characteristic and other element or characteristic shown in figure.It should be understood that the space relative terms is intended to comprise the different azimuth of device in using or operating except the orientation that is described in the drawings.For example; If device is reversed in the accompanying drawings, then be described as other element or characteristic " following " or " " element of other element or characteristic " below " will be positioned as subsequently other element or characteristic " above " or " " element or the characteristic of other element or characteristic " top ".Therefore, exemplary term " following " can comprise top and following two kinds of orientation.
Describe renewable according to an exemplary embodiment of the present invention flue gas desulfurization technique and system thereof below with reference to accompanying drawings in detail.
Figure 1A shows a kind of device sketch map that is used to realize the renewable flue gas desulfurization technique of first exemplary embodiment according to the present invention, and Figure 1B illustrates the renewable flue gas desulfurization technique sketch map of first exemplary embodiment according to the present invention.
Shown in Figure 1A, realize that the device of this exemplary embodiment can comprise: absorption system 100 absorbs sulfur in smoke through lean solution is contacted with pending flue gas adverse current, and forms rich solution and purified gas; Desorption system 200 makes the rich solution desorb to form new lean solution and desorption gas through desorber and reboiler; Desulfuration solution purifies resuscitation system 300, removes the foreign ion in the lean solution of desorb gained through the resin desalination; Desorption gas treatment system 600 uses the desorption gas condensation separator to obtain pure sulfur dioxide gas.
In the device of realizing this exemplary embodiment; The absorption tower of absorption system 100 comprise flue gas in turn through and the semi lean solution absorber portion 110 that separates each other, lean solution absorber portion 120 and desulfuration solution capture section 130; Semi lean solution absorber portion 110 is provided with semi lean solution inlet 111 and first rich solution outlet 112; Lean solution absorber portion 120 is provided with lean solution inlet 121 and second rich solution outlet 122, and desulfuration solution captures section 130 and is provided with cleaning solution inlet 131 and trapping solution outlet 132.
In the device of realizing this exemplary embodiment; The desorber of desorption system 200 comprises that first stripping stage 210 that separates each other and be communicated with is with below first stripping stage and second stripping stage 220 that links to each other with reboiler 230; First stripping stage 210 is provided with first rich solution inlet 211 and is provided with second rich solution inlet 221 and lean solution outlet 222 with semi lean solution outlet 212, the second stripping stages 220.
In the device of realizing this exemplary embodiment, semi lean solution inlet 111 links to each other with semi lean solution outlet 212 to use the semi lean solution that obtains from first stripping stage 210 semi lean solution absorber portion 110, to absorb sulfur in smoke through first pipeline 410; Lean solution inlet 121 links to each other with lean solution outlet 222 to use the lean solution that obtains from second stripping stage 220 lean solution absorber portion 120, to absorb sulfur in smoke through second pipeline 420; The outlet 112 of first rich solution links to each other to first stripping stage 210 and second stripping stage 220 rich solution to be provided with second rich solution inlet 221 with first rich solution inlet 211 through the 3rd pipeline 430; The outlet 122 of second rich solution links to each other with lean solution inlet 121 with semi lean solution inlet 111; Recycle the part of second rich solution is sent into semi lean solution absorber portion 110 and another part of second rich solution is sent into lean solution absorber portion 120; In addition; Second rich solution outlet 122 also links to each other with the 3rd pipeline 430; With when the content of sulfur dioxide in second rich solution is higher than the content of sulfur dioxide in the semi lean solution, the second whole rich solutions is sent into the 3rd pipeline send into desorption system 200 then and carry out desorb; Trapping solution outlet 132 links to each other with cleaning solution inlet 131 through circulating pump 137, trapping solution is come the desulfuration solution of carrying secretly in the circularly trapping flue gas with realization as cleaning solution; Be provided with second poor rich liquid heat exchanger 413 between first pipeline 410 and the 3rd pipeline 430; Be provided with first poor rich liquid heat exchanger 412 between second pipeline 420 and the 3rd pipeline 430.
In the device of realizing this exemplary embodiment; Desulfuration solution purifies resuscitation system 300 and comprises sedimentation filtration system 310, freezing and crystallizing system 320 and the resin desalination system of arranging in turn along the lean solution flow direction 330; Desulfuration solution purifies resuscitation system 300 and is arranged on second pipeline, and first poor rich liquid heat exchanger 412 is arranged between sedimentation filtration system 310 and the freezing and crystallizing system 320.
In the device of realizing this exemplary embodiment, above first stripping stage 210, be provided with desorption gas treatment system 600.Said desorption gas treatment system 600 comprises: condenser; Have desorption gas inlet, fog outlet and condensate outlet; And the desorption gas inlet is connected with the desorption gas outlet on first stripping stage, 210 tops; Be used for the desorption gas that condensation is discharged from desorption technique; To form condensate liquid and fog, said fog is the desorption gas of carrying desulfuration solution secretly; Gas-liquid separator; Have fog inlet, oxysulfide gas vent and discharge channel; And the fog inlet is connected with the fog outlet of condenser, and the desorption gas that is used for carrying desulfuration solution secretly is separated into oxysulfide gas (for example, sulfur dioxide gas and/or sulfur trioxide gas) and liquid phase; The sulfur filtration device; Have liquid inlet and filtrate (liquid; And the liquid inlet is connected with the condensate outlet of condenser and the discharge channel of gas-liquid separator; Top or filtrate (liquid that filtrate (liquid is connected to first stripping stage 210 are connected to the external world; Be used for filtering, filter that the filtrating obtain is sent into first stripping stage 210 with rich solution or filtrating that filtration is obtained effluxes to condensate liquid with from the liquid phase that gas-liquid separator separates goes out.
Shown in Figure 1B, the renewable flue gas desulfurization technique of this exemplary embodiment can comprise absorption technique and the desorption technique that couples together through circulating of desulfuration solution.
Wherein, absorption technique comprises the following steps of carrying out successively by the flow of flue gas direction: use semi lean solution in semi lean solution absorber portion 110, to absorb sulfur in smoke, form first rich solution; Use lean solution in lean solution absorber portion 120, further to absorb sulfur in smoke; Form second rich solution; The part of second rich solution is injected semi lean solution absorber portion 110 with the semi lean solution that forms first rich solution because of absorbing sulfur dioxide; Another part of second rich solution is injected the lean solution absorber portion with lean solution; When the content of sulfur dioxide in second rich solution is higher than the content of sulfur dioxide in the semi lean solution of discharging in first stripping stage 210, the second whole rich solutions is sent into desorption system 200 carry out desorb; Use industrial pure water to capture the desulfuration solution of carrying secretly in the flue gas, and the trapping solution that capture is obtained is once more as washing agent as washing agent, circulation repeatedly, the desulfuration solution concentration in trapping solution reaches after the predetermined value, reclaims the desulfuration solution in the trapping solution; Discharge clean flue gas.
Desorption technique may further comprise the steps: the part to first rich solution of discharging from semi lean solution absorber portion 110 is carried out a desorb, forms semi lean solution and desorption gas; Simultaneously the another part of first rich solution and the part of semi lean solution are carried out the secondary desorb, form lean solution and desorption gas; Condensation is also reclaimed the sulfur dioxide in the desorption gas.
In the present exemplary embodiment, may be recycled flue gas desulfurization process comprising: (1) via a third conduit 430 is supplied to a first rich process desorption solution and / or the second rich fluid (e.g., the first rich liquid and / or second rich liquid temperature of 45 ℃ ~ 55 ℃) and through the second conduit 420 lean solution (for example, poor liquid temperature of 95 ℃ ~ 120 ℃) in the first heat transfer fluid between rich and poor once the heat exchanger 412, thereby enhancing the first rich solution and / or the second rich fluid temperature and reduce the temperature of the lean solution (e.g., a heat exchanger after the first rich solution and / or the temperature of the second rich liquid 65 ℃ ~ 80 ℃, poor liquid temperature of 80 ℃ ~ 95 ℃); (2) right after the first heat after the first rich liquid and / or second rich liquid (for example, a temperature of 65 ℃ ~ 80 ℃ ) from the first desorption stage semi-lean solution 210 is discharged (for example, at a temperature of 95 ℃ ~ 110 ℃) rich fluid in the second heat exchanger 413 in the secondary heat exchanger, to further improve the first rich solution and / or the second rich fluid temperature, while reducing the temperature of the semi-lean solution (for example, by the second heat exchanger after the first rich solution and / or the temperature of the second rich liquid 80 ℃ ~ 95 ℃, the temperature of the semi-lean solution is 85 ℃ ~ 95 ℃).
In addition, in this exemplary embodiment,, also can carry out heat exchange once more, also can carry out heat exchange once more semi lean solution and cooling water to lean solution and cooling water for the lean solution that will pass through heat exchange or the temperature of semi lean solution further are reduced to below 60 ℃.
In this exemplary embodiment; To provide through the part of first rich solution after the heat exchange and/or second rich solution to second stripping stage 220 and directly carry out the secondary desorb, will all send into first stripping stage 210 through first rich solution behind a heat exchange and the secondary heat exchange and/or second rich solution and carry out a desorb.But the invention is not restricted to this; For example; Also can carry out a heat exchange and secondary heat exchange to the first whole rich solutions and/or second rich solution; And the part that will pass through first rich solution and/or second rich solution after the heat exchange sends into second stripping stage 220 and carries out the secondary desorb, and another part is sent into first stripping stage 210 and carried out a desorb.
In this exemplary embodiment, renewable flue gas desulfurization technique also comprises the step that the lean solution after resolving is purified recovery.Specifically; Lean solution through the secondary desorb in second stripping stage 220 gets into second pipeline 420 through lean solution outlet 222; Sedimentation filtration system 310, freezing and crystallizing system 320, resin desalination system 330 and the lean solution that purifies resuscitation system 300 through the desulfuration solution in turn lean solution absorber portion 120 on 121 entering absorption towers that enters the mouth then, thus realize recycling of desulfuration solution.Here, lean solution is carried out heat exchange at first heat exchanger, 412 places between sedimentation filtration system 310 and freezing and crystallizing system 320 and the rich solution in the 3rd pipeline 430, so that lean solution is lowered the temperature and rich solution is heated up.Sedimentation filtration system 310 is through adding precipitation by metallic ion agent and suspension filter aid in lean solution; Remove in the lean solution suspension (for example; Dust etc.) and/or metal ion; And can reduce the sedimentation of suspension in first heat exchanger 412 or second pipeline 420 after it, reduce the obstruction of second pipeline 420.Freezing and crystallizing system 320 removes and reclaims the sulfate radical plasma (SO in the lean solution through lean solution being carried out operations such as basicity adjusting and cooling
2- 4), thereby reduced the load of resin desalination system 320.Resin desalination system 330 is used for removing the chlorion (Cl of lean solution
-), nitrate ion (NO
- 3) and sulfate radical (SO
2- 4) wait the strong acid radical ion.
In this exemplary embodiment, renewable flue gas desulfurization technique comprises that also the desorption gas that desorption technique is obtained carries out condensation and reclaims the step of oxysulfide.Said condensation and the step that reclaims the oxysulfide in the desorption gas may further comprise the steps: desorption gas is carried out condensation to form condensate liquid and the desorption gas of carrying desulfuration solution secretly; The said desorption gas of carrying desulfuration solution secretly is carried out gas-liquid separation oxysulfide gas and liquid phase; Reclaim oxysulfide gas.In addition, said condensation and the step that reclaims the oxysulfide in the desorption gas also can comprise to condensate liquid with by the said liquid phase that gas-liquid separation obtains filters, and then filtrating is provided to a desorb or step that filtrating is effluxed.Said condensing steps is realized through condenser.Said gas-liquid separation realizes through gas-liquid separator.Said filtration realizes through the sulfur filtration device.
Embodiment 2
Fig. 2 A shows a kind of device sketch map that is used to realize the renewable flue gas desulfurization technique of second exemplary embodiment according to the present invention, and Fig. 2 B illustrates the renewable flue gas desulfurization technique sketch map of second exemplary embodiment according to the present invention.
Shown in Fig. 2 A, realize the device of this exemplary embodiment and realize that the difference of the device of embodiment 1 is following content:
(1) device of realizing this exemplary embodiment comprises washing system 500.Flue gas washing system 500 is arranged on before the absorption system, is used to wash the flue gas that contains sulfur dioxide that is about to get into absorption system 100, to remove the impurity such as dust that contain in the flue gas.In addition, for pending flue-gas temperature condition with higher (for example, pending flue gas is a metallurgy sintering smoke), washing system 500 can be reduced to the temperature of flue gas the temperature (for example, 30 ℃～60 ℃) that is suitable for absorbing with desulfuration solution oxysulfide wherein.Certainly; When not too being fit to absorb oxysulfide wherein if the temperature of pending flue gas is lower with desulfuration solution; Also can come with hot water the adjustment of pending flue gas to the temperature (for example, 30 ℃～60 ℃) that is suitable for absorbing oxysulfide wherein through washing system 500 with desulfuration solution.Here, when the desulfuration solution composition not simultaneously, its temperature that is suitable for absorbing oxysulfide also may be different.
(2) in the device of realizing this exemplary embodiment; First flue gas that semi lean solution absorber portion 110 can comprise the first rich solution groove 116 and have first preset distance each other rises gas hood 113 and first liquid distribution trough, 115, the first liquid distribution troughs 115 are communicated with semi lean solution inlet 111 and the first rich solution groove 116 exports 112 with first rich solution and is communicated with.Here; First preset distance is used for through increasing the mode of flue gas range ability; Make the abundant sedimentation of dust in flue gas, and first preset distance can be used for extremely being fit to the temperature of absorbing sulfur dioxide through the temperature that the semi lean solution and the abundant counter current contacting of flue gas of 115 distributions of first liquid distribution trough are regulated flue gas.In addition, when first flue gas rose gas hood 113 or first liquid distribution trough 115 and needs repairing, first preset distance can make things convenient for the staff to get into semi lean solution absorber portion 110 they are keeped in repair.In addition; Alternatively; Rise between the gas hood 113 and first liquid distribution trough 115 at first flue gas of present embodiment and can also be provided with first packing layer 114; And the distance that first packing layer 114 and first flue gas rise between the gas hood 113 is first preset distance; Thereby can make the abundant sedimentation of dust in flue gas, can make flue gas and semi lean solution carry out counter current contacting more fully again.
(3) in the device of realizing this exemplary embodiment; Lean solution absorber portion 120 comprises that second flue gas that has second preset distance each other rises gas hood 123, second packing layer 124, second liquid distribution trough 125 and the second rich solution groove, 126, the second liquid distribution troughs are communicated with the lean solution inlet and the second rich solution groove exports with second rich solution and is communicated with.Desulfuration solution captures section 130 and comprises that the 3rd flue gas that has second preset distance each other rises gas hood 133, the 3rd packing layer 134, the 3rd liquid distribution trough 135 and captures liquid bath 136, the three liquid distribution troughs 135 and cleaning solution and enter the mouth and 131 be communicated with and capture liquid bath 136 and export 132 with trapping solution and be communicated with.In addition, flue gas demist layer 140 can be arranged on place, top, absorption tower, and between the 3rd liquid distribution trough 135 of clean gas outlet and flue gas trapping section 130.Flue gas demist layer 140 can comprise two-layer demister, and has preset distance between this two-layer demister.In the present invention, the cleaning solution from cleaning solution inlet 131 entering desulfuration solutions capture sections 130 is industrial soft water, desalted water or a part of trapping solution.
(4) in realizing the device of this exemplary embodiment, the bottom of first stripping stage 210 is provided with second reboiler 230 ' to realize that the rich solution that gets into first stripping stage 210 is carried out the HTHP desorb; Second stripping stage 220 is not provided with reboiler; And the top of second stripping stage 220 is connected with the vacuum extractor (not shown) to realize that the rich solution that gets into second stripping stage 220 is carried out the flash distillation desorb; The desorption gas of extracting out through vacuum extractor can provide to desorption gas treatment system 600, and is provided with dividing plate 250 between said first stripping stage 210 and second stripping stage 220.
(5) in the device of realizing this exemplary embodiment; First stripping stage 210 comprises that first desorption gas that has second preset distance each other rises gas hood 213, the 4th packing layer 214, the 4th liquid distribution trough 215 and semi lean solution storage tank 216, and semi lean solution storage tank 216 is communicated with semi lean solution outlet 212; Second stripping stage 220 comprises that second desorption gas that has second preset distance each other rises gas hood 223, the 5th packing layer 224, the 5th liquid distribution trough 225 and lean solution storage tank 226, and lean solution storage tank 226 is communicated with lean solution outlet 222.In addition, desorber demist layer 240 can be arranged on desorber top place and between the 4th liquid distribution trough 215 of the desorption gas outlet and first stripping stage 210.Desorber demist layer 240 can comprise two-layer demister, and has preset distance between this two-layer demister.
(6) in the device of realizing this exemplary embodiment; The rich solution that obtains through the absorption tower transports through the 3rd pipeline 430; And, get into first stripping stage 210 and second stripping stage 220 through first rich solution inlet, 211 and second rich solution inlet 221 respectively successively through after first poor rich liquid heat exchanger 412 and 413 heat exchange of second poor rich liquid heat exchanger.
In realizing device of the present invention, said filler can be various structured packings or dumped packing.For example, plastics deflection plate filler, ripple deflection plate with holes, metallurgic orifice corrugated packing, plastic filler in bulk, ball-type dumped packing etc.In realizing device of the present invention, demister can be electrostatic precipitator, deflection plate demister or mesh mist eliminator.In realizing device of the present invention, it is that the staff keeps in repair each equipment for ease that second preset distance is set.In realizing device of the present invention, absorption tower and desorber inner such as liquid distribution trough, rise between the neighbouring device of gas hood, packing layer, demister etc. and all can have second preset distance, with convenient for maintaining.In realizing device of the present invention; The industrial clean water system that can setting be connected with equipment such as liquid distribution trough, packing layer, demisters; To realize cleaning to equipment such as liquid distribution trough, packing layer, demisters; For example, also can come equipment such as cleaning liquid distributor, packing layer, demister through injecting industrial clean water from the liquid inlet of each section of each section on absorption tower or desorber.
In realizing device of the present invention, the purpose that rises gas hood, packing layer, liquid distribution trough etc. is set in the absorption tower is to make flue gas and desulfuration solution to carry out counter current contacting fully, thereby improve the absorptivity of desulfuration solution sulfur dioxide; The purpose that rises gas hood, packing layer, liquid distribution trough is set in desorber is to prolong the time of staying of rich solution in desorber; So that the abundant desorb of rich solution; And make the gas of rich solution and reboiler generation carry out counter current contacting, rich solution is heated and improves desorption effect; The effect that demister is set is to remove desulfuration solution or the moisture in flue gas or the desorption gas.Therefore; Although described in this exemplary embodiment to be provided with in absorption tower and the desorber and risen gas hood, packing layer, liquid distribution trough, demister etc.; But those skilled in the art should understand that to the invention is not restricted to this, and can realize rising equipment such as gas hood, packing layer, liquid distribution trough, demister role in realizing device of the present invention through other similar devices.
Shown in Fig. 2 B, the renewable flue gas desulfurization technique of this exemplary embodiment can comprise absorption technique and the desorption technique that couples together through circulating of desulfuration solution.
Specifically, the renewable flue gas desulfurization technique of this exemplary embodiment comprises following content:
At first, treat smoke treatment and wash, so that it is lowered the temperature and dedusting.Preferably, said washing step can realize that through S shape flue and scrubbing tower wherein, said scrubbing tower can comprise void tower flue gas washing section, filler flue gas washing section and demist layer from the bottom up successively through making pending flue gas.In addition, said washing step can comprise that also the booster fan through being arranged on S shape flue front end makes the flue gas supercharging.
Then, absorb the oxysulfide in the flue gas, and remove impurity such as dust in flue gas, heavy metal element and oxysulfide simultaneously to realize purification to flue gas through absorption technique.Said absorption technique comprises the following steps of carrying out successively by the flow of flue gas direction: use semi lean solution in semi lean solution absorber portion 110, to absorb sulfur in smoke, form first rich solution; Use lean solution in lean solution absorber portion 120, further to absorb sulfur in smoke; Form second rich solution; The part of second rich solution is injected semi lean solution absorber portion 110 with the semi lean solution that forms first rich solution because of absorbing sulfur dioxide; Another part of second rich solution is injected the lean solution absorber portion with lean solution; When the content of sulfur dioxide in second rich solution is higher than the content of sulfur dioxide in the semi lean solution of discharging in first stripping stage 210, the second whole rich solutions is sent into semi lean solution absorber portion 210; Use industrial pure water to capture the desulfuration solution of carrying secretly in the flue gas, and the trapping solution that capture is obtained is once more as washing agent as washing agent, circulation repeatedly, the desulfuration solution concentration in trapping solution reaches after the predetermined value, reclaims the desulfuration solution in the trapping solution; Flue gas is carried out demist to be handled; Discharge clean flue gas.
Next, the rich solution that absorption technique is obtained carries out desorb, obtains lean solution, semi lean solution and desorption gas, and desorption gas is carried out condensation, filtration treatment, thereby obtains pure oxysulfide.Said desorption technique may further comprise the steps: the part to first rich solution of discharging from semi lean solution absorber portion 110 is carried out the HTHP desorb, forms semi lean solution and desorption gas; Simultaneously the another part of first rich solution and the part of semi lean solution are carried out the flash distillation desorb, form lean solution and desorption gas; Condensation is also reclaimed the oxysulfide in the desorption gas.
In this exemplary embodiment; Renewable flue gas desulfurization technique also can comprise: a heat exchange is carried out to providing through the 3rd pipeline 430 to first rich solution of desorption technique and the lean solution of second pipeline 420 of flowing through in (1) in first poor rich liquid heat exchanger 412, thereby improves the temperature of first rich solution and reduce the temperature of lean solution; (2) to second poor rich liquid heat exchanger 413, carrying out secondary heat exchange,, reduce the temperature of semi lean solution simultaneously with the temperature of further raising first rich solution through first rich solution after the heat exchange and the semi lean solution of discharging from first stripping stage 210.
In this exemplary embodiment; The first whole rich solution to obtaining from absorption technique carries out a heat exchange and secondary heat exchange; And the part that will pass through first rich solution after the heat exchange sends into second stripping stage 220 and carries out the HTHP desorb, and another part is sent into first stripping stage 210 and carried out the flash distillation desorb.
The technology of this exemplary embodiment also comprises the step that the lean solution after resolving is purified recovery.Specifically; Lean solution through the flash distillation desorb in second stripping stage 220 gets into second pipeline 420 through lean solution outlet 222; Sedimentation filtration system 310, freezing and crystallizing system 320, resin desalination system 330 and the lean solution that purifies resuscitation system 300 through the desulfuration solution in turn lean solution absorber portion 120 on 121 entering absorption towers that enters the mouth then, thus realize recycling of desulfuration solution.Here, lean solution is carried out heat exchange at first heat exchanger, 412 places between sedimentation filtration system 310 and freezing and crystallizing system 320 and the rich solution in the 3rd pipeline 430, so that lean solution is lowered the temperature and rich solution is heated up.Sedimentation filtration system 310 is through adding precipitation by metallic ion agent and suspension filter aid in lean solution; Remove in the lean solution suspension (for example; Dust etc.) and/or metal ion; And can reduce the sedimentation of suspension in first heat exchanger 412 or second pipeline 420 after it, reduce the obstruction of second pipeline 420.Freezing and crystallizing system 320 removes and reclaims the sulfate radical plasma (SO in the lean solution through lean solution being carried out operations such as basicity adjusting and cooling
2- 4), thereby reduced the load of resin desalination system 320.Resin desalination system 330 is used for removing the chlorion (Cl of lean solution
-), nitrate ion (NO
- 3) and sulfate radical (SO
2- 4) wait the strong acid radical ion.
In addition, renewable flue gas desulfurization technique of the present invention also can be included in the rich solution that before the heat exchange absorption technique is obtained and carry out step of buffering, provides to the flowing velocity of the rich solution of desorption technique with storage rich solution and adjusting, thereby regulates rhythm of production.Here, saidly rich solution is carried out step of buffering can realize through between first rich solution of semi lean solution absorber portion 110 outlet, 112 and first poor rich liquid heat exchanger 412, rich solution dashpot (not shown) being set.
In addition; Renewable flue gas desulfurization technique of the present invention also can be included in the step that the preceding rich solution that absorption technique is obtained of a heat exchange filters; With remove in the rich solution such as impurity such as suspension and dust, thereby help long-term, effective direct motion of renewable flue gas desulfurization technique of the present invention.The said step that rich solution is filtered can realize through between first rich solution outlet, 112 and first poor rich liquid heat exchanger 412 of semi lean solution absorber portion 110, the first rich solution filter (not shown) being set.Preferably, the said step that rich solution is filtered can be carried out before the step of buffering said rich solution is carried out.
In addition; Renewable flue gas desulfurization technique of the present invention also can comprise will providing of obtaining after the desorb to the semi lean solution of semi lean solution absorber portion is purified the recovery processed steps, to remove suspension, metal cation and the strong acid radical ion that contains in the semi lean solution.Wherein, saidly semi lean solution is purified the recovery treatment step can comprise sedimentation, filtration, freezing and crystallizing and the resin desalination step of carrying out in turn.In addition, said sedimentation and filtration step can carry out before semi lean solution carries out heat exchange, and said freezing and crystallizing and resin desalination step can be carried out after semi lean solution carries out heat exchange.In the present invention, said strong acid radical ion can comprise sulfate ion, chlorion and nitrate ion.In addition, said precipitation step also can comprise the step that in the lean solution of treating sedimentation, adds precipitation by metallic ion agent and suspension filter aid.In addition, said purification recovery treatment step also can comprise to adding alkali through sedimentation with filtering in the clear liquid that obtains, with the metal ion in the further removal clear liquid.Here, saidly semi lean solution is purified the recovery processed steps can purify the resuscitation system (not shown) and realize through second desulfuration solution is set in first pipeline 410.The structure of said second desulfuration solution purification resuscitation system and desulfuration solution purification resuscitation system 300 is basic identical; Difference is: second desulfuration solution purifies resuscitation system and is arranged on first pipeline 410; And comprise the second sedimentation filtration system (not shown), the second freezing and crystallizing system (not shown) and the second resin desalination system (not shown) of arranging in turn along the semi lean solution flow direction, and second poor rich liquid heat exchanger 413 is between the second sedimentation filtration system and the second freezing and crystallizing system.
In the device of realizing flue gas desulfurization technique of the present invention; The said sedimentation filtration system (310) or the second sedimentation filtration system can comprise the subsider and the filter of serial connection successively; What the said freezing and crystallizing system (320) or the second freezing and crystallizing system can comprise successively serial connection adds alkali groove, freezing and crystallizing device, centrifugal separator and freezing and crystallizing underground tank, and the said resin desalination system (330) or the second resin desalination system can comprise active carbon adsorption groove, resin adsorption groove and the solution tank of serial connection successively.In addition, said sedimentation filtration system (310) also comprises the precipitating reagent make-up tank that is connected with said subsider.In addition, said subsider also is directly connected to the said alkali groove that adds.Owing to be provided with the precipitating reagent make-up tank that is connected with subsider, said precipitation step also can comprise the step that in the lean solution of treating sedimentation, adds precipitation by metallic ion agent and suspension filter aid.
Specifically, the step that among the present invention desulfuration solution is purified recovery can realize by the following method:
(1) makes suspension, metal cation deposition: adopt self-cleaning recoil lean solution filter; Lean solution or semi lean solution are filtered; Add filter aid, metal-precipitator; Solution adopts sheet frame to carry out press filtration; Remove suspension and the precipitation by metallic ion thing of suspension particle diameter greater than 50um; Solution is sent into except that carbon filter after the press filtration, so that remove organic acid ion and desulfuration solution degradation material in a small amount.Solution behind de-carbon further carries out mechanical filter.Remove suspended sediment and the activated carbon particles of suspension particle diameter greater than 5um.Wherein filter aid is one or both of silica containing diatomite or diatomite and sial filter aid, and metal-precipitator is inorganic alkaline thing and organic substance, and inorganic base substance is mainly NaOH, KOH, NaH
2PO
4, Na
2HPO
4, K
2HPO
4, KH
2PO
4, the organic matter precipitating reagent is sodium diethyldithiocarbamate.
(2) freezing and crystallizing is to remove sulfate radical: regulate with the lean solution that is removed metal ion or the basicity of semi lean solution, form first mixing material, the further decrease temperature crystalline of first mixing material is second mixing material, and separates out a sodium sulphate shape crystal.
(3) resin removes strong acid radical ions such as chlorine root, nitrate anion; To send into resin bed with the lean solution that is removed metal ion or semi lean solution or second mixing material; So that need the liquid of resin treatment flow through the from the top down resin bed or the resin bed of flowing through from bottom to top, form the 3rd mixing material through the solution of purified treatment.In the resin washing process, can be provided with increases the air blow drying operation, reduces the adsorbance of resin to desulfuration solution.Loss when reducing the resin alkali cleaning.
In addition; In another exemplary embodiment of the present invention; The said step that desorption gas is carried out condensation can comprise multi-stage condensing in sequence; And the condensate liquid that the first order condensation in the said multi-stage condensing forms is discharged to the external world, the condensate liquid that other grade condensation in the said multi-stage condensing forms through with the desorption gas heat exchange after provide to desorption technique.For example, the said step that desorption gas is carried out condensation can comprise one-level condensation and B-grade condensation, and the condensate liquid that said one-level condensation forms is discharged to the external world, the condensate liquid that said B-grade condensation forms through with the desorption gas heat exchange after provide to desorption technique.Present embodiment can be realized through the desorption gas treatment system 600 among the embodiment 1 is set to following structure.In said desorption gas treatment system, condenser can be made up of first-stage condenser and secondary condenser.Wherein, first-stage condenser has desorption gas inlet, the outlet of first fog and first condensate outlet, and the desorption gas inlet exports with the desorption gas on first stripping stage, 210 tops and be connected, and the one-level condensate outlet is connected to the external world; Secondary condenser has first fog inlet, the outlet of second fog and second condensate outlet; First fog inlet is connected with the outlet of first fog; Second condensate outlet is connected with the liquid inlet of sulfur filtration device; The outlet of second fog is connected with the fog inlet of gas-liquid separator, and the filtrate (liquid of said sulfur filtration device is connected to the top of first stripping stage 210.The 3rd heat exchanger is set between the top of the said filtrate (liquid and first stripping stage 210; And the 3rd heat exchanger is between desorption gas outlet and condenser; Thereby can realize the filtrating and the heat exchange of high temperature desorption gas, so that the temperature of high temperature desorption gas is reduced and improves the temperature of the filtrating that is about to get into first stripping stage.
The above-mentioned step that desorption gas is carried out multi-stage condensing has the following advantages.Be that example illustrates above-mentioned advantage below with the condensed in two stages.Usually, (for example, can be 80～95 ℃ through the condensed acid gas of one-level (that is, through condensed desorption gas) temperature, condensate temperature can be 80～95 ℃ because the temperature of the condensate liquid that obtains of one-level condensation is higher than the temperature that B-grade condensation obtains; Acid gas temperature behind B-grade condensation can be 55～65 ℃; Condensate temperature can be 50～65 ℃); So the condensate liquid that first-stage condenser obtains contains water, a small amount of sulfurous acid, and the condensate liquid that secondary condenser obtains contains a small amount of desulfurizing agent, water, saturated sulfurous acid.The condensate liquid that first-stage condenser is obtained effluxes, and can avoid causing the concentration of the desulfuration solution in the flue gas desulphurization system low excessively owing in flue gas desulphurization system, introducing the moisture that contains in cleaning solution or industrial pure water or the flue gas; And the condensate liquid that secondary condenser obtains is returned desorption system, and can reduce the loss of desulfurizing agent in the desulfuration solution, improve the rate of recovery of oxysulfide, and avoid the reduction of the desulfuration solution concentration in the flue gas desulphurization system.Though specifically described the situation of desorption gas being carried out condensed in two stages above, it should be appreciated by those skilled in the art that in the present invention the step that desorption gas is carried out condensation also can comprise in sequence three grades of condensations or condensation more than three grades.
Although combined certain exemplary embodiment to describe renewable flue gas desulfurization technique of the present invention above; But those skilled in the art should be clear; Under the situation of the spirit and scope that do not break away from claim and limited, can make amendment and change above-mentioned exemplary embodiment.
Claims (27)
1. renewable flue gas desulfurization technique; It is characterized in that; Said renewable flue gas desulfurization technique comprises through using desulfuration solution to absorb the absorption technique of the oxysulfide that contains in the flue gas and coming desorb to be absorbed with the desorption technique of the desulfuration solution of oxysulfide with the recovery oxysulfide through heating; Wherein
Said absorption technique comprises the following steps of carrying out successively by the flow of flue gas direction: use first desulfuration solution to absorb the oxysulfide in the flue gas, form first rich solution; Use second desulfuration solution further to absorb the oxysulfide in the flue gas, form second rich solution, with second rich solution as second desulfuration solution or as first desulfuration solution; Use washing agent to capture the desulfuration solution of carrying secretly in the flue gas; Discharge clean flue gas;
Said desorption technique may further comprise the steps: the part of first rich solution is carried out a desorb, form semi lean solution and desorption gas; Simultaneously the another part of first rich solution and the part of semi lean solution are carried out the secondary desorb, form lean solution and desorption gas; Condensation is also reclaimed the oxysulfide in the desorption gas;
Another part of semi lean solution as first desulfuration solution, and is provided lean solution respectively to absorption technique as second desulfuration solution;
The oxysulfide content of said first rich solution or second rich solution is higher than the oxysulfide content of semi lean solution, and the oxysulfide content of said semi lean solution is higher than the oxysulfide content of lean solution.
2. renewable flue gas desulfurization technique as claimed in claim 1; It is characterized in that; Said renewable flue gas desulfurization technique comprises that also the oxysulfide content with the oxysulfide content of second rich solution and semi lean solution compares; When the oxysulfide content of second rich solution is higher, second rich solution is provided to said desorption technique with first rich solution.
3. renewable flue gas desulfurization technique as claimed in claim 1 is characterized in that, said absorption technique also comprises the step of using demister said clean flue gas to be carried out demist.
4. renewable flue gas desulfurization technique as claimed in claim 1 is characterized in that, in the capture step of said absorption technique, the trapping solution that will contain desulfuration solution returns as cleaning solution and uses.
5. renewable flue gas desulfurization technique as claimed in claim 1 is characterized in that, the capture step of said absorption technique also comprises through trapping solution being carried out concentration or trapping solution being sent into the step that desorption system reclaims desulfuration solution with rich solution.
6. renewable flue gas desulfurization technique as claimed in claim 1 is characterized in that, said cleaning solution is industrial soft water, desalted water or a part of trapping solution.
7. renewable flue gas desulfurization technique as claimed in claim 1 is characterized in that, said desulfuration solution is at least a in organic base solution or the ionic liquid.
8. renewable flue gas desulfurization technique as claimed in claim 7 is characterized in that said desulfuration solution also comprises activator, acid and water, and perhaps said desulfuration solution also comprises activator, acid, water, anti-inefficacy agent and surfactant.
9. renewable flue gas desulfurization technique as claimed in claim 1 is characterized in that, the secondary desorb in the said desorption technique comprises through reboiler coming first rich solution and/or second rich solution of part desorb are carried out desorb.
10. renewable flue gas desulfurization technique as claimed in claim 1; It is characterized in that; A desorb in the said desorption technique is that HTHP desorb and secondary desorb are the flash distillation desorb; Said HTHP desorb realizes through first stripping stage that the bottom is provided with reboiler; Said flash distillation desorb realizes through second stripping stage that is connected with vacuum extractor, is provided with dividing plate between said first stripping stage and second stripping stage.
11., it is characterized in that said renewable flue gas desulfurization technique washs flue gas before also being included in and getting into said absorption technique, so that flue gas is lowered the temperature and dedusting like any described renewable flue gas desulfurization technique in the claim 1 to 10.
12. renewable flue gas desulfurization technique as claimed in claim 11; It is characterized in that; Said washing step realizes that through S shape flue and scrubbing tower wherein, said scrubbing tower comprises void tower flue gas washing section, filler flue gas washing section and demist layer from the bottom up successively through making pending flue gas.
13. renewable flue gas desulfurization technique according to claim 11 is characterized in that, said washing step comprises that also the booster fan through being arranged on S shape flue front end makes the flue gas supercharging.
14. like any described renewable flue gas desulfurization technique in the claim 1 to 10; It is characterized in that; Said renewable flue gas desulfurization technique also comprises and carries out heat exchange to providing to first rich solution of desorption technique and/or second rich solution and lean solution and/or semi lean solution, with the temperature that improves first rich solution and/or second rich solution and reduce lean solution and/or the temperature of semi lean solution.
15. renewable flue gas desulfurization technique as claimed in claim 14; It is characterized in that; Said renewable flue gas desulfurization technique also comprises first rich solution that will carry out a desorb and/or second rich solution and desorption gas carried out heat exchange, with the temperature of further raising first rich solution and/or second rich solution and reduce the temperature of desorption gas.
16. renewable flue gas desulfurization technique as claimed in claim 14 is characterized in that, before said renewable flue gas desulfurization technique also is included in said heat exchange, first rich solution and/or second rich solution that obtains from said absorption technique is carried out step of buffering.
17. renewable flue gas desulfurization technique as claimed in claim 14 is characterized in that, before said renewable flue gas desulfurization technique also is included in said heat exchange, and the step that first rich solution that obtains from said absorption technique and/or second rich solution are filtered.
18. like any described renewable flue gas desulfurization technique in the claim 1 to 10; It is characterized in that; Said renewable flue gas desulfurization technique also comprises and purifies recovery to the lean solution of absorption technique and handle providing; Removing suspension, metal cation and the strong acid radical ion that contains in the lean solution, said purification recovery treatment step comprises in sedimentation, filtration, freezing and crystallizing and the resin desalination step of carrying out in turn preceding at least two.
19. renewable flue gas desulfurization technique as claimed in claim 18; It is characterized in that; Said renewable flue gas desulfurization technique also comprises and purifies recovery to the semi lean solution of absorption technique and handle providing; Removing suspension, metal cation and the strong acid radical ion that contains in the semi lean solution, said purification recovery treatment step comprises in sedimentation, filtration, freezing and crystallizing and the resin desalination step of carrying out in turn preceding at least two.
20. renewable flue gas desulfurization technique as claimed in claim 18 is characterized in that, said sedimentation and filtration step carry out before rich solution and lean solution are carried out heat exchange.
21. renewable flue gas desulfurization technique as claimed in claim 18 is characterized in that, said strong acid radical ion comprises sulfate ion, chlorion and nitrate ion.
22. renewable flue gas desulfurization technique as claimed in claim 18 is characterized in that, said precipitation step also comprises the step that in the lean solution of treating sedimentation, adds precipitation by metallic ion agent and suspension filter aid.
23. renewable flue gas desulfurization technique as claimed in claim 18 is characterized in that, said purification recovery treatment step also comprises to adding alkali through sedimentation with filtering in the clear liquid that obtains, with the metal ion in the further removal clear liquid.
24. like any described renewable flue gas desulfurization technique in the claim 1 to 10; It is characterized in that said condensation and the step that reclaims the oxysulfide in the desorption gas may further comprise the steps: desorption gas is carried out condensation to form condensate liquid and the desorption gas of carrying desulfuration solution secretly; The said desorption gas of carrying desulfuration solution secretly is carried out gas-liquid separation oxysulfide gas and liquid phase; Reclaim oxysulfide gas.
25. renewable flue gas desulfurization technique as claimed in claim 24; It is characterized in that; Said condensation and the step that reclaims the oxysulfide in the desorption gas also comprise to condensate liquid with by the said liquid phase that gas-liquid separation obtains filters; To filtrate then with the desorption gas heat exchange after provide to the step of a desorb, perhaps said condensation and the step that reclaims the oxysulfide in the desorption gas also comprise to condensate liquid with by the said liquid phase that gas-liquid separation obtains filters.
26. renewable flue gas desulfurization technique as claimed in claim 24; It is characterized in that; The said step that desorption gas is carried out condensation comprises multi-stage condensing in sequence; And the condensate liquid that the first order condensation in the said multi-stage condensing forms is discharged to the external world, the condensate liquid that other grade condensation in the said multi-stage condensing forms through with the desorption gas heat exchange after provide to desorption technique.
27. renewable flue gas desulfurization technique as claimed in claim 24; It is characterized in that; The said step that desorption gas is carried out condensation comprises one-level condensation and B-grade condensation; The condensate liquid that said one-level condensation forms is discharged to the external world, the condensate liquid that said B-grade condensation forms through with the desorption gas heat exchange after provide to desorption technique.
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| CN105148683A (en) * | 2015-08-21 | 2015-12-16 | 马鞍山艺诚机电有限公司 | Citrate process for purifying SO2 in smoke through negative-pressure multi-stage nested absorption and desorption |
| CN105251315A (en) * | 2015-08-21 | 2016-01-20 | 马鞍山艺诚机电有限公司 | Multistage absorption-desorption citrate process for purifying SO2 in flue gas |
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| CN106178951A (en) * | 2016-09-08 | 2016-12-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Flue gas desulfurization absorbs resolution system and analytic method |
| CN106268216A (en) * | 2016-09-08 | 2017-01-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Multifunctional smoke desulphurization system and sulfur method |
| CN107303456A (en) * | 2016-04-21 | 2017-10-31 | 李润超 | A kind of device of Collecting and dealing uncontrollable discharge gas |
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| CN109529579A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of process unit and process of hydrogen sulfide and sulfur dioxide reaction desulfuration |
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| CN102641647A (en) * | 2012-04-13 | 2012-08-22 | 金川集团有限公司 | Recovery processing method for low-concentration stray smoke S02 |
| CN105056711A (en) * | 2015-08-21 | 2015-11-18 | 马鞍山艺诚机电有限公司 | Multi-stage nested absorption-analysis citrate process for purifying SO2 in smoke |
| CN105148683A (en) * | 2015-08-21 | 2015-12-16 | 马鞍山艺诚机电有限公司 | Citrate process for purifying SO2 in smoke through negative-pressure multi-stage nested absorption and desorption |
| CN105251315A (en) * | 2015-08-21 | 2016-01-20 | 马鞍山艺诚机电有限公司 | Multistage absorption-desorption citrate process for purifying SO2 in flue gas |
| CN105289215A (en) * | 2015-11-20 | 2016-02-03 | 长沙华时捷环保科技发展有限公司 | Flue gas circulating desulfurization method and system |
| CN107303456A (en) * | 2016-04-21 | 2017-10-31 | 李润超 | A kind of device of Collecting and dealing uncontrollable discharge gas |
| CN106178951A (en) * | 2016-09-08 | 2016-12-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Flue gas desulfurization absorbs resolution system and analytic method |
| CN106268216A (en) * | 2016-09-08 | 2017-01-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Multifunctional smoke desulphurization system and sulfur method |
| CN109534297A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of method of hydrogen sulfide and sulfur dioxide reaction desulfuration |
| CN109529573A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | The process unit and process of hydrogen sulfide and sulfur dioxide liquid desulfuration |
| CN109529580A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | The process unit and process of sulfur dioxide and hydrogen sulfide liquid phase reactor desulfurization |
| CN109529578A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | The process unit and process of hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization |
| CN109529567A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of technique of hydrogen sulfide and sulfur dioxide reaction desulfuration |
| CN109529579A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of process unit and process of hydrogen sulfide and sulfur dioxide reaction desulfuration |
| CN112452109A (en) * | 2020-12-31 | 2021-03-09 | 双盾环境科技有限公司 | Desorption SO for improving desulfurization absorbent2Efficient process |
| CN113082946A (en) * | 2021-04-08 | 2021-07-09 | 成都达奇环境科技有限公司 | Method for treating waste gas from non-ferrous metal smelting |
| CN114317037A (en) * | 2021-12-31 | 2022-04-12 | 唐山中溶科技有限公司 | Method for preparing hydrogen from coke oven gas by utilizing decarbonization liquid regeneration through decomposition gas |
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