CN1706538A - Regeneration process of pregnant absorbing solution and washing solution for the alkaline desulfurizing procedure of SO2 containing gas - Google Patents
Regeneration process of pregnant absorbing solution and washing solution for the alkaline desulfurizing procedure of SO2 containing gas Download PDFInfo
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Abstract
The present invention is regeneration process of pregnant absorbing solution and washing solution for the alkaline desulfurizing process of SO2 containing gas, and belongs to the field of waste SO2 gas desulfurizing technology. The regeneration process of pregnant absorbing solution includes at least following steps: electrolytic acidification of the solution inside at least one three-chamber electrolyzer with double cationic exchange membrane to lower the pH value; and desorption inside one desorbing unit to release SO2 under the action of ultrasonic wave and/or negative pressure. The regeneration of the washing solution is to desorb to release SO2 under the action of ultrasonic wave and/or low pressure, and the desorbed solution is returned to the washing system for reuse. The present invention collects high density SO2 gas to avoid pollution to atmosphere environment and to develop the downstream product.
Description
Technical field
The present invention relates to a kind of SO of containing
2The alkali desulphurization process of gas absorbs the renovation process of rich solution and cleaning solution, belongs to the desulfur technology that contains sulfur dioxide gas.
Background technology
In various industry processes and life activity, discharge and much contain SO
2Deng the gas of oxysulfide, particularly the burning of the fuel that sulphur content content such as some coals, heavy oil are high produces a large amount of SO
2Deng oxysulfide.Directly enter atmosphere if will not remove and to form acid rain, contaminated environment.Especially energy resource structure is based on the country of fire coal, and the discharge capacity of sulfur dioxide is just bigger, so the sulfide in the waste gas must be removed.In long-term desulfurization practice, developed many kinds of desulfur technologies in the world, that drops into practical application also has a kind more than 20.Burning back desulfurization is flue gas desulfurization, because its multiple advantage that has becomes the main flow desulfurization method that present large-scale commercial applications is used.In the technology of flue gas desulfurization, wet desulphurization accounts for the desulphurization market of the world more than 85%.And wet type calcium method (lime/lime stone-gypsum method) accounts for about 80% of wet method.Though wet type calcium method has technology maturation, and is applied widely, desulfuration efficiency and sorbent utilization are than advantages such as height.But also exist investment big, operating cost height, shortcomings such as the easy fouling of equipment.In addition, though the gypsum that is produced in the processing procedure can be used as the utilization of resources,, because product quality, reasons such as market capacity are difficult to be fully utilized, and are also a lot of as the abandoned phenomenon of discarded object.Developed the two alkaline process of Sodium the seventies in 20th century again,, had two kinds of materials of Sodium and separation process thereof in the system, caused technology and equipment complexity, and consumed soda cost height though solved scale problems.Kai Fa sodium sulfite round-robin method (Wellman-Lord sodium method) was not though existed the scale problems of calcium method afterwards, its sodium absorption liquid is also renewable to be recycled, but owing to adopt thermal desorption method regeneration soda, energy consumption is big, and still need partly discharge sodium sulphate, operating cost is also high.
From technical standpoint, except that some traditional sulfur methods, some new technologies have appearred again, as sea water desulfuration, the CFB method, the NID method, electronic beam method etc., but these new technologies are because the restriction of various conditions, and application example is also few, fails to become popular technology.Because the appearance of Bipolar Membrane also once had the trial of the desulfurization used it for, but because Bipolar Membrane costs an arm and a leg, and reason such as performance is stable inadequately fails to become practical technique.
Make a general survey of existing desulfur technology, though method is numerous, the common issue with that exists is the cost height, not only becomes the heavy burden of pollution control enterprise thus, and the enforcement of restriction desulfurized treatment engineering.Therefore, the improvement of atmosphere pollution is badly in need of low-cost, can resource, and operational administrative is simple, the sulfur method of miniaturization and desulfurizer.
The present inventor has explored a kind of lower valency film electrolytic alkali regeneration of absorption solution circulation Wet-type desulfuration method, has realized low cost, can resource, and operational administrative is simple, the desulfurization of miniaturization.Promptly with the SO in soda (or potash) the absorption liquid absorption waste gas
2, it is transferred in the absorption liquid, reach the purpose of purifying exhaust air; With film electrolytic separation SO
2Solvent components reclaims as sulfuric acid, removes sulphur alkali lye afterwards and recycles as the regeneration absorption liquid.But produce dilute sulfuric acid in the regenerative process that absorbs rich solution, its purposes is restricted; Simultaneously, all with the film electrolysis sulfur dioxide that absorbs is separated with the form of dilute sulfuric acid, its power consumption also shows cost for the non-electricity industry higher.Therefore, the sulfur-containing compound that reclaims must be converted into and be easy to the product form that uses and transport, simultaneously, also need further to reduce cost.
Summary of the invention
The object of the present invention is to provide a kind of SO of containing
2The alkaline process of gas (alkaline process mainly refers to soda method and potash method) sweetening process absorbs the renovation process of rich solution and cleaning solution, and this method has miniaturization, operational administrative characteristics simply and cheaply.
The present invention is realized by following technical proposals, a kind of SO that contains
2The alkali desulphurization process of gas absorbs the renovation process of rich solution, it is characterized in that comprising following process at least: absorb rich solution liquid reduces its pH value through at least one three Room membrane electrolyser of being made of two cation-exchange membranes film electrolysis acidization, the liquid that reaches by the outlet of the medial compartment between these membrane electrolyser two films output enters desorption apparatus, under ultrasonic wave effect or suction function or ultrasonic wave and negative pressure acting in conjunction, emit the gas of sulfur dioxide, the total sulfur content that absorbs in the rich solution is reduced, absorb the desorption process that rich solution is regenerated.
Above-mentioned absorption rich solution liquid is in three Room membrane electrolyser acidification processes of two cation-exchange membranes, comprise the three Room membrane electrolysers of liquid, with the acidifying separating treatment process of three Room membrane electrolyser serial or parallel connections that constitute by each anion and cation exchange membrane at two cation-exchange membranes; Or with the acidifying separating treatment process of two Room membrane electrolyser serial or parallel connections that constitute by the single anion exchange membrane; Or with the acidifying separating treatment process of two kinds of membrane electrolyser serial or parallel connections of two Room membrane electrolysers of three Room membrane electrolysers of each anion and cation exchange membrane and single anion exchange membrane; Or liquid is with three Room membrane electrolysers of two cation-exchange membranes and the cell arrangement that desorption apparatus constitutes, the acidifying desorb separating treatment process of the three Room membrane electrolyser serial or parallel connections that this cell arrangement and are made of each anion and cation exchange membrane; Or the acidifying desorb separating treatment process of the two Room membrane electrolyser serial or parallel connections that constitute by the single anion exchange membrane of this cell arrangement and; Or the acidifying desorb separating treatment process of two Room membrane electrolyser serial or parallel connections of three Room membrane electrolysers of this cell arrangement and each anion and cation exchange membrane and single anion exchange membrane.
Above-mentioned absorption rich solution liquid is in three Room membrane electrolyser acidification processes of two cation-exchange membranes, the import liquid of the medial compartment of this membrane electrolyser comes from the absorption rich solution at the bottom of the absorption Tata, or come from the outlet liquid of the medial compartment of the three Room membrane electrolysers that constitute by each anion and cation exchange membrane, or coming from the stripping liquid of desorption apparatus, the outlet liquid of medial compartment is delivered to desorption apparatus; The liquid that its cathode chamber import flows into, the stripping liquid that comes from desorption apparatus, or come from it the cathode chamber of three Room membrane electrolysers of the anion and cation exchange membrane of serial or parallel connection or the liquid of medial compartment, or come from the liquid of cathode chamber outlet of two Room membrane electrolysers of single anion exchange membrane, pH value≤11.0 of the absorption liquid that the cathode chamber outlet is flowed out are delivered to absorption liquid lean solution jar or are imported the cathode chamber of three Room membrane electrolysers of the anion and cation exchange membrane of serial or parallel connection with it; Its anode chamber imports and exports to be connected and to carry out sulfuric acid with a sulfuric acid storage tank circulates, or the anode chamber of two Room membrane electrolysers of serial connection single anion exchange membrane imports and exports to be connected with sulfuric acid storage tank and carries out sulfuric acid and circulate, or the membrane electrolyser anode chamber, three Room of serial connection anion and cation exchange membrane imports and exports to be connected with sulfuric acid storage tank and carries out sulfuric acid and circulate, sulfate liquid storage tank upper gaseous phase position is by before pipeline and sulfur dioxide gas storage tank or the storage tank inlet, and the gas phase at the position after the desorption apparatus inlet is connected.
Above-mentioned ultrasonic wave effect desorb is in fluid temperature≤80 ℃, carries out with under 0.01～50 watt/square centimeter of the ultrasonic power density.
Above-mentioned suction function desorb is in fluid temperature≤80 ℃, and its absolute pressure is to carry out under the 0.06-0.098MPa.
Above-mentioned ultrasonic wave and negative pressure acting in conjunction desorb are in fluid temperature≤80 ℃, are to carry out under the 0.06-0.098MPa with 0.001～50 watt/square centimeter of ultrasonic power density and its absolute pressure.
A kind of SO that contains
2The renovation process of the alkali desulphurization process cleaning solution of gas, it is characterized in that cleaning solution is through ultrasonic wave effect desorb, or suction function desorb, or gaseous sulfur dioxide is emitted in ultrasonic wave effect and the two acting in conjunction desorb of suction function, collected utilization, the liquid after the desorb returns washing system and recycles.
Above-mentioned ultrasonic wave effect desorb is in fluid temperature≤80 ℃, carries out under 0.001～50 watt/square centimeter of the ultrasonic power density; The suction function desorb is in fluid temperature≤80 ℃, and its absolute pressure is to carry out under the 0.01-0.098MPa; Ultrasonic wave and negative pressure acting in conjunction desorb are in fluid temperature≤80 ℃, are to carry out under the 0.01-0.098MPa with 0.001～50 watt/square centimeter of ultrasonic power density and its absolute pressure.
Above-mentioned absorption liquid desorption process and cleaning solution desorption process are emitted the gas of sulfur dioxide, the sulfur dioxide gas that obtains concentrating through supercooling.
Below the present invention is described in detail:
One of key technology of the present invention is the film electrolytic process that absorbs rich solution, absorb rich solution because at three Room membrane electrolysers in this process by the dication exchange membrane, connect with three Room membrane electrolysers of anion and cation exchange membrane and two Room membrane electrolysers of single anion exchange membrane, the multiple combination different mode electrolytic process that is connected in parallel, not only effectively control the pH value of liquid behind the film electrolytic process 1.6～4.0, and when effectively separating inferior sulfate radical and bisulfite, sulfate radical also can be simultaneously separated, thereby accomplish not discharge absorption liquid the sulfate radical in the absorption liquid is controlled at below a certain value, lays a good foundation for reducing cost.
Two of key technology of the present invention is that the liquid desorb through electrolytic process is the gas of emitting sulfur dioxide under ultrasonic wave effect or suction function or ultrasonic wave and negative pressure acting in conjunction, the total sulfur content that absorbs in the rich solution is reduced, absorb the desorption process that rich solution is regenerated.This process is because action of ultrasonic waves has been accelerated the gas desorption speed of sulfur dioxide greatly, and realized far below the desorb under the boiling point of liquid temperature, suppressed the evaporation of moisture, solved the problem of the intrinsic highly energy-consuming of ebuillition of heated desorb and steam stripping very effectively, not only equipment therefor has the little characteristics of volume, and effectively discharge sulfur dioxide gas, thus reduce whole process expense and improve treatment effeciency, provide critical technical guarantee for reducing operating cost.
Three of key technology of the present invention is circulating with sulfuric acid solution of electrolysis unit anolyte, and sulfuric acid circulation fluid storage tank is set in this circulatory system.Its meaning is: owing to enter the major part of anolyte in the electrolytic process is bisulfite, can be oxidized at anode, but may be owing to the deficiency of the time of staying, or the material restriction of moving, part is not oxidized and enter sulfuric acid circulation fluid storage tank, sulfurous acid can resolve into sulfur dioxide in acid solution, becomes gaseous volatilization and comes out.Therefore, as the gas in the storage tank is directly diffused, then have sulfur dioxide and enter atmosphere.In the film electrolytic process, the anolyte storage tank upper gaseous phase position that the film electrolytic separation obtains is connected with desorption apparatus by pipeline.Thus, the sulfur dioxide that volatilizes in the anolyte can be collected, mix, enter gathering system with the high concentration sulfur dioxide that desorb obtains.So just the sulfur dioxide that prevents these effusions effectively distributes in atmosphere.
Four of key technology of the present invention is to contain SO
2The cleaning solution that produces in the washing process of gas is emitted gaseous sulfur dioxide through ultrasonic wave or negative pressure desorb or the two acting in conjunction desorb, and sulfur dioxide is collected and utilized, and the liquid after the desorb returns washing system and recycles.So not only avoided the volatilization generation secondary pollution of sulfur dioxide in the cleaning solution, the more important thing is that simultaneously the pH value that can control cleaning solution is in certain value, cleaning solution can be recycled, avoided the generation of a large amount of waste liquid to cause difficult treatment and processing cost to increase, thereby laid a good foundation for the low-cost stable operation of washing system.
Five of key technology of the present invention is the sulfur dioxide gas of emitting in each desorption process, the sulfur dioxide gas that obtains concentrating through supercooling.Although it is very low to have solved the possibility water content so effectively, but when utilizing this gas generation sulphur or the concentrated sulfuric acid may because of moisture also than the desired water content height of resource, and influence the problem of manufacture process or product quality, thereby provide advantageous conditions for follow-up resource.
The above alkaline process mainly refers to soda and potash, because absorption liquid recycles, therefore, although potash than soda price height, owing to do not efflux, is the cost increase of the trace of initial stage input, operating cost is not had influence.
The invention has the advantages that this process adopts the combination and the ultrasonic wave desorb of multiple membrane electrolyser, treatment effeciency height, not only equipment therefor has the little characteristics of volume, and avoided effluxing of absorption liquid, form recycling fully of absorption liquid, thereby reduced whole process expense.Simultaneously, the desorb of cleaning solution makes it to recycle, and has avoided the generation of a large amount of waste liquid to cause difficult treatment and processing cost to increase.In addition, collect the high concentration sulfur dioxide gas that obtains desorb, not only lay a good foundation, but also prevent that effectively the sulfur dioxide of these effusions from distributing in the pollution of atmosphere to environment for the simple substance sulphur and the concentrated sulfuric acid in its downstream of Development and Production.
Description of drawings
The process flow diagram of Fig. 1: embodiment 1;
The process flow diagram of Fig. 2: embodiment 2;
The process flow diagram of Fig. 3: embodiment 3;
The process flow diagram of Fig. 4: embodiment 4;
The process flow diagram of Fig. 5: embodiment 5;
The process flow diagram of Fig. 6: embodiment 6.
The specific embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments:
As shown in Figure 1, absorbing pH after the flue gas with soda lye is that cation-exchange membrane 5 and the tank house between the anion-exchange membrane 6 that 5.0 absorption rich solution 1 enters the three Room membrane electrolysers 2 that the negative and positive film forms is medial compartment 2b, bisulfite, anion such as inferior sulfate radical and sulfate radical enters the 2c of anode chamber that includes anode 4 by anion-exchange membrane 6, sodium ion passes cation-exchange membrane 5 and enters the cathode chamber 2a that includes negative electrode 3, and the absorption liquid 7 after electrolysis is discharged the medial compartment 8b that enters the three Room membrane electrolysers of being made up of two cation-exchange membranes 8 from the medial compartment of membrane electrolyser 2.At medial compartment 8b, hydrogen ion passes cation-exchange membrane 5 by the anode chamber and enters in the absorption liquid, and sodium ion passes cation-exchange membrane 5 and enters cathode chamber 8a simultaneously.Thus, the pH of the absorption liquid of medial compartment descends.The absorption liquid 9 that pH drops to after 2.5 is discharged importing ultrasonic wave desorption apparatus 10 from the medial compartment of membrane electrolyser 8.Through 0.52 watt/square centimeter, after the absorption liquid 19 of the ultrasonic wave effect of 20kHz after by desorb sulfur dioxide discharged, the medial compartment 8b that a part is returned membrane electrolyser 8 as circulation fluid can be lowered once more desorb behind the pH according to technological requirement, another part as desorb at the bottom of the liquid 19 cathode chamber 2a that delivers to regenerated liquid lean solution storage tank or import membrane electrolyser use as catholyte, enter the cathode chamber 8a of membrane electrolyser 8 from the liquid 20 of cathode chamber 2a discharge, raise at cathode chamber pH, liquid 21 after the discharge is sent into absorption liquid lean solution storage tank 22, and regeneration of absorption solution liquid 23 is sent to the absorption tower (not shown) and recycles.The sulfur dioxide gas that obtains through the ultrasonic wave desorb imports condensing unit 12, under the cooling of 25 ℃ water, with the condensing separation of steam of gasifying and entering simultaneously, obtain being stored in the sulfur dioxide gas holding vessel 14 behind the higher sulfur dioxide gas of purity 13, unstripped gas 15 as follow-up sulphur resource, be sent to sulphur production process 16, obtain product sulphur 17.In desorption device the gasification of steam seldom, sulfur dioxide gas purity is than under the condition with higher, the gas of desorb can not advance condenser 12 and directly import sulfur dioxide gas holding vessel 14.Membrane electrolyser 2 and 8 catholyte can be the absorption liquids 19 after the desorb, also can be the absorption liquids 7 of discharging in the membrane electrolyser 2.Anolyte adopts the mode of sulfate liquid circulation, i.e. sulfuric acid circulation fluid 24 circulation between the anode chamber of membrane electrolyser and sulfuric acid storage tank 25, after sulfuric acid runs up to a certain degree as 18 discharges of product sulfuric acid.
Embodiment 2:
As shown in Figure 2, the pH that obtains via as shown in Figure 1 membrane electrolyser drops to 2.2, and temperature is to import ultrasonic wave desorption apparatus 10 after 48 ℃ absorption liquid 9 is brought up to 65 ℃ by heater 26 with temperature.In ultrasonic unit, be pumped under the condition of negative pressure of absolute pressure 0.08Mpa by blower fan 27, the sulfur dioxide gas 11 that obtains through the ultrasonic wave desorb imports condensing unit 12 by blower fan 27 suctions, with the condensing separation of steam of gasifying and entering simultaneously, obtain being stored in the sulfur dioxide gas holding vessel 14 behind the higher sulfur dioxide gas of purity 13, unstripped gas 15 as follow-up sulphur resource, be sent to gas washing in SA production operation 28, obtain the product concentrated sulfuric acid 29.Other parts are identical with embodiment 1.
As shown in Figure 3, the method with the absorption rich solution regeneration after the soda lye absorption sulfur dioxide in flue gas is identical with embodiment 1.The cathode chamber 30a of different is pH is 4.8 absorption rich solution 1 enters two Room membrane electrolysers 30 that an anion-exchange membrane is housed, bisulfite, anion such as inferior sulfate radical and sulfate radical enters the 30c of anode chamber that includes anode 4 by anion-exchange membrane 6, and pH is elevated to 5.6 absorption liquid 31 and discharges the cathode chamber 8a that enters the three Room membrane electrolysers of being made up of two cation-exchange membranes 8 from membrane electrolyser 30 after electrolysis.At cathode chamber, passing cation-exchange membrane by the medial compartment sodium ion enters, and obtain the electronics releasing hydrogen gas owing to hydrogen ion at negative electrode, make that hydrogen ion reduces in the absorption liquid, sodium ion increases pH and further raises, after reaching 8.5-9.0, the absorption liquid 21 of discharging from the cathode chamber of membrane electrolyser 8 is imported into absorption liquid lean solution jar 22, sends into the absorption tower (not shown) as regeneration of absorption solution liquid 23 and recycles.
Simultaneously, absorption liquid rich solution 1 enters the medial compartment 8b of the three Room membrane electrolysers of being made up of two cation-exchange membranes 8.At medial compartment, hydrogen ion passes cation-exchange membrane by the anode chamber and enters in the absorption liquid, and sodium ion passes cation-exchange membrane and enters cathode chamber simultaneously.Thus, the pH of the absorption liquid of medial compartment descends.PH drops to absorption liquid 9 after 2.8 and discharges from the medial compartment of membrane electrolyser 8 and import desorption apparatus 10 and carry out desorb and obtain sulfur dioxide gas 11 and import sulfur dioxide gas storage tanks 14, uses as the unstripped gas 15 of follow-up sulphur resource.The end liquid (not shown) that desorb obtains imports absorption liquid lean solution jar.
In addition, 30c has the inferior sulfate radical that sees through from cathode chamber in the anode chamber of membrane electrolyser 30, and bisulfite and sulfate radical enter, in the oxidation of anode generation bisulfite.Sulfuric acid liquid 24 is from installing 30 8c of anode chamber that enter membrane electrolyser 8 after discharging, hydrogen ion enters medial compartment by cation-exchange membrane therein, equally, after the oxidation of anode generation bisulfite, enter sulfuric acid storage tank 25 for recycling after discharging with sulfuric acid circulation fluid 24 from the anode chamber.Sulphuric acid tank top may have sulfur dioxide gas and produce, its top with desorption apparatus 10 is linked to each other, with sulfur dioxide gas 32, enter desorption apparatus 10, the sulfur dioxide that obtains with desorb together enters sulfur dioxide gas storage tank 14, unstripped gas 15 as the sulphur resource uses for subsequent handling.
Embodiment 4:
The regeneration embodiment that absorbs the absorption rich solution after the sulfur dioxide in flue gas with soda lye is substantially the same manner as Example 3, and as shown in Figure 4, two Room membrane electrolysers 30 of different is individual anion-exchange membrane place after the desorption apparatus 10.Be that pH enters desorption apparatus 10 after medial compartment 8b that 4.8 absorption rich solution 1 enters membrane electrolyser 8 separates sodium ion and pH is reduced to 2.4, desorb obtains sulfur dioxide gas 11, thereafter with embodiment 3 identical (not shown)s.The cathode chamber 30a that end liquid 19 after the desorb enters individual anion-exchange membrane two Room membrane electrolysers 30 separates inferior sulfate radical, behind bisulfite and the sulfate radical as the circulation liquid 31 of the cathode chamber 8a of membrane electrolyser 8, be sent to absorption liquid lean solution jar 22 as the absorption liquid 21 after the regeneration after flowing through 8 cathode chamber 8a, be sent to the absorption tower with regeneration of absorption solution liquid 23 and recycle.
Embodiment 5:
As shown in Figure 5, absorbing pH after the sulfur in smoke with soda lye is the medial compartment 8b that 5.0 absorption rich solution 1 enters the three Room membrane electrolysers of being made up of two cation-exchange membranes 8.At medial compartment, hydrogen ion passes cation-exchange membrane by the anode chamber and enters in the absorption liquid, and sodium ion passes cation-exchange membrane and enters cathode chamber 8a simultaneously.Thus, the pH of the absorption liquid of medial compartment descends.The absorption liquid 9 that pH drops to after 2.1 is discharged importing ultrasonic wave desorption apparatus 10 from the medial compartment of membrane electrolyser 8.Through 1.0 watts/square centimeter, after the absorption liquid 19 of the ultrasonic wave effect of 20kHz after by part desorb sulfur dioxide discharged, the medial compartment that enters the membrane electrolyser 8 of next stage was lowered the desorption apparatus 10 that enters next stage behind the pH once more.The major part of the end liquid after the desorb and pH are 5.0 the medial compartment 2b that rich solution 1 together enters three Room membrane electrolysers 2 of zwitterion film composition that partially absorbs.Therein, bisulfite, anion such as inferior sulfate radical and sulfate radical enters the 2c of anode chamber that comprises by anode by anion-exchange membrane, sodium ion passes cation-exchange membrane and enters the cathode chamber 2a that includes negative electrode, absorption liquid 7 after electrolysis is discharged from the medial compartment of membrane electrolyser 2, major part wherein is imported into the cathode chamber 8a of the electrolysis unit 8 of dication exchange membrane composition, enter the cathode chamber 8a of the electrolysis unit 8 of the two positive membranes and three chambers of next stage after discharging from this chamber, at this two poles of the earth cathode chamber, since sodium ion enter and the hydrogen of negative electrode emit make that the pH of liquid is elevated to 9.8 after, regenerated liquid 21 with absorption liquid enters absorption liquid lean solution storage tank 22, absorbs for the absorption tower and uses.The part of the end liquid of discharging from second level desorption apparatus also can be mixed into absorption liquid lean solution storage tank 22 with the part of the discharge liquid 7 of the medial compartment of negative and positive membranes and three chambers membrane electrolyser 2.Simultaneously, the part of the end liquid 19 of discharging from second level desorption apparatus also imports the cathode chamber 2a of negative and positive membranes and three chambers membrane electrolyser 2, after pH raises, enters absorption liquid lean solution storage tank 22 to discharge liquid 20 therein.In addition, enter absorption liquid lean solution storage tank (not shown) after the part of the discharge liquid of the medial compartment of the negative and positive membranes and three chambers cathode chamber that also can enter the negative and positive membranes and three chambers makes pH raise.
The sulfur dioxide gas 11 that the two-stage desorption apparatus desorbs is sent into sulfur dioxide storage tank 14 through blower fan 27 suctions, and the unstripped gas 15 as the sulphur resource uses for subsequent handling.
Embodiment 6:
As shown in Figure 6, contain the flue gas 33 of sulfur dioxide, enter scrubbing tower 34, after circulating cleaning solution 43 washings, be sent to absorption tower (not marking among the figure), absorb desulfurization as washing back flue gas 35.The cleaning solution rich solution 36 that wash tower bottoms is discharged enters the cleaning solution rich solution jar 37 that has the precipitation function, and the cleaning solution 39 that separation is discharged behind the sediment 38 enters ultrasonic wave desorption apparatus 40, and the sulfur dioxide 41 that desorb obtains enters condensing unit 12.Simultaneously, the sulfur dioxide gas 42 that volatilizes in the cleaning solution rich solution jar 37 also is imported into condensing unit 12, concentrating the back as concentrating sulfur dioxide gas 13, sends into sulfur dioxide storage tank (not marking among the figure).Cleaning solution behind the desorb sulfur dioxide recycles as regenerated from washing liquid 43.
Claims (9)
1. one kind contains SO
2The alkali desulphurization process of gas absorbs the renovation process of rich solution, it is characterized in that comprising following process at least: absorb rich solution liquid reduces its pH value through at least one three Room membrane electrolyser of being made of two cation-exchange membranes film electrolysis acidization, the liquid that reaches by the outlet of the medial compartment between these membrane electrolyser two films output enters desorption apparatus, under ultrasonic wave effect or suction function or ultrasonic wave and negative pressure acting in conjunction, emit the gas of sulfur dioxide, the total sulfur content that absorbs in the rich solution is reduced, absorb the desorption process that rich solution is regenerated.
2. by the described renovation process of claim 1, it is characterized in that absorbing the three Room membrane electrolyser acidification processes of rich solution liquid at two cation-exchange membranes, comprise the three Room membrane electrolysers of liquid, with the acidifying separating treatment process of three Room membrane electrolyser serial or parallel connections that constitute by each anion and cation exchange membrane at two cation-exchange membranes; Or with the acidifying separating treatment process of two Room membrane electrolyser serial or parallel connections that constitute by the single anion exchange membrane; Or with the acidifying separating treatment process of two kinds of membrane electrolyser serial or parallel connections of two Room membrane electrolysers of three Room membrane electrolysers of each anion and cation exchange membrane and single anion exchange membrane; Or liquid is with three Room membrane electrolysers of two cation-exchange membranes and the cell arrangement that desorption apparatus constitutes, the acidifying desorb separating treatment process of the three Room membrane electrolyser serial or parallel connections that this cell arrangement and are made of each anion and cation exchange membrane; Or the acidifying desorb separating treatment process of the two Room membrane electrolyser serial or parallel connections that constitute by the single anion exchange membrane of this cell arrangement and; Or the acidifying desorb separating treatment process of two Room membrane electrolyser serial or parallel connections of three Room membrane electrolysers of this cell arrangement and each anion and cation exchange membrane and single anion exchange membrane.
3. by the described renovation process of claim 2, it is characterized in that absorbing the three Room membrane electrolyser acidification processes of rich solution liquid at two cation-exchange membranes, the import liquid of the medial compartment of this membrane electrolyser comes from the absorption rich solution at the bottom of the absorption Tata, or come from the outlet liquid of the medial compartment of the three Room membrane electrolysers that constitute by each anion and cation exchange membrane, or coming from the stripping liquid of desorption apparatus, the outlet liquid of medial compartment is delivered to desorption apparatus; The liquid that its cathode chamber import flows into, the stripping liquid that comes from desorption apparatus, or come from it the cathode chamber of three Room membrane electrolysers of the anion and cation exchange membrane of serial or parallel connection or the liquid of medial compartment, or come from the liquid of cathode chamber outlet of two Room membrane electrolysers of single anion exchange membrane, pH value≤11.0 of the absorption liquid that the cathode chamber outlet is flowed out are delivered to absorption liquid lean solution jar or are led people's cathode chamber of three Room membrane electrolysers of the anion and cation exchange membrane of serial or parallel connection with it; Its anode chamber imports and exports to be connected and to carry out sulfuric acid with a sulfuric acid storage tank circulates, or the anode chamber of two Room membrane electrolysers of serial connection single anion exchange membrane imports and exports to be connected with sulfuric acid storage tank and carries out sulfuric acid and circulate, or the membrane electrolyser anode chamber, three Room of serial connection anion and cation exchange membrane imports and exports to be connected with sulfuric acid storage tank and carries out sulfuric acid and circulate, sulfate liquid storage tank upper gaseous phase position is by before pipeline and sulfur dioxide gas storage tank or the storage tank inlet, and the gas phase at the position after the desorption apparatus inlet is connected.
4. by the described renovation process of claim 1, it is characterized in that ultrasonic wave effect desorb is in fluid temperature≤80 ℃, carry out with under 0.01～50 watt/square centimeter of the ultrasonic power density.
5. by the described renovation process of claim 1, it is characterized in that the suction function desorb is in fluid temperature≤80 ℃, its absolute pressure is to carry out under the 0.06-0.098MPa.
6. by the described renovation process of claim 1, it is characterized in that ultrasonic wave and negative pressure acting in conjunction desorb are in fluid temperature≤80 ℃, be to carry out under the 0.06-0.098MPa with 0.01～50 watt/square centimeter of ultrasonic power density and its absolute pressure.
7. one kind contains SO
2The renovation process of the alkali desulphurization process cleaning solution of gas, it is characterized in that cleaning solution is through ultrasonic wave effect desorb, or suction function desorb, or gaseous sulfur dioxide is emitted in ultrasonic wave effect and the two acting in conjunction desorb of suction function desorb pressure effect, collected utilization, the liquid after the desorb returns washing system and recycles.
8. by the described renovation process of claim 7, it is characterized in that ultrasonic wave effect desorb is in fluid temperature≤80 ℃, carry out under 0.01～50 watt/square centimeter of the ultrasonic power density; The suction function desorb is in fluid temperature≤80 ℃, and its absolute pressure is to carry out under the 0.06-0.098MPa; Ultrasonic wave and negative pressure acting in conjunction desorb are in fluid temperature≤80 ℃, are to carry out under the 0.06-0.098MPa with 0.01～50 watt/square centimeter of ultrasonic power density and its absolute pressure.
9. by claim 1 or 7 described renovation process, it is characterized in that desorption process emits the gas of sulfur dioxide, the sulfur dioxide gas that obtains concentrating through supercooling.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935318B (en) * | 2006-09-15 | 2010-06-16 | 江苏工业学院 | Ultrasonic disturbance-increasing oil gas absorption recovering method and apparatus |
| CN102101010A (en) * | 2009-12-18 | 2011-06-22 | 上海交通大学 | Electrolysis circulating flue gas desulfurization method utilizing reclamation semidry method |
| CN104324613A (en) * | 2014-09-16 | 2015-02-04 | 北京中天元环境工程有限责任公司 | Flue gas desulfurization method |
| CN109054916A (en) * | 2018-08-23 | 2018-12-21 | 张琪 | Methane decarbonization method and system |
| CN113350972A (en) * | 2021-06-30 | 2021-09-07 | 长沙华时捷环保科技发展股份有限公司创业创新分公司 | Method and system for removing thiosulfate radicals from desulfurization absorption liquid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0731842A (en) * | 1993-07-21 | 1995-02-03 | Asahi Glass Co Ltd | Waste gas desulfurization |
| JPH07204457A (en) * | 1994-01-19 | 1995-08-08 | Asahi Glass Co Ltd | Desulfurization of exhaust gas |
| JP2004344834A (en) * | 2003-05-26 | 2004-12-09 | Able:Kk | Desulfurization method of sulfur oxide-containing gas, apparatus for desulfurization, method of treating ash content, and method of treating sulfur oxide-containing solution |
| JP2005066599A (en) * | 2004-10-25 | 2005-03-17 | Mitsubishi Chemicals Corp | Method for electrodialysis and apparatus therefor, method for deionization and apparatus therefor, and method for treating exhaust gas |
-
2005
- 2005-04-21 CN CNB2005100133343A patent/CN100411713C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935318B (en) * | 2006-09-15 | 2010-06-16 | 江苏工业学院 | Ultrasonic disturbance-increasing oil gas absorption recovering method and apparatus |
| CN102101010A (en) * | 2009-12-18 | 2011-06-22 | 上海交通大学 | Electrolysis circulating flue gas desulfurization method utilizing reclamation semidry method |
| CN102101010B (en) * | 2009-12-18 | 2013-05-01 | 上海交通大学 | Electrolysis circulating flue gas desulfurization method utilizing reclamation semidry method |
| CN104324613A (en) * | 2014-09-16 | 2015-02-04 | 北京中天元环境工程有限责任公司 | Flue gas desulfurization method |
| CN109054916A (en) * | 2018-08-23 | 2018-12-21 | 张琪 | Methane decarbonization method and system |
| CN113350972A (en) * | 2021-06-30 | 2021-09-07 | 长沙华时捷环保科技发展股份有限公司创业创新分公司 | Method and system for removing thiosulfate radicals from desulfurization absorption liquid |
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| CN100411713C (en) | 2008-08-20 |
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