CN201889154U - Equipment for desulphurizing gas containing reducible sulfur - Google Patents
Equipment for desulphurizing gas containing reducible sulfur Download PDFInfo
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- CN201889154U CN201889154U CN2010205024989U CN201020502498U CN201889154U CN 201889154 U CN201889154 U CN 201889154U CN 2010205024989 U CN2010205024989 U CN 2010205024989U CN 201020502498 U CN201020502498 U CN 201020502498U CN 201889154 U CN201889154 U CN 201889154U
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Abstract
The utility model provides an equipment for desulphurizing gas containing reducible sulfur, which comprises a gas absorption tower (1), a bioreactor (2) and a solid liquid separator (3), the outlet of the gas absorption tower (1) is communicated with the inlet of the bioreactor (2), the outlet of the bioreactor (2) is communicated with the inlet of the solid liquid separator (3), the outlet of the solid liquid separator (3) is communicated with the inlet of the gas absorption tower (1). The equipment also comprises at least one ion exchanger (4). By using the equipment, the desulphurizing capacity of unit alkaline buffer solution is increased, the circulating volume of the alkaline buffer solution is decreased, and the investment and the practice cost are greatly lowered.
Description
Technical field
The utility model relates to a kind of equipment that removes the sulphur in the gas that contains reducible sulfur.
Background technology
Hydrogen sulfide is a kind of toxic and harmful, directly is discharged in the atmosphere to pollute the environment harm humans health.Wherein, the hydrogen sulfide in industrial chemicals and the fuel can change sulfur dioxide in synthetic or combustion process, and the discharging of sulfur dioxide can cause serious environmental to pollute equally.Strict day by day along with the national environmental protection rules sought to control hydrogen sulfide content in various industrial chemicals, fuel, waste gas and the tail gas and will be seemed and become more and more important.
At present, (for example, hydrogen sulfide) method has a lot, as Claus method, liquid phase catalytic oxidation, biological oxidation process etc. to remove sulphur in the gas.
The Claus method requires concentration of hydrogen sulfide to be not less than 30%, generally need also concentrate with the hydrogen sulfide that additive method absorbs in the gas, as after using alkyl alcoholamine method absorbing hydrogen sulphide, concentrate regeneration and release hydrogen sulfide to reach and put forward dense purpose, usually equipment investment is bigger, uses more in large-scale refinery and natural gas plant.
Liquid phase catalytic oxidation need use catalyst (as the complexing iron catalyst), utilize the hydrogen sulfide in sodium carbonate or the potassium alkaline solution absorption gas, by ferric ion the sulphion oxidation is become sulphur, self is reduced into ferrous ion, lose oxidability, subsequently bubbling air with the ferrous iron complex ion be oxidized to the ferric iron complex ion make its oxidability obtain regeneration, but have the discharging of waste liquid of a great deal of in the use, complex ion wherein is very difficult to degraded, can cause environmental pollution.
Biological oxidation process be by use can absorbing hydrogen sulphide alkaline buffer absorb hydrogen sulfide in the gas stream, the alkaline buffer that will absorb hydrogen sulfide is afterwards introduced bioreactor, is solid sulfur with sulfide oxidation under the effect of sulfide oxidation Thiobacillus.
For example, CN1238711A discloses a kind of method of removing the sulfide that comprises hydrogen sulfide, carbonyl sulfide and carbon disulfide from gas stream, wherein, this method is utilized moisture washing lotion washing gas, and under the condition that electron acceptor exists, utilize sulfide oxidation sulphur bar bacterial treatment washing lotion, so that the washing lotion that will handle is reused as washing lotion.Wherein, washing step and biological treatment step carry out in same reactor, with nitrate anion as electron acceptor.But the problem that this method exists is: the reproducibility sulfuration thing of part is by the sulfate radical of peroxidating formation a great deal of, and along with the circular flow of equipment, sulfate radical will constantly be accumulated, and the activity that this will reduce Thiobacillus influences the even running of equipment.
In addition, CN100418614C also discloses a kind of from comprising H
2Remove H in the air-flow of S and mercaptan compound
2The method of S and mercaptan, this method may further comprise the steps: (a) by making air-flow at H
2S-removes and contacts with the first aqueous base cleaning solution in the section and remove H from air-flow
2S obtains poor H
2The air-flow of S and the current that comprise sulfide; (b) by making poor H
2The air-flow of S contacts with the second aqueous base cleaning solution in the section and the poor H that obtains from step (a) at mercaptan-remove
2Remove mercaptan in the air-flow of S, obtain the air-flow and the current that comprise mercaptides of poor mercaptan; (c) in the presence of oxygen, in oxidation reactor, make by step (a) to contact with the bacterium of sulfide oxidation with the merging current that comprise sulfide and mercaptides that step (b) obtains, obtain the aqueous base cleaning solution of sulphur what slurry and regeneration; (d) from the aqueous base cleaning solution of regeneration, separate at least partially in the sulphur what slurry that obtains in the step (c); (e) the aqueous base cleaning solution with regeneration is recycled to the H of step (a)
2S removes in the mercaptan removal zone of section and step (b).This method also exists the partial vulcanization thing to be oxidized to the problem of sulfate radical, and along with the circular flow of equipment, sulfate radical will constantly be accumulated, and the activity that this will reduce Thiobacillus influences the even running of equipment.And too low owing to removing the used cushioning liquid pH of hydrogen sulfide, can't absorb mercaptan, make this equipment need increase the high-alkali absorption tower of another one and absorb mercaptan specially, cause complex process.
In the existing method that removes the sulphur in the gas that contains reducible sulfur owing to inevitably can produce sulfate ion in the sulfide biological oxidation process, along with doctor solution continue recycle, sulfate ion will constantly accumulation in doctor solution.In order to satisfy growth of microorganism, breeding and desulphurizing activated needs, usually need the total salt concentration of control doctor solution to be no more than 10%, the pH value is no more than 10, and the accumulation of the sulfate radical concentration that will tie up and dilute buffer salt solution in the desulfurization cleaning solution wherein, the ability drop of reproducibilities such as the unit's of making doctor solution absorbing hydrogen sulphide sulfuration thing.More seriously, when sulfate radical is accumulated to a certain degree, doctor solution will lose desulphurizing ability.In the existing method that removes hydrogen sulfide,, come dilute sulphuric acid root shared ratio in doctor solution by the discharge unit doctor solution and the method for replenishing fresh alkali lye.According to measuring and calculating, concerning the biological desulfurization apparatus of 500 tons of/hour internal circulating loads, the discharge capacity of sulfur-bearing acid group doctor solution reach the 1-2 ton/hour, and the concentration of sulfate is more than 5 times of carbonic acid (hydrogen) salt total concentration in the doctor solution, has seriously limited the ability that the unit doctor solution absorbs sulfur content.Therefore can only play the effect of sulfate concentration in the dilution doctor solution by the method for discharge unit system doctor solution and additional fresh alkali lye to a certain extent, and not reach the sulfate radical content purpose in the control doctor solution.And by discharging a large amount of doctor solutions to control sulfate ion concentration obviously also be unpractical.Usually, in order to reach predetermined desulfurized effect, can only realize that than, the mode that strengthens liquid circulation amount equipment volume increases, floor space strengthens, investment increases thereby cause by increasing liquid/gas, and the energy consumption in the running strengthens, running cost improves.Therefore, this method is also uneconomical.
For this reason, USP5976868 discloses a kind of biological desulphurization method, this method utilizes oxygen as electron acceptor, with thiobacillus thiooxidant the reproducibility sulfuration thing that elutes is oxidized to solid sulfur in aerobic reactor, certainly have a small amount of sulfide and turned to sulfate radical by peroxide, so this method connects an anaerobic reactor behind aerobic reactor, utilize the reducible sulfur bacillus when ethanol exists for electron donor, sulfate radical to be reduced to sulfide again, turn back to oxide solid sulphur in the aerobic reactor, to promote the even running of equipment.But be to use the sulfate ion concentration in this method control doctor solution still to have following several problem: (1), after the doctor solution that will contain sulfate radical carries out Anaerobic Treatment, need to turn back in the aerobic reactor and go, rather than directly enter gas absorbing device, determined that it can only be that a small amount of rather than whole doctor solutions enters the anaerobic reactor processing; (2), this method also needs to consume a large amount of reducing substanceses (as ethanol, hydrogen etc.) when the reduced sulphur acid ion, make the running cost of device improve; (3), because anaerobic reaction need be controlled pH be neutral substantially, it is not high that alkalescence is greatly, the higher doctor solution sulfate radical when Anaerobic Treatment of pH value is reduced to the efficient of sulfide.Therefore the method for Anaerobic Treatment can not effectively be controlled the sulfate ion content in the doctor solution.
Therefore, need urgently to develop and a kind ofly can effectively control sulfate concentration in the doctor solution to increase the doctor solution desulfurization capacity, to reduce the equipment of doctor solution internal circulating load.
The utility model content
The purpose of this utility model is in order to overcome the doctor solution sulfate concentration height that the existing equipment that is used for removing the sulphur of the gas that contains reducible sulfur exists, the desulfurization molten sulfur is molten low and internal circulating load is big, operating cost is high and need discharging doctor solution and additional fresh liquid to keep desulphurizing activated shortcoming, provides and can control sulfate concentration in the doctor solution, increases the doctor solution desulfurization capacity, reduces the equipment of doctor solution internal circulating load.
The utility model provides a kind of equipment that removes the sulphur in the gas that contains reducible sulfur, this equipment comprises: absorption column of gas, bioreactor and solid-liquid separator, the outlet of described absorption column of gas and the inlet of bioreactor are communicated with, the outlet of bioreactor and the inlet of solid-liquid separator are communicated with, the outlet of solid-liquid separator and the inlet of absorption column of gas are communicated with, wherein, this equipment also comprises at least one ion-exchanger, the position of each ion-exchanger one in the following situation of respectively doing for oneself:
(I) inlet of the outlet of absorption column of gas and ion-exchanger is communicated with, and the outlet of ion-exchanger and the inlet of bioreactor are communicated with;
(II) inlet of the outlet of bioreactor and ion-exchanger is communicated with, and the outlet of ion-exchanger and the inlet of solid-liquid separator are communicated with;
(III) inlet of the outlet of solid-liquid separator and ion-exchanger is communicated with, and the outlet of ion-exchanger and the inlet of absorption column of gas are communicated with.
The equipment of the sulphur that is used for removing the gas that contains reducible sulfur that the utility model provides has overcome in the alkaline buffer sulfate concentration accumulation desulfurization has been produced adverse effect, improved the desulfurization capacity of alkaline buffer solution, reduce the internal circulating load of alkaline buffer solution, reduced investment and use cost significantly.
Description of drawings
The structural representation of the equipment of the sulphur that is used for removing the gas that contains reducible sulfur that provides in a kind of embodiment of the utility model is provided Fig. 1;
The specific embodiment
As shown in Figure 1, the utility model provides a kind of equipment that removes the sulphur in the gas that contains reducible sulfur, this equipment comprises: absorption column of gas 1, bioreactor 2 and solid-liquid separator 3, the inlet of the outlet of described absorption column of gas 1 and bioreactor 2 is communicated with, the inlet of the outlet of bioreactor 2 and solid-liquid separator 3 is communicated with, the inlet of the outlet of solid-liquid separator 3 and absorption column of gas 1 is communicated with, wherein, this equipment also comprises at least one ion-exchanger 4, the position of each ion-exchanger 4 one in the following situation of respectively doing for oneself:
(I) inlet of the outlet of absorption column of gas 1 and ion-exchanger 4 is communicated with, and the inlet of the outlet of ion-exchanger 4 and bioreactor 2 is communicated with;
(II) inlet of the outlet of bioreactor 2 and ion-exchanger 4 is communicated with, and the inlet of the outlet of ion-exchanger 4 and solid-liquid separator 3 is communicated with;
(III) inlet of the outlet of solid-liquid separator 3 and ion-exchanger 4 is communicated with, and the inlet of the outlet of ion-exchanger 4 and absorption column of gas 1 is communicated with.
In one embodiment, the position of described ion-exchanger 4 is: the inlet of the outlet of bioreactor 2 and ion-exchanger 4 is communicated with by pipeline, and the inlet of the outlet of ion-exchanger 4 and solid-liquid separator 3 is communicated with by pipeline.
Under preferred situation, this equipment also comprises the fluid flow control device, and the inlet of the outlet of bioreactor 2 and solid-liquid separator 3 is communicated with by pipeline, and described this fluid flow control device is on the pipeline between the inlet of the outlet of bioreactor 2 and solid-liquid separator 3.
Replaceability ground, this equipment also comprises two fluid flow control device, and the inlet of the outlet of bioreactor 2 and solid-liquid separator 3 is communicated with by pipeline, wherein, fluid flow control device is on the pipeline between the inlet of the outlet of bioreactor 2 and solid-liquid separator 3, and another fluid flow control device is on the pipeline between the inlet of the outlet of bioreactor 2 and ion-exchanger 4 or on the pipeline between the inlet of the outlet of ion-exchanger 4 and solid-liquid separator 3.
A kind of preferred embodiment in, the position of described ion-exchanger 4 is: the inlet of the outlet of absorption column of gas 1 and ion-exchanger 4 is communicated with by pipeline, the inlet of the outlet of ion-exchanger 4 and bioreactor 2 is communicated with by pipeline.
Under preferred situation, this equipment also comprises the fluid flow control device, and the inlet of the outlet of described absorption column of gas 1 and bioreactor 2 is communicated with by pipeline, and described fluid flow control device is on the pipeline between the inlet of the outlet of described absorption column of gas 1 and bioreactor 2.
Replaceability ground, this equipment also comprises two fluid flow control device, and the inlet of the outlet of described absorption column of gas 1 and bioreactor 2 is communicated with by pipeline, wherein, fluid flow control device is on the pipeline between the inlet of the outlet of described absorption column of gas 1 and bioreactor 2, and another fluid flow control device is on the pipeline between the inlet of the outlet of described absorption column of gas 1 and ion-exchanger 4 or on the pipeline between the inlet of the outlet of described ion-exchanger 4 and bioreactor 2.
In another preferred embodiment, the position of described ion-exchanger 4 is: the inlet of the outlet of solid-liquid separator 3 and ion-exchanger 4 is communicated with by pipeline, and the inlet of the outlet of ion-exchanger 4 and absorption column of gas 1 is communicated with by pipeline.
Under preferred situation, this equipment also comprises the fluid flow control device, and the inlet of the outlet of described solid-liquid separator 3 and absorption column of gas 1 is communicated with by pipeline, and described fluid flow control device is on the pipeline between the inlet of the outlet of described solid-liquid separator 3 and absorption column of gas 1.
Replaceability ground, this equipment also comprises two fluid flow control device, and the inlet of the outlet of described solid-liquid separator 3 and absorption column of gas 1 is communicated with by pipeline, wherein, fluid flow control device is on the pipeline between the inlet of the outlet of described solid-liquid separator 3 and absorption column of gas 1, and another fluid flow control device is on the pipeline between the inlet of the outlet of described solid-liquid separator 3 and ion-exchanger 4 or on the pipeline between the inlet of the outlet of described ion-exchanger 4 and absorption column of gas 1.
In above-mentioned two kinds of preferred implementations, the position of ion-exchanger 4 can make the ion exchange resin in the ion-exchanger 4 be subjected to less impurity effect, thereby makes the better effects if of ion-exchange.
In the utility model, the kind of described fluid flow control device has no particular limits, and for example, can be one or more the combination in the device of measuring pump, valve, flowmeter and other adjustable fluid floies.
In the utility model, be filled with anion exchange resin in the described ion-exchanger, this anion exchange resin can be the various anion exchange resin that can optionally carry out ion-exchange with sulfate radical, under the preferable case, described anion exchange resin can be strong-base anion-exchange resin and/or weak-base anion-exchange resin, wherein, the duct kenel of described anion exchange resin both can be that gel-type also can be a macroporous type, be gel-type anion exchange resin and macroporous type gel-type anion exchange resin, its skeleton can be a polystyrene, acrylic acid series, epoxy system, vinylpyridine system, in the vinyl chloride one or more.
For example, described gel-type anion exchange resin can be in the gel-type anion exchange resin of the gel-type anion exchange resin of the gel-type anion exchange resin of the gel-type anion exchange resin of the gel-type anion exchange resin of polystyrene, acrylic acid series, epoxy system, vinylpyridine system and vinyl chloride one or more.The gel-type anion exchange resin of alkaline polystyrene can be commercially available, for example, and the anion exchange resin of 201 trades mark of resin Co., Ltd of Shanghai Nankai; The gel-type anion exchange resin of weakly alkaline polystyrene can be commercially available, for example, and the anion exchange resin of 301 trades mark of resin Co., Ltd of Shanghai Nankai.
Described macroporous type anion exchange resin can be in the macroporous type anion exchange resin of the macroporous type anion exchange resin of the macroporous type anion exchange resin of the macroporous type anion exchange resin of the macroporous type anion exchange resin of polystyrene, acrylic acid series, epoxy system, vinylpyridine system and vinyl chloride one or more.The macroporous type anion exchange resin of alkaline polystyrene can be commercially available, for example, and the anion exchange resin of the D201 trade mark of resin Co., Ltd of Shanghai Nankai.The macroporous type anion exchange resin of weakly alkaline polystyrene can be commercially available, for example, and the anion exchange resin of the D301 trade mark of resin Co., Ltd of Shanghai Nankai.The gel-type anion exchange resin of weakly alkaline acrylic acid series can be commercially available, for example, and 312 resins of Shanghai remittance pearl resin Co., Ltd.
According to the utility model; ion-exchange degree between the amount of the alkaline buffer of the regeneration of introducing in the described ion-exchanger and sulfate radical and the hydroxyl can guarantee that the sulfate ion in the cushioning liquid is controlled in the scope of requirement, and for example general's sulfate ion concentration wherein is controlled at and is no more than 10 grams per liters.By the method for ion-exchange, controlled the content of sulfate ion in the alkaline buffer, not only effectively improve the desulphurizing ability of the alkaline buffer of unit volume, and need not in system, to replenish in addition fresh alkaline buffer solution.
In the utility model, described sulfate ion is represented the anionic mixture of the sulphur of high valence state, for example can represent the mixture of sulfate ion, sulfite ion, thiosulfate ion etc.
In the utility model, the condition of described wash-out is as well known to those skilled in the art, and for example, the condition of described wash-out can comprise: the pH of alkaline buffer is 8-12, is preferably 8.5-10, and temperature is 10-50 ℃, is preferably 15-40 ℃.
In the utility model, the kind of described alkaline buffer has no particular limits, as long as can be used in the sulphur that absorbs in the gas that contains reducible sulfur, under the preferable case, described alkaline buffer can be in the following buffer system one or more: carbonate and acid salt thereof, phosphate and acid salt thereof, dihydric phosphate and NaOH and borax and NaOH; The buffer system of carbonate and acid salt thereof more preferably, described salt are sylvite and or sodium salt.
The concentration of described alkaline buffer solution has no particular limits, and under the preferable case, the concentration of described alkaline buffer solution can be 50-300 grams per liter, more preferably 80-150 grams per liter.
In a preferred implementation, described alkaline buffer solution is the buffer system of carbonate and acid salt thereof, and the total concentration of carbonate and bicarbonate ion is preferably 0.2-1.5mol/L, more preferably 0.5-1.2mol/L.
In the utility model, the described gas that contains reducible sulfur can be natural gas, biogas, refinery gas, water-gas, semiwater gas, Claus tail gas and other various sulphur-containing exhaust gas etc., and the sulphur in the described gas that contains reducible sulfur exists with the form of the reproducibility sulfuration thing of hydrogen sulfide, carbonyl sulfide, carbon disulfide and other kind.The reaction equation of elution process is as follows:
H
2S+OH
-→HS
-+H
2O
CO
2+OH
-→HCO
3 -
RSH+OH
-→RS
-+H
2O。
In the utility model, the gas that contains reducible sulfur is after alkaline buffer solution absorbs desulfurization, and the hydrogen sulfide content in the gas will be removed in the 1-100ppm scope, the scope of preferred 1-50ppm.
In the utility model, after alkaline buffer solution absorbs sulphur in the gas contain reducible sulfur, enter in the biotinylated biomolecule reactor, in bioreactor, feed a certain amount of compressed air, under action of microorganisms, the sulphur that relies on airborne oxygen will enter in the alkaline buffer solution is oxidized to elemental sulfur.Described bioreactor is the gas-lifting type aerobic reactor, and its running and condition of work are conventionally known to one of skill in the art.Fully be oxidized to elemental sulfur and avoid its peroxide to turn to sulfate radical as far as possible for guaranteeing to be absorbed in sulphur in the cushioning liquid, the oxidation-reduction potential in the described bioreactor need be controlled between-300 to-400 millivolts.
In the utility model, described microorganism can be the various bacteriums that can be used in oxidation-reduction quality sulfide, for example, described microorganism can be in Thiobacillus thioxidans (Thiobacillus.Thiooxidans), grate sulfur thiobacillus (Thiobacillus.thioparus), Thiobacillus ferrooxidans (Thiobacillus.ferrooxidans) and the thiobacillus denitrificans (Thiobacillus.denitrificans) one or more.
Described biooxidation reactions process is shown in following equation:
HS
-+1/2O
2→S+OH
-
RS
-+1/2O
2+H
2O→S+ROH+OH
-
HS
-+2O
2+OH
-→SO
4 2-+H
2O
RS
-+2O
2+OH
-→SO
4 2-+ROH。
In the utility model, separated from one another in solid-liquid separator through sulphur and alkaline buffer that biooxidation reactions obtains, sulphur can be used as product after washing, filtration, purification.
The kind of described solid-liquid separator is conventionally known to one of skill in the art, for example, and whizzer.The condition of Separation of Solid and Liquid also has no particular limits, as long as sulphur and alkaline buffer are separated.
In the utility model, be filled with anion exchange resin in the described ion-exchanger, utilize the ion-exchange performance of ion exchange resin that the sulfate ion in the cushioning liquid is exchanged for the OH-ion and turn back to alkaline buffer solution, therefore, the anion exchange resin of Shi Yonging should be the hydroxyl type anion exchanger resin first, this ion exchange resin has the selectivity exchange to the ion in the cushioning liquid, especially wherein sulfate ion had very strong exchange capacity, to carbonate and bicarbonate ion wherein, phosphate anions etc. have exchange capacity hardly.When cushioning liquid enters ion-exchanger, sulfate ion in the cushioning liquid is left on the ion exchange resin, and the OH-ion of corresponding amount of charge enters cushioning liquid, the OH-ion that generation because of sulfate radical is lost obtains regeneration, and process such as following reaction equation are represented:
H
2S+OH
-→HS
-+H
2O
HS
-+2O
2+OH
-→SO
4 2-+H
2O
H
2S+2O
2+ 2OH
-→ SO
4 2-+ 2H
2O (general equation formula)
SO
4 2-→ 2OH
-(ion-exchange)
From top reaction and ion exchange process, the OH of 2 molecules that consume in the course of reaction
-Ion is restored after ion-exchange, and the alkali number in the alkaline buffer solution obtains regeneration, and the ability of reproducibilities such as alkaline buffer solution absorbing hydrogen sulphide sulfuration thing is restored, and has kept the balance that whole system absorbs and reacts.Along with constantly carrying out of exchange process, the sulfate ion in the ion exchange resin is constantly accumulated, and is saturated until the ion exchange resin exchange.
After sulfate ion exchange in the anion exchange resin is saturated, need regenerate to anion exchange resin, as known in those skilled in the art, need the anion exchange resin of sulfate radical type be regenerated as the anion exchange resin of hydroxyl type with alkali.In the utility model, NaOH and/or potassium hydroxide are selected in regeneration of ion-exchange resin for use, preferred NaOH in regenerative process, is discharged sodium sulphate, discharge liquid pH value greater than 12 the time when detecting, be preferably greater than at 13 o'clock, regenerative process finishes, and can be directly switch to ion exchange process recited above, also can water flowing switch to above-mentioned ion exchange process after the washing, and the metabisulfite solution that produces in the regenerative process can directly discharge or crystallization after sell as product.
According to the equipment that the utility model provides, cushioning liquid can all enter ion-exchanger, also can partly enter ion-exchanger.The amount that cushioning liquid enters in the ion-exchanger is regulated automatically according to sulfate radical total concentration in the system, for example, when sulfate radical example concentration in the cushioning liquid surpasses 50 grams per liters, cushioning liquid all enters ion-exchanger and exchanges, when sulfate ion concentration in the cushioning liquid is between the 30-50 grams per liter, 2/3 cushioning liquid enters ion-exchanger and exchanges, when sulfate ion concentration in the cushioning liquid was lower than 30 grams per liters, the cushioning liquid below 1/3 entered ion-exchanger and exchanges.In this way, reach the purpose of the sulfate ion in the control cushioning liquid, for example control sulfate ion concentration in the cushioning liquid in 10 grams per liter %, in this case, kept the shared ratio of buffering salt in the alkaline buffer, not only effectively improve the desulphurizing ability of the alkaline buffer of unit volume, and need not in system, to replenish in addition fresh alkaline buffer solution.
In the utility model, ion-exchanger 4 can be one, also can be a plurality of, the use that can be connected in parallel of a plurality of ion-exchangers, when one of them entered the regeneration link, remaining can guarantee that cushioning liquid is continual and carry out ion-exchange, can also be arranged on a plurality of between different step, one or more as between absorption tower and bioreactor, being provided with, between bioreactor and separator, be provided with one or morely, be provided with one or more between separator and the absorption tower.
Below by specific embodiment the utility model is described in more details.
Embodiment 1
(1) biogas (is formed: CH
4Content 72.7%, CO
2Content 24%, N
2Content 2%, O
2Content 0.1%, H
2S content 1.2%) with 5m
3The flow of/h is incorporated into that (Henan, Beijing is great achievement lucite processing factory forever, bed stuffing height 0.8m, tower diameter 0.15m, gas treatment amount 5m in the absorption column of gas
3/ h), with the alkaline buffer (Na in the absorption column of gas
2CO
3Concentration: 0.1mol/L, NaHCO
3Concentration: 0.9mol/L; PH:8.7) wash-out is carried out in contact, and the gas liquid ratio of biogas and alkaline buffer is 30: 1 (volume ratio), cushioning liquid cumulative volume 1m
3, the cushioning liquid temperature is 35 ℃ behind the wash-out.
(2) alkaline buffer of the sulfur-bearing that step (1) is obtained is incorporated into bioreactor (airlift reactor, treating capacity 0.2m
3/ h) in, at thiobacillus denitrificans (German DSMZ, bacterial classification DSM12475, cell concentration 10
7Make sulphur contained in the alkaline buffer oxidized under individual/ml) effect, the oxidation-reduction potential of described bioreactor is-350 millivolts.
(3) in solid-liquid separator, isolate the sulphur that biological oxidation obtains in the step (2), and the alkaline buffer that obtains regenerating.
(4) 1/8 flow in the alkaline buffer of regeneration is incorporated into ion-exchanger (the inner D311 of filling type ion exchange resin (Shanghai converge pearl resin Co., Ltd), 0.5m
3) in carry out ion-exchange, will return through the alkaline buffer of ion-exchange in the absorption column of gas in the step (1) and reuse.
Comparative Examples 1
According to the sulphur in the method wash-out biogas identical with embodiment 1, difference is that the alkaline buffer of regenerating directly turns back in the absorption column of gas in the step (1) without ion-exchange and reuses.
Embodiment 2
According to the sulphur in the identical method wash-out biogas of embodiment 1, difference is that the alkaline buffer solution of regenerating all uses through turning back to after the ion-exchange in the absorption column of gas in the step (1).
According to the sulphur in the identical method wash-out biogas of embodiment 1, difference is that the gas liquid ratio of biogas and alkaline buffer solution is 50: 1.
Embodiment 4-6
After beginning reaction, when 4h, 24h, 72h, detect the H of gas behind the alkaline buffer solution wash-out among the embodiment 1-3 respectively
2S content returns the total content of sulfate radical, thiosulfate anion in the alkaline buffer on absorption tower, and the result is as shown in table 1.
Comparative Examples 2
According to the method identical, detect the H of gas behind the alkaline buffer solution wash-out in the Comparative Examples 1 at 4h, 24h, 72h place respectively with embodiment 4-6
2S content returns the total content of sulfate radical, thiosulfate anion in the alkaline buffer on absorption tower, and the result is as shown in table 1.
Table 1
From the data of last table 1 as can be seen, after reaching 72h circulation timei, gas is behind the alkaline buffer solution wash-out among the embodiment 4, hydrogen sulfide content in the gas only has 17ppm, with be circulation timei 24h quite, it is constant to remove the hydrogen sulfide ability, sulfate concentration is controlled at below the 1g/L in the alkaline buffer solution, compare with embodiment 5 (alkaline buffer solution of regeneration all passes through ion-exchange), do not influence its desulfurized effect substantially.And in the Comparative Examples 2 along with the prolongation of circulation timei, sulfate ion in the alkaline buffer solution and thiosulfate ion concentration all increase considerably, the pH value of solution value also descends to some extent, behind circulation 72h, hydrogen sulfide content after desulfurization is handled in the gas is 72ppm, compare it with 17ppm among the embodiment 4 and remove the hydrogen sulfide degree of depth and had very significantly and reduce, the raising of the desulfurization depth of alkaline buffer solution be described after the utility model ion-exchange treatment.After the gas liquid ratio among the embodiment 6 is increased to 50: 1, after its circulation 72h, hydrogen sulfide content after desulfurization is handled in the gas is 31ppm, still be that 30: 1 desulfurization depth wants high than the gas liquid ratio in the Comparative Examples 2, illustrate that alkaline buffer solution is through after the ion-exchange, the Sulfur capacity of unit alkaline buffer solution increases, and illustrates under same desulfurization depth, utilizes the internal circulating load of the alkaline buffer solution after the utility model is handled to reduce significantly.
Claims (13)
1. equipment that removes the sulphur in the gas that contains reducible sulfur, this equipment comprises: absorption column of gas (1), bioreactor (2) and solid-liquid separator (3), the inlet of the outlet of described absorption column of gas (1) and bioreactor (2) is communicated with, the inlet of the outlet of bioreactor (2) and solid-liquid separator (3) is communicated with, the inlet of the outlet of solid-liquid separator (3) and absorption column of gas (1) is communicated with, it is characterized in that, this equipment also comprises at least one ion-exchanger (4), the position of each ion-exchanger (4) one in the following situation of respectively doing for oneself:
(I) inlet of the outlet of absorption column of gas (1) and ion-exchanger (4) is communicated with, and the inlet of the outlet of ion-exchanger (4) and bioreactor (2) is communicated with;
(II) inlet of the outlet of bioreactor (2) and ion-exchanger (4) is communicated with, and the inlet of the outlet of ion-exchanger (4) and solid-liquid separator (3) is communicated with;
(III) inlet of the outlet of solid-liquid separator (3) and ion-exchanger (4) is communicated with, and the inlet of the outlet of ion-exchanger (4) and absorption column of gas (1) is communicated with.
2. equipment according to claim 1, it is characterized in that, the position of described ion-exchanger (4) is: the inlet of the outlet of absorption column of gas (1) and ion-exchanger (4) is communicated with by pipeline, and the inlet of the outlet of ion-exchanger (4) and bioreactor (2) is communicated with by pipeline.
3. equipment according to claim 2, it is characterized in that, this equipment also comprises the fluid flow control device, and the inlet of the outlet of described absorption column of gas (1) and bioreactor (2) is communicated with by pipeline, and described fluid flow control device is positioned on the pipeline between the inlet of the outlet of described absorption column of gas (1) and bioreactor (2).
4. equipment according to claim 2, it is characterized in that, this equipment also comprises two fluid flow control device, and the inlet of the outlet of described absorption column of gas (1) and bioreactor (2) is communicated with by pipeline, wherein, fluid flow control device is positioned on the pipeline between the inlet of the outlet of described absorption column of gas (1) and bioreactor (2), another fluid flow control device be positioned on the pipeline between the inlet of the outlet of described absorption column of gas (1) and ion-exchanger (4) or be positioned at the outlet of described ion-exchanger (4) and the inlet of bioreactor (2) between pipeline on.
5. equipment according to claim 1, it is characterized in that, the position of described ion-exchanger (4) is: the inlet of the outlet of solid-liquid separator (3) and ion-exchanger (4) is communicated with by pipeline, and the inlet of the outlet of ion-exchanger (4) and absorption column of gas (1) is communicated with by pipeline.
6. equipment according to claim 5, it is characterized in that, this equipment also comprises the fluid flow control device, and the inlet of the outlet of described solid-liquid separator (3) and absorption column of gas (1) is communicated with by pipeline, and described fluid flow control device is positioned on the pipeline between the inlet of the outlet of described solid-liquid separator (3) and absorption column of gas (1).
7. equipment according to claim 5, it is characterized in that, this equipment also comprises two fluid flow control device, and the inlet of the outlet of described solid-liquid separator (3) and absorption column of gas (1) is communicated with by pipeline, wherein, fluid flow control device is positioned on the pipeline between the inlet of the outlet of described solid-liquid separator (3) and absorption column of gas (1), another fluid flow control device be positioned on the pipeline between the inlet of the outlet of described solid-liquid separator (3) and ion-exchanger (4) or be positioned at the outlet of described ion-exchanger (4) and the inlet of absorption column of gas (1) between pipeline on.
8. equipment according to claim 1, it is characterized in that, the position of described ion-exchanger (4) is: the inlet of the outlet of bioreactor (2) and ion-exchanger (4) is communicated with by pipeline, and the inlet of the outlet of ion-exchanger (4) and solid-liquid separator (3) is communicated with by pipeline.
9. equipment according to claim 8, it is characterized in that, this equipment also comprises the fluid flow control device, and the inlet of the outlet of bioreactor (2) and solid-liquid separator (3) is communicated with by pipeline, and described fluid flow control device is positioned on the pipeline between the inlet of the outlet of bioreactor (2) and solid-liquid separator (3).
10. equipment according to claim 8, it is characterized in that, this equipment also comprises two fluid flow control device, and the inlet of the outlet of bioreactor (2) and solid-liquid separator (3) is communicated with by pipeline, wherein, fluid flow control device is positioned on the pipeline between the inlet of the outlet of bioreactor (2) and solid-liquid separator (3), another fluid flow control device be positioned on the pipeline between the inlet of the outlet of bioreactor (2) and ion-exchanger (4) or be positioned at the outlet of ion-exchanger (4) and the inlet of solid-liquid separator (3) between pipeline on.
11., it is characterized in that described fluid flow control device is one or more the combination in measuring pump, valve, the flowmeter according to claim 3,4,6,7,9 or 10 described equipment.
12. equipment according to claim 1 is characterized in that, described ion-exchanger is filled with anion exchange resin in (4).
13. equipment according to claim 1 is characterized in that, described bioreactor is equipped with Thiobacillus in (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010205024989U CN201889154U (en) | 2010-08-23 | 2010-08-23 | Equipment for desulphurizing gas containing reducible sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010205024989U CN201889154U (en) | 2010-08-23 | 2010-08-23 | Equipment for desulphurizing gas containing reducible sulfur |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN201889154U true CN201889154U (en) | 2011-07-06 |
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ID=44218629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010205024989U Expired - Lifetime CN201889154U (en) | 2010-08-23 | 2010-08-23 | Equipment for desulphurizing gas containing reducible sulfur |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN201889154U (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354666A (en) * | 2019-07-16 | 2019-10-22 | 中国石油化工股份有限公司 | A kind of commercial plant and application method reducing hydramine depriving hydrogen sulphide system operation cost |
| CN115974082A (en) * | 2023-02-23 | 2023-04-18 | 会东金川磷化工有限责任公司 | Device for preparing calcium carbide by recycling yellow phosphorus tail gas |
-
2010
- 2010-08-23 CN CN2010205024989U patent/CN201889154U/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354666A (en) * | 2019-07-16 | 2019-10-22 | 中国石油化工股份有限公司 | A kind of commercial plant and application method reducing hydramine depriving hydrogen sulphide system operation cost |
| CN115974082A (en) * | 2023-02-23 | 2023-04-18 | 会东金川磷化工有限责任公司 | Device for preparing calcium carbide by recycling yellow phosphorus tail gas |
| CN115974082B (en) * | 2023-02-23 | 2024-05-03 | 会东金川磷化工有限责任公司 | Retrieve yellow phosphorus tail gas preparation carbide's device |
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