CN111450673A - Desulfurization equipment and desulfurization method for recovering sulfur element into acid solution - Google Patents
Desulfurization equipment and desulfurization method for recovering sulfur element into acid solution Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 96
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 96
- 230000023556 desulfurization Effects 0.000 title claims abstract description 96
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 39
- 239000011593 sulfur Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 58
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 46
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 230000003647 oxidation Effects 0.000 claims abstract description 34
- 230000002745 absorbent Effects 0.000 claims abstract description 33
- 239000002250 absorbent Substances 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000005837 radical ions Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 239000013589 supplement Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- -1 hydrogen sulfate radical Chemical class 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000005864 Sulphur Substances 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 59
- 235000010269 sulphur dioxide Nutrition 0.000 description 17
- 230000006872 improvement Effects 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
- B01D53/965—Regeneration, reactivation or recycling of reactants including an electrochemical process step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Urology & Nephrology (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses desulfurization equipment and a desulfurization method for recovering sulfur element into acid solution. The desulfurization equipment for recovering the sulfur element into the acid solution comprises: the desulfurization unit at least reacts with sulfur dioxide in the gas to be treated by using an absorbent to generate soluble salt and discharges reaction liquid containing the soluble salt; the oxidation unit oxidizes the acid radical ions containing tetravalent sulfur in the reaction liquid into acid radical ions containing hexavalent sulfur; and the salt chamber of the bipolar membrane unit receives the reaction liquid treated by the oxidation unit and generates an alkali solution in the alkali chamber and an acid solution in the acid chamber respectively. Through setting up the oxidation unit, can make the elemental sulphur in the reaction solution mainly exist with the form of hydrogen sulfate radical and sulfate radical, so not only can reduce and even avoid producing gas in the acid chamber, elemental sulphur is retrieved with the sulfuric acid solution form moreover, can show the use value who reduces the energy consumption, extension equipment life and promote elemental sulphur.
Description
Technical Field
The invention relates to the technical field of sulfur-containing gas desulfurization, in particular to desulfurization equipment and a desulfurization method for recovering sulfur element into acid solution.
Background
The sulfur compounds in the sulfur-containing flue gas are mainly sulfur dioxide, wherein a small amount of sulfur dioxide (usually not more than 2% of the total volume of sulfur dioxide) may be oxidized to sulfur trioxide. The existing flue gas desulfurization technology is a gypsum method, namely slurry prepared by adding water into limestone powder is pumped into a desulfurization tower as an absorbent to be fully contacted and mixed with sulfur-containing flue gas, so that sulfur dioxide in the flue gas, calcium carbonate in the slurry and air blown from the lower part of the tower are subjected to oxidation reaction to generate calcium sulfate, and the calcium sulfate is crystallized to form dihydrate gypsum after reaching a certain saturation degree. The gypsum slurry discharged from desulfurizing tower is concentrated and dewatered to make its water content less than 10%, then transferred into gypsum storage bin by means of conveyer to stack.
The gypsum method has the advantages of rich source of the desulfurizer, low price, full utilization, over 95 percent of desulfurization efficiency and no limitation on unit capacity. The defects are that the system is complex, the occupied area is large, the investment is high, and a large amount of discharged residues are generated.
Disclosure of Invention
The invention mainly aims to provide desulfurization equipment and a desulfurization method for recovering sulfur element into acid solution, so as to solve the problem of discharging a large amount of residues in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a first desulfurization apparatus for recovering elemental sulfur into an acid solution. The desulfurization equipment for recovering the sulfur element into the acid solution comprises:
the desulfurization unit at least reacts with sulfur dioxide in the gas to be treated by using an absorbent to generate soluble salt and discharges reaction liquid containing the soluble salt;
a bipolar membrane unit having a salt chamber for receiving the reaction solution and generating an alkaline solution in a base chamber and an acidic solution in an acid chamber, respectively.
Firstly, the desulfurization equipment of the invention can not generate new solid, so that the technical problem of discharging a large amount of residue can not occur; compared with dihydrate gypsum, the sulfur element is recovered in the form of acid solution, so that the utilization value of the sulfur element can be improved. Secondly, the alkaline solution generated by the alkaline chamber of the bipolar membrane unit can be reused as the absorbent, so that the whole equipment can be independently and stably operated for a long time only by supplementing a proper amount of the absorbent during driving, and the operation cost is low.
In order to achieve the above object, according to one aspect of the present invention, there is provided a second desulfurization apparatus for recovering elemental sulfur into an acid solution. The desulfurization apparatus for recovering elemental sulfur into an acid solution includes:
the desulfurization unit at least reacts with sulfur dioxide in the gas to be treated by using an absorbent to generate soluble salt and discharges reaction liquid containing the soluble salt;
the oxidation unit oxidizes the acid radical ions containing tetravalent sulfur in the reaction liquid into acid radical ions containing hexavalent sulfur;
and the salt chamber of the bipolar membrane unit receives the reaction liquid treated by the oxidation unit and generates an alkali solution in the alkali chamber and an acid solution in the acid chamber respectively.
When the first desulfurization device is used, because no oxidation unit is arranged, sulfur elements in the reaction liquid mainly exist in the form of bisulfite and sulfite, so that in addition to sulfurous acid generated in an acid chamber of the bipolar membrane unit, more sulfur dioxide gas can be generated, and the gas can reduce the conductivity of the solution on one hand, thereby increasing energy consumption, and on the other hand, the process of generating and breaking bubbles can impact the membrane, thereby possibly affecting the service life of the membrane. Therefore, by arranging the oxidation unit, the sulfur element in the reaction liquid mainly exists in the forms of hydrogen sulfate and sulfate radical, so that the generation of gas in the acid chamber can be reduced or even avoided, and the sulfur element is recovered in the form of sulfuric acid solution, thereby obviously reducing the energy consumption, prolonging the service life of equipment and improving the utilization value of the sulfur element.
As a further improvement of the above two desulfurization apparatuses for recovering elemental sulfur into an acid solution, the oxidation unit includes a first oxidation unit including an aeration device that introduces supplemental oxygen as an oxidizing agent into the absorbent by stirring the absorbent; and/or the like and/or,
the oxidation unit comprises a second oxidation unit which comprises a first intermediate tank, wherein the first intermediate tank receives the reaction liquid discharged by the desulfurization unit and utilizes the oxidant in the first intermediate tank to oxidize the tetravalent sulfur in the reaction liquid.
The first oxidation unit and the second oxidation unit are preferably arranged simultaneously to maximize the reduction of the bisulphite and sulphite content and thereby avoid the generation of sulphur dioxide gas in the acid chamber.
As a further improvement of the two desulfurization devices for recovering elemental sulfur into an acid solution,
the bipolar membrane further comprises a gas collecting unit, wherein the gas collecting unit is used for collecting sulfur dioxide generated by the bipolar membrane; therefore, by arranging the gas collection unit, leakage of sulfur dioxide which is possibly generated can be avoided, and the purity of the collected sulfur dioxide is higher, and the sulfur dioxide can be further utilized, such as prepared into sulfuric acid.
The device also comprises a filtering unit, wherein the filtering unit is used for intercepting the particulate matters in the reaction liquid. Therefore, the abrasion of the pipeline of the equipment caused by the particles in the reaction liquid can be prevented.
As a further improvement of the two desulfurization devices for recovering sulfur element into acid solution, the desulfurization device further comprises a first concentration unit for concentrating the reaction solution and inputting concentrated water obtained by concentrating the reaction solution into a salt chamber of the bipolar membrane unit and inputting produced water obtained by concentrating the reaction solution into an alkali chamber and an acid chamber of the bipolar membrane unit. Therefore, on one hand, the energy consumption of the bipolar membrane unit can be reduced, on the other hand, the water supplement from the outside of the system to the acid chamber and the alkali chamber can be avoided or reduced, and the operation cost is further reduced.
As a further improvement of the two desulfurization devices for recovering the sulfur element into the acid solution, the desulfurization device further comprises a pH adjusting unit for adjusting the pH of the reaction liquid before concentration.
As a further improvement of the two desulfurization devices for recovering sulfur into acid solution, the desulfurization device further comprises a second concentration unit for concentrating the acid chamber product of the bipolar membrane unit and delivering the concentrated product water to the alkali chamber and the acid chamber of the bipolar membrane unit. Therefore, on one hand, the volume of the final product can be reduced, the transportation cost is saved, on the other hand, the water supplement from the outside of the system to the acid chamber and the alkali chamber can be avoided or reduced, and the operation cost is further reduced; it is of course also possible to determine whether and to what extent the second concentration unit is arranged according to the product distribution or the manner of use.
In order to achieve the above object, according to one aspect of the present invention, there is provided a desulfurization method for recovering elemental sulfur into an acid solution. The desulfurization method for recovering the sulfur element into the acid solution comprises the steps of adopting any one of the desulfurization devices for recovering the sulfur element into the acid solution; and during operation, an alkaline absorbent is added into the desulfurization unit as an initial absorbent, and a circulating liquid consisting of a reaction liquid discharged by the desulfurization unit with partial reflux, an alkali liquid generated by an alkali chamber of the bipolar membrane unit and an electrolyzed liquid generated by a salt chamber is used as a new absorbent.
Proved by verification, the desulfurization method can recover more than 95 percent of sulfur element in the gas to be treated in an acid form, and has high recovery rate and high economic benefit.
As a further improvement of the desulfurization method for recovering elemental sulfur into an acid solution, the absorbent is selected from any one of a hydroxide solution of an alkali metal, a hydroxide solution of an alkaline earth metal, a carbonic acid reaction solution of an alkali metal and a carbonic acid reaction solution of an alkaline earth metal; preferably, the absorbent is selected from any of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and potassium carbonate solution.
As a further improvement of the desulfurization method for recovering the sulfur element into the acid solution, the pH value of the circulating liquid is 5-8. Thus, the reaction solution can be ensured to contain less bisulfite and sulfite.
As a further improvement of the desulfurization method for recovering elemental sulfur into an acid solution, the method comprises the steps of inputting oxygen supplement gas serving as an oxidant into a desulfurization unit, wherein the oxygen supplement gas is preferably air and/or oxygen; and/or oxidizing the tetravalent sulfur in the reaction liquid by adopting any several of hydrogen peroxide, ozone, sodium peroxide and sodium persulfate.
The invention is further described with reference to the following figures and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
fig. 1 is a schematic configuration diagram of a desulfurization apparatus for recovering elemental sulfur into an acid solution according to example 1.
FIG. 2 is a schematic diagram of the operation of the bipolar membrane unit.
FIG. 3 is a schematic view showing the structure of a desulfurization apparatus for recovering elemental sulfur into an acid solution according to example 2.
FIG. 4 is a schematic view showing the constitution of a desulfurization apparatus for recovering elemental sulfur into an acid solution according to example 3.
FIG. 5 is a schematic view showing the constitution of a desulfurization apparatus for recovering elemental sulfur into an acid solution according to example 4.
FIG. 6 is a schematic view showing the constitution of a desulfurization apparatus for recovering elemental sulfur into an acid solution according to example 5.
FIG. 7 is a schematic view showing the constitution of a desulfurization apparatus for recovering elemental sulfur into an acid solution according to example 6.
The relevant references in the above figures are:
110-spray pump, 120-desulfurizing tower, 210-first oxidation unit, 220-second oxidation unit, 230-oxidant storage tank, 310-bipolar membrane unit, 320-gas collection unit, 400-pH regulation unit, 500-filtering unit, 600-first concentration unit, 700-second concentration unit
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions. .
Example 1
Fig. 1 is a schematic structural diagram of a desulfurization apparatus for recovering elemental sulfur into an acid solution according to this embodiment.
As shown in fig. 1, the desulfurization apparatus for recovering elemental sulfur into an acid solution includes a desulfurization unit, a pH adjustment unit 400, a filtration unit 500, a first concentration unit 600, and a bipolar membrane unit 310.
The desulfurization unit utilizes an absorbent to react with at least sulfur dioxide in the gas to be treated to generate soluble salt, and discharges reaction liquid containing the soluble salt; the desulfurization unit comprises a spray pump 110 and a desulfurization tower 120, and the absorbent is sprayed from the upper part of the desulfurization tower 120 through the spray pump 110 to enter the desulfurization tower 120 and then is mixed and reacted with the gas to be treated entering from the middle part of the desulfurization tower 120; a stirring device is provided at the bottom of the desulfurizing tower 120.
The pH adjusting unit 400 comprises a second intermediate tank which receives the reaction liquid and adjusts the pH of the reaction liquid by using a part of acid liquid generated by the acid chamber of the bipolar membrane unit 310; and a stirring device is arranged in the second intermediate tank.
The filtering unit 500 is used for intercepting the particulate matters in the reaction liquid treated by the pH adjusting unit 400. The filtering unit 500 adopts a tubular ultrafiltration membrane component with the interception rate of more than or equal to 90% for the particles with the granularity of more than or equal to 0.1 mm.
The first concentration unit 600 adopts a disc tube type reverse osmosis membrane module, the first concentration unit 600 inputs concentrated water obtained by concentrating a reaction solution into a salt chamber of the bipolar membrane unit 310, and the concentrated water obtained by concentrating the reaction solution is respectively input into an alkali chamber and an acid chamber of the bipolar membrane unit 310 according to a volume ratio of 1: 1.
The salt chamber of the bipolar membrane unit 310 receives the concentrated water of the first concentration unit 600, the alkali chamber and the acid chamber of the bipolar membrane unit 310 receive the water produced by the first concentration unit 600, and after power is turned on, an alkali solution is generated in the alkali chamber and an acid solution is generated in the acid chamber according to the principle shown in fig. 2.
Example 2
Compared with the embodiment 1, the desulfurization apparatus for recovering elemental sulfur into an acid solution according to the present embodiment has the following differences: as shown in fig. 3, the device further comprises a second concentration unit 700, wherein the second concentration unit 700 adopts a roll-type nanofiltration membrane module, and the second concentration unit 700 concentrates the acid chamber product of the bipolar membrane unit 310 and feeds the water obtained by concentration into the alkali chamber and the acid chamber of the bipolar membrane unit 310 respectively according to the volume ratio of 1: 1.
Example 3
Compared with the embodiment 2, the desulfurization apparatus for recovering elemental sulfur into an acid solution of the present embodiment has the following differences: as shown in fig. 4, the bipolar membrane further comprises a gas collecting unit 320, wherein the gas collecting unit 320 is used for collecting sulfur dioxide generated by the bipolar membrane.
Example 4
Fig. 5 is a schematic structural diagram of the desulfurization apparatus for recovering elemental sulfur into an acid solution according to this embodiment.
As shown in fig. 5, the desulfurization apparatus for recovering elemental sulfur into an acid solution includes a desulfurization unit, an oxidation unit, a pH adjustment unit 400, a filtration unit 500, a first concentration unit 600, and a bipolar membrane unit 310.
The desulfurization unit utilizes an absorbent to react with at least sulfur dioxide in the gas to be treated to generate soluble salt, and discharges reaction liquid containing the soluble salt; the desulfurization unit comprises a spray pump 110 and a desulfurization tower 120, and the absorbent is sprayed from the upper part of the desulfurization tower 120 through the spray pump 110 to enter the desulfurization tower 120 and then is mixed and reacted with the gas to be treated entering from the middle part of the desulfurization tower 120; a stirring device is provided at the bottom of the desulfurizing tower 120.
The oxidation unit oxidizes the acid radical ions containing tetravalent sulfur in the reaction liquid into acid radical ions containing hexavalent sulfur; the oxidation unit includes a first oxidation unit 210, and the first oxidation unit 210 includes an aeration device which is provided at the bottom of the desulfurization tower 120 and introduces make-up oxygen gas as an oxidant into the absorbent by stirring the absorbent.
The pH adjusting unit 400 comprises a second intermediate tank, wherein the second intermediate tank receives the reaction liquid of the first intermediate tank and adjusts the pH of the reaction liquid by using partial acid liquid generated by the acid chamber of the bipolar membrane unit 310; and a stirring device is arranged in the second intermediate tank.
The filtering unit 500 adopts a tubular ultrafiltration membrane component with the interception rate of more than or equal to 90% for the particles with the granularity of more than or equal to 0.1 mm.
The first concentration unit 600 adopts a disc tube type reverse osmosis membrane module, the first concentration unit 600 inputs concentrated water obtained by concentrating a reaction solution into a salt chamber of the bipolar membrane unit 310, and the concentrated water obtained by concentrating the reaction solution is respectively input into an alkali chamber and an acid chamber of the bipolar membrane unit 310 according to a volume ratio of 1: 1.
The salt chamber of the bipolar membrane unit 310 receives the concentrated water of the first concentration unit 600, the alkali chamber and the acid chamber of the bipolar membrane unit 310 receive the water produced by the first concentration unit 600, and after power is turned on, an alkali solution is generated in the alkali chamber and an acid solution is generated in the acid chamber according to the principle shown in fig. 2.
Example 5
Compared with the embodiment 4, the desulfurization apparatus for recovering elemental sulfur into an acid solution according to the embodiment has the following differences: as shown in fig. 6, the oxidation unit further includes a second oxidation unit 220; the second oxidation unit 220 includes a first intermediate tank that receives the reaction liquid discharged from the desulfurization unit and oxidizes tetravalent sulfur in the reaction liquid using an oxidant input into the first intermediate tank from an oxidant storage tank 230; and a stirring device is arranged in the first intermediate tank.
Example 6
Compared with the embodiment 5, the desulfurization apparatus for recovering elemental sulfur into an acid solution according to the present embodiment has the following differences: as shown in fig. 7, the device further comprises a second concentration unit 700, wherein the second concentration unit 700 adopts a roll-type nanofiltration membrane module, and the second concentration unit 700 concentrates the acid chamber product of the bipolar membrane unit 310 and feeds the water obtained by concentration into the alkali chamber and the acid chamber of the bipolar membrane unit 310 respectively according to the volume ratio of 1: 1.
When the desulfurization is carried out by adopting the equipment of any one of the above embodiments 1-6, only the alkaline absorbent is needed to be added into the desulfurization unit as the initial absorbent during the start-up, the alkaline absorbent is not needed to be added during the operation, and the circulating liquid formed by the reaction liquid discharged by the desulfurization unit with partial reflux, the alkali liquid generated in the alkali chamber of the bipolar membrane unit 310 and the electrolyzed liquid generated in the salt chamber is used as the new absorbent.
Wherein the alkaline absorbent is selected from any of alkali metal hydroxide solution, alkaline earth metal hydroxide solution, alkali metal carbonic acid reaction liquid and alkaline earth metal carbonic acid reaction liquid.
Wherein, oxygen is supplied as oxidant into the desulfurization unit through the aeration device; the first intermediate tank adopts any one of hydrogen peroxide, ozone, sodium peroxide and sodium persulfate to oxidize tetravalent sulfur in the reaction liquid.
In the desulfurization tower 120, the absorbent reacts with sulfur dioxide and sulfur trioxide in the gas to be treated as follows:
SO2+H2O→H2SO3；
HSO3 -+1/2O2→HSO4 -；
SO3+H2O→H2SO4；H2SO4→SO4 2-+2H+
the distribution quantity of various acid radical ions can be obtained by inquiring the pH value after a distribution fraction diagram is obtained by calculation according to the ionization equilibrium constant of acid, and the result is proved that when the pH value of the circulating liquid is 5-8, preferably 5-6, the absorption quantity of sulfur dioxide can be improved, and the content of sulfite radicals and hydrogen sulfite radicals in the reaction liquid can be reduced.
FIG. 2 is a schematic diagram of the operation of the bipolar membrane unit. As shown in FIG. 2, the positive valence metal ions M in the salt chamber are generated under the action of DC electric field by arranging the negative film and the positive film in a specific order+The hydroxide ions which enter the alkali chamber after passing through the anode membrane and are ionized at the bipolar membrane of the alkali chamber form alkali liquor, and the negative-valence acid radical ions X in the salt chamber-Hydrogen ions which enter the acid chamber after passing through the negative membrane and are ionized form acid liquor at the bipolar membrane of the acid chamber.
Wherein, the positive valence metal ion M+In the desulfurization apparatus of examples 5 to 6, the oxidation unit had both the first oxidation unit and the second oxidation unit so that most of the bisulfite was oxidized to bisulfite and thus penetratedThe negative acid radical ions of the cathode-passing film are mainly sulfate radical and hydrogen sulfate radical.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (10)
1. The desulfurization equipment for recovering the sulfur element into the acid solution is characterized by comprising:
the desulfurization unit at least reacts with sulfur dioxide in the gas to be treated by using an absorbent to generate soluble salt and discharges reaction liquid containing the soluble salt;
a bipolar membrane unit (310), wherein the salt chamber of the bipolar membrane unit (310) receives the reaction liquid and generates an alkali solution in the alkali chamber and an acid solution in the acid chamber respectively.
2. The desulfurization equipment for recovering the sulfur element into the acid solution is characterized by comprising:
the desulfurization unit at least reacts with sulfur dioxide in the gas to be treated by using an absorbent to generate soluble salt and discharges reaction liquid containing the soluble salt;
the oxidation unit oxidizes the acid radical ions containing tetravalent sulfur in the reaction liquid into acid radical ions containing hexavalent sulfur;
a bipolar membrane unit (310), wherein the salt chamber of the bipolar membrane unit (310) receives the reaction liquid treated by the oxidation unit and generates an alkali solution in the alkali chamber and an acid solution in the acid chamber respectively.
3. The desulfurization apparatus for recovering elemental sulfur as defined in claim 2, wherein: the oxidation unit comprises a first oxidation unit (210), the first oxidation unit (210) comprises an aeration device, and the aeration device is used for stirring the absorbent so as to introduce oxygen supplement gas as an oxidant into the absorbent; and/or the like and/or,
the oxidation unit comprises a second oxidation unit (220), and the second oxidation unit (220) comprises a first intermediate tank which receives the reaction liquid discharged by the desulfurization unit and oxidizes tetravalent sulfur in the reaction liquid by using an oxidizing agent in the first intermediate tank.
4. A desulfurization apparatus for recovering elemental sulfur as an acid solution according to any one of claims 1 to 3, characterized in that:
the bipolar membrane further comprises a gas collecting unit (320), wherein the gas collecting unit (320) is used for collecting sulfur dioxide generated by the bipolar membrane;
the device also comprises a filtering unit (500), wherein the filtering unit (500) is used for intercepting the particulate matters in the reaction liquid.
5. A desulfurization apparatus for recovering elemental sulfur as an acid solution according to any one of claims 1 to 3, characterized in that: the device also comprises a first concentration unit (600) which is used for concentrating the reaction liquid and inputting concentrated water obtained by concentrating the reaction liquid into a salt chamber of the bipolar membrane unit (310) and inputting produced water obtained by concentrating the reaction liquid into an alkali chamber and an acid chamber of the bipolar membrane unit (310).
6. The desulfurization apparatus for recovering elemental sulfur as claimed in claim 5, wherein: further comprises a pH adjusting unit (400) for adjusting the pH of the reaction solution before concentration.
7. A desulfurization apparatus for recovering elemental sulfur as an acid solution according to any one of claims 1 to 3, characterized in that: and a second concentration unit (700) which is used for concentrating the product in the acid chamber of the bipolar membrane unit (310) and inputting the concentrated product water into the alkali chamber and the acid chamber of the bipolar membrane unit (310).
8. A desulfurization method for recovering elemental sulfur into an acid solution, comprising using the desulfurization apparatus for recovering elemental sulfur into an acid solution according to any one of claims 1 to 7; when the system is started, an alkaline absorbent is added into the desulfurization unit to serve as an initial absorbent, and when the system is operated, circulating liquid consisting of reaction liquid discharged by the desulfurization unit with partial backflow, alkali liquid generated by an alkali chamber of the bipolar membrane unit (310) and electrolyzed liquid generated by a salt chamber serves as new absorbent.
9. The desulfurization method for recovering elemental sulfur as claimed in claim 8, wherein: the alkaline absorbent is selected from any of alkali metal hydroxide solution, alkaline earth metal hydroxide solution, alkali metal carbonic acid reaction liquid and alkaline earth metal carbonic acid reaction liquid; and/or the pH value of the circulating liquid is 5-8.
10. The desulfurization method for recovering elemental sulfur as claimed in claim 8, wherein: inputting oxygen supplement gas serving as an oxidant into the desulfurization unit, wherein the oxygen supplement gas is preferably air and/or oxygen; and/or oxidizing the tetravalent sulfur in the reaction liquid by adopting any several of hydrogen peroxide, ozone, sodium peroxide and sodium persulfate.
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Cited By (2)
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| CN112933907A (en) * | 2021-02-08 | 2021-06-11 | 上海交通大学 | System and method for wet absorption, regeneration and recovery of sulfur dioxide |
| CN113144660A (en) * | 2021-02-05 | 2021-07-23 | 成都思达能环保设备有限公司 | Crystallization method and system |
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