CN111470476A - Method for recycling and recovering sulfur from regenerated sulfur-containing tail gas subjected to active coke dry method flue gas treatment - Google Patents
Method for recycling and recovering sulfur from regenerated sulfur-containing tail gas subjected to active coke dry method flue gas treatment Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 171
- 239000011593 sulfur Substances 0.000 title claims abstract description 171
- 239000007789 gas Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000000571 coke Substances 0.000 title claims abstract description 38
- 239000003546 flue gas Substances 0.000 title claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 116
- 239000007788 liquid Substances 0.000 claims description 68
- 229910052742 iron Inorganic materials 0.000 claims description 58
- 238000010521 absorption reaction Methods 0.000 claims description 54
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 45
- 230000003647 oxidation Effects 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- 238000006477 desulfuration reaction Methods 0.000 claims description 32
- 230000023556 desulfurization Effects 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 25
- 230000008929 regeneration Effects 0.000 claims description 20
- 238000011069 regeneration method Methods 0.000 claims description 20
- 230000005587 bubbling Effects 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- 239000000428 dust Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 238000010309 melting process Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 6
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 abstract description 6
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 abstract description 6
- 239000000779 smoke Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 239000012071 phase Substances 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
- C01B17/0491—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with hydrogen or hydrogen-containing mixtures, e.g. synthesis gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0221—Melting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0232—Purification, e.g. degassing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/05—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by wet processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a method for recycling and recovering sulfur from regenerated sulfur-containing tail gas subjected to active coke dry-method flue gas treatment. The method of the invention utilizes the temperature of the sulfur-containing tail gas regenerated by the active coke of 300-; the complex iron-sulfur recovery technology is adopted to absorb the byproduct hydrogen sulfide in the hydrogenation process, qualified sulfur is produced by combining with sulfur melting, and the sulfur concentration of the discharged tail gas is reduced to 10mg/Nm3The following; the process of recycling and recovering the sulfur by resource utilization of the tail gas containing the sulfur generated by treatment of the active coke smoke has no discharge of three wastes, and has quite good effectEnvironmental protection benefit.
Description
Technical Field
The invention belongs to the technical field of flue gas treatment, and particularly relates to a method for recycling sulfur-containing tail gas by resource utilization in flue gas treatment by an active coke dry method.
Background
China is a country with abundant coal resources, and is also the largest coal producing country and consuming country in the world; the coal is directly combusted, the total amount of the coal is more than 80 percent, a large amount of coal is combusted to generate a large amount of pollutants such as sulfur dioxide, the emission amount of the sulfur dioxide is the first in the world, huge losses are caused to national economy and people property, and a large amount of sulfur resources in China are lost. The flue gas desulfurization technology is the most effective measure for treating the environmental pollution in China at present. Flue gas desulfurization is the current SO control of coal-fired boilers2Effective routes to emissions can be broadly divided into two categories, wet desulfurization processes and dry processes. Although the wet process has absolute advantages in the existing industrial device, the wet process has the defects that secondary pollution is easily caused due to the limitation of the use of the generated by-products due to large water consumption in the process, the flue gas after desulfurization is low in temperature and cannot be discharged by self, the equipment is large, the occupied area is large, and the matching with the existing industrial boiler is difficult. The active coke-drying technique is a mature treatment process for industrial flue gas pollution, although the cost is low and the operation is easyThe cost is high, but the comprehensive environmental protection effect is superior to that of the traditional wet desulphurization process, especially synchronous denitration, desulphurization, dust removal and whitening, and zero discharge of wastewater. The dry desulfurization process generally consists of two steps of desulfurization and regeneration. The regeneration may be carried out in a reducing or inert atmosphere, with sulfur in SO2Discharged, and therefore has a higher concentration of SO in an oxygen-free atmosphere2Is an important issue. At present, high concentration of SO2Three products can be generally produced: liquid SO2Sulfuric acid and sulfur. Adding SO2The reduction into sulfur is simple in process, so that the solid sulfur product is easy to process, store and transport, can meet the requirements of different industries on sulfur, and shows strong industrial application prospects. Most active coke dry method devices in China are matched with a byproduct (sulfuric acid) production system, sulfuric acid is used as a terminal byproduct, but the sulfuric acid production process is a high-risk link, and the sulfuric acid is also a dangerous chemical. In many urban regions, the construction of sulfuric acid plants is clearly forbidden in industrial policies, and meanwhile, domestic sulfuric acid production is excessive, so that if sulfur dioxide is converted into a high-purity sulfur product, the large-scale application of an active coke dry flue gas treatment technology is facilitated.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for recycling the sulfur from the regenerated sulfur-containing tail gas, which ensures that sulfur dioxide in the regenerated tail gas is completely converted into sulfur and is used for active coke dry method flue gas treatment.
In order to realize the aim, the method for recycling the sulfur-containing tail gas by resource utilization of the active coke dry method flue gas treatment comprises the following specific processes:
1) pretreatment of regenerated sulfur-containing tail gas
Regenerating sulfur-containing tail gas for dedusting;
2) hydrotreating of regenerated sulfur-containing tail gas
Mixing the regenerated sulfur-containing tail gas subjected to dust removal with hydrogen, feeding the mixture into a hydrogenation reactor 2 for reaction, cooling the reaction product, feeding the reaction product into a liquid separation tank, and separating out free water;
3) complex iron absorption oxidation of regenerated sulfur-containing tail gas after hydrogenation
The regenerated sulfur-containing tail gas after hydrogenation is subjected to heat exchange and temperature reduction and then enters a liquid separation tank to separate out free water, a gas phase part is introduced into an absorption compartment of a complex iron absorption oxidation reactor to carry out bubbling absorption, the regenerated sulfur-containing tail gas after desulfurization is subjected to liquid separation and then is directly discharged, air is introduced into a regeneration compartment to carry out bubbling regeneration, each bubbling compartment is separated by a descending compartment, a complex iron absorption solution flows into an adjacent bubbling compartment from one bubbling compartment through the descending compartment, and a sulfur concentrated part, namely sulfur slurry, is arranged at the bottom of a cone of the complex iron absorption oxidation reactor;
4) sulphur separation and refining
Pumping sulfur slurry from the bottom of the complex iron absorption oxidation reactor into a filter, returning filtrate to the complex iron absorption oxidation reactor, feeding filtered sulfur paste into a sulfur melting kettle, taking liquid sulfur in the sulfur melting process as product sulfur, and cooling clear liquid generated in the sulfur melting process by a clear liquid heat exchanger and then returning to the complex iron absorption oxidation reactor.
Further, in the step 1), the concentration of sulfur dioxide in the regenerated sulfur-containing tail gas is 5-40% v.
Further, in the step 2), the reaction temperature is controlled at 400 ℃ and the total proportion H of the hydrogenation reaction is controlled at 240-2:SO2The molar ratio is 2.1:1-3: 1.
Further, in the step 2), 1-4 layers of filling are arranged according to the concentration of sulfur dioxide in the catalyst filling in the hydrogenation reaction process; after the hydrogenation of the material of each catalyst bed layer at the last section, the reactant is led out to be subjected to heat exchange separation to obtain liquid sulfur, then the liquid sulfur is further subjected to heat exchange separation to enter the next section of catalyst bed layer for hydrogenation, and the liquid sulfur separated twice enters a liquid sulfur storage tank; and after the final-stage catalyst bed layer is hydrogenated, cooling to 180-200 ℃, further performing heat exchange on the separated liquid sulfur, cooling to 70-80 ℃, and separating out free water in a liquid separation tank.
Further, in the step 4), the complex iron desulfurization solution in the complex iron absorption oxidation reactor is a weakly alkaline aqueous solution containing organic chelated iron.
Compared with the prior art, the invention has the following advantages: the method utilizes the temperature of the active coke for regenerating the sulfur-containing tail gas of 300-400 ℃ and hydrogenThe special grade sulfur is produced by the sectional mixing hydrogenation, the yield of the sulfur is 85-97 percent, and the economic benefit is good; the complex iron-sulfur recovery technology is adopted to absorb the byproduct hydrogen sulfide in the hydrogenation process, qualified sulfur is produced by combining with sulfur melting, and the sulfur concentration of the discharged tail gas is reduced to 10mg/Nm3The following; the process of recycling and recovering the sulfur from the active coke flue gas treatment and regeneration sulfur-containing tail gas has no discharge of three wastes, and has quite good environmental protection benefit.
Drawings
FIG. 1 is a schematic flow chart of a method for recycling sulfur from regenerated sulfur-containing tail gas subjected to active coke dry flue gas treatment.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
The method aims at the problem of recycling the regenerated sulfur dioxide in the dry-process flue gas treatment of the active coke (also called active carbon), converts the sulfur dioxide into sulfur by the hydrogenation of the sulfur dioxide, and converts the byproduct hydrogen sulfide generated in the hydrogenation into the sulfur by the iron complexing technology, thereby ensuring that the sulfur dioxide in the regenerated sulfur-containing tail gas is completely converted into the sulfur and the three wastes are not discharged in the process.
The activated coke method (also called activated carbon method) is a dry desulfurization process, and SO is absorbed by the activated coke2And NOXPhysical and chemical adsorption is carried out, thereby achieving the effects of desulfurization and denitrification. When the activated coke adsorption purification device is used for desulfurization and denitrification of flue gas, the heat energy in the flue gas can be firstly recovered by using a waste heat boiler, and the flue gas is cooled and then is introduced into the activated coke adsorption purification device. The principle of the desulfurization and denitrification treatment process is as follows: under the action of catalyst, SO in flue gas in the desulfurization and denitrification purification tower2、O2、H2O molecules are captured by the active coke and generate sulfuric acid, NO in the flue gasXAt NH3React under reduction to generate nontoxic and pollution-free N2And H2And O, purifying and discharging the coke oven smoke qualified. Desorbing and regenerating the active coke adsorbed with the sulfuric acid in a regeneration tower at a certain temperature, namely, reacting the sulfuric acid with C in the regeneration tower to generate SO2And H2O and CO2And the regenerated active coke is recycled. The tail gas obtained by regeneration and desorption mainly comprises sulfur dioxide, carbon dioxide and water, and part of nitrogen, wherein the sulfur dioxide is converted into a sulfur product by resource utilization, and the economic benefit and the environmental protection benefit of the active coke flue gas treatment technology are greatly improved.
As shown in fig. 1, the method for recycling sulfur from regenerated sulfur-containing tail gas in active coke dry method flue gas treatment comprises a pretreatment process of the regenerated sulfur-containing tail gas, a tail gas hydrogenation process, a tail gas complex iron absorption oxidation process after hydrogenation, a sulfur slurry filtration process and a sulfur melting process;
the method comprises the following specific processes:
1) pretreatment of regenerated sulfur-containing tail gas
The regenerated sulfur-containing tail gas at 300-400 ℃ from the treatment of active coke (or active carbon) flue gas (desulfurization or desulfurization and denitrification) enters a dust remover 1 for dust removal, and dust carried in the regenerated sulfur-containing tail gas is captured; wherein the concentration of sulfur dioxide in the regenerated sulfur-containing tail gas is 5-40% v;
2) hydrotreating of regenerated sulfur-containing tail gas
Mixing the regenerated sulfur-containing tail gas after dust removal with hydrogen gas, feeding the mixture into a hydrogenation reactor 2, controlling the reaction temperature at 240-400 ℃, and controlling the total proportion H of hydrogenation reaction2:SO2The molar ratio is 2.1:1-3: 1;
wherein: in the hydrogenation reaction process, 1-4 layers of filling are arranged according to the concentration of sulfur dioxide, namely 1-4 sections of catalyst bed layers are arranged in the hydrogenation reactor 2; after the hydrogenation of the material of each catalyst bed layer at the last section, the reactant is led out to be subjected to heat exchange separation to obtain liquid sulfur, then the liquid sulfur is further subjected to heat exchange separation to enter the next section of catalyst bed layer for hydrogenation, and the liquid sulfur separated twice enters a liquid sulfur storage tank; after hydrogenation of the catalyst bed layer at the last stage, cooling to 180-200 ℃, further heat exchanging and cooling the separated liquid sulfur to 70-80 ℃, and then entering a liquid separation tank 3 to separate out the free water therein;
3) complex iron absorption oxidation of regenerated sulfur-containing tail gas after hydrogenation
Further exchanging heat and cooling the hydrogenated regenerated sulfur-containing tail gas to 70-80 ℃, allowing the cooled regenerated sulfur-containing tail gas to enter a liquid separation tank 3 to separate out free water in the regenerated sulfur-containing tail gas, introducing a gas phase part into an absorption compartment of a complex iron absorption oxidation reactor 4 for bubbling absorption, separating the desulfurized regenerated sulfur-containing tail gas and then directly discharging the desulfurized regenerated sulfur-containing tail gas, introducing air into the regeneration compartment for bubbling, separating each bubbling compartment by adopting a descending compartment, allowing a complex iron absorption solution to flow into adjacent bubbling compartments from one bubbling compartment through the descending compartment, and allowing a sulfur concentrated part, namely sulfur slurry, to be arranged at the bottom of a cone of the complex iron absorption oxidation reactor;
4) sulphur separation and refining
Pumping sulfur slurry from the bottom of the complex iron absorption oxidation reactor 4 and pumping the sulfur slurry into a filter 5, returning filtrate to the complex iron absorption oxidation reactor 4, feeding filtered sulfur paste into a sulfur melting kettle 6, taking liquid sulfur in the sulfur melting process as product sulfur, and returning clear liquid generated in the sulfur melting process to the complex iron absorption oxidation reactor 4 after cooling through a clear liquid heat exchanger. Wherein, the complex iron desulfurization solution in the complex iron absorption oxidation reactor 4 is a weak alkaline aqueous solution containing organic chelate iron.
The method has the advantages that the conversion rate of sulfur dioxide after hydrogenation of the regenerated sulfur-containing tail gas is 100 percent, the yield of sulfur is 85-97 percent, and the sulfide in the gas phase after hydrogenation of the regenerated sulfur-containing tail gas only contains hydrogen sulfide before the gas phase is cooled, separated and enters a complex iron absorption oxidation reactor.
The method of the invention utilizes the temperature of the sulfur-containing tail gas regenerated by the active coke of 300-; the complex iron-sulfur recovery technology is adopted to absorb the byproduct hydrogen sulfide in the hydrogenation process, qualified sulfur is produced by combining with sulfur melting, and the sulfur concentration of the discharged tail gas is reduced to 10mg/Nm3The following; the process of recycling and recovering the sulfur from the active coke flue gas treatment and regeneration sulfur-containing tail gas has no discharge of three wastes, and has quite good environmental protection benefit.
Example 1
When the active coke desulfurization device is heated to 400 ℃ in the regeneration process, the desorbed tail gas has the temperature of 400 ℃ and the pressure of 0.2MPa, and the components of the regenerated tail gas are shown in the table.
Tail gas desorbed from an active coke dry method desulfurization device at high temperature firstly enters a warm dust collector 1 to capture dust carried in the warm dust collector, then the tail gas at 400 ℃ and hydrogen are mixed in four sections and enter a hydrogenation reactor 2, and the total proportion H of hydrogenation reaction2:SO2The molar ratio is 2.1:1, the first-stage control temperature of the hydrogenation reaction is 400 ℃ in 300-; after four-stage hydrogenation, the temperature is further reduced to 80 ℃, the mixture enters a liquid separation tank 3 to separate free water in the mixture, then the mixture enters a complex iron absorption oxidation reactor 4, a complex iron absorption solution in an absorption compartment is in gas-liquid contact with tail gas containing hydrogen sulfide, gas-phase hydrogen sulfide enters a liquid phase to be converted into sulfur, the desulfurized tail gas is mixed with regenerated waste air and then is directly discharged, complex iron is converted into complex ferrous iron, desulfurized liquid containing sulfur enters a regeneration compartment, blown air is in gas-liquid contact with the desulfurized liquid, oxygen in the air oxidizes the complex ferrous iron to be converted into complex iron, sulfur particles grow continuously and fall to the bottom of a cone of the complex iron absorption oxidation reactor under the action of gravity, and the regenerated desulfurized liquid is pushed by the blown air to circulate to the absorption compartment for repeated use. Pumping the sulfur slurry at the bottom of the cone of the complexing iron absorption oxidation reactor 4 to a filter 5 for liquid-solid separation, returning the filtrate to the complexing iron absorption oxidation reactor 4, feeding the filtered sulfur paste into a sulfur melting kettle 6, returning the clear liquid of the sulfur melting kettle 6 to the complexing iron absorption oxidation reactor 4, and feeding the liquid sulfur discharged from the sulfur melting kettle 6 into a complexing iron liquid sulfur storage tank. The recovery rate of the tail gas hydrogenation liquid sulfur is 97 percent (excellent sulfur), and the recovery rate of the complex iron sulfur is 3 percent (qualified sulfur).
Example 2
When the active coke desulfurization device is heated to 400 ℃ in the regeneration process, the desorbed tail gas has the temperature of 400 ℃ and the pressure of 0.2MPa, and the components of the regenerated tail gas are shown in the table.
Tail gas desorbed from an active coke dry method desulfurization device at high temperature firstly enters a dust remover 1 to capture dust carried in the tail gas, then the tail gas with the temperature of 400 ℃ and hydrogen are mixed in three sections and enter a hydrogenation reactor 2, and the total proportion H of hydrogenation reaction2:SO2The molar ratio is 2.2:1, the first-stage control temperature of the hydrogenation reaction is 400 ℃ in 350-; after the tertiary hydrogenation, the temperature is further reduced to 80 ℃, the mixture enters a liquid separation tank 3 to separate free water in the mixture, then the mixture enters a complex iron absorption oxidation reactor 4, a complex iron absorption solution in an absorption compartment is in gas-liquid contact with tail gas containing hydrogen sulfide, gas-phase hydrogen sulfide enters a liquid phase to be converted into sulfur, the tail gas after desulfurization is mixed with regeneration waste air and then is directly discharged, complex iron is converted into complex ferrous iron, desulfurization liquid containing sulfur enters a regeneration compartment, blown air is in gas-liquid contact with the desulfurization liquid, oxygen in the air oxidizes the complex ferrous iron to be converted into complex iron, sulfur particles grow up continuously and fall to the bottom of a cone of the complex iron absorption oxidation reactor under the action of gravity, and the regenerated desulfurization liquid is circulated to the absorption compartment to be repeatedly used under the promotion of blown air. Pumping the sulfur slurry at the bottom of the cone to a filter 5 for liquid-solid separation, returning the filtrate to the complex iron absorption oxidation reactor 4, feeding the filtered sulfur paste into a sulfur melting kettle 6, returning the clear liquid of the sulfur melting kettle 6 to the complex iron absorption oxidation reactor 4, and feeding the liquid sulfur discharged from the sulfur melting kettle 6 into a complex iron liquid sulfur storage tank. The recovery rate of the tail gas hydrogenation liquid sulfur is 95 percent (superior sulfur), and the recovery rate of the complex iron sulfur is 5 percent (qualified sulfur).
Example 3
The tail gas desorbed from a certain active coke flue gas desulfurization and denitrification device is heated to 300 ℃ in the regeneration process, the temperature of the tail gas is 300 ℃, the pressure is 0.2Mpa, and the components of the regenerated tail gas are shown in the table.
Tail gas desorbed from an active coke dry method desulfurization device at high temperature firstly enters a dust remover 1 to capture dust carried in the tail gas, then the tail gas at 300 ℃ is mixed with hydrogen to enter a hydrogenation reactor 2, and the total proportion H of hydrogenation reaction2:SO2The molar ratio is 3:1, a first-stage bed layer is adopted for hydrogenation, the temperature of a hydrogenation reactor is controlled at 300 ℃ for hydrogenation, heat exchange is carried out to 180 ℃ after hydrogenation, and separated liquid enters a liquid sulfur storage tank; the hydrogenation tail gas is further cooled to 80 ℃ after separating out liquid sulfur, the hydrogenation tail gas enters a liquid separation tank 3 to separate out free water in the hydrogenation tail gas, then the hydrogenation tail gas enters a complex iron absorption oxidation reactor 4, a complex iron absorption solution in an absorption compartment is in gas-liquid contact with tail gas containing hydrogen sulfide, gas-phase hydrogen sulfide enters a liquid phase to be converted into sulfur, the tail gas after desulfurization is mixed with regeneration waste air and then is directly discharged, complex iron is converted into complex ferrous iron, desulfurization liquid containing sulfur enters a regeneration compartment, blown air is in gas-liquid contact with the desulfurization liquid, oxygen in the air oxidizes the complex ferrous iron to be converted into complex iron, sulfur particles continuously grow up and fall to the bottom of a cone of the complex iron absorption oxidation reactor under the action of gravity, and the regenerated desulfurization liquid is circulated to the absorption compartment under the pushing of the blown air to be repeatedly used. Pumping the sulfur slurry at the bottom of the cone to a filter 5 for liquid-solid separation, returning the filtrate to the complex iron absorption oxidation reactor 4, feeding the filtered sulfur paste into a sulfur melting kettle 6, returning the clear liquid of the sulfur melting kettle 6 to the complex iron absorption oxidation reactor 4, and feeding the liquid sulfur discharged from the sulfur melting kettle 6 into a complex iron liquid sulfur storage tank. The recovery rate of the tail gas hydrogenation liquid sulfur is 85 percent (superior sulfur), and the recovery rate of the complex iron sulfur is 15 percent (qualified sulfur).
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (5)
1. A method for recycling and recovering sulfur from regenerated sulfur-containing tail gas subjected to active coke dry method flue gas treatment is characterized by comprising the following steps of: the method comprises the following specific processes:
1) pretreatment of regenerated sulfur-containing tail gas
Regenerating sulfur-containing tail gas for dedusting;
2) hydrotreating of regenerated sulfur-containing tail gas
Mixing the regenerated sulfur-containing tail gas subjected to dust removal with hydrogen, feeding the mixture into a hydrogenation reactor for reaction, cooling the mixture, feeding the cooled mixture into a liquid separation tank, and separating out free water;
3) complex iron absorption oxidation of regenerated sulfur-containing tail gas after hydrogenation
The regenerated sulfur-containing tail gas after hydrogenation is subjected to heat exchange and temperature reduction and then enters a liquid separation tank to separate out free water, a gas phase part is introduced into an absorption compartment of a complex iron absorption oxidation reactor to carry out bubbling absorption, the regenerated sulfur-containing tail gas after desulfurization is subjected to liquid separation and then is directly discharged, air is introduced into a regeneration compartment to carry out bubbling regeneration, each bubbling compartment is separated by a descending compartment, a complex iron absorption solution flows into an adjacent bubbling compartment from one bubbling compartment through the descending compartment, and a sulfur concentrated part, namely sulfur slurry, is arranged at the bottom of a cone of the complex iron absorption oxidation reactor;
4) sulphur separation and refining
Pumping sulfur slurry from the bottom of the complex iron absorption oxidation reactor into a filter, returning filtrate to the complex iron absorption oxidation reactor, feeding filtered sulfur paste into a sulfur melting kettle, taking liquid sulfur in the sulfur melting process as product sulfur, and cooling clear liquid generated in the sulfur melting process by a clear liquid heat exchanger and then returning to the complex iron absorption oxidation reactor.
2. The method for recycling sulfur-containing tail gas from active coke dry method flue gas treatment according to claim 1, which is characterized by comprising the following steps: in the step 1), the concentration of sulfur dioxide in the regenerated sulfur-containing tail gas is 5-40% v.
3. The method for recycling sulfur-containing tail gas from active coke dry method flue gas treatment according to claim 1, which is characterized by comprising the following steps: in the step 2), the reaction temperature is controlled at 240-400 ℃, and the total proportion H of the hydrogenation reaction2:SO2The molar ratio is 2.1:1-3: 1.
4. The method for recycling sulfur-containing tail gas from active coke dry method flue gas treatment according to claim 1, which is characterized by comprising the following steps: in the step 2), 1-4 layers of filling are arranged according to the concentration of sulfur dioxide in the catalyst filling in the hydrogenation reaction process; after the hydrogenation of the material of each catalyst bed layer at the last section, the reactant is led out to be subjected to heat exchange separation to obtain liquid sulfur, then the liquid sulfur is further subjected to heat exchange separation to enter the next section of catalyst bed layer for hydrogenation, and the liquid sulfur separated twice enters a liquid sulfur storage tank; and after the final-stage catalyst bed layer is hydrogenated, cooling to 180-200 ℃, further performing heat exchange on the separated liquid sulfur, cooling to 70-80 ℃, and separating out free water in a liquid separation tank.
5. The method for recycling sulfur-containing tail gas from active coke dry method flue gas treatment according to claim 1, which is characterized by comprising the following steps: in the step 4), the complex iron desulfurization solution in the complex iron absorption oxidation reactor is a weakly alkaline aqueous solution containing organic chelated iron.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010096A (en) * | 2022-07-01 | 2022-09-06 | 武汉国力通能源环保股份有限公司 | Method for recycling high-quality sulfur from sulfur slag |
| WO2023093858A1 (en) * | 2021-11-29 | 2023-06-01 | 山东大学 | Integrated device and method for preparing sulfur by active coke regeneration and synergistic reduction |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1257096A (en) * | 1968-08-13 | 1971-12-15 | ||
| CN1435273A (en) * | 2002-01-29 | 2003-08-13 | 国家电站燃烧工程技术研究中心 | Cyclic fluidized bed active coke desulfurating and sulfur reutilization method |
| CN103318846A (en) * | 2013-06-21 | 2013-09-25 | 邵志辉 | Method for obtaining sulfur from sulfur compounds in coal chemical plant and electric power plant |
| CN103495333A (en) * | 2013-10-11 | 2014-01-08 | 陕西延长石油（集团）有限责任公司炼化公司 | Treatment technology for Claus tail gas containing sulfur dioxide, hydrogen sulfide and organic sulfur |
| CN104787730A (en) * | 2015-03-31 | 2015-07-22 | 武汉国力通能源环保有限公司 | System and method for reducing sulfur dioxide emission concentration of sulfur recovery device and desulfurization agent |
| CN108178131A (en) * | 2017-12-29 | 2018-06-19 | 山东大学 | Utilize SO in active coke desulphurizing regeneration gas2The fluidized bed plant and method of Recovered sulphur |
| CN208413852U (en) * | 2018-07-17 | 2019-01-22 | 西安赫立盖斯新能源科技有限公司 | A kind of complex iron reduction sulfur recovery facility |
-
2020
- 2020-03-31 CN CN202010246618.1A patent/CN111470476A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1257096A (en) * | 1968-08-13 | 1971-12-15 | ||
| CN1435273A (en) * | 2002-01-29 | 2003-08-13 | 国家电站燃烧工程技术研究中心 | Cyclic fluidized bed active coke desulfurating and sulfur reutilization method |
| CN103318846A (en) * | 2013-06-21 | 2013-09-25 | 邵志辉 | Method for obtaining sulfur from sulfur compounds in coal chemical plant and electric power plant |
| CN103495333A (en) * | 2013-10-11 | 2014-01-08 | 陕西延长石油（集团）有限责任公司炼化公司 | Treatment technology for Claus tail gas containing sulfur dioxide, hydrogen sulfide and organic sulfur |
| CN104787730A (en) * | 2015-03-31 | 2015-07-22 | 武汉国力通能源环保有限公司 | System and method for reducing sulfur dioxide emission concentration of sulfur recovery device and desulfurization agent |
| CN108178131A (en) * | 2017-12-29 | 2018-06-19 | 山东大学 | Utilize SO in active coke desulphurizing regeneration gas2The fluidized bed plant and method of Recovered sulphur |
| CN208413852U (en) * | 2018-07-17 | 2019-01-22 | 西安赫立盖斯新能源科技有限公司 | A kind of complex iron reduction sulfur recovery facility |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023093858A1 (en) * | 2021-11-29 | 2023-06-01 | 山东大学 | Integrated device and method for preparing sulfur by active coke regeneration and synergistic reduction |
| CN115010096A (en) * | 2022-07-01 | 2022-09-06 | 武汉国力通能源环保股份有限公司 | Method for recycling high-quality sulfur from sulfur slag |
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