CN114082298A - Energy-saving and difficult-to-block hydrogen sulfide deep removal tower and use method thereof - Google Patents
Energy-saving and difficult-to-block hydrogen sulfide deep removal tower and use method thereof Download PDFInfo
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- CN114082298A CN114082298A CN202111312515.1A CN202111312515A CN114082298A CN 114082298 A CN114082298 A CN 114082298A CN 202111312515 A CN202111312515 A CN 202111312515A CN 114082298 A CN114082298 A CN 114082298A
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002912 waste gas Substances 0.000 claims abstract description 49
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 30
- 230000001590 oxidative effect Effects 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 89
- 229910052717 sulfur Inorganic materials 0.000 claims description 33
- 239000011593 sulfur Substances 0.000 claims description 33
- 239000007853 buffer solution Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000007800 oxidant agent Substances 0.000 claims description 19
- 238000012856 packing Methods 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 15
- 238000005188 flotation Methods 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 12
- 239000013589 supplement Substances 0.000 claims description 12
- 238000003795 desorption Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 206010003497 Asphyxia Diseases 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to the technical field of chemical or biological purification of waste gas, and discloses an energy-saving hydrogen sulfide deep removal tower which is not easy to block and a using method thereof, wherein the waste gas subjected to low-temperature methanol washing is subjected to deep hydrogen sulfide removal in a mode of oxidizing hydrogen sulfide into elemental sulfur, the redox reaction is not limited by Henry's law, and the removal effect is improved without causing abrupt improvement of energy consumption, so that a low-temperature methanol washing device only needs to reduce the hydrogen sulfide in the waste gas to 10-20ppm, thereby greatly reducing the liquid-gas ratio required by an absorption tower in the low-temperature methanol washing device, and further obviously reducing the energy consumption of the whole device; in the invention, the inventor finds that if a certain part in the tower is intensively reacted, the elemental sulfur generated by oxidation at the certain part is easy to cause blockage, and a series of means are adopted to avoid the concentrated reaction of each area in the tower, thereby ensuring that the blockage does not occur in the tower.
Description
Technical Field
The invention relates to the technical field of chemical or biological purification of waste gas, in particular to an energy-saving hydrogen sulfide deep removal tower which is not easy to block and a using method thereof.
Background
Hydrogen sulfide (H)2S) is a colorless, inflammable and toxic gas with the odor of a smelly egg, the olfactory threshold is extremely low, and the concentration of a few ppm of hydrogen sulfide in the environment can be sensed by people and causes uncomfortable reaction of people. The hydrogen sulfide has great harm to human bodies, low-concentration hydrogen sulfide can cause fever, dizziness and dyspnea, and high-concentration hydrogen sulfide can cause asphyxia. Industrially, the acidic and corrosive nature of hydrogen sulfide can cause severe corrosion of equipment and piping. Therefore, the requirements of the environmental protection department on the content of hydrogen sulfide in the discharged waste gas are very strict at present, and the concentration of the hydrogen sulfide is not higher than 1 ppm.
The demand for removing hydrogen sulfide exists in various occasions such as ammonia synthesis, methanol synthesis and other carbonyl synthesis, hydrogen production, city gas and natural gas desulfurization, and the most common hydrogen sulfide removing means at present is a low-temperature methanol washing process which adopts methanol at minus 50 ℃ as an absorbent to physically absorb hydrogen sulfide.
However, the low-temperature methanol washing process has certain problems, and the biggest problem is energy consumption. Since the low-temperature methanol washing process is a physical absorption process, it can be known from henry's law that if the concentration of hydrogen sulfide in a gas phase needs to be reduced to be low enough, the liquid-gas ratio required in an absorption tower will be increased rapidly, so that the energy consumption of a circulating pump of the absorption tower and the energy consumption of a desorption tower are increased rapidly, and the energy consumption of refrigeration and preheating between the desorption tower and the absorption tower is increased rapidly due to the large temperature difference between the desorption tower and the absorption tower. In practical operation, we find that it is economical to reduce the hydrogen sulfide in the waste gas to 10-20ppm by using the low-temperature methanol washing process, and if the hydrogen sulfide concentration in the waste gas is continuously reduced to below 1ppm by using the low-temperature methanol washing process, the energy consumption of the whole device is increased by one order of magnitude.
Disclosure of Invention
The invention provides an energy-saving hydrogen sulfide deep removal tower not easy to block and a using method thereof.
The technical problem to be solved is that: the low-temperature methanol washing process is a physical absorption process and is limited by Henry's law, and the energy consumption is rapidly increased when the content of hydrogen sulfide in the waste gas is reduced to below 1 ppm.
In order to solve the technical problems, the invention adopts the following technical scheme: an energy-saving hydrogen sulfide deep removal tower which is not easy to block adopts a mode of oxidizing hydrogen sulfide into elemental sulfur to carry out deep hydrogen sulfide removal on waste gas washed by low-temperature methanol, the waste gas to be treated and air with an oxidizing effect enter from the bottom of a tower and are discharged from the top of the tower, and the waste gas and the air are in countercurrent contact with a buffer solution containing a catalyst in the tower; the desorption tower comprises a Venturi rod layer and a plurality of packing layers which are arranged in the tower at intervals from bottom to top, a waste gas bubbler used for introducing waste gas to be treated into the kettle liquid, an air bubbler used for introducing air into the kettle liquid, a main circulating pump with a liquid inlet pipe communicated with the kettle liquid and a liquid outlet pipe communicated with the upper part of the packing layer at the topmost layer, a buffer solution storage tank with an outlet communicated with the liquid inlet pipe of the main circulating pump along a dosing pump, an emergency oxidant storage tank with an outlet communicated with the liquid inlet pipe of the main circulating pump along the dosing pump, a catalyst solution storage tank with an outlet communicated with the liquid inlet pipe of the main circulating pump along the dosing pump, and a sulfur particle filtering system with an inlet and an outlet respectively communicated with the kettle liquid.
Further, the buffer solution is a sodium bicarbonate solution, the emergency oxidant is hydrogen peroxide or a sodium hypochlorite solution, and the catalyst solution is a sulfonated cobalt phthalocyanine solution.
Further, the waste gas bubbler is composed of a plurality of hard pipes which are respectively communicated with the air inlet pipeline and vertically inserted into the kettle liquid downwards, the lower end of each hard pipe is higher than the air bubbler, and the air bubbler is positioned at the bottom of the tower kettle.
Further, the sulfur particle filtering system comprises an air flotation machine and a sulfur foam filtering machine, wherein a liquid phase inlet and a fluid outlet of the air flotation machine are communicated with the kettle liquid, a gas phase inlet is communicated with an air inlet pipeline of the air bubbler, a foam outlet is communicated with an inlet of the sulfur foam filtering machine, and a liquid phase outlet of the sulfur foam filtering machine is communicated with a liquid phase outlet of the air flotation machine.
Furthermore, liquid distributors are arranged above and below the Venturi rod layers and above and below each packing layer, the liquid distributors are water distribution plates, and a liquid outlet pipe of the main circulating pump enters the tower through a spraying device at a position higher than the liquid distributor at the top.
Further, the desorption tower also comprises a demister which is arranged at the top in the tower and used for demisting the discharged waste gas.
Furthermore, the desorption tower also comprises a gas phase balance pipe, one end of which is communicated with the kettle liquid, and the other end of which is extended upwards and then is communicated with the gas phase of the underground emptying groove downwards.
And furthermore, the removal tower also comprises an overflow pipe, one end of the overflow pipe is communicated between the Venturi rod layer and the packing layer at the bottommost layer, the other end of the overflow pipe extends upwards and then is inserted downwards into the position below the liquid level of the underground emptying tank, the highest position of the side surface of the overflow pipe is communicated with the gas phase balance pipe through a pipeline, and the lowest position of the overflow pipe is communicated with the bottom of the kettle liquid through a bottom flow pipe with a manual valve.
Further, a self-operated adjusting valve is arranged on an air inlet pipeline of the air bubbler, and the self-operated adjusting valve is arranged at a position where the air inlet pipeline is branched to be communicated with the air floatation machine and the air bubbler.
The application method of the energy-saving and difficult-to-block hydrogen sulfide deep removal tower is used for removing hydrogen sulfide in waste gas, and comprises the following steps:
the method comprises the following steps: injecting a buffer solution containing a catalyst into the tower kettle, and starting a main circulating pump to enable the buffer solution to fully infiltrate the filler layer and the venturi rod layer; then continuously blowing air along the air bubbler to dissolve oxygen in the kettle liquid;
step two: blowing the waste gas along a waste gas bubbler;
step three: mixing waste gas and air, passing through the kettle liquid, Venturi rod layer and filler layer in sequence, making countercurrent contact with buffer solution containing catalyst, catalytic oxidizing in the buffer solution, and removing fog;
step four: after sulfur particles appear in the kettle liquid, starting an air flotation machine and a sulfur foam filter to concentrate, enrich, separate and recover the sulfur particles in the kettle liquid;
step five: during the operation of the system, the following maintenance work is carried out:
monitoring the concentration of hydrogen sulfide at the outlet of the removal tower, adding an emergency oxidant as an auxiliary oxidation means to strengthen the oxidation of the hydrogen sulfide once the content of the hydrogen sulfide in the outlet gas is monitored to exceed the standard, and adding the emergency oxidant intermittently in a single excessive way;
washing the demister regularly by process water or compressed air, and increasing the washing frequency when the differential pressure of the demister exceeds 100 Pa;
and monitoring the liquid level and the pH value of the kettle liquid, and maintaining the liquid level and the pH value of the kettle liquid to be stable by means including buffer solution supplement, process water supplement, emergency oxidant supplement, catalyst solution supplement and partial kettle liquid discharge.
Compared with the prior art, the energy-saving hydrogen sulfide deep removal tower not easy to block and the use method thereof have the following beneficial effects:
according to the invention, the waste gas subjected to low-temperature methanol washing is subjected to deep hydrogen sulfide removal by oxidizing hydrogen sulfide into elemental sulfur, the redox reaction is not limited by Henry's law, and the removal effect is improved without causing abrupt improvement of energy consumption, so that the low-temperature methanol washing device only needs to reduce the hydrogen sulfide in the waste gas to 10-20ppm, thus the liquid-gas ratio required by an absorption tower in the low-temperature methanol washing device is greatly reduced, and the energy consumption of the whole device is further obviously reduced;
in the invention, the inventor finds that if a certain part in the tower is intensively reacted, the elemental sulfur generated by oxidation at the certain part is easy to cause blockage, and the air bubbler is not easy to be blocked by sulfur particles generated by the concentrated reaction at the opening by making the air bubbler lower than the waste gas bubbler; the waste gas bubbler is a hard pipe, so that the waste gas bubbler is not easy to be blocked by sulfur particles generated by concentrated reaction at an opening like a conventional bubbler; the Venturi rod layer which is difficult to block and violent in turbulence is arranged below the packing layer, so that most of hydrogen sulfide in waste gas is consumed in the Venturi rod layer in advance before entering the packing layer, and meanwhile, the mode of multilayer packing and multilayer liquid distributors is adopted, uneven gas-liquid distribution in the packing layer is avoided, and the blockage in the tower is avoided.
Drawings
FIG. 1 is a schematic structural diagram of an energy-saving and difficult-to-block deep hydrogen sulfide removal tower of the present invention;
the method comprises the following steps of 11-Venturi rod layer, 12-packing layer, 21-liquid distributor, 22-waste gas bubbler, 23-air bubbler, 31-main circulating pump, 32-dosing pump, 41-buffer storage tank, 42-emergency oxidant storage tank, 43-catalyst solution storage tank, 51-air flotation machine, 52-sulfur foam filter, 6-demister, 71-underground emptying tank, 72-gas phase balance pipe, 73-overflow pipe, 74-bottom pipe and 8-kettle liquid.
Detailed Description
As shown in figure 1, the energy-saving hydrogen sulfide deep removal tower which is not easy to block adopts a mode of oxidizing hydrogen sulfide into elemental sulfur to carry out deep hydrogen sulfide removal on waste gas subjected to low-temperature methanol washing, and the waste gas to be treated and air with oxidation enter from the bottom of the tower and are discharged from the top of the tower and are in countercurrent contact with a buffer solution containing a catalyst in the tower; the desorption tower comprises a Venturi rod layer 11 and a plurality of packing layers 12 which are arranged in the tower at intervals from bottom to top, a waste gas bubbler 22 for introducing waste gas to be treated into the kettle liquid 8, an air bubbler 23 for introducing air into the kettle liquid 8, a main circulating pump 31 with a liquid inlet pipe leading to the kettle liquid 8 and a liquid outlet pipe leading to the upper part of the packing layer 12 at the topmost layer, a buffer solution storage tank 41 with an outlet leading to the liquid inlet pipe of the main circulating pump 31 along a dosing pump 32, an emergency oxidant storage tank 42 with an outlet leading to the liquid inlet pipe of the main circulating pump 31 along the dosing pump 32, a catalyst solution storage tank 43 with an outlet leading to the liquid inlet pipe of the main circulating pump 31 along the dosing pump 32, and a sulfur particle filtering system with an inlet and an outlet leading to the kettle liquid 8 respectively.
The venturi layer 11 is not only required to ensure that less hydrogen sulfide enters the packing layer 12, but also to sufficiently dissolve oxygen and hydrogen sulfide in the buffer solution by the strong turbulence of the layer. Meanwhile, because the pores are uniform and have large turbulence, the sulfur particles are difficult to grow up, and even if the sulfur particles with large particles are not blocked.
The buffer solution is sodium bicarbonate solution, and the buffer solution mainly provides a homogeneous catalytic reaction environment and cannot react with hydrogen sulfide to be consumed. The buffer is alkaline to promote the entry of hydrogen sulfide into the buffer, and potassium bicarbonate is also an option. The buffer solution should be selected from various weak dibasic acid salts of hydrogen, but the commonly used hydrogen phosphate salt is not selected, and the common hydrogen phosphate salt can become dihydrogen phosphate after long-term use, and the solution is acidic, so that hydrogen sulfide is prevented from entering the buffer solution.
The emergency oxidant is hydrogen peroxide or sodium hypochlorite solution, impurities which influence normal use of the buffer solution cannot be introduced into the buffer solution, and meanwhile, the buffer solution can stop loss in time when the content of hydrogen sulfide in the discharged waste gas exceeds the standard.
The catalyst solution is sulfonated cobalt phthalocyanine solution and is used for catalyzing the reaction of hydrogen sulfide and oxygen.
The waste gas bubbler 22 is a plurality of hard pipes which are respectively communicated with the gas inlet pipeline and vertically inserted into the kettle liquid 8 downwards so as to avoid blockage; the lower end of each hard pipe is higher than the air bubbler 23, and the air bubbler 23 is positioned at the bottom of the tower kettle, so that oxygen in the air is dissolved in the kettle liquid 8. In practical use, when the air bubbler 23 is higher than the exhaust gas bubbler 22, the opening of the air bubbler 23 is easily clogged by a large amount of sulfur particles generated by concentrated reaction.
The sulfur particle filtering system comprises an air flotation machine 51 and a sulfur foam filtering machine 52, wherein a liquid phase inlet and a fluid outlet of the air flotation machine 51 are communicated with the kettle liquid 8, a gas phase inlet is communicated with an air inlet pipeline of the air bubbler 23, a foam outlet is communicated with an inlet of the sulfur foam filtering machine 52, and a liquid phase outlet of the sulfur foam filtering machine 52 is communicated with a liquid phase outlet of the air flotation machine 51. This is a common usage and will not be described further herein.
The stripping tower also comprises a demister 6 which is arranged at the top in the tower and is used for demisting the discharged waste gas. This is a common usage and is not described in detail here as such.
The stripping column further comprises a gas phase equilibrium tube 72 in the gas phase, one end of which leads to the still liquid 8 and the other end of which extends upwards and then leads downwards to the underground sump 71, for maintaining the gas phase equilibrium between the stripping column and the sump,
the stripping column further comprises an overflow pipe 73 having one end opening between the venturi rod layer 11 and the bottom filler layer 12 and the other end extending upward and then being inserted downward into the lower part of the liquid surface of the underground evacuation tank 71, the pipe being for avoiding the liquid level of the kettle liquid 8 from being too high, and being relatively tortuous, and thus being thickened in fig. 1 to distinguish it from other pipes;
the highest position of the side surface of the overflow pipe 73 is communicated with the gas phase balance pipe 72 through a pipeline, and the highest position is matched with the inverted U-shaped overflow pipe 73 to prevent siphonage; the lowest part of the side surface of the overflow pipe 73 is communicated with the bottom of the kettle liquid 8 through an underflow pipe 74 with a manual valve. Note that neither the conduit for this connection nor the overflow 73 communicates with the conduit for the off-gas to the removal column, and the cross-over in figure 1 is marked with a special symbol.
The air intake duct of the air bubbler 23 is provided with a self-operated regulating valve, and the self-operated regulating valve is arranged at a position before the air intake duct branches to the air flotation machine 51 and the air bubbler 23.
Once the air in the stripping tower is cut off, the source of the oxidant in the tower is cut off rapidly, and the concentration of the hydrogen sulfide in the waste gas discharged from the tower exceeds the standard rapidly, so that the automatic valve on the pipeline needs to be ensured to have sufficient reliability.
The application method of the energy-saving and difficult-to-block hydrogen sulfide deep removal tower is used for removing hydrogen sulfide in waste gas, and comprises the following steps:
the method comprises the following steps: injecting a buffer solution containing a catalyst into the tower kettle, and starting a main circulating pump 31 to enable the buffer solution to fully infiltrate the filler layer 12 and the venturi rod layer 11; then, continuously blowing air along the air bubbler 23 to dissolve oxygen in the kettle liquid 8;
step two: blowing the exhaust gas along the exhaust gas bubbler 22;
step three: mixing waste gas and air, passing through the kettle liquid 8, the Venturi rod layer 11 and the filler layer 12 in sequence, making countercurrent contact with a buffer solution containing a catalyst, performing catalytic oxidation in the buffer solution, and discharging from the top of the tower after demisting;
step four: after sulfur particles appear in the kettle liquid 8, starting an air floatation machine 51 and a sulfur foam filter 52 to concentrate, enrich, separate and recover the sulfur particles in the kettle liquid 8;
step five: during the operation of the system, the following maintenance work is carried out:
monitoring the concentration of hydrogen sulfide at the outlet of the removal tower, adding an emergency oxidant as an auxiliary oxidation means to strengthen the oxidation of the hydrogen sulfide once the content of the hydrogen sulfide in the outlet gas is monitored to exceed the standard, and adding the emergency oxidant intermittently in a single excessive way;
the dosing pump 32 is a metering pump electrically connected with the DCS control system, and meanwhile, the pipeline for the waste gas to enter and exit the absorption tower is provided with a sensor for measuring the concentration of the hydrogen sulfide, and the two sensors are electrically connected with the DCS system. When the content of hydrogen sulfide in the waste gas entering the removing tower is increased or the waste gas flow is increased, a PID control mode is adopted to correspondingly increase the flow of air serving as an oxidant; meanwhile, when the content of hydrogen sulfide in the waste gas leaving the desorption tower exceeds the standard, excessive emergency oxidant is injected at one time according to the exceeding degree.
The demister 6 is flushed regularly by means of process water or compressed air, and the flushing frequency is increased when the differential pressure of the demister 6 exceeds 100 Pa.
And monitoring the liquid level and the pH value of the kettle liquid 8, and maintaining the liquid level and the pH value of the kettle liquid 8 to be stable by means including buffer solution supplement, process water supplement, emergency oxidant supplement, catalyst solution supplement and partial kettle liquid 8 discharge.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. An energy-saving hydrogen sulfide deep removal tower which is not easy to block adopts a mode of oxidizing hydrogen sulfide into elemental sulfur to carry out deep hydrogen sulfide removal on waste gas washed by low-temperature methanol, the waste gas to be treated and air with an oxidizing effect enter from the bottom of a tower and are discharged from the top of the tower, and the waste gas and the air are in countercurrent contact with a buffer solution containing a catalyst in the tower; the method is characterized in that: the device comprises a Venturi rod layer (11) and a plurality of packing layers (12) which are arranged in a tower at intervals from bottom to top, a waste gas bubbler (22) used for introducing waste gas to be treated into kettle liquid (8), an air bubbler (23) used for introducing air into the kettle liquid (8), a main circulating pump (31) which is arranged above the packing layer (12) and is communicated with the kettle liquid (8) through a liquid inlet pipe, a buffer solution storage tank (41) which is communicated with the liquid inlet pipe of the main circulating pump (31) through a dosing pump (32) through an outlet pipe, an emergency oxidant storage tank (42) which is communicated with the liquid inlet pipe of the main circulating pump (31) through the dosing pump (32) through an outlet, a catalyst solution storage tank (43) which is communicated with the liquid inlet pipe of the main circulating pump (31) through the dosing pump (32) through an outlet, and a sulfur particle filtering system which is respectively communicated with the kettle liquid (8) through an inlet and an outlet.
2. The energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 1, is characterized in that: the buffer solution is a sodium bicarbonate solution, the emergency oxidant is hydrogen peroxide or a sodium hypochlorite solution, and the catalyst solution is a sulfonated cobalt phthalocyanine solution.
3. The energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 1, is characterized in that: the waste gas bubbler (22) is composed of a plurality of hard pipes which are respectively communicated with the gas inlet pipeline and vertically inserted into the kettle liquid (8) downwards, the lower end of each hard pipe is higher than the air bubbler (23), and the air bubbler (23) is positioned at the bottom of the tower kettle.
4. The energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 1, is characterized in that: the sulfur particle filtering system comprises an air flotation machine (51) and a sulfur foam filtering machine (52), wherein a liquid phase inlet and a fluid outlet of the air flotation machine (51) are communicated with the kettle liquid (8), a gas phase inlet is communicated with an air inlet pipeline of the air bubbler (23), a foam outlet is communicated with an inlet of the sulfur foam filtering machine (52), and a liquid phase outlet of the sulfur foam filtering machine (52) is communicated with a liquid phase outlet of the air flotation machine (51).
5. The energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 1, is characterized in that: liquid distributors (21) are arranged above and below the Venturi rod layer (11) and above and below each filler layer (12), the liquid distributors (21) are water distribution plates, and liquid outlet pipes of the main circulating pump (31) enter the tower through spraying devices at positions higher than the liquid distributors (21) at the top.
6. The energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 1, is characterized in that: the desorption tower also comprises a demister (6) which is arranged at the top in the tower and is used for demisting the discharged waste gas.
7. The energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 1, is characterized in that: the stripping tower also comprises a gas phase equilibrium pipe (72) which is communicated with the kettle liquid (8) at one end and is communicated with the gas phase of the underground emptying groove (71) after the other end extends upwards.
8. The energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 7, is characterized in that: the removing tower also comprises an overflow pipe (73) with one end communicated between the Venturi rod layer (11) and the packing layer (12) at the bottommost layer and the other end upwards extended and then downwards inserted into the position below the liquid level of the underground emptying groove (71), the highest position of the side surface of the overflow pipe (73) is communicated with the gas phase balance pipe (72) through a pipeline, and the lowest position is communicated with the bottom of the kettle liquid (8) through a bottom flow pipe (74) with a manual valve.
9. The energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 4, is characterized in that: and a self-operated adjusting valve is arranged on an air inlet pipeline of the air bubbler (23), and is arranged at a position where the air inlet pipeline is branched to the air floatation machine (51) and before the air bubbler (23).
10. The use method of the energy-saving hydrogen sulfide deep removal tower which is not easy to block is characterized by comprising the following steps: the method for removing the hydrogen sulfide in the waste gas by using the energy-saving hydrogen sulfide deep removal tower which is not easy to block as claimed in claim 1, and comprises the following steps:
the method comprises the following steps: injecting a buffer solution containing a catalyst into the tower kettle, and starting a main circulating pump (31) to enable the buffer solution to fully infiltrate the filler layer (12) and the venturi rod layer (11); then continuously blowing air along the air bubbler (23) to dissolve oxygen in the kettle liquid (8);
step two: blowing the exhaust gas along an exhaust gas bubbler (22);
step three: mixing waste gas and air, passing through the kettle liquid (8), the Venturi rod layer (11) and the filler layer (12) in sequence, making countercurrent contact with a buffer solution containing a catalyst, performing catalytic oxidation in the buffer solution, and discharging from the top of the tower after demisting;
step four: after sulfur particles appear in the kettle liquid (8), starting an air flotation machine (51) and a sulfur foam filter (52) to concentrate, enrich, separate and recover the sulfur particles in the kettle liquid (8);
step five: during the operation of the system, the following maintenance work is carried out:
monitoring the concentration of hydrogen sulfide at the outlet of the removal tower, adding an emergency oxidant as an auxiliary oxidation means to strengthen the oxidation of the hydrogen sulfide once the content of the hydrogen sulfide in the outlet gas is monitored to exceed the standard, and adding the emergency oxidant intermittently in a single excessive way;
the demister (6) is flushed regularly by process water or compressed air, and the flushing frequency is increased when the differential pressure of the demister (6) exceeds 100 Pa;
and monitoring the liquid level and the pH value of the kettle liquid (8), and maintaining the liquid level and the pH value of the kettle liquid (8) stable by means including buffer solution supplement, process water supplement, emergency oxidant supplement, catalyst solution supplement and partial kettle liquid (8) discharge.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114904369A (en) * | 2022-06-28 | 2022-08-16 | 中冶京诚工程技术有限公司 | Combined packing absorption tower and flue gas purification process |
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| CN103908879A (en) * | 2014-03-14 | 2014-07-09 | 中国石油大学(北京) | Flue gas dust removal desulphurization system of double-circulation Venturi rod tower |
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