CN113117502A - Method and device for treating low-concentration organic waste gas - Google Patents
Method and device for treating low-concentration organic waste gas Download PDFInfo
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- CN113117502A CN113117502A CN201911418209.9A CN201911418209A CN113117502A CN 113117502 A CN113117502 A CN 113117502A CN 201911418209 A CN201911418209 A CN 201911418209A CN 113117502 A CN113117502 A CN 113117502A
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- 239000007789 gas Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000010815 organic waste Substances 0.000 title claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 133
- 239000007788 liquid Substances 0.000 claims abstract description 89
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- 238000011069 regeneration method Methods 0.000 claims abstract description 86
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 61
- 239000002912 waste gas Substances 0.000 claims abstract description 49
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- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 27
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- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 12
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- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 3
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- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/14—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 by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
-
- 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
- B01D53/14—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 by absorption
- B01D53/1487—Removing organic compounds
-
- 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
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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
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
Abstract
The invention relates to a method and a device for treating low-concentration organic waste gas, wherein the waste gas firstly enters a washing unit and is washed by a detergent to remove low-concentration hydrocarbon substances, sludge droplets, sulfides and other pollutants in the waste gas, the washing exhaust gas is discharged after reaching the standard, and washing liquid is recycled; according to the concentration of organic pollutants in the purified gas, part of the washing liquid is pumped out to enter a regeneration unit, the regeneration depends on the catalytic oxidation unit to carry out cyclic regeneration, and the regeneration liquid returns to the washing unit. The invention solves the problems of the traditional biological method and the adsorption method, the waste gas treatment is stable and efficient, secondary pollution of water and gas is basically avoided, the absorbent can be regenerated and recycled, and the waste gas treatment investment and the operation cost are greatly reduced.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a method and a device for treating low-concentration organic waste gas.
Background
The sewage treatment plant is an important sewage treatment facility in oil refineries and municipal facilities. The biochemical treatment technology has the advantages of low cost, good treatment effect and the like, and is an important step of sewage treatment, wherein the aerobic biochemical treatment needs to introduce a large amount of air into the sewage, and the sewage is evaporated to cause a sewage treatment field to discharge large-amount low-concentration waste gas to the atmosphere. The exhaust gas has large gas quantity but low concentration of harmful components, and the total hydrocarbon concentration normally meets the emission standard but has large fluctuation, and the total hydrocarbon concentration can be dozens to hundreds of mg/m3. The main reasons for the need of treatment of such waste gas are the malodorous smell, which is mainly from activated sludge droplets, trace hydrogen sulfide and other sulfur compounds, low molecular organic acids, ammonia, phenols, etc. contained therein, seriously affects the surrounding environment and poses a threat to human health. Wherein macromolecular water-soluble organic matters such as phenols and the like are harmful to the common active carbon adsorption material.
The waste gas discharged from sewage treatment plant has large gas quantity and low pollutant concentration, so that the suitable treatment technology is limited. Conventional methods for treating such exhaust gas, such as adsorption, incineration, catalytic combustion, condensation, absorption, etc., are not economical. The adsorbent used in the adsorption method has large dosage, difficult regeneration and unstable operation. The burning method and the catalytic burning method both need to supplement a large amount of fuel, and have high energy consumption and poor economical efficiency. The condensation method and the absorption method are less suitable for such low-concentration exhaust gas. The biological purification method has the advantages of low operation cost and no secondary pollution, and is an ideal treatment method for the waste gas, however, the biological purification method generally needs multi-stage treatment, the device scale is large, and the purification efficiency is unstable.
CN1745883A discloses a method for treating odor pollution, in particular odor pollution emitted by a petrochemical sewage treatment plant and a method for purifying low-concentration organic waste gas, wherein immobilized microbial film filler is adopted, 1-3-grade microorganisms are adopted for treatment, a wet dust removal tower can be used for pretreatment before the microorganism treatment, and an adsorbent can be used for advanced treatment after the microorganism treatment. The method needs to adopt immobilized microbial membrane filler, has higher requirement on microbes, and needs to use an adsorbent for treatment after treatment.
CN109939534A discloses a device of VOCs waste gas is handled with catalytic combustion coupling to adsorption concentration, is applicable to the VOCs waste gas treatment of big amount of wind, low concentration, and it adopts the absorption as VOCs waste gas discharge control means, and the absorption desorption gas goes catalytic combustion unit to handle, and the hot tail gas of catalytic combustion is used as the absorption heat desorption gas. However, if sulfur is contained in the exhaust gas, the sulfur enters the catalytic oxidation unit, and the safe and stable operation of the catalytic oxidation unit cannot be maintained.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a device for treating low-concentration organic waste gas. The invention solves the problems of the traditional biological method and the adsorption method, the waste gas treatment is stable and efficient, secondary pollution of water and gas is basically avoided, the absorbent can be regenerated and recycled, and the waste gas treatment investment and the operation cost are greatly reduced.
The invention provides a method for treating low-concentration organic waste gas, which comprises the following steps: (1) the waste gas firstly enters a washing unit to be washed by a washing agent, so that pollutants such as low-concentration hydrocarbon substances, sludge droplets, sulfides and the like in the waste gas are removed, the washing exhaust gas is discharged after reaching the standard, and the washing liquid is recycled; (2) according to the concentration of organic pollutants in the purified gas, part of the washing liquid is pumped out to enter a regeneration unit, the regeneration depends on the catalytic oxidation unit to carry out cyclic regeneration, and the regeneration liquid returns to the washing unit.
In the invention, the low-concentration organic waste gas in the step (1) is waste gas discharged from a sewage treatment plant, mainly comes from a biological aeration water treatment facility in an oil refinery and a municipal facility, the waste gas has large gas quantity but low concentration of harmful components, and the total hydrocarbon concentration has large fluctuation under normal conditions, namely, the total hydrocarbon concentration is dozens to hundreds of mg/m3The concentration of sulphide is generally less than 100mg/m3。
In the invention, the detergent is cyclodextrin alkaline solution, the mass concentration of cyclodextrin is 1-30%, and the mass concentration of alkali liquor is 0.1-5%. The cyclodextrin may be at least one selected from alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and the like, preferably gamma-cyclodextrin. The alkali is at least one of strong alkali such as sodium hydroxide, potassium hydroxide and the like.
In the present invention, the liquid-gas ratio in the washing column of the washing unit in the step (1) is controlled to be generally 2 to 8L/m3Preferably 3 to 6L/m3And washing at normal temperature and normal pressure.
In the invention, the regeneration unit in the step (2) mainly comprises a washing liquid regeneration tower, a regeneration washing liquid pump, a regeneration fan, a catalytic oxidation reactor and the like, and further comprises a catalytic oxidation heat exchanger and a catalytic oxidation heater. The washing tower and the washing liquid regeneration tower are filled with filling materials which can be at least one of stainless steel pall rings or Raschig rings, and the catalytic oxidation reactor is filled with catalytic oxidation catalysts.
In the invention, the carrier of the catalytic oxidation catalyst in the step (2) is a cordierite honeycomb ceramic carrier coated with alumina, the density of honeycomb pores is 200-400 meshes, the active metal is Pt/Pd, and the active component accounts for 0.1-2% of the total weight of the catalyst in terms of element; and other additives such as cerium and the like can be contained. In the catalytic oxidation unit, the inlet temperature of the reactor is 150-450 ℃, preferably 250-400 ℃, and the volume space velocity of the waste gas passing through the catalyst bed is 1000--1。
In the invention, the catalytic oxidation reactor in the step (2) leads out high-temperature purified gas through a regeneration fan, and the high-temperature purified gas enters a washing liquid regeneration tower to carry out thermal regeneration on part of the led-out washing liquid, wherein the regeneration temperature is 60-200 ℃, and the generated regenerated gas mainly contains hydrocarbon substances and enters the catalytic oxidation reactor to be treated.
In the invention, the extracted washing liquid in the step (2) is related to the treatment effect of the washing unit, when the concentration of VOCs discharged by the washing unit is high, the amount of the regenerated washing liquid can be increased, generally 10-50% of the circulating amount of the washing liquid, and the air ratio of the circulating regenerated liquid is 0.5-10L/m3。
According to the concentration of the organic pollutants in the purified gas, the amount of the extracted washing liquid is adjusted to carry out regeneration treatment, and when the concentration of the organic pollutants in the purified gas is increased, the regeneration amount of the washing liquid can be increased; when the pH of the wash liquor drops to 7-9, a certain amount of spent wash liquor is drained and fresh detergent is replenished.
The invention also provides a treatment device for the low-concentration organic waste gas, which mainly comprises a washing unit and a regeneration unit, wherein the washing unit mainly comprises a washing tower, a washing liquid circulating pump and the like, and the regeneration unit mainly comprises a washing liquid regeneration tower, a regeneration washing liquid pump, a regeneration fan, a catalytic oxidation heat exchanger, a catalytic oxidation heater and a catalytic oxidation reactor; the washing tower and the washing liquid regeneration tower are filled with fillers such as stainless steel pall rings, Raschig rings and the like, and the catalytic oxidation reactor is filled with a catalytic oxidation catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention takes the cyclodextrin alkaline solution as the washing agent, which is beneficial to the long-term and rapid absorption of pollutants such as low-concentration hydrocarbons and the like, and the purified gas reaches the discharge standard.
(2) The invention utilizes catalytic oxidation high-temperature purified gas to heat and regenerate the washing liquid, the regenerated washing liquid can be recycled, the consumption of fresh detergent is reduced, and the treatment cost is lower.
(3) The method does not need an additional heating source, the gas containing the hydrocarbon substances is regenerated by the absorption liquid, so that the catalytic oxidation energy can be automatically and automatically operated, and the high-temperature gas is used for the cyclic regeneration of the absorption liquid, so that the operation cost of waste gas treatment is greatly reduced.
(4) The cyclodextrin alkaline detergent can also absorb sulfide, and cannot be desorbed at the temperature of regenerated hydrocarbon substances, so that the adverse effect of the sulfide on the subsequent catalyst oxidation is avoided, and the sulfur poisoning of the catalytic oxidation catalyst is avoided.
Drawings
FIG. 1 is a process flow diagram of the treatment process of the present invention;
wherein: a-a washing tower, B-a washing liquid circulating pump, C-a washing liquid regeneration tower, D-a regeneration washing liquid pump, E-a regeneration fan, an F-catalytic oxidation heat exchanger, a G-a catalytic oxidation heater and an H-a catalytic oxidation reactor; a-washing tower and regeneration tower packing, b-catalytic oxidation catalyst;
1-waste gas, 2-purified gas, 3-circulating washing liquid, 4-discharging partial washing liquid to a regeneration tower, 5-regenerating washing liquid, 6-starting or supplementing air by a regeneration unit, 7-high-concentration regenerated gas, 8-circulating regeneration of high-temperature purified gas, and 9-discharging partial regenerated purified gas.
Detailed Description
The following will further explain the processing method and effect of the present invention with reference to the specific embodiments. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the invention, the non-methane total hydrocarbon is detected by gas chromatography in HJ/T38 determination of non-methane total hydrocarbon in exhaust gas of fixed pollution source; the sulfide is detected by gas chromatography in GB/T14678 determination of air quality hydrogen sulfide, methyl mercaptan, methyl sulfide and the like.
The system disclosed by the invention adopts a figure 1, and mainly comprises a washing unit and a regeneration unit, wherein the washing unit mainly comprises a washing tower A, a washing liquid circulating pump B and the like, and the regeneration unit mainly comprises a washing liquid regeneration tower C, a regeneration washing liquid pump D, a regeneration fan E, a catalytic oxidation heat exchanger F, a catalytic oxidation heater G, a catalytic oxidation reactor H and the like; stainless steel packing a (pall ring or Raschig ring) is filled in the washing tower A and the washing liquid regeneration tower C; the catalytic oxidation reactor H is filled with a catalytic oxidation catalyst b.
The treatment method adopting the device shown in the attached figure 1 is characterized in that low-concentration waste gas 1 is introduced into a washing tower A, and is washed by a circulating washing liquid 3 conveyed by a washing liquid circulating pump B, so that pollutants in the waste gas are removed, and a washing purified gas 2 reaches the standard and is discharged; after the washing unit reaches a stable state, discharging part of washing liquid 4 to a washing liquid regeneration tower C of the regeneration unit, returning regenerated washing liquid 5 to the washing tower A through a regenerated washing liquid pump D, wherein the regeneration is realized through catalytic oxidation circulation regeneration, and high-temperature purified gas discharged by catalytic oxidation is subjected to the action of a regeneration fan E8, the washing liquid is regenerated after entering a regeneration tower C, the generated high-concentration regenerated gas 7 enters a catalytic oxidation reactor H through a catalytic oxidation heat exchanger F and a catalytic oxidation heater G, and organic matters in the waste gas are oxidized into CO2And H2O; according to the regeneration purification situation, fresh air 6 is supplemented and regeneration purification air 9 is discharged.
Example 1
The concentration of non-methane total hydrocarbon in low-concentration organic waste gas of a certain sewage treatment field is 60-500mg/m3The concentration of sulfide is generally 5-20mg/m310000Nm of waste gas3/h。
Waste gas firstly enters a washing tower, gamma-cyclodextrin alkaline aqueous solution (the mass concentration of sodium hydroxide in the solution is 2 percent, and the mass concentration of cyclodextrin is 15 percent) is sprayed for circular washing, and the liquid-gas ratio is controlled to be 3L/m3Washing at normal temperature and normal pressure to remove low-concentration hydrocarbon substances, sludge droplets, sulfides and other pollutants in the waste gas, discharging the washing exhaust gas after reaching the standard, and recycling the washing liquid, wherein the characteristic pollutants such as benzene series, sulfides and the like are lower than the detection limit.
Part of the washing liquid continuously enters a regeneration unit, high-temperature purified gas generated by a catalytic oxidation reactor is adopted for thermal regeneration, the regeneration temperature is controlled to be 80-150 ℃, the regenerated gas generated by hydrocarbon-containing substances enters the catalytic oxidation reactor for treatment, in the catalytic oxidation unit, the inlet temperature of the reactor is 280-300 ℃, and the volume space velocity of waste gas passing through a catalyst bed layer is 10000h-1. Wherein the carrier of the hydrocarbon oxidation catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb pores is 200 meshes, the active metals are Pt and Pd, the content of Pt is 0.2%, and the content of Pd is 0.15%. The regeneration amount of the washing liquid is related to the treatment effect of the washing unit, when the concentration of VOCs discharged by the washing unit is high, the regeneration washing liquid amount can be increased, generally 10-50% of the circulation amount of the washing liquid, and the gas-to-gas ratio of the circulation regeneration liquid is 0.5-10L/m3。
The device stably operates for more than 1 year, the scale and the operation energy consumption of the device are greatly reduced, the investment and the operation cost of the waste gas treatment device built by the treatment method are reduced by more than 90 percent compared with the direct catalytic oxidation, and the catalyst poisoning or the overproof exhaust gas is not generated.
Example 2
The concentration of non-methane total hydrocarbon in low-concentration organic waste gas of a certain sewage treatment field is 20-300mg/m3The concentration of the sulfide is generally 5-10mg/m3Amount of exhaust gas 20000Nm3/h。
The waste gas firstly enters a washing tower, gamma-cyclodextrin alkaline aqueous solution (the mass concentration of sodium hydroxide in the solution is 1 percent, and the mass concentration of cyclodextrin is 10 percent) is sprayed for circular washing, the liquid-gas ratio is controlled to be 3, the waste gas is washed at normal temperature and normal pressure, pollutants such as low-concentration hydrocarbon substances, sludge droplets, sulfides and the like in the waste gas are removed, the washing exhaust gas is discharged after reaching the standard, characteristic pollutants such as benzene series, sulfides and the like are lower than the detection limit, and the washing liquid is recycled.
Part of the washing liquid continuously enters a regeneration unit, high-temperature purified gas generated by a catalytic oxidation reactor is adopted for thermal regeneration, the regeneration temperature is controlled to be 80-150 ℃, the regenerated gas generated by hydrocarbon-containing substances enters the catalytic oxidation reactor for treatment, in the catalytic oxidation unit, the inlet temperature of the reactor is 280-300 ℃, and the volume space velocity of waste gas passing through a catalyst bed layer is 10000h-1. Wherein the carrier of the hydrocarbon oxidation catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb pores is 200 meshes, the active metals are Pt and Pd, the content of Pt is 0.2%, and the content of Pd is 0.15%. The regeneration amount of the washing liquid is related to the treatment effect of the washing unit, when the concentration of VOCs discharged by the washing unit is high, the regeneration washing liquid amount can be increased, generally 10-50% of the circulation amount of the washing liquid, and the gas-to-gas ratio of the circulation regeneration liquid is 0.5-10L/m3。
The device stably operates for more than 1 year, the device scale and the operation energy consumption are greatly reduced, the investment and the operation cost of the waste gas treatment device built by the treatment method are reduced by more than 90 percent compared with the direct catalytic oxidation, and the catalyst poisoning or the overproof exhaust gas is not generated.
Example 3
The concentration of non-methane total hydrocarbon in low-concentration organic waste gas of a certain sewage treatment field is 20-800mg/m3The concentration of sulfide is 15-35mg/m310000Nm of waste gas3/h。
Waste gas firstly enters a washing tower and is sprayed with gamma-cyclodextrin alkaline aqueous solution (solution)The mass concentration of sodium hydroxide in the solution is 3 percent, the mass concentration of cyclodextrin is 20 percent) to carry out circular washing, and the liquid-gas ratio is controlled to be 3-5L/m3Washing at normal temperature and normal pressure to remove low-concentration hydrocarbon substances, sludge droplets, sulfides and other pollutants in the waste gas, discharging the washing exhaust gas after reaching the standard, and recycling the washing liquid, wherein the characteristic pollutants such as benzene series, sulfides and the like are lower than the detection limit.
Part of the washing liquid continuously enters a regeneration unit, high-temperature purified gas generated by a catalytic oxidation reactor is adopted for thermal regeneration, the regeneration temperature is controlled to be 80-150 ℃, the regenerated gas generated by hydrocarbon-containing substances enters the catalytic oxidation reactor for treatment, in the catalytic oxidation unit, the inlet temperature of the reactor is 280-300 ℃, and the volume space velocity of waste gas passing through a catalyst bed layer is 10000h-1. Wherein the carrier of the hydrocarbon oxidation catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb pores is 200 meshes, and the active metals are Pt and Pd, wherein the content of Pt is 0.2 percent, and the content of Pd is 0.15 percent. The washing liquid is related to the treatment effect of the washing unit, when the concentration of VOCs discharged by the washing unit is high, the regenerated washing liquid amount can be increased, generally 10-50% of the circulation amount of the washing liquid, and the gas-to-gas ratio of the circulating regenerated liquid is 0.5-10L/m3。
The device stably operates for more than 1 year, the scale and the operation energy consumption of the device are greatly reduced, the investment and the operation cost of the waste gas treatment device built by the treatment method are reduced by more than 90 percent compared with the direct catalytic oxidation, and the catalyst poisoning or the overproof exhaust gas is not generated.
Example 4
The same as in example 1, except that α -cyclodextrin was used. The gas-liquid ratio of the absorption liquid is designed to be 6L/m3The mass concentration of the cyclodextrin is 20 percent. The regeneration amount of the washing liquid is larger, generally is 30-50% of the circulation amount of the washing liquid, and the investment and operation cost is reduced by about 60% compared with the direct catalytic oxidation treatment.
Example 5
The same as in example 1, except that beta-cyclodextrin was used. The gas-liquid ratio of the absorption liquid is designed to be 8L/m3The mass concentration of the cyclodextrin is 3 percent. The regeneration amount of the washing liquid is larger, generally 40-50% of the circulation amount of the washing liquid, and the investment and operation cost is reduced by about 50% compared with the direct catalytic oxidation treatment.
Comparative example 1
The same as in example 1, except that a gamma-cyclodextrin solution was used, no base was added. Because the waste gas contains sulfide, after the sulfide is absorbed by the washing liquid, the acidity of the washing liquid is gradually enhanced, so that the cyclodextrin is partially hydrolyzed, the absorption effect on the waste gas is reduced, and the phenomenon that the discharged gas exceeds the standard is caused.
Comparative example 2
The same as example 1, except that absorption with lye is used. Only sulfide in the waste gas can be removed, organic pollutants cannot be removed, and the organic pollutants in the exhaust gas often exceed the standard.
Comparative example 3
The same as example 1, except that activated carbon adsorption was used. Because the waste gas of the sewage farm contains heavy components such as phenols, the waste gas is not easy to desorb and regenerate from the activated carbon, and the contained sludge droplets are easy to block the activated carbon bed layer. The device stably operates for 3 months, the pressure drop of the activated carbon bed layer is obviously increased, and the phenomenon of overproof exhaust gas occurs.
Claims (14)
1. A method for treating low-concentration organic waste gas is characterized by comprising the following steps: (1) the waste gas firstly enters a washing unit to be washed by a washing agent, so that pollutants such as low-concentration hydrocarbon substances, sludge droplets, sulfides and the like in the waste gas are removed, the washing exhaust gas is discharged after reaching the standard, and the washing liquid is recycled; (2) according to the concentration of organic pollutants in the purified gas, part of the washing liquid is pumped out to enter a regeneration unit, the regeneration depends on the catalytic oxidation unit to carry out cyclic regeneration, and the regeneration liquid returns to the washing unit.
2. The method of claim 1, wherein: the low-concentration organic waste gas in the step (1) mainly comes from waste gas discharged by a biological aeration water treatment facility in an oil refinery and a municipal facility, the waste gas has large gas quantity but low concentration of harmful components, and the concentration of total hydrocarbon has large fluctuation under normal conditions, namely dozens to hundreds of mg/m3The concentration of sulfide is less than 100mg/m3。
3. The method of claim 1, wherein: the detergent in the step (1) is cyclodextrin alkaline solution, the mass concentration of cyclodextrin is 1-30%, and the mass concentration of alkali liquor is 0.1-5%.
4. The method of claim 3, wherein: the cyclodextrin may be selected from at least one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin, preferably gamma-cyclodextrin.
5. The method of claim 3, wherein: the alkali is at least one of sodium hydroxide and potassium hydroxide strong alkali.
6. The method of claim 1, wherein: controlling the liquid-gas ratio in the washing tower of the washing unit in the step (1) to be 2-8L/m3Preferably 3 to 6L/m3And washing at normal temperature and normal pressure.
7. The method of claim 1, wherein: the regeneration unit in the step (2) mainly comprises a washing liquid regeneration tower, a regeneration washing liquid pump, a regeneration fan and a catalytic oxidation reactor, wherein fillers are filled in the washing tower and the washing liquid regeneration tower, and a catalytic oxidation catalyst is filled in the catalytic oxidation reactor.
8. The method of claim 1, wherein: the carrier of the catalytic oxidation catalyst in the step (2) is a cordierite honeycomb ceramic carrier coated with alumina, the density of honeycomb pores is 200-400 meshes, the active metal is Pt/Pd, and the active component accounts for 0.1% -2% of the total weight of the catalyst by element.
9. The method according to claim 1 or 8, characterized in that: in the catalytic oxidation unit, the inlet temperature of the reactor is 150-450 ℃, preferably 250-400 ℃, and the volume space velocity of the waste gas passing through the catalyst bed is 1000--1。
10. The method of claim 1, wherein: and (3) leading out the high-temperature purified gas from the catalytic oxidation reactor in the step (2) through a regeneration fan, and carrying out thermal regeneration on part of the led-out washing liquid in a washing liquid regeneration tower at the regeneration temperature of 60-200 ℃, wherein the generated regenerated gas mainly contains hydrocarbon substances and enters the catalytic oxidation reactor for treatment.
11. The method of claim 1, wherein: step (2) when the concentration of VOCs discharged by the washing unit is high, the amount of the regenerated washing liquid is increased to 10% -50% of the circulation amount of the washing liquid, and the gas-to-gas ratio of the circulating regenerated liquid is 0.5-10L/m3。
12. The method of claim 1, wherein: and (2) adjusting the amount of the extracted washing liquid to perform regeneration treatment according to the concentration of the organic pollutants in the purified gas, and increasing the regeneration amount of the washing liquid when the concentration of the organic pollutants in the purified gas is increased.
13. The method of claim 1, wherein: and (2) when the pH value of the washing liquid is reduced to 7-9, discharging a certain amount of waste washing liquid and supplementing fresh detergent.
14. A treatment device for the low-concentration organic waste gas according to any one of claims 1 to 13, which is characterized by mainly comprising a washing unit and a regeneration unit, wherein the washing unit mainly comprises a washing tower and a washing liquid circulating pump, and the regeneration unit mainly comprises a washing liquid regeneration tower, a regeneration washing liquid pump, a regeneration fan, a catalytic oxidation heat exchanger, a catalytic oxidation heater and a catalytic oxidation reactor; the washing tower and the washing liquid regeneration tower are filled with fillers such as stainless steel pall rings, Raschig rings and the like, and the catalytic oxidation reactor is filled with a catalytic oxidation catalyst.
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