CN105650651A - Purification treatment method of high-concentration organic waste gas - Google Patents
Purification treatment method of high-concentration organic waste gas Download PDFInfo
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Abstract
The invention discloses a purification treatment method of high-concentration organic waste gas. Organic waste gas is introduced into a catalytic combustion reactor after being subjected to heat exchange and preheating, isolated catalyst bed layers are arranged inside the reactor, each bed layer is provided with a waste gas inlet and a waste gas outlet, each waste gas inlet pipeline is provided with an oxygen supplying port and a pipeline mixer, and organic matter in waste gas is subjected to partial catalytic combustion reaction in each bed layer in a segmented oxygen supplying mode. In the waste gas flowing direction, the waste gas outlet of the former catalyst bed layer is connected with the waste gas inlet of the next catalyst bed layer through a heat energy recycling device, so that reaction heat released by catalytic combustion is fetched, and heat energy recovery is achieved. Potential safety hazards caused by detonation of combustible gas can be avoided, catalyst sintering caused by too high temperature of the catalyst bed layers is prevented, the scale and operation energy consumption of related devices for waste gas treatment are reduced, and the purification treatment method is especially suitable for purification treatment of organic waste gas with high organic matter concentration and low oxygen content in the petrochemical engineering industry.
Description
Technical field
The invention belongs to waste gas purification field, relate to a kind of purifying treatment method of high-concentration organic waste gas, be applicable to the high organic concentration discharging in petroleum chemical industry production process, the purified treatment of low oxygen content organic exhaust gas.
Background technology
In the production process of some petroleum chemical industry, can give off high-concentration organic waste gas, the composition of this waste gas is taking organic component as main, and such as benzene, cyclohexane, dimethylbenzene, oxirane etc., in waste gas, total hydrocarbon concentration is several thousand to hundreds of thousands mg/m3Between. If the not treated direct discharge of this waste gas, not only can violate national environmental protection regulation, and these harmful substances are in the diffusion of filling the air in device district, seriously damage again the healthy of Enterprise Staff, even threat to life. Therefore, must take effective governing measure to this class high-concentration organic waste gas.
To the processing of this type of high-concentration waste gas, catalytic combustion is a kind of effectively processing means. But in the time adopting traditional Production by Catalytic Combustion Process to process, due to the oxygen content deficiency in some waste gas, therefore need to supplement a large amount of oxygen or air. Direct disposable supplemental oxygen or air carry out catalytic combustion processing, not only there is the potential safety hazard of waste gas detonation, and the catalyst combustion reaction heat release of organic component is higher, also can cause the temperature of catalytic combustion reactor to raise, exceed the bearing temperature of reactor and catalyst, sintering of catalyst was lost efficacy. Although can add Macrodilution air to dilute, can make the design treatment scale of device be multiplied, thereby increase investment cost and the operation energy consumption of device.
CN200310104990.5 discloses a kind of purification method of high-concentration organic waste gas, by waste gas after pretreatment, by blower fan supercharging, heat up through heat exchanger, electric heater, then enter catalytic combustion reactor, reactor outlet gas enters heat exchanger and waste gas heat exchange, and the waste gas after heat exchange steam further occurs or produces hot water. The main feature of this invention is that the reactor outlet gas that enters heat exchanger arranges by-pass line and adjusts the tolerance of by-pass line, makes heat exchanger cold air outlet temperature lower than the reactor inlet temperature of setting, and keeps heater at micro-heated condition; By-pass line is set and adjusts bypass flow at electric heater, obviously reducing gas by heater pressure drop, keep reactor inlet temperatures stable. This inventive method is mainly protection heat exchanger and is provided with heat exchanger bypass, but does not solve the overtemperatute of catalytic combustion reactor, and the organic exhaust gas concentration that is applicable to processing is at 10000mg/m3Below, still need to add large quantity of air dilution for the higher waste gas of concentration.
CN201110217412.7 discloses a kind of purification method of high-concentration organic waste gas, high-concentration organic waste gas enters one section of catalytic combustion reactor after heat exchange-preheating, a part for one section of catalytic combustion reactor emission and the heat exchange of one section of catalytic combustion reactor entrance waste gas, after heat exchange, be mixed into two sections of catalytic combustion reactors with the remainder of one section of catalytic combustion reactor discharge gas, after two sections of catalytic combustion reactor effluent gas recovery heats, discharge. This inventive method waste gas after two-stage catalytic burning is processed, purified gas qualified discharge, simultaneously recyclable large energy also. But the method also will be carried out suitable dilution according to organic exhaust gas concentration, if or hypoxgia in waste gas, need to supplement air, heat transmission equipment and firing equipment scale all need to increase.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of purifying treatment method of high-concentration organic waste gas. The potential safety hazard that the present invention can avoid combustible gas deflagrating to produce, prevent the too high sintering of catalyst causing of reaction bed temperature, reduced scale and the operation energy consumption of waste gas treatment equipment, be particularly suitable for that petroleum chemical industry produces the purified treatment of organic exhaust gas of high organic concentration, low oxygen content.
The purifying treatment method of high-concentration organic waste gas of the present invention comprises following content: organic exhaust gas passes into catalytic combustion reactor after heat exchange-preheating, the beds of some sections of isolation is set in reactor, every section of beds is provided with waste gas and imports and exports, on exhaust gas inlet pipeline, be provided with oxygen supplement mouth and pipe-line mixer, after being mixed with waste gas, oxygen enters catalytic combustion reactor, every section of bed outlet EGT of mode control by sectional oxygen supply is 350～600 DEG C, makes organic matter in waste gas in every section of bed, carry out partially catalyzed combustion reaction; By exhaust gas flow direction, the last period, the organic exhaust gas outlet of beds was connected with the organic exhaust gas import of rear one section of bed by heat reclaim unit, making waste air temperature at inlet is 150～400 DEG C, thereby takes out the reaction heat that every section of catalytic combustion discharges, and realizes the recovery of heat.
Organic exhaust gas of the present invention is the high organic concentration of petroleum chemical industry generation, the organic exhaust gas of low oxygen content, and in waste gas, organic concentration is 1.5 ten thousand～300,000 mg/m3, be preferably 30,000～150,000 mg/m3Oxygen-free or oxygen content is extremely low, preferably the volume content of oxygen is less than 5%, as can be has the organic exhaust gas of volatile organic matter material storage tank discharge or the organic exhaust gas of some anoxybiotics or the discharge of hypoxemia commercial plant etc., concrete as aromatic hydrocarbons storage tank discharging waste gas, volatile chemicals storage tank discharging waste gas, product oil storage tank discharging waste gas etc. This class storage tank, for safety, generally has nitrogen protection, and oxygen content is extremely low.
In catalytic combustion reactor of the present invention, organic exhaust gas is 6000～200000h through the volume space velocity (under standard state) of every section of beds-1, be preferably 10000～100000h-1; The waste air temperature at inlet of every section of beds is 150～400 DEG C, is preferably 200～300 DEG C; Outlet EGT is 350～600 DEG C, preferably 400～550 DEG C; The temperature rise of every section of beds, the temperature difference that exports EGT and waste air temperature at inlet is 150～400 DEG C. The present invention determines catalyst amount according to exhausted air quantity and organic concentration, and required beds quantity is relevant with exhaust emission substrate concentration, along with the increase of pollutant levels in waste gas, and the corresponding increase of bed quantity.
In catalytic combustion reactor of the present invention, load honeycomb type noble metal catalyst, carrier is honeycomb ceramic body, supports active component Pt, Pd etc. on it, and wherein Pt content is 0.2wt%～0.5wt%, and Pd content is 0.1wt%～0.3wt%.
Organic exhaust gas of the present invention reaches the required temperature of catalytic combustion reactor entrance by heat exchange and preheating, enters after catalytic combustion reactor, and under the effect of catalyst, oxidation operation is carbon dioxide and water, thoroughly pollution abatement. Heat exchange mode is the hot logistics of catalytic combustion reactor discharge and the cold logistics heat exchange of entrance, can reach under normal circumstances the temperature requirement of catalytic combustion reactor entrance by heat exchange, now just not needing heater preheating, heater is mainly to use in start-up process.
The high temperature organic exhaust gas that the present invention discharges enters and enters next section of beds after heat reclaim unit heat-obtaining and proceed catalyst combustion reaction, and the EGT reclaiming after heat meets the required initial reaction temperature of catalyst combustion reaction. By repetitive segment oxygen supply and segmentation heat-obtaining, until pollutant levels reach below discharge standard in waste gas, final purification gas exhaust temperature is 300～500 DEG C, after the cold organic exhaust gas before preheating enters catalytic combustion reactor, discharges by aiutage. Heat reclaim unit can be that heat exchanger heating water, steam generator are produced the material to be heated in steam or heat exchanger heating production etc., and independently heat exchanger channels is set, and ensures the independence of each section of waste gas heat exchange.
Catalyst combustion reaction of the present invention can fill into air or oxygen, preferably fills into oxygen, because oxygen can consume in catalyst combustion reaction process, can obviously not increase exhaust-gas treatment amount, thereby has ensured the stable of exhausted air quantity in whole waste gas treatment process. If use air to carry out delivery of supplemental oxygen, exhausted air quantity increases gradually in whole processing procedure, if the catalyst of each beds filling same amount is processed air speed and successively increased; If ensure that the air speed of each beds is constant, the catalytic amount of each bed filling will increase gradually, and catalytic combustion reactor design scale will be considered design according to capacity. The present invention is no more than maximum temperature and oxygen concentration is no more than in flammable gas explosion maximum oxygen concentration situation at every section of beds outlet EGT, delivery of supplemental oxygen as much as possible, the at utmost organic matter in oxidation gaseous effluent, give full play to the effect of catalyst, thereby can reduce the catalyst bed number of plies.
Organic exhaust gas of the present invention can carry out pretreatment entering before catalytic combustion reactor, and what contain in waste gas as removed makes the poisoning material of catalyst for catalytic combustion (as sulfide, halogen etc.); In the time that exhaust gas concentration fluctuation is very large, take necessary concentration homogenize measure; In the time containing particle in waste gas, filter plant need to be set and be removed; Storage-tank waste gas also has corresponding pressure control, and in the time that in storage tank, gaseous pressure exceedes setting pressure, storage tank breather valve is opened, and enters by pipeline from the gas of discharging in tank.
The present invention adopts the purifying processing device of the high-concentration organic waste gas of above-mentioned purifying treatment method, comprise air-introduced machine, heat exchanger, heater, catalytic combustion reactor, heat reclaim unit, aiutage, filter collector, pipe-line mixer and temperature control system, the beds of some sections of isolation is set in wherein said catalytic combustion reactor, every section of beds is all provided with organic exhaust gas and imports and exports, on exhaust gas inlet pipeline, be provided with oxygen supplement mouth and pipe-line mixer, after oxygen is mixed with waste gas, enter catalytic combustion reactor and carry out partially catalyzed combustion reaction, by exhaust gas flow direction, the last period, the organic exhaust gas outlet of beds was connected with the organic exhaust gas import of rear one section of bed by heat reclaim unit, thereby took out the reaction heat that every section of catalytic combustion discharges, and realized the recovery of heat.
Compared with prior art, the present invention has following outstanding feature: multiple beds of isolation are completely set in catalytic combustion reactor, by every section of bed being carried out to the degree of segmentation oxygenating control catalyst combustion reaction, thereby the temperature of organic exhaust gas in control bed, the waste gas of every section of bed is drawn in time and carried out heat-obtaining simultaneously, the EGT that can control after heat-obtaining when reclaiming heat meets next section of initial reaction temperature that catalyst combustion reaction is required. The inventive method needn't be used a large amount of air that exhaust gas concentration is diluted to the concentration for the treatment of that single bed allows, and has reduced scale (as pipeline, blower fan, exhaust gas heat exchanger and heater) and the operation energy consumption of waste gas treatment equipment. By controlling the magnitude of recruitment of each beds oxygen, make organic pollution generation partial oxidation, in ensureing that catalytic combustion carries out smoothly, the potential safety hazard of effectively avoiding combustible gas deflagrating to produce, prevents from arranging a beds simultaneously and makes the too high sintering of catalyst causing of bed temperature. Mode by segmentation heat-obtaining fully reclaims reaction heat, utilizes organic oxidation heat liberation in waste gas, produces hot water, steam or heats material to be heated, reaches energy-conservation object.
Brief description of the drawings
Fig. 1 is the process chart of the inventive method;
Fig. 2 is the structural representation of sectional oxygen supply of the present invention and segmentation heat-obtaining.
Detailed description of the invention
Below by embodiment, the present invention program is described in further detail.
The purifying processing device of high-concentration organic waste gas of the present invention, comprise air-introduced machine, heat exchanger, heater, catalytic combustion reactor, heat reclaim unit, aiutage, pipe-line mixer and temperature control system, some beds of isolation are completely set in wherein said catalytic combustion reactor, every section of beds is all provided with organic exhaust gas and imports and exports, each bed inlet line is provided with oxygen supplement mouth and pipe-line mixer, oxygen and organic exhaust gas enter beds after mixing in pipe-line mixer. Every section of bed outlet EGT of mode control by sectional oxygen supply is 350～600 DEG C, thereby makes the organic matter in waste gas carry out partially catalyzed combustion reaction at every section of bed; According to exhaust gas flow direction, the last period, the organic exhaust gas outlet of beds was connected with the organic exhaust gas import of next section of bed by heat reclaim unit, thereby controlling every section of bed waste air temperature at inlet is 150～400 DEG C, and take out by heat reclaim unit the reaction heat that every section of catalytic combustion discharges, realize the recovery of heat.
The oxygenating amount of the import waste gas of every section of beds is controlled by the outlet temperature of every section of beds, and every section of bed outlet EGT is 350～600 DEG C, thereby controls the magnitude of recruitment of oxygen, and the heat release that too much causes burning of anti-block amount is excessive; Every section of beds inlet temperature during lower than a certain design temperature between 150～400 DEG C, regulates respective valves automatically, and the amount that regulates high-temp waste gas to enter heat reclaim unit, realizes inlet temperature control.
Embodiment 1
Certain chemical enterprise has multiple expoxy propane storage tanks, is provided with nitrogen protection, and the average discharge amount of exhaust gas of storage tank is 200Nm3/ h, propylene oxide concentrations is 138000mg/m3, oxygen concentration is less than 1%, and all the other are N2。
If use conventional this waste gas of catalytic combustion PROCESS FOR TREATMENT, in order to make bed temperature rise be no more than 220 DEG C, propylene oxide concentrations is no more than 9000mg/m3, need exhaust gas dilution more than 15 times. Therefore, emission-control equipment scale is 3000Nm3/ h, the scale of the equipment such as catalytic combustion reactor in treatment process, air-introduced machine, heat exchanger, heater is 3000Nm3/ h, equipment investment and running expense are all very high, and the volume space velocity of beds is 20000h-1, need catalyst for catalytic combustion 150L. Catalytic combustion reactor loads cellular noble metal catalyst, in catalyst, containing Pt0.26wt%, contains Pd0.13wt%.
Adopt technique of the present invention and device to process this organic exhaust gas, the scale of catalyst use amount and catalytic combustion reactor is identical with above-mentioned catalytic combustion system, 15 sections of beds are set in catalytic combustion reactor, and controlling every section of catalyst bed layer operation air speed is 20000h-1, the equipment scale such as air-introduced machine, heat exchanger, heater is still 200Nm3/ h, does not need to increase the treatment scale of these equipment, greatly reduces equipment investment and running expense.
Each beds waste air temperature at inlet is 230-250 DEG C, and controlling bed temperature rise is 180-220 DEG C, and supplemental oxygen is controlled oxygenating amount and made every section of beds burning 8000-9000mg/m3Expoxy propane, after reaction, the outlet EGT of every section of beds is 410-470 DEG C, through heat recovery, cools the temperature to 230-250 DEG C, then enters next section of beds and continues reaction. Final stage beds emission purification gas, total hydrocarbon concentration is less than 100mg/m3, heating is discharged after entering the cold organic exhaust gas of first paragraph beds.
In whole catalyticing combustion process, oxygen replenishment amount is 40-50Nm3/ h, organic pollution is through every section of beds burning heat release, and the heat of recovery, for the production of steam, uses the boiler water supply of 40 DEG C, produces 170 DEG C, the about 180kg/t of 0.8MPa steam.
Embodiment 2
Certain chemical enterprise has benzene chemical plant installations tail gas, the about 500Nm of tolerance3/ h, total hydrocarbon concentration is about 53000mg/m3, major pollutants are benzene, toluene, aniline, cyclohexylamine, cyclohexane etc., and oxygen concentration is less than 2%, and all the other are N2。
If use conventional this waste gas of catalytic combustion PROCESS FOR TREATMENT, in order to make bed temperature rise be no more than 250 DEG C, organic compound combustion amount is no more than 7500mg/m3(in total hydrocarbon concentration), needs exhaust gas dilution more than 7 times, and emission-control equipment scale is 3500Nm3/ h, the scale of the equipment such as catalytic combustion reactor in treatment process, air-introduced machine, heat exchanger, heater is 3500Nm3/ h, equipment investment and running expense are all very high. The volume space velocity of beds is 18000h-1, need catalyst for catalytic combustion 195L. Catalytic combustion adopts cellular noble metal catalyst, contains Pt0.26wt%, contains Pd0.13wt% in catalyst.
Adopt technique of the present invention and device to process this organic exhaust gas, the scale of catalyst use amount and catalytic combustion reactor is identical with above-mentioned catalytic combustion system reactor, 7 sections of beds are set in catalytic combustion reactor, and controlling every section of catalyst bed layer operation air speed is 18000h-1, the equipment scale such as air-introduced machine, heat exchanger, heater is still 500Nm3/ h, does not need to increase the treatment scale of these equipment, greatly reduces equipment investment and running expense.
Each beds waste air temperature at inlet is 230-250 DEG C, and controlling bed temperature rise is 200-250 DEG C, and supplemental oxygen is controlled oxygenating amount and made every section of beds burning 7000-8000mg/m3Organic matter (in total hydrocarbon concentration), after reaction, the outlet EGT of every section of beds is 430-500 DEG C, through heat recovery, cools the temperature to 230-250 DEG C, then enters next section of beds and continues reaction. Final stage beds emission purification gas, total hydrocarbon concentration is less than 80mg/m3, each pollution concentrations such as benzene, toluene are all lower than discharge standard, and heating is discharged after entering the cold material of first paragraph beds.
In whole catalyticing combustion process, oxygen replenishment amount is 55-70Nm3/ h, organic pollution is through every section of beds burning heat release, and the heat of recovery, for the production of steam, uses the boiler water supply of 80 DEG C, produces 170 DEG C, the about 260kg/h of 0.8MPa steam.
Claims (11)
1. the purifying treatment method of a high-concentration organic waste gas, it is characterized in that comprising following content: organic exhaust gas passes into catalytic combustion reactor after heat exchange-preheating, the beds of isolation is set in reactor, every section of beds is provided with waste gas and imports and exports, on exhaust gas inlet pipeline, be provided with oxygen supplement mouth and pipe-line mixer, after being mixed with waste gas, oxygen enters catalytic combustion reactor, make organic matter in waste gas in every section of bed, carry out partially catalyzed combustion reaction by the mode of sectional oxygen supply, controlling every section of bed outlet EGT is 350～600 DEG C, by exhaust gas flow direction, the last period, the organic exhaust gas outlet of beds was connected with the organic exhaust gas import of rear one section of bed by heat reclaim unit, making waste air temperature at inlet is 150～400 DEG C, thereby takes out the reaction heat that catalytic combustion discharges, and realizes the recovery of heat。
2. method according to claim 1, is characterized in that: described organic exhaust gas is the high organic concentration of petroleum chemical industry generation, the organic exhaust gas of low oxygen content, and in waste gas, organic concentration is 1.5 ten thousand～300,000 mg/m3, the volume content of oxygen is less than 5%.
3. method according to claim 2, is characterized in that: described organic exhaust gas is aromatic hydrocarbons storage tank discharging waste gas, volatile chemicals storage tank discharging waste gas or product oil storage tank discharging waste gas, and in waste gas, organic concentration is 30,000～150,000 mg/m3。
4. method according to claim 1, is characterized in that: in catalytic combustion reactor, organic exhaust gas is 6000～200000h through the volume space velocity of every section of beds-1, the waste air temperature at inlet of every section of beds is 150～400 DEG C, and outlet EGT is 350～600 DEG C, and the temperature rise of every section of beds is 50～400 DEG C.
5. method according to claim 4, is characterized in that: in catalytic combustion reactor, organic exhaust gas is 10000～100000h through the volume space velocity of every section of beds-1, the waste air temperature at inlet of every section of beds is 200～300 DEG C, outlet EGT is 400～550 DEG C.
6. method according to claim 1, it is characterized in that: honeycomb type noble metal catalyst is housed in catalytic combustion reactor, and carrier is honeycomb ceramic body, supports active component Pt, Pd on it, wherein Pt content is 0.2wt%～0.5wt%, and Pd content is 0.1wt%～0.3wt%.
7. method according to claim 1, it is characterized in that: the high temperature organic exhaust gas that every section of bed is discharged enters heat reclaim unit and reclaims and enter next section of beds after heat and proceed catalyst combustion reaction, the EGT reclaiming after heat meets the required initial reaction temperature of catalyst combustion reaction, final purification gas exhaust temperature is 300～500 DEG C, after the cold organic exhaust gas before preheating enters catalytic combustion reactor, discharge by aiutage.
8. method according to claim 1, is characterized in that: heat reclaim unit is that heat exchanger heating water, steam generator are produced the material to be heated in steam or heat exchanger heating production, and independently heat exchanger channels is set.
9. method according to claim 1, it is characterized in that: catalyst combustion reaction fills into air or oxygen, be no more than maximum temperature and oxygen concentration is no more than in flammable gas explosion maximum oxygen concentration situation at every section of beds outlet EGT, delivery of supplemental oxygen as much as possible, the at utmost organic matter in oxidation gaseous effluent.
10. method according to claim 1, is characterized in that: described organic exhaust gas carries out pretreatment entering before catalytic combustion reactor, remove in waste gas, contain make the poisoning material of catalyst for catalytic combustion; In the time that exhaust gas concentration fluctuation is very large, take necessary concentration homogenize measure; In the time containing particle in waste gas, filter plant is set and is removed.
The purifying processing device of the arbitrary described processing high-concentration organic waste gas of 11. claim 1 to 10, comprise air-introduced machine, heat exchanger, heater, catalytic combustion reactor, heat reclaim unit, aiutage, filter collector, pipe-line mixer and temperature control system, the beds of some isolation is set in wherein said catalytic combustion reactor, every section of beds is all provided with organic exhaust gas and imports and exports, on exhaust gas inlet pipeline, be provided with oxygen supplement mouth and pipe-line mixer, after oxygen is mixed with waste gas, enter catalytic combustion reactor and carry out partially catalyzed combustion reaction, by exhaust gas flow direction, the last period, the organic exhaust gas outlet of beds was connected with the organic exhaust gas import of rear one section of bed by heat reclaim unit, thereby took out the reaction heat that catalytic combustion discharges, and realized the recovery of heat。
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