CN105650651B - A kind of purifying treatment method of high-concentration organic waste gas - Google Patents
A kind of purifying treatment method of high-concentration organic waste gas Download PDFInfo
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Abstract
The invention discloses a kind of purifying treatment method of high-concentration organic waste gas, organic exhaust gas is passed through catalytic combustion reactor after heat exchange preheats, the beds of isolation are set in reactor, every section of bed is imported and exported provided with waste gas, oxygen supplement mouth and pipe-line mixer are provided with exhaust gas inlet pipeline, organic matter in waste gas is carried out partially catalyzed combustion reaction in every section of bed by way of sectional oxygen supply；By exhaust gas flow direction, the waste gas outlet of the last period beds is connected by heat reclaim unit with the exhaust gas inlet of latter section of bed, so as to take out the reaction heat that catalysis burning discharges, realizes the recovery of heat.The present invention can avoid potential safety hazard caused by combustible gas deflagrating, sintering of catalyst caused by preventing reaction bed temperature too high, and the scale and operation energy consumption of exhaust-gas treatment relevant device are reduced, the purified treatment particularly suitable for high organic concentration caused by petroleum chemical industry, the organic exhaust gas of low oxygen content.
Description
Technical field
The invention belongs to waste gas purification field, is related to a kind of purifying treatment method of high-concentration organic waste gas, suitable for stone
The high organic concentration that is discharged in oily chemical industry production process, the purified treatment of low oxygen content organic exhaust gas.
Background technology
In the production process of some petroleum chemical industries, high-concentration organic waste gas, the composition of this waste gas can be given off
Based on organic component, such as benzene, hexamethylene, dimethylbenzene, oxirane etc., total hydrocarbon concentration arrives hundreds of thousands thousands of in waste gas
mg/m3Between.If this waste gas directly discharges without processing, national environmental protection regulation, and these nuisances can be not only violated
Matter and seriously damages the health of Enterprise Staff, or even threat to life in the diffusion that diffuses in device area.Therefore, to this kind of
High-concentration organic waste gas must take effective governing measure.
Processing to such high-concentration waste gas, catalysis burning is a kind of effective processing means.But urged using traditional
When changing combustion method processing, due to the oxygen content deficiency in some waste gas, it is therefore desirable to supplement a large amount of oxygen or air.Directly once
Property supplemental oxygen or air carry out being catalyzed burning processing, do not only exist the potential safety hazard of waste gas detonation, and organic component is urged
Change that combustion reaction heat release is higher, the temperature rise of catalytic combustion reactor is also resulted in, beyond holding for reactor and catalyst
By temperature, sintering of catalyst is set to fail.Although Macrodilution air can be added to be diluted, can make at the design of device
Reason scale is multiplied, so as to increase the investment cost of device and operation energy consumption.
CN200310104990.5 discloses a kind of purification method of high-concentration organic waste gas, by waste gas by pre-processing
Afterwards, it is pressurized by blower fan, is heated up by heat exchanger, electric heater, subsequently into catalytic combustion reactor, reactor outlet gas enters
Heat exchanger exchanges heat with waste gas, and steam or production hot water further occur for the waste gas after heat exchange.The invention is mainly characterized in that entrance
The reactor outlet gas of heat exchanger sets by-pass line and adjusts the tolerance of by-pass line, makes heat exchanger cold air outlet temperature low
In the reactor inlet temperature of setting, heater is kept in micro- heated condition；By-pass line is set in electric heater and adjusts side
Road flow, while substantially gas is reduced by heater pressure drop, keep reactor inlet temperatures stable.Inventive method master
Recuperator bypass is provided with for protection heat exchanger, but without the overtemperatute for solving catalytic combustion reactor, is adapted to processing
Organic exhaust gas concentration in 10000mg/m3Hereinafter, 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, and high-concentration organic waste gas is through changing
Enter one section of catalytic combustion reactor, a part for one section of catalytic combustion reactor emission and one section of catalysis after heat-preheating
Combustion reactor inlet exhaust gases exchange heat, and the remainder after heat exchange with one section of catalytic combustion reactor discharge gas is mixed into two sections
Catalytic combustion reactor, discharge after two sections of catalytic combustion reactor effluent gas recovery heats.The inventive method waste gas passes through two sections
After being catalyzed burning processing, purified gas qualified discharge, while also recyclable big energy.But this method also will be according to organic waste
Gas concentration carries out appropriate dilution, or if hypoxgia is, it is necessary to supplement air in waste gas, heat transmission equipment and firing equipment scale
It is both needed to increase.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of purifying treatment method of high-concentration organic waste gas.This hair
It is bright to avoid potential safety hazard caused by combustible gas deflagrating, sintering of catalyst caused by preventing reaction bed temperature too high,
The scale and operation energy consumption of waste gas treatment equipment are reduced, it is dense particularly suitable for the high organic matter caused by petroleum chemical industry
Spend, the purified treatment of the organic exhaust gas of low oxygen content.
The purifying treatment method of high-concentration organic waste gas of the present invention includes following content：Organic exhaust gas passes through heat exchange-preheating
After be passed through catalytic combustion reactor, the beds of some sections of isolation are set in reactor, and every section of beds are provided with useless
Gas is imported and exported, and oxygen supplement mouth and pipe-line mixer are provided with exhaust gas inlet pipeline, oxygen is entered after being well mixed with waste gas and is urged
Change combustion reactor, it is 350~600 DEG C that every section of bed outlet exhaust temperature is controlled by way of sectional oxygen supply so that waste gas
Middle organic matter carries out partially catalyzed combustion reaction in every section of bed；By exhaust gas flow direction, the last period beds have
Machine waste gas outlet is connected by heat reclaim unit with the organic exhaust gas import of latter section of bed so that waste air temperature at inlet is
150~400 DEG C, so as to take out the reaction heat that every section of catalysis burning discharges, realize the recovery of heat.
Organic exhaust gas of the present invention is high organic concentration, the organic waste of low oxygen content caused by petroleum chemical industry
Gas, organic concentration is 1.5 ten thousand~300,000 mg/m in waste gas3, preferably 30,000~150,000 mg/m3, not oxygen-containing or oxygen content is extremely low,
It is preferred that the volume content of oxygen such as can be to have the organic exhaust gas of volatile organic matter material tank discharge less than 5% or be one
Organic exhaust gas of a little anoxybiotic or hypoxemia commercial plant discharges etc., it is specific such as aromatic hydrocarbons tank discharge waste gas, volatile chemical drum
Discharge waste gas, product oil tank discharge waste gas etc..This kind of storage tank typically has a nitrogen protection for safety, and oxygen content is extremely low.
Organic exhaust gas passes through the volume space velocity of every section of beds in catalytic combustion reactor of the present invention（Standard state
Under）For 6000~200000h-1, preferably 10000~100000h-1；The waste air temperature at inlet of every section of beds is 150
~400 DEG C, preferably 200~300 DEG C；Outlet exhaust temperature is 350~600 DEG C, preferably 400~550 DEG C；Every section of catalyst bed
The temperature rise of layer, i.e. outlet exhaust temperature and the temperature difference of waste air temperature at inlet are 150~400 DEG C.The present invention is according to exhausted air quantity and has
Machine thing concentration determines catalyst amount, and required catalyst bed layer number is related to exhaust emission concentration, with being polluted in waste gas
The increase of thing concentration, bed quantity accordingly increase.
Honeycomb type noble metal catalyst is loaded in catalytic combustion reactor of the present invention, carrier is honeycomb ceramic body, is carried on a shoulder pole thereon
Active component Pt, Pd etc. is carried, wherein Pt contents are 0.2wt%~0.5wt%, and Pd contents are 0.1wt%~0.3wt%.
Organic exhaust gas of the present invention reaches temperature needed for catalytic combustion reactor entrance by exchanging heat and preheating, into catalysis
After combustion reactor, in the presence of catalyst, oxidation operation is carbon dioxide and water, thoroughly eliminates pollution.Heat exchange mode
The cold logistics of hot logistics and entrance for catalytic combustion reactor discharge exchanges heat, and can be reached by heat exchange urge under normal circumstances
Change the temperature requirement of combustion reactor entrance, be now just not required to heater preheating, heater is mainly in start-up process
Use.
The high temperature organic exhaust gas that the present invention discharges enter after taking heat into heat reclaim unit next section of beds after
It is continuous to carry out catalyst combustion reaction, reclaim the EGT after heat and meet initial reaction temperature needed for catalyst combustion reaction.Pass through
Repetitive segment supplies oxygen and segmentation takes heat, and until pollutant concentration reaches below discharge standard in waste gas, the discharge of final purification gas is warm
Spend for 300~500 DEG C, after preheating the cold organic exhaust gas before entering catalytic combustion reactor, discharged by aiutage.Heat
Retracting device can be the material to be heated in heat exchanger heating water, steam generator production steam or heat exchanger heating production
Material etc., independent heat exchanger channels are set, ensure the independence of each section of waste gas heat exchange.
Catalyst combustion reaction of the present invention can fill into air or oxygen, preferably fill into oxygen, because oxygen fires in catalysis
Burning in course of reaction to consume, and will not substantially increase exhaust-gas treatment amount, so as to ensure that waste gas in whole waste gas treatment process
The stabilization of amount.If carrying out delivery of supplemental oxygen using air, exhausted air quantity gradually increases in whole processing procedure, if each catalysis
Agent bed loads same amount of catalyst, then handles air speed and successively increase；If ensure the air speed of each beds not
Become, then the catalytic amount of each bed filling will gradually increase, and catalytic combustion reactor design scale will be according to capacity
Consider design.The present invention is no more than maximum temperature and oxygen concentration no more than flammable in every section of beds outlet exhaust temperature
In the case of gas burst maximum oxygen concentration, delivery of supplemental oxygen as far as possible, at utmost the organic matter in oxidation gaseous effluent, gives full play to and urges
The effect of agent, so as to reduce the catalyst bed number of plies.
Organic exhaust gas of the present invention can be pre-processed before catalytic combustion reactor is entered, and such as be gone in removing exhaust gas
The material for making catalyst for catalytic combustion be poisoned contained（Such as sulfide, halogen）；When exhaust gas concentration fluctuation is very big, taking must
The concentration homogenizing measure wanted；When containing particulate matter in waste gas, it is necessary to set filter plant to be removed；Storage-tank waste gas also has phase
The Stress control answered, when gaseous pressure exceedes setting pressure in storage tank, storage tank breather valve is opened, and the gas discharged out of tank leads to
Piping enters.
The purifying processing device of high-concentration organic waste gas of the invention using above-mentioned purifying treatment method, including air-introduced machine,
Heat exchanger, heater, catalytic combustion reactor, heat reclaim unit, aiutage, filter collector, pipe-line mixer and temperature
Control system, wherein setting the beds of some sections of isolation in the catalytic combustion reactor, every section of beds are all
Imported and exported provided with organic exhaust gas, oxygen supplement mouth and pipe-line mixer are provided with exhaust gas inlet pipeline, oxygen is mixed with waste gas
Enter catalytic combustion reactor after even and carry out partially catalyzed combustion reaction；By exhaust gas flow direction, the last period beds
Organic exhaust gas outlet is connected by heat reclaim unit with the organic exhaust gas import of latter section of bed, so as to take out every section of catalysis combustion
The reaction heat discharged is burnt, realizes the recovery of heat.
Compared with prior art, the present invention has following prominent characteristics：Set in catalytic combustion reactor multiple complete
The beds of isolation, by every section of bed be segmented the degree of oxygenating control catalyst combustion reaction, so as to control bed
The temperature of organic exhaust gas in layer, while the waste gas of every section of bed is drawn in time and carries out taking heat, it can be controlled while reclaiming heat
Produce the EGT after heat and meet initial reaction temperature needed for next section of catalyst combustion reaction.The inventive method need not use
Exhaust gas concentration is diluted to the concentration for the treatment of of single bed permission by substantial amounts of air, reduces the scale of waste gas treatment equipment（Such as
Pipeline, blower fan, exhaust gas heat exchanger and heater）And operation energy consumption.By controlling the magnitude of recruitment of each beds oxygen, make to have
Partial oxidation occurs for organic pollutants, while ensureing that catalysis burning is smoothed out, effectively avoids caused by combustible gas deflagrating
Potential safety hazard, while prevent from setting a beds to cause the too high caused sintering of catalyst of bed temperature.Pass through segmentation
Take the mode of heat fully to reclaim reaction heat, using the oxidation heat liberation of organic matter in waste gas, it is to be heated to produce hot water, steam or heating
Material, reach the purpose of energy-conservation.
Brief description of the drawings
Fig. 1 is the process chart of the inventive method；
Fig. 2 is the structural representation that sectional oxygen supply of the present invention and segmentation take heat.
Embodiment
The present invention program is described in further detail below by embodiment.
The purifying processing device of high-concentration organic waste gas of the present invention, including air-introduced machine, heat exchanger, heater, catalysis burning
Reactor, heat reclaim unit, aiutage, pipe-line mixer and temperature control system, wherein in the catalytic combustion reactor
Some completely isolated beds are set, and every section of beds are designed with organic exhaust gas inlet and outlet, each bed import
Pipeline is provided with oxygen supplement mouth and pipe-line mixer, after oxygen and organic exhaust gas are well mixed in pipe-line mixer, into catalysis
Agent bed.It is 350~600 DEG C that every section of bed outlet exhaust temperature is controlled by way of sectional oxygen supply, so that in waste gas
Organic matter carry out partially catalyzed combustion reaction in every section of bed；According to exhaust gas flow direction, the last period beds have
Machine waste gas outlet is connected by heat reclaim unit with the organic exhaust gas import of next section of bed, so as to control every section of bed import
EGT is 150~400 DEG C, and takes out every section of reaction heat for being catalyzed burning and discharging by heat reclaim unit, is realized
The recovery of heat.
The oxygenating amount of the inlet exhaust of every section of beds is controlled by the outlet temperature of every section of beds,
Every section of bed outlet exhaust temperature is 350~600 DEG C, so as to control the magnitude of recruitment of oxygen, prevents oxygen amount from excessively causing combustion heat release
It is excessive；When every section of beds inlet temperature is less than a certain design temperature between 150~400 DEG C, respective valve is automatically adjusted
Door, regulation high-temp waste gas enter the amount of heat reclaim unit, realize inlet temperature control.
Embodiment 1
Certain chemical enterprise has multiple expoxy propane storage tanks, is protected provided with nitrogen, storage tank average exhaust gas discharge capacity is 200Nm3/
H, propylene oxide concentrations 138000mg/m3, for oxygen concentration less than 1%, remaining is N2。
If handling the waste gas using Conventional catalytic burning process, in order that obtaining bed temperature rise is no more than 220 DEG C, epoxy third
Alkane concentration is no more than 9000mg/m3, then need more than 15 times of exhaust gas dilution.Therefore, emission-control equipment scale is 3000Nm3/
The scale of the equipment such as h, catalytic combustion reactor, air-introduced machine, heat exchanger, heater in handling process is 3000Nm3/ h, if
Standby investment and running expense are very high, and the volume space velocity of beds is 20000h-1, it is necessary to catalyst for catalytic combustion 150L.
Catalytic combustion reactor loads cellular noble metal catalyst, 0.26wt% containing Pt, 0.13wt% containing Pd in catalyst.
The scale of the organic exhaust gas, catalyst usage amount and catalytic combustion reactor is handled using present invention process and device
It is identical with above-mentioned catalytic combustion system, 15 sections of beds are set in catalytic combustion reactor, control every section of catalyst bed
Layer operation air speed is 20000h-1, then the equipment scale such as air-introduced machine, heat exchanger, heater remain as 200Nm3/ h, it is not necessary 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 it is 180-220 DEG C to control bed temperature rise, delivery of supplemental oxygen
Gas, control oxygenating amount cause every section of beds burning 8000-9000mg/m3Expoxy propane, every section of catalyst after reaction
The outlet exhaust temperature of bed is 410-470 DEG C, by heat recovery, 230-250 DEG C is cooled the temperature to, subsequently into next section
Beds continue to react.Final stage beds discharge purified gas, and total hydrocarbon concentration is less than 100mg/m3, heating entrance
Discharged after the cold organic exhaust gas of first paragraph beds.
In whole catalyticing combustion process, oxygen replenishment amount is 40-50Nm3/ h, organic pollution pass through every section of catalyst bed
Layer combustion heat release, the heat of recovery are used to produce steam, and using 40 DEG C of boiler water supply, 170 DEG C of production, 0.8MPa steam are about
180kg/t。
Embodiment 2
Certain chemical enterprise has benzene chemical plant installations tail gas, tolerance about 500Nm3/ h, total hydrocarbon concentration are about 53000mg/m3, mainly
Pollutant is benzene, toluene, aniline, cyclohexylamine, hexamethylene etc., and oxygen concentration is less than 2%, and remaining is N2。
If handling the waste gas using Conventional catalytic burning process, in order that obtaining bed temperature rise is no more than 250 DEG C, organic matter
Quantity combusted is no more than 7500mg/m3（In terms of total hydrocarbon concentration）, then need more than 7 times of exhaust gas dilution, then emission-control equipment is advised
Mould is 3500Nm3The scale of the equipment such as/h, catalytic combustion reactor, air-introduced machine, heat exchanger, heater in handling process is
3500Nm3/ h, equipment investment and running expense are very high.The volume space velocity of beds is 18000h-1, it is necessary to it is catalyzed burning
Catalyst 195L.Catalysis, which is burnt, uses cellular noble metal catalyst, 0.26wt% containing Pt, 0.13wt% containing Pd in catalyst.
The scale of the organic exhaust gas, catalyst usage amount and catalytic combustion reactor is handled using present invention process and device
It is identical with above-mentioned catalytic combustion system reactor, 7 sections of beds are set in catalytic combustion reactor, control every section of catalysis
Agent bed operation air speed is 18000h-1, then the equipment scale such as air-introduced machine, heat exchanger, heater remain as 500Nm3/ h, it is not necessary to
Increase the treatment scale of these equipment, greatly reduce equipment investment and running expense.
Each beds waste air temperature at inlet is 230-250 DEG C, and it is 200-250 DEG C to control bed temperature rise, delivery of supplemental oxygen
Gas, control oxygenating amount cause every section of beds burning 7000-8000mg/m3Organic matter（In terms of total hydrocarbon concentration）, reaction
The outlet exhaust temperature of every section of beds is 430-500 DEG C afterwards, by heat recovery, cools the temperature to 230-250 DEG C, so
Continue to react into next section of beds afterwards.Final stage beds discharge purified gas, and total hydrocarbon concentration is less than 80mg/
m3, each pollution concentration such as benzene, toluene is below discharge standard, and heating is into discharging after the cold material of first paragraph beds.
In whole catalyticing combustion process, oxygen replenishment amount is 55-70Nm3/ h, organic pollution pass through every section of catalyst bed
Layer combustion heat release, the heat of recovery are used to produce steam, and using 80 DEG C of boiler water supply, 170 DEG C of production, 0.8MPa steam are about
260kg/h。
Claims (10)
1. a kind of purifying treatment method of high-concentration organic waste gas, it is characterised in that including following content：Organic exhaust gas is by changing
Catalytic combustion reactor is passed through after heat-preheating, the beds of isolation are set in reactor, every section of beds are provided with useless
Gas is imported and exported, and oxygen supplement mouth and pipe-line mixer are provided with exhaust gas inlet pipeline, oxygen is entered after being well mixed with waste gas and is urged
Change combustion reactor, it is anti-that partially catalyzed burning is carried out in every section of bed by organic matter in the mode waste gas of sectional oxygen supply
Should, it is 350~600 DEG C to control every section of bed outlet exhaust temperature, is no more than most in every section of beds outlet exhaust temperature
High-temperature and oxygen concentration are no more than in the case of flammable gas explosion maximum oxygen concentration, as far as possible delivery of supplemental oxygen, at utmost oxygen
Change the organic matter in waste gas；By exhaust gas flow direction, the organic exhaust gas outlet of the last period beds is filled by heat recovery
Put and be connected with the organic exhaust gas import of latter section of bed so that waste air temperature at inlet is 150~400 DEG C, so as to take out catalysis combustion
The reaction heat discharged is burnt, realizes the recovery of heat；The organic exhaust gas is that high organic matter caused by petroleum chemical industry is dense
Spend, the organic exhaust gas of low oxygen content, organic concentration is 1.5 ten thousand~300,000 mg/m in waste gas3, the volume content of oxygen is less than 5%.
2. according to the method for claim 1, it is characterised in that：The organic exhaust gas is aromatic hydrocarbons tank discharge waste gas, Yi Hui
Chemical drum discharge waste gas or product oil tank discharge waste gas are sent out, organic concentration is 30,000~150,000 mg/m in waste gas3。
3. according to the method for claim 1, it is characterised in that：Organic exhaust gas is by every section of catalysis in catalytic combustion reactor
The volume space velocity of agent bed is 6000~200000h-1, the waste air temperature at inlet of every section of beds is 150~400 DEG C, is gone out
Mouth EGT is 350~600 DEG C, and the temperature rise of every section of beds is 50~400 DEG C.
4. according to the method for claim 3, it is characterised in that：Organic exhaust gas is by every section of catalysis in catalytic combustion reactor
The volume space velocity of agent bed is 10000~100000h-1, the waste air temperature at inlet of every section of beds is 200~300 DEG C, is gone out
Mouth EGT is 400~550 DEG C.
5. according to the method for claim 1, it is characterised in that：Catalytic combustion reactor is built with honeycomb type precious metal catalyst
Agent, carrier are honeycomb ceramic body, support active component Pt, Pd thereon, and wherein Pt contents are 0.2wt%~0.5wt%, Pd contents
For 0.1wt%~0.3wt%.
6. according to the method for claim 1, it is characterised in that：The high temperature organic exhaust gas of every section of bed discharge returns into heat
Continue catalyst combustion reaction into next section of beds after receiving apparatus recovery heat, reclaim the EGT after heat
Meet initial reaction temperature needed for catalyst combustion reaction, final purification gas exhaust temperature is 300~500 DEG C, is entered by preheating
After cold organic exhaust gas before catalytic combustion reactor, discharged by aiutage.
7. according to the method for claim 1, it is characterised in that：Heat reclaim unit is heat exchanger heating water, steam generation
Device produces the material to be heated in steam or heat exchanger heating production, sets independent heat exchanger channels.
8. according to the method for claim 1, it is characterised in that：Catalyst combustion reaction fills into air or oxygen.
9. according to the method for claim 1, it is characterised in that：The organic exhaust gas is entering catalytic combustion reactor advance
Row pretreatment, the material for making catalyst for catalytic combustion be poisoned for going to contain in removing exhaust gas；When exhaust gas concentration fluctuation is very big, take
Necessary concentration is homogenized measure；When containing particulate matter in waste gas, filter plant is set to be removed.
10. the purifying processing device of any processing high-concentration organic waste gas of claim 1 to 9, including air-introduced machine, heat exchange
Device, heater, catalytic combustion reactor, heat reclaim unit, aiutage, filter collector, pipe-line mixer and temperature control
System, wherein setting the beds of some isolation in the catalytic combustion reactor, every section of beds have been designed with
Machine waste gas is imported and exported, and oxygen supplement mouth and pipe-line mixer are provided with exhaust gas inlet pipeline, oxygen is well mixed with waste gas laggard
Enter catalytic combustion reactor and carry out partially catalyzed combustion reaction；By exhaust gas flow direction, the organic waste of the last period beds
Gas outlet is connected by heat reclaim unit with the organic exhaust gas import of latter section of bed, is discharged so as to take out catalysis burning
Reaction heat, realize the recovery of heat.
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