CN104566404B - Organic waste gas purification method - Google Patents
Organic waste gas purification method Download PDFInfo
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- CN104566404B CN104566404B CN201310518786.1A CN201310518786A CN104566404B CN 104566404 B CN104566404 B CN 104566404B CN 201310518786 A CN201310518786 A CN 201310518786A CN 104566404 B CN104566404 B CN 104566404B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides an organic waste gas purification method, which comprises the following contents that a mobile heat storage ball heat exchange system is used for recovering reaction heat, and organic waste gas is heated to reach reaction temperature; and catalytic combustion treatment is carried out, under the effects of catalysts, harmful substances in the waste gas are removed, wherein the heat storage ball heat exchange system comprises a heat storage pipe, a heat storage ball, a gear pump and a heat exchange section, the heat storage pipe forms a closed loop in a way of surrounding a catalytic combustion reactor, the gear pump pushes the heat storage ball to cyclically move in the heat storage pipe, the heat exchange section is a crossing part of a gas inlet pipe, a gas outlet pipe and the heat storage pipe, and is divided into a heat release section and a heat storage section, and the crossing cross sections of the gas and the heat storage ball are separated by a pipe net with holes. The organic waste gas purification method has the advantages that the mobile heat storage bal heat exchange system is used for realizing the heat exchange, the problem of too high temperature of the heat exchanger due to organic waste gas concentration increase is solved, the method is applicable to the waste gas of various production devices from petrochemical industry enterprises, and is particularly suitable for organic waste gas with higher organic pollutant concentration and lower oxygen contents.
Description
Technical field
The present invention relates to a kind of purification method of organic exhaust gas, and in particular to one kind processes high using catalytic combustion reactor
The method of concentration organic exhaust gas.Various process units waste gas suitable for coming from petrochemical enterprise, are particularly suitable for having
The organic exhaust gas that organic pollutants concentration is higher and oxygen content is relatively low.
Background technology
Catalytic combustion technology refers at a lower temperature, and the thorough oxygen of combustible component in waste gas is made in the presence of catalyst
Change and decompose, so that the method that waste gas is purified process.It is flammable or decomposable organic at high temperature that the method is applied to process
Gas.The advantage of catalysis burning has：Less is limited to combustible component concentration and calorific value, it is applied widely；Initiation temperature is low, big portion
Organic substance and CO is divided to complete reaction at 200~400 DEG C, therefore auxiliary fuel consumption is few, energy saving；Belong to without flame combustion
Burn, safety is good.And equipment is simple, small investment is easy to operate, and purification is thorough, therefore is that current most widely used, economy has
The treatment technology of effect.
The temperature of organic exhaust gas is generally below l00 DEG C, and concentration is also unstable, and heat can not be self-supporting, therefore anti-entering
Answer and need before device heat temperature raising.The typical process flow of catalytic combustion technology is：Organic exhaust gas are heated to through heater
Initiation temperature needed for catalyst combustion reaction, then enters catalytic combustion reactor, by waste gas purification in the presence of catalyst.By
Gas temperature is high after purification（400~600 DEG C）, it is to reclaim this partial heat, after the advanced preheater of waste gas being adopted and being purified
Gas converting heat, the method for reheating.CN03211736.1 discloses a kind of flow process of catalytic burning organic waste gas, and it is by wind
The integrated apparatus of the compositions such as machine, catalytic combustion reactor, electrical control cabinet, heat exchange of heat pipe；Catalytic combustion reactor is built-in
There are infrared ray heating pipe and catalyst；Catalytic combustion reactor exterior has air circulating umbilical；Blower fan is frequency conversion fan；Heat pipe is changed
Hot device in normal operation, air quantity and heat exchange of heat pipe is controlled to heat by frequency conversion fan for round trip and built with fin heat pipe
Recovery.The handling process heat transfer efficiency that the invention is proposed is high, energy saving, but if for the higher organic waste of concentration for the treatment of
, then there is certain drawback in gas.Because exhaust gas concentration is higher, catalytic reactor temperature is higher, and reaction generates the temperature of gas also therewith
It is substantially increased.Can so make heat exchange of heat pipe running temperature too high, for a long time at high temperature operation accelerates heat pipe scale velocity.
When the oxygen content in waste gas is lower, the speed of heat exchanger coking can be faster.And heat exchange of heat pipe not easy cleaning, fouling makes heat transfer
Coefficient is reduced, and the thermal efficiency is reduced, and service life shortens.If, always more than 500 DEG C, heat exchange of heat pipe can only for high temperature heat source temperature
Normal work 6 months or so.And in the case of larger for exhaust gas concentration fluctuation, if concentration increases suddenly, make heat exchanger temperature
Degree steeply rises, and results even in fire incident generation.So, using the method for heat exchange of heat pipe preheating waste gas, for highly concentrated
Degree and the relatively low organic exhaust gas of oxygen content and do not apply to.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of purification method of organic exhaust gas.The present invention adopts heat-storing sphere
Heat-exchange system realizes heat exchange, solves the problems, such as that heat exchange temperature is too high caused by the increase of organic exhaust gas concentration, it is adaptable to
Come from the various process units waste gas in petrochemical enterprise, be particularly suitable for that organic pollution concentration is higher and oxygen content compared with
Low organic exhaust gas.
The purification method of organic exhaust gas of the present invention, including following content：Reclaim anti-using portable heat-storing sphere heat-exchange system
Should be hot, heating organic exhaust gas reach reaction temperature；Then catalysis burn processing is carried out again, by waste gas in the presence of catalyst
Harmful substance removal；Wherein heat-storing sphere heat-exchange system includes heat accumulation pipe, heat-storing sphere, gear pump and heat exchanging segment, and heat accumulation pipe is surrounded
Catalytic combustion reactor forms closed-loop path, and gear pump promotes heat-storing sphere to move in heat accumulation pipe interior circulation, and heat exchanging segment is air inlet pipe
With escape pipe and the intersection of heat accumulation pipe, it is divided into heat release section and heat accumulating sections, gas uses pipe with holes with the section of intersecting of heat-storing sphere
Net separates.
In the present invention, heat-storing sphere adopts ceramic hollow heat-storing sphere, and ceramic heat-storing sphere has that heat-resisting, intensity is big, thermal capacitance is big, easy
The advantages of cleaning.The size of heat-storing sphere is 10~20mm of φ, is promoted by gear pump, is moved in pipeline.Heat-storing sphere is through heat exchange
The time of section is 20~60s.
In the present invention, air inlet pipe and escape pipe preferably carry out expanding in heat release section and heat accumulating sections, and expanding rear size is Primordial Qi
2~5 times of body caliber.Air inlet pipe and escape pipe and the caliber ratio of heat accumulation pipe are 8:1~1:1.
In the present invention, organic concentration is preferably 10000~12500mg/m in waste gas3, oxygen content is 1.0%~10%（V/
V）.Under nominal situation, waste gas flow velocity is 20000~25000Nmh-1。
In the present invention, heat-storing sphere exchanges heat in heat accumulating sections and purified gas, and heat-storing sphere temperature is increased to 300~450 DEG C；Move again
Exchange heat with untreated organic exhaust gas to heat release section, EGT is increased to 200~300 DEG C.It is not little in reactor outlet temperature
In the case of 350 DEG C, organic exhaust gas can be heated to reaction condition.
In the present invention, built with honeycomb type noble metal catalyst, carrier is honeycomb ceramic body to catalytic combustion reactor, thereon
Precious metals pt, Pd isoreactivity components are supported, wherein 0.2wt% containing Pt~0.5wt%, Pd 0.1wt%~0.3wt%.In catalyst
In the presence of, the organic component in waste gas is catalytically oxidized to carbon dioxide and water.The inlet temperature one of catalytic combustion reactor
As be 200~300 DEG C, using air speed be 10000~60000h-1.Catalytic combustion reactor outlet temperature be generally 400~
600℃.The use temperature and air speed of catalyst are adjusted according to the species and concentration of contained Organic substance in organic exhaust gas, it is higher
Reaction temperature can make organic exhaust gas have preferable clean-up effect, avoid organic exhaust gas to exchange heat with heat-storing sphere again but then
When, heat-storing sphere heat-exchange system can be entered.Device inside should be answered equipped with anti-explosion electric heater, if EGT does not reach requirement, can
It is further heated to require temperature.If exhaust gas concentration is little, reactor outlet temperature is low, and heat exchange is not enough, can open in reactor
Heater, it is ensured that catalysis ignition temperature.
In the present invention, blower fan selects frequency conversion fan, controls air quantity to ensure waste gas into reactor by frequency conversion fan
Concentration is not exceeded and waste gas is not mixed into heat-storing sphere heat-exchange system.Blower fan makes the pressure of organic exhaust gas more than the pressure of purified gas, wind
Amount is more than exhausted air quantity, so can ensure that waste gas may not flow into heat accumulation pipe.In addition, if exhaust gas concentration has exceeded catalysis burning instead
The inlet gas concentration of device is answered, air is added before preheating by blower fan, to reduce exhaust gas concentration, it is to avoid waste gas is anti-in catalytic bed
Seasonable heat release is more and cause catalyst because of high temperature deactivation.The addition of air can be controlled manually, or automatically control,
The signal for automatically controlling is from catalytic combustion reactor outlet temperature.
The present invention instead of traditional heat exchanger to be catalyzed burning as core using portable heat-storing sphere heat-exchange system, real
Show the heat exchange that gas passes in and out catalytic combustion reactor, on the one hand can meet organic exhaust gas into the temperature of reactor,
Ensure the purification efficiency of waste gas；On the other hand the reuse of heat can be realized with the reaction heat of gas after reclaiming clean.Meanwhile, solution
The drawbacks of heat exchanger coking that Conventional catalytic of having determined burning flow process is brought when high-concentration organic waste gas are processed is difficult to cleaning.This
The bright fluctuation to due to process units caused by exhaust gas concentration unexpected increase, with higher operating flexibility, will not exchange
Hot systems have a negative impact；And the heat-storing sphere for using is difficult coking and fouling, it is easy to clean, making for heat-exchange system is extended
Use the life-span.
Description of the drawings
Fig. 1 is the outline flowchart of apparatus of the present invention；
Wherein：1- air inlet pipe, 2- heat release sections, 3- blower fans, 4- catalytic combustion reactors, 5- heat accumulating sections, 6- escape pipes, 7- stores
Heat pipe, 8-gear pump.
Fig. 2 is the structural representation of heat accumulating sections and heat release section in heat-storing sphere heat-exchange system of the present invention；
Wherein：9- heat-storing spheres, 10- pipe networks with holes；Waste gas before 11- heat exchange, waste gas after 12- heat exchange, accumulation of heat before 13- heat exchange
Ball, heat-storing sphere after 14- heat exchange.
Specific embodiment
The purifier of organic exhaust gas of the present invention as depicted in figs. 1 and 2, including air inlet pipe 1, heat release section 2, blower fan 3, catalysis
Combustion reactor 4, heat accumulating sections 5, escape pipe 6, heat accumulation pipe 7, gear pump 8, heat-storing sphere 9 and pipe network with holes 10.Heat accumulation pipe 7 is surrounded and urged
Change combustion reactor 4 and form closed-loop path, gear pump 8 promotes heat-storing sphere 9 to move in heat accumulation pipe 7.Heat exchanging segment includes heat release section 2
With heat accumulating sections 5, air inlet pipe 1 is heat release section 2 with the intersection of heat accumulation pipe 7, and escape pipe 6 is heat accumulating sections with the intersection of heat accumulation pipe 7
5.In order to ensure heat-storing sphere normal movement, gas is separated with the section of intersecting of heat-storing sphere 9 using pipe network with holes 10.The knot of heat exchanging segment
Structure flow process is as shown in Fig. 2 waste gas 11 absorbs or releasing heat, waste gas 12 after becoming to exchange heat after heat-storing sphere heat exchange before exchanging heat；
And heat is released or absorbed to heat-storing sphere 13 after with exhaust gas contact before exchanging heat, become heat-storing sphere 14 after heat exchange.Heat-storing sphere is pottery
The hollow heat-storing sphere of porcelain, size is 10~20mm of φ.Heat-storing sphere is exchanged heat in accumulation of heat in-pipe through heat accumulating sections and heat release section
Time be 20~60S.To ensure heat transfer effect, air inlet pipe and escape pipe preferably carry out expanding, expansion in heat release section and heat accumulating sections
2~5 times of raw-gas pipe diameter are preferably dimensioned to be behind footpath, increase gas-solid heat exchange area.The caliber of gas pipeline and heat accumulation pipe
Than being preferably 8:1~1:1.Blower fan is set after heat release section, makes vacuum herein be more than heat accumulation pipe, waste gas is not mixed into heat-storing sphere and changes
Hot systems.So waste gas is heated to uniform temperature through heat release section by most of reaction recuperation of heat, and waste gas enters after blower fan
Enter catalytic combustion reactor, in the presence of catalyst, the organic component in waste gas is oxidized catalysis carbon dioxide and water, purification
Gas qualified discharge.Reactor built with honeycomb type noble metal catalyst, the inlet temperature of catalytic combustion reactor is generally 200~
300 DEG C, be 10000~60000h using space velocity range-1.Inside reactor is equipped with anti-explosion electric heater, if EGT reaches
Less than requiring, can be further heated to require temperature.
The present invention is further elucidated with reference to example, but is not limited to protection scope of the present invention.
Embodiment 1
One Chemical Manufacture tail gas, capacity is 2000~3000Nm3/ h, 80 DEG C of waste gas discharge temperature, waste gas is consisted of：
Nitrogen, oxygen, benzene, dimethylbenzene, ethylbenzene etc., waste gas total hydrocarbon concentration is 10000~25000 mg/m3, oxygen content is 4%~6%（V/
V）.
Processed using the device shown in Fig. 1 of the present invention.Heat-storing sphere is ceramic hollow heat-storing sphere, and size is φ 10mm.
Heat-storing sphere is 60s through the time that heat accumulating sections and heat release section are exchanged heat.The caliber of air inlet and escape pipe is 300mm, in heat release
Section and heat accumulating sections carry out expanding, and expanding rear size is 600mm, increases gas-solid heat exchange area, and the caliber of heat accumulation pipe is 80mm.Catalysis
Burning adopts cellular noble metal catalyst, 0.26wt% containing Pt, Pd 0.13wt% in catalyst.Due to the total hydrocarbon of the waste gas it is dense
Spend for 10000~25000 mg/m3, it is the safe operation for ensureing catalytic combustion reactor, it is therefore desirable to mix air by waste gas
Concentration dilution is to 10000 mg/m3.When reactor inlet temperatures are 230~245 DEG C, gas temperature is 560 after outlet purification
DEG C or so, after heat accumulating sections heat exchange, gas temperature drops to 350 DEG C.Heat-storing sphere, by heat accumulating sections, is heated to 410 in 60s
DEG C, heat release section is moved to, heating is newly entered waste gas, makes waste gas be heated to 240 DEG C, reaches catalyst combustion reaction requirement.Waste gas flow velocity
For 25000Nm.h-1.Heat transfer effect is shown in Table 1.
The heat transfer effect of heat-storing sphere heat-exchange system in the embodiment of table 1
Through catalysis burn processing, purified gas can meet discharging standards requirement to waste gas.Catalysis burn processing effect is shown in
Table 2.
Catalytic combustion reactor treatment effect in the embodiment of table 2
Embodiment 2
One Chemical Manufacture tail gas, capacity is 2000~3000Nm3/ h, 80 DEG C of waste gas discharge temperature, waste gas is consisted of：
Nitrogen, oxygen, benzene, dimethylbenzene, ethylbenzene etc., waste gas total hydrocarbon concentration is 10000~25000 mg/m3, oxygen content is 4%~6%（V/
V）.
Processed using the device shown in Fig. 1 of the present invention.Heat-storing sphere is ceramic hollow heat-storing sphere, and size is φ 20mm.
Heat-storing sphere is 30s through the time that heat accumulating sections and heat release section are exchanged heat.The caliber of air inlet pipe and escape pipe is 250mm, is being put
Hot arc and heat accumulating sections carry out expanding, and expanding rear size is 600mm, increases gas-solid heat exchange area, and the caliber of heat accumulation pipe is 600mm.
Catalysis burning adopts cellular noble metal catalyst, 0.26wt% containing Pt, Pd 0.13wt% in catalyst.It is total due to the waste gas
Hydrocarbon concentration is 10000~25000 mg/m3, it is the safe operation for ensureing catalytic combustion reactor, it is therefore desirable to which mixing air will
Exhaust gas concentration is diluted to 12500 mg/m3.When reactor inlet temperatures are 220~235 DEG C, gas temperature is after outlet purification
510 DEG C or so, after heat accumulating sections heat exchange, gas temperature drops to 300 DEG C.Heat-storing sphere, by heat accumulating sections, is heated in 30s
400 DEG C, heat release section is moved to, heating is newly entered waste gas, makes waste gas be heated to 230 DEG C, reaches catalyst combustion reaction requirement.Waste gas stream
Speed is 25000Nm.h-1.Heat transfer effect is shown in Table 3.
The heat transfer effect of heat-storing sphere heat-exchange system in the embodiment of table 3
Through catalysis burn processing, purified gas can meet discharging standards requirement to waste gas.Catalysis burn processing effect is shown in
Table 4.
Catalytic combustion reactor treatment effect in the embodiment of table 2
From result above, using the heat-storing sphere heat-exchange system of the present invention, heat-exchange system operating flexibility is larger, both can be with
Ensure the high-efficient purification of waste gas, effective reuse of heat with the reaction heat of gas after reclaiming clean, can be realized again.
Claims (10)
1. a kind of purification method of organic exhaust gas, it is characterised in that including following content：Using portable heat-storing sphere heat-exchange system
Reaction heat is reclaimed, heating organic exhaust gas reach reaction temperature, catalysis burn processing is then carried out again, will in the presence of catalyst
Harmful substance removal in waste gas；Wherein heat-storing sphere heat-exchange system includes heat accumulation pipe, heat-storing sphere, gear pump and heat exchanging segment, accumulation of heat
Pipe forms closed-loop path around catalytic combustion reactor, and gear pump promotes heat-storing sphere to move in heat accumulation pipe interior circulation, and heat exchanging segment is
Air inlet pipe and escape pipe and the intersection of heat accumulation pipe, are divided into heat release section and heat accumulating sections, and gas is used with the section of intersecting of heat-storing sphere
Pipe network with holes separates；Blower fan selects frequency conversion fan, and by frequency conversion fan air quantity is controlled, and the pressure for making organic exhaust gas is more than purified gas
Pressure, air quantity be more than exhausted air quantity；If exhaust gas concentration exceedes the inlet gas concentration of catalytic combustion reactor, by blower fan in preheating
Add air before, to reduce exhaust gas concentration.
2. method according to claim 1, it is characterised in that：Heat-storing sphere adopts ceramic hollow heat-storing sphere, and size is φ 10
~20mm.
3. method according to claim 1 and 2, it is characterised in that：Heat-storing sphere is 20~60s through the time of heat exchanging segment.
4. method according to claim 1 and 2, it is characterised in that：Air inlet pipe and escape pipe enter in heat release section and heat accumulating sections
Row is expanding, and expanding rear size is 2~5 times of raw-gas caliber.
5. method according to claim 4, it is characterised in that：Air inlet pipe or escape pipe and the caliber ratio of heat accumulation pipe are 8:1
~1:1.
6. method according to claim 1, it is characterised in that：Organic concentration is 10000~12500mg/m in waste gas3,
Oxygen content is 1.0%~10%（V/V）.
7. method according to claim 1, it is characterised in that：Waste gas flow velocity is 20000~25000Nmh-1。
8. method according to claim 1, it is characterised in that：Heat-storing sphere exchanges heat in heat accumulating sections and purified gas, heat-storing sphere temperature
Degree is increased to 300~450 DEG C；Moving again to heat release section to exchange heat with untreated organic exhaust gas, EGT is increased to 200~
300℃。
9. method according to claim 1, it is characterised in that：Catalytic combustion reactor is built with honeycomb type precious metal catalyst
Agent, carrier is honeycomb ceramic body, and precious metals pt, Pd are supported thereon, wherein 0.2wt% containing Pt~0.5wt%, Pd 0.1wt%~
0.3wt%。
10. the method according to claim 1 or 9, it is characterised in that：The inlet temperature of catalytic combustion reactor be 200~
300 DEG C, be 10000~60000h using air speed-1；Catalytic combustion reactor outlet temperature is 400~600 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105066148B (en) * | 2015-08-13 | 2017-09-29 | 中国石油化工股份有限公司青岛安全工程研究院 | The method that Low Temperature Storage hot type catalysis oxidation administers VOCs gases |
| CN105091001B (en) * | 2015-09-01 | 2017-11-14 | 黎明化工研究设计院有限责任公司 | A kind of waste gas burning processing equipment |
| CN105169938A (en) * | 2015-09-30 | 2015-12-23 | 马军 | Flowing particle heat exchange type organic waste gas oxidation equipment |
| CN106765218B (en) * | 2016-12-01 | 2024-03-22 | 广州斯而德农业科技有限公司 | VOCs waste gas comprehensive treatment heat energy utilization equipment |
| CN107152691A (en) * | 2017-06-22 | 2017-09-12 | 南京艾尔普特环保科技有限公司 | Low NOx afterburnings and the efficient minimizing technologies of VOC and system based on RTO |
| CN108031277B (en) * | 2017-12-08 | 2020-07-31 | 上海汉克威自动化科技有限公司 | VOC-containing waste gas catalytic purification treatment method |
| CN110030567B (en) * | 2019-04-10 | 2023-11-07 | 中国船舶重工集团公司第七一八研究所 | Organic waste gas catalytic combustion integrated device |
| CN110296424A (en) * | 2019-07-30 | 2019-10-01 | 天津理工大学 | A kind of thermal oxidation method of good antiscale property fluidized bed regenerative oxidation device and VOCs gas |
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