CN106642165A - Processing method for volatile organic compounds of refinery plant - Google Patents
Processing method for volatile organic compounds of refinery plant Download PDFInfo
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- CN106642165A CN106642165A CN201710059016.3A CN201710059016A CN106642165A CN 106642165 A CN106642165 A CN 106642165A CN 201710059016 A CN201710059016 A CN 201710059016A CN 106642165 A CN106642165 A CN 106642165A
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- volatile organic
- regenerator
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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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/60—Combustion in a catalytic combustion chamber
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
Abstract
The invention provides a processing method for VOCs (volatile organic compounds) of a refinery plant. The processing method is used for solving the problems of high cost, easiness in eroding equipment, secondary pollution, and the like, of a VOCs burning treatment process. The processing method comprises the following steps: introducing VOCs into a catalytic cracking regenerator along with main air, and then performing combustion reaction under the combustion-supporting effect of coke under the existence of a regenerating catalyst, wherein the temperature of the combustion reaction is 650-750 DEG C and the concentration of the VOCs before entering the regenerator is less than or equal to 30000mg/m<3>. The manner of introducing VOCs into the regenerator is random. For example, VOCs are accessed to a main air pipeline of an FCC regenerator and is mixed with main air, and then the mixture enters a gas distributor, is fully and uniformly mixed with main air (air) and then enters the regenerator for combustion treatment, or VOCs directly enter the regenerator through a standby fuel oil inlet and then is normally combusted in the regenerator.
Description
Technical field
The present invention relates to petrochemical industry, more particularly, to a kind of processing method of refinery's volatile organic matter.
Background technology
Volatile organic matter (VOCs) is the main predecessor of photochemical pollution, is to affect city and regional environmental quality
One of important pollutant.Petrochemical Enterprises can give off a certain amount of volatile organic matter in production, transport and sales process
(VOCs).The volatile organic matter of these discharges not only can be impacted to environment, produced harm to health, be will also result in
The very big economic loss of enterprise.Control volatile organic matter discharge and to discharge volatile organic matter processed into
The vital task reduce discharging for industry energy conservation, increased economic efficiency with environmental protection.
The emission source of Petrochemical Enterprises VOCs is broadly divided into leakage emission source and loss emission source.The VOCs for being discharged has dirt
Species are more for dye, emission point distribution is wide, quantization difficulty feature, the discharge of its VOCs essentially from crude oil and product storage tank,
Device leakage, wastewater treatment, boiler smoke, combustion process, technique heating, technique unit, handling and cooling tower etc..The place of VOCs
Reason method is divided into absorption method and method of elimination according to the state of tail gas after process.VOCs recovery technologies mainly include membrane separation process, inhale
Attached method, condensation method and absorption process etc., the organic pollution of recovery are also needed through further disposal, and technique is relative complex, cost
It is higher, and easily cause the secondary pollution of environment.The selectivity and separating effect of membrane separation process and absorption method is poor；And condensation method and
The high energy consumption of absorption process, and need to consume a certain amount of absorbent.And technology for eliminating mainly includes combustion method (flame combustion/urge
Change burning), photocatalytic oxidation and bioanalysises etc., its principle is by chemical or biological reactionss, in light, thermocatalyst and micro- life
Organic substance is converted into into water and CO under the effect such as thing2Deng innocuous substance.By contrast, direct method of elimination is except a small amount of water and temperature
Room gas CO2Discharge is outer, does not result in secondary pollution, and process the most thoroughly, general clearance is made up to more than 96%
Its application is more universal.
Combustion method processes the characteristics of VOCs has process is simple, purification efficiency is high, but is separately provided at burner at present
Reason VOCs, brings to enterprise that operating cost is relatively higher, equipment is perishable, have secondary pollution problems, especially cost therewith
Problem, this is related to Business survival problem, directly determines enterprise's whether positive treatment VOCs pollution problem.
In view of this, it is special to propose the present invention.
The content of the invention
It is an object of the invention to provide a kind of processing method of volatile organic matter, described processing method is solved
VOCs burning treatment process high costs, equipment are perishable, secondary pollution problems.
In order to realize object above, the invention provides technical scheme below：
Volatile organic matter is passed through catalytic cracking regenerator by a kind of processing method of refinery's volatile organic matter
In, the combustion-supporting lower generation combustion reaction of coke in regenerated catalyst, the temperature of the combustion reaction is 690-750 DEG C, can be waved
The concentration that the property sent out Organic substance is entered before regenerator is≤30000mg/m3。
Main wind of the present invention refers mainly to the oxygen of air, or various purity.
Wherein, the mode that VOCs is passed through regenerator be it is arbitrary, for example：
VOCs accesses the air main line of FCC regeneratoies, after mixing with main wind, initially enters a gas distributor, so that
VOCs is sufficiently mixed uniformly with main wind (air), carries out burn processing subsequently into regenerator.Waste gas after burning enters original
The environmental protecting device such as dedusting, desulfurization and denitration, empty after conformance with standard.
Or, VOCs is directly entered regenerator by guarantee fuel oil-in, and then normal combustion is processed in the regenerator.
Compared with prior art, main innovative point of the invention be by refinery existing equipment catalytic cracking regenerator and
Regenerated flue gas processing equipment makes full use of, and realizes one-object-many-purposes, so as to solve conventional VOCS processing method high costs, secondary dirt
The problems such as dye, equipment corrosion.It is specific as follows.
Fluid catalytic cracking (FCC) regenerator is one of indispensable equipment of existing petroleum catalytic cracking technique, its main work(
Can be that regeneration is circulated to the catalyst used by catalytic cracking, the present invention is exactly carried out to VOCs using this existing equipment
Burn processing, so as to avoid increasing sky high cost and the issuable secondary pollution problem brought by new equipment.
A bit more crucial, the present invention process VOCs using FCC regeneratoies and the regenerative process of catalyst can't be produced
Any adverse effect, i.e. VOCs and regenerated catalyst can occur combustion reaction in same FCC regeneratoies simultaneously, be respectively completed
The burning of VOCs and the regeneration of catalyst.
Further, since the present invention selects specific temperature and certain density volatile organic matter, make VOCs burn and produce
It is negligible that raw heat compares catalyst reactivation heat, therefore without the need for transform to interior heat collecting device.
To sum up, processing method of the invention possesses following characteristics：
1st, save the cost for increasing that equipment brings.
2nd, VOCs can be coexisted with catalyst, while carrying out combustion reaction, i.e., the present invention is not any to the regeneration of catalyst
Substantial effect.
Said method is spirit of the invention, and each of which step or process conditions further can also be improved, for example：
Preferably, volatile organic matter is≤30000mg/m into the concentration before regenerator3, preferably≤25000mg/
m3, preferably≤20000mg/m3, preferred 16000mg/m3。
Effective control enters the VOCs concentration of regenerator, can both realize the efficient removal of VOCs, also will not be to original
The normal production run of FCC regeneratoies produces any bad impact, has simply just initially entered regenerator and its concentration in VOCs
(it is 20000mg/m with the mixed concentration of main wind when higher3And more than), in regenerator, temperature slightly rises, but recovers quickly
To normal.In addition when VOCs concentration reaches 20000mg/m3And during the above, diesel oil absorption technique is preferably used by high concentration
VOCs is reclaimed, and then carries out burn processing in FCC regeneratoies again.Under normal production conditions, the VOCs of high concentration is in regeneration
Burnt in device rapidly and generate a small amount of carbon dioxide and water, will be controlled in certain model into the VOCs concentration before regenerator
In enclosing, i.e. VOCs concentration is not higher than 20000mg/m3, the relatively minimal amount of vapor for being generated will not be to regenerator catalyst
Activity and stability produce substantial impact, and reaction heat is less, and temperature does not have larger fluctuation, it is not necessary to original
The hot facility that takes having is transformed, and the danger of combustion explosion more crucially will not be produced because the concentration of VOCs is higher.
In order to improve the removal efficiency of volatile organic matter, it is preferable that the temperature of the combustion reaction is 650-710 DEG C,
Consider the factor such as energy consumption and removal efficiency and catalyst regeneration efficiency, temperature is preferred 680-700 DEG C, such as 680 DEG C, 685
DEG C, 690 DEG C, 700 DEG C.
Under normal circumstances, there is smoke processing system after the catalytic cracking master device of refinery, to process catalytically cracked material
In sulfur, the compound such as the nitrogen SOx that formed in a regenerator and NOx and the dust produced by catalyst itself etc..VOCs
In sulfur, the compound such as nitrogen can also form the harmful gass such as SOx and NOx in combustion, therefore need not increase extra
Flue gas aftertreatment technology and equipment, directly using the purifier of original process FCC regenerated flue gas, are carried out to its technological parameter
Corresponding appropriate adjustment, you can reach requirement, meet discharge standard.
Preferably, the method for the purified treatment is：
The flue gas is contacted with desulphurization circulating liquid in chilling desulfurizing tower, carry out cooling down, dedusting, desulfurization, the cigarette after desulfurization
Gas SOx concentration is less than 150mg/m3；
Denitrating tower bottom is entered after flue gas removing dust demister after the desulfurization, is inversely contacted with denitration liquid, after purification
Flue gas empty Jing after mechanical demister, realize the target of minimum discharge.
Above purifying treatment method realizes the minimum discharge of flue gas with relatively low cost.
Compared with prior art, the present invention is not only that various differences are purified process combination, but considers desulfurization comprehensively
Denitration cost, SOx removal efficiencies, NOx removal rate etc., flue gas is carried out cooling down by alkali cleaning, dedusting, desulfurization, the flue gas after desulfurization
Middle SOx maximum concentrations are no more than 150mg/m3, the consumption of follow-up denitration liquid is reduced as far as possible, reduces desulphurization denitration cost, then Jing
Cross dedusting demister and further remove flue fog drip and particulate matter, both purified flue gas, reduce again because flue gas carry secretly into
Enter the amount of the doctor solution of denitrating tower, reduce the consumption of follow-up denitration liquid, reduce denitration cost.Chlorite is recycled finally
Doing oxidant carries out deep desulfuration, denitration, the compositional liquor of the chlorite after advantageous embodiment and hypochlorite, after purification in flue gas
Sulfoxide concentration is substantially zeroed, and NOx is 30mg/m3Hereinafter, reach the target of minimum discharge.
Preferably, the circulation desulfurization liquid is soda lye, and its pH value is 5～9, such as 6,7,8,9.
Preferably, the denitration liquid is that, containing chloritic alkaline solution, its pH value is 7～13, and mass percent is dense
Spend for 0.1～10wt%, preferably 0.1～5wt%, such as 0.2wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 7wt%,
9wt%.
When chlorite concentration is higher, denitrification efficiency is high, but corresponding cost also increases, while utilization rate is reduced,
It is not suitable for industrial applications, is 0.1～10wt% chlorites and auxiliary combination after-purification effect from mass percent concentration
More preferably, cost performance is higher, and more preferably mass percent concentration is 0.1～5wt%.
Preferably, also contain hypochlorite in the denitration liquid, it is weaker that hypochlorite compares chlorite oxidation's property, but with
After chlorite compounding, its oxidisability is also stronger than single chlorite, and hypochlorite low cost, so using both
Compositional liquor, it is ensured that while high removal efficiency, can be with reduces cost, and preferred mass percent concentration is 0.1～10wt%, preferably
0.1～5wt%, for example, 0.5wt%, wt%, 0.7wt%, 0.8wt%, 1wt%, 2wt%, 3wt%, 4wt%.
Preferably, in the denitration liquid, hypochlorite and chloritic mol ratio are 0.01～15:1, preferably 0.01～
8:1。
Preferably, the response time during denitration is 0.1～5 second, preferably 0.5～2 second.
To sum up, compared with prior art, invention achieves following technique effect：
(1) cost is substantially reduced, real to lighten the burden for enterprise.
(2) solve the pollution problem that VOCs burnings are produced.
(3) it is compatible with existing equipment, it is easier to promote.
(4) the ultra-clean discharge of flue gas can be realized：SOx in purifying smoke realizes that zero-emission, NOx content control exist substantially
30mg/Nm3Below.
Specific embodiment
Technical scheme is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that, following described embodiment is a part of embodiment of the invention, rather than the embodiment of whole,
The present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment obtained under the premise of creative work is not made by art personnel, belongs to the model of present invention protection
Enclose.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer are carried out.Agents useful for same or instrument
Unreceipted production firm person, is the conventional products that can pass through that commercially available purchase is obtained.
Embodiment 1
On FCC pilot-plants, in 690 DEG C of regenerator temperature, main air quantity 1.0m3/ h, with catalytic gasoline as simulate VOCs
Under conditions of charging, the concentration (referring both to relative to main wind) of VOCs is 5160mg/m3When, removal efficiency is up to 100%.
Embodiment 2
On FCC pilot-plants, in 690 DEG C of regenerator temperature, main air quantity 1.0m3/ h, with catalytic gasoline as simulate VOCs
Under conditions of charging, the concentration of VOCs is 12900mg/m3When, removal efficiency is up to 99.5%.Embodiment 3
On FCC pilot-plants, in 690 DEG C of regenerator temperature, main air quantity 1.0m3/ h, with catalytic gasoline as simulate VOCs
Under conditions of charging, VOCs concentration is 20000mg/m3When, removal efficiency is 97.8%.
Embodiment 4
On FCC pilot-plants, in 690 DEG C of regenerator temperature, main air quantity 1.0m3Under conditions of/h, when with virgin kerosene
For simulation charging, VOCs concentration is 10000mg/m3When, removal efficiency is 99.8%.
Embodiment 5
On FCC pilot-plants, in 690 DEG C of regenerator temperature, main air quantity 1.0m3Under conditions of/h, when with virgin kerosene
For simulation charging, VOCs concentration is 20000mg/m3When, removal efficiency is 97.6%, and removal efficiency has reached good result.
Embodiment 6
Following purified treatment is carried out to the flue gas that embodiment 5 is produced：
Desulfurization：
It is fully contacted with circulation fluid in chilling scrubbing tower from FCC regenerator devices waste heat boiler flue gas out, passes through
Fresh soda lye is added, and circulation fluid pH value is controlled for 5～9.Chilling scrubbing tower is void tower.SO 2 from fume concentration after purification
For 30mg/m3, desulfurization degree is 83.3%.
Denitration：
Inversely it is fully contacted from desulfurizing tower flue gas out into denitration tower bottom and denitration liquid, denitrating tower is packed tower.
Sodium chlorite solution is adopted for absorbent, its mass fraction is 4%.It is 50 DEG C to absorb temperature, and the time of staying is 1s, and liquid-gas ratio is
0.5L/m3.Jing after counter current contacting, SOx, NOx are substantially oxidized absorption, and sulfur dioxide in flue gas concentration is substantially zeroed, in flue gas
NOx concentration is down to 30mg/m3。
Embodiment 7
From the difference of embodiment 6 be purified treatment condition it is different：
Desulfurization
It is fully contacted with circulation fluid in chilling scrubbing tower from FCC regenerator devices waste heat boiler high-temperature flue gas out,
By adding fresh soda lye, circulation fluid pH value is controlled for 5～9.Chilling scrubbing tower is void tower.SO 2 from fume after purification
Concentration is 29.5mg/m3, desulfurization degree is 88%.
Denitration
Inversely it is fully contacted from desulfurizing tower flue gas out into denitration tower bottom and denitration liquid, denitrating tower is packed tower.
Sodium chlorite solution is adopted for absorbent, its mass fraction is 1.5%.It is 50 DEG C to absorb temperature, and the time of staying is 1s, liquid-gas ratio
For 0.4L/m3.Jing after counter current contacting, SOx, NOx are substantially oxidized absorption, and sulfur dioxide in flue gas concentration is substantially zeroed, flue gas
Middle NOx concentration is down to 15mg/m3。
Embodiment 8
From the difference of embodiment 6 be purified treatment condition it is different：
Desulfurization
It is fully contacted with circulation fluid in chilling scrubbing tower from FCC regenerator devices waste heat boiler flue gas out, passes through
Fresh soda lye is added, and loop slurry pH value is controlled for 5～9.Chilling scrubbing tower is void tower.SO 2 from fume after purification is dense
Spend for 42mg/m3, desulfurization degree is 85.5%.
Denitration
Inversely it is fully contacted from desulfurizing tower flue gas out into denitration tower bottom and denitration liquid, denitrating tower is packed tower.
Temperature be 50 DEG C, liquid-gas ratio be 0.3L/m3, denitration liquid NaClO2When mass concentration is 2.5%, time of staying 1.1S, SOx,
NOx is substantially oxidized absorption, and after denitration, sulfur dioxide in flue gas concentration is substantially zeroed, and NOx is 25mg/m3。
Embodiment 9
NaClO when difference with embodiment 8 is denitration2Mass percent concentration is 6%.
After denitration, sulfur dioxide in flue gas concentration is substantially zeroed, and NOx is 5mg/m3Below.
To sum up, all embodiment results show：The present invention can be realized using FCC regeneratoies while carrying out VOCs burnings
Process and catalyst regeneration, the VOCs of low cost, quickly and efficiently removing Petrochemical Enterprises, it is also possible to realize the ultralow row of flue gas
Put.
Finally it should be noted that：Various embodiments above only to illustrate technical scheme, rather than a limitation；To the greatest extent
Pipe has been described in detail to the present invention with reference to foregoing embodiments, it will be understood by those within the art that：Its according to
So the technical scheme described in foregoing embodiments can be modified, or which part or all technical characteristic are entered
Row equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of processing method of refinery's volatile organic matter, it is characterised in that volatile organic matter is passed through into catalysis and is split
Change in regenerator, the combustion-supporting lower generation combustion reaction of coke in regenerated catalyst, the temperature of the combustion reaction is 650-750
DEG C, the concentration that volatile organic matter is entered before regenerator is≤30000mg/m3。
2. the processing method of refinery's volatile organic matter according to claim 1, it is characterised in that volatile is organic
It is≤25000mg/m that thing enters the concentration of regenerator3。
3. the processing method of refinery's volatile organic matter according to claim 2, it is characterised in that volatile is organic
It is≤20000mg/m that thing enters the concentration of regenerator3。
4. the processing method of refinery's volatile organic matter according to claim 3, it is characterised in that volatile is organic
It is≤16000mg/m that thing enters the concentration of regenerator3。
5. the processing method of refinery's volatile organic matter according to claim 1, it is characterised in that the combustion reaction
Temperature be 690-710 DEG C.
6. the processing method of the refinery's volatile organic matter according to any one of claim 1-5, it is characterised in that in institute
While stating volatile organic matter generation combustion reaction, the volatile organic matter and the regenerated catalyst occur simultaneously
Combustion reaction；Smoke processing system is entered together with the flue gas that flue gas after VOCS burnings regenerates generation with regenerated catalyst.
7. the processing method of refinery's volatile organic matter according to claim 6, it is characterised in that the fume treatment
Method be：
The flue gas is contacted with desulphurization circulating liquid in chilling desulfurizing tower, carry out cooling down, dedusting, desulfurization, the flue gas SOx after desulfurization
Concentration is less than 150mg/m3；
Denitrating tower bottom is entered after flue gas removing dust demister after the desulfurization, is inversely contacted with denitration liquid, the cigarette after purification
Gas is emptied Jing after mechanical demister.
8. the processing method of refinery's volatile organic matter according to claim 7, it is characterised in that the circulation fluid is
Soda lye, its pH value are 5～9.
9. the processing method of refinery's volatile organic matter according to claim 7, it is characterised in that the denitration liquid is
Containing chloritic alkaline solution, its pH value be 7～13, mass percent concentration be 0.1～10wt%, preferably 0.1～
5wt%.
10. the processing method of refinery's volatile organic matter according to claim 9, it is characterised in that the denitration liquid
In also contain hypochlorite, mass percent concentration is 0.1～10wt%, preferably 0.1～5wt%.
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Cited By (5)
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| CN107420922A (en) * | 2017-08-01 | 2017-12-01 | 中石化炼化工程（集团）股份有限公司 | The processing method of refinery's volatile organic matter |
| CN108870420A (en) * | 2018-07-17 | 2018-11-23 | 中石化（洛阳）科技有限公司 | A kind of processing method of coal chemical industry enterprises volatile organic matter |
| CN109224756A (en) * | 2018-10-19 | 2019-01-18 | 南京工业大学 | A kind of skid-mounted system using deep cooling condensation method recycling VOCs |
| CN111617596A (en) * | 2019-02-28 | 2020-09-04 | 中国石化工程建设有限公司 | Method for treating gas containing VOCs |
| CN113117520A (en) * | 2019-12-31 | 2021-07-16 | 中国石化工程建设有限公司 | Device and method for processing VOCs |
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