CN101637687A - Method for processing light hydrocarbons oxidation sweetening tail gas - Google Patents
Method for processing light hydrocarbons oxidation sweetening tail gas Download PDFInfo
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- CN101637687A CN101637687A CN200810012687A CN200810012687A CN101637687A CN 101637687 A CN101637687 A CN 101637687A CN 200810012687 A CN200810012687 A CN 200810012687A CN 200810012687 A CN200810012687 A CN 200810012687A CN 101637687 A CN101637687 A CN 101637687A
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Abstract
The invention discloses a method for processing light hydrocarbons oxidation sweetening tail gas. The method takes diesel distillate as an absorbent and adopts a countercurrent pulsed bubbling absorption tower; a gas phase is dispersed by a nozzle of the absorption tower, and is contacted with the absorbent in a bubbling absorption area to absorb volatile hydrocarbons in the gas phase; the nozzleof the absorption tower has a bubbling pulse valve structure; and the absorbent flows downwards through a downflow spout arranged on a tower plate of the bubbling absorption area. The method has the advantages of simple process, economy and reasonability, and accordance with environmental protection standards, and can be used for processing various light hydrocarbons oxidation sweetening tail gases.
Description
Technical field
The present invention relates to a kind of processing method of hydrocarbon-contained waste gas, particularly the processing method of light hydrocarbons material oxidation sweetening tail gas.
Background technology
The mercaptans content of light hydrocarbons material is one of important quality index, as liquid hydrocarbon, gasoline, kerosene etc.The light hydrocarbons of many explained hereafter all contains a certain amount of mercaptan, therefore needs suitable method to remove processing.Hydrogenation technique can be used for the light hydrocarbons removal of mercaptans, but hydrogenation method device complexity, and investment is big, the operating cost height, and some index of light hydrocarbons (as the octane number of gasoline) is influenced, as the disclosed gasoline desulfating method of CN1478866A etc.Oxidation sweetening is the important method of light hydrocarbons removal of mercaptans, promptly under certain condition, is disulphide etc. with air with the mercaptan oxidation in the light hydrocarbons, and further separates and remove, as US4, and 090,954 disclosed air sweetening method etc.The air sweetening process is carried out the air sweetening reaction with excessive air generally at a certain temperature, because the boiling point of light hydrocarbons material is relatively low, so contains a large amount of hydro carbons in the oxidized tail gas, general volume fraction can reach 5%～65%.
Owing to contain a large amount of hydro carbons in the oxidation sweetening tail gas, the processing method that adopts comprises that incinerator burns, directly enters atmosphere, enters atmosphere, condensation and methods such as Catalytic Oxygen combines after absorbing at present.The deficiency of incineration treatment method is to cause the ample resources waste, and has potential safety hazard owing to also containing oxygen in the tail gas.Directly enter atmosphere and not only waste resource, also cause serious environmental to pollute.Absorption process is to enter atmosphere after a kind of can reclaim most of hydro carbons, but because the increasingly stringent of environmental regulation can not be realized qualified discharge.Demercaptaning for gasoline by catalyst cracking exhaust gas treating method as " oil refining design " the 28th volume the 6th phase the 31st～32 page of introduction, adopt packed tower to absorb, hydro carbons in the removal of mercaptans tail gas is dropped to 0.5v%, usually below 2v%, this method adopts conventional absorption techniques, and its treatment effect needs further to improve.Condensation combines promptly with Catalytic Oxygen can reclaim most of volatile hydrocarbon, also can realize the tail gas qualified discharge, but its weak point is that technological process is long, the operating cost height, and economy is affected.
The economy of oxidation sweetening tail gas processing procedure is to realize the important indicator of commercial Application.Reclaim the hydro carbons in the tail gas to greatest extent, can additional income, but in general, after the hydrocarbon rate of recovery reaches certain limit, further increasing rate of recovery necessary operations expense again will increase greatly, thereby total economy descends; How the requirement of comprehensive qualified discharge determines oxidation sweetening tail gas processing method and controlled condition again, guarantees to reach under the prerequisite of discharge standard, realizes maximum economy, is the required primary study of oxidation sweetening tail gas processing method.
Summary of the invention
At the deficiencies in the prior art, the invention provides that a kind of process is simple, economical rationality, can meet the processing method of the light hydrocarbons material oxidation sweetening tail gas of environmental protection standard.
By research to light hydrocarbon oxidation sweetening tail gas character, the organic exhaust gas in this tail gas and other source has tangible difference, promptly has certain pressure, in general light hydrocarbon oxidation sweetening tail gas pressure can reach about 0.2MPa (gauge pressure), utilize the pressure design a kind of absorption process and the equipment of this tail gas, can simplify absorption process, reduce equipment scale, improve back rate efficient, increase process economy with pressure loss raising gas liquid contacting efficiency.
Light hydrocarbon oxidation sweetening tail gas processing method of the present invention, comprise following content: the selection diesel oil distillate is an absorbent, adopt adverse current pulsed bubbling absorption tower, gas phase is by contacting the volatile hydrocarbon that absorbs wherein with absorbent after the nozzle dispersion on absorption tower in the bubbling uptake zone, nozzle is a bubbling pulse valve structure, the bubbling pulse valve comprises that the bottom passes the logical tube of circle of bubbling uptake zone column plate, steel ball and steel ball limited cap, circular logical tube top movable is placed sealed steel ball, the steel ball limited cap is arranged on the steel ball top, steel ball limited cap and steel ball top are provided with suitable space, steel ball can be free movable between circle logical tube upper end open and steel ball limited cap, the steel ball limited cap is fixedlyed connected with circular logical tube, the steel ball limited cap is offered sieve aperture, and absorbent flows downward by the downspout that is arranged on the bubbling uptake zone column plate.
The inventive method adverse current pulsed bubbling can be provided with 1～5 grade of bubbling uptake zone in the absorption tower, and the height of liquid layer of every grade of bubbling uptake zone can be 100～1000mm, preferred 200～600mm, and absorption tower inlet liquid gas volume ratio is 50～500L/m
3, operating temperature can be carried out at ambient temperature, also can adopt the suitable type of cooling to reduce operating temperature.
The absorbent that the inventive method is used is diesel oil distillate, and preferred initial boiling point is the diesel oil distillate more than 200 ℃, and most preferably initial boiling point is the diesel oil distillate more than 220 ℃, specifically as catalytic diesel oil, normal two wires straight-run diesel oil, atmosphere 3rd side cut straight-run diesel oil etc.Absorbent absorbs and can directly loop back original diesel oil after the volatile component in the oxidation sweetening tail gas and heat up in a steamer treatment system, as hydrogenation system or fractionating system etc., can not impact the operation of original system.
Adopt in the tail gas after the present invention handles and still contain certain density volatile component, directly discharging does not still meet GB16297-1996 " discharge standard of air pollutants ".Think that by research though the tail gas concentration after the absorption does not meet discharge standard, because tolerance is less, total emission volumn is far below relevant national standard GB16297-1996 " discharge standard of air pollutants ".Therefore the inventive method recommends to adopt air dilution back discharging with low cost.Generally be provided with devices such as catalytic cracking system, hydrogenation system, fractionating system with the air sweetening device fitting, be equipped with the aerial cooler of some in these system and devices, the air mass flow of aerial cooler air blast is bigger, tail gas after the inventive method absorption is caused the aerial cooler air inlet, need not increase equipment and both finish the air dilution qualified discharge problem that absorbs back tail gas, not increase any operating cost yet.
The inventive method has the characteristics of certain pressure at light hydrocarbon oxidation sweetening tail gas, a kind of adverse current pulsed bubbling absorption tower has been used in design, this absorption tower is converted into gas phase homodisperse power in liquid phase by suitable nozzle arrangements with the pressure of oxidation sweetening tail gas, improved gas-liquid contact effect greatly, absorptivity and operating flexibility have been improved, reduce equipment scale, saved occupation of land.
Description of drawings
Fig. 1 is a kind of concrete process flow diagram of the present invention.
Fig. 2 is the installation diagram of a kind of concrete structure pulsed bubbling tower of the inventive method use.
Fig. 3 is a bubbling uptake zone tower tray modular construction schematic diagram.
Fig. 4 drenches liquid dish structural representation for the bubbling uptake zone.
Fig. 5 spatters plate dispensing arrangement schematic diagram for what drench the liquid dish.
Wherein: 1 is the gas outlet, and 2 is the upper end end socket, and 3 is demister, 4 is the liquid phase distributor, and 5 is bubbling uptake zone tower tray assembly, and 6 for drenching the liquid dish, 7 is liquid seal trough, and 8 is downspout, and 9 is cylindrical shell, 10 is vapor distributor, and 11 is air inlet, and 12 is low head, 13 is liquid outlet, 5-1 is a bubbling uptake zone column plate, and 5-2 is the circular logical tube of bubbling pulse valve, and 5-3 is a steel ball, 5-4 is the steel ball limited cap, 6-1 is the cylindrical shape cofferdam, and 6-2 is for drenching the liquid column plate, and 6-3 is for spattering the plate distributor, 6-3-1 is a pull bar, 6-3-2 is that plate is spattered on top, and 6-3-3 is that plate is spattered in the centre, and 6-3-4 is that plate is spattered in the bottom.
The specific embodiment
A kind of concrete structure on the pulsed bubbling absorption tower that the inventive method is used comprises cylindrical shell, vapor distributor, the liquid phase distributor, downspout and at least one bubbling uptake zone, in order to reach suitable absorptivity, the bubbling uptake zone is traditionally arranged to be 2～5 layers, vapor distributor is arranged on the cylindrical shell bottom, the liquid phase distributor is arranged on cylindrical shell top, the bubbling uptake zone is arranged between vapor distributor and the vapor distributor, bottom, bubbling uptake zone is the tower tray assembly, the tower tray assembly comprises that bubbling uptake zone column plate and distribution are arranged on the nozzle on the bubbling uptake zone column plate, nozzle is a bubbling pulse valve structure, bubbling pulse valve structure comprises that the bottom passes the logical tube of circle of bubbling uptake zone column plate, steel ball and steel ball limited cap, circular logical tube top movable is placed sealed steel ball, the steel ball limited cap is arranged on the steel ball top, steel ball limited cap and steel ball top are provided with suitable space, steel ball can be free movable between circle logical tube upper end open and steel ball limited cap, the steel ball limited cap is fixedlyed connected with circular logical tube, the steel ball limited cap is offered sieve aperture, and downspout is the logical barrel structure by bubbling uptake zone column plate.
In the bubble tower, below at least one bubbling uptake zone (being bubbling uptake zone layer), spray section is set, be provided with below the bubbling uptake zone and drench the liquid dish, downspout imports the liquid on the bubbling uptake zone and drenches the liquid dish, drenches the liquid dish liquid dispersion is contacted with the gas phase that upwards flows.The structure of drenching the liquid dish comprises drenches liquid column plate, cylindrical shape cofferdam and spatters the plate distributor, the cylindrical shape cofferdam distributes to be arranged on and drenches on the liquid column plate, the pouring liquid column plate of inside, cylindrical shape cofferdam is provided with opening, and the opening below is hung and spattered the plate distributor, and upper end, cylindrical shape cofferdam has the V-arrangement teeth groove.Spatter that the plate distributor spatters plate by at least one and pull bar constitutes, pull bar will spatter the plate distributor to be hung drenching liquid column plate bottom, spatters and offers sieve aperture on the plate.
The liquid level that downspout upper end open height need be controlled according to the bubbling uptake zone determines that upper end open is offered the V-arrangement teeth groove, and the downspout lower end is provided with liquid seal trough.
In the bubble tower of the present invention, bubble tower top is provided with inlet and gas outlet, and the bottom is provided with air inlet and liquid outlet, and vapor distributor communicates with air inlet, and the liquid phase distributor communicates with inlet.The liquid phase distributor is made of ring pipe, adapter and flange; The ring pipe lower surface is offered some apertures.Vapor distributor is made of concetrated pipe, some arms and flange; The arm lower surface is offered some apertures.
Spatter the plate distributor and can be the multi-deck screen plate structure, several layers spatter plate from top to bottom its diameter successively decrease, and with pull bar several layers is spattered plate and links together.Liquid seal trough is made of cylindrical shell and circular bottom plate, and several V-type teeth groove are offered in the cylindrical shell upper edge of liquid seal trough.
The sieve diameter that the steel ball limited cap is offered is Φ 1～Φ 5mm, and preferred diameter is Φ 3mm, and percent opening 10%～50% is preferably 30%.Downspout is tubular, and several V-type teeth groove are offered in the downspout upper edge, do not have changeover portion between teeth groove, 30 °～120 ° of teeth groove angles, preferred 60 °, tooth depth 3mm～20mm, preferred 10mm.Drench upper edge, liquid dish cylindrical shape cofferdam and offer several V-type teeth groove, do not have changeover portion between teeth groove, 30 °～120 ° of teeth groove angles, preferred 60 °, tooth depth 3mm～10mm, preferred 5mm.Spattering the plate distributor is the multi-deck screen plate structure, spatters to offer sieve aperture on the plate, and sieve diameter is Φ 5mm, and percent opening 20%～50% is preferably 30%.Several layers sieve plate its diameter from top to bottom successively decreases, and with pull bar several layers is spattered plate and link together.Liquid seal trough is made of cylindrical shell and circular bottom plate.Several V-type teeth groove are offered in the cylindrical shell upper edge of liquid seal trough, do not have changeover portion between teeth groove, 30 °～120 ° of teeth groove angles, preferred 60 °, tooth depth 3mm～20mm, preferred 10mm.Liquid seal trough is welded on and drenches on the liquid dish, and is higher than pouring liquid dish certain altitude, makes liquid seal trough top form the profile of tooth weir plate.
Bubble tower of the present invention is when work, and liquid phase enters into the liquid phase distributor that is arranged on cylindrical shell top by inlet, and some apertures of offering from the ring pipe lower surface are sprayed onto bed; Gas phase enters into vapor distributor from the tower bottom import, offers being distributed in the tower of some apertures from concetrated pipe arm lower surface.Downspout exceeds bubbling uptake zone column plate certain altitude, and liquid phase forms liquid layer on bubbling uptake zone column plate, and several V-type teeth groove are offered in the downspout upper edge, and whole bed liquid phase is evenly flowed.Gas phase is passed and is spattered the plate distributor, enter the bubbling pulse valve, generate bubble at steel ball limited cap place, be distributed in the liquid layer on the bubbling uptake zone column plate, because the steel ball limited cap is provided with sieve aperture, steel ball is in the unsettled air-flow, steel ball can continuously open and close, and gas phase forms pulsation stream, generates evenly on bubbling uptake zone column plate and the bubble of coalescence not, gas-liquid two-phase is realized the bubbling contact at this, carries out mass transfer and reaction.When tolerance (pressure) reduced, pulse valve cut out automatically, provided time of gathering to gas phase, and when tolerance (pressure) reaches when numerical value is set, pulse valve is opened automatically, and therefore, exercisable scope is very wide.
From flowing to liquid seal trough, the cylindrical shell upper edge of liquid seal trough is higher than drenches the liquid dish to liquid phase from downspout, and the cylindrical shell upper edge offers several V-type teeth groove, and liquid phase is evenly distributed to drenches on the liquid dish.Liquid phase is evenly distributed to each and spatters on the plate distributor, and liquid phase drops down onto in gravity effect tenesmus spatters on the plate, forms splash stream, forms countercurrent spray with from bottom to top gas phase and contact realization mass transfer and reaction.Said structure organically is combined in bubbling and two kinds of gas-liquid contact mass transfer means of spray in the equipment, has made full use of the device space simultaneously, has improved the serviceability of equipment.
The pulsed bubbling tower that the inventive method is used is provided with some inner members according to gas-liquid mass transfer and reaction process characteristics, and during work, liquid phase enters into the liquid phase distributor that is arranged on cylindrical shell top by inlet, is sprayed onto bed; Gas phase enters into vapor distributor from the tower bottom import, is distributed in the tower.Downspout exceeds the column plate certain altitude, and liquid phase forms liquid layer on bubbling uptake zone column plate; Several bubbling pulse valves have been installed on the bubbling uptake zone column plate, form air chamber between bubbling uptake zone column plate and pouring liquid column plate, open and close along with the bubbling pulse valve, this air chamber internal pressure generation rule fluctuation, gas phase forms pulsation stream, makes evenly and not coalescence of the bubble that generates in the liquid layer of gas phase on bubbling uptake zone column plate; Gas-liquid two-phase is realized the bubbling contact at this, carries out mass transfer and reaction.From flowing to liquid seal trough, the cylindrical shell upper edge of liquid seal trough is higher than drenches the liquid column plate to liquid phase from downspout, and liquid phase is evenly distributed to drenches on the liquid column plate, drench cylindrical shape cofferdam and respective numbers be set on the liquid column plate spatter the plate distributor; Liquid phase stream is gone into the cofferdam and is dropped down onto in gravity effect tenesmus and spatter on the plate, forms splash stream, forms countercurrent spray with from bottom to top gas phase and contact realization mass transfer and reaction.So far finish the bubbling-spray contact process of a bed.Above-mentioned mass transfer structure (structure that realizes the structure of bubbling and realize spraying) is made the vertical multi-stage cascaded structure, and gas-liquid two-phase is realized bubbling-spray contact process repeatedly, and realization liquid phase and gas phase are finished top-down adverse current " bubbling-spray " haptoreaction.This pulsed bubbling tower helps gaseous pressure is transformed the power of gas phase dispersion, simultaneously in same mass transfer apparatus with two kinds of gas-liquid way of contact combinations, gas liquid contacting efficiency height.
Embodiment 1
The laboratory small test.
Adopt one-level pulsed bubbling absorption tower, comprise a bubbling uptake zone, the absorption tower inner member is determined by preference data in the specific embodiment.Bubbling uptake zone liquid phase layer thickness is 400mm, and the spray section height is 300mm.Absorbent is three kinds of different diesel oil distillates.Absorbing back tail gas discharges with air dilution back.
Simulate oxidation sweetening tail gas with the air bubbling by gasoline fraction (70～170 ℃ of boiling ranges) and benzinum (30～60 ℃ of boiling ranges), absorb recovery test, the gas phase inlet pressure is 0.1MPa (gauge pressure), and the absorption tower outlet is normal pressure, the results list 1, table 2, table 3.(Nm
3Expression standard state cubic meter)
The different diesel oil distillates of table 1 are to the assimilation effect of gasoline oil gas
Table 2 catalytic diesel oil absorbs the influence of gasoline oil gas liquid-gas ratio to assimilation effect
Table 3 catalytic diesel oil absorbs benzinum oil gas effect
Embodiment 2
Certain gasoline oxidation removal of mercaptans tail gas hydrocarbon-containifirst 32v% of enterprise (volume fraction, down together), 53 ℃ of exhaust temperatures, oxygen content 17v%, pressure are 0.2MPa (gauge pressure), flow is 70Nm
3About/h.Adopt tertiary vein towards bubble absorbing tower, comprise three bubbling uptake zones and three spray uptake zones, the absorption tower inner member is determined by preference data in the specific embodiment.Bubbling uptake zone liquid phase layer thickness is 350mm, and the spray section height is 250mm.Absorbent is a catalytic diesel oil, and liquid-gas ratio is 100L/m
3, operating temperature is 25～40 ℃.Catalytic diesel oil after the absorption advances hydrogenation plant with other catalytic diesel oil, and the tail gas after the absorption causes catalytic cracking unit air cooler air inlet.
After absorbing processing, the volatile organic matter rate of recovery reaches 99% (quality) in the gasoline oxidation removal of mercaptans tail gas, and tail gas from absorption tower is a normal pressure, the about 50Nm of flow
3/ h, organic concentration is about 20g/Nm
3, the hydrocarbon rate of discharge is about 1kg/h.Absorb back tail gas and cause catalytic cracking unit aerial cooler air inlet, detect organic concentration from exhaust outlet and be about 90mg/Nm
3Tail gas concentration and mass rate of emission through aerial cooler all meet national environmental protection rules GB16297-1996 " discharge standard of air pollutants ".
Embodiment 3
With embodiment 2,, measure about 50Nm through absorbing the tail gas after handling
3/ h, organic concentration is about 20g/Nm
3, the hydrocarbon rate of discharge is about 1kg/h.Be diluted to total hydrocarbon concentration 50093000mg/Nm with air
3, adopt conventional heat-accumulation combustion device to handle, Purge gas meets existing discharging standards.
Embodiment 4
With embodiment 2,, measure about 50Nm through absorbing the tail gas after handling
3/ h, organic concentration is about 20g/Nm
3, the hydrocarbon rate of discharge is about 1kg/h.Be diluted to total hydrocarbon concentration 300098000mg/Nm with air
3, adopt conventional catalytic combustion system to handle, Purge gas meets existing discharging standards.
Embodiment 5
With embodiment 2,, measure about 50Nm through absorbing the tail gas after handling
3/ h, organic concentration is about 20g/Nm
3, the hydrocarbon rate of discharge is about 1kg/h, and this tail gas advances conventional absorbent charcoal adsorber to be handled, and the Purge gas body meets existing discharging standards.
Claims (10)
1, a kind of processing method of light hydrocarbon oxidation sweetening tail gas, comprise following content: the selection diesel oil distillate is an absorbent, adopt adverse current pulsed bubbling absorption tower, gas phase is by contacting the volatile hydrocarbon that absorbs wherein with absorbent after the nozzle dispersion on absorption tower in the bubbling uptake zone, it is characterized in that: the nozzle on absorption tower is a bubbling pulse valve structure, the bubbling pulse valve comprises that the bottom passes the logical tube of circle of bubbling uptake zone column plate, steel ball and steel ball limited cap, circular logical tube top movable is placed sealed steel ball, the steel ball limited cap is arranged on the steel ball top, steel ball limited cap and steel ball top are provided with suitable space, the steel ball limited cap is fixedlyed connected with circular logical tube, the steel ball limited cap is offered sieve aperture, and absorbent flows downward by the downspout that is arranged on the bubbling uptake zone column plate.
2, in accordance with the method for claim 1, it is characterized in that: described method adverse current pulsed bubbling is provided with 1～5 grade of bubbling uptake zone in the absorption tower.
3, in accordance with the method for claim 1, it is characterized in that: the height of liquid layer of described bubbling uptake zone is 100～1000mm, and absorption tower inlet liquid gas volume ratio is 50～500L/m
3
4, in accordance with the method for claim 1, it is characterized in that: described absorbent diesel oil distillate initial boiling point is more than 200 ℃.
5, in accordance with the method for claim 1, it is characterized in that: directly loop back original diesel oil after the volatile component in the absorbent absorption oxidation sweetening tail gas and heat up in a steamer treatment system.
6, according to claim 1 or 5 described methods, it is characterized in that: the fractionating system that loops back the hydrogenation system or the diesel oil distillate of diesel oil distillate after the volatile component in the absorbent absorption oxidation sweetening tail gas.
7, in accordance with the method for claim 1, it is characterized in that: the tail gas after adverse current pulsed bubbling absorption tower absorbs causes aerial cooler air inlet place.
8, in accordance with the method for claim 1, it is characterized in that: described pulsed bubbling absorption tower comprises cylindrical shell, vapor distributor, liquid phase distributor and downspout, vapor distributor is arranged on the cylindrical shell bottom, the liquid phase distributor is arranged on cylindrical shell top, and the bubbling uptake zone is arranged between vapor distributor and the vapor distributor.
9, in accordance with the method for claim 1, it is characterized in that: below at least one bubbling uptake zone, spray section is set, be provided with below the bubbling uptake zone and drench the liquid dish, downspout imports the liquid on the bubbling uptake zone and drenches the liquid dish, drenches the liquid dish liquid dispersion is contacted with the gas phase that upwards flows.
10, in accordance with the method for claim 9, it is characterized in that: the structure of described pouring liquid dish comprises drenches liquid column plate, cylindrical shape cofferdam and spatters the plate distributor, the cylindrical shape cofferdam distributes to be arranged on and drenches on the liquid column plate, the pouring liquid column plate of inside, cylindrical shape cofferdam is provided with opening, and the opening below is hung and spattered the plate distributor.
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