CN104815519A - Recovery technology for volatile oil gas in lightweight aromatic hydrocarbons filling process - Google Patents
Recovery technology for volatile oil gas in lightweight aromatic hydrocarbons filling process Download PDFInfo
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- 238000011084 recovery Methods 0.000 title claims abstract description 44
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 37
- 238000005429 filling process Methods 0.000 title claims abstract description 20
- 238000005516 engineering process Methods 0.000 title abstract description 5
- 239000000341 volatile oil Substances 0.000 title 1
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- 238000003795 desorption Methods 0.000 claims abstract description 53
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 230000008929 regeneration Effects 0.000 claims abstract description 11
- 238000011069 regeneration method Methods 0.000 claims abstract description 11
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- 238000005859 coupling reaction Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000005086 pumping Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002156 adsorbate Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 48
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- 238000010407 vacuum cleaning Methods 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 description 3
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a recovery technology for volatile aromatic hydrocarbons oil gas in filling process of lightweight aromatic hydrocarbons such as benzene, toluene, xylene and mixed aromatic hydrocarbons, a regeneration technology by combining normal pressure adsorption, vacuum desorption and vacuum cleaning is employed, the lightweight aromatic hydrocarbons after recovery is condensed to liquid by condensers of two condensing sections, and the processed purifying tail gas can satisfy a national discharge standard.
Description
Technical field
The present invention relates to the recovery process that a kind of light aromatics stores the aromatic hydrocarbons oil gas that the filling process in transit link produces.Exactly, be a kind of recovery process light aromatics such as benzene,toluene,xylene, BTX aromatics being loaded a kind of volatile aromatic oil gas produced in the process of the containers such as tank wagon, train tank car, oil tanker, storage tank.
Background technology
The light aromatics such as benzene,toluene,xylene BTX aromatics are the important raw materials of industry, are widely used in the every field of national economy.At the storage transit link of these light aromatics, filling process is very general, as the light aromatics such as benzene,toluene,xylene, BTX aromatics liquid is loaded the containers such as tank wagon, train tank car, oil tanker, storage tank.In filling process, part light aromatics component can evaporate from liquid, the mist (hereinafter referred to as aromatic hydrocarbons oil gas) of light aromatics component and air is formed with the inert gas be present in container (as air), along with light aromatics liquid to filling in container, the aromatic hydrocarbons oil gas of generation can be forced to discharge container.Aromatic naphtha tolerance and concentration that filling process produces are with the boiling point size of aromatic hydrocarbons and to fill temperature different and different, as often filled 1m at 30 DEG C of temperature
3benzene discharges 1.1m
3the benzene oil gas of left and right, the benzene concentration of benzene oil gas can reach 5 ~ 15v%, is equivalent to 175 ~ 520g/m
3, namely often fill 1t benzene, run the benzene damaging about 0.5kg with oil gas.Because light aromatics is stronger relative to volatility other heavy arene, toxicity is larger, if do not recycled the volatile aromatic oil gas that light aromatics filling process produces, not only cause the waste of resource, and affect the healthy of charging operation personnel, increase the danger of fire and blast, pollutant atmosphere.According to the regulation of country " discharge standard of air pollutants " GB16297-1996, the concentration of emission limit value of waste gas containing benzene is 12mg/m
3, toluene is 40mg/m
3, dimethylbenzene is 70mg/m
3.The aromatic hydrocarbons oil gas that visible light aromatics filling process produces can not qualified discharge without process.
US Patent No. .Pat.No.4066423, US.Pat.No.4276058, US.Pat.No.4462811, US.Pat.No.5480475, US.Pat.No.5951741 etc., propose the method for absorption method separation and recovery hydrocarbon component the mist of hydrocarbon component and the air produced from filling process in succession.According to above-mentioned patent, the oil-gas closed collection of discharging when filling hydrocarbon liquids is entered two blocked operations, load the adsorbent bed of active carbon, active carbon is utilized to have stronger absorption affinity and the feature more weak to air adsorption power to hydrocarbon component, being adsorbed by hydrocarbon component in adsorption process, then there is not absorption and directly enters air through bed in air.When the adsorbent in adsorbent bed reaches certain adsorption saturation, adsorbent bed is switched to reproduced state, by the negative pressure that vavuum pump provides, absorption hydrocarbon component desorption is on the sorbent got off, obtain the desorption gas higher than feed gas hydrocarbon concentration, then after vavuum pump boosting, be introduced into absorption tower, finally with absorbent, hydrocarbon component absorbed.In the later stage of regeneration stage, injecting appropriate air to being in adsorbent bed, making adsorbent obtain deep regenerative.Finally the adsorbent bed completing regeneration is pressurized to normal pressure.Two adsorbent beds alternating sorbent regenerative operation under program, makes whole removal process continuous.These patents are mainly applicable to the oil gas reclaiming the generation of the light-end products such as gasoline, naphtha filling process, hydrocarbon component in this kind of oil gas is the alkane of C3 ~ C6, alkene and micro-aromatic hydrocarbons mainly, the recovery problem of more light hydrocarbons component that what therefore these technology solved is.
Chinese Patent Application No. 2013105230808.1 proposes the recovery method of the gas that a kind of benzene produces in terminal ship process.The oil gas blower fan that process of being loaded onto ship by benzene produces collects and enters lime set tank, gas in lime set tank enters adsorption tanks absorption, gas tail gas through absorption enters air, the saturated rear beginning desorption and regeneration of adsorption tanks, the material that adsorption tanks desorption goes out enters heat exchanger cooling, cooled material enters intermediate storage tank, and the gas phase in intermediate storage tank returns adsorption tanks, and the liquid phase of recovery delivers to storage tank.The adsorbent that this patent adopts is active carbon, and adopt the mode vacuumized to carry out desorb to adsorbent material, the rate of recovery of benzene vapour can reach more than 95%.Also introduce after its evacuated pressure reaches 5kpa in this patent Example, introduce a small amount of nitrogen and active carbon is purged.But this patent is just for the recovery of the benzene vapour produced in benzene shipment process.Also come with some shortcomings in patent, first, the recovery process of the hydrocarbon component oil gas produced due to the recovery process that adopts and operating condition and gasoline filling process is close, and therefore the rate of recovery of benzene vapour just reaches more than 95%, still has the benzene of a great deal of not to be recycled; Secondly, owing to adopting adsorbent to be active carbon, there is the risk of safety in utilization; Again, condensed fixed gas is returned adsorption tanks from intermediate storage tank by this patent, can reduce the organic efficiency of whole technique; In addition, vacuumize rear employing nitrogen to carry out purging and can not have any problem for much having the occasion of nitrogen to realize this technique.
Summary of the invention
The object of the invention is to propose one and be not only suitable for benzene oil gas, and be applicable to the aromatic hydrocarbons oil gas recovery process of other light aromatics oil gas;
Another object of the present invention proposes one to be not only suitable for shipment, and be applicable to the recovery process of the aromatic hydrocarbons oil gas that entrucking and light aromatics tank discharge go out;
Another object of the present invention is that a kind of rate of recovery of proposition is higher, recovering effect better aromatic hydrocarbons oil gas recovery process;
Another object of the present invention proposes a kind of security better aromatic hydrocarbons oil gas recovery process;
Another object of the present invention proposes the higher aromatic hydrocarbons oil gas recovery process of a kind of removal process efficiency;
Another object of the present invention proposes a kind of aromatic hydrocarbons oil gas recovery process more easily realized.
Solution of the present invention is, adopt normal pressure absorption, the aromatic hydrocarbons oil gas recovery process of vacuum desorption and coupling vacuum stripping combination regeneration, have more than two or two inside to load the adsorbent bed of adsorbent, every adsorbent bed experiences following operating procedure successively:
A. adsorption step---the attached bed entrance of unstripped gas aromatic hydrocarbons oil gas self-priming enters adsorbent bed, at atmospheric pressure and temperature through in adsorbent bed process, easily by the light aromatics component of adsorbing by the adsorbent loaded in adsorbent bed, not easily discharged from adsorbent bed outlet by the cleaning of off-gas adsorbed, when in adsorbent bed, the absorption forward position of light aromatics component exports close to adsorbent bed, cleaning of off-gas concentration, close to when reaching limit value, stops absorption;
B. vacuum step---adsorbent bed is vacuumized from adsorbent bed entrance with vaccum-pumping equipment, adsorbent bed is progressively evacuated to evacuated pressure, in vacuum, along with the reduction of adsorbent bed pressure, partial adsorbates light aromatics component on the sorbent gradually desorption is got off, what formation light aromatics concentration of component raised gradually vacuumizes desorption gas, vacuumizing desorption gas boosts to a little more than after atmospheric pressure through vaccum-pumping equipment, enter the condenser be made up of two sections of condensations, successively condensing cooling to the first condensation temperature and the second condensation temperature, reclaim the light aromatics liquid obtained bottom condenser, the circulation of fixed gas condenser bottom returns and mixes with unstripped gas,
C. vacuum stripping step---while vaccum-pumping equipment vacuumizes adsorbent bed, a small amount of air is introduced continuously or discontinuously from adsorbent bed outlet, by vacuumizing the synergy reducing stagnation pressure and air stripping reduction dividing potential drop, further the light aromatics component desorption of remainder on adsorbent is got off, the desorption gas that coupling vacuum stripping process obtains equally also boosts to a little more than after atmospheric pressure through vaccum-pumping equipment, enter condenser, successively condensing cooling to the first condensation temperature and the second condensation temperature, reclaim the light aromatics liquid obtained bottom condenser, the circulation of fixed gas condenser bottom returns and mixes with unstripped gas, adsorbent bed is made to maintain coupling vacuum stripping pressure limit by adjustment stripping air capacity in coupling vacuum stripping process,
D. pressurising step---slowly in adsorbent bed, introduce air from adsorbent bed outlet equably, progressively make adsorbent bed return to normal pressure;
E. circulation step a is to steps d.
The said light aromatics of the present invention refers to the single light aromatics component such as benzene,toluene,xylene, BTX aromatics, or the mixture of these light aromatics components, or with these aromatic hydrocarbons for the main mixture containing the close compound of other boiling point a small amount of simultaneously; Aromatic hydrocarbons oil gas refers to the mist of light aromatics liquid at the light aromatics component of discharging from the exhaust outlet of these containers in filling process in the containers such as tank wagon, train tank car, steamer cargo tank, storage tank and air, according to the composition of filled light aromatics component and the difference filling temperature, the average density of aromatic hydrocarbon of aromatic hydrocarbons oil gas is at about 1 ~ 15v%.
According to the research of the present inventor, pore volume, aperture, resin, silica gel and active carbon that specific area is suitable have good adsorption/desorption performance to light aromatics, these adsorbents separately or their compound can as the adsorbent of aromatic hydrocarbons petroleum vapor recovery.But due to can heat of adsorption be discharged in aromatic naphtha aspiration additive process, cause at the higher focus of the adsorption zone formation temperature of bed, and active carbon is inflammability adsorbent, therefore, uses active carbon to there is security risks as adsorbent.Therefore, more preferably adsorbent of the present invention is resin or silica gel, or lower floor's loaded resin or silica gel, the composite adsorption bed of upper strata filling active carbon.Because resin and silica gel are noninflammability adsorbents, and adsorbent bed upper strata filling active carbon to make use of active carbon specific area large, pore-size distribution is wide, be applicable to the light aromatics component of interception trace, as long as ensure that active carbon is in the non-adsorption zone of adsorbent bed all the time, just need not worry the problem of active carbon spontaneous combustion, thus ensure that the security of adsorption process.
Essentially, the regeneration of adsorbent of the present invention is the adsorbate dividing potential drop by reducing adsorbent bed gas phase, and the adsorbate desorption be adsorbed on by adsorption step on adsorbent bed gets off to realize.Mainly to realize with the combination of coupling vacuum stripping two steps by vacuumizing specifically.
The pressure of vacuum step adsorbent bed progressively reduces, and at the end of vacuum step, the pressure of adsorbent bed is called as evacuated pressure.Evacuated pressure is lower, more favourable to adsorbent reactivation; But evacuated pressure is lower, investment and the operating cost cost of vaccum-pumping equipment are larger.According to the research of the present inventor, suitable evacuated pressure scope is 0.1 ~ 20kpa, and preferred evacuated pressure scope is 1 ~ 10kpa.
Vacuum stripping step is the indispensable important step of present invention process, particularly obtains the cleaning of off-gas of lower density of aromatic hydrocarbon and the light aromatics rate of recovery of Geng Gao.When after adsorbent beds to evacuated pressure, in adsorbent bed, introduce appropriate air from adsorbent bed outlet, the effect reducing adsorbate dividing potential drop further can be played.After introducing stripping air, the pressure of adsorbent bed is called as coupling vacuum stripping pressure, can raise to some extent than evacuated pressure, stripping air capacity is larger, and coupling vacuum stripping pressure raises more, and Srteam Stripping effect is better, but coupling vacuum stripping hypertonia, have too much stripping air and introduce adsorbent bed, cause the reduction of desorption gas concentration, this can produce the fixed gas that more circulates.According to the research of the present inventor, suitable coupling vacuum stripping pressure limit is 1 ~ 20kpa, and preferred coupling vacuum stripping pressure limit is 2 ~ 10kpa.Different from the petroleum vapor recovery technique of gasoline filling process, the vacuum stripping step of aromatic hydrocarbons oil gas recovery process plays prior effect in whole regenerative process, and the adsorbate of a great deal of is got off by desorption in this process.The present inventor studies discovery, and the duration share of vacuum stripping step shared by whole regenerative process should not be less than 20%, and the duration share of preferred vacuum stripping step shared by whole regenerative process should not be less than 50%.
Just by strengthening and optimize the combination of above-mentioned vacuum step and vacuum stripping step, adsorbent bed is better regenerated, thus make can obtain the lower cleaning of off-gas of density of aromatic hydrocarbon at ensuing adsorption step, also just obtain the higher light aromatics rate of recovery simultaneously.
The stripping gas of vacuum stripping step of the present invention is air, and main benefit is conveniently easy to get and needs cost hardly.The comparative study of the present inventor proves, air or nitrogen, as stripping gas, regeneration effect are not significantly distinguished.Not only will consume nitrogen with nitrogen as stripping gas, the more important thing is that a lot of light aromatics liquid fills scene and often do not have ready-made nitrogen system, this can make recovery project implementation become difficulty.And make stripping gas with air problem is greatly simplified.
The present invention is temperature by reducing vacuum pump outlet desorption gas at ambient pressure and the light aromatics in desorption gas is condensed into liquid and reclaims.Therefore final condensation temperature, said second condensation temperature of namely the present invention is lower, and the light aromatics liquid that one way condensation is got off is more, and fixed gas circulation back amount is less.Freezing point due to benzene is 5.5 DEG C, and therefore for the recovery process of benzene oil gas, the second condensation temperature preferable range is 6 ~ 10 DEG C; For the recovery process of other light aromatics oil gas, the second condensation temperature is 10 ~-40 DEG C.
At vaccum-pumping equipment, desorption gas is boosted in the pressure-fired process of outlet by the negative pressure of entrance, desorption air pressure compression process is released heat and is caused vacuum pump outlet gas temperature to reach more than 100 DEG C, if direct low temperature cold source cools desorption gas, need larger low temperature load.Desorption air cooling is coagulated cooling procedure and is divided into two sections by the present invention, and first paragraph is with air or circulating water, desorption gas is cooled to first condensation temperature of 20 ~ 45 DEG C; Second segment cryogenic media cools, and desorption gas is cooled to the second condensation temperature further.According to the computer Simulation calculation of the present inventor to desorption gas condensation process, the condensation load of first paragraph desorption gas accounts for more than 60% of the total condensation load of desorption gas.Therefore the cooling load of desorption gas of the present invention two sections of condensation process is all lower by about 60% with one section of condensation process of cryogenic media cooling than desorption gas.
The present inventor notices, in the different phase of aromatic hydrocarbons oil gas recovery process adsorbent reactivation process, desorption gas concentration is in regular change, and the desorption gas concentration in early stage of vacuum step is lower, and later stage and the vacuum stripping step desorption gas concentration of vacuum step are higher.Trace it to its cause, be due to vacuum step early stage, along with the reduction of adsorbent bed pressure, the air retained in that adsorbent adsorbs and adsorbent bed void volume first by desorption out, and the light aromatics that adsorbent adsorbs not yet reaches the pressure of substantive desorption, the mainly air of thus this one-phase vaccum-pumping equipment extraction.Fixed gas outlet port is located on the storage tank of the light aromatics liquid collecting recovery by prior art, such vacuum step not yet reaches the low concentration desorption gas of dew point after withdrawal liquid storage tank early stage after two sections of coolings, light aromatics in gas phase in storage tank is carried out, form the fixed gas of concentration higher than self concentration of desorption gas, thus cause the increase of the light aromatics component internal circulating load returning adsorbent bed.Consider this factor just, fixed gas outlet port is located at condenser by the present invention, and when vacuum step low concentration desorption gas in earlier stage not yet reaches dew point after two sections of coolings, fixed gas returns unstripped gas with self concentration circulating of desorption gas.Thus decrease the light aromatics component internal circulating load returning adsorbent bed, removal process efficiency is improved.
In addition, by caliber and the valve of choose reasonable absorbent particles size, adsorbent bed ratio of height to diameter and oil gas pipeline, the Pressure Drop of aromatic naphtha gas recovering device petroleum system can be down to below 3kpa, even lower, the aromatic hydrocarbons oil gas that nearly all so large light aromatics liquid filling process produces can directly recycle by access to plant.Certainly, if oil-gas transportation distance, hydrocarbon transfer system Pressure Drop is excessive, also can solve by arranging the method for drawing phoenix supercharging equipment on oil gas pipeline.By taking above measure, in conjunction with employing adsorbent of the present invention, technological process and operating condition, technique of the present invention is not only suitable for shipment, and is applicable to the aromatic hydrocarbons oil gas recovery process that entrucking and light aromatics storage tank filling process give off.
Other benefit of the present invention can be found out by the following examples.
Be described further below in conjunction with the recovery process of drawings and Examples to the aromatic hydrocarbons oil gas that the said light aromatics filling process of the present invention produces.It is emphasized that drawings and Examples just understand the present invention better in order to help, can not limiting to the claimed invention be understood to be.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the recovery process of the aromatic hydrocarbons oil gas that light aromatics filling process produces.
Detailed description of the invention
In the flow process shown in Fig. 1, capital equipment comprises adsorbent bed (1/1) and (1/2) that 2 replace handover operation, 1 vavuum pump (2), 1 condenser (3), 1 cover cool brine refrigeration unit (5), and 1 withdrawal liquid storage tank (6).
The aromatic hydrocarbons oil gas that light aromatics filling process produces enters any 1 in adsorbent bed (1/1) and (1/2) through pipeline (11), such as enter adsorbent bed (1/1), adsorbent bed (1/1) experiences following operating procedure subsequently successively:
Adsorption step: at this moment, imported valve (12/1) and the outlet valve (14/1) of adsorbent bed (1/1) are opened, all the other valve closings (namely the following undeclared valve opened is the valve of closing) of adsorbent bed (1/1), raw material aromatic hydrocarbons oil gas introduces adsorbent bed from adsorbent bed entrance, passing in adsorbent bed process, easily got off by adsorbent by the light aromatics component of adsorbing in aromatic hydrocarbons oil gas, not easily then passed adsorbent bed by the air adsorbed, enter air from adsorbent bed outlet along pipeline (16) as cleaning of off-gas.When the light aromatics component absorption forward position of adsorbent bed is close to outlet, according to the setting adsorption time parameter handover operation such as (or oil and gas content parameter), adsorbent bed (1/1) proceeds to regenerative operation.
Regeneration of adsorbent beds operation has 2 steps and forms, and is vacuum step and vacuum stripping step respectively.
Vacuum step: open valve (13/1), vacuumizes adsorbent bed (1/1) through pipeline (18) vavuum pump (2) from adsorbent bed entrance side, makes adsorbent bed pressure progressively be down to evacuated pressure.In vacuum, along with the reduction of pressure, the light aromatics component that adsorbent adsorbs progressively is got off by desorption, the desorption gas obtained is after vavuum pump (2) boosts to the pressure a little more than normal pressure, the condenser (3) be made up of two condensation segments is entered through pipeline (19), be located at first condensation segment (3-1) be made up of many finned tubes on condenser (3) top, enter the desorption gas of condenser (3) from top to bottom through in the first condensation segment process, with the air heat-exchange being flowed through tube side by blower fan (4) air blast, desorption gas is condensed and is cooled to the first condensation temperature of a little higher than ambient air temperature.Leave the desorption gas after the first condensation segment to continue to enter the second condensation segment (3-2) be made up of many finned tubes downwards, with to be exported by refrigeration unit (5), via pipeline (22) and the second condensation segment tube side, return the cool brine heat exchange forming circulation again through pipeline (23), finally reach the second condensation temperature.With the heat transfer process of two condensation segment finned tubes, the light aromatics component major part in desorption gas is condensed into liquid and falls into condenser (3) bottom, enters storage tank (6) through pipeline (21).Leave fixed gas that the second condensation segment do not coagulate then to import unstripped gas pipeline through pipeline (20) and mix with unstripped gas.
Vacuum stripping step: continue Open valve (13/1), and open valve (15/1), air enters adsorbent bed (1/1) via pipeline (17) from adsorbent bed outlet, control the stripping air capacity entered, to maintain coupling vacuum stripping pressure, under the double action vacuumized and inject stripping air, the light aromatics that adsorbent adsorbs is got off by further desorption, form the desorption gas of coupling vacuum stripping process, after vavuum pump (2) boosting, same flow process is experienced with the desorption gas that vacuum step obtains, final desorption gas is condensed to the second condensation temperature, most of light aromatics component is wherein condensed into liquids recovery and gets off, fixed gas circulation returns unstripped gas pipeline and mixes with unstripped gas.
Pressurising step: after regenerative process terminates, slowly opens valve (14/1) step by step, purifies air or air, adsorbent bed pressure is progressively returned to normal pressure from adsorbent bed (1/1) outlet introducing.
So far, adsorbent bed (1/1) adsorption regeneration cycle terminates, and then circulation enters next adsorption regeneration cycle.
Adsorbent bed (1/2) also runs in the mode identical with adsorbent bed (1/1), and at adsorption step, valve (12/2) and valve (14/2) are opened; At vacuum step, valve (13/2) is opened; At vacuum stripping step, valve (15/2) and valve (13/2) are opened; In pressurising step, valve (14/2) is slowly opened step by step.Other operating process is identical with adsorbent bed (1/1), repeats no more herein.Two adsorbent beds like this alternately switch, and whole process, under the logic control of PLC, is run according to the sequential step of program setting, realizes the continuous of whole adsorption/desorption process.
Embodiment
Embodiment 1
Certain liquid benzene automobile loading platform, the annual benzene loading of freight waggon 150,000 tons, during car loading operation, liquid benzene entrucking speed 200t/h, entrucking liquid benzene temperature is 30 DEG C, and entrucking process produces the benzene oil gas 245Nm that average benzene concentration is 12v%
3/ h, takes benzene amount 97.1kg/h out of with oil gas.Adopt recovery process process benzene oil gas of the present invention, adsorbent adopts silica gel, and evacuated pressure 2kpa, coupling vacuum stripping pressure 4kpa, the first condensation temperature is 40 DEG C, and the second condensation temperature controls at 7 ± 1 DEG C.The average benzene concentration 3mg/m of cleaning of off-gas after retracting device recycling
3, lower than the discharging standards of 12mg/m3.Benzene amount=245* (1-12%) the * 3=647mg/h=0.000647kg/h of air is entered, the benzene rate of recovery=(97.1-0.000647)/97.1=99.999% ≈ 100%, annual withdrawal liquid benzene 73t with cleaning of off-gas.
Embodiment 2
Certain liquid toluene train loading platform, the annual toluene loading of freight waggon 100,000 tons, during car loading operation, liquid benzene entrucking speed 300t/h, entrucking liquid toluene temperature is 30 DEG C, and entrucking process produces the toluene oil gas 350Nm that average toluene concentration is 4v%
3/ h, takes toluene amount 54.5kg/h out of with oil gas.Adopt recovery process process toluene oil gas of the present invention, adsorbent adopts resin, evacuated pressure 1kpa0 coupling vacuum stripping pressure 3kpa, the first condensation temperature is 40 DEG C, the second condensation temperature control 0 DEG C through retracting device recycling after the average benzene concentration 2mg/m of cleaning of off-gas
3, far below 40mg/m
3discharging standards.Air toluene amount=350* (1-4%) * 2=672mg/h=0.000672kg/h is entered, toluene recovery rate=(54.5-0.000672)/54.5=99.998% ≈ 100%, annual withdrawal liquid toluene 18t with cleaning of off-gas.
Claims (10)
1. the recovery process of the aromatic hydrocarbons oil gas of a light aromatics filling process generation, it is characterized in that: adopt normal pressure absorption, vacuum desorption and coupling vacuum stripping combination regeneration technique, have more than two or two inside to load the adsorbent bed of adsorbent, every adsorbent bed experiences following operating procedure successively:
A. adsorption step---the attached bed entrance of unstripped gas aromatic hydrocarbons oil gas self-priming enters adsorbent bed, at atmospheric pressure and temperature through in adsorbent bed process, easily by the light aromatics component of adsorbing by the adsorbent loaded in adsorbent bed, not easily being discharged from adsorbent bed outlet by the cleaning of off-gas adsorbed of removing light aromatics component, when in adsorbent bed, the absorption forward position of light aromatics component exports close to adsorbent bed, cleaning of off-gas concentration, close to when reaching limit value, stops absorption;
B. vacuum step---from adsorbent bed entrance, vacuum pumping is carried out to adsorbent bed with vaccum-pumping equipment, adsorbent bed is progressively evacuated to evacuated pressure, in vacuum, along with the reduction of adsorbent bed pressure, partial adsorbates light aromatics component on the sorbent gradually desorption is got off, what formation light aromatics concentration of component raised gradually vacuumizes desorption gas, vacuumizing desorption gas boosts to a little more than after atmospheric pressure through vaccum-pumping equipment, enter the condenser be made up of two sections of condensations, successively condensing cooling to the first condensation temperature and the second condensation temperature, reclaim the light aromatics liquid obtained bottom condenser, the circulation of fixed gas condenser bottom returns and mixes with unstripped gas,
C. vacuum stripping step---while vaccum-pumping equipment vacuumizes adsorbent bed, a small amount of air is introduced continuously or discontinuously from adsorbent bed outlet, by vacuumizing the synergy reducing stagnation pressure and air stripping reduction dividing potential drop, further the light aromatics component desorption of remainder on adsorbent is got off, the desorption gas that coupling vacuum stripping process obtains equally also boosts to a little more than after atmospheric pressure through vaccum-pumping equipment, enter condenser, successively condensing cooling to the first condensation temperature and the second condensation temperature, reclaim the light aromatics liquid obtained bottom condenser, the circulation of fixed gas condenser bottom returns and mixes with unstripped gas, adsorbent bed is made to maintain coupling vacuum stripping pressure limit by adjustment stripping air capacity in coupling vacuum stripping process,
D. pressurising step---slowly in adsorbent bed, introduce air from adsorbent bed outlet equably, progressively make adsorbent bed return to normal pressure;
E. circulation step a is to steps d.
2. technological process according to claim 1, is characterized in that: in adsorbent bed, the adsorbent of filling is resin, or silica gel, or active carbon, or their combination.
3. technological process according to claim 1, is characterized in that: evacuated pressure scope is 0.1 ~ 8kpa.
4. technological process according to claim 1, is characterized in that: coupling vacuum stripping pressure limit is 1 ~ 10kpa.
5. technological process according to claim 1, is characterized in that: the duration share of vacuum stripping step shared by whole regenerative process is not less than 20%.
6. technological process according to claim 1 or 5, is characterized in that: the duration share of vacuum stripping step shared by whole regenerative process is not less than 50%.
7. technological process according to claim 1, is characterized in that: the stripping gas of vacuum stripping step is air.
8. technological process according to claim 1, is characterized in that: the second condensation temperature preferable range being applicable to the recovery process of benzene oil gas is 6 ~ 10 DEG C.
9. technological process according to claim 1, is characterized in that: the second condensation temperature being applicable to the recovery process of other light aromatics oil gas except benzene is 10 ~-40 DEG C.
10. technological process according to claim 1, is characterized in that: desorption gas adopts two sections of condensation process, first paragraph air or circulating water, and second segment cryogenic media cools.
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Application publication date: 20150805 |