CN114307530A - Refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification process and system - Google Patents
Refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification process and system Download PDFInfo
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Abstract
The invention discloses a flame-retardant temperature swing adsorption FrTSA purification process and a system for tail gas of VOCs (volatile organic compounds) in a refinery plant, relates to temperature swing adsorption purification of tail gas, and aims to solve the problem of potential safety hazard caused by combustion or chemical reaction in the existing treatment of the tail gas of the VOCs in the refinery plant Thereby causing potential safety hazard.
Description
Technical Field
The invention belongs to the field of treatment and recycling of industrial tail gas, relates to temperature swing adsorption purification of tail gas, and particularly relates to a process and a system for purifying VOCs (volatile organic compounds) tail gas by flame-retardant temperature swing adsorption FrTSA (FrTSA) in a refinery plant.
Background
During the processing of crude oil and the production of chemical products in refinery plants, some tail gas or waste gas containing or having high volatility and high concentration light hydrocarbons or benzene ring hydrocarbon components is generated, and the volatile hydrocarbon components (VOCs) are complex, so that not only hydrocarbon loss is caused, but also foul odor pollution of the surrounding environment is caused.
Currently, the methods generally used for treating tail gas or waste gas containing VOCs include adsorption, combustion, catalytic combustion, condensation, and absorption. The adsorption method has the advantages of mature technology, simplicity, easy implementation, low treatment cost, wide application range and the like, has a large market share in the VOCs tail gas or waste gas treatment technology, and is widely applied to the fields of refinery plants, peculiar smell treatment and the like.
The conventional adsorption method for purifying or recovering hydrocarbons usually adopts a conventional axial flow fixed bed Temperature Swing Adsorption (TSA) process, and most of adsorbents loaded in an adsorption tower are activated carbon or activated carbon fibers, or one-tower off-line regeneration or two-tower on-line regeneration, for example, the published patents CN03254728.5, CN03254729.3, CN200410023944.7, CN02805902.6 and CN00118594.2 all propose a method of adsorbing hydrocarbons by fixed bed Temperature Swing Adsorption (TSA) of activated carbon, and then performing steam desorption condensation recovery or vacuum desorption solvent absorption recovery. The method has the main advantages of large adsorption capacity, high adsorption efficiency, low cost and easy achievement of the environmental protection index requirement of the discharged tail gas. However, since the fixed bed adsorbent regeneration usually requires a relatively high temperature steam or inert regeneration gas for regeneration, the larger the adsorption amount or the easier the adsorption, the more difficult the adsorbent desorption regeneration becomes, and especially, the more likely the fixed bed adsorbent regeneration is to cause a safety accident caused by fire, pulverization, or runaway of the adsorbent due to burning or chemical reaction with water vapor containing oxygen atoms when deep adsorption is performed on refinery off gas having a high concentration of VOCs or the concentration of VOCs components on the adsorbent is high. In addition, the cycle operation process of temperature rise and cooling in the Temperature Swing Adsorption (TSA) and desorption is longer, and in order to realize the alternate continuous purification of one tower for adsorbing and the other tower for regenerating, the adsorption cycle can be prolonged, so that the deep adsorption or the concentration degree of VOCs is increased, and the probability of safety accidents is further increased. Therefore, three or four adsorption towers are additionally connected in parallel in the TSA process in industry to cope with the working condition of longer desorption regeneration period. The risk of deep adsorption or safety accidents has not been completely eliminated.
Apart from the traditional axial flow fixed bed TSA process and system for VOCs tail gas treatment and recovery, a rotary wheel temperature swing adsorption (RWSAS) process and system are provided at home and abroad, the TSA rotary wheel adsorber is different from the traditional plurality of fixed bed adsorbers, and the TSA rotary wheel adsorber circularly passes through three operation areas with different functions of fixed adsorption, heating regeneration and cooling by the rotation of an adsorption rotary wheel to achieve the aim of continuously purifying gas without a series of adsorbers and program control valves. Because it mostly adopts the honeycomb structured adsorbent with fast mass transfer, easy desorption and small pressure, the cycle period can be greatly shortened, the device is more compact and reliable in operation, the potential safety hazard is avoided, and the method is particularly suitable for treating the low-pressure waste gas containing VOCs discharged by the industries of chemical engineering, semiconductors, automobiles, synthetic leather and the like. However, the RWTSA process and system are used in a working condition with a low concentration of VOCs, for example, the concentration of VOCs is less than 0.1 to 1.0%, the concentration degree of VOCs reaches 10 to 20 times, the removal rate also reaches more than 97%, and the RWTSA process and system are generally used as a gas pre-concentration system of a waste gas incineration device to reduce the incineration cost. The RWSAS adsorber and the regular adsorbent are mostly made of inorganic materials, so that the incombustibility of the adsorbent is safer than that of activated carbon when VOCs are treated, but the accidents of smoldering of a zeolite rotating wheel caused by excessive high-boiling-point VOCs accumulated on the surface of the RWSAS adsorption rotating wheel also occur, and therefore, the high-boiling-point VOCs deposited on the rotating wheel are periodically washed by water to recover the adsorption performance. Some of the adsorbent cannot be cleaned by washing with water, and only the adsorbent can be cleaned by dismantling and using a high-temperature (300-1000 ℃) calcination carbonization and steam activation method, but the microporous structure of the regular adsorbent is easily damaged, so that the adsorption capacity is lost, the runner is forced to be replaced, and the cost is greatly increased. As the tail gas of the VOCs of the refinery has more high boiling point hydrocarbon substances, a condenser is required to be added, and the hydrocarbon substances are removed or recovered in a condensing mode so as to prevent the hydrocarbon substances from blocking an airflow channel and an adsorption surface of a rotating wheel, thereby prolonging the service life of the rotating wheel adsorber. If the temperature of the exhaust gas is too high, the exhaust gas must also be cooled to ambient temperature. Secondly, the disadvantages of the rotary-wheel adsorber are that the bed height is short, the mass transfer efficiency is lower than that of the axial flow fixed bed adsorber, the purification degree is inferior to that of the axial flow fixed bed adsorber, the treatment capacity is limited, when the treatment scale is large, a plurality of RWSAS adsorbers are required to be operated in parallel, and the investment is greatly increased. In addition, the RWTSA device has high requirements on dynamic sealing, and the relatively low removal rate of the RWTSA device affects the application of the equipment when the Volatile Organic Chemicals (VOCs) tail gas treatment working conditions containing more complex components need to remove adsorbates with higher toxicity or polarity, such as ammonia, phenylnaphthalene and derivatives thereof.
Disclosure of Invention
The invention aims to: in order to solve the problem of potential safety hazard caused by combustion or chemical reaction of high-concentration and high-boiling-point components accumulated in the process of Temperature Swing Adsorption (TSA) circulation operation in the existing refinery VOCs tail gas treatment, the invention provides a refinery VOCs tail gas flame-retardant type temperature swing adsorption FrTSA purification process and a system TSA) are accumulated during the cyclic operation, with safety hazards arising from combustion or chemical reactions.
The invention specifically adopts the following technical scheme for realizing the purpose:
a refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification process comprises the following steps:
the raw gas is refinery VOCs tail gas, the raw gas respectively enters from the bottoms of an adsorption tower A and an adsorption tower B which are loaded with granular adsorbents and flows through an adsorbent layer from bottom to top for adsorption, the VOCs are used as adsorption phase gas to be adsorbed by the adsorbents, the non-adsorption phase gas is purified gas from which the VOCs are removed, and the content of the VOCs in the purified gas is less than or equal to 10-50 ppmv;
the adsorbents with saturated adsorption in the adsorption tower A and the adsorption tower B respectively flow out of the discharge ports at the bottom of the adsorption tower A and the adsorption tower B and descend to enter an inclined rotatable regeneration furnace for desorption and regeneration; fresh regeneration gas is heated by a heater and then enters an inclined rotatable regeneration furnace for cyclic utilization, and is in reverse contact with a rotating and descending saturated adsorbent; the desorbed and regenerated adsorbent flows out of the outlet of the regeneration furnace after being cooled and condensed respectively, is lifted to an adsorbent hopper of the adsorbent lifting system through the adsorbent lifting system, and is unloaded into the adsorption tower A or the adsorption tower B for cyclic utilization for the next round of adsorption; fresh lifting gas or lifting gas escaping from the adsorbent hopper is filtered by a filter to form cyclic lifting gas which enters an adsorbent lifting system for cyclic use; the method comprises the following steps that VOCs-enriched regeneration waste gas flowing out of a regeneration furnace flows through a heat exchanger to be cooled and then enters a VOCs condenser to be condensed, the generated condensate is used as VOCs liquid to be directly output and treated or enters a recovery process to be recycled, and the removal rate (removal rate) of VOCs impurity components is more than or equal to 98-99%; non-condensable gas generated by the VOCs condenser enters a heat exchanger to exchange heat with regenerated waste gas to form circulating regenerated gas, and the circulating regenerated gas enters a heater to be recycled;
the adsorption tower A and the adsorption tower B alternately perform adsorption, and the adsorption tower B performs desorption regeneration when the adsorption tower A performs adsorption purification; when the adsorption tower A carries out desorption regeneration, the adsorption tower B carries out adsorption purification.
Therefore, the cycle period of the adsorption and desorption regeneration of the flame-retardant temperature swing adsorption (FrTSA) is 360-1600 seconds.
Furthermore, the raw gas comprises VOCs active (organization) tail gas generated in oil refining and chemical engineering procedures of a refinery, and diffused unstructured VOCs waste gas generated in the processes of transportation, storage, transfer and processing of petroleum and chemical engineering liquid raw materials and products and transportation, transfer and sale of finished oil (gasoline, diesel oil and the like);
the VOCs active tail gas comprises catalytic dry gas, coking dry gas, triple-top gas, reformed gas, hydrogenation tail gas, PSA desorption gas, ethylene cracking tail gas and oil absorption tail gas.
Furthermore, the raw material gas contains high hydrocarbons above C5, benzene ring hydrocarbons, carbon dioxide, ammonia gas and peculiar smell organic volatile matters, the concentration of VOCs is 0.1-5% (v/v), the temperature is 20-80 ℃, and the pressure is from normal pressure to low pressure.
Further, heating fresh regeneration gas to 120-180 ℃ by a heater, and then feeding the fresh regeneration gas into an inclined rotatable regeneration furnace for cyclic utilization; and respectively cooling the desorbed and regenerated adsorbent to 20-60 ℃, then enabling the adsorbent to flow out of an outlet of the regeneration furnace, lifting the adsorbent to an adsorbent hopper of an adsorbent lifting system through the adsorbent lifting system, and unloading the adsorbent into the adsorption tower A or the adsorption tower B for cyclic utilization.
A refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification system comprises an adsorption tower A, an adsorption tower B, an inclined rotatable regeneration furnace, a filter, a heater, a heat exchanger, a VOCs condenser and an adsorbent lifting system;
the raw gas is the tail gas of VOCs in a refinery, the raw gas respectively enters from the bottoms of an adsorption tower A and an adsorption tower B which are loaded with granular adsorbents and flows through an adsorbent layer from bottom to top for adsorption, the VOCs is used as adsorption phase gas to be adsorbed by the adsorbents, and the non-adsorption phase gas is purified gas from which the VOCs are removed;
the adsorbents with saturated adsorption in the adsorption tower A and the adsorption tower B respectively flow out of the discharge ports at the bottom of the adsorption tower A and the adsorption tower B and descend to enter an inclined rotatable regeneration furnace for desorption and regeneration; heating fresh regeneration gas by a heater and then entering an inclined rotatable regeneration furnace for cyclic utilization; the desorbed and regenerated adsorbent flows out of the outlet of the regeneration furnace after being cooled and condensed respectively, is lifted to an adsorbent hopper of the adsorbent lifting system through the adsorbent lifting system, and is discharged into the adsorption tower A or the adsorption tower B for cyclic utilization; circulating lift gas formed after the lift gas escaping from the adsorbent hopper is filtered by a filter returns to the adsorbent lifting system for recycling; the regenerative waste gas which flows out of the regenerative furnace and is enriched with VOCs flows through a heat exchanger to be cooled and then enters a VOCs condenser to be condensed, and the generated condensate is taken as VOCs liquid to be directly output and treated or enters a recovery process to be recycled; non-condensable gas generated by the VOCs condenser enters a heat exchanger to exchange heat with regenerated waste gas to form circulating regenerated gas, and the circulating regenerated gas enters a heater to be recycled;
the adsorption tower A and the adsorption tower B alternately perform adsorption, and the adsorption tower B performs desorption regeneration when the adsorption tower A performs adsorption purification; when the adsorption tower A carries out desorption regeneration, the adsorption tower B carries out adsorption purification.
Furthermore, the tilting type rotatable regeneration furnace comprises a tilting type rotatable regeneration furnace body and a driving rotating mechanism for driving the tilting type rotatable regeneration furnace body to rotate, a plurality of detachable baffles are arranged in the tilting type rotatable regeneration furnace body, the number of the baffles is 5-9, the baffles and the ground form an adjustable inclination angle alpha, the adjustable inclination angle alpha is 5-30 degrees, the rotation speed omega of the tilting type rotatable regeneration furnace body is 100-400 s/rad, the rotation direction is clockwise, and the stay time of an adsorbent in the tilting type rotatable regeneration furnace body is 200-1000 s.
Furthermore, the adsorption tower A and the adsorption tower B both comprise a tower body, a plurality of openable grid tower plates are sequentially assembled in an adsorption cavity in the tower body along the height direction of the tower body, a movable tower bottom plate bolt chain is arranged below each grid tower plate, the tower bottom plate bolt chain is in hooking, opening and closing connection with a piston bottom chain in a telescopic piston pipeline arranged in the center of the tower body, and an adsorbent is filled on the grid tower plates;
after adsorption is finished, piston bottom chain hooks in the telescopic piston pipeline move downwards, grid tower plates are opened from bottom to top in sequence, and adsorbents on the grid tower plates are unloaded in sequence and flow out of the adsorption tower; then piston bottom chain hooks in the telescopic piston pipeline move upwards, the grid tower plates are sequentially closed from bottom to top, and the adsorbents discharged from the adsorbent hopper are sequentially stacked on the grid tower plates from bottom to top to perform next round of adsorption.
Further, adsorption tower A, adsorption tower B all include the tower body, install in the upper cover of tower body and be used for even gas distribution and prevent that the updraft from carrying the last net baffle that the adsorbent granule flows out, install in the lower cover of tower body and be used for even gas distribution and prevent that the downdraft carries the lower net baffle that the adsorbent granule flows out, go up and all be equipped with mobilizable tower bottom plate tether under net baffle and the lower net baffle, the piston bottom chain hook switching in the scalable piston pipeline that tower bottom plate tether and tower body central authorities set up closes and is connected.
Further, the adsorbent is one or more of activated carbon, activated carbon fiber, carbon molecular sieve and carbon nano tube.
Furthermore, the regeneration gas is water vapor, air or inert gas nitrogen, and the lifting gas in the adsorbent lifting system is inert gas nitrogen or air; the circulating regenerated gas and the circulating lift gas are mixed and then split into two gas flows which respectively enter a heater and a lift fan, and the respective flow rates and the new supplement flow rates of the fresh lift gas and the fresh regenerated gas are adjusted according to the cycle operation period of adsorption and desorption regeneration.
The invention has the following beneficial effects:
1. according to the invention, the adsorbent in the axial flow fixed bed adsorption tower sinks and flows into an inclined rotatable regeneration furnace for regeneration through natural gravity after adsorption is finished, the regenerated adsorbent is sent into the axial flow fixed bed adsorption tower for adsorption through a lifting system, one adsorption tower performs adsorption while the other adsorption tower performs desorption regeneration, the two towers alternately and continuously treat VOCs tail gas of a large-scale refinery plant, the removal efficiency is high, the matching performance of the cycle operation periods of adsorption and desorption regeneration is high, the cycle operation periods of adsorption and desorption regeneration can be effectively adjusted according to the fluctuation working condition of waste gas, and the potential safety hazard caused by combustion or chemical reaction of accumulated VOCs components in the process of Temperature Swing Adsorption (TSA) cycle operation is prevented.
2. According to the invention, the flame-retardant temperature swing adsorption (FrTSA) process and device formed by combining the axial flow fixed bed adsorption tower and the inclined rotatable adsorbent regeneration furnace can completely avoid potential safety hazards caused by burning of high-concentration VOCs components on the adsorbent at a higher desorption regeneration temperature, fire or pulverization of the adsorbent and the like in the tail gas purification working condition of a refinery VOCs with a high removal rate (more than or equal to 98-99%).
3. In the invention, the temperature of desorption and regeneration of the adsorbent is much lower than that of the traditional fixed bed Temperature Swing Adsorption (TSA) process, the matching degree of the cyclic operation period of adsorption and desorption regeneration is high, and the phenomenon that the deep adsorption or desorption regeneration period is too long and the adsorption period is difficult to match in the traditional fixed bed Temperature Swing Adsorption (TSA) process is avoided.
4. According to the invention, the operating parameters of the detachable baffle (n), the adjustable inclination angle (alpha) and the rotation speed (omega) of the inclined rotatable regeneration furnace in the FrTSA system are flexibly adjusted to adapt to the working condition of large fluctuation of VOCs tail gas in the raw material gas, and the matching, safety, reliability and effectiveness of adsorption and desorption regeneration cyclic operation are ensured.
5. In the invention, through the selection of the adsorbent, the regeneration gas and the lifting gas, the operation of the FrTSA system is more effective, economic and safe, and the method can be suitable for the working condition of raw material gas which is more complex and is compatible with water (steam) or can generate chemical reaction on the adsorbent.
6. In the invention, the openable and closable grid tower plate and the net partition plate are arranged in the adsorption tower, the dismountable baffle plate is arranged in the inclined rotatable regeneration furnace, and the inclination angle and the rotation speed can be adjusted, so that the loss rate of the adsorbent in the adsorption and desorption regeneration cycle process, including abrasion, pulverization or fire, is much smaller than that of the traditional adsorbent circulating bed adsorption and desorption regeneration process, and the service life of the adsorbent is greatly prolonged.
Drawings
FIG. 1 is a schematic flow chart of example 1;
FIG. 2 is a schematic flow chart of example 2;
FIG. 3 is a schematic flow chart of example 3;
FIG. 4 is a schematic flow chart of example 4.
Detailed Description
In order to make those skilled in the art better understand the present invention, the technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention.
Example 1
As shown in fig. 1, the present embodiment provides a fire-retardant temperature swing adsorption FrTSA purification process and system for tail gas of VOCs in refinery plants, which includes an adsorption tower a, an adsorption tower B, an inclined rotatable regenerator, a filter, a heater, a heat exchanger, a VOCs condenser, an adsorbent lifting system, and certainly includes pipes and control valves connected to the material gas and the process gas entering and exiting the adsorption tower, the inclined rotatable regenerator, the filter/heater/heat exchanger/VOCs condenser, and the adsorbent lifting system. The adsorption tower A and the adsorption tower B are two parallel axial flow fixed bed adsorption towers with the height-diameter ratio of 4-6, granular adsorbents are loaded in the adsorption tower A and the adsorption tower B, the adsorbents are one or more combinations of activated carbon, activated carbon fibers, carbon molecular sieves and carbon nanotubes, and the preferred combination is the combination of the activated carbon and the activated carbon fibers. The inclined rotatable regeneration furnace is arranged between the adsorption tower A and the adsorption tower B and comprises an inclined rotatable regeneration furnace body, a driving rotating mechanism for driving the inclined rotatable regeneration furnace body to rotate, an adjustable supporting frame, an adjustable adsorbent feeding hole, a regeneration waste gas outlet pipe, a (hot) regeneration gas input pipe and an adsorbent cooling and condensing (coil pipe) taking steam/air as media, 7 detachable baffles are arranged in the inclined rotatable regeneration furnace body, an adjustable inclination angle alpha formed by the baffles and the ground is 20 degrees, the rotation speed omega of the inclined rotatable regeneration furnace body is 240s/rad, the rotation direction is clockwise, and the stay time of the adsorbent in the inclined rotatable regeneration furnace body is 600 s. The filter is a 300-mesh filter. The adsorbent lifting system comprises a lifting fan, a lifting pipe and an adsorbent hopper.
The material gas related to the system is raw material gas and purified gas after purification, lifting gas/circulation lifting gas, regeneration gas/regeneration waste gas and non-condensable gas generated by a VOCs condenser are used as regeneration circulation gas and air cooling/condensation gas at an outlet of an adsorbent after regeneration of the inclined rotatable regeneration furnace.
Wherein, the raw material gas is the tail gas of VOCs in the refinery, which is the saturated dry gas containing VOCs generated in the process of catalytic cracking, coking delay, hydrogenation and the like in the refinery. The main components of the VOCs are C5 and C5 high alkanes, benzene, toluene, xylene and the like, and a small amount of butadiene, isobutene, pentene and other olefins, the total concentration of the VOCs is 3%, the temperature is 30-40 ℃, the pressure is 0.1MPa, and the flow is 10000Nm 3/h.
Wherein the VOCs active tail gas comprises catalytic dry gas, coking dry gas, triple-top gas, reformed gas, hydrogenation tail gas, PSA desorption gas, ethylene cracking tail gas and oil absorption tail gas
The specific purification process flow of the system is as follows:
raw material gas respectively enters an adsorption tower A and an adsorption tower B from the bottoms of the adsorption tower A and the adsorption tower B through a delivery pump, flows through adsorbent beds in the adsorption tower A and the adsorption tower B from bottom to top for adsorption, VOCs (volatile organic compounds) are adsorbed by an adsorbent as adsorption phase gas, and non-adsorption phase gas is purified gas which is saturated dry gas without VOCs and is output; wherein the content of VOCs in the purified saturated dry gas is less than or equal to 10ppmv, and C2/C3 is recovered from the output of the system or the hydrogen extraction section of PSA or the absorption tower.
After the adsorption step is finished, a desorption regeneration step is carried out, the adsorbents which are adsorbed in saturation in the adsorption tower A and the adsorption tower B respectively flow out of the bottom discharge holes of the adsorption tower A and the adsorption tower B and descend by means of self gravity to enter an inclined type rotatable regeneration furnace for desorption regeneration, and the regeneration period of the adsorbents in the regeneration furnace is 600-800 s; the method comprises the following steps that fresh regeneration gas is nitrogen, the fresh regeneration gas is heated to 130-160 ℃ by a heater, then enters an inclined rotatable regeneration furnace and reversely contacts with a rotating and descending saturated adsorbent, the temperature of the adsorbent regenerated by desorption is reduced to 30-40 ℃ after being cooled and condensed by air at the outlet end of the regeneration furnace, the adsorbent flows out of an outlet of the regeneration furnace and is lifted to an adsorbent hopper by an adsorbent lifting system consisting of nitrogen serving as lifting gas, a lifting fan, a lifting pipe and the adsorbent hopper, the adsorbent is unloaded to an adsorption tower A and an adsorption tower B for next round of adsorption, and the circulating lifting gas formed by filtering the lifting gas (N2) escaping from the adsorbent hopper by a filter returns to the adsorbent lifting system for recycling; the regeneration waste gas which flows out from the regeneration furnace and is enriched with VOCs enters a VOCs condenser for condensation after being cooled by a heat exchanger, the generated condensate is directly output as VOCs (liquid), or enters a rectifying tower of a toluene/PX/PTA procedure for separation and recovery, or enters a rectifying tower of other procedures for recovery, and the removal rate (removal rate) of VOCs impurity components in the saturated dry gas of the refinery is more than or equal to 98 percent; and the non-condensable gas generated by the VOCs condenser enters a heat exchanger to be subjected to heat exchange with the regenerated waste gas for heating, and the formed circulating regenerated gas enters a heater for recycling.
In the adsorption purification and desorption regeneration processes, the adsorption tower A and the adsorption tower B are used for alternately carrying out adsorption, and when the adsorption tower A carries out adsorption purification, the adsorption tower B carries out desorption regeneration; when the adsorption tower A carries out desorption regeneration, the adsorption tower B carries out adsorption purification.
Therefore, the cycle period of the adsorption and desorption regeneration of the flame-retardant temperature swing adsorption FrTSA is 800-1200 seconds.
Example 2
As shown in fig. 2, based on embodiment 1, the inclined rotatable regeneration furnace comprises an inclined rotatable regeneration furnace body which is provided with 7 detachable baffles and has an adjustable inclination angle (α) of 20 ° with the ground and a clockwise rotation speed (ω) of 240s/rad, a driving rotation mechanism for regulating the rotation speed (ω) of the regeneration furnace body, an adjustable support frame, an adjustable adsorbent feeding port, a regenerated waste gas outlet pipe, a (hot) regenerated gas inlet pipe, and an adsorbent cooling and condensing (coil) using steam/air as a medium, wherein the 7 detachable baffles in the regeneration furnace body (inner) with a total length of about 1.8-2.0 meters and a diameter of about 0.5-0.6 meters are staggered at uniform intervals so that the adsorbent forms uniform tumbling mixing and cutting and continuously sliding down to perform reverse heat transfer regeneration with hot nitrogen when rotating in the rotary regeneration furnace, and is not damaged by the shearing force or throwing off force generated by rotation, the residence time of the adsorbent in the regeneration furnace is 600-800 s.
Example 3
As shown in fig. 3, based on example 1, each of the adsorption towers a and B includes a tower body, 7 openable grid trays are installed in the tower body, a plurality of movable tower bottom plate tether chains are provided under each grid tray, the tower bottom plate tether chains are in open-close connection with piston bottom chain hooks in a telescopic piston pipeline provided in the center of the tower body, and an adsorbent is filled on the grid trays.
When the adsorption purification of the adsorption tower A is finished, a piston pipeline control system on the adsorption tower is started, piston bottom chain hooks in the telescopic piston pipeline are controlled to move downwards, and a fastening chain under each grid tower plate is opened, wherein the fastening chain under the bottommost grid tower plate of the adsorption tower is firstly opened, an adsorbent is unloaded from the 7 th grid tower plate of the bottommost layer and flows out of the adsorption tower firstly, then fastening chains under the 6 th grid tower plate above the bottommost layer are opened in sequence, and the adsorbent flows out of the adsorption tower from the tower plates of the layer in sequence until the adsorbent on the 1 st grid tower plate of the uppermost layer is unloaded and flows out of the adsorption tower; then, the piston rod control system controls the piston bottom chain hook in the telescopic piston pipeline to move upwards, firstly, the 7 th grid tower plate at the bottommost layer is closed, the adsorbent discharged from the adsorbent hopper flows into the adsorption tower and is fully stacked on the closed 7 th grid tower plate at the lowest layer, then, the tying chains below the 6 th grid tower plate at the upper part of the bottommost layer are sequentially closed, the adsorbent is discharged from the hopper and is fully stacked on the grid tower plate at the layer until the adsorbent on the 1 st grid tower plate at the uppermost layer is fully stacked, and the next round of adsorption is carried out.
When the adsorption and purification in the adsorption tower B are completed, the process is the same as that in the adsorption tower a.
In addition, an upper end enclosure and a lower end enclosure of the adsorption tower A are respectively provided with an upper net partition plate and a lower net partition plate which can be opened and closed, a plurality of movable tower bottom plate bolt chains are arranged below the upper net partition plate and the lower net partition plate, the tower bottom plate bolt chains are in open-close connection with a piston bottom chain hook in a telescopic piston pipeline arranged in the center of the tower body, and the upper net partition plate and the lower net partition plate are opened and closed together with a grid tower plate in the adsorption tower.
The structures and the opening modes of the upper net partition plate and the lower net partition plate in the adsorption tower B are the same as those of the adsorption tower A.
Example 4
As shown in fig. 4, based on example 1, the regeneration gas and the lift gas are inert gas nitrogen (N2), the recycle regeneration gas and the recycle lift gas are combined and divided into two gases respectively entering a heater and a lift fan, and the respective flow rates are adjusted according to the cycle operation periods of the adsorption and desorption regeneration, in this case 1.5:1, and the flow rate of the newly supplemented nitrogen (N2) is 1.5:1:0.5 (newly supplemented), so as to completely match the cycle periods of the adsorption and desorption regeneration.
It should be apparent that the above-described embodiments are only some, but not all, of the embodiments of the present invention. All other embodiments and structural changes that can be made by those skilled in the art without inventive effort based on the embodiments described in the present invention or based on the teaching of the present invention, all technical solutions that are the same or similar to the present invention, are within the scope of the present invention.
Claims (10)
1. A refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification process is characterized by comprising the following steps:
the raw gas is the tail gas of VOCs in a refinery, the raw gas respectively enters from the bottoms of an adsorption tower A and an adsorption tower B which are loaded with granular adsorbents and flows through an adsorbent layer from bottom to top for adsorption, the VOCs is used as adsorption phase gas to be adsorbed by the adsorbents, and the non-adsorption phase gas is purified gas from which the VOCs are removed;
the adsorbents with saturated adsorption in the adsorption tower A and the adsorption tower B respectively flow out of the discharge ports at the bottom of the adsorption tower A and the adsorption tower B and descend to enter an inclined rotatable regeneration furnace for desorption and regeneration; heating fresh regeneration gas by a heater and then entering an inclined rotatable regeneration furnace for cyclic utilization; the desorbed and regenerated adsorbent flows out of the outlet of the regeneration furnace after being cooled and condensed respectively, is lifted to an adsorbent hopper of the adsorbent lifting system through the adsorbent lifting system, and is discharged into the adsorption tower A or the adsorption tower B for cyclic utilization; fresh lifting gas or lifting gas escaping from the adsorbent hopper is filtered by a filter to form cyclic lifting gas which enters an adsorbent lifting system for cyclic use; the regenerative waste gas which flows out of the regenerative furnace and is enriched with VOCs flows through a heat exchanger to be cooled and then enters a VOCs condenser to be condensed, and the generated condensate is taken as VOCs liquid to be directly output and treated or enters a recovery process to be recycled; non-condensable gas generated by the VOCs condenser enters a heat exchanger to exchange heat with regenerated waste gas to form circulating regenerated gas, and the circulating regenerated gas enters a heater to be recycled;
the adsorption tower A and the adsorption tower B alternately perform adsorption, and the adsorption tower B performs desorption regeneration when the adsorption tower A performs adsorption purification; when the adsorption tower A carries out desorption regeneration, the adsorption tower B carries out adsorption purification.
2. The FrTSA purification process of refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA as claimed in claim 1, wherein the feed gas comprises VOCs active tail gas generated by refinery in oil refining and chemical engineering processes, and emitted unstructured VOCs waste gas generated in transportation, storage, transfer and processing of petroleum and chemical liquid raw materials and products and transportation, transfer and sale links of finished oil;
the VOCs active tail gas comprises catalytic dry gas, coking dry gas, triple-top gas, reformed gas, hydrogenation tail gas, PSA desorption gas, ethylene cracking tail gas and oil absorption tail gas.
3. The FrTSA purification process of refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA according to claim 2, wherein the feed gas contains C5-above high hydrocarbons, benzene ring hydrocarbons, carbon dioxide, ammonia gas and odorous organic volatiles, the concentration of VOCs is 0.1-5% (v/v), the temperature is 20-80 ℃, and the pressure is from normal pressure to low pressure.
4. The FrTSA purification process by flame retardant temperature swing adsorption of VOCs tail gas in a refinery plant as claimed in claim 1, wherein fresh regeneration gas is heated to 120-180 ℃ by a heater and then enters an inclined rotatable regeneration furnace for cyclic utilization; and respectively cooling the desorbed and regenerated adsorbent to 20-60 ℃, then enabling the adsorbent to flow out of an outlet of the regeneration furnace, lifting the adsorbent to an adsorbent hopper of an adsorbent lifting system through the adsorbent lifting system, and unloading the adsorbent into the adsorption tower A or the adsorption tower B for cyclic utilization.
5. A refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification system is characterized in that: the system comprises an adsorption tower A, an adsorption tower B, an inclined rotatable regeneration furnace, a filter, a heater, a heat exchanger, a VOCs condenser and an adsorbent lifting system;
the raw gas is the tail gas of VOCs in a refinery, the raw gas respectively enters from the bottoms of an adsorption tower A and an adsorption tower B which are loaded with granular adsorbents and flows through an adsorbent layer from bottom to top for adsorption, the VOCs is used as adsorption phase gas to be adsorbed by the adsorbents, and the non-adsorption phase gas is purified gas from which the VOCs are removed;
the adsorbents with saturated adsorption in the adsorption tower A and the adsorption tower B respectively flow out of the discharge ports at the bottom of the adsorption tower A and the adsorption tower B and descend to enter an inclined rotatable regeneration furnace for desorption and regeneration; heating fresh regeneration gas by a heater and then entering an inclined rotatable regeneration furnace for cyclic utilization; the desorbed and regenerated adsorbent flows out of the outlet of the regeneration furnace after being cooled and condensed respectively, is lifted to an adsorbent hopper of the adsorbent lifting system through the adsorbent lifting system, and is discharged into the adsorption tower A or the adsorption tower B for cyclic utilization; circulating lift gas formed after the lift gas escaping from the adsorbent hopper is filtered by a filter returns to the adsorbent lifting system for recycling; the regenerative waste gas which flows out of the regenerative furnace and is enriched with VOCs flows through a heat exchanger to be cooled and then enters a VOCs condenser to be condensed, and the generated condensate is taken as VOCs liquid to be directly output and treated or enters a recovery process to be recycled; non-condensable gas generated by the VOCs condenser enters a heat exchanger to exchange heat with regenerated waste gas to form circulating regenerated gas, and the circulating regenerated gas enters a heater to be recycled;
the adsorption tower A and the adsorption tower B alternately perform adsorption, and the adsorption tower B performs desorption regeneration when the adsorption tower A performs adsorption purification; when the adsorption tower A carries out desorption regeneration, the adsorption tower B carries out adsorption purification.
6. The refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification system of claim 5, which is characterized in that: the inclined rotatable regeneration furnace comprises an inclined rotatable regeneration furnace body and a driving rotating mechanism for driving the inclined rotatable regeneration furnace body to rotate, a plurality of detachable baffles are arranged in the inclined rotatable regeneration furnace body, the number of the baffles is 5-9, an adjustable inclination angle alpha is formed between each baffle and the ground, the adjustable inclination angle alpha is 5-30 degrees, the rotating speed omega of the inclined rotatable regeneration furnace body is 100-400 s/rad, the rotating direction is clockwise, and the stay time of an adsorbent in the inclined rotatable regeneration furnace body is 200-1000 s.
7. The refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification system of claim 5, which is characterized in that: the adsorption tower A and the adsorption tower B both comprise a tower body, a plurality of openable grid tower plates are sequentially assembled in an adsorption cavity in the tower body along the height direction of the tower body, a movable tower bottom plate bolt chain is arranged below each grid tower plate, the tower bottom plate bolt chain is in open-close connection with a piston bottom chain hook in a telescopic piston pipeline arranged in the center of the tower body, and an adsorbent is filled on the grid tower plates;
after adsorption is finished, the piston rod control system controls a piston bottom chain hook in the telescopic piston pipeline to move downwards, grid tower plates are opened from bottom to top in sequence, and adsorbents on the grid tower plates are unloaded in sequence and flow out of the adsorption tower; then piston rod control system control piston bottom chain hook among the scalable piston pipeline upwards moves, from bottom to top grid column plate closes in proper order, and the adsorbent that the adsorbent hopper unloaded is from bottom to top in proper order piled up grid column plate.
8. The refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification system of claim 5, which is characterized in that: adsorption tower A, adsorption tower B all include the tower body, install in the upper cover of tower body and be used for even gas distribution and prevent that the updraft from carrying the last web partition board that the adsorbent granule flowed, install in the lower cover of tower body and be used for even gas distribution and prevent that the downdraft carries the lower web partition board that the adsorbent granule flowed, go up and all be equipped with mobilizable tower bottom plate tether under web partition board and the lower web partition board, the piston bottom chain hook switching in the scalable piston pipeline of tower bottom plate tether and the central setting of tower body closes and is connected.
9. The refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification system of claim 5, which is characterized in that: the adsorbent is one or more of activated carbon, activated carbon fiber, carbon molecular sieve and carbon nano tube.
10. The refinery VOCs tail gas flame-retardant temperature swing adsorption FrTSA purification system of claim 5, which is characterized in that: the regeneration gas is water vapor, air or inert gas nitrogen, and the lifting gas in the adsorbent lifting system is inert gas nitrogen or air; the circulating regenerated gas and the circulating lift gas are mixed and then split into two gas flows which respectively enter a heater and a lift fan, and the respective flow rates and the new supplement flow rates of the fresh lift gas and the fresh regenerated gas are adjusted according to the cycle operation period of adsorption and desorption regeneration.
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