Title of Invention

"FIXED BED HYPERSORBER AND A PROCESS FOR FRACTIONATION OF FLUID MIXTURES USING THE SAME"

Abstract The present invention relates to a fixed bed hypersorber having moving ports for injecting and withdrawing fluids which can be used for fractionation of gaseous mixtures in a fixed bed filled with absorbents/adsorbents, where separation is brought about by contacting gaseous mixture in a counter-current fashion. The moving ports may take the form of pistons or pairs of tubes arranged concentrically, where one of the tubes has a straight slot and the other tube has a helical slot. Rotation of the tubes with respect to each other produces the moving port.
Full Text Field of Invention
The present invention relates to a fixed bed hypersorber having moving ports for injecting and withdrawing fluids. The improved fixed bed hypersorber of the present invention can be used for fractionation of gaseous mixtures in fixed beds filled with adsorbent unlike that in a conventional Hypersorber, where separation is brought about by contacting the gas mixtures in a countercurrent manner with moving adsorbent. The said moving port system effectuates countercurrent n-olid-gas/solid-liquid contact in a fixed bed. More particularly, the present invention is directed towards two alternate methods of injection and withdrawal of fluids through moving ports - one with the concept of a moving port with helical slots, and the other being a piston type moving port system. The process of contacting the solid-gas/solid-liquid in a countercurrent fashion to emulate a hypersorber in fixed beds is effectuated in the present application either by the moving ports, or by a sequential switching of the fixed beds realized by altering the streams that enter and leave each bed using solenoid valves that could be activated either electrically or pneumatically. The Fixed Bed Hyper: ber of the present invention with moving ports can fractionate the gas mixtures into the raffinate and extract products, both with high purity as well as recovery. Series of fixed beds with moving ports can effectuate chromatographic type separation of liquid mixtures with elutant, reaction and separation in tandem and regenerative type heat exchange.
Background and Prior Art
Gas separation by moving solids came into existence with the invention of the first continuous adsorption unit invented by F.D. Soddy ' 1922 (U.S. Patent 1,422,007 and 1,422,008). The renaissance of Soddy's process for the separation of gas mixtures came around 1946, when C. Berg published results on a moving charcoal bed for fractionation of refinery off gases (Berg. C., AIChE Journal, 42, 665 August 25, 1946). The process was named Hypersorption. Hypersorption as a separation process never gained popularity as a sound unit operation to replace conventional operations due to the mechanical problems that persisted in solid handling, mainly the attrition and consequent loss of the by the adsorbents. The hypersorber had distinct zones as in distillation. It had a stripping section and an enriching section above and below tu~ feed point location. It had a two
shell and tube heat exchangers; one at the bottom for regenerating the bed by steam heating and another at the top for cooling the hot regenerated adsorbent before the adsorbent is recycled back to the stripping section. Regeneration by heating is known as thermal swing and was employed in the conventional Hypersorber. However in the proposed process the regeneration is done by dep Separation brought out in manner similar to that of a Hypersorber was not observed and reported in prior works in fixed beds. The separation mechanism and power of Hypersorption has always remained in relative obscurity, and that is why the concept of a Hypersorber was not emulated for gas separation in fixed beds in earlier works. This is possibly because the idea of a unified approach to separation processes has not been conceived, and hence the real concept of Reflux common to all separation processes was not palpable. The concept of reflux on which the proposed process underlies has been discussed extensively in the paper by D.P. Rao - "The Futility of Raffinate Reflux Revisited" (The Canadian Journal of Chemical Engineering, Volume 77, Feb., 1999). The proposed process can bring about effective fractionation of any gas mixtures (with separation factor even lower than 2) unlike that in the previous works, wherein the fractionation of air alone was claimed and that too with high selectivity adsorbents. In literature for equilibration separation processes the inherent separation factor corresponds to those product compositions which will be obtained when simple equilibrium is attained between the product phases.
A conventional Pressure swing adsorption (CPSA) unit is employed for separation of binary and multicomponent gas mixtures. A CPSA unit basically involves cycles during which few beds are getting loaded with some component of the gas mixture and few beds that are getting regenerated. The cycle is complete when the said activities in the corresponding bed are complete, and the activities that are opposite to that which took place in the earlier cycle are initiated. This repeated loading and regeneration in each bed will end up in a cyclic steady state over a period of cycles and a separation is achieved. When the separation factor is very large (about 10) sharp separation is possible. However, if the separation factor is between 1.5 and 10, sharp separation cannot be achieved. We get one component to be nearly pure but the recovery is poor. For example,
separation of propylene (50 mol %) and propane (50 mol %) by PSA yields about 95% propylene, but the yield is low as low as 50%, which Means the rest of propylene is lost with propane. Da Silva and Rodrigues carried out a VSA process with 13 X Zeolite that could generate a propylene enriched stream of 98% mol relative to propylene/ propane mixture, with 3.2 % of nitrogen, a recovery of 19%, and productivity of 0.785 mol/kg/h (Propylene/Propane Separation by Vacuum Swing Adsorption using 13X Zeolite, AIChE Journal, Feb. 2001 Vo. 47, No. 2). However, the said scheme of fractionation with fixed bed hypersorber like process yields sharp separation; i.e. we get nearly pure propylene and propane. The yield is better than 98%.
Air fractionation in fixed beds has been reported in the patent by Sircar et al. (US Patent 4,013,429) with four steps carried out in two trains (2 beds per train). The four steps that have been reported are - Adsorption, Nitrogen Rinse, Desorption and Presaturation. A patent by Knaebel.K.S (US Patent 5,032,150) claims a six step PSA process for the production of high purity nitrogen, and a product oxygen rich gas from air using a fixed bed. The steps are - Slowdown, Purge, Pressurization, Feed, Pressure Equalization and Rinse.
Fractionation of liquid mixtures is achieved using an elutant (desorbent). These processes are well known as Sorbex processes. The Sorbex process is the generic name for similar processes that carry the UOP's (Des Plaines, Illinois, USA) trade names like Parex, Ebex, Molex and Sarex. Morbidelli and his coworkers (see Baciocchi et al. (1996) have demonstrated the fractionation gas mixture using Sorbex process. Ruthven and Ching (1989) presented a state-of-the-art review of the countercurrent and simulated countercurrent adsorbers. In the UOP Sorbex process, a single rotary valve having several ports is used to realize the switching of the ports for t; injection or withdrawal of liquid. Several pipes have to be connected to the valve and the bed. The bed needs to be sectionalized. The movement of port is discrete.
Ideally, a continuous countercurrent system should involve a bed of adsorbent moving downward in plug flow and a gas/liquid mixture flowing upward in plug flow through the void space. Unfortunately, due to problems of adsorbent attrition, liquid channeling and
non-uniform flow of adsorbent particles; such a system has not been successfully developed. The Inventors have noticed that it is possible to use fluidized beds or moving beds to achieve countercurrency. However, the attendant mechanical complexity involved in handling of solids and the loss of adsorbent due to attrition have inhibited the use of the continuous countercurrent processes. These problems are responsible for the demise of the hypersorption process. As an alternative to the moving bed, UOP developed a simulated periodic moving-bed adsorb: with a fixed bed. The input and output ports of the adsorber are periodically switched among sections of the bed to achieve countercurrent contact of solid and liquid phases using a rotary valve (US Patent 3,192,954).
Of late sorption enhanced adsorptive reactors have come to limelight as a good prospect for many industrially important reactions that are limited by equilibrium. Hydrogen synthesis reaction by steam reforming of natural gas and ammonia synthesis reaction from synthesis gas (effluent gas obtained by cracki ' naphtha or natural gas) are two such reactions whose industrial importance has been widely accepted. Rodrigues et al. (Simulation of Five-Step One-Bed Sorption Enhanced Reaction Process, AIChE Journal, December 2002, Vol. 48, No. 12) discusses in detail the modeling and simulation of the steam reforming of natural gas to synthesize hydrogen based on sorption enhanced reaction process. However industrial reactors are normally followed by a huge separation train of varying configurations.
It is felt that fixed bed hypersorber can be suitable for such processes once a proper countercurrent solid-gas/solid-liquid contacting method is devised. Also, such fixed bed hypersorbers can stage process intensification of housing both the reaction as well as separation within a single bed. Thus there is a grave need to develop novel systems for injecting and withdrawing fluids in fixed bed hypersorbers which can effectuate countercurrent solid-gas/solid-liquid contacting.
Objectives
The main object of the present invention is to emul?fp the moving bed hypersorber in a fixed bed hypersorber.
Another object of the present invention is to provide a fixed bed hypersorber having moving ports for injecting and withdrawing fluids which effectuates countercurrent solid-gas/solid-liquid contacting.
Yet another object of the present invention is to realize moving bed hypersorber in a fixed bed hypersorber by moving the inlet ports or by sequential switching the streams that enter and leave each bed.
Still another object of the present invention is to effectively fractionate any gas mixture into two product streams - the Raffinate product stream and the Extract product stream.
One more object of the present invention is to effectively fractionate any gas mixture into two streams - the Raffinate stream and the Extract stream in four fixed beds using five steps that are staggered in between the beds in such a way the process is continuous.
One another object of the present application is to effectuate process intensification with only two fixed beds in the claimed method for gas mixture fractionation, rather than with four fixed beds.
It effectuates chromatographic separation of liquid mixtures in a fixed bed using an elutant. Sorbex like process performed with moving ports rather with rotary valves.
It effectuates single \ multiple bed reactor cum separator, using the concept of moving ports.
It effectuates effective heat exchange between a hot gas stream and a cold gas stream across the bed of solids using the concept of heat regeneration, i.e. it accomplishes a twin bed regenerative heat exchanger using the concept of moving ports.
Summary
A method to emulate the moving\fluidized bed hypersorption process in fixed beds has been conceived by incorporating moving port system in the presently available fixed bed system. The hypersorber had a bed of adsorbent moving downward in plug flow and a
gas/liquid mixture flowing upward in plug flow through the void space. The moving ports bring about countercurrent solid-gas/solid-liquid contact in the fixed bed. Two methods of injection and withdrawal of fluid from the moving ports have been conceived. The first method is with helical slots, and the other being a piston type moving port system. The said moving-ports enable to move continuously the ports of injection or withdrawal of liquid or gas across the entire bed. The said moving-ports can be used to design simulated moving beds for separation of gas and liquid mixtures and also to effectively exchange heat between gases. The motive behind the moving port concept is to bring about process intensification in the process that is being claimed ftr *as mixture fractionation, and also in the development of regenerative heat exchangers using moving ports. The streams that enter and leave each fixed bed can also be switched sequentially using solenoid valves that could be activated either electrically or pneumatically to realize the process of contacting the solid-gas/solid-liquid in a countercurrent fashion.
Brief description of the Accompanying Drawings
In the drawings accompanying the specification,
Figure 1 (a) represents the moving-port system with striight and helical slots.
Figure 1 (b) represents sequential movement of the port.
Figure 2 represents the piston type of moving-port system
Figure 3 represents the phase diagrams - adsorption vs. absorption
Figure 4 represents the countercurrent process - adsorption vs. absorption
Figure 5 represents the mechanistic view of absorption
Figure 6 represents the mechanistic view of fixed bed adsorption
Figure 7 represents the adsorption equilibrium for binary system
Figure 8 represents the Conceptual similarity betweei. Jsorption and distillation.
Figure 9 represents the mechanistic view of distillation process.
Figure 10 represents the conditions of fixed bed hypersorption process during a cycle.
Figure 11 represents the hypersorber with single moving port in each bed.
Figure 12 represents the two bed hypersorber with two moving ports in each bed.
Figure 13 represents the two bed hypersorber with three moving ports in each bed.
Figure 14 represents the chromatographic separation of liquid mixtures using moving
ports
Figure 15 represents the chromatographic reactor cum separator
Figure 16 represents the schematic of single bed heat regeneration with four moving
ports.
Details of Invention
Accordingly, the present application provides a fixed bed hypersorber effectuating countercurrent solid-gas/solid-liquid contacting, said hypersorber comprising:
a column comprising solid absorbent/adsorbent material in the form of packed bed section, and
one or more moving port fluid injection and withdrawal systems incorporated inside the column for injecting and withdrawing the gas/liquid to be purified.
In an embodiment of the present application, the moving port fluid injection and
withdrawal system comprises of conduit or piston moving in to and fro direction through
the column comprising the solid absorbent/adsorbent.
In another embodiment of the invention, the moving port fluid injection and withdrawal
system comprises of a pair of tube arranged in a concentric fashion, wherein one of the
tubes is provided with a straight slot and the other tube is provided with a helical slot, and
both the tubes are rotated with respect to each other by means of a motor.
The present also provides a method for fractionation of a mixture of fluids, said process
comprising the steps of:
passing the mixture of fluids to be fractionated through one or more hypersorbers provided with one or more variable inlet means for influx of the mixture of fluids, one or more fixed beds filled with one or more adbosrbers being placed in proximity of the inlet means, and at least two outlets means through which the fractionated fluids can be withdrawn;
(a) introducing the mixture of fluids to be fractionated into the variable inlet means in order to form an axial and radial flow of the "'•lids, wherein the axial and radial
flow of the mixture of fluids is such that the fluids come out of the inlet means from different controllable locations;
(b) contacting the mixture of fluids to be fractionated coming out of the variable inlet
means with the fixed bed filled with the adsorld's to adsorb a raffinate component
from the mixture of the fluids and to provide a substantially pure extract
component;
(c) removing the substantially pure extract component of step (c) from at least one of
the said outlet means, and
(d) removing the fixed adsorbent bed having the raffinate component adsorbed on it
and de-adsorbing the raffinate component from the bed to obtain substantially
pure raffinate component.
In another embodiment of the present application, the mixture of fluids to be fractionated is selected from the group consisting of a mixture of two or more gases, a mixture of one or more gases and one or more liquids and a mixture of two or more liquids.
In yet another embodiment of the present application, the mixture of fluids to be fractionated is selected from the group consisting of a mixture of two or more gases and a mixture of one or more gases and one or more liquids.
In still another embodiment of the present application, the variable inlet means for influx of the mixture of fluids is a hollow movable piston with a piton head wherein said piston head is provided with plurality of holes.
In one more embodiment of the present application, the holes are provided on a circumfrential side of the piston head.
In one another embodiment of the present application, the hollow piston is connected to a supply of the mixture of fluids.
In a further embodiment of the present application, the mixture of fluids are fed to the piston at elevated pressure.
In a further more embodiment of the present applicati -a, the piston is attached to a motor through a connecting means for providing back and forth motion to the piston.
In another embodiment of the present application, the piston is attached to a motor through a linear screw for providing back and forth motion to the piston.
In yet another embodiment of the present application, the variable inlet means for influx of the mixture of fluids comprises of a pair of tubes arranged in a concentric fashion and being provided with one or more slots.
In still another embodiment of the present application, the variable inlet means for influx of the mixture of fluids comprises of a pair of concentric tubes wherein an inner tube is provided with a traverse slot running parallel to a vertical axis of the tube and an outer tube provided with a helical slot running parallel to a vertical axis of the tube or vice versa such that a trapezoidal opening is formed where both the slots overlap.
In one more embodiment of the present application, the outer tube is rotated with respect to the inner tube to move the trapezoidal opening froi, one end of the tube to the other.
In one another embodiment of the present application, the variable inlet means for influx of the mixture of fluids comprises of a pair of tubes arranged in a concentric fashion such that an inner tube is provided with a series of valves on its outer surface and an outer tube is provided with a means for opening the valves in a predetermined fashion on its interior surface.
In a further embodiment of the present application, the variable inlet means for influx of the mixture of fluids comprises of a pair of tubc.s arranged in a concentric fashion such that an inner tube is provided with a series of push-button valves on its outer surface and an outer tube is provided a helical strip on its interior surface for opening the valves in a sequential fashion.
A fixed bed hypersorber like process has been proposed that can be realized with or without moving ports for the fractionation of gaseous mixtures in fixed beds filled with absorbent.

The regeneration of the fixed beds is done using pressure swing and the process involves concurrent reflux of both products, namely the Extract Reflux and Raffmate Reflux. The extract reflux is a continuous reflux. The Raffmate reflux however is discrete, i.e. the effect of raffinate reflux similar to distillation is realized only after the High Pressure Raffmate Reflux Step in a cycle is over, and when the bed which underwent this step is switched for the High Pressure Adsorption\Stripping Step. The said process can fractionate the gas mixtures into the Raffinate and Extract products, both with high purity as well as recovery. The process accomplished withYwithout moving ports in fixed beds for gas fractionation has five steps. The steps are - High Pressure Adsorption\Stripping step, High Pressure Extract Reflux/Enriching step, Low Pressure Regeneration Step, Low Pressure Raffinate Recycle step, and High Pressure Raffinate Reflux step. During any moment of the process - adsorption, enriching, and regeneration steps occurs in an individual bed each; and the Raffinate Recycle step a iow pressure and Raffinate Reflux step at high pressure occurs in a same bed. The said steps are staggered in between the beds in such a way the process is made continuous. The said staggering is possible by the excitation and non-excitation of normally closed solenoid valves in a sequential and systematic manner.
The Inventors have now invented moving-ports, and two methods by which the port of injection or withdrawal of liquid or gas is continuously moved in a controlled fashion, thereby achieving countercurrent action. The said Election and withdrawal of fluids using moving ports accomplish the realization of countercurrent solid-gas contact in moving beds with fixed beds only. The moving ports can be used to design simulated moving beds for separation of gas and liquid mixtures and also to effectively exchange heat between gases. The two types of moving ports developed in the present application for effecting the countercurrent contacting of solid-gas or solid-liquid are (a) helical slot moving port system, and (b) piston type moving port system. The said moving ports can accomplish a Hypersorber like process in fixed beds. Depending on the type of gas mixtures the said ports can bring out - fractionatiou jf gas mixtures in four beds, and absorption like separation in three beds. The former case can be accomplished with two fixed beds only when used with three moving ports in each bed, and results in process
intensification. If the process intensification is compromised the fractionation will occur in fixed beds without moving ports.
The streams flowing in and out of the four beds are sequenced such that exact flow sequence occurring in the moving bed hypersorber is emulated in the fixed-bed hypersorption like PSA. The steps are - High Pressure Adsorption \ Stripping step, High Pressure Extract Reflux / Enriching step, Low Pressure Regeneration Step, Low pressure Raffinate Purge with Total Recycle, and High Pressure Raffinate Reflux step. This flow coordination actually stages fractionation of any gas mixture like that in a moving bed hypersorber, and this is unlikely of any existing conventional PSA systems. For binary gas mixtures the said process can bring aK'irt effective fractionation into two highly pure product streams with excellent recoveries. For example - a binary mixture of ethane and ethylene can be effectively fractionated using the said process to yield highly pure ethane as the Raffinate product and highly pure ethylene as the Extract product with excellent recoveries at both ends. For multicomponent gas mixtures the said process can bring about fractionation in such a manner that either the light component is taken as the pure Raffinate Product, or the intermediate components along with the heavy component is drawn as the Extract Product, or the vice-versa. For example - a ternary mixture of methane, ethane and propane can be fractionated ustiig the said process to yield highly pure methane as the Raffinate product, or highly pure propane as the Extract product. Multi-component mixtures can be also be fractionated at desired cuts in the said process.
1. Novel idea on the Concept of Moving Ports
We have invented moving-ports, which enable us to move continuously the ports of injection or withdrawal of liquid or gas. These can be used to design simulated moving beds for separation of gas and liquid mixtures and also to exchange heat between gases. We have proposed two methods of injection and - ;>.hdrawal of fluid mixtures using moving ports. Method-1:
The first type of moving-port system is shown in Figure la. It has an inner tube with a straight slot and an outer tube with helical slot. The slots can be placed the other way. Where these slots intersect forms a rhombus shaped port or opening. If one of these tubes
is rotated, the port moves from one end to the other and returns abruptly. The stepper motor or motor with a gear train or other means can be used to rotate the outer tube. The inner tube can be connected to a fluid line. A fluid can be introduced or withdrawn through the port. The gasket can be fixed around the slots to prevent leakage through slots from the portion other than the opening. Introducing or withdrawing fluid through a port amounts a 'point' feed or withdrawal.
It is also possible to have a line feed or withdrawal, which may be advantageous in some cases. Such moving-port systems can be embedded in packed beds to achieve countercurrent processes. The sequential movement of the port has been shown in Figure Ib.
Alternately, one of these tubes can be fixed with a number of push-button valves. These valves can be opened using a helical strip fixed on the other tube to realize the moving-port operation. The later version can be used where even a minor leak of liquid or gas from the portion other than port has severe detrimental effect.
Method-2:
This is a piston type of moving-port system. Sketch of this version is given in Figure 2. The outer tube is perforated one. Inner one is a loose fitting tube with one end closed. In between the ends, a smaller tube is fixed to so as to feed liquid or gas as shown in figure. The fluid flows out radially outward through the perforations. The inner tube can be moved back and forth using a linear screw and motor with suitable arrangement. The movement of the inner tube is such that the port can be smoothly moved from one end to the other. Unlike the system with slots, the port has to be drawn back to restart the operation. It is possible to have a leak-proof system.
A single system can be used to inject or withdraw fluid from more than one point. The
moving-port systems can be used to build moving-bed adsorber, combination reactor and
separators or heat exchangers.
2. Mechanism of separation
For the sake of clarity, we consider here separation mechanism of a binary gas mixture.
The conventional PSA is a kin to absorption. Only one of the components gets adsorbed
as with the H2-CH4 mixture or the separation factor has to be very high for effective separation. On the other hand, the proposed Hypersorber like process accomplished in fixed beds with or without moving ports is a kin to distillation. It is effective for separation of mixtures with separation factor as low as 1.5. There are several systems" for which the separation factor is in between 1.5 to 15 (see, Myers). The said process can fractionate binary mixtures into two product streams and can bring about sharp separation as in distillation.
In the following we have the similarities between absorption and conventional PSA on one hand, and distillation and Fixed bed Hypersorber with moving ports on the other. Though, these are well known, they are presented to set Fixed bed Hypersorber with or without moving ports in a proper perspective.
Absorption and Conventional PSA
The phase diagrams for absorption and adsorption where only one component (solute) gets transferred into solvent or adsorbent is given Figure 3.
The corresponding countercurrent processes are shown in Figure 4. The adsorbent is regenerated by pressure or thermal swing or elution. The solvent is regenerated by steam stripping, which can be viewed as thermal swing combined with elution or it can be done by pressure swing.
Figures 5 and 6, shows the mechanism of separation in absorption and in a bed of conventional PSA. The yellow region represents the solvent or adsorbent phase and the blue region represents the gas phase. The colored spots represent gas molecules and roughly their density in the gas and solid phases.
Distillation and Fixed Bed Hypersorber with or without moving ports
The comparison of fractionation achieved by distillation to that achieved by moving-bed adsorption has been discussed first. The phase diagrams of both are similar and the phase diagram of binary system adsorption has been shown m Figure 7.The conceptual similarity between Adsorption and distillation has been shown in FIG. 8. Both processes have enriching section (7 and 11) and stripping section (6 and 10) in common. The Presaturation section (5) in adsorption is similar to the reboiler (9) in distillation and desorption section (8) in adsorption is similar to condenser (12) in distillation. The actual fractionation takes place in the enriching and stripping sections. The mechanism of separation is shown in FIG. 9. More details are given elsewhere (Rao, D. P., "The futility of Raffinate Reflux Revisited", C and. J. Chem. Eng).
The moving-bed operation is emulated in four fixed beds and is analogous to a Hypersorption like process carried out in fixed beds. The 'operation' of the fixed bed Hypersorption like process is similar to conventional PSA and operates in a cyclic manner. The cycle has five steps. During a cycle, each bed goes through High Pressure Adsorption\Stripping step. High Pressure Extract Reflux/Enriching step. Low Pressure Regeneration Step, Low pressure Raffinate Purge with Total Recycle, and High Pressure Raffinate Reflux step. The conditions of the beds in all four steps are shown the FIG. 10.
The Feed is stored in feed tank (17) and from there is it fed to a stripping section (18) having a mass transfer zone (19), the raffinate is obtained from the top of the stripping section and is stored in a raffinate tank (20). The thus stored raffinate is fed to a purge and pressurization section (21). A vacuum pump (22) is connected to the output of the purge and pressurization section which draws the contents from this section and feeds it to the feed tank (17). Once the stripping process is complete, the stripping section is taken up for blow down process. In the blow down process, the extract is obtained from the adsorbent/absorbent contained in the blow down section (25), and stored in an extract tank (27) using a vacuum pump (26). Thereafter the section is enriched in an enriching process to obtain an enriched section (23) which is ready for use in stripping process.
The lengths of mass transfer zones of each of the sections are only a few centimeters as is the case with the conventional PSA. In the ideal case wherein there is complete regeneration of adsorbent. Then the bed that undergoes regeneration by pressure swing is identical to condenser in its function. Then, the Low pressure Raffinate Purge with Total
Recycle is not required. The mixture can be separated into pure components. However in practice, complete regeneration is not possible. Therefore, the Low pressure Raffinate Purge with Total Recycle is required to get nearly pure products. Our simulation studies show that, the Low pressure Raffinate Purge with Total Recycle can be adjusted such that the composition of the stream at the end of this step is same as the feed and it can be recycled after being compressed along with feed. Thus, we ensure that there is no waste stream. The recycle is valuable if the components are of high economic value.
As with distillation, we have concurrent reflux at both ends—extract reflux and raffinate reflux. They are not independent. They are linked in a manner as the boil-up ratio and reflux ratio in distillation. For specified separation, there is a minimum reflux ratio. This can be accurately found on the diagram similar to the Ponchon-Savarit diagram or approximately on the McCabe-Thiele diagram. We can find the optimum reflux ratio based on the economic analysis. We can use the Underwood equation to determine the reflux ratio for multi component mixtures.
In distillation, the separation factor is usually referred as the relative volatility. As the relative volatility tends infinity the minimum reflux ratio tends to zero and the distillation tends to stripping process. The same is the case in adsorption. The fractionation tends to the simple stripping as is the case with the H2-CH4 mixture. We can separate this mixture into pure H2and pure CH4, in principle, with three columns employing the total recycle of Low pressure Raffinate Purge stream.
3.A Fixed Bed Hypersorber Like Process with Moving Ports
3.1 Four-Bed Hypersorber with Single Movins-Port in Each Bed.
Hypersorber with one moving-port in each bed has been shown in FIG. 11. The moving-ports are depicted as a piston pushing the mass transfer zone. However the process can be carried out in more than four beds or less than four beds depending on the nature of the gas mixture that is to be fractionated and the degree of process intensification that one looks for. The feed containing a binary mixture is stored in feed tank (28) and from there
is it fed to a stripping section (29) having a mass transfer zone (30), the raffinate is obtained from the top of the stripping section and is stored in a raffinate tank (31). A part of the raffinate thus obtained is fed to a purge and pressurization section (32). A vacuum pump (33) is connected to the output of the purge and pressurization section which draws the contents from this section and feeds it to the feed tank (28). Once the stripping process is complete, the stripping section is taken up for blow down process. In the blow down process, the extract is obtained from the adsorbent/absorbent contained in the blow down section (34), and stored in an extract tank (35) using a vacuum pump (36). Thereafter the section is enriched in an enriching process to obtain an enriched section (37) which is ready for use in stripping process.
3.2 Two-Bed Hypersorber with Two Movins-Port Systems in Each Bed
The schematic of the arrangement is shown in FIG. 12.
In this scheme two mass transfer zones are accommodated in a single bed. Such a system comprises only two section working together. One of the section is called a separation section (40), while the other section is called a regeneration section (41). The separation section is divided into a stripping zone (42) and an enriching zone (43), whereas the regeneration section is divided into blow down zone and a purge and pressurization zone (not shown in FIG. 12). Both these sections are connected to a raffinate tank (44), a feed tank (45), an extract tank (46), and a waste tank (47) using pumps (48 and 49). While the fractionation is taking place in one bed (with active moving ports), the other bed (with inactive moving ports) is undergoing the pre-saturation steps with the Raffinate product.
3.3 Two-Bed Hypersorber with Three Moving-Port Systems in Each Bed
The beds with three moving ports are similar to previous case except that there are three moving-ports in each bed. This scheme typically emulates the SMB unit. In this scheme the ports movement is visualized as the movement of the bed. A typical configuration has been shown in FIG. 13. Here the separation section (50) as well as the regeneration section (51) is connected to the raffinate tank (52), the feed tank (53), the extract tank (54) and the waste tank (55) through 2 vacuum pumps (56 and 57). The separation
section is divided into stripping zone (58) and enriching zone (59) whereas the regeneration section is divided into blow down zone and a purge and pressurization zone (not shown in FIG. 13).
The stripping and enriching mass transfer zones along with the Regeneration step of the above scheme has been simulated and the results given below.
In FIG. 11, the bed prior to undergoing High Pressure Adsorption\Stripping step is pre-saturated with the light component, i.e. the Raffmate Product, by the Low Pressure and High Pressure Raffmate Reflux step. The gas mixture to be fractionated is fed to the bed undergoing High Pressure Adsorption\Stripping step from a feed tank through the moving port. During this step the Light component pre-saturated in the solid phase is stripped out of it by the adsorption of the heavy component in the feed into it. Light component Stripping takes place along the bed across a mass transfer zone that is developed during this step. A stream highly rich in the light component can be drawn as the Raffmate Product if the said mass transfer zone does not break through across the bed. The said Raffmate product is collected in Raffmate tank. The High Pressure Adsorption\Stripping step is stopped before the breakthrough of the said mass transfer zone occurs. After the High Pressure Adsorption\Stripping step the bed is saturated with feed composition.
In the bed undergoing the High Pressure Extract Reflux/Enriching step, a predetermined portion of the Extract product stream highly rich in the heavy component is refluxed into the bed from the Extract tank using a moving port. The reflux is made in a direction co-current to the direction of feed in the High Pressure Adsorption\Stripping step. Initially this bed is saturated with feed composition by the High Pressure Adsorption\Stripping due to the adsorption of the heavy component and displacement of the light component out of it. Heavy component enriching takes place along the bed across a mass transfer zone that is developed during this step. This step is stopped when the said mass transfer zone break through across the bed. After the High Pressure Extract Reflux/Enriching step the bed is saturated with the Heavy Component both in the solid and gas phase. The stream coming out of this bed is recycled back to the d tank.
In bed undergoing Low Pressure Regeneration Step, the regeneration of the bed saturated with the Heavy Component is accomplished by using a vacuum pump to perform the pressure swing. The regeneration is performed in a direction co-current to the direction of feed in the High Pressure Adsorption\Stripping step. The heavy component discharged during the regeneration is drawn as the Extract product into the Extract tank. A portion of the extract product is compressed and used for reflux in the High Pressure Extract Reflux/Enriching step.
Both the Low pressure Raff incite Purge with Total Recycle step and High Pressure Raffinate Reflux step are performed in a single bed. Initially the bed regenerated by pressure swing in the previous cycle is refluxed with a predetermined quantity of the Raffinate Product. The exit stream during this step can be recycled to the feed tank, or could be vented out. The Low pressure Raffinate Purge with Total Recycle step is performed at the regeneration pressure. The Low pressure Raffinate Purge with Total Recycle step is stopped by stopping the withdrawal «f the said stream to the feed tank. During the High Pressure Raffinate Reflux step the reflux of the Raffinate product to the bed is continued. Both the Low pressure Raffinate Purge with Total Recycle step and High Pressure Raffinate Reflux step are performed in a direction co-current to the direction of feed in the High Pressure Adsorption\Stripping step. The Low Pressure and High Pressure Raffinate Reflux step pre-saturates the bed with the light component.
The beds undergoing the High Pressure Adsorption\Stripping step and Pressure Extract Reflux/Enriching step are similar to the adsorption and the enriching sections of a conventional Hypersorber. The bed undergoing Low Pressure Regeneration Step is similar to the steam heater in the conventional Hypersorber, the difference only being in the mode of regeneration. While thermal swing has been employed in the conventional Hypersorber for regeneration, pressure swing has been employed for regeneration in our process. The bed undergoing the Low pressure Raffinate Purge with Total Recycle step and High Pressure Raffinate Reflux step is similar to the cooler in a conventional
Hypersorber. Thus the process being claimed accomplishes a true Hypersorption like process in four fixed beds using one moving port in each bed.
What is shown in figure is one step of the four steps in a cyclic operation. There are four steps. In a cycle, each bed undergoes all the five steps in that sequence (in sequence as listed above). A cycle is said to have been completed when each bed completes the entire five steps. The time to perform a cycle is defined as the cycle time. By sequential excitation and non-excitation of normally closed soienoid valves, we will be able to realize the cyclic operation. The proper choice of flow rates of the streams is essential to realize the sharp separation. Such a choice is not obvious. We have obtained the possible separations using computer simulations for three systems for cases wherein the moving ports are held stationary at a position in each bed and the results have been tabulated in Tables 1-3.
Table 1; Propane-propylene system, Isothermal, D=50%F, PH=latm, PL=0.01atm
(Table Removed)
Table 2: Methane-ethane system, Isothermal, D=50%F, PH=latm, PL=0.01atm
(Table Removed)
Table 3: Oxygen-Nitrogen system, Isothermal, D=79%F, PH=latm, PL=0.1atm

(Table Removed)
The fractionation of the binary mixtures is achieved in the mass transfer zones of the stripping and enriching beds. The extract product (strongly adsorbed component) is recovered in the regeneration step and a part of it is sent as reflux to the enriching section. The raffinate product is recovered from the stripping bed and a part is used to purge the bed that underwent regeneration step.
Simulation of the scheme shown in Figure 5 which emulates a 8MB in two fixed beds with three moving ports each has been simulated and results given in Tables 4-6. Table 4: Isothermal propylene (l)-propane (2) system with total waste stream recycled. D = 50% F, RR =0.1% B PH = 5 atm, PL = 0.0001 atm

(Table Removed)
Table 5: Isothermal ethane (l)-methane (2) system with total waste stream recycled. D = 50% F, RR =0.1% B PH = latm, PL = 0.0001 atm
(Table Removed)
TABLE 6 Isothermal nitrogen (l)-oxygen (2) system with total waste stream recycled. D = 79% F, RR = 0.1% B. PH = 5 atm, PL = 0.0001 atm

(Table Removed)
4, Single Bed Chromatographic Separator for Separation of Liquid Mixtures With Four Moving-Port Systems Using an Elutant
The process is, in fact, SORBEX. It is carried out using moving systems rather than with 5 rotary valves, and an elutant as shown in FIG. 14.
The single column (60) is divided into 4 different sections which are as follows:
I-Adsorption of B
II~Adsorption of A
III~Desorption of B
IV~Desorption of A
A pump (61) is used to transfer the elutant from one end to the other. This type of SORBEX system uses 4 moving ports.
5. Single Multiple bed Reactor cum Separator
The gaseous reaction and separation can be carried out in series of beds with mixed catalyst and adsorbent particles. It is possible to drive the reaction to completion and separate the reactants and products. This eliminates, or considerably simplifies the down stream processes. This is likely to alter the way chemical processes are carried out. For instance, it is possible to feed N2 and H2 and obtain pure NH3 from the reactor separator. The reactor cum separator with two beds having two moving ports each is shown in FIG. 15. The scheme for product regeneration by using elutant has been shown in the figure. However the regeneration can also be effected by pressure swing. The packed bed here acts as a reaction zone (71) as well as a stripping zone (72). When the mixture of the products is fed from the feed tank (73), the packed bed acts as reaction zone and when the elutant is fed from the elutant tank (74), the packed bed acts as stripping zone. The contents of the packed bed column is removed and collected in a product tank (75) from where it is sent for elutant separation.
6. Single Bed Beat Regenerator with Four Moving-Bed Systems
The exchange of heat between gas streams requires bulk equipment, as the heat transfer coefficient is very low. The exchange can be accomplished in two beds of solids with two-ports each as shown in FIG. 16.
The packed bed column having multiple inlet means is operated as cooling zone (81) and as a heating zone (82). The hot gas is fed to the cooling zone and exhausted hot gas is removed from the cooling zone, while cold gas is fed into the heating zone and heat enriched gas is withdrawn. We have simulated such a regenerator, which can replace the blast furnace stoves. There was 70 times volume reduction based on single bed heat regenerator modeled using Intra-particle Conduction model and 97 times volume reduction on a using Schumann model with axial dispersion.
Accordingly the present invention provides a novel process for gas fractionation emulating the hypersorber in fixed beds that can fractionate any gas mixtures; the said
beds are filled with specific adsorbents for individual mixtures and range from activated carbon, silica gel, various variants of zeolite, cation impregnated n-complexed Alumina\silica based adsorbents.
A novel concept of moving port systems to bring out effective solid gas contact; the said moving port systems accomplish the realization of countercurrent solid-gas contact in moving beds with fixed beds only.
A method of injection and withdrawal with a pair of two tubes with different diameter having helical slot and straight slot wherein the rotation of either of the tubes will result in movement of the port from one end of the tube to the other and has an abrupt return to the starting position for the next movement; the gasMiquid to be distributed within the fixed bed is connected to the inside tube with helical slot and gas is distributed into the fixed bed through the port formed with the outside tube having straight slot.
A method of injection and withdrawal with a pair of two tubes with different diameter; the bigger diameter tube being the outer tube with perforations and the inner tube connected to the fluid that is to be distributed has a piston like appearance; gas/liquids flows out only through the perforations in the outer tube that overlap with the opening in the inner tube.
A novel process of fractionating any gas mixture in four fixed beds with or without moving ports wherein in a step of a cycle Bed 1 undergoes the High Pressure Adsorption\Stripping Step, Bed 2 undergoes the High Pressure Extract Reflux\Enriching Step, Bed 3 undergoes the Low Pressure Regeneration Step, and Bed 4 undergoes both the Low pressure Raffinate Purge with Total Recycle and the High Pressure Raffinate Reflux Step; after the said processes are completed in each bed the flow streams in and out of each bed are redirected such that in the next step of the cycle the processes that occurred in Bed 1, Bed 2, Bed 3 and Bed 4 of the previous step are switched and carried out in Bed 2, Bed 3, Bed 4 and Bed 1 correspondingly; after two more such shifts each bed would have performed all the individual steps ai:_ a cycle is complete; and the time to complete this is the cycle time. In a step of a cycle -
(a) Bed 1 with or without moving ports prior to be fed with the feed is presaturated
with the raffinate product in a direction co-current to the direction of feed in the
High pressure raffinate reflux step; with accomplishment of the said
presarturation the feed is fed with moving ports held in a fixed position in the bed
or moving across the bed; the said feeding continued until breakthrough of the
mass transfer zone is impending; the effluent from this step collected as raffinate
product and a part of it is used for the low pressure and high pressure raffinate
reflux.
(b) Bed 2 with or without moving ports is refluxed with the Extract product in a
direction co-current to the direction of feed; prior to this reflux step the bed has
been saturated with feed during High Pressure adsorption\Stripping Step of the
previous step of the cycle; the said reflux saturates the bed with extract product;
the said reflux shall be made with moving ports held in a fixed position in the bed
or moving across the bed; the effluent of this reflux step is relatively rich in the
extract component than with the actual feed; the said effluent is totally recycled
back along with the feed for the High Pressure adsorption\Stripping Step; the said
reflux step is continued until the mass transfer zone generated in the bed
breakthrough across the bed.
(c) Bed 3 with or without moving ports with the entire inlet to it ceased is regenerated
by reducing the pressure to sub-atmospheric and the effluent is drawn as the
extract product in a direction co-current to the direction of feed; the said bed is
saturated with the extract component during the High Pressure Extract
RefluxYEnriching Step of the previous step of the cycle; the said regeneration is
done by withholding the moving ports at a fixed position; the said effluent drawn
as the extract product is compressed and part of it used as reflux for the High
Pressure Extract RefluxVEnriching Step.
(d) Bed 4 with or without moving ports is reflux... with the raffinate product at low
pressure; the effluent of the said low pressure reflux is compressed and totally
recycled back along with the feed for the High Pressure adsorption\Stripping
Step; the said low pressure reflux displaces off the extract component that remain
unregenerated in bed during the Low Pressure Regeneration Step of the previous

step of the cycle; after the said Low pressure Raffinate Purge with Total Recycle and with the entire streams out of the be ceased the said bed is refluxed further with the raffinate to pressurize the bed to make it ready for the next High Pressure adsorption\Stripping Step; the said refluxes of the raffinate both at low as well as high pressure is accomplished by withholding the moving ports at a fixed position.
Variant of the fractionation process of gas mixtures in fixed bed with more than one moving ports; one of the said variant shall be accomp'ished in two fixed beds with two moving ports each with one of the said beds undergoing separation has active moving ports and the other bed undergoing regeneration has inactive moving ports; the other variant same as the previous one but for the three moving ports in each bed.
Application of the moving port for Sorbex like separation in fixed beds without rotary valves; the said application is accomplished with four moving ports in a fixed bed which partitions the bed into four distinct zone and thereby perform the Sorbex like process without rotary valves.
Application of the moving port to carry out a chemical reaction and separation concurrently in SingleYMultiple bed Reactor cum Separator; the said reaction is accomplished in a reaction zone formed between two moving ports with the reactants being fed with one moving port and the unreacted reactants removed through another; the said separation is accomplished in a separating zone formed by another two moving ports where the product that is adsorbed in the bed is regenerated either by pressure swing or by using an elutant; the said process with regeneration of product from the fixed bed by pressure swing can be accomplished only in multiple beds and the least with two beds.
Application of the moving port to carry out heat exchange in a two bed regenerative type heat exchanger; the said heat exchange is accomplished with four moving ports which form two distinct zones with a pair each; the hot gas to be cooled is fed to the cooling zone through a moving port where the bed is heated and the effluent cold gas is removed out of the zone through another moving port which along with the first moving port has
formed the cooling zone; the cold gas to be heated is fed through the moving port which along with another moving port that carries the effluent hot gas forms the heating zone; the said heating and cooling zones are not allowed to mix with each other having a strategic control over the pressure in the said zones.

















We claim:
1. A fixed bed hypersorber effectuating clean separation of a gas mixture by
countercurrent solid-gas/solid-liquid contacting, said hypersorber comprising:
a) one or more columns comprising solid absorbent/adsorbent material in the form of packed bed section; and
b) one or more piston-like moving port fluid injection and withdrawal systems incorporated inside the column for injecting and withdrawing the gas/liquid to be purified, the said piston like moving port comprises of a perforated outer tube encircling a piston head perforated along the circumference;
characterized in that, said piston head being attached to cylindrical annulus head for preventing back entry of the injected fluids and a cylindrical annulus head enclosure being provided outside the bed to guide the movement of the cylindrical annulus head.
2. The fixed bed hypersorber as claimed in claim 1, wherein the holes are provided on a circumferential side of the piston head.
3. The fixed bed hypersorber as claimed in claim 1, wherein the hollow piston is connected to a supply of the mixture of fluids which are fed to the piston at elevated pressure.
4. The fixed bed hypersorber as claimed in claim 1, wherein the piston is attached to a motor through a connecting means such as a linear screw for providing to and fro motion to the piston.
5. A process for fractionation of a mixture of fluids using one or more hypersorbers (1, 2, 3 or 4), each of the said hypersorbers being in accordance with claim 1, said process comprising the steps of:
(a) providing one or more hypersorbers (1, 2, 3 or 4), each of the said hypersorbers comprising one or more variable inlet means for influx of the mixture of fluids, one or more fixed beds filled with one or more adsorbers being placed in proximity of the inlet means, and at least two outlet means through which the fractionated
fluids can be withdrawn, wherein the variable inlet means comprises of one or more piston-like moving port fluid injection and withdrawal systems; the said piston like moving port comprises of a perforated outer tube encircling a piston head perforated along the circumference; said piston head being attached to a cylindrical annulus head for preventing back entry of the injected fluids and a cylindrical annulus head enclosure being provided outside the bed to guide the movement of the cylindrical annulus head;
(b) introducing the mixture of fluids to be fractionated into the variable inlet means in order to form an axial and radial flow of the fluids, wherein the axial and radical flow of the mixture of fluids is such that the fluids come out of the inlet from different controllable locations;
(c) contacting the mixture of fluids to be fractionated coming out of the variable inlet means with the fixed bed filled with the adsorbers saturated with the raffinate component to adsorb (6) an extract component preferentially from the mixture of the fluids and to provide a substantially pure raffinate component;
(d) removing the substantially pure raffinate component of step (c) from at least one of the said outlet means (5);
(e) extracting product reflux from at least one of said inlet means in the portion of the bed saturated with the feed mixture such that the said reflux saturates the bed with the extract component (7);
(f) desorbing (8) the extract component from the fixed adsorbent bed saturated with the extract to obtain substantially pure extract component; and
g) regenerating the described fixed adsorbent bed by purge and pressurizing purging the same with raffinate component.
6. The process as claimed in claim 5, wherein the mixture of fluids to be fractionated is selected from the group consisting of a mixture of two or more gases, a mixture of one or more gases and one or more liquids and a mixture of two or more liquids.
7. The process as claimed in claim 5, wherein the mixture of fluids are fed to the piston at elevated pressure.
8. The process as claimed in claim 5, wherein the variable inlet means for influx of the
mixture of fluids comprises of a pair of tubes arranged in a concentric fashion and being
provided with one or more slots.
9. The process claimed in claim 8, wherein the variable inlet means for influx of the
mixture of fluids comprises of a pair of concentric tubes wherein an inner tube is
provided with a traverse slot running parallel to a vertical axis of the tube and an outer
tube provided with a helical slot running parallel to a vertical axis of the tube or vice
versa such that a trapezoidal opening is formed where both the slots overlap.
10. The process as claimed in claim 8, wherein outer tube is rotated with respect to the
inner tube to move the trapezoidal opening one end of the tube to the other.
11. The process as claimed in claim 5, wherein variable inlet means for influx of the
mixture of fluids comprises of a pair of tubes arranged in a concentric fashion such that
an inner tube is provided with a series of valves on its outer surface and an outer tube is
provided with a means for opening the valves in a predetermined fashion on its interior
surface.
12. The process as claimed in claim 11, wherein the variable inlet means for influx of the mixture of fluids comprises of a pair of tubes arranged in a concentric fashion such that an inner tube is provided with a series of push-button valves on its outer surface and an outer tube is provided with a helical strip on its interior surface for opening the valves in a sequential fashion.

Documents:

0705-del-2003-abstract.pdf

0705-del-2003-claims.pdf

0705-del-2003-correspondence-others.pdf

0705-del-2003-correspondence-po.pdf

0705-del-2003-description (complete).pdf

0705-del-2003-drawings.pdf

0705-del-2003-form-1.pdf

0705-del-2003-form-18.pdf

0705-del-2003-form-2.pdf

0705-del-2003-form-26.pdf

0705-del-2003-form-3.pdf

0705-del-2003-form-5.pdf

705-DEL-2003-Abstract-(14-05-2010).pdf

705-DEL-2003-Claims-(05-06-2012).pdf

705-DEL-2003-Claims-(14-05-2010).pdf

705-DEL-2003-Correspondence Others-(05-06-2012).pdf

705-DEL-2003-Correspondence-Others-(14-05-2010).pdf

705-DEL-2003-Description (Complete)-(14-05-2010).pdf

705-DEL-2003-Drawings-(14-05-2010).pdf

705-DEL-2003-Form-1-(14-05-2010).pdf

705-DEL-2003-Form-3-(14-05-2010).pdf

705-DEL-2003-Petition-137-(14-05-2010).pdf


Patent Number 254118
Indian Patent Application Number 705/DEL/2003
PG Journal Number 39/2012
Publication Date 28-Sep-2012
Grant Date 20-Sep-2012
Date of Filing 19-May-2003
Name of Patentee GAS AUTHORITY OF INDIA LIMITED
Applicant Address 16 BHIKAJI CAMA PLACE R.K. PURUM NEW DELHI-110016
Inventors:
# Inventor's Name Inventor's Address
1 DAVULURI PRAHLADA RAO DEPARTMENT OF CHEMICAL ENGINEERING, INDIAN INSTITUTE OF TECHNOLOGY KANPUR-208016, INDIA
2 BOJANKI GOVINDA RAMA PRASAD DEPARTMENT OF CHEMICAL ENGINEERING, KANPUR 208 016, INDIA
PCT International Classification Number C01B 31/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA