WO2009101282A1 - Dispositif perfectionne de separation en lit mobile simule - Google Patents
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- WO2009101282A1 WO2009101282A1 PCT/FR2008/001677 FR2008001677W WO2009101282A1 WO 2009101282 A1 WO2009101282 A1 WO 2009101282A1 FR 2008001677 W FR2008001677 W FR 2008001677W WO 2009101282 A1 WO2009101282 A1 WO 2009101282A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
- B01D15/1821—Simulated moving beds
- B01D15/1842—Simulated moving beds characterized by apparatus features
Definitions
- the invention relates to the field of separations of natural or chemical products, which can be difficult to separate by distillation.
- a family of methods, and associated devices known as “chromatographic” or “simulated moving bed” or “simulated counter-current” separation methods, or “in co-operation", are then used.
- simulated current which will be referred to hereafter as” SMB ".
- the fields concerned include, and are not limited to: - the separation between normal paraffins on the one hand and branched paraffins, naphthenes, and aromatics on the other,
- chromatographic separation SMB is well known in the state of the art.
- a simulated moving bed comprises at least three chromatographic zones, and possibly four or five, each of these zones being constituted by at least one bed or a portion of a column and lying between two successive points of supply or withdrawal.
- a desorbent D sometimes called eluant
- R and one extract E are withdrawn.
- the feed and withdrawal points are modified over time, typically staggered down a bed and this synchronously.
- each of the operating zones is designated by a number:
- Zone 1 desorption zone of the desired product (contained in the extract) between the injection of the desorbent D and the extraction of the extract E;
- Zone2 zone of desorption of the compounds of the raffinate, between the taking of the extract E and the injection of the charge to be fractionated F;
- Zone 3 adsorption area of the desired product, between the injection of the feedstock and the withdrawal of raffinate R, and;
- the SMB devices typically comprise at least one column (and often two), adsorbent beds Ai arranged in this column, separated by trays Pi chamber (s) Ci distribution and / or fluid extraction in or to from the different beds of adsorbent, and controlled means of sequential distribution and extraction of fluids.
- Some devices use not one or more columns, but a plurality of adsorbents with single adsorbent bed, separated and connected by transfer lines. In general, it is possible to either pass the entire fluid or main flow in the column according to a diagram described in US Pat. No. 2,985,589, or to bring out a large part or all of this flux to the outside according to a method described in US Patent 5,200,075.
- the controlled means of dispensing and extracting fluids from an SMB are typically one of two major types of technology:
- valves controlled all or nothing for the supply or removal of fluids are typically located in the immediate vicinity of the corresponding plate, and comprising in particular for each tray Pi at least 4 valves controlled all or nothing with 2 channels for respectively the fluid supply F and D and the withdrawals of fluids E and R.
- Each of the trays Pi typically comprises a plurality of distributor-mixer-extractor panels or "DMEs" fed by lines or “spiders” distribution / extraction ".
- the trays may be of any type and any geometry, in particular with panels forming sectors adjacent to the section of the column, for example panels with angular sectors as presented in US Pat. No. 6,537,451, FIG. 8, which are powered (spider ) symmetrical, or parallel sectors as cut in a circumference, as indicated in the published US patent application 03 / 0,127,394, which are asymmetrically fed.
- the separation column comprises DME trays of parallel sector type and asymmetrical power supplies (according to the invention, it will speak indifferently of panels or sectors).
- the adsorbent is installed in dense loading. This makes it possible to use a larger quantity of adsorbent in a given column, and to increase the purity of the desired product and / or the loading rate of the SMB.
- each of the beds requires a collection of the flow from the previous bed (main fluid flowing along the main axis of the column), the possibility of injecting an auxiliary fluid or secondary fluid while mixing the best possible these two fluids or the possibility of taking a portion of the collected fluid, extracting it to send it outwardly of the device and also redistributing a fluid on the next bed.
- Pi distribution chambers Ci, k injection / extraction
- Pi trays are known to one or more chambers, either fed (or withdrawn) separately by different fluids at a given instant, or fed (or withdrawn) simultaneously and in parallel by the same fluid at a given instant.
- the plateau is said to have several distribution networks, whereas it is a single distribution network in the second case.
- a generic problem of the set of SMB devices is to minimize the pollution generated by the liquid found in the different zones and volumes of the circuits for supplying and withdrawing fluids from the trays, during modifications of the feed points and racking during operation of the SMB. Indeed, when, during the operating sequence, a line, chamber, or feed zone of a plate Pi is no longer swept by a process fluid, it becomes a dead zone in which the liquid stagnates, and is only restarted when another process fluid is circulating again. Since, due to the operation of the SMB, it is a process fluid that is different, the liquid of the dead zone is necessarily displaced. by a liquid of significantly different composition. The mixing, or the short-time flow of fluids of significantly different compositions introduces a disturbance compared to the ideal operation, for which the discontinuities of composition are to be avoided.
- Another problem lies in the possible (but frequent) recirculation between different zones of the same plate, and more generally of the entire distribution / extraction system of the same plate, due to very small pressure differences between different areas of the plateau, which then also induces a disturbance compared to the ideal operation.
- a flow from a neighboring plateau is typically performed for most of the time or continuously so that the lines and zones of the delivery / extraction system are no longer "dead” but scanned.
- Such a system with scanning via branch lines is shown in Figure 1 of US Patent 5,972,224 and taken again in a simplified manner in Figure 1 of the present application.
- the term "singular” refers hereinafter to any non-selective empty volume portion that is non-uniformly distributed in the circuit. This term is defined more precisely below.
- a typical example is a pipe that connects one column to another, or a column bottom recycle line to the top of that column (when the adsorbent is loaded in a single column), with all equipment associated with that or those pipes (for example: pump, measuring or sampling means, sampling loop, etc.) - These types of empty volumes of adsorbent are non-selective because they do not perform selective adsorption.
- the patent FR 2 721 527 proposes a compensation of singular non-selective empty volumes by increasing the flow rate of the recycling pump between the moment when the extraction point of the extract (if the extract is the flow containing the product to be separated) is between the exit of bed n-1 and the exit of bed n (page 6).
- the flow rate is increased when the extract is taken at the ninth bed (the one which contains a higher non-selective empty volume than the others). This increase in flow rate increases the flow rate for all the beds during this time as shown in Example 1B (according to the invention) of this patent.
- US Pat. No. 6,896,812 also solves the problem of disturbances caused by non-selective empty volumes by a change in the flow rate of the zone in which these non-selective volumes are located.
- the solutions recommended in US Pat. Nos. 6,896,812 and 2,721,527 differ essentially in the fact that FR 2,721,527 increases the flow rate in the recycling pump and therefore throughout the adsorber, whereas US 6,896,812 increases the injection flow rate. (charge or desorbent) but at the same time decreases a withdrawal rate (extract or raffinate) by an equivalent amount so that the increase in flow rate is only experienced by a part (a zone) of the adsorber.
- Patent FR 2 721 528 proposes to increase the switch-time period each time an injection current (charge or desorbent) or withdrawal (extract or raffinate) passes the recycling pump and therefore the volume of the non-selective discrete section.
- This patent nevertheless imposes two conditions so that its implementation is possible: it is necessary that each circuit can be permuted independently.
- each of the streams introduced or withdrawn must be managed either by a n-position valve or by n all-or-nothing valves (page 8) (which excludes this compensation mode for the case of a simulated moving bed of which the feeding is ensured by means of one or more rotary valve (s)) it is necessary that each zone has at least two beds, since at certain particular moments, when the exit of a zone passes the anisotropy (eg the non-selective empty volume of the recycling pump) whose effects are to be corrected, this zone is shortened by one bed (page 9). This condition can be very limiting, especially in the case where the number of beds is reduced (4 to 12 for example).
- Patent FR 2,721,529 proposes to reduce the volume of the bed n by a volume equivalent to the volume of the non-selective discrete section so that, overall, this bed has a volume identical to that of the other beds. This makes it possible to eliminate, as indicated (p7 line 26), the great majority of disturbances, residual disturbances remaining. In this case, the bed contains less molecular sieve than the other beds. The correction therefore becomes not perfectly adapted, all the more so since the product under consideration is strongly adsorbed. This is particularly disadvantageous when the product that is to be separated is the most adsorbed product. Several advantageous variants make it possible to improve the operation of this type of unit by using asynchronous permutations.
- these asynchronous permutations serve to compensate for the dead volume (s) of the recirculating pump (s), as indicated in US Pat. No. 5,578,215, to work with a constant recycling rate on the recirculation pump so as to eliminate jolts of flow and pressure, as indicated in US Pat. No. 5,762,806, or finally to operate with at least two chromatographic zones, each of which is equivalent to a non-integer number of beds; adsorbent.
- This latter variant as disclosed in US 6,136,198, US 6,375,839, US 6,712,973, and US 6,413,419 is known as Varicol. These three variants can be combined.
- Asynchronous permutations introduce additional complexity. It should also be noted that a multi-turn rotary valve putting in communication on the one hand the incoming and outgoing fluids and on the other hand the beds arranged in the adsorption column or columns only allows a synchronous type permutation. For asynchronous permutations, a plurality of all-or-nothing valves is essential.
- Adsorbent being here equivalent to it.
- the adsorbent used depends in fact on the separation used. In the case of high industrial importance of the separation of paraxylene or metaxylene from a section of aromatics with 8 carbon atoms, a zeolitic adsorbent is used.
- adsorbents are used as adsorption agents in the liquid or gas phase processes, preferably of the simulated countercurrent type similar to those described in US Pat. No. 2,985,589, which apply inter alia to C8 aromatic cuts (a section comprising aromatic hydrocarbons). to 8 carbon atoms).
- the zeolitic adsorbents are in the form of powder or in the form of agglomerates consisting mainly of zeolite and up to 15 to 20% by weight of inert binder.
- agglomerates whether in the form of platelets, beads or extrudates, generally consist of a zeolite powder, which constitutes the active element (in the sense of the adsorption) and a binder intended to ensure the cohesion of the crystals in the form of grains and to give the grains a mechanical strength sufficient to withstand the vibrations and movements to which they are subjected during their implementation.
- agglomerates are carried out for example by mashing zeolite powder with a clay paste, in proportions of about 70 to 85% by weight of zeolite powder for 30 to 15% by weight of binder, then forming into balls, platelets or extrudates, and high temperature heat treatment for clay firing and reactivation of the zeolite, the barium exchange can be carried out before and / or after agglomeration of the zeolite powder with the binder.
- patent EP 0 154 855 indicates (page 5 line 32-33) that the zeolite X / binder ratio varies from 70/30 to 90/10 by weight.
- 3,960,774 indicates (column 6 lines 42-44) that X or Y zeolites may be present in the precursor in concentrations generally ranging from 75% to 98% by weight.
- EP 0,115,068 proposes (page 6 line 23) an adsorbent in the form of zeolite X exchanged with barium containing 20% of a clay binder.
- Zeolite bodies whose particle size is a few tenths of a millimeter or a few millimeters are obtained, and which, if the choice of the binder and the granulation are made in the rules of the art, have a set of satisfactory properties, in particular porosity, mechanical strength, abrasion resistance.
- the adsorption properties of these agglomerates are obviously reduced relative to the active starting powder by the presence of inert agglomeration binder.
- An important characteristic of a bed (or batch) of solid adsorbent is its adsorption capacity, ie the ratio of the volume of fluid that it is capable of adsorbing to that of the volume of the bed ( or batch) of adsorbent.
- Dubinin volume is generally chosen, and conventionally according to the invention, to measure this capacity.
- the volume of Dubinin is thus independent of the compound which it is desired to adsorb and separate, and depends only on the adsorbent: 11 is calculated according to the Dubinin-Radushkevich relation, as described by LOWELL et al. in the book “Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density", Chapter 9, “Micropore Analysis", pages 143- 145; KLUWER Academy Publishers, 2004, Dordrecht (NL). p
- logV logV 0 - D (log -) 2 connects the volume V of adsorbed nitrogen in the material
- the volume of Dubinin is the volume V 0 , the maximum volume of nitrogen vapor that can be condensed in the micropores of the adsorbent material. It is expressed in cm 3 of nitrogen vapor (reduced to normal conditions) per gram of adsorbent.
- the sample Prior to the measurement, the sample is pretreated at 500 ° C. for 12 hours under vacuum (P ⁇ 5.10 6 Torr, ie 6.7 ⁇ 10 -4 Pa). The measurement is then carried out on an ASAP 2010 M type apparatus from Micromeritics. The isothermal plot is made using a pressure table of at least 35 points between 0.01 and 1 P / Po. The value of log V as a function of (log (P / P 0 )) 2 is plotted on a diagram. The volume of Dubinin is obtained from the ordinate at the origin of the linear regression line of points whose (log (P / P 0 )) 2 is between 1 and 2 (ie 0.039 ⁇ P / P o ⁇ 0.1). The measurement uncertainty is ⁇ 0.003.
- the object of the invention is a simulated moving bed separation device having improved performances compared to the devices of the prior art, in particular by relating to the problems and performance falls associated with the existence of one or more particular non-selective empty volume areas increased due to the presence of singular non-selective volumes.
- the improvement in performance provided may be different depending on the intended purpose, by adapting the specificities and the adjustment parameters used in the separation process using the device in question.
- the improvement (s) may for example include: reducing desorbent demand, reducing the desorbent / feed ratio, increasing the purity or recovery efficiency of the desired product, or increasing the productivity of the process.
- the invention also relates to the use of the device for particular separations, in particular for the separation of a xylene (in particular paraxylene or metaxylene) from a C8 (to 8 carbon atoms) aromatic section. .
- a xylene in particular paraxylene or metaxylene
- the invention thus proposes a device for separating a charge F by simulated moving bed adsorption comprising a plurality of elementary zones Z 1 in series operating in a closed loop, each of these zones comprising, between two successive points of sequential injection (charge or eluent) or sequential extraction (of extract or raffinate), a single bed U of adsorbent solid of volume VAj and a volume of circulation in the loop which is empty of adsorbent, said non-selective empty volume Vj, in which at least 3 Zi zones each comprise a single adsorbent bed of substantially identical volume equal to VA, and an essentially identical non-selective empty volume equal to V 1, these zones being called ordinary elementary zones, the device also comprising, among the zones Z 1 , at least one elementary zone Z 0 , called the particular elementary zone, which is different from the ordinary zones, Z 0 comprising a non-selective empty volume V 0 greater than V and a single bed L
- the volume adsorption capacity C 0 of S 0 being greater than that, ie C, of the solid S, so that the overall adsorption capacity C 0 x VA 0 of the particular elemental zone Z 0 is closer to or equal to the overall adsorption capacity C x VA of each of the ordinary elementary zones that the global adsorption capacity of Z 0 calculated as if the solid adsorbent of the bed L 0 of Z 0 was not the average solid S 0 but the average solid S.
- the differences in the overall adsorption capacity of the particular elemental zone Z 0 are reduced by at least 30%, and very preferably by at least 70%, with respect to the overall adsorption capacity of each of the ordinary elementary areas.
- the overall adsorption capacities of all zones are equal, and: 0.
- V 0 + VA 0 very close to V + VA, for example deviating from V + VA of at most 3%, or the same, is used.
- solid means simply that the adsorbent solid is not necessarily homogeneous, even if it can be.
- the average adsorbent solid S 0 is thus a mixture of at least two adsorbent solids S 1 and S 2 of different adsorption capacity, respectively Ci and C 2 , with C 1 > C 2 , Si being the adsorbent solid. included in the device and having the highest capacity for adsorption by volume, the percentage of Si in each of the beds of the ordinary elementary zones being either zero or less than the percentage of Si in the bed L 0 of the particular elemental zone Z 0 .
- the volume adsorption capacity of the particular elemental zone Z 0 is therefore increased by using in this zone an adsorbent solid S 1 with a higher adsorption capacity by volume, present in a proportion greater than that used in each of the zones. ordinary.
- the ordinary elementary zone beds may optionally contain a medium adsorbent solid S whose percentage of adsorbent solid S 1 is equal to zero.
- the beds of the ordinary elementary zones may optionally consist of a single homogeneous adsorbent solid S of volume adsorption capacity C.
- the average adsorbent solid S 0 comprises at least one other adsorbent solid Si with a higher adsorption capacity.
- One way to implement the invention is to manufacture and install in the particular elementary zone or zones an adsorbent solid of microporous volume greater than that of the adsorbent used in ordinary elementary zones.
- zeolite adsorbent comprising zeolite crystals agglomerated with a binder
- the binder is typically inert as to adsorbent performance.
- various means have been proposed: It has been proposed the use of more cohesive binders which then reduce the amount of binder used or the transformation of the binder, for all or part, in zeolite or zeolitization. To easily perform this operation, uses zeolitisable binders belonging to the family of kaolinite, previously calcined at temperatures between 500 0 C and 700 0 C.
- FR 2 767 524 A1 provides an adsorbent whose binder content (page 3 lines 25-27) does not exceed 20% by weight before transformation of at least a portion of the binder into zeolite, and (page 4 line 4) with a content of not more than 10% of inactive material after this transformation.
- the application WO 99/10096 indicates (page 3 lines 11-12) that the practical binder content of the agglomerate does not generally exceed 30% and preferably 20% of the total mass of the adsorbent.
- the same document indicates (page 3 lines 23-26) that after transformation of the binder into zeolite, the resulting adsorbent generally consists of at least 85% and preferably at least 90% of active faujasite type zeolite. and at most 15%, preferably at most 10%, of inactive material for adsorption.
- US 3,119,660 indicates (column 14 lines 62-64) that composites made by mixing zeolite powder 4A with a clay binder have a capacity factor of about 0.56.
- Table IV of the same document indicates that these same agglomerates, after transformation of at least a part of the binder into zeolite, have adsorption factors of between 0.70 and 0.74 according to the operating procedure chosen for the binder transformation step.
- both types of adsorbent from the same adsorbent made from a typically large number of batches of the same manufacture (for example, successive fabrications or in parallel according to the same process): This can be done by measuring the adsorption capacity of each batch, and selecting the higher capacity batches for the particular elemental area.
- the invention also proposes a method of loading in a simulated moving bed adsorption separation device, this device comprising n elementary zones Z n being between 3 and 30, of an adsorbent available in the form of N batches of manufacture of this adsorbent according to the same manufacturing method, N being between 60 and 3000, in which:
- a) the adsorption volume capacity of each of the production batches is individually measured; b) a first adsorbent S, which is loaded in the elementary zones, is selected from the individual adsorption capacity measurements thus obtained; and a second adsorbent S 0 of adsorption capacity greater than that of S, which is loaded in the particular zone Zo, so that the device is a device as described above.
- a selection can be made within a molecular sieve production intended for an SMB separation unit comprising 24 elementary zones Z 1 , including 23 ordinary zones and a particular zone Z 0 . If, for example, 1000 t of molecular sieve is to be loaded, this product may be packaged in batches of 1t, for example unit manufacturing batches of 1t. For each batch, it is possible to measure the volume of Dubinin (or the adsorbed volume of a compound other than nitrogen, in a strictly proportional manner, for example the hydrocarbon that one wants to separate). For an average volume of Dubinin, or its equivalent expressed in volume, of 19% for example, 100% of the batches will typically be between 18% and 20%.
- the rest of the manufacture will have an average capacity of 18.95% of volume for l 'adsorption.
- an adsorbent having an adsorption capacity on average 5% greater than that of the remainder of the adsorbent loaded into the ordinary elementary zones will be loaded.
- the invention also relates to the use of the device for the realization of particular separations.
- It relates in particular to the use of the device for the separation of a xylene, for example paraxylene or metaxylene from a section of aromatic hydrocarbons containing 8 carbon atoms.
- It also relates to the use of the device for the separation of an olefinic hydrocarbon from a section comprising this hydrocarbon mixed with other non-olefinic hydrocarbons.
- It also relates to the use of the device for the separation of at least one linear paraffin from a section comprising this or these linear paraffins mixed with other hydrocarbons which are not linear paraffins.
- Figure 1 shows schematically a portion of a simulated moving bed separation device according to the invention.
- non-empty volumes for example the volumes of the metal parts of the distributor / extractor trays or support beams of these trays are not counted as non-selective empty volumes.
- the volumes between the adsorbent grains and those internal to the adsorbent grains are not counted either.
- volumes not accessible to fluids circulating in a loop in the column or in external bypass lines are finally not counted either. This is the case, for example, of the volumes of the supply / extraction tips of the incoming (fed) and outgoing (withdrawn) fluids, which are not swept by the main fluid circulating in the column or by the main fluid circulating in the lines. external bypass, but only by one or more incoming or outgoing fluids.
- a number of volumes outside the column are also counted in the "non-selective empty volume":
- the volumes not swept by the main fluid during the operation of the branch lines are not counted in the non-selective empty volume corresponding to an elementary zone. 1, up to the upstream multi-channel valve not shown or up to various upstream two-way valves not shown managing the sequential operation of the device).
- a tip not swept by the main fluid, but only by one or more incoming or outgoing fluids, enters the column its volume is also not counted for the part upstream of its point of entry into the "mixing box" with the main fluid circulating in a loop in the column (this mixing box is not shown in the figure).
- These different singular volumes typically comprise the internal volumes of these lines but also the internal volume or volumes of pump (s) or compressor (s) for the closed loop circulation of fluid in the device. They can also include internal volumes of measuring devices such as analyzers etc.
- Each bed L 1 of solid adsorbent conventionally belongs according to the invention to an elementary zone Z 1, which also comprises a non-selective void volume V 1, typically composed of several distinct different non-selective empty volumes.
- each non-selective empty volume corresponding to a plateau located between two successive adsorbent beds is half of the area Zj comprising the adsorbent bed Li immediately upstream, and the other half to the zone Zj + i comprising the adsorbent bed Lj + 1 immediately downstream.
- the device of FIG. 1 has a common distribution / extraction network, as indicated by the two-way arrows of lines 1/1 ', 3/3', 4,4 ', 6,6'.
- Zone Z ⁇ comprises, in addition to adsorbent bed Li, half of the non-selective empty volume of the upstream distribution system (at the top of the column) and half of the non-selective empty volume of the downstream distribution system (between the Li beds and L 2 ). It also includes the internal volume of the external branch line 2, if it exists, that is to say in this case that lines 1 ', 2 and 3', also counted as non-selective empty volume while the volume tips 1 and 3 are not.
- the zone Z 23 below the bed L 22 , comprises elements similar to those of zone Z-.
- zones Z 1 and Z 23 are ordinary elementary zones, each having a substantially identical adsorbent bed volume and a substantially identical non-selective empty volume.
- the zone Z 24 is particular: It comprises additional singular non-selective empty volumes corresponding to the recycling line 7 and then 9, as well as to the recycling pump 8. These additional non-selective empty volumes are not negligible. to the non-selective empty volume of each of the ordinary elementary areas. Therefore, to correct the adverse effect of these additional non-selective void volumes, using a volume of solid weaker adsorbent for the adsorbent bed 24 of the L Z 24 area.
- an average adsorbent So is different from the average adsorbent S used in the other zones (ordinary elementary zones).
- This adsorbent S 0 has a volume capacity of adsorption Co greater than the adsorption capacity C of the adsorbent solid S used in ordinary elementary zones, so that it compensates for the reduction in volume of the adsorbent bed L 24 , whose overall adsorption capacity can be maintained.
- It can in particular be constituted by a homogeneous adsorbent Si with a higher adsorption capacity, or by mixing a first quantity of such an adsorbent Si with another suitable quantity of the adsorbent S.
- Paraxylene is separated from a feedstock composed of 20% paraxylene, 25% orthoxylene, 50% metaxylene and 5% ethyl benzene.
- the simulated moving bed separation SMB installation comprises 24 beds of adsorbent solid installed in a column of internal diameter 7m.
- the beds No. 1 to 23, numbered starting from the column head, have an identical height equal to 1.13 m.
- a recycling line of non-selective empty volume equal to 10% of the common volume of the beds No. 1 to 23, and including the recycling pump, connects the bed No. 24 at the bottom of the column to the bed n c 1 located at the head of column.
- This recycling line is located in the elementary zone between, on the one hand, the point of injection / extraction situated between the beds n ° 23 and n D 24, and on the other hand the point of injection / extraction located at the top column, upstream of bed n ° 1.
- This recycling line therefore belongs to the particular elementary zone corresponding to the adsorbent bed No. 24.
- the volume of the 24 th bed of an equivalent volume is reduced.
- This 24 th bed is height 1, 02 m instead of 1, 13 m.
- the adsorbent solid S used is a single homogeneous adsorbent, identical for all beds, namely a BaX-type zeolite, manufactured as described in Example 1 of Patent FR2789914 (page 7-8) or in Example 1 of the patent. US6884918 (column 6). Its microporous volume measured according to the Dubinin-Radushkevich method is 0.22 cm 3 / g.
- the eluent used is paradiethyl benzene (PDEB).
- PDEB paradiethyl benzene
- the average temperature is 175 ° C, and the pressure is 1.5 MPa.
- the distribution of the beds is as follows:
- Example 2 The same separation is carried out as in Example 1, under identical conditions (pressure, temperature, permutation time), in a column of the same diameter also comprising 24 beds, with the same distribution of beds per zone, using the same eluent PDEB.
- the recycling line is identical to that of Example 1.
- the adsorbent solid S used in beds No. 1 to 23 is identical to that used in Example 1 above, and these beds also have a height of 1.13m.
- the only difference with respect to Example 1 relates to bed No. 24 at the bottom of the column: Its height is also reduced by about 10% to 1.02 m instead of 1.13 m, but according to In the present invention, an adsorbent solid S 0 is used in this bed No. 24 different from the adsorbent solid S used in the other beds:
- the adsorbent solid S 0 is manufactured as described in Example 2 of the patent FR2789914 (page 8-9) or in Example 2 of US6884918 (columns 6-7).
- a microporous volume of 0.244 cm 3 / g is thus obtained.
- the volume adsorption capacity of the solid adsorbent S 0 of the 24 th bed is therefore greater than that of the adsorbent solid S in the remainder of the device by approximately 10%, which compensates for the reduction in the volume of adsorbent in the particular elemental zone.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CN200880121935.8A CN101903073B (zh) | 2007-12-21 | 2008-12-01 | 用于模拟移动床分离的改进的装置 |
BRPI0821033A BRPI0821033B1 (pt) | 2007-12-21 | 2008-12-01 | dispositivo aperfeiçoado de separação em camada móvel simulada |
US12/809,858 US8821732B2 (en) | 2007-12-21 | 2008-12-01 | Device for simulated moving bed separation |
JP2010538825A JP5808914B2 (ja) | 2007-12-21 | 2008-12-01 | 擬似移動床分離のための改良された機器 |
Applications Claiming Priority (2)
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FR0709127A FR2925350B1 (fr) | 2007-12-21 | 2007-12-21 | Dispositif perfectionne de separation en lit mobile simule. |
FR07/09127 | 2007-12-21 |
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WO2009101282A1 true WO2009101282A1 (fr) | 2009-08-20 |
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PCT/FR2008/001677 WO2009101282A1 (fr) | 2007-12-21 | 2008-12-01 | Dispositif perfectionne de separation en lit mobile simule |
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US (1) | US8821732B2 (fr) |
JP (1) | JP5808914B2 (fr) |
KR (1) | KR101555393B1 (fr) |
CN (1) | CN101903073B (fr) |
BR (1) | BRPI0821033B1 (fr) |
FR (1) | FR2925350B1 (fr) |
SA (1) | SA108290815B1 (fr) |
TW (1) | TWI348932B (fr) |
WO (1) | WO2009101282A1 (fr) |
Cited By (2)
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---|---|---|---|---|
JP2008013670A (ja) * | 2006-07-06 | 2008-01-24 | Kao Corp | 重合性リン酸エステル組成物 |
US20210236982A1 (en) * | 2020-02-04 | 2021-08-05 | Tda Research, Inc. | Air separation sorbent and vacuum assisted pressure swing adsorption process using the same |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2925350B1 (fr) | 2007-12-21 | 2009-12-11 | Inst Francais Du Petrole | Dispositif perfectionne de separation en lit mobile simule. |
US8329975B2 (en) * | 2010-12-20 | 2012-12-11 | Uop Llc | Elimination of residual transfer line raffinate from feed to increase normal paraffin separation unit capacity |
CN102895800B (zh) | 2011-07-28 | 2016-05-25 | 中国石油化工股份有限公司 | 模拟移动床吸附分离方法和设备 |
CN106390518B (zh) * | 2015-07-28 | 2019-11-15 | 中国石油化工股份有限公司 | 一种用液相模拟移动床同时吸附分离多股原料的方法 |
EP3397593A4 (fr) * | 2015-12-29 | 2019-08-28 | Uop Llc | Adsorbants zéolitiques sans liant et procédés de production d'adsorbants zéolitiques sans liant |
TWI610712B (zh) * | 2016-05-19 | 2018-01-11 | 喬璞科技有限公司 | 串聯模擬移動床系統 |
FR3072885B1 (fr) * | 2017-10-27 | 2019-11-15 | IFP Energies Nouvelles | Nouveau systeme de distribution par panneaux meridiens pour un procede de separation en lit mobile simule utilisant n-colonnes en serie |
CN108310902A (zh) * | 2018-04-02 | 2018-07-24 | 苏州阿洛斯环境发生器有限公司 | VOCs处理设备 |
FR3082755B1 (fr) * | 2018-06-20 | 2022-12-30 | Ifp Energies Now | Procede et dispositif de separation en lit mobile simule a nombre de lits reduit avec debit de fluide de derivation |
CN113087587A (zh) * | 2019-12-23 | 2021-07-09 | 内蒙古伊泰煤基新材料研究院有限公司 | 一种利用模拟移动床分离烷烃和烯烃的方法 |
CN112843788B (zh) * | 2021-01-19 | 2022-10-28 | 温州大学新材料与产业技术研究院 | 一种采用流动相独立环外置换的温度梯度模拟移动床装置及其分离方法 |
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FR2721529A1 (fr) * | 1994-06-22 | 1995-12-29 | Inst Francais Du Petrole | Procédé de séparation par chromatographie en lit mobile simulé avec correction de volume mort par diminution de longueur. |
FR2785196A1 (fr) * | 1998-10-29 | 2000-05-05 | Inst Francais Du Petrole | Procede et dispositif de separation avec des zones chromatographiques a longueur variable |
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US6896812B1 (en) * | 2003-07-17 | 2005-05-24 | Uop Llc | Process to compensate for a discrete non-separating section in simulated moving bed adsorptive separation processes |
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CN2112437U (zh) * | 1992-03-17 | 1992-08-12 | 林兴盛 | 模拟移动床色谱分离装置 |
US6106702A (en) * | 1998-12-29 | 2000-08-22 | Uop Llc | Olefinic hydrocarbon separation process |
FI20020936A (fi) * | 2002-05-17 | 2003-11-18 | Finnfeeds Finland Oy | Kromatografinen erottelu |
JP5016266B2 (ja) | 2006-06-30 | 2012-09-05 | 三井化学株式会社 | 光学プラスチックレンズ用プライマー |
FR2925350B1 (fr) | 2007-12-21 | 2009-12-11 | Inst Francais Du Petrole | Dispositif perfectionne de separation en lit mobile simule. |
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2007
- 2007-12-21 FR FR0709127A patent/FR2925350B1/fr not_active Expired - Fee Related
-
2008
- 2008-12-01 CN CN200880121935.8A patent/CN101903073B/zh not_active Expired - Fee Related
- 2008-12-01 WO PCT/FR2008/001677 patent/WO2009101282A1/fr active Application Filing
- 2008-12-01 KR KR1020107015898A patent/KR101555393B1/ko active IP Right Grant
- 2008-12-01 BR BRPI0821033A patent/BRPI0821033B1/pt not_active IP Right Cessation
- 2008-12-01 US US12/809,858 patent/US8821732B2/en not_active Expired - Fee Related
- 2008-12-01 JP JP2010538825A patent/JP5808914B2/ja not_active Expired - Fee Related
- 2008-12-18 TW TW097149470A patent/TWI348932B/zh not_active IP Right Cessation
- 2008-12-20 SA SA108290815A patent/SA108290815B1/ar unknown
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FR1330356A (fr) * | 1962-05-22 | 1963-06-21 | Universal Oil Prod Co | Procédé pour séparer les dérivés aromatiques polycycliques des dérivés aromatiques monocycliques dans les hydrocarbures |
FR2721529A1 (fr) * | 1994-06-22 | 1995-12-29 | Inst Francais Du Petrole | Procédé de séparation par chromatographie en lit mobile simulé avec correction de volume mort par diminution de longueur. |
FR2785196A1 (fr) * | 1998-10-29 | 2000-05-05 | Inst Francais Du Petrole | Procede et dispositif de separation avec des zones chromatographiques a longueur variable |
EP1205224A1 (fr) * | 2000-11-09 | 2002-05-15 | Nippon Rensui Co. | Procédé de séparation chromatographique |
US6896812B1 (en) * | 2003-07-17 | 2005-05-24 | Uop Llc | Process to compensate for a discrete non-separating section in simulated moving bed adsorptive separation processes |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008013670A (ja) * | 2006-07-06 | 2008-01-24 | Kao Corp | 重合性リン酸エステル組成物 |
US20210236982A1 (en) * | 2020-02-04 | 2021-08-05 | Tda Research, Inc. | Air separation sorbent and vacuum assisted pressure swing adsorption process using the same |
US11786859B2 (en) * | 2020-02-04 | 2023-10-17 | Tda Research, Inc. | Air separation sorbent and vacuum assisted pressure swing adsorption process using the same |
Also Published As
Publication number | Publication date |
---|---|
FR2925350A1 (fr) | 2009-06-26 |
TWI348932B (en) | 2011-09-21 |
TW200936224A (en) | 2009-09-01 |
CN101903073A (zh) | 2010-12-01 |
BRPI0821033B1 (pt) | 2018-07-17 |
FR2925350B1 (fr) | 2009-12-11 |
US20110166406A1 (en) | 2011-07-07 |
US8821732B2 (en) | 2014-09-02 |
KR101555393B1 (ko) | 2015-09-23 |
JP2011506091A (ja) | 2011-03-03 |
CN101903073B (zh) | 2013-02-06 |
BRPI0821033A2 (pt) | 2015-06-16 |
JP5808914B2 (ja) | 2015-11-10 |
SA108290815B1 (ar) | 2012-05-16 |
KR20100106494A (ko) | 2010-10-01 |
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