CN1047489A - Fluoridize the aromatics strippant to the application in the adsorption method of separation of alkylaromatic hydrocarbon - Google Patents
Fluoridize the aromatics strippant to the application in the adsorption method of separation of alkylaromatic hydrocarbon Download PDFInfo
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Abstract
The method of from a kind of para-isomeride that contains dialkyl group aromatic hydrocarbons and the other mixture of isomers that is at least a kind of this hydrocarbon, separating the para-isomeride of dialkyl group aromatic hydrocarbons, it comprises this mixture is contacted with a kind of crystalline aluminosilicate sorbent material that crystalline aluminosilicate sorbent material contains BaO/K on its tradable cation position
2The mol ratio of O is 0.6: 1 to 1.2: 1 barium yoxko and a potassium cationic, under selected adsorption conditions, realize absorption to said para-isomeride, the sorbent material that contains para-isomeride is contacted, to realize reclaiming said para-isomeride with desorb material in being selected from a fluorine aromatic substance, difluoro aromatic substance or their mixture.
Description
Technical field under the present invention is the fractionation by adsorption of hydrocarbon.More particularly, the present invention relates to a kind of method of from the incoming mixture that contains its another isomer at least, separating the aromatics para-isomeride of dialkyl group replacement.Particularly by from the raw mix of two kinds of isomer containing the said aromatic isomers that comprises para-isomeride at least, isolating p-Xylol, and this law is added a concrete explanation.This law is used a kind of specific zeolite adsorbents and as certain fluoro aromatic hydrocarbon of strippant.
As everyone knows, in isolation technique, some crystalline aluminosilicate can be used to certain type hydrocarbon is separated from the hydrocarbon of another kind of type.For example, can utilize A type zeolite to finish and isolate n-paraffin from branched paraffin, the aperture of zeolite is 3～5
About.Such separation method is disclosed in No. 3201491, the United States Patent (USP) of No. 2985589, people's such as Broughton United States Patent (USP) and Stine.It is by allowing less or normal hydrocarbons enter into the space of zeolite adsorbents, being achieved and the what that molecule will be bigger or side chain is refused is outer that these sorbent materials make the different separation of basic what molecule physical dimension.
Except being separated the method for all kinds hydrocarbon with what, the sorbent material that comprises X type or y-type zeolite is also separated with what in all methods of each isomer of hydrocarbon out of the ordinary.In said these methods, for example No. 3626020, the United States Patent (USP) of Neuzil, No. 3663638, No. 3665046, the United States Patent (USP) of de Rosset, No. 3668266, people's such as Chen United States Patent (USP), No. 3686342, people's such as Neuzil United States Patent (USP), No. 3700744, people's such as Berger United States Patent (USP), No. 3734974, the United States Patent (USP) of Neuzil, No. 3894109, the United States Patent (USP) of Rosback, in United States Patent (USP) B426274 number of No. 3997620, the United States Patent (USP) of Neuzil and Hedge, special zeolite adsorbents is used to the para-isomeride of the monocyclic aromatics that the separation dialkyl group replaces from its other isomer, particularly isolates p-Xylol from other xylene isomer.People's such as Stine United States Patent (USP) is pointed out for No. 3707550, (as one of numerous possibility purposes), and the X type zeolite of a kind of silver or silver/potassium exchange can be used what C
8The separation of each isomer of aromatics, and only then it seems and must remove o-Xylol in " segregation section " by traditional distillation.
Have in above-mentioned each patent and much be to use benzene, toluene or p-Diethylbenzene as strippant.Previous people just recognized, when benzene contacts as the lower boiling strippant and with sorbent material, had many shortcomings (referring to No. 3686342, the United States Patent (USP) of Neuzil).In the method for separating dimethyl benzene isomer, when reclaiming strippant by extract and raffinate, toluene will be suffered a loss, and this is because the boiling point of toluene is died near very much with the boiling point of separated isomer.Thereby, wish to have more lower boiling material, it can satisfy the selectivity requirement of discussing at this as strippant.Other above-mentioned patents all relate to uses zeolite separating paraxylene from each isomer of dimethylbenzene, and zeolite exchanged with the Ba and the K of certain weight ratio.For example see United States Patent (USP) No. 3663638, No. 3878127, No. 3878129, No. 3686342 and No. 3558732.No. 5155/62, day patent application of the present disclosure, disclose the March 3 nineteen sixty applying date by by with metal for example the adsorption of the X type zeolite of exchanges such as barium, calcium, sodium come the isolation of aromatic isomer.Replacement fluids can be benzene, toluene, chlorobenzene, 1-fluoroalkane, α, ω-saturated dihalide, halogeno-benzene, benzyl halide, this depends on the what incoming mixture, for example benzene is used to dimethylbenzene and/or ethylbenzene, toluene is used to trimethylbenzene or ethyltoluene, and chlorobenzene is used to the halogenated aromatic isomer mixture.
The United States Patent (USP) of Barthomeuf discloses a kind of method of separating ethylbenzene by the selection absorption of β-zeolite from dimethylbenzene for No. 4584424.Though p-Diethylbenzene is preferred strippant in this kind sepn process, phenyl-monohalide, particularly iodobenzene are also referred.
In one embodiment, the present invention can be a kind of method of separating the para-isomeride of the aromatic hydrocarbon that dialkyl group replaces from incoming mixture by summary, and this mixture contains the aromatics para-isomeride that said dialkyl group replaces and be at least a kind of other isomer of it.In preferred embodiments, p-Xylol is from containing p-Xylol and being at least the incoming mixture of a kind of other xylene isomer or ethylbenzene isolating.This method is included in charging is contacted with the sorbent material that contains crystalline aluminosilicate such as X type or y-type zeolite.Zeolite contains Ba positively charged ion and K positively charged ion on the tradable cation position of the crystal structure of sorbent material, their mol ratio is with corresponding BaO and K
2The mol ratio of O represents to be about 0.6: 1 to being about 1.2: 1, and preferably 0.9: 1.1.Then charging is removed from the sorbent material that contains para-isomeride.Under desorption condition, utilize and contain a fluorine or the aromatic hydrocarbons of difluoro replacement or the desorb material of their mixture, reclaim the dense effluent of para-isomeride by desorption.
Some other embodiment of the present invention includes some details of closing incoming mixture, schema and operational condition, will disclose all these details in the following discussion.
Figure 1A is with Ba and the y-type zeolite sorbent material of K exchange and the color atlas of phenyl-difluoride strippant separating paraxylene from the mixture of each isomer of dimethylbenzene and ethylbenzene.Figure 1B, 1C and 1D and 1A are similar, and just each ionic concn in condition and the sorbent material is different.For the purpose of simplifying the result and knowing, in Figure 1A, 1B, 1C, 1D and Fig. 5 A, 5B and 6A, the tracer of an ortho position and a position dimethylbenzene is omitted.In addition, these results and Fig. 2 and 3 results that presented are similar.BaO and K in Figure 1A～1D
2The mol ratio of O is respectively 0.63,0.71,0.98 and 5.17.
Remove BaO and K
2The mol ratio of O is outside 1.2, and Fig. 2 is similar to Figure 1A.Also have, Fig. 2 demonstrates all isomer.
Remove BaO and K
2The mol ratio of O be 1.2 and strippant be outside the fluorobenzene, Fig. 3 is similar to Figure 1A.
Remove BaO and K
2The mol ratio of O be 1.05 and strippant for outside 30% the phenyl-difluoride liquid in normal heptane, Fig. 4 is similar to Figure 1A.
Fig. 5 A and 5B remove BaO and K
2The mol ratio of O is outside 1.13, and is similar with 1D to Fig. 1 C respectively.
Fig. 6 A and 6B remove BaO and K
2The mol ratio of O is outside 0.99, and is similar with 1D to Fig. 1 C respectively.
Employed each term is explained that will help what is well understood to operation of the present invention, purpose and advantage at the very start to entire description.
" incoming mixture " is meant and a kind ofly is added to containing one or more and extract components and one or more carry the mixture of surplus component in present method sorbent material.Term " incoming flow " is meant the incoming mixture stream that passes in the method in sorbent used.
" extraction component " is meant a single compound or a compounds such as aromatic isomers, and its (or they) is easier to be adsorbed agent and to select absorption, and " carrying surplus component " is meant a compound or a compounds, and it is more difficult to be adsorbed the selected absorption of agent.In the method, the para-isomeride of dimethylbenzene is single extraction component, and other C of one or more kinds
8Aromatic hydrocarbons is then for carrying surplus component.Term " is carried residual current " or " carrying surplus discharging current " means a logistics, carries surplus component by it and is removed from sorbent material.The composition of carrying residual current can change to being essentially 100% the raffinate from being essentially 100% desorb material (seeing to give a definition).Term, " extracting stream " or " extraction discharging current " mean a logistics.To be removed from sorbent material by the extracting substance of desorb material desorb by it.The composition that extracts stream can change to being essentially 100% the extraction component from being essentially 100% desorb material equally.Though utilize method of the present invention can obtain highly purified extraction product (opinion) or raffinate product (definition sees below) with the high rate of recovery to give a definition, but people know, extract component and be adsorbed agent absorption till the ass ascends the ladder fully, it is adsorbed that the raffinate component is not adsorbed agent till the ass ascends the ladder fully yet.Therefore, in extracting stream, may exist and a spot ofly carry surplus component, and in raffinate stream, also may have a spot of extraction component.Then according in each other logistics, extracting component and the specific concentration ratio of carrying surplus component, further will extract stream and raffinate and distinguished with incoming mixture.For example, the para-isomeride of easier selected absorption and the concentration ratio that is difficult for ortho position, meta-isomer or the ethylbenzene of selected absorption will be for the highest in extracting stream, and the residence is inferior in incoming mixture, and is minimum in raffinate stream.In other words, the concentration ratio of para-isomeride that is difficult for ortho position, meta-isomer or the ethylbenzene of selected absorption and easier selected absorption is the highest in raffinate stream, in incoming mixture according to time, and in extracting stream, be minimum.Term " desorb material " generally means and can make the material that extracts the component desorb.Term " desorbent stream " or " strippant inlet flow " are meant a kind of logistics that the desorb material is passed to sorbent material by it.When extracting stream and raffinate stream and contain the desorb material, deliver to tripping device (general fractionator) with being at least the extraction stream of part and preferably being at least the raffinate stream that comes self-absorbent partly, under isolating condition, the desorb separating substances of part can be obtained extracting product and raffinate product at least.Term " extraction product " and " raffinate product " mean the product that its respectively high what of concentration that extracts component and raffinate component of being produced by present method extracts stream and raffinate stream.The definition of " the selectivity pore volume " of term sorbent material be can be from incoming mixture selective adsorption extract the volume of the sorbent material of component." the non-selective void volume " of term sorbent material be meant can not be from incoming mixture selective retention extract the volume of the sorbent material of component.This volume comprises sorbent material cavity and the idle space between the absorbent particles gap that does not contain any adsorption site.Selectivity pore volume and non-selective void volume volume numerical table Shi ， And commonly used is under the sorbent material condition of specified rate, and decision is passed into that the reasonable flow rate of required fluidic aspect has great importance to realize valid function in the process.
The incoming mixture that can be used for the inventive method comprises a kind of C
8, C
9, C
10, C
11Or C
12The dialkyl group substituted arene para-isomeride and be at least a kind of other isomer of they, therefore being included in this scope is the dialkyl benzene of para-orientation, for example ethyltoluene (C
9), diethylbenzene (C
10), isopropyl toluene (C
10), ethyl isopropyl benzene (C
11) and diisopropyl benzene (C
12).
Though the dialkyl benzene of many above-mentioned para-orientation can obtain in a large number according to alkylation process, for example produce the various mixtures of isopropyl toluene isomer by the alkylated reaction of toluene, but also have many other sources, and the dialkyl benzene of the para-orientation in all these sources all can be used as the raw material of the inventive method.Mainly contain p-Xylol and other C
8The mixture of aromatic isomers is generally by reforming and the production of isomerized method.These methods are known to refining and petroleum chemistry technology.Also having some to need the currently known methods of isolating each isomery component with the what manufacturing in addition is alkylating and dehydrocyclization dimerisation.
In each reforming process, mineral oil feed contacts with the catalyzer of platiniferous-halogen of selecting in the working depth process, produces to contain C
8The effluent of aromatic isomers.In general, subsequently will be with the reformate fractionation, to concentrate C
8C in the cut
8Aromatic isomers.This cut will comprise C
8Aromatic isomers and C
8Non-aromatic compound.
Xylene isomerization method isomerization of xylenes mixture, this mixture lacks one or more isomer under isomerisation conditions, so that can not produce each C that contains near equal amount
8Aromatic isomers and each C
8The effluent of non-aromatic compound.Table 1 is listed in the equilibrium composition at various temperatures of xylene isomer and ethylbenzene:
Table 1
Each C during balance
8The aromatics component
Temperature, ℃ 327 427 527
Each C
8Aromatic isomers
Molecular fraction
Ethylbenzene 68 11
P-Xylol 22 22 21
M-xylene 50 48 45
O-Xylol 22 22 23
- - -
100 100 100
Incoming mixture can contain a spot of straight-chain paraffin or branched paraffin, naphthenic hydrocarbon, or olefinic substances.Select the material of absorption to pollute for the product that prevents this law gained can not be adsorbed agent by these, it is minimum that their amount preferably should be.The amount of preferred above-mentioned impurity should little what be fed to 20% of incoming mixture volume in present method.
For from containing p-Xylol and being at least other a kind of C
8Separating paraxylene in the incoming mixture of aromatic substance makes mixture contact with sorbent material, and p-Xylol is adsorbed agent to be adsorbed more selectively and keep; And relatively not being adsorbed ， And, do not remove other each components from the idle space between absorbent particles and the adsorbent surface.The sorbent material that contains the p-Xylol of more selection absorption is called " richness " sorbent material, contains the p-Xylol of more selected absorption.Rich sorbent material and desorb material are contacted, and from rich sorbent material, reclaim p-Xylol.
In order to separate the para-isomeride in above-mentioned other raw materials, can use the same step described in the epimere mainly to be contained the extraction cut of para-isomeride.Can use the desorption procedure described in the hypomere, obtain similar results in much at one mode.
The desorb material can be a kind of flowing material that can remove selected adsorbed feed component from sorbent material.Normally in the shaking table device, from sorbent material, selected adsorbed feed component is removed by purge flow.The selection of desorb material be not have very conclusive, the desorb material that contains the gas of hydrocarbon gas such as methane, ethane etc. or other kinds such as nitrogen or hydrogen can use under high temperature or low pressure or high temperature, low pressure, from sorbent material the feed components that is adsorbed is removed effectively.Yet, in the adsorption method of separation that uses zeolite adsorbents, normally under constant basically pressure and temperature, carry out operate continuously in order to guarantee liquid-phase condition, must suitably select reliable desorb material to satisfy strict index.At first, the desorb material must from sorbent material, replace have a quite big mass velocity respectively extract component, and itself is not adsorbed by brute force and cause to stop inadequately and extract displacement desorption material in the component sorption cycle below.With the words (will be discussed in more detail hereinafter) that term " selectivity " is expressed, preferably sorbent material has bigger selectivity than it to the desorb material to extracting component for carrying surplus component.Secondly, the desorb material must be compatible with specific sorbent material and incoming mixture.More particularly, the desorb material can not reduce or damage the selectivity to the strictness of extracting component of sorbent material with respect to raffinate.In addition, in the inventive method used desorb material must be with present method in the segregative material of incoming mixture that feeds.After the extraction component of charging is by desorb, generally with form of mixtures with the desorb material with extract component and from sorbent material, remove.Equally, a kind of or several carry surplus component usually with desorb material blended form and from sorbent material, discharging mutually, there is not a kind of method to separate to be at least desorb material partly, for example with regard to distillation, the purity of gained extraction product or to put forward surplus degree of purity of production all not really high.Therefore, must think over any desorb material that is used for this law and should have the mean boiling point that is different in essence in incoming mixture in advance, making and be situated between inhaling material and can separate by simple fractionation, in this law, reusing the suction material that is situated between therefrom with each material component in extracting solution stream and the raffinate stream.The difference that term used herein " is different in essence " between the mean boiling point of the mean boiling point that means the desorb material and incoming mixture is at least 5 ℃, is preferably 40 ℃.The boiling range of desorb material can high what or the boiling range of low what incoming mixture, but considers that from the operation economic interests preferably the boiling range than incoming mixture is low.
Have now found that when sorbent material was the X type of barium and potassium cationic exchange or y-type zeolite, the amount of barium and potassium cationic was by corresponding BaO and K herein
2The ratio of O is counted 0.6: 1 to 1.2: 1, and effectively the desorb material comprises that a fluorine replaces or the aromatic hydrocarbon of difluoro replacement such as the phenyl-difluoride of phenyl-monofluoride or an ortho position or a position, or their mixture.An ortho position of the present invention or a position phenyl-difluoride are known compound ， And and can be according to document such as Kirk-Othmer, 1980 the tenth volumes, the 904th～14 page of preparation.The preparation of fluorobenzene also is known, as described in the 781st～3 page of Kirk-Othmer the 9th volume (1966).
Even it is not absolute necessity that prior art has realized that, for the successful operation of selecting adsorption method of separation, wish that still sorbent material has some characteristic.These characteristics have: the adsorptive power of extracting component in some parts of volumes of every volume of adsorbent absorption; The selection to extracting component for carrying surplus component and desorb material is adsorbed; The adsorption rate and enough fast desorption rate by sorbent material desorb extraction component of enough fast sorbent material to extracting component.
Certainly, one or more the ability of extraction component of absorption designated volume is absolutely necessary concerning sorbent material, and not having the sorbent material of such ability is otiose to the what fractionation by adsorption.And sorbent material is high more to the adsorptive power of extracting component, and sorbent material is just good more.The increase of the adsorptive power of a certain particular adsorbent makes might reduce in the incoming mixture of separation with specific feeding rate adding and extracts the required quantity of sorbent of component.Concerning a certain specific fractionation by adsorption, the minimizing of required quantity of sorbent can reduce the expense of sepn process.In the usage period of economic consideration, importantly during the sepn process that reality is used, keep the good initial adsorption ability of sorbent material whole.
The sorbent characteristics of second necessity is the ability of each component in the sorbent material separating feed; Perhaps, in other words be that sorbent material has the adsorption selectivity of comparing with another kind of component (B) to a kind of component.Relative selectivity not only can be used to express the comparison of a kind of feed components and another kind of feed components, but also can be used to express the comparison of any feed components and desorb material.When by in the specification sheets of what entire chapter the time, selectivity (B) is defined under the equilibrium conditions ratio of in the absorption mutually ratio of two kinds of components and the ratio of two kinds of components same in non-absorption mutually.
Relative selectivity is represented with following equation 1:
Equation 1
Selectivity, (B)=((volume percent C/ volume percent D) A)/((volume percent C/ volume percent D) U)
Wherein C and D are two components of the charging represented with volume percent, footnote A and U represent respectively absorption mutually with non-absorption mutually.When the feed material by adsorption bed when no longer changing it after adsorption bed contacts and form, equilibrium conditions just is determined.In other words, the net transfer of material does not take place between absorption phase exactly and the non-absorption mutually.
When the selectivity of two kinds of components near 1.0 the time, just do not exist a kind of component to be adsorbed the preferentially adsorbed of agent with respect to another kind of component; The degree that they are adsorbed (or not being adsorbed) each other much at one.When (B) little what or big what 1.0, the another kind of component sorbent material of what exists the preferentially adsorbed effect to a kind of component relatively.When adsorption selectivity on component D of component C relatively, when (B) big what 1.0, show that sorbent material is preferentially adsorbed to component C; Show that sorbent material is preferentially adsorbed to component D when (B) little what 1.0, the non-absorption that stays contains more component C mutually, and absorption contains more component D mutually.When extracting component and surpass 1.0 with respect to the adsorption selectivity of carrying surplus component is firm, isolating from carry surplus component and extracting component is possible in theory, preferably makes such selectivity approaching or greater than 2.The same with relative volatility, selectivity more high score from carrying out with regard to easy more; Selectivity is high more, and is just few more with the amount of the sorbent material in what this law.Theoretically, for all extracted component, the selectivity of desorb material must wait what or little what 1, thus all extraction components are extracted as a class, and whole surplus components of carrying is discharged in the raffinate stream significantly.
The 3rd important feature is to extract the exchange rate of component in the incoming mixture; In other words, extract the relative desorption rate of component exactly.This characteristic be used in this law in directly relevant for from sorbent material, reclaim extracting the desorb amount of substance that component institute must use.Rate of exchange can be reduced to remove and extract component and required desorb amount of substance faster.Thereby, the process cost of this law is reduced.Rate of exchange is fast more, and must pump into this law and separated back and to be used further to the desorb amount of substance of this law also just few more from extract stream.
For specific incoming mixture,, can use a dynamic checkout unit to measure the sorbent characteristics of adsorptive power, selectivity and rate of exchange etc. in order to test various sorbent materials and desorb material.This device is about 70 cubic centimetres adsorption chamber by volume and forms, and the opposite end of adsorption chamber has import partly and the outlet part.Adsorption chamber is put in the what temperature-control device.The applying pressure operating device is controlled at adsorption chamber under the predetermined constant voltage in addition.Chromatogram analysis equipment can be connected on the egress line of adsorption chamber, be used for the effluent liquid stream that leaves adsorption chamber in the analysis process.
Use said apparatus and following step commonly used to carry out pulse testing, it is to be used for measuring the selectivity of each absorption system and other data.The specific desorb material that filled with adsorbent made it and passed adsorption chamber balances each other.At the appropriate time, injecting feeding pulse several minutes.Contain the paraffinic hydrocarbons tracer agent (for example positive nonane) and the particular aromatic isomer of the non-absorption of concentration known in the feed pulse, they are diluted mistake in strippant all.Reclaim desorbent stream, tracer agent and aromatic isomers are composed in the operation by wash-out in liquid one fixation.Effluent can be analysed by the chromatographic equipment branch in the flow process, and And draws the envelope curve track at each corresponding component peak.On the other hand, can periodically collect the effluent liquid sample, analyze respectively by gas-chromatography subsequently.
According to the data that the chromatogram trace obtains, the performance of sorbent material can by to a kind ofly extract the adsorptive power index of component, to the selectivity of a kind of isomer with respect to another kind of isomer, and strippant is determined a kind of desorption rate that extracts component.The adsorptive power index can be represented with the peak envelope curve central authorities of the isomer of selected property absorption and the peak envelope curve central authorities of spike component or the distance between a certain other known reference point.It also can be represented according to the cubic centimetre number of the strippant that is pumped at interval during this period of time.Extracting component can be by the expression recently of distance between extraction component peak envelope curve central authorities and tracer agent (or other reference point) central authorities and the respective distance between raffinate peak envelope curve central authorities and the tracer agent peak envelope curve central authorities with respect to the selectivity of carrying surplus component (B).Usually, extract the exchange rate C of component and strippant
9The difference of (tracer agent) and p-Xylol (being adsorbed sample) the peak envelope curve width (being write as W here sometimes) when a half intensity is represented.Peak envelope curve width is narrow more, and desorption rate is fast more.Jie inhales the central authorities of all right tracer agent peak of speed envelope curve and has just been represented by the distance between the peak envelope curve central authorities of the extraction component of the disappearance of desorb.The volume of the strippant that this distance pumps in also can be used on is during this period of time at interval represented.
Be included in the sorbent material of what the inventive method and have the barium of specified proportion, the crystalline aluminosilicate of potassium cationic on its commutative position.Crystalline aluminosilicate of the present invention comprises the cage structure of crystalline aluminosilicate, and wherein aluminum oxide and silicon dioxide tetrahedron closely are connected in the unlimited three-dimensional network.Partly or before whole zeolite dehydrations, tetrahedron is by sharing Sauerstoffatom and position being connected together by the occupied space of water molecules between tetrahedron.The dehydration of zeolite makes crystal and the structure cell weave in molecular dimension.Therefore, the crystalline aluminosilicate is commonly called " molecular sieve ".Effectively centrifugation depends primarily on the charging bulk of molecule, for example, makes less n-paraffin molecule and bigger isoparaffin molecular separation by specific molecular sieve.Yet, in the method for the invention, though use term " molecular sieve " in a large number, but this is inappropriate strictly speaking, because the separation of particular aromatic isomer is depended on the different aromatic isomers and the different ， Er And of the electro-chemical attraction power of sorbent material significantly and is not depended on the difference of the clean physical dimension of isomer molecule.
In hydrated form, the crystalline aluminosilicate generally includes the various zeolites of being represented by following molecular formula:
Molecular formula 1
M
2/nO∶Al
2O
3∶WSiO
2∶YH
2O
Wherein " M " is balance tetrahedron electrovalent positively charged ion ， And and is considered to tradable cation position usually; " n " represents cationic valence mumber; " W " represents SiO
2Mole number; " Y " represents H
2The mole number of O.Generalized positively charged ion " M " can be positively charged ion univalent, divalence or tervalent or their mixture.
Prior art generally acknowledges that the sorbent material that comprises X type and y-type zeolite can be used to some adsorption separation process.These zeolites are known in the prior art.
The zeolite of the X type structure of hydration or part hydrated form can be represented with the various mole oxide compounds shown in the following molecular formula 2:
Molecular formula 2
（0.9-0.2）M
2/nO∶Al
2O
3∶（2.5-0.5）SiO
2∶YH
2O
Wherein " M " representative is at least the positively charged ion of one the little what 3 of valence mumber; The valence mumber of " n " representative " M "; And Y depends on the identity and the crystalline hydrauture of what " M ", and how its value is can be to about 9.Suc as formula 2 pointed, SiO
2/ Al
2O
3Mol ratio be 2.5-0.5." M " can be one or more positively charged ion, for example hydrogen cation, alkali metal cation or alkaline earth metal cation, or other selected positively charged ions, and be commonly called tradable cation position.Because when initial preparation X type zeolite, positively charged ion " M " mainly is sodium usually, therefore be called as sodium-X type zeolite.Yet also may there be other the above-mentioned positively charged ions as impurity in the difference according to the reactant purity of used manufacturing zeolite.
Can represent with the various mole oxide compounds shown in the following molecular formula 3 like the zeolites of the y-type structure of hydration or part hydrated form:
Molecular formula 3
（0.9-0.2）M
2/nO∶Al
2O
3∶WSiO
2∶YH
2O
Wherein " M " representative is at least the positively charged ion of one the little what 3 of valence mumber; The valence mumber of " n " representative " M "; The big what 3 of the value of " W " is until 6; The value of " Y " depends on the identity and the crystalline hydrauture of what " M ", can be up to 9.Therefore, the SiO of y-type structure zeolite
2/ Al
2O
3Mol ratio can be from about 3～about 6.The same with the zeolite of X type structure, positively charged ion " M " can be one or more different positively charged ions, during still owing to the initial preparation y-type zeolite, and the main usually still sodium of positively charged ion " M ".Therefore, the y-type zeolite that mainly contains sodium cation on tradable cation position is claimed sodium-y-type zeolite.
Above-mentioned representative zeolite is a zeolite useful among the present invention.Yet, must carry out cationic exchange with the barium of specified proportion and the mixture of potassium ion to prepared zeolite.Barium and potassium ion with proportional exchange, and make BaO/K in the zeolite molecules formula
2The last mol ratio of O is 0.6: 1 to 1.2: 1, is preferably 0.9: 1 to 1.1: 1.This exchange is available to be in Ba in the proportional range and one step of mixture of K finishes, and makes the above-mentioned scope of molecular formula place what of final gained zeolite; Perhaps carry out several times exchange in succession, an amount of ion of exchange in each step, the zeolite in the correct and scope of desireing of what everywhere.Have now found that, must use to be in above-mentioned BaO/K
2Zeolite in the O scope; Otherwise if ratio is too big, it is very big that the retention volume of p-Xylol will become.High retention volume shows that desorption time will be very long.If ratio is lower than the scope of regulation, illustrate that sorbent material is too strong to the selectivity of strippant, and p-Xylol displacement desorption agent effectively in the next round circulation.
In general, use the sorbent material in each separation method all to contain the crystalline zeolite material that is dispersed in amorphous substance or the inorganic matrix.Have raceway groove or cavity in amorphous substance or inorganic matrix, they can make liquid enter into crystalline material.Amorphous substance or inorganic matrix are also as the binding agent of zeolite powder.Silicon-dioxide, aluminum oxide or some clay and their mixture are the exemplary of such inorganic matrix material.Binding agent helps the moulding and the aggegation of crystalline particles, and not so it will become fine powder.Therefore, sorbent material can be taked to have institute and be desireed the size particles form, and for example extrudate, aggregate, flap, microballoon or small-particle, particle diameter are preferably about 16 orders (USS order) (250～1190 microns) about 60 orders.It is favourable containing less water in sorbent material, and it causes that the less water of product pollutes.Sorbent material can be with fixed bed form use closely, and it alternately contacts with the desorb material with incoming mixture, and in this case, sepn process only is semi-continuous.In another embodiment, can use suitable valve is housed one group two or more fixed bed of sorbent, so that, inhale a plurality of fixed bed of sorbent that material can pass through another or another group and be situated between simultaneously when incoming mixture during by a plurality of fixed bed of sorbent of or a group.Flowing of incoming mixture and desorb material can be up or down by the sorbent material in the bed.Any conventional equipment with the contact of what fixed bed fluid one solid all can use.
Yet moving-bed or simulation moving-bed flow-through appt have much higher separation efficiency than fixed bed device, are therefore preferentially selected for use.In moving-bed or simulation moving-bed method, keep and replacement operator all carries out continuously, not only provide continuously to extract stream and carry residual current, and can use incoming flow and displacement liquid to flow continuously.A preferable embodiment of this law is used the simulation moving-bed counter current system that is called well known in the prior art.In such system, the liquid that multichannel enters is moved down into molecular sieve chamber continuously, and model molecule sieves moving up of molecular sieve contained in the chamber thus.Can be with reference to No. 2985589 United States Patent (USP) of D.B.Broughton, its principle of operation and order of this current system of having determined that be situated between.Can also be the paper of " continuous adsorption operation-a kind of new isolation technique " with reference to exercise question, this paper be that D.B.Broughton proposed to the 34th annual meeting of the chemical engineering association that holds in the Tokyo on April 2nd, 1969.Release in order further the flow process of simulation moving-bed counter-current process to be situated between, special to enroll these two pieces of reference at this for reference.
Another is applicable to the embodiment of the simulation moving-bed current system of the inventive method efficient simulation moving-bed method of disclosed following current that is Gerhold in No. 4402832, United States Patent (USP), and is for reference at this full text in conjunction with it.
Expection has at least a part of extraction discharging current will be passed into tripping device, wherein has at least the desorb material partly can be separated under isolating condition, produces the extraction product that contains lower concentration desorb material.Best, but non-ly to the operation And of this law requisitely be, make the raffinate output stream that is at least part pass to tripping device, wherein have at least the desorb material of part can be separated under separation condition, produce can be again with the desorbent stream of what present method with contain the raffinate product of lower concentration desorb material.In general, wish to be lower than 5% volume, preferably be lower than 1% volume in extraction product and the concentration of carrying desorb material in the surplus product.Tripping device is generally fractional column, its design and to operate in the isolation technique be known.
Though liquid-phase operation and vapor-phase operation can both be used in many adsorption method of separations, but method of the present invention is preferably used liquid-phase operation, because method of the present invention requires lower temperature and utilize the high what of yield of liquid-phase operation gained extraction product to utilize the vapor-phase operation gained to extract the yield of product.Adsorption conditions comprises temperature and pressure.Temperature range is about 20 ℃ to 250 ℃, preferably is about 100 ℃ to 200 ℃; Pressure is for being enough to keep liquid phase, and it can be pressed onto the gauge pressure of 600 pounds/square inch (4238 kPas) from atmosphere.Desorption condition comprises used pressure in the temperature of same scope and the adsorption conditions.
Can change to the suitability for industrialized production scale from laboratory scale (example is seen United States Patent (USP) No. 3706812) with the big I of the device of what present method, flow range can from little to several cubic centimetres/hours to several thousand gallons per hours greatly extremely.
For effect of the present invention is described, special releasing in order to be situated between makes method of the present invention become possible various selectivity relations, and the spy provides following embodiment.
The embodiment I
In this experiment, use aforesaid device to carry out pulse testing to estimate the C of method of the present invention from other
8The ability of separating paraxylene (138 ℃ of boiling points) in the aromatic substance (136 ℃～145 ℃ of boiling points).The y-type zeolite that used sorbent material exchanges for barium and potassium cationic with following pointed ratio.Use a small amount of amorphous bonding material argillaceous.Zeolite contains potassium and barium positively charged ion on nearly all tradable ion position, its consumption and ratio by example in the table in.Cationic exchange is achieved in that 1.5 liters of 1 mole of KCl solution of 50 ℃ upwards with 500 cubic centimetres/hour the flow rate adsorbent bed by 200 cubic centimetres, then with 1 liter/hour the flow rate BaCl with 0.2M
2Solution recirculation was passed through bed 4 hours, at last with the speed washing of 1 premium on currency with 500 cubic centimetres/hour.At 300 ℃ of calcining sorbent materials.
To each pulse testing, in order to keep the gauge pressure that liquid-phase operation remains on fractional column 150 ℃ and 150 pounds/square inch (1136 kPas).For the composition of the outflow material that is determined at the given timed interval, and gas chromatographicanalyzer is received in the effluent liquid stream of fractional column.The used incoming mixture of each test contains the positive nonane that is used as tracer agent of the various xylene isomers that respectively are about 5% volume, the ethylbenzene that is about 5% volume, 5% volume and the desorb material of 75% volume.In A, B and C test, the desorb material contains the m-difluorobenzene (m-DFB) of 30% volume.All the other are normal heptane.Desorb material in test D all is a m-difluorobenzene.The operation that each test is carried out is as follows: the desorb material continuously flows with about 1.20 cubic centimetres/minute speed.Stop to feed speed logical 10 minute the incoming mixture of desorb material ， And with 1 upright centimeters/minute in a reasonable time gap.Again desorbent stream is passed into adsorption column continuously subsequently, all till the adsorption column wash-out, this is to observe to determine by the stratographic to the outflow material that leaves adsorption column until aromatic substance.
Test-results is listed in table 2.Chromatogram Figure 1A, 1B and 1C have illustrated the present invention.The elution curve of each p-Xylol obviously separates with fine isolating other curves of expression.Fig. 1 D is that to be used for the comparison Xiao Guo And figure explanation that is situated between isolating, but is considered to unpractical owing to desorption time is very long, and Fig. 1 D also shows: work as BaO/K
2When the mol ratio of O increases in the pointed scope of the invention described above, desorb intensity will descend.Employed BaO/K in the test report of Fig. 1 D
2The mol ratio of O is 5.17: 1.As follows by the corresponding data that each opisometer is calculated: being the difference of p-Xylol peak envelope curve and positive nonane tracer agent peak envelope curve width when the half-peak height Δ W(CC), also is the yardstick of strippant rate of displacement.
Therefore, use the data in the table II, concerning embodiment 1C, 1A and 1B,
B
1C＝14.5/10.8＝1.34
B
1A＝8.0/14.6＝0.55
B
1B＝0.76
Therefore, for p-Xylol, the selectivity of the sorbent material of embodiment 1C is very superior, and the selectivity of the sorbent material among embodiment 1A and the 1B will be unfavorable.Another trend that can see in the present embodiment is, along with BaO/K
2The increase of O ratio, strippant will become more weak, (being that retention volume increases).
Table 2
With various Ba/K ratios carry out barium-potassium-
The result of Y type faujusite pulse testing
The embodiment I
I A I B I C I D
100%
Strippant---30%m-DFB---m-DFB
N-C
9The half-peak bag
Line width (H.W) 11.5 9.94 12.3 12.9
Selectivity (B)
Bp/eb 3.27 3.53 3.32 4.64
Bp/m 4.04 4.47 4.13 5.22
Bp/o 3.40 3.64 3.56 5.16
The guarantor of p-Xylol
Stay volume, cc 16.4 17 34.7 78.9
△W,cc 0.04 1.3 6.9 32.5
SiO
260.6 60.9 60.7 59.0
Al
2O
319.6 18.6 18.7 18.0
K
2O 8.8 8.6 6.9 2.2
BaO
9.1 10.0 11.0 18.5
Na
2O 0.72 0.53 0.68 0.58
Mol ratio BaO/K
2O 0.63 0.71 0.98 5.17
The embodiment II
Except that temperature is reduced to the step that repeats embodiment I C 125 ℃.By following table 3 as can be seen, its result does not almost change:
Table 3
Bp/e 3.37
Bp/m 4.21
Bp/o 3.70
ΔW，CC 7.6
N-C
9H.W. centimetres 12.00
The retention volume of p-Xylol, CC 34.0
Mol ratio BaO/K
2O 0.98
Sorbent material is barium-potassium-Y type faujusite, and strippant is the n-C of 30%m-DFB
7Liquid is all identical with embodiment 1C.
The embodiment III
Remove BaO/K
2The mol ratio of O is outside 1.2, under as the identical condition of embodiment I and utilize identical material to carry out another pulse testing.Strippant is and normal heptane (n-C
7) the m-DFB(boiling point of blended 30% is 82 ℃).(B) is as follows for the selectivity of each isomer of p-Xylol:
Bp/eb＝3.02
Bp/m＝3.94
Bp/o＝3.00
The retention volume of p-Xylol is 22.8, and this expresses gratifying desorption time.N-C
9The width of half-peak eminence is 11.9CC.Δ W(such as above definition) be 1.1CC.Consisting of of sorbent material:
SiO
2Weight percent 60.6
Al
2O
3Weight percent 19.1
The weight percent 13.1 of BaO
K
2The weight percent 6.7 of O
Na
2The weight percent 0.6 of O
BaO/K
2The O(mol ratio) 1.2
The result also is illustrated by the color atlas among Fig. 2, and it shows at BaO/K
2The mol ratio of O is 1.2: 1 o'clock, and p-Xylol can be separated from other isomer.
The embodiment IV
Except that used strippant is 100% fluorobenzene (boiling point is 85 ℃), repeat the pulse testing of embodiment III.Selectivity (B) for each isomer of dimethylbenzene is:
Bp/eb＝2.25
Bp/m＝2.80
Bp/o＝3.50
The retention volume of p-Xylol is 25.7CC.At n-C
7The width of half-peak eminence is 12.3CC.Δ W(such as above-mentioned definition) be 18.3CC.BaO/K
2The mol ratio of O is 1.2: 1.Critical slope
Be 7.9CC.The desorb slope
Be 46.4CC.The results are shown in the color atlas 3 of pulse testing.Though it is close to use toluene to make the resulting selectivity of strippant at this resulting selectivity and those.But fluorobenzene has identical advantage with other at this disclosed fluorobenzene class material, promptly lower boiling point, thereby by distilling the recovery that can realize strippant.
The embodiment V
Repeat the pulse testing of embodiment III, except used strippant is at n-C
7In 30%m-DFB, the BaO/K of barium-potassium-y-type zeolite
2The mol ratio of O is that 1.05: 1 And have outside the following composition:
SiO
2Weight percent be 60.8
Al
2O
3Weight percent be 18.8
The weight percent of BaO is 11.8
K
2The weight percent of O is 6.9
Na
2The weight percent of O is 0.63
Selectivity (B) for each isomer of dimethylbenzene is:
Bp/eb＝2.72
Bp/m＝3.85
Bp/o＝3.40
The retention volume of p-Xylol is 39.6CC.N-C
7Width in the half-peak eminence is 10.1CC.Δ W(is as defined above) be 6.71CC.Gained is each result show in the what color atlas 4.
The embodiment VI
Removing strippant is at 70%n-C
7In 30% 1,2-Difluorobenzene repeat the pulse testing of embodiment III outward.BaO/K
2The mol ratio of O is 1.05.The selectivity (B) of each isomery structure body of p-Xylol is the same high with m-difluorobenzene.
Bp/eb＝2.4
Bp/m＝3.23
Bp/o＝4.45
The retention volume of p-Xylol is 32.2, and this is expressed as medium desorption time.N-C
7Width in the half-peak eminence is 10.1CC.Δ W(definition is as above) be 9.7CC.
The embodiment VII
Remove BaO/K
2The mol ratio of O be 1.13 and embodiment VII A with M-DFB, the embodiment VII B of 30% volume with beyond the 100% volume m-DFB, repeat the pulse testing of embodiment III.Fig. 5 A and 5B and table 4 have illustrated at constant BaO/K
2Result during the O ratio.When the concentration of m-DFB when 30% increases to 100%, selectivity (B) also will increase.
Table 4
Embodiment
VII A VII B
BaO/K
2The mol ratio 1.13 1.13 of O
The m-DFB of m-DFB 100% volume of strippant 30% volume
Bp/e 2.50 3.95
Bp/m 3.63 4.46
Bp/o 3.21 3.82
The retention volume 47.89CC 17.97CC of p-Xylol
△W 10.84CC -0.7CC
n-C
9H.W. 9.64CC 11.8CC
9.32CC 7.2CC
The embodiment VIII
Repeat the pulse testing of embodiment VII, remove BaO/K
2The mol ratio of O is outside 0.99: 1.Its result is illustrated by following Fig. 6 A and 6B and table 5.In Fig. 6 A, before removing the ethylbenzene fraction, reclaim the m-xylene that is contained in the charging; But in Fig. 6 B, m-xylene can not separate from ethylbenzene and/or o-Xylol, thereby is recovered together.It should be noted that the result with Fig. 6 A compares with the result of Fig. 5 A of embodiment VII, and the result of Fig. 6 B is compared with the result of Fig. 5 B, along with BaO/K
2The increase of O ratio, the desorb intensity of m-DFB (retention volume with p-Xylol is represented) will descend.For example, contrast ratio be 0.99 o'clock (embodiment VIII A and Fig. 6 A) retention volume is 37.17CC, and (embodiment VII and Fig. 5 A) retention volume is 47.89CC when ratio is 1.13, above both is the situation at 30%m-DFB.Equally, the m-DFB situation 100%, mol ratio is 0.99 when retention volume is 11.44CC; And mol ratio is 1.13 when retention volume is increased to 17.97CC.In addition, relative what strippant, sorbent material is bigger to the selectivity of p-Xylol than strippant to the selectivity (B) of p-Xylol, thereby is gratifying:
Table 5
Embodiment
VIII A VIII B
BaO/K
2The mol ratio 0.99 0.99 of O
Strippant 30% volume m-DFB 100% volume m-DFB
Bp/e 2.86 3.84
Bp/m 3.77 4.18
Bp/o 3.44 3.94
The retention volume 37.17CC 11.44CC of p-Xylol
△W 6.02CC -2.39CC
n-C
9H.W. 9.91CC 13.05CC
9.05CC 8.6CC
The embodiment IX
As above-mentioned pulse testing in, the ability of using another kind of charging from the mixture of p-Diethylbenzene (p-deb) and NSC 62102 (m-deb) and adjacent diethylbenzene (o-deb), to separate p-Diethylbenzene with the Y type faujusite of measuring barium-potassium exchange.The BaO/K of barium potassium Y type sorbent material
2The mol ratio of O is 0.99: 1.Use the clay bond identical with the embodiment I.Its dependent variable is identical with the embodiment I basically, and strippant is the normal heptane liquid of 30% m-difluorobenzene.Selectivity for strippant (B) is 1.09.The result is shown among following table 6 and Fig. 7.
Table 6
BaO/K
2The mol ratio 0.99 of O
Strippant n-C
7In 30%m-DFB
Bp/m 2.30
Bp/o 3.78
The retention volume 43.27CC of p-Diethylbenzene
n-C
9H.W. 9.72CC
11.7CC
B 1.09
Claims (5)
1, a kind of method of from incoming flow, separating the para-isomeride of dialkyl group substituted arene, incoming flow contains a kind of said para-isomeride and the other mixture of isomers that is at least a kind of said aromatic hydrocarbons, this method comprises makes said incoming flow contact with a kind of crystalline aluminosilicate sorbent material, and crystalline aluminosilicate sorbent material contains BaO/K on the tradable cation position of its sorbent material crystal structure
2The mol ratio of O is 0.6: 1 to 1.2: 1 barium and a potassium cationic, under selected sorbent material condition, realize of the absorption of said sorbent material to said para-isomeride, a kind of in then making the sorbent material that contains para-isomeride and being selected from a fluorine replaces and difluoro replaces aromatic hydrocarbons and their mixture is situated between and inhales material and flow with respect to the product that incoming flow contains spissated para-isomeride in selected the causing ， And output that contacts under Jie's suction condition of removing said para-isomeride from said sorbing material.
2, according to the process of claim 1 wherein that said sorbent material is X type zeolite or y-type zeolite or their mixture.
3, according to the method for claim 1 or 2, wherein said strippant is m-difluorobenzene or 1,2-Difluorobenzene or their mixture.
4, according to claim 1,2 or 3 method, wherein said absorption or desorption condition comprise from about 20 ℃ to about 250 ℃ temperature be enough to keep the pressure of liquid phase.
5, according to the method for arbitrary claim in the claim 1 to 4, BaO/K wherein
2The mol ratio of O is 0.9: 1 to 1.1: 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU892522A HU205057B (en) | 1987-06-15 | 1989-05-22 | Process for the adsorption separation of paraalkyl aromatic hydrocarbons by using fluoroaromatic adsorbent |
| CN89104713.1A CN1022826C (en) | 1987-06-15 | 1989-05-25 | Use of fluore-aromatic desorbent in process for adsorptive separation of para-alkylaromatic hydrocarbons |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/061,948 US4886929A (en) | 1987-06-15 | 1987-06-15 | Separation of para-xylene |
| CA000600093A CA1322176C (en) | 1987-06-15 | 1989-05-18 | Use of a fluoro-aromatic desorbent in a process for adsorptive separation of para-alkylaromatic hydrocarbons |
| HU892522A HU205057B (en) | 1987-06-15 | 1989-05-22 | Process for the adsorption separation of paraalkyl aromatic hydrocarbons by using fluoroaromatic adsorbent |
| RO139905A RO103750B1 (en) | 1987-06-15 | 1989-05-25 | Separation method of para-xylene out of a hydrocarbonate flow |
| CN89104713.1A CN1022826C (en) | 1987-06-15 | 1989-05-25 | Use of fluore-aromatic desorbent in process for adsorptive separation of para-alkylaromatic hydrocarbons |
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| Publication Number | Publication Date |
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| CN1047489A true CN1047489A (en) | 1990-12-05 |
| CN1022826C CN1022826C (en) | 1993-11-24 |
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| CN89104713.1A Expired - Lifetime CN1022826C (en) | 1987-06-15 | 1989-05-25 | Use of fluore-aromatic desorbent in process for adsorptive separation of para-alkylaromatic hydrocarbons |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5884777A (en) * | 1994-10-22 | 1999-03-23 | Yangzi Petro-Chemical Corp. Sinopec | Simulated moving bed absorption separation process |
| CN1044470C (en) * | 1994-12-29 | 1999-08-04 | 中国石化金陵石油化工公司 | Method for separating m-xylene and ortho-xylene from mixed xylene and ethyl benzene |
| CN111629800A (en) * | 2017-12-22 | 2020-09-04 | 阿科玛法国公司 | Barium, strontium, potassium and sodium based zeolite adsorbents, method for their preparation and their use |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038031C (en) * | 1994-10-22 | 1998-04-15 | 中国石化扬子石油化工公司 | Improved method for producing high pure para-xylene through adsorption separation |
-
1989
- 1989-05-25 CN CN89104713.1A patent/CN1022826C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5884777A (en) * | 1994-10-22 | 1999-03-23 | Yangzi Petro-Chemical Corp. Sinopec | Simulated moving bed absorption separation process |
| CN1044470C (en) * | 1994-12-29 | 1999-08-04 | 中国石化金陵石油化工公司 | Method for separating m-xylene and ortho-xylene from mixed xylene and ethyl benzene |
| CN111629800A (en) * | 2017-12-22 | 2020-09-04 | 阿科玛法国公司 | Barium, strontium, potassium and sodium based zeolite adsorbents, method for their preparation and their use |
| CN111629800B (en) * | 2017-12-22 | 2022-06-03 | 阿科玛法国公司 | Barium, strontium, potassium and sodium based zeolite adsorbents, method for their preparation and their use |
| US11439975B2 (en) | 2017-12-22 | 2022-09-13 | Arkema France | Zeolite adsorbents based on barium, strontium, potassium and sodium, preparation process therefor, and uses thereof |
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| CN1022826C (en) | 1993-11-24 |
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