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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
  • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
  • B01J20/041—Oxides or hydroxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
  • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/02—Monocyclic hydrocarbons
  • C07C15/067—C8H10 hydrocarbons
  • C07C15/08—Xylenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
  • C07C201/06—Preparation of nitro compounds
  • C07C201/16—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/82—Purification; Separation; Stabilisation; Use of additives
  • C07C209/86—Separation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
  • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
  • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
  • C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/106—Silica or silicates
  • B01D2253/108—Zeolites
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
  • C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
  • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
  • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton

Definitions

• the invention relates to adsorbents based on agglomerated crystals of zeolite X comprising barium and potassium, their preparation process and their uses.
• adsorbents may be used more particularly for the production in the liquid phase or gas phase of very pure para-xylene from an aromatic hydrocarbon feed containing isomers containing 8 carbon atoms.
• adsorbents comprising crystalline aluminosilicates can be used to separate certain hydrocarbons from mixtures containing them.
• aromatic hydrocarbon separation and in particular the separation of aromatic C8 isomers, it is generally recognized that the use of particular cations in cationic sites of zeolitic crystalline aluminosilicates improves the selectivity of the zeolite for C8-aromatic isomers.
• This differentiated adsorption within the zeolite allows the separation of the different C8-aromatic isomers, which is used industrially for the production of very pure para-xylene from an aromatic hydrocarbon feed containing 8-atom isomers. carbon.
• zeolitic adsorbents consisting of X or Y zeolites comprising, besides sodium cations, barium, potassium or strontium ions, alone or in mixtures, for selectively adsorbing the para-xylene in the liquid phase in a liquid phase.
• mixture of aromatic hydrocarbons is well known from the prior art.
• zeolites for aromatic hydrocarbons containing 8 carbon atoms vary. very finely depending on the size and shape of the pores as well as the position of the cations inside the structure that affect both the electrostatic field present inside the zeolite and the shape accessible volume in the pores.
• Other parameters, such as the polarizability of cations and molecules or the flexibility of the structure can also have an influence. It is therefore extremely difficult to predict theoretically and precisely the adsorption characteristics of a zeolite with respect to aromatic hydrocarbons containing 8 carbon atoms.
• Patent FR 2,903,978 teaches that potassium ions may represent up to 1/3 of exchangeable sites occupied by barium and potassium, but this patent does not fill any adsorbent containing potassium and provides no teaching allowing to anticipate the impact of potassium on adsorption selectivities.
• US Pat. Nos. 8,283,274 and 8,557,028 describe adsorbents having potassium content by weight of between 0.25% and 0.9% by weight, corresponding to molar ratios K20 / (BaO + K 2 0 + Na 2). 0) of between 1.3% and 4.5%.
• US Pat. No. 8,557,028 claims adsorbents having potassium content by weight of between 0.9 and 1.5%, equivalent to K20 / (BaO + K 2 0 + Na 2 0) molar ratios of between 4.5% and 7.5%.
• the examples of the latter patent show that productivity and operating costs are improved with adsorbents having potassium contents of between 0.7% and 1.2% by weight.
• CN 1267185 discloses adsorbents having molar ratios BaO / K 2 0 of between 10 and 40 corresponding to molar ratios K 2 0 / (BaO + K 2 0 + Na 2 0) of between 2.4% and 9, 1%.
• the recent patent US 2015/0105600 describes meanwhile an adsorbent based on zeolite X, barium and potassium, having a molar ratio K 2 0 / (BaO + K 2 0 + Na 2 0) between 15 % and 40%.
• zeolites The synthesis of zeolites leads to crystals (generally in the form of powder) whose use on an industrial scale is particularly difficult (significant pressure losses during handling). Agglomerated forms of these crystals, in the form of grains, yarns and other agglomerates, are preferred, these forms being able to be obtained by extrusion, pelletizing, and other agglomeration techniques known to those skilled in the art. These agglomerates do not have the disadvantages inherent to the pulverulent materials.
• agglomerates whether in the form of platelets, beads, extrudates, and the like, are generally formed of zeolite crystals (s), which constitute the active element (in the sense of adsorption ) and a binder intended to ensure the cohesion of the crystals in the form of agglomerates and to give them sufficient mechanical strength to withstand the vibrations and the movements to which they are subjected during the operations of separating the isomers of the aromatic cuts in C8 .
• zeolite crystals which constitute the active element (in the sense of adsorption ) and a binder intended to ensure the cohesion of the crystals in the form of agglomerates and to give them sufficient mechanical strength to withstand the vibrations and the movements to which they are subjected during the operations of separating the isomers of the aromatic cuts in C8 .
• the adsorption properties of these agglomerates are obviously reduced compared to the crystal powder, because of the presence of agglomeration binder inert with respect to
• zeolitization To easily perform this operation, zeolitizable binders are used, most often clays belonging to the family of kaolinite, and preferably previously calcined at temperatures generally between 500 ° C and 700 ° C.
• patent application FR 2 789 914 describes a process for the production of agglomerates of zeolite X, with an Si / Al ratio of between 1, 15 and 1.5, containing barium and optionally potassium.
• the agglomerates thus obtained, after zeolization of the binder, have, from the point of view of the adsorption of the para-xylene contained in the C8 aromatic cuts, improved properties compared with adsorbents prepared from the same amount of zeolite X and binder, but whose binder is not zeolite.
• the important factors that influence the performance of an adsorption separation process include in particular the adsorption selectivity, the adsorption capacity and the material transfer kinetics which defines the adsorption rates and desorption of the various compounds.
• the adsorbent must therefore have good material transfer properties in order to guarantee a sufficient number of theoretical plates to achieve effective separation of the species in mixture, as Ruthven indicates in the book entitled “Principles of Adsorption and Adsorption Processes"("Principles of Adsorption and Adsorption Processes”), John Wiley & Sons, (1984), pages 326 and 407.
• the diffusional resistance between the crystals (also called macroporous resistance) is in turn proportional to the square of the rays of the agglomerates and inversely proportional to the diffusivity of the molecules in the macropores.
• the diffusivities are fixed, and the only way to improve the transfer of material is to reduce the crystal diameter. A gain on the overall transfer will thus be obtained by reducing the size of the crystals.
• agglomerated zeolite adsorbents having both good xylenes adsorption capacity and good selectivity for para-xylene, have very good separation properties.
• xylenes when they are made from small zeolite crystals in liquid phase processes for separating para-xylene contained in C8 aromatic cuts, for example of simulated countercurrent type.
• Those skilled in the art are, however, unable to define a priori or theoretically and precisely the adsorption characteristics of a FAU zeolite, especially of type X, having a particular composition of barium and potassium, opposite aromatic hydrocarbons having 8 carbon atoms.
• the present invention aims to provide novel adsorbents based on zeolite X comprising barium, potassium and sodium and having a particular composition of barium, potassium and sodium, optimal for simultaneously maximize productivity and minimize the production costs of the para-xylene separation process contained in the C8 aromatic cuts.
• the present invention also provides a process for the separation of xylenes using an X-zeolite adsorbent having a particular composition of barium, potassium and sodium, allowing the production of high purity para-xylene with a improved productivity from an aromatic hydrocarbon feed containing 8-carbon isomers.
• the invention relates to a zeolitic adsorbent comprising crystals of zeolite X and comprising barium, potassium and sodium, in which the molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0) (species in the form of oxides) is between 9.5% and 14.5%, preferably between 10% and 14%, and preferably between 11% and 13%.
• the molar ratio in K 2 0 / (K 2 0 + BaO + Na 2 O) is equal to 12%.
• the molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0) is expressed as a percentage of the number of moles of K 2 0 relative to the sum of the number of moles of (K 2 0 + BaO + Na 2 O).
• the sodium oxide content Na 2 0 is preferably less than 0.3% by weight and preferably less than 0.2% by weight relative to the total mass of the adsorbent.
• the total content of oxides of alkaline or alkaline earth ions other than barium oxide BaO, potassium oxide K 2 0 and sodium oxide Na 2 0 is advantageously less than 1% by weight, preferably between 0 and 0.5% by weight, and very preferably between 0 and 0.3% by weight, relative to the total mass of the adsorbent.
• the zeolite crystals X advantageously have an Si / Al atomic ratio of between 1, 00 and 1, 50, preferably between 1, 05 and 1, 50 and more preferably between 1, 10 and 1, 50.
• the number average diameter of the zeolite crystals X is less than or equal to 1.5 ⁇ , preferably between 0.1 ⁇ and 1.2 ⁇ , more preferably between 0.1 ⁇ and 1, 0 ⁇ .
• the loss on ignition of the adsorbent according to the invention measured at 950 ° C according to the standard NF EN 196-2 is advantageously between 4.0 and 7.7% and preferably between 4.5 and 6 , 5% and most preferably between 4.8 and 6% by weight.
• the average diameter in number of the adsorbent according to the invention may be between 0.2 mm and 2 mm, in particular between 0.2 mm and 0.8 mm and preferably between 0.2 mm and 0 mm. , 65 mm.
• the invention also relates to a process for preparing an adsorbent as described above, comprising at least the steps of:
• the process for preparing the adsorbent implements a step b) of zeolitization of the binder.
• Preference or solutions of barium ions, or potassium or barium and potassium steps c) and d) have a concentration between 0.2M and 2M.
• the invention also relates to an adsorbent as described above, obtainable according to the preparation method above.
• the invention also relates to the use of said adsorbent according to the invention in the processes of:
• the invention also relates to a process for recovering para-xylene from cuts of aromatic hydrocarbon isomers containing 8 carbon atoms, in the liquid phase, by adsorption of para-xylene by means of said adsorbent according to US Pat. invention in the presence of a desorbent, preferably selected from toluene and para-diethylbenzene.
• Said method may be simulated moving bed type, preferably simulated counter current.
• the invention also relates to a process for recovering para-xylene from aromatic hydrocarbon isomer cuts containing 8 carbon atoms, in the gas phase, by adsorption of para-xylene by means of said adsorbent according to US Pat. invention in the presence of a desorbent, preferably selected from toluene and para-diethylbenzene.
• the invention further relates to a process for separating polyhydric alcohols using said adsorbent according to the invention.
• the invention further relates to a process for separating isomers of substituted toluene such as nitrotoluene, diethyltoluene, toluenediamine, using said adsorbent according to the invention.
• the invention finally relates to a process for separating cresols using said adsorbent according to the invention.
• the present invention thus has for its first object zeolite X-based zeolite adsorbents. These adsorbents are particularly suitable for use in a process for separating para-xylene in the liquid phase, preferably of simulated countercurrent type.
• the present invention relates to a zeolite adsorbent comprising zeolite X crystals and comprising barium, potassium and sodium, in which the molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0) is between 9.5% and 14.5%, preferably between 10% and 14%, and preferably between 11% and 13%.
• the molar ratio in K 2 0 / (K 2 0 + BaO + Na 2 0), expressed in terms of oxides is equal to 12%.
• the adsorbents according to the invention may also comprise a non-zeolitic phase, that is to say a non-crystalline phase which is essentially inert with respect to the adsorption.
• a non-zeolitic phase the molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0) takes into account the oxides included in said non-zeolitic phase.
• the content of sodium oxide Na 2 0 in the adsorbent according to the invention is advantageously less than 0.3% by weight and preferably less than 0.2% by weight relative to the total mass of the adsorbent.
• the total content of oxides of alkaline or alkaline-earth ions other than barium oxide BaO, potassium oxide K 2 0 and sodium oxide Na 2 0 in the adsorbent according to the invention is advantageously less than at 1% by weight, preferably between 0 and 0.5% by weight, and very preferably between 0 and 0.3% by weight, relative to the total mass of the adsorbent.
• the zeolitic adsorbent according to the present invention is an adsorbent based on zeolite crystals FAU type X.
• zeolite X is meant zeolites whose Si / Al atomic ratio is between 1, 00 and 1, 50, preferably between 1, 05 and 1, 50 and even more preferably between 1, 10 and 1 50.
• zeolites X it is now generally accepted to recognize two subgroups called zeolites LSX and zeolites MSX.
• the LSX zeolites have an Si / Al atomic ratio equal to about 1 and the MSX zeolites have an Si / Al atomic ratio of between about 1.05 and about 1.15.
• the term "zeolite type FAU X" means the zeolites FAU type X defined above, said zeolites being hierarchically porous that is, zeolites of type X with hierarchical porosity (or zeolite XPH), zeolites of MSX type with hierarchical porosity (or MSXPH) and zeolites of LSX type with hierarchical porosity (or LSXPH), and more especially the FAU zeolites with a hierarchical porosity and Si / Al atomic ratio of between 1, 00 and 1, 50, preferably between 1.05 and 1.5, more preferably between 1.05 and 1.40, and even more preferred, between 1, 15 and 1, 40.
• the invention also comprises zeolitic adsorbents comprising mixtures of two or more FAU zeolites with hierarchical porosity as they have just been defined.
• zeolite By “hierarchically porous zeolite” is meant a zeolite having both micropores and mesopores, ie a zeolite both microporous and mesoporous.
• mesoporous zeolite By “mesoporous zeolite” is meant a zeolite whose microporous zeolite crystals have, together with the microporosity, internal cavities of nanometric size (mesoporosity), easily identifiable by observation by means of a Transmission Electron Microscope (TEM or "TEM"). In the English language), as described for example in US Pat. No.
• TEM transmission electron microscopy
• the crystalline structure of the X-type FAU zeolite in the zeolite adsorbent of the present invention is identifiable by X-ray diffraction (known to those skilled in the art under the acronym DRX).
• the zeolite adsorbent has an Si / Al atomic ratio of between 1.00 and 2.00, preferably between 1.00 and 1.80, more preferably between 1.15 and 1. , 80, and even more preferably between 1, 15 and 1, 60.
• the term "number average diameter" or "size” is used for zeolite crystals and for zeolite agglomerates. The method of measuring these quantities is explained later in description.
• the number average diameter of the zeolite crystals X is less than or equal to 1.5 ⁇ , preferably between 0.1 ⁇ and 1.2 ⁇ , more preferably included between 0.1 ⁇ and 1,0 ⁇ .
• the zeolite adsorbent of the invention is preferably in the form of an agglomerate, that is to say it consists of zeolite crystals (s) and at least one non-zeolite phase which may comprise an agglomeration binder allowing the cohesion of the crystals between them.
• agglomerated agglomerated
• the mass fraction of zeolite X in the adsorbent according to the present invention may be at least 80% by weight of zeolite (s) X relative to the total weight of the adsorbent, preferably at least 90% by weight. %, this mass fraction being up to 100% and typically up to 99.5% by weight.
• the zeolite adsorbent according to the invention has a loss on ignition measured at 950 ° C according to the NF EN 196-2 standard of between 4.0% and 7.7%, preferably between 4.5 and 6.5% and advantageously between 4.8 and 6%.
• the zeolitic adsorbent according to the present invention preferably has a mechanical strength generally greater than or equal to 1.8 MPa, typically greater than or equal to 2.1 MPa. This mechanical resistance is measured by the Shell method SMS1471 -74 series suitable for agglomerates of size less than 1, 6 mm.
• the adsorption capacity is measured by measuring the microporous volume of the adsorbent evaluated according to the Dubinin-Raduskevitch equation by adsorption of nitrogen (N 2 ) at a temperature of 77K, after degassing. under vacuum at 300 ° C for 16 hours.
• the microporous volume of the zeolite adsorbents of the invention was thus measured to be greater than 0.250 cm 3 / g, typically in a range from 0.256 cm 3 / g to 0.288 cm 3 / g.
• the invention relates to a method for preparing zeolite agglomerates as just defined, which process comprises at least the steps of:
• the process for preparing zeolite agglomerates implements a step b) of zeolitization of the binder.
• Preference or solutions of barium ions, or potassium or barium and potassium steps c) and d) have a concentration between 0.2M and 2M.
• the size of the zeolite X crystals used in step a) is measured by observation under a scanning electron microscope (SEM) or observation by transmission electron microscope (TEM). This observation MEB or MET also confirms the presence of non-zeolite phase comprising for example the binder or the unconverted residual binder during the optional zeolitization step or any other amorphous phase in the agglomerates.
• SEM scanning electron microscope
• TEM transmission electron microscope
• the zeolite X used in step a) comprises, preferably is, an X type FAU zeolite with hierarchical porosity.
• the X-type FAU zeolite crystals with a hierarchical porosity having a large external surface can be obtained according to various methods known to those skilled in the art and for example according to the synthesis described by Inayat et al. (Angew Chem Int.Ed., (2012), 51, 1962-1965).
• the post-treatment processes generally consist in eliminating atoms of the zeolite network already formed, either by one or more acid treatments which dealuminate the solid, treatment (s) followed by one or more washing (s) to sodium hydroxide (NaOH) in order to eliminate the aluminum residues formed, as described for example by D. Verboekend et al. ⁇ Adv. Funct. Mater., 22, (2012), pp. 916-928), or else by treatments which combine the action of an acid and that of a structuring agent which improve the efficiency of the acid treatment, as described for example in the application WO2013 / 106816.
• the agglomeration and the shaping (step a) can be carried out according to all the techniques known to those skilled in the art, such as extrusion, compaction, agglomeration, and others.
• the proportions of agglomeration binder, optionally zeolitizable (see definition below) and zeolite (s) used are typically those of the prior art, that is to say from 5 parts to 20 parts by weight binder for 95 parts to 80 parts by weight of zeolite.
• the agglomerates resulting from stage a), whether in the form of beads, extrudates or the like, generally have a number average diameter (or their largest dimension when they are not spherical) between 0.degree. , 2 mm and 2 mm, and in particular between 0.2 mm and 0.8 mm and preferably between 0.2 mm and 0.65 mm.
• the finer agglomerates particles can be removed by cycloning and / or sieving and / or too large particles by sieving or crushing, in the case of extrudates, for example.
• the agglomeration binder used in step a) can be zeolitizable. It then contains at least 80% preferably, at least 90%, more preferably at least 95%, more particularly at least 96%, by weight, of zeolitic clay and may also contain other inorganic binders such as bentonite, attapulgite, and others.
• zeolitizable clay is meant a clay or a mixture of clays which are capable of being converted into zeolite material (that is to say, active material in the sense of adsorption), most often by action of a basic alkaline solution.
• Zeolizable clay generally belongs to the family of kaolin, kaolinite, nacrite, dickite, halloysite and / or metakaolin. Kaolin is preferred and most commonly used.
• clays such as in particular sepiolite or attapulgite may also be used.
• the clays can be used in their raw state or may be previously subjected to one or more treatments, for example selected from calcination, acid treatment, chemical modification, and others.
• the zeolite X powder used in step a) can be derived from the synthesis of zeolite X crystals comprising predominantly, see only sodium cations, for example NaX zeolites, but we would not go outside the box. of the invention using a powder having undergone one or more cationic exchanges, after its synthesis and before its implementation in step a).
• one or more additives may also be added, for example additives intended to facilitate the agglomeration or to improve the hardening of the formed agglomerates such as lignin, starch, carboxymethylcellulose, and other additives known to those skilled in the art.
• Silica can also be added.
• the possible source of silica may be of any type known to those skilled in the art, specialist in the synthesis of zeolites, by example of colloidal silica, diatoms, perlite, fly ash in English, sand, or any other form of solid silica.
• step a After drying in step a), the calcination is conducted at a temperature generally between 500 ° C and 600 ° C.
• this step makes it possible to transform the zeolite clay, typically kaolin, into metakaolin which can after being converted into zeolite during the zeolitization step (step b)) .
• the principle is set forth in D.W. Breck's "Zeolite Molecular Sieves," John Wiley and Sons, New York, (1973), p. 314-315.
• the zeolitization of the agglomeration binder is carried out according to any method known to those skilled in the art and may for example be carried out by immersion of the product of step a) in an alkaline basic solution, generally aqueous, for example an aqueous solution of sodium hydroxide and / or potassium hydroxide.
• an alkaline basic solution generally aqueous, for example an aqueous solution of sodium hydroxide and / or potassium hydroxide.
• the concentration of the alkaline zeolitization solution is preferably between 0.5M and 5M.
• the zeolitization is preferably carried out hot, at a temperature above room temperature, and typically at room temperature. temperatures of the order of 80 ° C to 100 ° C, for example between room temperature (about 20 ° C) and the boiling temperature of the alkaline solution of zeolitization.
• the duration of the zeolitization process is generally between a few tens of minutes and a few hours, preferably between about 1 hour and 8 hours.
• Steps c) and d) of barium and / or potassium exchange of the zeolite X cations are carried out according to the conventional methods known to those skilled in the art, and most often by contacting the agglomerates from step a) or step b) with a salt, such as barium chloride (BaCl 2 ) for barium exchange and / or potassium chloride (KCl) for exchange at potassium, in aqueous solution at a temperature between room temperature and 100 ° C, and preferably between 80 ° C and 100 ° C.
• a salt such as barium chloride (BaCl 2 ) for barium exchange and / or potassium chloride (KCl) for exchange at potassium
• one or more ion exchange (s) are made using solutions aqueous solutions of barium ions and aqueous solutions of potassium ions, for example potassium chloride and barium chloride, at concentrations typically between 0.05 M and 1.5 M, preferably between 0.1 M and 1 M , 2 M.
• at least one ion exchange is carried out using an aqueous solution of barium ions and potassium ions (corresponding to step c)).
• step d) of the method of the invention is not performed. This embodiment is the preferred mode.
• At least one ion exchange is first carried out using an aqueous solution of barium ions (corresponding to step c)), then at least one ion exchange is carried out in using an aqueous solution of potassium ions (corresponding to step d)).
• At least one ion exchange is first carried out using an aqueous solution of potassium ions (corresponding to step c)), then at least one ion exchange is carried out in using an aqueous solution of barium ions (corresponding to step d)).
• Each exchange step can be performed one or more times.
• the exchange or exchanges are carried out according to the techniques well known to those skilled in the art, for example at temperatures between room temperature (ie about 20 ° C) and 100 ° C, preferably between 80 and 100 ° C, generally at atmospheric pressure, the exchange or exchanges being generally carried out for periods ranging from a few minutes to a few hours, preferably typically between 30 minutes and 3 hours.
• the adjustment of the molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0) is carried out according to any methods known to those skilled in the art, and for example by exchanging with a large excess of barium ions so to obtain rapidly low levels of sodium oxide Na 2 0, ie less than 1%, preferably less than 0.3%, and then performing an exchange with an aqueous solution of potassium ions containing the necessary molar amount of potassium ions to obtain the desired molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0).
• step a) it is also possible to agglomerate in step a) of the zeolite X powder already containing potassium ions (pre-exchange of the cations present in the starting zeolite X, typically sodium cations, by potassium ions before step a)) and free or not potassium exchanges in steps c) and / or d).
• the activation which follows the drying is carried out in a conventional manner, according to the methods known to those skilled in the art, for example at a temperature in general of between 100 ° C. and 400 ° C., preferably between 200 ° C. C and 300 ° C.
• This step f) The purpose of the activation is to set the optimum water content and loss of the adsorbent for the intended use.
• thermal activation is carried out preferably between 200 ° C and 300 ° C for a predetermined period depending on the desired water content and loss on fire, typically 1 to 6 hours.
• the invention relates in particular to a process for recovering para-xylene at high purity from aromatic isomer cuts with 8 carbon atoms comprising the use, as para-xylene adsorption agent, of a zeolite adsorbent according to the invention, implemented in processes in the liquid phase but also in the gas phase.
• para-xylene of high purity we mean a product suitable for use in the production of terephthalic acid or dimethyl terephthalate, that is to say a purity of at least 99.5% by weight, preferably at at least 99.7% by weight, preferably at least 99.8% by weight and more preferably at least 99.9% by weight.
• the purity of para-xylene can be determined by chromatographic methods.
• a gas chromatographic method that can be used both for determining the purity of para-xylene and specific amounts of impurities is ASTM Method D-3798.
• the process for recovering para-xylene according to the invention using the adsorbent described according to the invention has the advantage of maximizing productivity but also of minimizing the operating costs of the process, that is to say both to maximize the load flow to be treated and to minimize the desorbent flow required. This is particularly true under the following simulated countercurrent industrial adsorption unit operating conditions: • number of beds: 6 to 30,
• Desorbent / charge flow ratio between 0.7 and 2.5, for example between 0.9 and 1.8, for a single adsorption unit (stand alone) and between 0.7 and 1.4 for a unit. adsorption combined with a crystallization unit,
• Recycling rate i.e. ratio of the average recycling rate (average of zone flow weighted by the number of beds per zone) to the load flow rate) between 2.5 and 12, preferably between 3.5 and 6.
• the desorption solvent may be any desorbent known to those skilled in the art and whose boiling point is lower than that of the filler, such as toluene but also a desorbent whose boiling point is greater than that of the feed, such as para-diethylbenzene (PDEB).
• PDEB para-diethylbenzene
• the selectivity of the adsorbents according to the invention for the adsorption of para-xylene contained in C8 aromatic cuts is optimal when their loss on ignition measured at 950 ° C. is generally between 4.0% and 7.7%. and preferably between 4.5% and 6.5%, and very preferably between 4.8% and 6.0%.
• the estimation of the number average diameter of the zeolite X crystals used in step a) and the zeolite X crystals contained in the agglomerates is carried out by observation under a scanning electron microscope (SEM) or by microscopic observation. transmission electronics (MET).
• SEM scanning electron microscope
• MET transmission electronics
• An elemental chemical analysis of the final product obtained at the end of steps a) to f) described above, can be carried out according to various analytical techniques known to those skilled in the art. Among these techniques, mention may be made of the technique of chemical analysis by X-ray fluorescence as described in standard NF EN ISO 12677: 201 1 on a wavelength dispersive spectrometer (WDXRF), for example Tiger S8 of the Bruker company.
• WDXRF wavelength dispersive spectrometer
• X-ray fluorescence is a non-destructive spectral technique exploiting the photoluminescence of atoms in the X-ray domain to establish the elemental composition of a sample.
• the excitation of the atoms generally by an X-ray beam or by bombardment with electrons, generates specific radiations after return to the ground state of the atom.
• the X-ray fluorescence spectrum has the advantage of relying very little on the chemical combination of the element, which offers a precise determination, both quantitative and qualitative. A measurement uncertainty of less than 0.4% by weight is obtained conventionally after calibration for each oxide.
• the barium, silicon, and aluminum contents are preferably measured by the X-ray fluorescence method described above.
• ICP-OES inductively coupled plasma
• ICP is a method of analysis by atomic emission spectrometry whose source is a plasma generated by inductive coupling. This method is also commonly used to determine the contents of various elements such as silicon, aluminum, potassium, sodium and barium.
• the sodium and potassium contents are preferably measured by the ICP method according to the UOP 961-12 standard.
• the sodium an uncertainty of less than 0.01% is obtained for the content by weight of the sodium oxide in the adsorbent and for potassium an uncertainty on the measurement of less than 0.02% for the content by weight of the potassium oxide in the adsorbent.
• the quality of the ion exchange is related to the number of moles of sodium oxide, Na 2 0, remaining in the zeolite agglomerate after exchange. More specifically, the exchange rate by the barium ions is determined by the ratio between the number of moles of barium oxide, BaO, and the number of moles of the whole (BaO + K 2 0 + Na 2 0). . Similarly, the exchange rate by the potassium ions is determined by the ratio between the number of moles of potassium oxide, K 2 0, and the number of moles of the whole (BaO + K 2 0 + Na 2 0). BaO, K 2 0 and Na 2 0 are expressed as oxides.
• the total exchange rate by barium and potassium ions is estimated from the sum of the two exchange rates described above, corresponding to the ratio between the sum of the number of moles of barium oxide and potassium oxide (BaO + K 2 0) and the number of moles of the group (BaO + K 2 0 + Na 2 0). It should be noted that the contents of various oxides are given in percentage by weight relative to the total weight of the anhydrous zeolite adsorbent. In the description of the present invention, the measurement uncertainty on the molar ratio K 2 0 / (K 2 O + BaO + Na 2 0) is 0.3%.
• the determination of the number average diameter of the zeolite adsorbents obtained at the end of step a) of agglomeration and shaping is carried out by analysis of the particle size distribution of an agglomerate sample by imaging according to ISO 13322-2: 2006, using a treadmill that allows the sample to pass in front of the camera lens.
• the number average diameter is then calculated from the particle size distribution by applying the ISO 9276-2: 2001 standard.
• the term "average number diameter” or "size” is used for zeolite agglomerates.
• the accuracy is of the order of 0.01 mm for the agglomerate size range of the invention.
• SMS1471 -74 series Shell Method Series SMS1471 -74 Determination of Bulk Crushing Strength of Catalysts, Compression-Sieve Method "), associated with the" BCS Tester "apparatus marketed by Vinci Technologies, this method initially intended for characterization catalysts from 3 to 6 mm is based on the use of a screen of 425 ⁇ which will allow in particular to separate the fines created during the crash.
• the use of a 425 ⁇ sieve remains suitable for particles with a diameter greater than 1.6 mm, but must be adapted according to the particle size of the zeolitic adsorbents that are to be characterized.
• ASTM D7084-04 which also describes a method for measuring the catalyst bed crush strength ("Determination of Bulk Crush Strength of Catalysts and Catalyst Carriers") defines the passage of the sieve to be used as being equal to the half the diameter of the catalyst particles to be characterized. The method provides a preliminary step of sieving the sample of catalysts or adsorbents to be characterized. If an amount equal to 10% weight of the sample passes through the grid, a smaller pass screen will be used.
• the agglomerates of the present invention generally in the form of beads or extrudates, generally have a number average diameter or a length, ie the largest dimension in the case of non-spherical agglomerates, of between 0.2 mm. and 2 mm, and in particular between 0.2 mm and 0.8 mm and preferably between 0.2 mm and 0.65 mm. Therefore, a suitable screen such that less than 10% by weight of the sample passes through the grid during a prior sieving step is used in place of the 425 ⁇ sieve mentioned in the standard Shell method SMS1471 -74 .
• the measuring protocol is as follows: a 20 cm 3 sample of agglomerated adsorbents, previously sieved with the appropriate sieve and previously dried in an oven for at least 2 hours at 250 ° C. (instead of 300 ° C.) C mentioned in the standard Shell method SMS1471 -74), is placed in a metal cylinder of known internal section. An increasing force is imposed in stages on this sample by means of a piston, through a bed of 5 cm 3 of steel balls in order to better distribute the force exerted by the piston on the agglomerates of adsorbents (use balls of 2 mm diameter for particles of spherical shape of diameter strictly less than 1, 6 mm). The fines obtained at the different pressure levels are separated by sieving (with a suitable sieve) and weighed.
• the crush resistance in bed is determined by the pressure in megaPascal (MPa) for which the amount of cumulative fines passing through the sieve is 0.5% by weight of the sample. This value is obtained by plotting the mass of fines obtained as a function of the force applied on the adsorbent bed and by interpolating at 0.5% by mass of cumulated fines.
• the mechanical resistance to crushing in a bed is typically between a few hundred kPa and a few tens of MPa and generally between 0.3 MPa and 4 MPa. The accuracy is conventionally less than 0.1 MPa. Determination of zeolite fractions of zeolite adsorbents:
• the crystallinity of the agglomerates is also evaluated by measuring their microporous volume by comparing it with that of a suitable reference (100% crystalline zeolite under identical cationic treatment conditions or theoretical zeolite). This microporous volume is determined from the measurement of the gas adsorption isotherm, such as nitrogen, at its liquefaction temperature. Prior to adsorption, the zeolite adsorbent is degassed between 300 ° C. and 450 ° C. for a period of 9 hours to 16 hours, under vacuum (P ⁇ 6.7 ⁇ 10 -4 Pa).
• 77K nitrogen adsorption is then carried out on a Micromeritics ASAP 2010 M type apparatus, taking at least 35 measurement points at relative pressures of P / P 0 ratio between 0.002 and 1.
• the microporous volume is determined according to Dubinin and Rohskevitch from the obtained isotherm, applying the ISO 15901 -3: 2007 standard
• the microporous volume evaluated according to Dubinin and Rohskevitch is expressed in cm 3 of liquid adsorbate per gram of adsorbent. measurement is ⁇ 0.003.
• the loss on ignition is determined in an oxidizing atmosphere, by calcination of the sample in air at a temperature of 950 ° C. ⁇ 25 ° C., as described in standard NF EN 196-2 (April 2006). The standard deviation of measurement is less than 0.1%.
• the technique used to characterize the adsorption of molecules in liquid phase on a porous solid is the so-called drilling technique, described by Ruthven in “Principles of Adsorption and Adsorption Processes” (Chapters 8 and 9, John Wiley & Sons, 1984) which defines the technique of breakthrough curves as the study of the response to the injection of a step of adsorbable constituents.
• the analysis of the average time of exit (first moment) of the drilling curves provides information on the adsorbed quantities and also makes it possible to evaluate the selectivities, that is to say the separation factor, between two adsorbable constituents.
• the injection of a non-adsorbable component used as a tracer is recommended for the estimation of non-selective volumes.
• a homogeneous mixture is prepared and 800 g of NaX zeolite crystals are agglomerated according to the procedure described in the patent application FR 2 999 098 (synthesis of Example B) with 105 g of kaolin (expressed as calcined equivalent). and 45 g of colloidal silica sold under the trade name Klebosol ® 30 (containing 30% by weight of Si0 2 and 0.5% Na 2 0) with the amount of water which allows the extrusion of the mixture. The extrudates are dried, crushed so as to recover grains whose number average diameter is equal to 0.5 mm, and then calcined at 550 ° C. under a stream of nitrogen for 2 hours.
• agglomerates obtained 200 g are placed in a glass reactor equipped with a controlled double jacket at a temperature of 100 ° C. ⁇ 1 ° C., and then 1.5 L of an aqueous solution of hydroxide is added. of 2.5 M sodium concentration and the reaction medium is left stirring for a period of 4 hours.
• the agglomerates are washed in 3 successive operations of washing with water followed by the emptying of the reactor.
• the effectiveness of the washing is ensured by measuring the final pH of the washings between 10.0 and 10.5.
• the sodium cations of the agglomerates obtained are exchanged with barium and potassium ions using an aqueous solution of 0.5M potassium chloride and barium chloride at 95 ° C in 4 steps.
• the concentrations of potassium chloride and barium chloride in the solution are adapted in order to reach the targeted barium and potassium contents in the adsorbent and thus the K 2 0 / (K 2 0 + BaO + Na 2 0 molar ratios. ) referred to ( Figure 1).
• the molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0) of 12.0% is achieved with an aqueous solution of barium chloride of 0.36 M concentration and 0 concentration potassium chloride.
• the volume ratio of solution to mass of solid is 20 ml / g and the exchange is continued for 3 hours each time. Between each exchange, the solid is washed several times in order to rid it of excess salt. The agglomerates are then dried at 80 ° C for 2 hours and finally activated at 250 ° C for 2 hours under a stream of nitrogen. [00104]
• the measured loss on ignition, as described above, is 5.6% ⁇ 0.1% for each sample.
• the barium-potassium exchange rate of the agglomerates calculated from elemental analyzes of barium and sodium oxides by X-ray fluorescence as described in the characterization techniques is 99.7 ⁇ 0.2%.
• the content of sodium oxide Na 2 0 is 0.05% by weight relative to the total weight of the adsorbent
• the content of barium oxide BaO is 33.83% by weight relative to the total weight of the adsorbent
• the content of K 2 0 potassium oxide is 2.85% by weight relative to to the total weight of the adsorbent
• a drilling test (frontal chromatography) is then performed on the agglomerates obtained in Example 1 to evaluate their effectiveness.
• the amount of adsorbent used for this test is about 30 g.
• the pressure is sufficient for the charge to remain in the liquid phase, ie 1 MPa.
• the adsorption temperature is 175 ° C.
• the composition of the load used for the tests is as follows:
• This equation 8 refers to the adsorptivity K, of the various constituents, as well as to the parameter 3 ⁇ 4 of each section j defined by equation 7:
• the binary selectivity a i / k between the compounds i and k is equal to the ratio of the adsorptivities K, / K k .
• the reduced flow rate of each section of the unit is defined as the ratio of the flow rate of the liquid phase to the flow rate of the adsorbed phase. Equation 8 indicates which flow rates are reduced for each section.
• the feed rate corresponds to the difference between the flow rate in zone 3 and the flow rate in zone 2
• the desorbent flow rate corresponds to the difference between the flow rate in zone 1 and the flow in zone 4.
• a high performance adsorbent is that which allows both to maximize the flow rate of the feedstock to be treated and to minimize the necessary desorbent flow rate.
• the composition of the liquid phase which gives the strongest stress in zone 2 and in zone 3 is the composition of the liquid phase at the point of injection of the charge into unit. Indeed, from this point the concentration of para-xylene, which is the most adsorbed compound, increases in the direction of circulation of the solid in zone 2, and decreases in the direction of circulation of the liquid in zone 3. to approximate the composition of this point to the composition of the charge to be treated, and it is this composition that will be used to evaluate the term ⁇ 2 and ⁇ 3 of equation 8.
• the terms ⁇ 2 and ⁇ 3 being defined by the equation 7 mentioned above.
• the composition of the liquid phase which gives the strongest stress in zone 1 and in zone 4 is the composition of the liquid phase at the desorbent injection point in the unit . At this point, the liquid phase essentially contains desorbent.
• the reduced flow rate min (m De ) is calculated from the binary selectivity values measured experimentally.
• the ratio between max (m ch arge) and min (m D és) allows at the same time to maximize the productivity and minimize the operating costs of the paraxylene separation process contained in the C8 aromatic cuts.
• the ratio of reduced flows between max (m Ch arge) and min (m De ) is plotted against the molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0) ( Figure 1). It can be seen that the ratio max (m Ch arge) / min (m De ) is improved for a molar ratio K 2 0 / (K 2 0 + BaO + Na 2 0) of between 9.5% and 14.5 %.

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