EP0791642A1 - Reinigungsverfahren für paraffinische Fraktion - Google Patents

Reinigungsverfahren für paraffinische Fraktion Download PDF

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Publication number
EP0791642A1
EP0791642A1 EP97400307A EP97400307A EP0791642A1 EP 0791642 A1 EP0791642 A1 EP 0791642A1 EP 97400307 A EP97400307 A EP 97400307A EP 97400307 A EP97400307 A EP 97400307A EP 0791642 A1 EP0791642 A1 EP 0791642A1
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EP
European Patent Office
Prior art keywords
ratio
faujasite
zeolites
less
zeolite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97400307A
Other languages
English (en)
French (fr)
Other versions
EP0791642B1 (de
Inventor
Dominique Plee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Carbonisation et Charbons Actifs CECA SA
Original Assignee
Carbonisation et Charbons Actifs CECA SA
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Publication of EP0791642A1 publication Critical patent/EP0791642A1/de
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Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • the invention relates to the separation of hydrocarbons and more particularly to a process for purifying a hydrocarbon fraction of the aromatic compounds which it contains. More specifically, the invention deals with the possibility of carrying out the cited operation by adsorption on a molecular sieve. Its more specific object is the purification of normal paraffin sections containing aromatic compounds as impurities. It is of primary importance that normal paraffins which are widely used chemicals are as pure as possible with regard to their aromatic content.
  • the paraffins in question constitute the basis for synthesizing detergent molecules such as alkylsulfonates or alkylarylsulfonates. Apart from this use in the detergency industry, paraffins have various uses as solvents or as chemical intermediates, for example, in aromatization or alkylation reactions.
  • paraffins are often polluted by aromatic compounds is to be sought in the fact that they are produced from gasoline, kerosene or diesel fuel cuts formed from very different molecules among which we can cite aromatic compounds, naphthenic compounds , olefinic type compounds or linear or branched saturated compounds.
  • US Patent 3,969,223 discloses a method of separating an olefin from a mixture of hydrocarbons consisting of olefins and saturated compounds using a type X zeolite treated for a certain time in a solution of soda then washed; the aim of this treatment is to extract a small fraction of the silica and the alumina present in the sieve or in the agglomeration binder (consisting of silica, alumina or by a silica-alumina) and, as an alleged side effect, to bring the ratio NA 2 O / Al 2 O 3 as close to 1 as possible.
  • Another method of separating hyrocarbons relates to the adsorption on activated carbon or carbon molecular sieve of 1,3-butadiene from a mixture comprising at least one other C4 hydrocarbon and is described in US 4,567,309 in the name of UOP.
  • the following pairs are cited: 1,3-butadiene / n-butane; 1,3-butadiene / isobutylene; 1,3-butadiene / trans-butene or 1,3-butadiene / cis-butene.
  • zeolites are capable of selectively fixing certain molecules. In some cases, the selectivity is practically total, which means that in a mixture of two types of molecules, one can be almost completely adsorbed and the other, almost completely excluded: it is this property that has earned zeolites the term molecular sieves and which follows from the fact that zeolites are, in the majority of cases, crystalline aluminosilicates formed by the condensation of silica tetrahedra and alumina tetrahedra by means of bridging oxygen. The arrangement of these species in space requires the provision of pores and cavities whose dimensions are particularly uniform. Only molecules whose size is smaller than the diameter of the pore will be able to penetrate into the crystal and adsorb.
  • the pores vary between around 3 and 8 Angstroms (0.3 to 0.8 nm) depending on the types of zeolites, but for a given zeolite, the pores have a perfectly calibrated size.
  • a description of these products can be found in "Molecular Sieves Zeolites" by D.W. BRECK, John Wiley and Sons, 1974.
  • zeolites endowed with molecular sieve properties and which are used for this purpose, mention may be made of products of natural origin such as clinoptilolite, chabazite, mordenite, erionite or products of origin synthetic such as type A zeolites (LTA in the international classification), type X or Y zeolites (FAU in the international classification), pentasil type zeolites (MFI or MEL).
  • Other products also exist which have molecular sieving properties but whose use rather covers catalysis, such as zeolites of the offretite (OFF), omega (MAZ), ferrierite (FER) or mordenite (MIR) type.
  • zeolites of the faujasite type to which the X and Y belong, are very often used because of their large pore volume and the pore size which allows the penetration of relatively large molecules such as aromatics, or even polyaromatics.
  • the interest of these solids is based on the fact that the Si / Al ratio can be varied in large proportions, which modifies, sometimes considerably, the interactions between molecules and crystal or within the structure.
  • type X zeolites whose pores have an opening of 8 Angstroms (0.8 nm) demonstrate a strong affinity for species such as n-dodecylbenzene, naphthalene or dibenzothiophene compared to molecules, either paraffinic or naphthenic (see in this regard SATTERFIELD CN and CHEN, CS AichE Journal, vol. 18, N ° 4, p. 720, 1972, or AHMETOVIC D. and SVEL-CEROVECKI S., Zeolites, Synthesis, Technology and Applications, 1985, p. 683).
  • the adsorbents used until now for the elimination of aromatic compounds are therefore molecular sieves of the faujasite type which are commonly called in the profession 13X or 10X.
  • These materials constituted by the arrangement of tetrahedrons of silicon oxide and aluminum oxide have a negative electric charge due to the presence of aluminum, trivalent element, in substitution of silicon, tetravalent element.
  • the charge in question is compensated by a cation, generally chosen from alkaline elements or alkaline earth elements; these cations are naturally hydrated in the cavities of the zeolite and can be exchanged by simple contact of the latter with a solution of another cation, in the form of chloride, nitrate, oxyalate, acetate, sulfate.
  • the 13X or 10X molecular sieves refer to faujasites whose Si / Al ratio is between 1.2 and 1.5, the usual range of composition for these products.
  • the designation 13X refers more particularly to a solid whose compensating cation is sodium and the designation 10X to a solid whose compensating cation is calcium.
  • the Si / Al ratio (for values greater than 2.5) could have an importance in the selectivity between aromatics and paraffins, it can be seen from reading the industrial property documents, that the adsorbents used are very generally 13X zeolites, 10X zeolites or Y zeolites whose Si / Al ratio is between 1.5 and 3; curiously the domain of ratios lower than 1.2 has not been explored for this application.
  • the faujasites which are the means of the invention are used in the form of beads or granules. We prefer small diameter balls (0.5 - 1 mm).
  • the industrial treatment is preferably carried out by percolation on columns, which makes it possible to regulate the conditions for obtaining paraffins with the degree of purity that is desired, possibly at aromatic contents undetectable by ordinary means of the analysis. Faujasites saturated with aromatic compounds can be regenerated according to methods well known to those skilled in the art.
  • the paraffinic sections resulting from the MOLEX separation processes benefit particularly from the treatment according to the invention.
  • a zeolite of the faujasite type and an Si / Al ratio equal to 1 according to Example 1 of FR-A-2,669,242 (CECA SA) is synthesized in which a gel of composition is prepared: 4.87 Na 2 O 1.63 K 2 O-2SiO 2 -Al 2 O 3 -H 2 O which is subjected first of all to a ripening of about twenty hours at 50 ° C. and then to a crystallization of 4 hours at 100 ° C. The crystals after filtration and washing are identified by X-ray diffraction as being made up of pure faujasite.
  • the solid thus obtained is exchanged with calcium or with lithium by making several contacts with molar solutions of these salts, at a temperature of the order of 70 ° C.
  • the solids thus exchanged are then calcined at 550 ° C for 2 hours under an atmosphere of dry nitrogen, then stored away from air. Simultaneously, the calcination of a 13X zeolite from CECA SA marketed under the same conditions is carried out.
  • the 13X and FAU 1 zeolites exchanged with calcium (called respectively CaX and CaFAU 1) are brought into contact with the mother solution under the conditions already described.
  • the 13X zeolites exchanged with potassium and barium (also called KX and BaX respectively) are also brought into contact with the mother solution.
  • the selectivity results are reported in the table below: Adsorbent Selectivity CaX 610 KX 500 BaX 360 CaFAU1 1200

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Steroid Compounds (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Saccharide Compounds (AREA)
EP97400307A 1996-02-21 1997-02-11 Reinigungsverfahren für paraffinische Fraktion Expired - Lifetime EP0791642B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9602151A FR2745006B1 (fr) 1996-02-21 1996-02-21 Procede de purification d'une coupe paraffinique
FR9602151 1996-02-21

Publications (2)

Publication Number Publication Date
EP0791642A1 true EP0791642A1 (de) 1997-08-27
EP0791642B1 EP0791642B1 (de) 2000-12-27

Family

ID=9489443

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97400307A Expired - Lifetime EP0791642B1 (de) 1996-02-21 1997-02-11 Reinigungsverfahren für paraffinische Fraktion

Country Status (12)

Country Link
US (1) US5731488A (de)
EP (1) EP0791642B1 (de)
JP (1) JP3855137B2 (de)
KR (1) KR100443293B1 (de)
CN (1) CN1102637C (de)
AT (1) ATE198347T1 (de)
CA (1) CA2197899C (de)
DE (1) DE69703757T2 (de)
DK (1) DK0791642T3 (de)
ES (1) ES2153166T3 (de)
FR (1) FR2745006B1 (de)
GR (1) GR3035433T3 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2767524B1 (fr) * 1997-08-21 1999-09-24 Ceca Sa Procede ameliore d'obtention de paraxylene a partir de coupes de c8 aromatiques
US6274207B1 (en) 1999-05-21 2001-08-14 The Board Of Regents, The University Of Texas System Method of coating three dimensional objects with molecular sieves
US6287645B1 (en) 1999-05-21 2001-09-11 Board Of Regents, The University Of Texas System Preparation of laser deposited oriented films and membranes
MY157216A (en) * 2009-04-24 2016-05-13 Sasol Chemical Ind Ltd Waxes
CN113702131A (zh) * 2021-09-06 2021-11-26 海南大学 一种油茶花芽的石蜡切片及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0164905A1 (de) * 1984-05-11 1985-12-18 Kuwait Institute For Scientific Research Reinigung flüssiger Paraffine
FR2669242A1 (fr) * 1990-11-16 1992-05-22 Ceca Sa Adsorbants industriels a base de zeolites x a basse teneur en silice pour la separation non cryogenique des gaz de l'air et leur procede de preparation.

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2988502A (en) * 1957-04-26 1961-06-13 Exxon Research Engineering Co High efficiency hydrocarbon separation process employing molecular sieve adsorbents
NL297661A (de) * 1962-09-12
US3278422A (en) * 1965-08-23 1966-10-11 Exxon Research Engineering Co Process for improving stability
US3723561A (en) * 1971-12-01 1973-03-27 Universal Oil Prod Co The selective separation of butene-1 from a c{11 {11 hydrocarbon mixture employing zeolites x and y
US3969223A (en) * 1973-12-10 1976-07-13 Universal Oil Products Company Olefin separation process
US4567309A (en) * 1984-05-29 1986-01-28 Uop Inc. Separation of 1,3-butadiene
US5220099A (en) * 1988-08-31 1993-06-15 Exxon Chemical Patents Inc. Purification of a hydrocarbon feedstock using a zeolite adsorbent
US5171923A (en) * 1988-08-31 1992-12-15 Exxon Chemical Patents Inc. Recycle for process for purification of linear paraffins
US5198102A (en) * 1991-07-15 1993-03-30 Exxon Research And Engineering Company Benzene removal from a heartcut fraction of gasoline boiling range streams

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0164905A1 (de) * 1984-05-11 1985-12-18 Kuwait Institute For Scientific Research Reinigung flüssiger Paraffine
FR2669242A1 (fr) * 1990-11-16 1992-05-22 Ceca Sa Adsorbants industriels a base de zeolites x a basse teneur en silice pour la separation non cryogenique des gaz de l'air et leur procede de preparation.

Also Published As

Publication number Publication date
ATE198347T1 (de) 2001-01-15
KR100443293B1 (ko) 2004-10-14
FR2745006B1 (fr) 1998-04-03
JP3855137B2 (ja) 2006-12-06
DE69703757T2 (de) 2001-05-23
ES2153166T3 (es) 2001-02-16
JPH09235565A (ja) 1997-09-09
CN1167809A (zh) 1997-12-17
FR2745006A1 (fr) 1997-08-22
CN1102637C (zh) 2003-03-05
CA2197899A1 (fr) 1997-08-22
EP0791642B1 (de) 2000-12-27
KR970061305A (ko) 1997-09-12
DK0791642T3 (da) 2001-04-17
CA2197899C (fr) 2001-08-07
GR3035433T3 (en) 2001-05-31
US5731488A (en) 1998-03-24
DE69703757D1 (de) 2001-02-01

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