CA2095333A1 - Process for producing isopropyl naphthaline - Google Patents
Process for producing isopropyl naphthalineInfo
- Publication number
- CA2095333A1 CA2095333A1 CA002095333A CA2095333A CA2095333A1 CA 2095333 A1 CA2095333 A1 CA 2095333A1 CA 002095333 A CA002095333 A CA 002095333A CA 2095333 A CA2095333 A CA 2095333A CA 2095333 A1 CA2095333 A1 CA 2095333A1
- Authority
- CA
- Canada
- Prior art keywords
- naphthalene
- reaction
- dipn
- zeolites
- mipn
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/20—Polycyclic condensed hydrocarbons
- C07C15/24—Polycyclic condensed hydrocarbons containing two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Abstract of the Disclosure Process for the preparation of isopropylnaphthalene A process for the preparation of isopropylnaphthalene by the alkylation of naphthalene with the aid of catalysts, wherein the catalysts used are EU-1 zeolites.
Description
~933~
Wo 92/07810 PCT~EP91/01951 Description Process for the preparntion of isopropylnaphthalene The pre~ent invention relatec to a proce~s for the preparation of i~opropylnaphthalene by the alkylation of naphthalene with EV-1 zeolites as catalysts, only ~mall amounts of diisopropylnaphthalenes being formed.
Wo 92/07810 PCT~EP91/01951 Description Process for the preparntion of isopropylnaphthalene The pre~ent invention relatec to a proce~s for the preparation of i~opropylnaphthalene by the alkylation of naphthalene with EV-1 zeolites as catalysts, only ~mall amounts of diisopropylnaphthalenes being formed.
2-(Mono)isopropylnaphthalene (2-MIPN) i8 a valuable intermediate for the preparation of 2-naphthol by the Hock process. 2-Naphthol i8 normally prepared by the sulfonstion of naphthalene in the 2-position, followed by saponification of the Na salt of the naphthalenesulfonic acid in a ~odium hydroxide melt. A larqe ~mount of salts i8 obtain~d in this proce3s. The Hock procass substantially avoids this disadvantage.
Apart from 2-MIPN, 2,6-dii~opropylnaphthalene (2t6- DIPN) is alRo a valuable intermediate for many highly refined products. Thus it i8 used inter alia as a starting material for the preparation of naphthalene-2,6-dicarboxylic acid, 2,6-dihydroxynaphthalene and 6-hydroxynaphthalene-2-carboxylic acid. These compounds are used as monomers for high-performance polymers.
In practice, the demand for 2-MIPN is considerably greater than for 2,6-DIPN because of the comparatively large amount of 2-naphthol produced. It iB therefore desirable to direct th~ alkylation of naphthalene 80 that, with a high degree of conversion, a large proportion of ~IPN and a ~mall proportion of DIPN are formed.
It is known to use a very wide variety of acid catalysts for the alkylation of naphthalene to MIPN and also DIPN.
When the alkylation iB carried out with Friedel-~rafts catalysts such as AlClt or BF3, 8alt8 are formed on 2~333 wo 92/07810 - 2 - PCT/EP31J01951 working-up and ~he catalyst t 8 ~d~stroyed. ~oreover, resi~ous compounds, which imp~de t:he working- up, ~r~
formed in the ~ourse of the reaction. Separation of the products from the c~talyst is generally expensive. For 5 some tLme ~ ~ttsmptB have therefore been made to replace catalysts of this ~ype with solid acids.
German patent 2 644 624 de~cxibes a process for the preparation of 2-MIPN using P2O5/SiO2. Here the naphthalene has to be used in large excess in ordsr to prevent the form~tion of polyalkylated products. In addition, the unreacted naphthalene hAs to be ~eparated off and recycled into the alkylation. Again, when using acid-activated montmorillonite (German Offenlegung~schrift 2 20B 363) or perfluorinated sulfonic acid resins (US patent 4 288 646), the naphthalene has to be used in e~cess in order to prevent the formation of large amounts of polyalkylated products. The low degree of conversion of the naphthalene in all these processes represents a considerable di~advantage.
Acidic zeolites have also been used as catalyst6 for the alkylation of naphthalene. European patent application A-338 292 describes the reaction of naphthalene with propylene on dealuminized Y zeolites in the presence of decahydronaphthalene. At 220C ~nd with a naphthalene conversion of approx. 50~, the selectivity of this reaction is between 68 and 75% in re~pect of NIPN, between 24 and 30% in respect of DIPN and between 1.5 and 3~ in respect of triisopropylnaphthalenes (~IPN). In this process, the ratio MIPN/(DIPN + TIPN) is very low at 2 to 3.
In other studies, the possibility of ~hape-selective catalysis is utllized in the preparation of 2-alkyl- and 2,6-dialkyl-naphthalenes. Shape-selective catalysismeans that the dLmensions of the molecules or transition states participating in the reaction are of the same order of ~ ~3 J .) .~
wO 92/07810 - 3 - PCT~EP31/Olg51 ma~nitude as those of the cataly~t: pores. The course of the reaction c~n be influenced b~y ~teric forc~. Thus .g. in the alkyl~tion of naphthalene with methanol using zeolites of the ZS~-5 type, the ~ omer~ of low storic bulk (2-methyl- and 2,6- dLmethyl-naphthalen~) can be obtained with high selectivity (e.g. D. FrAenkel et ~1., J. Catsl. 101 (1986) 273-283, and European patent application ~A-280 055). However, the naphthalene conversion is llmited in these proce~es A8 well, becau&e the diffu~ion of the bulky molecule~ through the zeolite pores i~ greatly hindered.
The proce~s of European patent applica~ion A-317 907 u6ed a dealuminized mordenite zeolite for the alkyl8tion of naphthalene with propylene. A naphthalene converRion of 97.3~ was achieved. The yield of DIPN was 68%, including 50% of 2,6-DIPN. Nothing was said about the yi21d of MIPN
or the composition of thi~ fr~ction. A dealuminiæed mordenite zeolite i~ also used in the process of WO 90/03961 for the selective preparation of 2,6-DIPN. It is stated that, by virtue of this type of zeolite, the proportion of 2,6-DIPN in the DIPN fraction is greater than the proportion in thermodynamic equilibrium and that the ratio 2,6-/2,7- DIPN i8 greater than 1.2. Thus, for example, with a naphthalene conversion of 27~, the proportion of 2,6- DIPN i6 ~aid to be 70%, the ratio 2,6-/2,7-DIPN 3.0 and the ratio MIPN/tDIPN + TIPN) 5.1. If the conversion increa~es to 78%, the proportion of 2,6-DIPN drops to 624, the ratio 2,6-/2,7-DIPN to 2.6 and the ratio MIPN/ (DIPN + TIPN~ to 1.1. No information i8 given about the composition of the MIPN fraction.
These Example~ &how that mordenite catalysts strongly ~uppreqs the formation of MIPN in favor of DIPN as the naphthalene conversion increases.
The object of the present invention was to provide a process for the preparation of MIPN by the alkylation of ~9 i333 naphthalene which produces the min~lum possible ~mount of DIPN with a high naphthalene conversion.
Thi~ object is achieved according to the invention by the use of EU-l ~eolites as catalysts. In this proces~, monoalkylated product~ ars formed 1with high Relectivity and dialkylated compounds are only formed in minor amounts. This process hardly produces any more highly alkylated compound~ such as TIPN.
The invention now relates to a process for the preparation of isopropylnaphthalene by the alkylation o naphthalene with the aid of ca~alysts, wherein the catalysts used are EU-l zeQlites.
Zeolites are crystalline nluminosilicate~. Si and Al atoms arP tetrahedrally surrounded by O atoms. The tetrahedra are linked via common O atoms and form a crystalline structure through which defined pores and cavities pass tcf. D.W. Breck, Zeolite Molecular Sieves, John Wiley & Sons, (1974) p. 29-185). The zeolites of the EU-l type used according to the invention are characterized by a typical X-ray diffraction pattern, which is indicated in European patent ~pplication A-4~ 226. The pores in this zeolite are bounded by 10 O
atoms and have a width of 0.41 x 0.58 nm. They have lateral extensions formed by 12 O atoms. These bulges are 0.58 x O.68 nm wide and 0.81 nm deep (N.A. Briscoe et al., Zeolite6 B, (1988) 74-76).
It is surprising that this precise type of zeolite makes it possible to achieve the desired high selectivity in respect of the MIPNs and the low rate of formation of DIPN, since the use, described in European patent application A-317 907l of mordenite catalysts with pores of 0.67 x 0.70 nm, which are larger than those of EU-l zeolites, as well as the use of zeolites of the ZSM-5 type with somewhat narrower pore~ of 0.52 x O.55 nm and 2~ J j3,`~, O.54 x O.56 nm, result in the formation of ~ far greater proportion of DIPN.
The different selectivities of thes~ catalysts are compared in the Examples.
S The EU-l zeolites u~ed according to the invention can be prepared by known processes of hydrothermal synthesis (e.g. European patent application A-42 2263. ~lkylated polymethylenediamine6, preferably N,N,N,N',N',N' hexa-methyl-l,6-hexamethylenediammoniumbromide(hexamethonium brsmide), are u~ed as the template. An SiO2~Al2O3 ratio in the range from 10 to 150 can be obtained by direct synthesis, but higher SiO2/Al203 ratios can also be achieved by sub~eguent dealuminization. The aluminum content can be reduced in a variety of ways here. Some methods are described e.g. in J. Scherzer, Catalytic Materials, Relationship between Structure and Reac~ivity, ACS Symp. Ser. 248 (1984) 175-200. EU-1 zeolites with SiO2/Al2O3 ratios of between 15 and 200, preferably of between 20 and 100, are particularly ~uitable for the process according to the invention.
After crystallization, the zeolite is filtered off, washed, dried and then calcined in an oxidizing atmosphere, preferably in air, in order to remove the organic template from the pore~.
To convert the zeclite to a catalytically active form, any Nat ion~ pre3ent are exchanged by ion exchange with divalent or trivalent ions of the alkaline earth metals or rare earth metals of atomic number 57 to 71, or with ammonium ion~ or protons. Ion exchange with NH~t or H+ iB
particularly preferred. It i8 convenient here if at lea~t 50%, preferably at least 90%, of the lattice charges are compensated by ~aid other ions. The zeolite i8 then converted to the catalytically active form by dehydration tand deammoniation in the case of NH4t forms) at 200 to 2~3 '`3 ~O 92/07810 - 6 - PCT/EP91/01951 800~C, preferably at 40U and 550~C.
For the use according to the invention, the zeolites can advantageously be converted to ~ ~uitable applicatlon form, e.g. ~trand~, with the aid of binders. P~rticularly ~uitable binders ~re the oxides, hydroxides or hydroxychlorides o aluminum and the oxides of silicon, titanium and zirconium, as well a~ clay materials.
The alkyla~ion reaction can be carried out in the ga~
phase or, preferably, in the liquid phase. Example~ of alkylating agent~ which can be used are i-propyl bromide and chloride, propylene and i-propancl. In the ga~ phase reaction, it is preferable to react naphthalene with propylene or i-propanol. When the alkylation is carried out in the liquid phase, it is preferable to use propylene. ~he reaction temperature i8 conveniently between about 100 and 500C, preferably between about 150 and 300C. An elevated pressure favor~ the course of the alkylation, especially if the alkylating agent i6 propylene. ~he reaction can be carried out at reduced pressure, at atmospheric pressur~ or at an elevated pressure, e.g. of up to about 100 bar, preferably between about 2 and 20 bar.
The alkylation in the liquid phase can be carried out in any suitable apparatus, most 8imply in a stirred tank, with pulverulent catalyst suspended in molten naphthalene. The alkylating agent is then passed through the suspension or forced in under pressure up to the desired value, at the reaction temperature. The reaction is preferably carried out without a ~olvent, but solvents which are inert towards the reactants and catalysts, such as higher-boiling paraffins or naphthenes, may also be present. Inert gases such as nitrogen can also be used to attain the reaction pressure.
The process can be carried out continuously or batchwise.
~ i3~3~, wO 92/07810 - 7 - PCT/EP91~01951 In the batch procedure, it i8 favorable to use about O.S
to 50% by weight of catalyst, preferably about 1 to lO~
by weight, ba~ed on the weight of naphthalene u~ed. The reaction time can be between about half an hour ~nd several day~, especially between 2 and 10 h, depending on the reaction condition~ and th~ deEIired conver ion. When the reaction i~ complete, the zeolite c~n ea~ily be 6eparated from the reaction mixtur~, e.g. by filtration.
To carry out the reaction in the gas phase, it i8 possible in principle to u~e any apparatus sui~able for gas phase reactions. A fixed bed continuou~-flow reactor is ~echnicslly the ~imple~t to operate. The cataly~t can be introduced into the reactor in the form of pellet~, which can be prepared by compressing the ~eolite on its own or together with a binder such a~ Al203 or SiO2. The naphthalene can be metered into the reactor in the molten state or dis601ved in an inert 601vent and vaporized upstream of the catalyst bed, or can already be in the gaseous state when it i~ introduced into the reactor.
i-Propanol can be metered in the ~ame way as naphthalene.
Propylene i8 introduced in the gaseou state. The reactants can be used on their own or mixed with a gas which is inert towards the reaction, such as hydrogen or nitrogen. The reaction products are conden~ed after leaving the reactor.
The molar ratio of naphthalene to alkylatin~ agent i~
conveniently in the range from about 0.1 to 10, preferably from about 0.5 to 2.
The re~idence time of the reactants i8 generally between about O.OS and 20 B, preferably between 1 and 10 B . The loading (LHSV = liquid hourly ~pace velocity = ml of charge per ml of cataly~t volume and per hour~ can preferably be %et in the range from 0.1 to 5 h-1, the range from 0.5 to 2 h~l being particularly favorable.
2~9~33 ~
WO 92/07810 - 8 - PCT~EPgl/01951 The catalyst r~t~ins it~ activity over ~ long period and can be used ~everal tLme~ for the reaction. If it iB
deactivated, it can be regenerated by calcin~tion in an oxidizin~ stmosphere, preferably in air, at about 350 to 800JC, preferably at about 500 to 600~C.
The product mixture can initially be separated by distillation into unreacted naphthalene, MIPN, DIPN and TIPN. If desired, 2-MIPN can be separated from the MIPN
fraction by crystallization, if ppropriate from a solvent ~uch as methanol or i-prop~nol (see e.g. ~erm~n Offenlegungsschrift 2 517 591). The filtrate enriched in l-MIPN can be reconverted to R mixture rich in 2- MIPN by isomerization on various zeolites (see e.g. US pstent 4 026 959). 2,6-DIPN can similarly be separated from the DIPN fraction by crystallization (~ee e.g. European patent 216 009). An adsorptive separation is described e.g. in Japanese patent application 01 199 921. Together with naphthalene, the rest of the DIPN fraction, substantially freed of 2,6-DIPN, can be reconverted to MIPN by transalkylation.
The crude 2-MIPN and 2,6-DIPN can be further purified to the desired degree by conventional working-up processes.
Examples The EU-l zeolites used were ~ynthesized with different SiO2/Al2O3 ratios according to instructions from th~
literature (European patent 42 226, ~S patent 4 537 754, G.W. Dodwell et al., Zeolit~s 5 (1985) 153-157~. All zeolites are used in the proton form (ion exchange with NH4NO3 solution and subsequent calcination).
i and 2) The ~xample6 and the Comparative Examples C1 to C3 were carried out in a ~tirred tank. Before the reaction, the zeolite was dried for 1 h at 300~C and then ~u~pended in powder form in 128 g of molten naphthalene.
Propylene was passed through the suspension at 6.5 l/h (or ~t 12 l~h in Example 2) a~ atmo~pheric pres~ure. The reaction temperature wz~ 200C. The experimental results are collated in Table 1.
T~ble l Exa~ple Cl C2 C3 1 2 Zeoli~e ZSM-5 MORDENITE EU-l ~U-1 Naphthalene conversion, ~olX23 22 76 23 75 S~lectivities, molX
DIPN lO 11 44 5 32 MIPN/(DIPN+TIPN)7.3 8.1 1.219.0 1.6 A comparison of C1, C2 and Example 1 shows that the selectivity with which MIPN i8 formed i8 greatly increased by the u~e of EU-l zeolites when the naphthalene conversions are not too high; the results are also markedly improved for high conversion~ (comparison of C3 and Example 2).
3 to 5) The Example~ and the Comparative Example~ C4 to C7 were c~rrled out in ~ fixed bed continuou~-flow reactor at atmospheric preR~ure. The cataly~t was used in the form of ~trand~. EU-l was compre~sed with 21% by weigh~ of SiO2 8i; a binder and mordenite with 4û% of Al2O3. ZSM-5 wa~ compre~ed to tablets without a binder.
Naphthalene was metered into the reactor in the molten state. Propylene wa used in twice the molar amount.
After leaving the re~ctor, the reaction products were conden~ed at certain time intervals and analyzed by ga8 chromatography. The re~ults (where T = 280C, LHSV - 0 . 5 h-l (ba~ed on naphthalene), catalyst volume = 25 ml, quantity ratio of naphthalene to propylene = 1:2) are collated in Table 2.
3 ~
Tabl~ 2 Ex~ple 3 4 5 C4 C5 C6 C7 Zeolit~ EU-l MORDE~ITE ZSM-5 Time, h 1.1 2.1 5.11.23.1 7.1 2.1 S Nsphth~le~e conversion, molX 39 30 28 36 23 9 3 Selectivities, molX
MIPN 78 83 a4 64 71 85 53 MIPN/(DIPN+TIPN) 3.95.25.6 1.8 2.4 5.7 1.1 A comparison of Example~ 3 to 5 with Comparstive Examples C4 to C7 ~how~ that markedly higher naphthalene conversions are ~chieved after the ~ame times when using EU-l zeolites, this type of zeolite also being markedly superior in respect of the selectivity with which ~IPN is formed. ~oreover, the EU-l zeolites exhibit a lower deactivation after longer period~.
Apart from 2-MIPN, 2,6-dii~opropylnaphthalene (2t6- DIPN) is alRo a valuable intermediate for many highly refined products. Thus it i8 used inter alia as a starting material for the preparation of naphthalene-2,6-dicarboxylic acid, 2,6-dihydroxynaphthalene and 6-hydroxynaphthalene-2-carboxylic acid. These compounds are used as monomers for high-performance polymers.
In practice, the demand for 2-MIPN is considerably greater than for 2,6-DIPN because of the comparatively large amount of 2-naphthol produced. It iB therefore desirable to direct th~ alkylation of naphthalene 80 that, with a high degree of conversion, a large proportion of ~IPN and a ~mall proportion of DIPN are formed.
It is known to use a very wide variety of acid catalysts for the alkylation of naphthalene to MIPN and also DIPN.
When the alkylation iB carried out with Friedel-~rafts catalysts such as AlClt or BF3, 8alt8 are formed on 2~333 wo 92/07810 - 2 - PCT/EP31J01951 working-up and ~he catalyst t 8 ~d~stroyed. ~oreover, resi~ous compounds, which imp~de t:he working- up, ~r~
formed in the ~ourse of the reaction. Separation of the products from the c~talyst is generally expensive. For 5 some tLme ~ ~ttsmptB have therefore been made to replace catalysts of this ~ype with solid acids.
German patent 2 644 624 de~cxibes a process for the preparation of 2-MIPN using P2O5/SiO2. Here the naphthalene has to be used in large excess in ordsr to prevent the form~tion of polyalkylated products. In addition, the unreacted naphthalene hAs to be ~eparated off and recycled into the alkylation. Again, when using acid-activated montmorillonite (German Offenlegung~schrift 2 20B 363) or perfluorinated sulfonic acid resins (US patent 4 288 646), the naphthalene has to be used in e~cess in order to prevent the formation of large amounts of polyalkylated products. The low degree of conversion of the naphthalene in all these processes represents a considerable di~advantage.
Acidic zeolites have also been used as catalyst6 for the alkylation of naphthalene. European patent application A-338 292 describes the reaction of naphthalene with propylene on dealuminized Y zeolites in the presence of decahydronaphthalene. At 220C ~nd with a naphthalene conversion of approx. 50~, the selectivity of this reaction is between 68 and 75% in re~pect of NIPN, between 24 and 30% in respect of DIPN and between 1.5 and 3~ in respect of triisopropylnaphthalenes (~IPN). In this process, the ratio MIPN/(DIPN + TIPN) is very low at 2 to 3.
In other studies, the possibility of ~hape-selective catalysis is utllized in the preparation of 2-alkyl- and 2,6-dialkyl-naphthalenes. Shape-selective catalysismeans that the dLmensions of the molecules or transition states participating in the reaction are of the same order of ~ ~3 J .) .~
wO 92/07810 - 3 - PCT~EP31/Olg51 ma~nitude as those of the cataly~t: pores. The course of the reaction c~n be influenced b~y ~teric forc~. Thus .g. in the alkyl~tion of naphthalene with methanol using zeolites of the ZS~-5 type, the ~ omer~ of low storic bulk (2-methyl- and 2,6- dLmethyl-naphthalen~) can be obtained with high selectivity (e.g. D. FrAenkel et ~1., J. Catsl. 101 (1986) 273-283, and European patent application ~A-280 055). However, the naphthalene conversion is llmited in these proce~es A8 well, becau&e the diffu~ion of the bulky molecule~ through the zeolite pores i~ greatly hindered.
The proce~s of European patent applica~ion A-317 907 u6ed a dealuminized mordenite zeolite for the alkyl8tion of naphthalene with propylene. A naphthalene converRion of 97.3~ was achieved. The yield of DIPN was 68%, including 50% of 2,6-DIPN. Nothing was said about the yi21d of MIPN
or the composition of thi~ fr~ction. A dealuminiæed mordenite zeolite i~ also used in the process of WO 90/03961 for the selective preparation of 2,6-DIPN. It is stated that, by virtue of this type of zeolite, the proportion of 2,6-DIPN in the DIPN fraction is greater than the proportion in thermodynamic equilibrium and that the ratio 2,6-/2,7- DIPN i8 greater than 1.2. Thus, for example, with a naphthalene conversion of 27~, the proportion of 2,6- DIPN i6 ~aid to be 70%, the ratio 2,6-/2,7-DIPN 3.0 and the ratio MIPN/tDIPN + TIPN) 5.1. If the conversion increa~es to 78%, the proportion of 2,6-DIPN drops to 624, the ratio 2,6-/2,7-DIPN to 2.6 and the ratio MIPN/ (DIPN + TIPN~ to 1.1. No information i8 given about the composition of the MIPN fraction.
These Example~ &how that mordenite catalysts strongly ~uppreqs the formation of MIPN in favor of DIPN as the naphthalene conversion increases.
The object of the present invention was to provide a process for the preparation of MIPN by the alkylation of ~9 i333 naphthalene which produces the min~lum possible ~mount of DIPN with a high naphthalene conversion.
Thi~ object is achieved according to the invention by the use of EU-l ~eolites as catalysts. In this proces~, monoalkylated product~ ars formed 1with high Relectivity and dialkylated compounds are only formed in minor amounts. This process hardly produces any more highly alkylated compound~ such as TIPN.
The invention now relates to a process for the preparation of isopropylnaphthalene by the alkylation o naphthalene with the aid of ca~alysts, wherein the catalysts used are EU-l zeQlites.
Zeolites are crystalline nluminosilicate~. Si and Al atoms arP tetrahedrally surrounded by O atoms. The tetrahedra are linked via common O atoms and form a crystalline structure through which defined pores and cavities pass tcf. D.W. Breck, Zeolite Molecular Sieves, John Wiley & Sons, (1974) p. 29-185). The zeolites of the EU-l type used according to the invention are characterized by a typical X-ray diffraction pattern, which is indicated in European patent ~pplication A-4~ 226. The pores in this zeolite are bounded by 10 O
atoms and have a width of 0.41 x 0.58 nm. They have lateral extensions formed by 12 O atoms. These bulges are 0.58 x O.68 nm wide and 0.81 nm deep (N.A. Briscoe et al., Zeolite6 B, (1988) 74-76).
It is surprising that this precise type of zeolite makes it possible to achieve the desired high selectivity in respect of the MIPNs and the low rate of formation of DIPN, since the use, described in European patent application A-317 907l of mordenite catalysts with pores of 0.67 x 0.70 nm, which are larger than those of EU-l zeolites, as well as the use of zeolites of the ZSM-5 type with somewhat narrower pore~ of 0.52 x O.55 nm and 2~ J j3,`~, O.54 x O.56 nm, result in the formation of ~ far greater proportion of DIPN.
The different selectivities of thes~ catalysts are compared in the Examples.
S The EU-l zeolites u~ed according to the invention can be prepared by known processes of hydrothermal synthesis (e.g. European patent application A-42 2263. ~lkylated polymethylenediamine6, preferably N,N,N,N',N',N' hexa-methyl-l,6-hexamethylenediammoniumbromide(hexamethonium brsmide), are u~ed as the template. An SiO2~Al2O3 ratio in the range from 10 to 150 can be obtained by direct synthesis, but higher SiO2/Al203 ratios can also be achieved by sub~eguent dealuminization. The aluminum content can be reduced in a variety of ways here. Some methods are described e.g. in J. Scherzer, Catalytic Materials, Relationship between Structure and Reac~ivity, ACS Symp. Ser. 248 (1984) 175-200. EU-1 zeolites with SiO2/Al2O3 ratios of between 15 and 200, preferably of between 20 and 100, are particularly ~uitable for the process according to the invention.
After crystallization, the zeolite is filtered off, washed, dried and then calcined in an oxidizing atmosphere, preferably in air, in order to remove the organic template from the pore~.
To convert the zeclite to a catalytically active form, any Nat ion~ pre3ent are exchanged by ion exchange with divalent or trivalent ions of the alkaline earth metals or rare earth metals of atomic number 57 to 71, or with ammonium ion~ or protons. Ion exchange with NH~t or H+ iB
particularly preferred. It i8 convenient here if at lea~t 50%, preferably at least 90%, of the lattice charges are compensated by ~aid other ions. The zeolite i8 then converted to the catalytically active form by dehydration tand deammoniation in the case of NH4t forms) at 200 to 2~3 '`3 ~O 92/07810 - 6 - PCT/EP91/01951 800~C, preferably at 40U and 550~C.
For the use according to the invention, the zeolites can advantageously be converted to ~ ~uitable applicatlon form, e.g. ~trand~, with the aid of binders. P~rticularly ~uitable binders ~re the oxides, hydroxides or hydroxychlorides o aluminum and the oxides of silicon, titanium and zirconium, as well a~ clay materials.
The alkyla~ion reaction can be carried out in the ga~
phase or, preferably, in the liquid phase. Example~ of alkylating agent~ which can be used are i-propyl bromide and chloride, propylene and i-propancl. In the ga~ phase reaction, it is preferable to react naphthalene with propylene or i-propanol. When the alkylation is carried out in the liquid phase, it is preferable to use propylene. ~he reaction temperature i8 conveniently between about 100 and 500C, preferably between about 150 and 300C. An elevated pressure favor~ the course of the alkylation, especially if the alkylating agent i6 propylene. ~he reaction can be carried out at reduced pressure, at atmospheric pressur~ or at an elevated pressure, e.g. of up to about 100 bar, preferably between about 2 and 20 bar.
The alkylation in the liquid phase can be carried out in any suitable apparatus, most 8imply in a stirred tank, with pulverulent catalyst suspended in molten naphthalene. The alkylating agent is then passed through the suspension or forced in under pressure up to the desired value, at the reaction temperature. The reaction is preferably carried out without a ~olvent, but solvents which are inert towards the reactants and catalysts, such as higher-boiling paraffins or naphthenes, may also be present. Inert gases such as nitrogen can also be used to attain the reaction pressure.
The process can be carried out continuously or batchwise.
~ i3~3~, wO 92/07810 - 7 - PCT/EP91~01951 In the batch procedure, it i8 favorable to use about O.S
to 50% by weight of catalyst, preferably about 1 to lO~
by weight, ba~ed on the weight of naphthalene u~ed. The reaction time can be between about half an hour ~nd several day~, especially between 2 and 10 h, depending on the reaction condition~ and th~ deEIired conver ion. When the reaction i~ complete, the zeolite c~n ea~ily be 6eparated from the reaction mixtur~, e.g. by filtration.
To carry out the reaction in the gas phase, it i8 possible in principle to u~e any apparatus sui~able for gas phase reactions. A fixed bed continuou~-flow reactor is ~echnicslly the ~imple~t to operate. The cataly~t can be introduced into the reactor in the form of pellet~, which can be prepared by compressing the ~eolite on its own or together with a binder such a~ Al203 or SiO2. The naphthalene can be metered into the reactor in the molten state or dis601ved in an inert 601vent and vaporized upstream of the catalyst bed, or can already be in the gaseous state when it i~ introduced into the reactor.
i-Propanol can be metered in the ~ame way as naphthalene.
Propylene i8 introduced in the gaseou state. The reactants can be used on their own or mixed with a gas which is inert towards the reaction, such as hydrogen or nitrogen. The reaction products are conden~ed after leaving the reactor.
The molar ratio of naphthalene to alkylatin~ agent i~
conveniently in the range from about 0.1 to 10, preferably from about 0.5 to 2.
The re~idence time of the reactants i8 generally between about O.OS and 20 B, preferably between 1 and 10 B . The loading (LHSV = liquid hourly ~pace velocity = ml of charge per ml of cataly~t volume and per hour~ can preferably be %et in the range from 0.1 to 5 h-1, the range from 0.5 to 2 h~l being particularly favorable.
2~9~33 ~
WO 92/07810 - 8 - PCT~EPgl/01951 The catalyst r~t~ins it~ activity over ~ long period and can be used ~everal tLme~ for the reaction. If it iB
deactivated, it can be regenerated by calcin~tion in an oxidizin~ stmosphere, preferably in air, at about 350 to 800JC, preferably at about 500 to 600~C.
The product mixture can initially be separated by distillation into unreacted naphthalene, MIPN, DIPN and TIPN. If desired, 2-MIPN can be separated from the MIPN
fraction by crystallization, if ppropriate from a solvent ~uch as methanol or i-prop~nol (see e.g. ~erm~n Offenlegungsschrift 2 517 591). The filtrate enriched in l-MIPN can be reconverted to R mixture rich in 2- MIPN by isomerization on various zeolites (see e.g. US pstent 4 026 959). 2,6-DIPN can similarly be separated from the DIPN fraction by crystallization (~ee e.g. European patent 216 009). An adsorptive separation is described e.g. in Japanese patent application 01 199 921. Together with naphthalene, the rest of the DIPN fraction, substantially freed of 2,6-DIPN, can be reconverted to MIPN by transalkylation.
The crude 2-MIPN and 2,6-DIPN can be further purified to the desired degree by conventional working-up processes.
Examples The EU-l zeolites used were ~ynthesized with different SiO2/Al2O3 ratios according to instructions from th~
literature (European patent 42 226, ~S patent 4 537 754, G.W. Dodwell et al., Zeolit~s 5 (1985) 153-157~. All zeolites are used in the proton form (ion exchange with NH4NO3 solution and subsequent calcination).
i and 2) The ~xample6 and the Comparative Examples C1 to C3 were carried out in a ~tirred tank. Before the reaction, the zeolite was dried for 1 h at 300~C and then ~u~pended in powder form in 128 g of molten naphthalene.
Propylene was passed through the suspension at 6.5 l/h (or ~t 12 l~h in Example 2) a~ atmo~pheric pres~ure. The reaction temperature wz~ 200C. The experimental results are collated in Table 1.
T~ble l Exa~ple Cl C2 C3 1 2 Zeoli~e ZSM-5 MORDENITE EU-l ~U-1 Naphthalene conversion, ~olX23 22 76 23 75 S~lectivities, molX
DIPN lO 11 44 5 32 MIPN/(DIPN+TIPN)7.3 8.1 1.219.0 1.6 A comparison of C1, C2 and Example 1 shows that the selectivity with which MIPN i8 formed i8 greatly increased by the u~e of EU-l zeolites when the naphthalene conversions are not too high; the results are also markedly improved for high conversion~ (comparison of C3 and Example 2).
3 to 5) The Example~ and the Comparative Example~ C4 to C7 were c~rrled out in ~ fixed bed continuou~-flow reactor at atmospheric preR~ure. The cataly~t was used in the form of ~trand~. EU-l was compre~sed with 21% by weigh~ of SiO2 8i; a binder and mordenite with 4û% of Al2O3. ZSM-5 wa~ compre~ed to tablets without a binder.
Naphthalene was metered into the reactor in the molten state. Propylene wa used in twice the molar amount.
After leaving the re~ctor, the reaction products were conden~ed at certain time intervals and analyzed by ga8 chromatography. The re~ults (where T = 280C, LHSV - 0 . 5 h-l (ba~ed on naphthalene), catalyst volume = 25 ml, quantity ratio of naphthalene to propylene = 1:2) are collated in Table 2.
3 ~
Tabl~ 2 Ex~ple 3 4 5 C4 C5 C6 C7 Zeolit~ EU-l MORDE~ITE ZSM-5 Time, h 1.1 2.1 5.11.23.1 7.1 2.1 S Nsphth~le~e conversion, molX 39 30 28 36 23 9 3 Selectivities, molX
MIPN 78 83 a4 64 71 85 53 MIPN/(DIPN+TIPN) 3.95.25.6 1.8 2.4 5.7 1.1 A comparison of Example~ 3 to 5 with Comparstive Examples C4 to C7 ~how~ that markedly higher naphthalene conversions are ~chieved after the ~ame times when using EU-l zeolites, this type of zeolite also being markedly superior in respect of the selectivity with which ~IPN is formed. ~oreover, the EU-l zeolites exhibit a lower deactivation after longer period~.
Claims (9)
1. A process for the preparation of isopropylnaphthalene by the alkylation of naphthalene with the aid of catalysts, wherein the catalysts used are EU-1 zeolites.
2. The process as claimed in claim 1, wherein the EU-1 zeolite has an SiO2/Al2O3 ratio of about is to 200, preferably of 20 to 100.
3. The process as claimed in claim 1 or 2, wherein at least 50%, preferably at least 90%, of the lattice charges in the EU-1 zeolites are compen ated by protons, ammonium ions, alkaline earth metal ions and/or ions of the rare earth metals of atomic number 57 to 71 in the Periodic Table of the elements.
4. The process as claimed in one or more of claims 1 to 3, wherein the reaction is carried out in the liquid phase.
5. The process as claimed in one or more of claims 1 to 4, wherein the reaction is carried out at temperatures from about 100 to 500°C, preferably from about 150 to 300°C.
6. The process as claimed in one or more of claims 1 to 5, wherein the reaction is carried out at a pressure of up to about 100 bar, preferably at 2 to 20 bar.
7. The process as claimed in one or more of claims 1 to 6, wherein i-propyl bromide, i-propyl chloride, propylene or i-propanol is used as the alkylating agent.
8. The process as claimed in one or more of claims 1 to 7, wherein the naphthalene is used in a molar ratio of 0.1 to 10, preferably 0.5 to 2, relative to the alkylating agent.
9. The process as claimed in one or more of claims 1 to 8, wherein about 0.5 to 50% by weight, preferably about 1 to 10% by weight, of catalyst is used in the batch procedure, based on the weight of naphthalene used.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4034748.6 | 1990-11-01 | ||
| DE4034748 | 1990-11-01 | ||
| PCT/EP1991/001951 WO1992007810A1 (en) | 1990-11-01 | 1991-10-15 | Process for producing isopropyl naphthaline |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2095333A1 true CA2095333A1 (en) | 1992-05-02 |
Family
ID=6417446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002095333A Abandoned CA2095333A1 (en) | 1990-11-01 | 1991-10-15 | Process for producing isopropyl naphthaline |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0555253B1 (en) |
| JP (1) | JP2524447B2 (en) |
| KR (1) | KR960004179B1 (en) |
| AT (1) | ATE127772T1 (en) |
| CA (1) | CA2095333A1 (en) |
| DE (1) | DE59106495D1 (en) |
| DK (1) | DK0555253T3 (en) |
| ES (1) | ES2079679T3 (en) |
| MX (1) | MX9101857A (en) |
| WO (1) | WO1992007810A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5396012A (en) * | 1991-11-30 | 1995-03-07 | Hoechst Aktiengesellschaft | Process for the preparation of monoisopropylnaphthalene |
| FR2765206B1 (en) * | 1997-06-25 | 1999-08-06 | Inst Francais Du Petrole | ZEOLITHE EU-1, CATALYST AND METHOD FOR IMPROVING THE FLOW POINT CONTAINING PARAFFINS |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5623406B2 (en) * | 1974-04-22 | 1981-05-30 | ||
| EP0338292B1 (en) * | 1988-03-28 | 1992-11-11 | Tosoh Corporation | A method for the preparation of diisopropyluaphthalenes |
-
1991
- 1991-10-15 EP EP91918140A patent/EP0555253B1/en not_active Expired - Lifetime
- 1991-10-15 WO PCT/EP1991/001951 patent/WO1992007810A1/en active IP Right Grant
- 1991-10-15 JP JP3516407A patent/JP2524447B2/en not_active Expired - Lifetime
- 1991-10-15 CA CA002095333A patent/CA2095333A1/en not_active Abandoned
- 1991-10-15 ES ES91918140T patent/ES2079679T3/en not_active Expired - Lifetime
- 1991-10-15 DE DE59106495T patent/DE59106495D1/en not_active Expired - Fee Related
- 1991-10-15 AT AT91918140T patent/ATE127772T1/en not_active IP Right Cessation
- 1991-10-15 DK DK91918140.4T patent/DK0555253T3/en active
- 1991-10-30 MX MX9101857A patent/MX9101857A/en unknown
-
1993
- 1993-04-30 KR KR93701312A patent/KR960004179B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES2079679T3 (en) | 1996-01-16 |
| EP0555253B1 (en) | 1995-09-13 |
| JP2524447B2 (en) | 1996-08-14 |
| DK0555253T3 (en) | 1996-01-22 |
| DE59106495D1 (en) | 1995-10-19 |
| KR960004179B1 (en) | 1996-03-27 |
| JPH06501006A (en) | 1994-01-27 |
| EP0555253A1 (en) | 1993-08-18 |
| WO1992007810A1 (en) | 1992-05-14 |
| KR930702258A (en) | 1993-09-08 |
| ATE127772T1 (en) | 1995-09-15 |
| MX9101857A (en) | 1992-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0439632B2 (en) | Process for the alkylation of benzene | |
| US5227558A (en) | Aromatic alkylation process employing steam modified zeolite beta catalyst | |
| US4927979A (en) | Process for the preparation of p-ethylphenol | |
| US4724275A (en) | Crystalline aluminosilicates and their use in the conversion of methanol to low molecular weight hydrocarbons | |
| US5672799A (en) | Process for the preparation of cumene | |
| EP0056698A2 (en) | Process for making epsilon-caprolactam | |
| US5157180A (en) | Alkylation and transalkylation processes | |
| EP0589876B1 (en) | Alkylation of aromatic compounds | |
| US5003120A (en) | Process for selective manufacture of 2,6-diisopropylnaphthalenes with equilibration reactor | |
| EP0432132B1 (en) | A method for preparation of mono- and diisopropylnaphthalenes | |
| CA1327611C (en) | Process for selective diisopropylation of naphthyl compounds using shape selective acidic crystalline molecular sieve catalysts | |
| US4237329A (en) | Process for the production of alkylbenzenes | |
| US5202516A (en) | Process of recovering monoalkylbenzene and pure 1,3,5-trialkylbenzene from a mixture of dialkyl- and trialkylbenzenes | |
| CA2095333A1 (en) | Process for producing isopropyl naphthaline | |
| JPS607604B2 (en) | Selective method for producing para-substituted benzene | |
| US5880322A (en) | Method for producing diarylmethane | |
| US5396012A (en) | Process for the preparation of monoisopropylnaphthalene | |
| EP3389858B1 (en) | Catalyst composition, its preparation and process using such composition | |
| CA1214449A (en) | Silica-modified catalyst and use for selective production of para-dialkyl substituted benzenes | |
| EP0422727B1 (en) | Method for recovering trimethylbenzenes from mixtures which contain them | |
| FI76005C (en) | ALUMINUM-BOR-SILICATE CATALYST, FREQUENCY FOR FRAMSTAELLNING AV DENNA OCH ALKYLERINGSPROCESS. | |
| JPS6253489B2 (en) | ||
| DE4115263C2 (en) | Modified beta zeolite | |
| JP2545649B2 (en) | Improved zeolite β catalyst and method for producing diisopropylbenzene using improved zeolite β catalyst | |
| JPH11193253A (en) | Direct production of styrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |