CN105601459A - Method for preparing 2-methyl-6-tert-butylnaphthalene from 2-methylnaphthalene through alkylation - Google Patents
Method for preparing 2-methyl-6-tert-butylnaphthalene from 2-methylnaphthalene through alkylation Download PDFInfo
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Abstract
The invention provides a method for preparing 2-methyl-6-tert-butylnaphthalene from 2-methylnaphthalene through alkylation, belonging to the field of chemistry and chemical engineering. The method uses 2-methylnaphthalene (beta-methylnaphthalene) as a raw material and highly selectively prepares 2-methyl-6-tert-butylnaphthalene by subjecting 2-methylnaphthalene (beta-methylnaphthalene) and tert-butyl alcohol or isobutene to alkylation. A siloxane-based compound modified molecular sieve catalyst is used for catalyzing a reaction of 2-methylnaphthalene with tert-butyl alcohol or isobutene to prepare 2-methyl-6-tert-butylnaphthalene, and the selectivity of 2-methyl-6-tert-butylnaphthalene in products and a ratio of 2-methyl-6-tert-butylnaphthalene to 2-methyl-7-tert-butylnaphthalene can be effectively increased. The method is simple to operate and low in cost and has potential application value.
Description
Technical field
The invention belongs to chemical field, be specifically related to the alkylation of a kind of 2-methyl naphthalene and prepare 2-methyl-6-tert butylThe method of naphthalene.
Background technology
2,6-dialkyl group naphthalene is the critical materials of producing high-performance poly ester fiber and plastics, its oxidation product 2,6-naphthalene diformazanAcid is a kind of new polyester that has potentiality and application prospect with the PEN (PEN) that ethylene glycol polymerization makesMaterial. PEN has unique heat resistance, mechanicalness, gas barrier property, chemical stability and radiation resistance etc., can be widely used inThe manufacturings such as electronic component, instrument and meter, insulating materials, food packing film, beer bottle and Aero-Space. At presentThe bottleneck of PEN large-scale application is its critical materials 2, and the preparation process of 6-dialkyl group naphthalene is loaded down with trivial details, and production cost is high.
China's naphthalene and methyl naphthalene aboundresources, synthesize 2,6-with cheap, abundant naphthalene or methyl naphthalene by alkylated reactionDialkyl group naphthalene, can widen raw material sources, improves the added value of naphthalene and methyl naphthalene, shortens process route, is preparation 2,6-dioxaneThe route that base naphthalene is desirable. Same group dialkyl group naphthalene has ten kinds of isomers, because each isomers boiling point is close, separates very tiredDifficulty, what therefore how to improve 2,6-dialkyl group naphthalene is selectively to realize preparing 2,6-dialkyl group naphthalene by naphthalene/2-methyl naphthalene one-step methodKey. The ZSM-5 molecular sieve that CN1807243 replaces taking the Zr isomorphous carries out methylating instead of 2-methyl naphthalene and methyl alcohol as catalystShould prepare 2,6-dimethylnaphthalene, 2,6-dimethylnaphthalene be selectively that the ratio of 56.8%, 2,6/2,7-dimethylnaphthalene is 2.18,But the conversion ratio of 2-methyl naphthalene is only 5.62%. Patent CN102746101 and CN102746102A adopt respectively SAPO-11,CoAPO-11 is the alkylated reaction that catalyst carries out naphthalene and methyl alcohol, and the conversion ratio of naphthalene is more 40～60%, the choosing of dimethylnaphthaleneSelecting property all lower than 30%, 2,6-dimethylnaphthalene in ten kinds of isomers selectively lower than 40%, 2,6/2,7-dimethylnaphthaleneRatio is up to 1.93. CN101417234A discloses the Y molecular sieve of preparing taking organic acid dealuminzation as catalyst is by naphthalene and uncleButanols reaction preparation 2,6-di-t-butyl naphthalin, the conversion ratio of naphthalene is 70%, only has the tertiary fourth of 2,6-bis-in the product of di-t-butyl naphthalinBase naphthalene and 2,7-di-t-butyl naphthalin, the two ratio is up to 9. KeithSmith etc. (Org.Biomol.Chem., 2003,1,1552 – 1559) adopt alkylated reaction, 2,6-di-t-butyl naphthalin and the tertiary fourth of 2,7-bis-of MOR molecular sieve catalytic naphthalene and the tert-butyl alcoholThe ratio of base naphthalene is the highest can reach 50.
In sum, in naphthalene/2-methyl naphthalene and methyl alcohol methylation reaction product 2,6-dimethylnaphthalene is selective and 2,6/The ratio of 2,7-dimethylnaphthalene is all lower, and in naphthalene and tert-butyl alcohol alkylation reaction product 2, and 6-di-t-butyl naphthalin is selective and 2,The ratio of 6/2,7-di-t-butyl naphthalin all significantly improves, and this shows taking the tert-butyl alcohol as alkylating reagent its steric effect or selects shape effectFruit is stronger, but 2, the carbon atom loss in subsequent oxidation process of 6-di-t-butyl naphthalin is many, and Atom economy is poor. If utilized2-methyl naphthalene and the tert-butyl alcohol or isobutene alkylation, can select shape high selectivity by catalyst prepares 2-methyl-6-on the one handT-butyl naphthalin, can reduce carbon atom loss in subsequent oxidation process on the other hand, and therefore this will be the skill that has application prospect mostArt route.
Summary of the invention
The object of this invention is to provide the alkylation of a kind of 2-methyl naphthalene and prepare the method for 2-methyl-6-tert butyl naphthalene.
A method for 2-methyl-6-tert butyl naphthalene is prepared in the alkylation of 2-methyl naphthalene, and the method adopts siloxy group chemical combinationThing is modified the molecular sieve catalyst of preparation, and 2-methyl naphthalene and the tert-butyl alcohol or isobutene alkylated reaction high selectivity are prepared 2-firstBase-6-t-butyl naphthalin; Concrete steps are:
(1) add in reactor after first 2-methyl naphthalene, the tert-butyl alcohol being mixed with atent solvent, then add siloxy groupCompound is modified the molecular sieve catalyst of preparation, with pressurising after inert gas replacement, and sealing;
Or: after first 2-methyl naphthalene being mixed with atent solvent, solution adds in reactor, then adds siloxy groupCompound is modified the molecular sieve catalyst of preparation, with passing into isobutene in the backward reactor of inert gas replacement, then passes into indifferent gasBody pressurising, sealing;
(2) be then 100～250 DEG C in reaction temperature, pressure is 1～3MPa, and the reaction time is 0.5～8 hour conditionUnder; Preparation 2-methyl-6-tert butyl naphthalene;
Wherein, 2-methyl naphthalene in step (1) reaction system: the tert-butyl alcohol (isobutene): atent solvent mol ratio is 1:1～3:5～60, the mass ratio of catalyst and 2-methyl naphthalene is 0.05～2.
The molecular sieve catalyst of the compound-modified preparation of described siloxy group, its preparation method carries out step according to the following stepsFor:
First molecular sieve is placed in Muffle furnace in 550 DEG C of air roasting 3-6 hour; Afterwards by normal molecular sieve after roastingTemperature is immersed in 2-24 hour in siloxy group compound, and after centrifugation, solid sample, at 120 DEG C of air dryings, then existsIn Muffle furnace, 550 DEG C of roasting 3-6 hour in air atmosphere, obtain the compound-modified molecular sieve catalyst of siloxy group.
The molecular sieve of above-mentioned employing is HZSM-5, HZSM-12, HBeta, HY, SAPO-5, HZSM-18 or HMOR.
The preferred SAPO-5 of molecular sieve, the HZSM-18 or the HMOR that adopt.
Described siloxy group structural formula of compound is shown below:
In formula, R1、R2、R3And R4For the alkyl of 1-10 carbon atom.
Described siloxy group compound is preferably a kind of or several in quanmethyl silicate, tetraethyl orthosilicate and silicic acid orthocarbonatePlant and be mixed by any ratio.
Described atent solvent is that one or both in cyclohexane, mesitylene are mixed by any ratio.
Described inert gas be in helium, argon gas, nitrogen any one.
The present invention adopts the compound-modified molecular sieve catalyst of siloxy group, catalysis 2-methyl naphthalene and the tert-butyl alcohol or isobutylAllylic alkylationization reaction, the conversion ratio of 2-methyl naphthalene is greater than 40%, and in product, 2-methyl-6-tert butyl naphthalene is selectively greater thanThe ratio of 95%, 2-methyl-6-tert butyl naphthalene/2-methyl-7-t-butyl naphthalin is greater than 20.
Beneficial effect of the present invention is:
(1) provide a kind of 2-methyl naphthalene and the tert-butyl alcohol or isobutene alkylation high selectivity to prepare 2-methyl-6-tert-butylThe method of base naphthalene. Under the condition of optimizing, the conversion ratio of 2-methyl naphthalene reaches more than 40%, 2-methyl-6-tert butyl in productNaphthalene selectively can reach more than 95%, and the ratio of 2-methyl-6-tert butyl naphthalene/2-methyl-7-t-butyl naphthalin can reach 20Above.
(2) the high ratio of 2-methyl-6-tert butyl naphthalene/2-methyl-7-t-butyl naphthalin is conducive to 2-methyl-6-tert butyl naphthalenePurify, the preparation of high selectivity 2-methyl-6-tert butyl naphthalene simultaneously, can reduce carbon atom loss in subsequent oxidation process.
(3) to adopt zeolite molecular sieve be catalyst in the present invention, and catalyst is easy with separating of reaction substrate, process environmental protection.
(4) the present invention modifies molecular sieve catalyst outer surface acidity and duct by siloxy group compound, presses downMake the generation of side reaction, improved raw material availability and selectivity of product.
Therefore, the present invention not only has novelty, and has advantage and industrial applications prospect economically.
Detailed description of the invention
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiment.
Embodiment 1
The preparation of catalyst
By 50gHZSM-5, HZSM-12, HY, HBeta, HZSM-18, HMOR, SAPO-5 550 DEG C of roastings 4 in Muffle furnaceHour, put into 50g quanmethyl silicate and flood 8 hours,, after centrifugation, solid sample dries in 120 DEG C of air atmospheres,550 DEG C of roastings 3 hours, obtain the molecular sieve catalyst after modifying, respectively called after HZSM-5-01, HZSM-12-01, HY-01,HBeta-01、HZSM-18-01、HMOR-01、SAPO-5-01。
Embodiment 2
The preparation of catalyst
By 50gHZSM-18, HMOR, SAPO-5 550 DEG C of roastings 4 hours in Muffle furnace, put into 50g tetraethyl orthosilicateFlood 12 hours, after centrifugation, solid sample dries in 120 DEG C of air atmospheres, 550 DEG C of roastings 4 hours, after obtaining modifyingMolecular sieve catalyst, respectively called after HZSM-18-02, HMOR-02, SAPO-5-02.
Embodiment 3
The preparation of catalyst
By 50gHMOR 550 DEG C of roastings 4 hours in Muffle furnace, put into 50g silicic acid orthocarbonate and flood 24 hours, centrifugalAfter separation, solid sample dries in 120 DEG C of air atmospheres, 550 DEG C of roastings 3 hours, obtains the molecular sieve catalyst after modifying,Called after HMOR-03.
Embodiment 4
Reaction evaluating
HZSM-5-01 molecular sieve catalyst prepared by embodiment 1 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 0.74g, cyclohexane 16.83g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:1:20 (mol ratio), stirsMix. Then 1.00gHZSM-5-01 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3 timesAfter be pressurized to 1.0MPa, be warming up to 150 DEG C of isothermal reactions 4 hours. After taking out, reactant liquor adopts gas chromatograph assay products groupBecome, reaction result is as table 1 (Run1).
Embodiment 5
Reaction evaluating
HZSM-12-01 molecular sieve catalyst prepared by embodiment 1 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 0.74g, cyclohexane 16.83g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:1:20 (mol ratio), stirsMix. Then 1.00gHZSM-12-01 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3After inferior, be pressurized to 1.0MPa, be warming up to 150 DEG C of isothermal reactions 4 hours. After taking out, reactant liquor adopts gas chromatograph assay productsComposition, reaction result is as table 1 (Run2).
Embodiment 6
Reaction evaluating
HY-01 molecular sieve catalyst prepared by embodiment 1 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 0.74g, cyclohexane 16.83g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:1:20 (mol ratio), stirsMix. Then 0.50gHY-01 catalyst is added in reactor. By reactor sealing, fill after using nitrogen replacement 3 timesBe depressed into 1.0MPa, be warming up to 150 DEG C of isothermal reactions 4 hours. After taking out, reactant liquor adopts gas chromatograph assay products composition, and anti-Should result as table 1 (Run3).
Embodiment 7
Reaction evaluating
HBeta-01 molecular sieve catalyst prepared by embodiment 1 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 0.74g, cyclohexane 16.83g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:1:20 (mol ratio), stirsMix. Then 0.50gHBeta-01 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3 timesAfter be pressurized to 1.0MPa, be warming up to 150 DEG C of isothermal reactions 4 hours. After taking out, reactant liquor adopts gas chromatograph assay products groupBecome, reaction result is as table 1 (Run4).
Embodiment 8
Reaction evaluating
HZSM-18-01 molecular sieve catalyst prepared by embodiment 1 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 0.74g, cyclohexane 16.83g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:1:20 (mol ratio), stirsMix. Then 0.50gHZSM-18-01 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3After inferior, be pressurized to 1.0MPa, be warming up to 150 DEG C of isothermal reactions 4 hours. After taking out, reactant liquor adopts gas chromatograph assay productsComposition, reaction result is as table 1 (Run5).
Embodiment 9
Reaction evaluating
HMOR-01 molecular sieve catalyst prepared by embodiment 1 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 0.74g, cyclohexane 16.83g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:1:20 (mol ratio), stirsMix. Then 0.50gHMOR-01 catalyst is added in reactor. By reactor sealing, use after nitrogen replacement 3 timesBe pressurized to 1.0MPa, be warming up to 150 DEG C of isothermal reactions 4 hours. After taking out, reactant liquor adopts gas chromatograph assay products composition,Reaction result is as table 1 (Run6).
Embodiment 10
Reaction evaluating
Molecular sieve catalyst SAPO-5-01 prepared by embodiment 1 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 0.74g, cyclohexane 33.66g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:1:40 (mol ratio), stirsMix. Then 1.40gSAPO-5-01 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3 timesAfter be pressurized to 1.0MPa, be warming up to 180 DEG C of isothermal reactions 3 hours. After taking out, reactant liquor adopts gas chromatograph assay products groupBecome, reaction result is as table 1 (Run7).
Embodiment 11
Reaction evaluating
The HMOR-01 catalyst of respectively being prepared by embodiment 1 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 200ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 1.48g, cyclohexane 50.49g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:2:60 (mol ratio), stirsMix. Then 1.00gHMOR-01 catalyst is added in reactor. By reactor sealing, use after nitrogen replacement 3 timesBe pressurized to 2.0MPa, be warming up to 130 DEG C of isothermal reactions 8 hours. After taking out, reactant liquor adopts gas chromatograph assay products composition,Reaction result is as table 1 (Run8).
Embodiment 12
Reaction evaluating
The HMOR-02 catalyst of respectively being prepared by embodiment 2 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene2.84g, tert-butyl alcohol 2.96g, cyclohexane 8.41g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:2:5 (mol ratio), stirs mixedClose evenly. Then 0.05gHMOR-02 catalyst is added in reactor. By reactor sealing, fill after using nitrogen replacement 3 timesBe depressed into 2.0MPa, be warming up to 160 DEG C of isothermal reactions 8 hours. After taking out, reactant liquor adopts gas chromatograph assay products composition, and anti-Should result as table 1 (Run9).
Embodiment 13
Reaction evaluating
The HZSM-18-02 catalyst of respectively being prepared by embodiment 2 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 2.22g, cyclohexane 42.08g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:3:50 (mol ratio), stirsMix. Then 0.50gHZSM-18-02 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3After inferior, be pressurized to 2.0MPa, be warming up to 250 DEG C of isothermal reactions 0.5 hour. After taking out, reactant liquor adopt gas chromatograph to divide divisionThing composition, reaction result is as table 1 (Run10).
Embodiment 14
Reaction evaluating
The SAPO-5-02 catalyst of respectively being prepared by embodiment 2 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction.
Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml), in still, add first respectively 2-methyl naphthalene1.42g, tert-butyl alcohol 1.48g, cyclohexane 42.08g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:2:50 (mol ratio), stirsMix. Then 1.0gSAPO-5-02 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3 timesAfter be pressurized to 2.0MPa, be warming up to 100 DEG C of isothermal reactions 8 hours. After taking out, reactant liquor adopts gas chromatograph assay products groupBecome, reaction result is as table 1 (Run11).
Embodiment 15
Reaction evaluating
HMOR-03 catalyst prepared by embodiment 3 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction. Employing liner is poly-Tetrafluoroethene stainless steel cauldron (volume 100ml) first adds 2-methyl naphthalene 1.42g, tert-butyl alcohol 2.22g, hexamethylene in stillAlkane 16.80g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:3:20 (mol ratio), is uniformly mixed. Then by 0.50gHMOR-03 catalyst adds in reactor. By reactor sealing, be pressurized to 3.0MPa after using nitrogen replacement 3 times, be warming up to160 DEG C of isothermal reactions 2 hours. After reactant liquor takes out, adopt gas chromatograph assay products composition, reaction result is as table 1 (Run12)
Embodiment 16
Reaction evaluating
HMOR-02 catalyst prepared by embodiment 2 is for 2-methyl naphthalene and isobutene alkylated reaction. Employing liner is poly-Tetrafluoroethene stainless steel cauldron (volume 100ml) first adds 2-methyl naphthalene 1.42g in still, and cyclohexane 16.80g stirsMix. Then 1.00gHMOR-02 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3 times.Isobutene 1.12g is passed in reactor, i.e. 2-methyl naphthalene: isobutene: cyclohexane=1:2:20 (mol ratio), logical nitrogen pressurisingTo 2.0MPa, be warming up to 160 DEG C of isothermal reactions 3 hours. After taking out, reactant liquor adopts gas chromatograph assay products composition, reactionResult is as table 1 (Run13)
Embodiment 17
Reaction evaluating
SAPO-5-02 catalyst prepared by embodiment 2 is for 2-methyl naphthalene and isobutene alkylated reaction. Adopt linerPolytetrafluoroethylene (PTFE) stainless steel cauldron (volume 100ml) first adds 2-methyl naphthalene 1.42g in still, and cyclohexane 16.80g, stirsMix and mix. Then 1.0gSAPO-5-02 catalyst is added in reactor. By reactor sealing, use nitrogen replacement 3Inferior. Isobutene 1.12g is passed in reactor, i.e. 2-methyl naphthalene: isobutene: cyclohexane=1:2:20 (mol ratio), logical nitrogenBe pressurized to 2.0MPa, be warming up to 160 DEG C of isothermal reactions 3 hours. After taking out, reactant liquor adopts gas chromatograph assay products composition,Reaction result is as table 1 (Run14)
Comparative example 1
Unmodified HZSM-5, HZSM-12, HY, HBeta, HZSM-18, HMOR, SAPO-5 catalyst are used for to 2-methyl naphthaleneWith tert-butyl alcohol alkylated reaction. Adopt inner liner polytetrafluoroethylene stainless steel cauldron (volume 100ml). First in still, add respectivelyEnter 2-methyl naphthalene 1.42g, tert-butyl alcohol 0.74g cyclohexane 16.8g, i.e. 2-methyl naphthalene: the tert-butyl alcohol: cyclohexane=1:1:20 (rubsYou), be uniformly mixed. Then respectively by 0.50gHZSM-5, HZSM-12, HY, HBeta, HZSM-18, HMOR, SAPO-5Catalyst adds in reactor. By reactor sealing, be pressurized to 1.0MPa after using nitrogen replacement 3 times, be warming up to 150 DEG C of constant temperatureReact 4 hours. After reactant liquor takes out, adopt gas chromatograph assay products composition, reaction result is as table 2 (Run15-21).
Table 1 modified catalyst is for 2-methyl naphthalene and the tert-butyl alcohol or isobutene alkylated reaction
The unmodified catalyst of table 2 is for 2-methyl naphthalene and tert-butyl alcohol alkylated reaction
Claims (8)
1. a method for 2-methyl-6-tert butyl naphthalene is prepared in the alkylation of 2-methyl naphthalene, it is characterized in that the method adopts silicaAlkyl compound is modified the molecular sieve catalyst of preparation, 2-methyl naphthalene and the tert-butyl alcohol or isobutene alkylated reaction high selectivity systemStandby 2-methyl-6-tert butyl naphthalene; Concrete steps are:
(1) add in reactor after first 2-methyl naphthalene, the tert-butyl alcohol being mixed with atent solvent, then add siloxy group compoundModify the molecular sieve catalyst of preparation, by reactor sealing, with pressurising after inert gas replacement;
Or: after first 2-methyl naphthalene being mixed with atent solvent, solution adds in reactor, then adds siloxy group compoundModify the molecular sieve catalyst of preparation, by reactor sealing, with passing into isobutene in the backward reactor of inert gas replacement, more logicalEnter inert gas pressurising;
(2) be then 100～250 DEG C in reaction temperature, pressure is 1～3MPa, and the reaction time is under 0.5～8 hour condition; SystemStandby 2-methyl-6-tert butyl naphthalene;
Wherein, 2-methyl naphthalene in step (1) reaction system: the tert-butyl alcohol (isobutene): the mol ratio of atent solvent is 1:1～3:5～60, the mass ratio of catalyst and 2-methyl naphthalene is 0.05～2.
2. prepare the method for 2-methyl-6-tert butyl naphthalene according to a kind of 2-methyl naphthalene claimed in claim 1 alkylation, its featureBe the molecular sieve catalyst of the compound-modified preparation of described siloxy group, its preparation method carries out according to the following steps step and is:
First molecular sieve is placed in Muffle furnace in 550 DEG C of air roasting 3-6 hour; Afterwards molecular sieve normal temperature after roasting is soakedStain 2-24 hour in siloxy group compound, after centrifugation, solid sample is at 120 DEG C of air dryings, then horse not550 DEG C of roasting 3-6 hour in furnace air atmosphere, obtain the compound-modified molecular sieve catalyst of siloxy group.
3. the method for 2-methyl-6-tert butyl naphthalene, its feature are prepared in a kind of 2-methyl naphthalene according to claim 2 alkylationBe that adopted molecular sieve is HZSM-5, HZSM-12, HBeta, HY, SAPO-5, HZSM-18 or HMOR.
4. the method for 2-methyl-6-tert butyl naphthalene, its feature are prepared in a kind of 2-methyl naphthalene according to claim 3 alkylationBe the preferred SAPO-5 of adopted molecular sieve, HZSM-18 or HMOR.
5. the method for 2-methyl-6-tert butyl naphthalene is prepared in a kind of 2-methyl naphthalene according to claim 1 and 2 alkylation, itsBe characterised in that described siloxy group structural formula of compound is shown below:
In formula, R1、R2、R3And R4For the alkyl of 1-10 carbon atom.
6. the method for 2-methyl-6-tert butyl naphthalene, its feature are prepared in a kind of 2-methyl naphthalene according to claim 5 alkylationBe described siloxy group compound be preferably in quanmethyl silicate, tetraethyl orthosilicate and silicic acid orthocarbonate one or more byArbitrarily than mixing.
7. the method method of 2-methyl-6-tert butyl naphthalene is prepared in a kind of 2-methyl naphthalene according to claim 1 alkylation, itsBe characterised in that described atent solvent is that one or both in cyclohexane, mesitylene are mixed by any ratio.
8. the method method of 2-methyl-6-tert butyl naphthalene is prepared in a kind of 2-methyl naphthalene according to claim 1 alkylation, itsBe characterised in that described inert gas be in helium, argon gas, nitrogen any one.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109433253A (en) * | 2018-11-30 | 2019-03-08 | 中国科学院大连化学物理研究所 | The catalyst and its preparation method and application of 2,6- di-t-butyl naphthalin is prepared for naphthalene form selected methylation |
| CN114558611A (en) * | 2022-03-24 | 2022-05-31 | 中国科学院大连化学物理研究所 | Catalyst, preparation method thereof and application thereof in preparation of 2, 6-diisopropyl naphthalene |
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| CN101417234A (en) * | 2007-10-24 | 2009-04-29 | 中国科学院大连化学物理研究所 | Preparation method of catalyst for shape-selective alkylation of naphthalene to produce 2,6-di(tert butyl)naphthalene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109433253A (en) * | 2018-11-30 | 2019-03-08 | 中国科学院大连化学物理研究所 | The catalyst and its preparation method and application of 2,6- di-t-butyl naphthalin is prepared for naphthalene form selected methylation |
| CN109433253B (en) * | 2018-11-30 | 2020-11-27 | 中国科学院大连化学物理研究所 | Catalyst for preparing 2, 6-di-tert-butyl naphthalene by naphthalene shape-selective alkylation and preparation method and application thereof |
| CN114558611A (en) * | 2022-03-24 | 2022-05-31 | 中国科学院大连化学物理研究所 | Catalyst, preparation method thereof and application thereof in preparation of 2, 6-diisopropyl naphthalene |
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|---|---|
| CN105601459B (en) | 2018-06-19 |
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