CN102260134A - Preparation method of 2-sec-butylnaphthalene - Google Patents
Preparation method of 2-sec-butylnaphthalene Download PDFInfo
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- CN102260134A CN102260134A CN2010101825677A CN201010182567A CN102260134A CN 102260134 A CN102260134 A CN 102260134A CN 2010101825677 A CN2010101825677 A CN 2010101825677A CN 201010182567 A CN201010182567 A CN 201010182567A CN 102260134 A CN102260134 A CN 102260134A
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Abstract
The invention relates to a preparation method of 2-sec-butylnaphthalene. According to the preparation method, 2-sec-butylnaphthalene is prepared by shape-selecting alkylation of naphthalene in the presence of 2-butene used as an alkylating agent under the catalysis of a Mg<2+> modified USY zeolite molecular sieve. After the reaction is finished, a product mixed liquid in which the content of 2-sec-butylnaphthalene is up to 99.7% is obtained, and the conversion rate of 2-butene reaches 100%. The method has the advantages of mild reaction conditions, simple technological process, low energy consumption and high yield.
Description
Technical field:
The present invention relates to the method that a kind of naphthalene selectivity sec-butylization prepares 2-sec-butyl naphthalene.
Background technology:
The 2-alkylnaphthalene is important Organic Chemicals, and the two kinds of product beta naphthals and the butanone that obtain through oxidation, after decomposing all are important organic synthesis raw materials.Wherein, beta naphthal can be used for making matching stain and ball pen ink through the sulfonated product; Itself and aniline condensation product N-phenyl-2-naphthylamines are widely used in the various dark rubber item of natural rubber and synthetic rubber manufacturing; Beta naphthal is methylated, can make the medical drugs Naproxen Base through a series of processes such as acetylizes again, this medicine is mainly used in the anti-inflammatory and the analgesia of chronic arthritis, pain in the back, acute upper respiratory tract inflammation etc.In addition, beta naphthal also can be used for producing multiple agricultural, medical, industrial Chemicals such as leather retanning agent, electrolytic solution washing composition, and range of application is very extensive.Butanone is called methylethylketone again, is a kind of low boiling point organic solvent of excellent property, is used for industries such as medicine, electronic component cleaning, oil refining, tackiness agent in a large number.Butanone still is a kind of important fine chemical material, can be used as the building-up process that light-sensitive catalyst acts on aliphatic amide, aromatic amine, or improves the combustion efficacy of oil fuel in oil engine, process furnace and boiler as additive, and Application Areas is also very extensive.
Along with China becomes world DYE PRODUCTION big export country, China is to the demand of beta naphthal, and especially dyestuff intermediate consumption enlarges day by day, is once occurring the situation that supply falls short of demand in recent years.The preparation method of the existing beta naphthal of China has sulfonated alkali fusion method, transalkylation, 2-chloronaphthalene hydrolysis method and hydrogen peroxide method, wherein sulfonated alkali fusion method and transalkylation are comparatively ripe, but the two all exists " three wastes " many, and the equipment corrosion important disadvantages needs further perfect.Hydrolysis of 2-chloronaphthalene and hydrogen peroxide rule be because the production cost height, and economic benefit is low and be that people are used less.American Cyanamid Company adopts the Y zeolite low-temp reaction to generate the 2-isopropyl naphthalene, again with two kinds of rare earth elemental metals ion La
3+And Ce
4+The Y zeolite of modification carries out two step transalkylation reactions, and 2-isopropyl naphthalene content is brought up to more than 95%, carries out oxidation, decomposition, purification, refining purity and all more excellent beta naphthal product of colourity of obtaining at last again.This method is a kind of method of comparatively environmental protection at present, economy, and its committed step is the composite part of 2 isopropyl naphthalenes.But the boiling point of this method gained alkylate complicated component, especially 1-isopropyl naphthalene and 2-isopropyl naphthalene is approaching, separates relatively difficulty, and two step isomerisation temperature are higher, the energy consumption height.Synthetic 2-the alkylnaphthalene of highly selective how makes the product separate easily, thereby the production cost that reduces raw material has become current research focus.
The method of extracting 1-methylnaphthalene and 2-methylnaphthalene from coal tar that a kind of employing comprises an alkanisation polymerization reactor and three placed in-line rectifying tower devices has been described among the Chinese patent CN 1721380A.Yet the employed catalyzer of this method is acid, and is serious to equipment corrosion, the feed composition complexity, and separation difficulty is only applicable to small-scale production.
Described in the U.S. Pat 5177284 and a kind of overstable gamma zeolite molecular sieve and beta-zeolite molecular sieve have been mixed jointly method as catalyzer synthesis of alkyl naphthalene.Yet the required temperature of reaction of this method is higher, and product purity is low, is unfavorable for suitability for industrialized production.
Li Yu equality people (Li Yu equality. the naphthalene and the trimethyl carbinol liquid phase alkylation reaction on zeolite. coal conversion, in July, 2004,27 (3): 85～88) chosen bigger micro-pore zeolite HY, HX, H β and the HM in aperture, their catalytic performances have been investigated in the liquid phase alkylation reaction of the naphthalene and the trimethyl carbinol, and to choose the HY zeolite be catalyzer, investigated the influence to reaction of temperature, time and proportioning raw materials.Found that 2-t-butyl naphthalin yield is 52%, do not have the generation of 2-sec-butyl naphthalene, and have a large amount of dialkyl group naphthalene products to generate in the product, reaction preference is not ideal enough, and temperature of reaction is higher, and power consumption is big.
Chinese patent CN 101205161A has described a kind of method for preparing long-chain 2-alkylnaphthalene.This method is with the superfine silicon dioxide carried heteropoly acid catalyst, is 1～10: 1 C with mol ratio
10～C
24Long-chain olefin and naphthalene react.Reaction can be finished under than the demulcent condition, obtains product and is easy to separate, and colourity is lower, and is also lower to equipment requirements, relatively is suitable for industrial production.But there is the product component complexity in this method, and the shortcoming that the alkylnaphthalene yield is not high still remains to be improved.
United States Patent (USP) 4604491 has been described the alkylated reaction that is used for naphthalene and alpha-olefin with the sial carclazyte as catalyzer, this method need be carried out 6 hours under 200 ℃ continuously, the temperature of reaction height, and the catalyst consumption amount is very big, separate purification to product and cause certain difficulty, be unfavorable for industrial applications.
Summary of the invention:
The objective of the invention is to alkylation for naphthalene and prepare the 2-alkylnaphthalene a kind of new method is provided, promptly naphthalene is selected the shape sec-butylization and is prepared 2-sec-butyl naphthalene, to solve in the 2-alkylnaphthalene preparation process, the purpose selectivity of product is poor, the product separation difficulty, complex process, by product are many, the problem that energy consumption is high.This method reaction conditions gentleness, catalyst system therefor has than high reaction activity, and is good to 2-sec-butyl naphthalene selectivity, convenient product separation.
The method is characterized in that used modified zeolite molecular sieve catalyzer is containing metal Mg
2+Inorganic salt.These inorganic salt cheaply are easy to get, and modifying process is simple to operate, and are pollution-free.The duct size of zeolite molecular sieve obtains modulation to a certain degree after the modification, and specific surface area also changes to some extent, and hydrothermal stability is good, character homogeneous, repeating utilization factor height.Use it in the sec-butyl reaction of naphthalene, reactive behavior obviously improves before than modification, and 2-sec-butyl naphthalene selectivity is near 100%.So this method is compared than modified catalysts such as the used rare metals of additive method, it is low to have a cost, and " three wastes " are few, the advantage that economic benefit is high.
This method operation steps is as follows:
A. naphthalene, inorganic salt dewatering agent, inert organic solvents mixing are added the high pressure that has induction stirring and add reactor; in mixed still liquid, add the zeolite [molecular sieve that accounts for mixed solution total mass 1%～5% then; be to stir 0.5 hour under 120～180 ℃ the condition in protection of inert gas, temperature; naphthalene in molar ratio then: 2-butylene=1: 0.08～0.8 feeds reaction system with 2-butylene; continue reaction 4～6h, be cooled fast to room temperature then.
B. still liquid is filtered, filtrate is used deionized water wash, leaves standstill, and divides oil-yielding stratum.
Used inorganic salt dewatering agent is an anhydrous sodium sulphate among the above-mentioned steps a, and the adding quality is 2～5g, and used inert organic solvents does not participate in reaction, preferred normal hexane or hexanaphthene, and add-on is the mol ratio naphthalene: solvent=1: 15～30.
Used zeolite molecular sieve is for using Mg among the above-mentioned steps a
2+The USY molecular sieve of part exchange, its preparation method is an equi-volume impregnating: taking by weighing a certain amount of above-mentioned HUSY molecular sieve, measure water-absorbent in watch-glass, is the Mg (NO of 0～1mol/L by the water regain compound concentration
3)
26H
2O solution evenly is added drop-wise in the molecular sieve.At room temperature leave standstill 24h, evaporating water with 550 ℃ of roasting 5h, obtains different concns Mg
2+The USY zeolite [molecular sieve of modification, wherein Mg
2+Exchange capacity is 0～200mmol/100gCat.
Used inertia protection gas is nitrogen among the above-mentioned steps a.
Embodiment:
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1:
Take by weighing 8g HUSY molecular sieve, measuring water regain in watch-glass is 13ml, by water regain preparation Mg
2+Concentration is the Mg (NO of 0.5mol/L
3)
26H
2O solution evenly is added drop-wise in the molecular sieve.At room temperature leave standstill 24h, and then 120 ℃ of oven dry 2h evaporating water in the baking oven, again in retort furnace with 550 ℃ of roasting 5h, obtain Mg
2+The USY zeolite [molecular sieve of modification, wherein Mg
2+Exchange capacity is the 81.25mmol/100g catalyzer.
Embodiment 2:
Take by weighing the 6.42g refined naphthalene, solid water-free sodium sulfate 3.5g adds it in high pressure reacting by heating still that has induction stirring with the 100ml normal hexane, stirs to add the above-mentioned Mg of 0.5g down
2+The USY zeolite [molecular sieve of modification, the sealed reaction system, heat temperature raising to 200 ℃ under the nitrogen protection keeps 0.5h, and with the mol ratio naphthalene: the ratio of 2-butylene=1: 0.2 feeds 2-butylene in system.200 ℃ of temperature of reaction, reaction pressure 2MPa behind the reaction times 6h, is quickly cooled to room temperature, obtains containing the still liquid of 2-sec-butyl naphthalene component, filters, and uses deionized water wash, and standing demix divides oil-yielding stratum.Oil reservoir gas chromatograph analysis revealed, the 2-butylene transformation efficiency is 100%, does not have 1-sec-butyl naphthalene to generate, and it is 99.7% that 2-sec-butyl naphthalene is received, and di-secondary dibutyl naphthalene selectivity is 0.3%.
Embodiment 3:
Take by weighing the 6.42g refined naphthalene; solid water-free sodium sulfate 3.5g; it is added in the high pressure reacting by heating still that has induction stirring with the 100ml normal hexane; stir and add 0.5g HUSY zeolite [molecular sieve down; the sealed reaction system; heat temperature raising to 200 ℃ under the nitrogen protection keeps 0.5h, and with the mol ratio naphthalene: the ratio of 2-butylene=1: 0.2 feeds 2-butylene in system.200 ℃ of temperature of reaction, reaction pressure 2MPa behind the reaction times 6h, is quickly cooled to room temperature, obtains containing the still liquid of 2-sec-butyl naphthalene component, filters, and uses deionized water wash, and standing demix divides oil-yielding stratum.Oil reservoir gas chromatograph analysis revealed, 2-butylene transformation efficiency are 100%, and 1-sec-butyl naphthalene selectivity is 0.73%, and it is 88.99% that 2-sec-butyl naphthalene is received, and di-secondary dibutyl naphthalene selectivity is 10.28%.
Embodiment 4:
Take by weighing the 6.42g refined naphthalene, solid water-free sodium sulfate 3.5g adds it in autoclave that has induction stirring with the 100ml normal hexane, stirs to add the above-mentioned Mg of 0.5g down
2+The USY zeolite [molecular sieve of modification, the sealed reaction system, heat temperature raising to 160 ℃ under the nitrogen protection keeps 0.5h, and with the mol ratio naphthalene: the ratio of 2-butylene=1: 0.1 feeds 2-butylene in system.160 ℃ of temperature of reaction, reaction pressure 2MPa behind the reaction times 4h, is quickly cooled to room temperature, obtains containing the still liquid of 2-sec-butyl naphthalene component, filters, and uses deionized water wash, and standing demix divides oil-yielding stratum.Oil reservoir gas chromatograph analysis revealed, 2-butylene transformation efficiency are 100%, and 1-sec-butyl naphthalene selectivity is 10.37%, and it is 84.53% that 2-sec-butyl naphthalene is received, and di-secondary dibutyl naphthalene selectivity is 5.1%.
Subordinate list is the contrast table of (two routine experiment conditions and step are identical) reaction result under embodiment 2,3 conditions.
Subordinate list
Claims (9)
1.2-the preparation method of sec-butyl naphthalene is characterized in that at Mg
2+Under the USY Zeolite molecular sieve catalysis of modification, with the naphthalene is raw material A, with the 2-butylene is raw material B, with the inert organic solvents is raw material C, will be by raw material A, raw material B, raw material C with A: B: C=1: the mixture that 0.08～0.8: 15～30 mol ratio is formed, under 100～300 ℃ temperature of reaction, under the reaction pressure of 1～4MPa, in having the autoclave of induction stirring, react 2～12h and come Synthetic 2-sec-butyl naphthalene.
2. the preparation method of 2-sec-butyl naphthalene according to claim 1 is characterized in that catalyzer is a zeolite molecular sieve, and it is to use Mg
2+Concentration is the Mg (NO of 0～1mol/L
3)
26H
2The USY zeolite molecular sieve that O solution partly exchanges, exchange capacity 0～200mmol/100g Cat..
3. according to the preparation method of claim 1,2 described 2-sec-butyl naphthalenes, it is characterized in that catalyzer should activate 4～6h down at 550 ℃ before reaction.
4. the preparation method of 2-sec-butyl naphthalene according to claim 1, the mol ratio that it is characterized in that each raw material in raw material A, B, the C mixture is A: B: C=1: 0.1～0.6: 16～25.
5. the preparation method of 2-sec-butyl naphthalene according to claim 1 is characterized in that temperature of reaction is 160～240 ℃.
6. the preparation method of 2-sec-butyl naphthalene according to claim 1 is characterized in that reaction pressure is 1.5～3MPa.
7. the preparation method of 2-sec-butyl naphthalene according to claim 1 is characterized in that the reaction times is 4～10h.
8. the preparation method of 2-sec-butyl naphthalene according to claim 1 is characterized in that inert organic solvents does not participate in reaction in reaction process, and the organic compound that dissolves each other with naphthalene and 2-butylene.
9. according to the preparation method of claim 1,8 described 2-sec-butyl naphthalenes, it is characterized in that inert organic solvents is a normal hexane.
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| CN2010101825677A CN102260134A (en) | 2010-05-26 | 2010-05-26 | Preparation method of 2-sec-butylnaphthalene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826980A (en) * | 2012-09-04 | 2012-12-19 | 华东理工大学 | Method for preparing methyl ethyl ketone by performing gas phase dehydration on 2,3-butanediol |
-
2010
- 2010-05-26 CN CN2010101825677A patent/CN102260134A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826980A (en) * | 2012-09-04 | 2012-12-19 | 华东理工大学 | Method for preparing methyl ethyl ketone by performing gas phase dehydration on 2,3-butanediol |
| CN102826980B (en) * | 2012-09-04 | 2014-10-15 | 华东理工大学 | Method for preparing methyl ethyl ketone by performing gas phase dehydration on 2,3-butanediol |
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Application publication date: 20111130 |