CN103739422B - Preparation method of dialkyl benzene - Google Patents
Preparation method of dialkyl benzene Download PDFInfo
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- CN103739422B CN103739422B CN201410040830.7A CN201410040830A CN103739422B CN 103739422 B CN103739422 B CN 103739422B CN 201410040830 A CN201410040830 A CN 201410040830A CN 103739422 B CN103739422 B CN 103739422B
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Abstract
The invention relates to the field of chemical product production, and particularly relates to a preparation method of dialkyl benzene. The preparation method of the dialkyl benzene comprises the following steps: mixing alkylbenzene and alpha-olefin in a molar ratio of 1-4:1, wherein side chain groups of the alkylbenzene and the alpha-olefin have different carbon numbers, taking amphoteric metal chloride as a catalyst, and continuously reacting for 15-60min at a reaction temperature of 20-80 ℃ after mixing; and adding solid strong base into the product obtained after the reaction in the step to neutralize the catalyst, stirring for 5-30min to obtain a neutralized solution, and then distilling and filtering to obtain the dialkyl benzene. The product of the preparation method of the dialkyl benzene provided by the invention is the asymmetric dialkyl benzene, the method fills the blank that no preparation method for preparing the asymmetric dialkyl benzene product exists in the technical field, and the prepared asymmetric dialkyl benzene product can fully meet the market demand.
Description
Technical field
The present invention relates to chemical products production field, in particular to the preparation method of a kind of pair of alkylbenzene.
Background technology
Asymmetric pair of alkylbenzene has numerous characteristics such as condensation point is low, viscosity is low, can be used for preparing two alkyl benzene sulphonates and its esters product, the benzene sulfonic acid of preparing and its esters product have fabulous cleansing performance and low temperature flowability, but also do not have now a kind of preparation method who is used for preparing asymmetric pair of alkylbenzene to produce asymmetric pair of alkylbenzene, therefore can not meet the demand of the two alkylbenzene products of the right title in market.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of pair of alkylbenzene, to solve the above problems.
The preparation method of two alkylbenzenes of the embodiment of the present invention, comprises the following steps:
(A) alkylbenzene is mixed with mol ratio 1-4:1 with alpha-olefin, wherein the side-chain radical of alkylbenzene is different carbon numbers from alpha-olefin, taking amphoteric metal chloride as catalyst, after mixing, continue to react 15-60min under reaction temperature is the condition of 20-80 DEG C;
(B) product above-mentioned steps having been reacted adds solid alkali with catalyst neutralisation, stirs after 5-30min and obtains neutralizer, distills afterwards, filters and obtain pair alkylbenzenes.
The preparation method of two alkylbenzenes that the embodiment of the present invention provides, product is asymmetric pair of alkylbenzene, this method has been filled up and has been never had in the art the blank for the preparation of the preparation method of asymmetric pair of alkylbenzene product, and the asymmetric pair of alkylbenzene product of preparing can fully meet the demand in market.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail.
A preparation method for pair alkylbenzene, comprises the following steps:
(A) alkylbenzene is mixed with mol ratio 1-4:1 with alpha-olefin, wherein the side-chain radical of alkylbenzene is different carbon numbers from alpha-olefin, taking amphoteric metal chloride as catalyst, after mixing, continue to react 15-60min under reaction temperature is the condition of 20-80 DEG C;
(B) product above-mentioned steps having been reacted adds solid alkali with catalyst neutralisation, stirs after 5-30min and obtains neutralizer, distills afterwards, filters and obtain pair alkylbenzenes.
The product that two Production from Alkyl Benzene Preparation Methods of the embodiment of the present invention obtain can meet the demand of market to two alkylbenzene products, in preparation process because alpha-olefin price in raw material is more expensive, so can allow alpha-olefin participate in reaction completely in course of reaction, alkylbenzene can be excessive.
In the time that the carbon number of alkylbenzene and these two kinds of raw materials of alpha-olefin is lower, product oil-soluble is poor, and higher its oil-soluble of carbon number also can be become better and better, along with carbon number raises, its viscosity also can be increasing, also can affect the operation in preparation process, therefore carbon number should not be too high also should not be too low, the side-chain radical carbon number of alkylbenzene is preferably C8-C16, the carbon number of alpha-olefin is preferably C8-C24, carbon number had both had good oil-soluble in this scope, also relatively good operation.
Due in course of reaction, thereby the self-polymeric reaction that is also accompanied by alpha-olefin can affect the efficiency of pcr product of main reaction, therefore preferably, in step (A), alpha-olefin adopts the mode dripping to react with alkylbenzene, wherein the temperature of the dropping of alpha-olefin is 20-80 DEG C, and the time of dropping is 60-120min, and operating like this alpha-olefin can drip while react with alkylbenzene, and can there is not on a large scale autohemagglutination phenomenon, the autohemagglutination that only has little amount produces.
Preferably, catalyst is the 1-10% of alpha-olefin quality, the effect of catalyst is relatively good within the scope of this, and the too large catalytic effect of catalyst amount can further not promote the waste that can cause on the contrary catalyst, the too little catalytic effect that do not have of catalyst amount more yet.
Preferably, the mass ratio of solid alkali and catalyst is 1-8:1, and for catalyst neutralisation, the amount of highly basic too conference causes waste also can increase recovery difficult, measures the too little effect that does not have neutralization, therefore will select suitable alkali number.
In order to improve filter efficiency, the filter aid that first to add with the mass ratio of catalyst in neutralizer before therefore preferably, in step (B), distilling, filtering be 0.5-3:1.
In order to improve the efficiency of filtration, filter and preferably adopt heat filtering, before because the low specific filtration resistance of the viscosity of the high product of temperature is easier to, therefore preferably, distilling, filtering, first neutralizer is warming up to 80-200 DEG C and adds again filter aid.
Preferably, in step (B), also adding the water of the 50-300% of catalyst quality in adding solid alkali, is in order to promote the decentralization of solid alkali in product can better neutralize catalyst wherein thereby add water.
Preferably, catalyst is one or more in iron chloride, zinc chloride, aluminium chloride and stannous chloride, and the catalytic capability of these several catalyst is more intense.
Preferably, highly basic is one or more in NaOH, potassium hydroxide, calcium hydroxide and calcium oxide.
Embodiment 1
To insert in heating jacket and install thermometer, reflux condensing tube with the four-hole boiling flask stirring, be C to adding side chain carbon number in four-hole boiling flask9Alkylbenzene 92.0g and C8Alpha-olefin 92.0g, after catalyst aluminium chloride 0.9g, setting reaction temperature is 20 DEG C, after reaction 15min, in the material having reacted, add in calcium oxide 10g and stir 5min, again through distillation, filter and prepare two alkylbenzene product 54.4g, except efficiency of pcr product and olefin conversion do not carry out the detection of other indexs of product.
Embodiment 2
To insert in heating jacket and install thermometer, reflux condensing tube and separatory funnel with the four-hole boiling flask stirring, be C to adding side chain carbon number in four-hole boiling flask8Alkylbenzene 95g and catalyst stannous chloride 1.68g after, in separatory funnel, add C24Alpha-olefin 168g drips alpha-olefin with separatory funnel while stirring in four-hole boiling flask, drips process temperature and is controlled at 20 DEG C, in 60min, dropwises. Setting reaction temperature is 80 DEG C, reacts after 60min, in the material having reacted, adds in water 2g and NaOH 1.7g and stirs 30min, is then warming up to 80 DEG C, adds filter aid 15g, then prepares two alkylbenzene product 185g through distillation, filtration.
Embodiment 3
To insert in heating jacket and install thermometer, reflux condensing tube and separatory funnel with the four-hole boiling flask stirring, be C to adding side chain carbon number in four-hole boiling flask16Alkylbenzene 1210g and catalyst aluminium chloride 6.5g, after zinc chloride 4.7g, in separatory funnel, add C8Alpha-olefin 112g drips alpha-olefin with separatory funnel while stirring in four-hole boiling flask, drips process temperature and is controlled at 80 DEG C, in 120min, dropwises. Setting reaction temperature is 40 DEG C, after reaction 45min, in the material having reacted, add in water 30g and potassium hydroxide 12.8g and stir 20min, being then warming up to 200 DEG C, adding filter aid 33.8g to prepare asymmetric couple of alkylbenzene product 295g through distillation, filtration again.
Embodiment 4
To insert in heating jacket and install thermometer, reflux condensing tube and separatory funnel with the four-hole boiling flask stirring, be C to adding side chain carbon number in four-hole boiling flask12Alkylbenzene 196.0g and catalyst iron chloride 6.2g after, in separatory funnel, add C20Alpha-olefin 112.0g drips alpha-olefin with separatory funnel while stirring in four-hole boiling flask, drips process temperature and is controlled at 70 DEG C, in 100min, dropwises. Setting reaction temperature is 50 DEG C, after reaction 50min, in the material having reacted, add in water 10g and calcium hydroxide 49g and stir 15min, being then warming up to 150 DEG C, adding filter aid 18.5.0g to prepare asymmetric couple of alkylbenzene product 189.8g through distillation, filtration again.
Embodiment 5
To insert in heating jacket and install thermometer, reflux condensing tube and separatory funnel with the four-hole boiling flask stirring, be C to adding side chain carbon number in four-hole boiling flask12Alkylbenzene 246g and catalyst aluminium chloride 2.0g, after stannous chloride 1.75g, in separatory funnel, add C16Alpha-olefin 75g drips alpha-olefin with separatory funnel while stirring in four-hole boiling flask, and dropping temperature is controlled at 30 DEG C, in 100min, dropwises. Setting reaction temperature is 25 DEG C, after reaction 60min, in the material having reacted, add in water 3g and calcium hydroxide 15g and stir 20min, being then warming up to 120 DEG C, adding filter aid 8g to stir 10min and prepare asymmetric couple of alkylbenzene product 141g through distilling, filtering again.
The concrete outcome of physical and chemical index, efficiency of pcr product and the olefin conversion of two alkylbenzene products that embodiment 1-5 prepares sees the following form 1:
Physical and chemical index, efficiency of pcr product and the olefin conversion of table 1 pair alkylbenzene product
As can be seen from Table 1, two alkylbenzene product yield that the embodiment of the present invention is prepared are higher, raw material conversion ratio is also higher, the physical and chemical indexs such as this pair of viscosity of alkylbenzene own, condensation point are also relatively good, the demand that the asymmetric pair of alkylbenzene that utilizes the preparation method of the embodiment of the present invention to prepare can meet the two alkylbenzenes of right title on market, realizes product balance between supply and demand.
In the present invention, because the alpha-olefin in raw material transforms completely, while therefore calculating, calculate taking alkene as primary standard substance, the specific formula for calculation of raw material olefin conversion and efficiency of pcr product is as follows:
Efficiency of pcr product=(product quality/alkene quality) × 100%
Olefin conversion=[1-(cut quality × cut bromine number/alkene bromine number × alkene quality)] × 100%
Embodiment 6
Three kinds of same conditions of alkylbenzene such as the asymmetric pair of alkylbenzene of respectively embodiment 3 being prepared, commercially available monoalkyl benzene and C12 symmetric double alkylbenzene are carried out sulfonation and calcify reaction, obtain three kinds of sulfonate with high base number calcium products. Its product physical and chemical index and simulation evaluation correction data are in table 2 and table 3.
The different alkylbenzene calcium alkylbenzenesulfonate of table 2 physical and chemical index
The different alkylbenzene calcium alkylbenzenesulfonate of table 3 simulation evaluation data
The asymmetric pair of alkylbenzene of preparing with embodiment 3 is as can be seen from Table 2 that the synthetic sulfonate with high base number calcium product physical and chemical index of raw material is all better than latter two, because actual physical and chemical index detection data are that the numerical value of calcium content, total base number is higher, the quality of viscosity, the lower sulfoacid calcium of producing of turbidity is better, and cleannes are higher.
Simulation evaluation data in table 3 are shortcoming scoring according to state's calibration method introduction, therefore the lower explanation properties of product of mark are better, therefore from table 3, obviously find out that the asymmetric pair of alkylbenzene of preparing with embodiment 3 is that the synthetic sulfonate with high base number calcium product serviceability of raw material is all better than latter two.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations. Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. a preparation method for two alkylbenzenes, is characterized in that, comprises the following steps:
(A) alkylbenzene is mixed with mol ratio 1-4:1 with alpha-olefin, wherein saidThe side-chain radical of alkylbenzene is different carbon numbers from alpha-olefin, with iron chloride, zinc chloride, chlorinationOne or more in aluminium and stannous chloride are catalyst, continue in reaction temperature to be after mixingUnder the condition of 20-80 DEG C, react 15-60min;
Wherein, alpha-olefin adopts the mode dripping to react with described alkylbenzene, Qi ZhongsuoThe temperature of stating the described dropping of alpha-olefin is 20-80 DEG C, and the time of described dropping is60-120min, catalyst is the 1-10% of described alpha-olefin quality;
The side-chain radical carbon number of described alkylbenzene is C8-C16, the carbon number of described alpha-olefin isC8-C24；
(B) product above-mentioned steps having been reacted adds solid alkali to urge described in neutralizingAgent, stirs after 5-30min and obtains neutralizer, distills afterwards, filters and obtain pair alkylbenzenes.
2. the preparation method of according to claim 1 pair of alkylbenzene, is characterized in that,The mass ratio of described solid alkali and described catalyst is 1-8:1.
3. the preparation method of according to claim 1 pair of alkylbenzene, is characterized in that,In described step (B), before distilling, filtering, first in described neutralizer, addWith the mass ratio of the described catalyst filter aid that is 0.5-3:1.
4. the preparation method of according to claim 1 pair of alkylbenzene, is characterized in that,In described step (B), in adding solid alkali, also add described catalyst qualityThe water of 50-300%.
5. the preparation method of according to claim 1 pair of alkylbenzene, is characterized in that,Described highly basic is a kind of or several in NaOH, potassium hydroxide, calcium hydroxide and calcium oxideKind.
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| CN104119199A (en) * | 2014-07-16 | 2014-10-29 | 中科合成油技术有限公司 | Deacidification method for hanging type tetrahydrodicyclopentadiene |
| CN105237325A (en) * | 2015-10-08 | 2016-01-13 | 江苏汉光实业股份有限公司 | Ultrahigh-purity alkyl benzene |
| CN113004150B (en) * | 2021-03-08 | 2021-10-29 | 江苏极易新材料有限公司 | Synthesis method of diphenylamine L57 and L67 |
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| CN1092755A (en) * | 1991-12-23 | 1994-09-28 | 环球油品公司 | Carry out the method for benzene alkylation with fluorizated sial and straight chain mono-olefins |
| CN101641308A (en) * | 2007-03-20 | 2010-02-03 | 埃克森美孚研究工程公司 | Alkylaromatic lubricant fluids |
| CN102344824A (en) * | 2011-09-06 | 2012-02-08 | 刘峰 | Preparation method of arene-containing synthetic hydrocarbon |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092755A (en) * | 1991-12-23 | 1994-09-28 | 环球油品公司 | Carry out the method for benzene alkylation with fluorizated sial and straight chain mono-olefins |
| CN101641308A (en) * | 2007-03-20 | 2010-02-03 | 埃克森美孚研究工程公司 | Alkylaromatic lubricant fluids |
| CN102344824A (en) * | 2011-09-06 | 2012-02-08 | 刘峰 | Preparation method of arene-containing synthetic hydrocarbon |
Non-Patent Citations (1)
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| 双烷基苯磺酸钠的合成及张力性能研究;张立明等;《化工进展》;20071231;第26卷(第8期);第1129-1131,1144页 * |
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