CN102924213B - Method for producing isoalkanes from n-alkanes through catalysis - Google Patents

Method for producing isoalkanes from n-alkanes through catalysis Download PDF

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CN102924213B
CN102924213B CN201210466208.3A CN201210466208A CN102924213B CN 102924213 B CN102924213 B CN 102924213B CN 201210466208 A CN201210466208 A CN 201210466208A CN 102924213 B CN102924213 B CN 102924213B
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acid
alkyl
ionic liquid
reaction
isomerization
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CN102924213A (en
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杨淑清
竺柏康
郑贤敏
张仁坤
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Zhejiang Ocean University ZJOU
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Zhejiang Ocean University ZJOU
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Abstract

The invention relates to a sulfonic acid-functionalized ionic liquid used as a catalyst and a method for producing isoalkanes from n-alkanes, in particular to a method for producing isohexane form n-hexane. The ionic liquid is [A]n<+>[B]n<->, wherein [A]n<+> is a sulfonic group-containing organic cation and [B] n<-> is the corresponding organic anion or inorganic anion. According to the invention, the process, which applys the ionic liquid, has the advantages of low reaction temperature, low catalyst cost, high conversion of n-alkanes and high selectivity of isoalkanes, and has good social and economic benefits.

Description

A kind of catalysis normal alkane isomerization is produced the method for isoparaffin
Technical field
The present invention relates to a kind of isomerized method of N-alkanes, relate to especially and a kind ofly take sulfonate functional ionic liquid as catalyzer, catalysis normal alkane isomerization is produced the method for isoparaffin, belongs to petrochemical industry.
Background technology
Octane value is a most important parameters weighing gasoline engine fuel capability of antidetonance quality.It is the first-selected index of considering motor spirit quality.The octane value of gasoline is higher, the capability of antidetonance is just better, engine just can use higher compression ratio, thereby can improve engine power and efficiency of combustion, this not only can increase the actual service life of vehicle, again can considerable ground fuel economy, thus to improve gasoline dynamic performance, slow down the consumer process important in inhibiting of non-renewable petroleum resources.
In recent decades; fast development along with automotive industry; within the scope of All Around The World; demand sustainable growth to stop bracket gasoline; and be accompanied by the automobile exhaust emission standard to the pay attention to day by day of environment protection and various countries' increasingly stringent; low sulfur-bearing, containing alkene, aromatic hydrocarbons, more and more do not become important high octane gasoline component as the isoparaffin of the impurity such as benzene; and saturated normal alkane isomerization is become to isoparaffin, it is an important method that obtains isomerized alkyl; this can improve the octane value of gasoline significantly, and then has improved its combustionproperty.With regard to China, along with the increase day by day of imported crude oil quantity in recent years, also increase gradually in the source of C5/C6 benzoline, C5/C6 normal paraffin is passed through to isomerization process, lower positive structure C5, the C6 alkane isomerization of octane value can be become to isoparaffin, can improve thus gasoline octane value, improve the low-temperature fluidity of gasoline.But so far, the gasoline production of China mainly comes from the catalytic cracking of oil, C5/C6 alkane isomerization does not form larger suitability for industrialized production ability yet.Therefore, the C5/C6 catalyst for normal paraffin isomerization of exploitation high reactivity, highly selective and efficiently normal alkane isomerization technique have also become a study hotspot in refining of petroleum field, have very good prospects for commercial application and huge economic value.
In current prior art document, C5/C6 alkane isomerization industry catalyzer mostly is dual-function catalyst, described " dual-function catalyst " refers to the metal/acid carrier dual-function catalyst using in alkane isomerization technique, metal wherein comprises precious metals pt, Pd or non-noble metal Ni, Co etc., acid carrier wherein mainly comprises oxide compound and molecular sieve, as the Al of acid treatment 2o 3, molybdenum oxide, Si-Al molecular sieve, phosphate aluminium molecular sieve etc.This dual-function catalyst is divided into high temperature modification (temperature of reaction >=320 ℃), middle warm type (200 ℃ of < temperature of reaction <320 ℃) and low temperature modification (temperature of reaction≤200 ℃) three classes according to the difference of operant response temperature; they are mainly used in hydroisomerization reaction, and described " facing hydrogen " refers to operate under hydrogen existence or hydrogen shield and carry out.Such dual-function catalyst need operate at higher temperature, and isomerization reaction is thermopositive reaction, and temperature of reaction lower on thermodynamics is more favourable, so improve catalyzer, reduce temperature of reaction, is the development trend of such catalyzer.
Except dual-function catalyst, solid acid catalyst is also study hotspot and the emphasis in alkane isomerization catalyst field.
People (Garin F., Andriamasinoro D., Abdulsamad A., the Sommer J..Conversion of butane over the solid superacid ZrO such as Garin F. 2/ SO 4 2-in the presence ofhydrogen.J.Catal.1991,131 (1), 199) prepared the SO of supporting Pt 4 2-/ ZrO 2solid acid catalyst, and for Butane isomerization, find after 500 minutes, still to there is good activity in reaction.
(Lei T., Xu J.S., Tand Y., Hua W.M., the Gao Z.New solid superacidcatalysts for n-butane isomerization: γ-Al such as Lei T. 2o 3or SiO 2supported sulfated zirconia.Appl.Catal.A:General, 2000,192,181) make γ-Al 2o 3and SiO 2load SO 4 2-/ ZrO 2solid acid catalyst, uses it for Butane isomerization.
CN1094787 is by amorphous ZrO (OH) xwith H 2wO 4carry out mechanically mixing, thereby obtain WO x-ZrO 2heteropolyacid catalyst, when using it for n-heptane isomerization, at the temperature of 320 ℃ and 400 ℃, the transformation efficiency of normal heptane is respectively 44.3% and 48.7%, although can be for the isomerization of normal heptane, temperature of reaction is higher.
A.Corma, the people such as J.M.Serra (A.Corma, J.M.Serra, A.Chica.Discovery of newparaffin isomerization catalysts based on SO 4 2-/ ZrO 2and WO x/ ZrO 2applyingcombinatorial techniques.Catalysis Today, 2003,81 (3): the 495-506) SO of exploitation 4 2-/ MXOY type catalyst acid intensity is large, environmentally friendly, and thermostability is high, but in application process SO 4 2-easily run off, and more difficult supplementing.Another shortcoming is that specific surface area is little, and acid being difficult for regulates.
And a kind of as in solid acid catalyst, heteropolyacid catalyst has been subject to attention with the advantages such as acidity, multifunctionality, reacting field homogeneous and " false liquid phase " behavior of its uniqueness in isomerization catalytic field, for example, at M.S.Jose, C.Antonio, C.Avelino.Heteropolyanions based catalystsfor paraffins isomerization.Catalysis Today, 65 (2-4): be described in detail in 355-361.
Heteropolyacid catalyst is mainly divided into heteropolyacid salt catalyst and carried heteropoly acid salt catalyst.
People (the Na K such as Na K, Okuhara T, Misono M, Skeletal Isomerization ofn-Butane Catalyzed by an Acidic Cesium Salt of 12-Tungstophosphoric Acid.Chem Lett, 1993,7:1141-1144) studied H 3pW 12o 40, Cs 2.5h 0.5pW 12o 40, SO 4 2-/ ZrO 2, the catalytic performance to normal butane skeletal isomerization after H-ZSM-5 and their supporting Pt, Pd, find H 3pW 12o 40active and to the selectivity of Trimethylmethane all far away higher than SO 4 2-/ ZrO 2although the activity of H-ZSM-5 is very high, very poor to the selectivity of Trimethylmethane.
People (Miyaji A, Ohnishi R, the Okuhar T.Skeletal isomerizaiton ofn-heptane over Pd-H such as Miyaji A 4siW 12o 40supported on SiO 2: Comparative Study withTypical Bifuncitional Catalysts, Applied Catalysis A:General, 2004,262 (2): 143-148) studied Pd-H 4siW 12o 40/ SiO 2the reaction of catalysis n-heptane isomerization, result shows with typical dual-function catalyst as Pd-H beta-molecular sieve, Pt-SO 4 2-/ ZrO 2and Pd-WO 3/ ZrO 2compare Pd-H 4siW 12o 40/ SiO 2catalyzer has better activity and isomerization selectivity.
Acidic ion liquid is a kind of novel reaction medium that development in recent years is got up, it has the high-density reactive behavior of liquid acid and the non-volatility of solid acid simultaneously, in addition its structure and acid adjustable sex change, thus the potentiality that replace traditional industry acid catalytic material there are.
Existing many pieces of prior art documents disclose acidic ion liquid at low grade normal paraffin as the application in C5/C6 isomerization reaction.
Shi Zhenmin etc. delivered many pieces of articles (for example, referring to Shi Zhenmin, Wu Xiaohui, Liu Zhichang, Meng Xianghai, the impact of initiator on ionic liquid-catalyzed Isomerization of Hexane reaction, chemistry of fuel journal, 2008,36 (3): 306-310; Shi Zhenmin, Wu Xiaohui, Liu Zhichang, Meng Xianghai, the research of ionic liquid at room temperature catalysis Isomerization of Hexane reaction, chemistry of fuel journal, 2008,36 (5): 594-600) ionic liquid-catalyzed normal alkane isomerization has been carried out to following large quantity research:
[1] aluminum trichloride (anhydrous) has synthesized the ionic liquid at room temperature with different acidity according to different mol ratio from Triethylammonium chloride, and its acidity has been carried out analyzing and investigating its catalytic performance to Isomerization of Hexane reaction.Found that AlCl while synthesizing along with ionic liquid 3the increase of ratio, the acidity of ionic liquid strengthens, ionic liquid 2AlCl 3/ Et 3nHCl demonstrates good catalytic performance to Isomerization of Hexane, and has investigated reaction times, temperature of reaction and catalyst levels (the agent oil volume ratio) impact on Isomerization of Hexane reactivity worth.Result shows, reaction conditions optionally affects not quite isoparaffin, but feed stock conversion, isoparaffin productive rate and liquid yield are had to larger impact.Optimum reaction condition is: temperature of reaction is 50 ℃, and the reaction times is 45min, and agent oil volume ratio is 1: 1.
[2] in order further to improve the catalytic performance of above-mentioned [1], can in reaction system, add initiator as propyl carbinol, iso-butylene, Trimethylmethane and iso-pentane, discovery can improve speed of response, especially when adding iso-pentane, the transformation efficiency of normal hexane can reach 85.54%, liquid yield 80.08%, but in product 2,2-dimethylbutane and 2,3-dimethylbutane selectivity is still on the low side, is respectively 7.6% and 3.75%.
US6797853B discloses a kind of method of ionic liquid isomerized alkyl, wherein said ionic-liquid catalyst comprises containing N heterocycle and/or aliphatic organic cation, and derived from the inorganic anion of metal halide or its mixture, this reaction is carried out under as existence such as methylcyclohexanes at cyclic hydrocarbon additive.
US20030109767A1 discloses a kind of C5-C8 alkane isomerization process, the ionic-liquid catalyst that wherein used is containing N heterocycle and/or the combination with negatively charged ion derived from one or more metal halides containing N aliphatic series organic cation, described is partly ammonium salt compound and/or alkyl substituted pyridines, piperidines, quinoline etc. containing N, and negatively charged ion is AlCl 4 -, AlBr 4 -, GaCl 4 -, Al 2cl 7 -deng.
In WO2010074835A, disclose a kind of ionic-liquid catalyst with high Al/N mol ratio, it comprises ammonium chloro-aluminate, has at least 2.0 Al/N mol ratio.When working with vulkacit H Cl mono-, this ionic liquid can be used for Isoparaefin-olefin as the alkylation of Trimethylmethane-butylene.
Although the light hydrocarbon isomerization that the chlorine aluminic acid type ionic liquid of take is catalyst reaction, its transformation efficiency and selectivity are all better, and chlorine aluminic acid type ionic liquid still has many unsatisfactory parts.First, cl content higher (> 100mg/kg) in isomerized oil also exists mainly with the form of the organochlorines such as chloroparaffin, a large amount of studies show that, remove halohydrocarbon very difficult, although there is report to show by the raw material of the synthetic ionic liquid of purifying, can significantly reduce the halohydrocarbon content in isomerization product, but its cost is higher, and is not suitable for large-scale commercial production.Secondly, chlorine aluminic acid ionic liquid is to water sensitive, produce and use procedure in the etching problem that causes very serious, this greatly reduces ionic liquid in reaction process Green, environmental protection, original idea easy to use.The 3rd, the ionic liquid of the type is difficult for regeneration, and cost is higher, is difficult to realize large-scale industrial production.Again, the permanent stability of this chloro-aluminate are poor, and catalytic efficiency decay is very fast.
In recent years, functionalized ion liquid has become study hotspot.While introducing sulfonic group on the positively charged ion of ionic liquid, ionic liquid just becomes acidic ion liquid.This SO 3h-functionalized ion liquid is non-chlorine aluminic acid type ionic liquid, has the features such as good fluidity, non-volatile, non-corrosiveness, can replace conventional acid catalyst, has great industrial application potentiality.
Compare with chlorine aluminic acid type ionic-liquid catalyst, sulfonate functional ionic liquid has following characteristics: (1) is more gentle compared with aluminum chloride ionic liquid, less to equipment corrosion, comparatively stable to water and air, ionic liquid is repeatedly reusable, be easy to regeneration, catalyzer subsequent disposal is simple; (2) not halogen-containing in isomerization product, less to the corrosion of equipment in ionic liquid preparation and use procedure, product separation is easy.
CN101177371A discloses a kind of method of presence of acidic ionic liquid catalyst isoparaffin and olefin alkylation reaction, wherein use Trimethylmethane and C4 alkene as reactant, the positively charged ion of acidic ionic liquid catalysts is selected from glyoxaline cation or pyridylium, and negatively charged ion is selected from trifluoromethane sulfonic acid root, tosylate, bisulfate ion.Although can be with sulfonic group on positively charged ion wherein, it only clearly states the alkylated reaction for isoparaffin and C4 alkene, and more non-simple himself the isomerization reaction of non-n-alkane.
In US20110137098A, disclose under alkene exists and used the isomerized method of super acids ionic-liquid catalyst catalysis saturated alkane, described ionic liquid comprises positively charged ion and inorganic anion, and described negatively charged ion is super acid aluminum chloride-Lewis acid affixture.Although wherein can there is sulfonic acid substituting group as cationic pyridine, imidazoles etc., but it just speaks in general terms, and the negatively charged ion of this reaction is still for the above-mentioned aluminum chloride that has many defects of pointing out, so further distinguish at negatively charged ion, is aluminum chloride with the affixture of Lewis acid and reacts and must under a certain amount of alkene existence, carry out.
Although disclose the method for using sulfonic acid type ion liquid catalyst isomerized alkyl in prior art, but its raw material is isoparaffin, and must add alkene together to react, this causes complicated component in products therefrom, the isoparaffin content of expectation is too low, and then has affected the performance of final product.
Up to now, although p-sulfonic acid type ionic liquid has carried out large quantity research, have no without alkene any report that directly carries out normal alkane isomerization.From easy and simple to handle, composition is controlled, separation is simple, and have good isoparaffin optionally angle set out, for normal alkane isomerization method, still have strong and urgent demand.
Summary of the invention
Technical problem underlying to be solved by this invention, is to provide and a kind ofly take sulfonate functional ionic liquid and be that catalyst normal alkane isomerization produces the method for isoparaffin, particularly a kind of method of Isomerization of Hexane.By to the concrete selection of catalyzer and the control of isomerisation conditions, can, improving raw material normal paraffin particularly in hexane conversion rate, can improve significantly the selectivity of isoparaffin.
For achieving the above object, the invention provides and a kind ofly take sulfonate functional ionic liquid as catalyst normal paraffin is as the method for Isomerization of Hexane reaction, the method at least comprises the steps:
(1). make sulfonate functional ionic liquid or add the composite sulfoacid functionalized ion liquid after metallic compound to it, under pressure, by maintaining to stir, isomerization reaction occurs with normal paraffin raw material.
After reacting completely, can carry out a series of aftertreatments, described method also optionally comprises following steps:
(2). after reaction finishes, stop stirring, cooling, release, reaction product and the layering of sulfonate functional ionic liquid, upper strata is not the normal paraffin raw material of complete reaction and the mixture of the isoparaffin generating.
Wherein:
Pressure in step (1) is not particularly limited, as long as can make reaction, for example can be environmental stress (being normal atmosphere 0.1Mpa)-2.0Mpa, it comprises any sub-range scope that is positioned at this scope, exemplarily for example 0.2-1.5Mpa, 0.5-1.3Mpa, 0.7-1.1Mpa, 0.8-1.0Mpa; And comprised any concrete force value within the scope of this, exemplarily for example 0.3Mpa, 0.4Mpa, 0.6Mpa, 0.9Mpa, 1.2Mpa, 1.4Mpa, 1.6Mpa, 1.7Mpa, 1.8Mpa, 1.9Mpa.
Ionic-liquid catalyst in step (1) or the volume ratio of composite sulfoacid functionalized ion liquid catalyzer and normal paraffin are not particularly limited, as long as can this isomerization reaction of catalysis, for example can be 1:1-1:30, it comprises any sub-range scope that is positioned at this scope, 1:25 for example exemplarily, 1:20, 1:15, 1:10, 1:5, and comprised any concrete ratio within the scope of this, 1:29 for example exemplarily, 1:28, 1:27, 1:26, 1:24, 1:23, 1:22, 1:21, 1:19, 1:18, 1:17, 1:16, 1:14, 1:13, 1:12, 1:11, 1:9, 1:8, 1:7, 1:6, 1:4, 1:3, 1:2.
Temperature of reaction in step (1) is not particularly limited, as long as can make this reaction, for example can be 30-160 ℃, it comprises any sub-range scope that is positioned at this scope, exemplarily for example 40-150 ℃, 50-140 ℃, 60-130 ℃, 70-120 ℃, 80-110 ℃, 90-100 ℃, and comprised any actual temp value within the scope of this, exemplarily for example 32 ℃, 34 ℃, 36 ℃, 38 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃, 132 ℃, 134 ℃, 136 ℃, 138 ℃, 142 ℃, 144 ℃, 146 ℃, 148 ℃, 152 ℃, 154 ℃, 156 ℃ and 158 ℃.
Reaction times in step (1) is not particularly limited, as long as can make this reaction, for example can be 5-200 minute, it comprises any sub-range scope that is positioned at this scope, exemplarily for example 10-190 minute, 20-180 minute, 30-170 minute, 40-160 minute, 50-150 minute, 60-140 minute, 70-130 minute, 80-120 minute, 90-110 minute; And comprised any concrete time value within the scope of this, exemplarily for example 15 minutes, 25 minutes, 35 minutes, 45 minutes, 55 minutes, 65 minutes, 75 minutes, 85 minutes, 95 minutes, 105 minutes, 115 minutes, 125 minutes, 135 minutes, 145 minutes, 155 minutes, 165 minutes, 175 minutes, 185 minutes, 195 minutes.
In order more at large to describe the present invention, as follows a plurality of features and/or key element is wherein described in detail.
[sulfonate functional ionic liquid]
Described sulfonate functional ionic-liquid catalyst of the present invention is comprised of organic cation and organic or inorganic negatively charged ion, and it can be represented by following formula [I]:
[A] n +[B] n-[I]
Wherein:
N is the integer of 1-4, and as 1,2,3 and 4, most preferably n is 1.
[A] +for containing sulfonic organic cation, [B] n-for monovalence, divalence, trivalent or tetravalence organic anion or inorganic anion.
Particularly, [A] +in can comprise one or more in N, O, S, P atom, for example 1,2,3 or more N atom, for example, can be nitrogen heterocyclic ring positively charged ion, acyclic quaternary ammonium cation, oxygen positively charged ion, sulfonium cation Huo phosphonium cation.Preferably, [A] +for nitrogen heterocyclic ring positively charged ion or acyclic quaternary ammonium cation.
[1]. as [A] +during for nitrogen heterocyclic ring positively charged ion, it can comprise at least 1 N atom and optional 0-3 O or S atom, for example, can comprise 2 N atoms.This nitrogen heterocyclic ring can be 5-7 ring, as 5 rings or 6 rings, exemplarily [A] +the positively charged ion with following structure:
In the structural formula of above-mentioned a-f:
R is-(CR 6r 7) m-SO 3h, wherein R 6, R 7identical or different, be selected from independently of one another H, alkyl, alkoxyl group, alkyl-carbonyl, amino, be preferably H simultaneously; M is the integer of 1-10, for example, can be 2,3,4,5,6,7,8,9.
R 1, R 2, R 3, R 4, R 5identical or different, be selected from independently of one another H, alkyl, alkoxyl group, thiazolinyl, alkynyl, during preferred difference, be H.
[2]. as [A] +during for acyclic quaternary ammonium cation, it is for having structural formula-N +(R 8r 9r 10r) positively charged ion, an only N atom is the cationic positive charge carrier in this ionic-liquid catalyst.
R 8, R 9, R 10identical or different, be selected from independently of one another H, alkyl, alkoxyl group, thiazolinyl, alkynyl, during preferred difference, be H;
R is-(CR 6r 7) m-SO 3h, wherein R 6, R 7identical or different, be selected from independently of one another H, alkyl, alkoxyl group, alkyl-carbonyl, amino, be preferably H simultaneously; M is the integer of 1-10, for example, can be 2,3,4,5,6,7,8,9.
Wherein, preferred R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10identical or different, be selected from independently of one another H, C 1-9alkyl, C 1-9alkoxyl group.
Except as otherwise noted, all " alkyl " in group definition refers to the straight or branched alkyl with 1-20 carbon atom, for example, be C 3-17alkyl, C 5-14alkyl, C 7-12alkyl, C 9-10alkyl, it has comprised the arbitrary combination of any two endpoint values in these scopes, as C 1-3alkyl, C 1-5alkyl, C 1-7alkyl, C 1-9alkyl, C 3-5alkyl, C 3-7alkyl, C 3-9alkyl, C 5-7alkyl, C 5-9alkyl, C 7-9alkyl etc., and be any alkenyl or alkynyl of these scopes.The concrete group of exemplary alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, Pentadecane base, Octadecane base etc.
Except as otherwise noted, all " alkoxyl groups " in group definition refer to that " alkyl " defined above is connected with-O-and the group that forms.
Except as otherwise noted, all " carbalkoxys " in group definition refer to " alkyl " defined above and-C (O)-be connected and the group that forms.
Except as otherwise noted, all " thiazolinyl " in group definition refers to the straight or branched thiazolinyl with 2-20 carbon atom, for example C 3-17thiazolinyl, C 5-14thiazolinyl, C 7-12thiazolinyl, C 9-10thiazolinyl, it has comprised the arbitrary combination of any two endpoint values in these scopes, as C 2-3thiazolinyl, C 2-5thiazolinyl, C 2-7thiazolinyl, C 2-9thiazolinyl, C 3-5thiazolinyl, C 3-7thiazolinyl, C 3-9thiazolinyl, C 5-7thiazolinyl, C 5-9thiazolinyl, C 7-9thiazolinyls etc., the concrete group of exemplary thiazolinyl is as vinyl, propenyl, n-butene base, isobutenyl, positive pentenyl, new pentenyl, n-hexylene base, 2-methylpent thiazolinyl, 3-methylpent thiazolinyl, nhepene base, positive octenyl, positive nonene base, positive decene base, positive hendecene base, positive laurylene base, positive ten pentaene bases, positive octadecylene base etc.
Except as otherwise noted, all " alkynyl " in group definition refers to the straight or branched alkynyl with 2-20 carbon atom, for example C 3-17alkynyl, C 5-14alkynyl, C 7-12alkynyl, C 9-10alkynyl, it has comprised the arbitrary combination of any two endpoint values in these scopes, as C 2-3alkynyl, C 2-5alkynyl, C 2-7alkynyl, C 2-9alkynyl, C 3-5alkynyl, C 3-7alkynyl, C 3-9alkynyl, C 5-7alkynyl, C 5-9alkynyl, C 7-9alkynyls etc., the concrete group of exemplary alkynyl is as ethynyl, proyl, positive butynyl, isobutyl alkynyl, positive pentynyl, new pentynyl, positive hexin base, 2-methylpent alkynyl, 3-methylpent alkynyl, positive heptyne base, positive octyne base, positive n-heptylacetylene base, positive decynyl, positive undecyne base, positive dodecyne base, positive 15 alkynyls, positive octadecyne base etc.
[B] n-for the acid radical anion from sour, described acid can be mineral acid or organic acid, can exemplify sulfuric acid, phosphoric acid, methylsulfonic acid, trifluoromethanesulfonic acid, tosic acid, trifluoroacetic acid etc. to indefiniteness.Therefore, exemplarily [B] n-can be (HSO 4) -, (CH 3sO 3) -, (CF 3sO 3) -, (H 2pO 4) -, (CF 3cOO) -, (p-CH 3c 6h 4sO 3) -deng.
[normal paraffin]
Normal paraffin in the present invention refers to straight chain, there is no the alkane of side chain, and for example it can be C4-C8 normal paraffin, exemplarily as be normal butane, Skellysolve A, normal hexane, normal heptane and octane.
In the lighter hydrocarbons that straight run or hydrocracking obtain, the C5/C6 cut that separation obtains mainly contains Skellysolve A and normal hexane, their octane value is more much lower than its corresponding isomer, therefore, in order to improve the octane value of the product that straight run or hydrocracking obtain, and particularly preferably normal paraffin of the present invention is C6 normal paraffin, i.e. normal hexane.
[metallic compound]
Can optionally add the metallic compound in sulfonate functional ionic liquid is organic acid salt or the inorganic acid salt of common metal.
Described metal can be the metallic element of IB, IIB, IVB, VIB, VIIB, VIII and IIAHe IIIA family, such as can be copper, zinc, silver, nickel, iron, calcium, aluminium, titanium, manganese etc., is preferably copper, zinc, silver.
Organic acid or mineral acid in described " organic acid salt " or " inorganic acid salt " are not particularly limited, and indefiniteness ground is such as can be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, methylsulfonic acid, three fluosulfonic acid, trifluoromethanesulfonic acid, tosic acid, trifluoroacetic acid etc.
Described metallic compound is preferably copper trifluoromethanesulfcomposite [Cu (OTf) 2], copper methane sulfonate [Cu (OMs) 2], copper p-toluenesulfonate [Cu (OTs) 2], trifluoroacetic acid copper, and trifluoromethanesulfonic acid zinc [Zn (OTf) 2], methylsulfonic acid zinc [Zn (OMs) 2], tosic acid zinc [Zn (OTs) 2], trifluoroacetic acid zinc, silver trifluoromethanesulfonate, methylsulfonic acid silver, tosic acid is silver-colored, trifluoroacetic acid is silver-colored.
The inventor finds, by adding metallic compound, on the basis that can have a significant improvement with respect to prior art tool in technical solution of the present invention and/or improve, further improve significantly the transformation efficiency of normal alkane isomerization reaction, the selectivity of isoparaffin, thereby further improved the octane value of product.Produce this more the reaction mechanism of excellent effect be still not clear, the inventor thinks it may is by adding metallic compound, can more be conducive to formation and the reaction of carbonium ion, thereby accelerate the carrying out of isomerization reaction and improve the selectivity of transformation efficiency and the product of raw material.
[preparation of ionic liquid]
Sulfonate functional ionic liquid of the present invention or composite sulfoacid functionalized ion liquid are prepared as required, also can be prepared according to many currently known methodss of reporting in prior art.
Take Sulfonated acyclic quaternary ammonium cation ionic liquid, Sulfonated glyoxaline cation ionic liquid and Sulfonated pyridylium ionic liquid is example, the following preparation method who describes the sulfonated ionic liquid of the present invention or composite sulfoacid functionalized ion liquid, is mainly divided into following two steps:
[a]. synthesizing of ionic liquid presoma
Under environment solvent-free or that organic solvent exists as methyl alcohol, by (CH 3(CH 2) m) 3n or pyridine or Methylimidazole and propyl sulfonic acid lactone or butyl sulfonic acid lactone are with the mol ratio of 1:1-3, preferably 1: 1-2 mol ratio, most preferably equimolar ratio example is mixed, in room temperature-50 ℃, preferably under room temperature condition, stir 15-30 minute, be heated to 40-120 ℃, preferred 50-110 ℃, more preferably 60 ℃-100 ℃, 70-90 ℃ more preferably, most preferably be 80 ℃, continue to stir 1-48 hour, preferred 5-40 hour, more preferably 10-30 hour, most preferably 20 hours, make to react completely, obtain white solid, suction filtration, vacuum-drying, obtain corresponding sulfonate functional ionic liquid presoma, reaction formula is as follows:
[b]. the preparation of ionic liquid
In solvent-free or conventional organic solvent, ionic liquid presoma obtained above and mineral acid or organic acid are mixed with equimolar ratio example as sulfuric acid, tosic acid or trifluoromethanesulfonic acid, be heated to 40-120 ℃, preferred 50-110 ℃, more preferably 60 ℃-120 ℃, more preferably 70-110 ℃, most preferably is 80-100 ℃, be particularly preferably 90 ℃, stir 8-36 hour.Preferred 12-32 hour, more preferably 16-28 hour, most preferably is 20-24 hour.After reacting completely, remove desolventizing, vacuum-drying, obtain sulfonate functional ionic liquid.Wherein said organic solvent is the conventional organic solvent in organic synthesis field, and indefiniteness ground is as one or more mixed solvents of acetone, ethyl acetate, methylene dichloride, chloroform, tetrahydrofuran (THF) etc.This preparation method's reaction formula is as follows:
Above-mentioned reaction formula is the use for exemplifying just, but not be used for limiting or limiting to sulfonate functional ionic liquid of the present invention.Those skilled in the art after reading above-mentioned reaction formula, because reaction site and reaction mechanism all do not relate to substituting group, therefore can recognize apparently can use contain above-mentioned a-f positively charged ion or-N +(R 7r 8r 9r) respective compound is reacted with the various respective acids that comprise above-mentioned negatively charged ion, and obtains the sulfonate functional ionic liquid of the present invention [A] of formula [I] n +[B] n-, and can not think to synthesize and obtain above-mentioned a few concrete ionic-liquid catalyst of the present invention.
Optionally, in the sulfonate functional ionic liquid of synthesized, add above-mentioned any metallic compound, metallic compound is 1:1-10 with the amount of substance of ionic liquid than (being mol ratio), it has comprised any sub-range scope within the scope of this, exemplarily as 1:2-9,1:3-8,1:4-7,1:5-6, and most preferably be 1:5.Add after metallic compound, the mixture obtaining is heated to 60-180 ℃, preferably 80-160 ℃, further preferred 100-140 ℃, most preferably 120 ℃, return stirring 15-24 hour, preferred 17-22 hour, most preferably 19-20 hour, can obtain compound ion liquid of the present invention.
The present invention is by structure choice and acid adjustment of p-sulfonic acid functionalized ion liquid, thereby when by this ionic liquid for catalysis normal paraffin during as the isomerization reaction of normal hexane, when improving N-alkanes transformation efficiency, can improve targetedly the selectivity of isoparaffin, thereby improve significantly the octane value of products therefrom.
Accompanying drawing explanation
Fig. 1 is the MimN (CH of embodiment 1 preparation 2) 4sO 3h[HSO 4] infrared absorpting light spectra;
Fig. 2 is the PyN (CH of embodiment 3 preparations 2) 4sO 3h[HSO 4] infrared absorpting light spectra;
Fig. 3 is N-(4-sulfonic group) butyl-triethylamine hydrosulfate infrared absorpting light spectra of embodiment 4 preparations.
Embodiment
Below by specific embodiment, the present invention is described in detail, but these exemplary embodiments not form any type of any restriction to real protection scope of the present invention.
1. the preparation of ionic liquid
Preparation Example 1
Under condition of no solvent, by 1 of N-Methylimidazole and amount of substance such as grade, 4-butane sultone mixes in there-necked flask, under room temperature condition, stir 20 minutes, be heated to 80 ℃ and stir 24 hours, obtain white solid, through organic solvent cleaning, vacuum-drying, obtaining containing sulfonic alkyl imidazole salt is that 1-methyl-3-(4-sulfonic group butyl)-imidazole salts [is abbreviated as MimN (CH 2) 4sO 3].
Sulfuric acid (H by alkyl imidazole salt obtained above with amount of substance such as grade 2sO 4) in there-necked flask, mix, at 60 ℃, stir 24 hours, obtaining sulfonate functional ionic liquid is that 1-methyl-3-(4-sulfonic group butyl)-imidazole bisulfate [is abbreviated as MimN (CH 2) 4sO 3h[HSO 4]], after vacuum-drying, be collected in moisture eliminator standby.As shown in Figure 1, absorption peak ownership is as follows for its infrared absorpting light spectra:
1-methyl-3-(4-sulfonic group butyl)-imidazole bisulfate ir data
Preparation Example 2
PS is dissolved in appropriate methyl alcohol, then the pyridine of amount of substance such as adds, at room temperature stir 20 minutes, be heated to 80 ℃ and stir 24 hours, obtain white solid, through organic solvent cleaning, vacuum-drying, obtain containing sulfonic N-(3-sulfonic group) propyl group-pyridinium salt.
Trifluoromethanesulfonic acid (CF by pyridinium salt obtained above with amount of substance such as grade 3sO 3h) in there-necked flask, mix, at 80 ℃, stir 12 hours, making sulfonate functional ionic liquid is that N-(3-sulfonic group) propyl group-pyridine fluoroform sulphonate [is abbreviated as PyN (CH 2) 3sO 3h[CF 3sO 3]], after vacuum-drying, be collected in moisture eliminator standby.
Preparation Example 3
Remove with 1,4-butane sultone replaces 1,3-propane sultone, with sulfuric acid, replace outside trifluoromethanesulfonic acid, with the same procedure with Preparation Example 2, having made sulfonate functional ionic liquid is that N-(4-sulfonic group) butyl-pyridine hydrosulfate [is abbreviated as PyN (CH 2) 4sO 3h[HSO 4]], after vacuum-drying, be collected in moisture eliminator standby.As shown in Figure 2, absorption peak ownership is as follows for its infrared absorpting light spectra:
N-(4-sulfonic group) butyl-pyridine hydrosulfate ir data
Preparation Example 4
Isosorbide-5-Nitrae-butane sultone is dissolved in appropriate methyl alcohol, then the triethylamine of amount of substance such as adds, at 30 ℃, stir 20 minutes, be heated to 75 ℃ and stir 20 hours, steam after solvent, vacuum-drying, obtains containing sulfonic N-(4-sulfonic group) butyl three second ammoniums.
Ammonium salt obtained above is mixed in there-necked flask with waiting sulfuric acid of amount of substance, at 80 ℃, stir 13 hours, making sulfonate functional ionic liquid is N-(4-sulfonic group) butyl-tri-second ammonium bisulphate salt, after vacuum-drying, is collected in moisture eliminator standby.As shown in Figure 3, absorption peak ownership is as follows for its infrared absorpting light spectra:
N-(4-sulfonic group) butyl-triethylamine hydrosulfate ir data
Preparation Example 5
In the sulfonate functional ionic liquid obtaining to Preparation Example 1, add metallic compound copper trifluoromethanesulfcomposite Cu (OTf) 2, Cu (OTf) 2with the ratio of the amount of substance of ionic liquid be 1:5, and add a small amount of normal heptane hydrotropy, continue to increase the temperature to about 100-120 ℃, stir about 24 hours, until Cu (OTf) 2participating in reaction completely (is Cu (OTf) 2solid disappears change into liquid completely), steam normal heptane, obtain compound ion liquid [MimN (CH 2) 4sO 3h] [HSO 4]/Cu (OTf) 2.
Preparation Example 6-8
With the method identical with embodiment 5, respectively by copper methane sulfonate [Cu (OMs) 2], copper p-toluenesulfonate [Cu (OTs) 2] or trifluoroacetic acid copper join in the sulfonate functional ionic liquid that embodiment 1 obtains, thereby make respectively corresponding compound ion liquid.
Preparation Example 9-12
With the method identical with embodiment 5, respectively by copper trifluoromethanesulfcomposite Cu (OTf) 2, copper methane sulfonate [Cu (OMs) 2], copper p-toluenesulfonate [Cu (OTs) 2] or trifluoroacetic acid copper join in the sulfonate functional ionic liquid that embodiment 3 obtains, thereby make corresponding PyN (CH 2) 4sO 3h[HSO 4] compound ion liquid.
Preparation Example 13-16
With the method identical with embodiment 5, respectively by copper trifluoromethanesulfcomposite Cu (OTf) 2, copper methane sulfonate [Cu (OMs) 2], copper p-toluenesulfonate [Cu (OTs) 2] or trifluoroacetic acid copper join in the sulfonate functional ionic liquid that embodiment 4 obtains, thereby make corresponding N-(4-sulfonic group) butyl-tri-second ammonium bisulphate salt compound ion liquid.
2. the preparation of normal paraffin isomerized products
Following isomerization reaction of take normal hexane is example, further sets forth technical scheme of the present invention and consequent advantage.
Wherein gaseous sample adopts Aglient 6890 gas-chromatographies to analyze, and with HP Station, data is processed, and obtains each component volume fraction in product, then according to equation for ideal gases, obtains the massfraction of each component.
In isomerization reaction, being accompanied by disproportionation reaction, except the isomer that contains hexane, also having butane, pentane and the above component of C6, is the catalytic performance of accurate description ionic-liquid catalyst of the present invention, adopts following parameter to investigate:
Hexane conversion rate=[(residue normal hexane quality after the quality-reaction of charging normal hexane)/charging normal hexane quality] * 100%.
Isoparaffin selectivity=(the gross product quality that isoparaffin quality in product/reaction generates) * 100%.
embodiment 1
In autoclave, add 10ml ionic liquid [MimN (CH 2) 4sO 3h] [HSO 4], airtight stirring, control pressure is about 0.5MPa, and temperature 50 C adds 100ml normal hexane continue to stir, and react after 50 minutes, stops stirring, and ON cycle water is its cool to room temperature, product and ion liquid system AUTOMATIC ZONING, upper strata is reaction product.
Through gas chromatographic analysis, find, hexane conversion rate is 91%, in isomerization product: 2, the selectivity of 2-dimethylbutane is that the selectivity of 10.83%, 2,3-dimethylbutane is 5.93%, the selectivity of 2-methylpentane is that the selectivity of 14.76%, 3-methylpentane is 7.12%.
embodiment 2
In autoclave, add 20ml ionic liquid [PyN (CH 2) 3sO 3h] [CF 3sO 3], airtight stirring, control pressure is 0.6MPa, temperature is about 60 ℃, add 600ml normal hexane to carry out isomerization reaction, continue to stir, react after 60 minutes, reaction finishes, stop stirring, be cooled with circulating water room temperature, product and ion liquid system AUTOMATIC ZONING, upper strata is reaction product.
Through gas chromatographic analysis, find, the transformation efficiency of normal hexane reaches 92%, in isomerization product: 2, the selectivity of 2-dimethylbutane is that the selectivity of 11.12%, 2,3-dimethylbutane is 7.56%, the selectivity of 2-methylpentane is that the selectivity of 17.21%, 3-methylpentane is 6.34%.
embodiment 3
In autoclave, add 10ml ionic liquid [(CH 3) 3n (CH 2) 4sO 3h] [CH 3phSO 3], airtight stirring, control pressure is 0.5MPa, temperature is about 50 ℃, add 200ml normal hexane, carry out isomerization reaction, react after 60 minutes, reaction finishes, stop stirring, be cooled with circulating water room temperature, product and ion liquid system AUTOMATIC ZONING, upper strata is reaction product.
Through gas chromatographic analysis, find, the transformation efficiency of normal hexane reaches 90%, in isomerization product: 2, the selectivity of 2-dimethylbutane is that the selectivity of 12.79%, 2,3-dimethylbutane is 7.62%, the selectivity of 2-methylpentane is that the selectivity of 13.34%, 3-methylpentane is 6.45%.
embodiment 4
In autoclave, add 10ml compound ion liquid [MimN (CH 2) 4sO 3h] [HSO 4]/Cu (OTf) 2, airtight stirring, control pressure is 0.5MPa, temperature is approximately 50 ℃, add 50ml normal hexane, carry out isomerization reaction, react after 60 minutes, reaction finishes, stop stirring, be cooled with circulating water room temperature, product and ion liquid system AUTOMATIC ZONING, upper strata is reaction product.
Through gas chromatographic analysis, find, the transformation efficiency of normal hexane reaches 96%, in isomerization product: 2, the selectivity of 2-dimethylbutane is that the selectivity of 21.49%, 2,3-dimethylbutane is 10.72%, the selectivity of 2-methylpentane is that the selectivity of 24.74%, 3-methylpentane is 9.97%.
As can be seen here, after adding metallic compound, on the excellent properties basis of this sulfonic acid type ion liquid, the transformation efficiency of normal hexane and the selection of isoparaffin have all had further raising and have improved, produce good synergy, further improved catalytic performance.
embodiment 5-15
Except replacing the compound ion liquid [MimN (CH in embodiment 4 with the compound ion liquid in Preparation Example 6-16 respectively 2) 4sO 3h] [HSO 4]/Cu (OTf) 2with the same procedure with embodiment 4, carried out the isomerization reaction of normal hexane outward.
Through gas chromatographic analysis, find, the transformation efficiency of normal hexane is all more than 95%, in isomerization product: 2, the selectivity of 2-dimethylbutane is all greater than 20%, 2, the selectivity that the selectivity that the selectivity of 3-dimethylbutane is all greater than 11%, 2-methylpentane is all greater than 25%, 3-methylpentane is all greater than 10%.
comparative example
This comparative example is according to Shi Zhenmin etc.: < < chemistry of fuel journal > >, " research of ionic liquid at room temperature catalysis Isomerization of Hexane reaction ", Vol.36, no.5, technical scheme in 2008 10 months is carried out, and wherein with aluminum trichloride (anhydrous) and Triethylammonium chloride, has obtained ionic liquid 2AlCl 3/ Et 3nHCl, with the isomerization reaction of its catalysis normal hexane, and this reaction is to carry out under iso-pentane initiator exists.
Even if add under initiator and optimal conditions, be catalyzer be while reacting under 1:1 with the ratio of normal hexane, the transformation efficiency of normal hexane is only also 84.54%, 2, the selectivity of 2-dimethylbutane is that the selectivity of 7.6%, 2,3-dimethylbutane is 3.75%, the selectivity of 2-methylpentane is that the selectivity of 10.35%, 3-methylpentane is 4.8%.
As can be seen here, ionic liquid of the present invention has the isoparaffin selectivity of larger normal paraffin transformation efficiency and Geng Gao, thereby has shown excellent catalytic performance and selectivity of product, has better prospects for commercial application and researching value.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, modification and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.

Claims (5)

1. a catalysis normal alkane isomerization is produced the method for isoparaffin, it is characterized in that: use composite sulfoacid functionalized ion liquid as catalyzer, described composite sulfoacid functionalized ion liquid is to add the ionic liquid obtaining after metallic compound in sulfonate functional ionic liquid, and described sulfonate functional ionic liquid structure is as follows:
[A] n +[B] n-
Wherein:
N is the integer of 1-4;
[A] +for thering is the positively charged ion of following structure:
Or [A] +for thering is structural formula-N +(R 8r 9r 10r) positively charged ion;
Wherein:
R is-(CR 6r 7) m-SO 3h, R 6, R 7identical or different, be selected from independently of one another H, alkyl, alkoxyl group, alkyl-carbonyl, amino, the integer that m is 1-10;
R 1, R 2, R 3, R 4, R 5identical or different, be selected from independently of one another H, alkyl, alkoxyl group, thiazolinyl, alkynyl;
R 8, R 9, R 10identical or different, be selected from independently of one another H, alkyl, alkoxyl group, thiazolinyl, alkynyl;
[B] n-for the acid radical anion from sulfuric acid, phosphoric acid, methylsulfonic acid, trifluoromethanesulfonic acid, tosic acid or trifluoroacetic acid,
Described normal paraffin refers to straight chain, there is no the C4-C8 normal paraffin of side chain,
Described alkyl refers to the straight or branched alkyl with 1-20 carbon atom,
Described alkoxyl group refers to that described alkyl is connected with-O-and the group that forms,
Described alkyl-carbonyl refers to described alkyl and-C (O)-be connected and the group that forms,
Described thiazolinyl refers to the straight or branched thiazolinyl with 2-20 carbon atom,
Described alkynyl refers to the straight or branched alkynyl with 2-20 carbon atom,
Described metallic compound is copper trifluoromethanesulfcomposite, copper methane sulfonate, copper p-toluenesulfonate, trifluoroacetic acid copper, trifluoromethanesulfonic acid zinc, methylsulfonic acid zinc, tosic acid zinc, trifluoroacetic acid zinc, silver trifluoromethanesulfonate, methylsulfonic acid silver, tosic acid is silver-colored or trifluoroacetic acid is silver-colored.
2. the method for claim 1, is characterized in that: R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10identical or different, be selected from independently of one another H, C 1-9alkyl, C 1-9alkoxyl group.
3. method as claimed in claim 1 or 2, is characterized in that: [B] n-for (HSO 4) -, (CH 3sO 3) -, (CF 3sO 3) -, (H 2pO 4) -, (CF 3cOO) -or (p-CH 3c 6h 4sO 3) -.
4. the method for claim 1, is characterized in that: the reaction pressure of isomerization reaction is that the volume ratio of environmental stress-2.0MPa, catalyzer and normal paraffin is that 1:1-1:30, temperature of reaction are that 30-160 ℃, reaction times are 5-200 minute.
5. the method for claim 1, is characterized in that: described normal paraffin is normal hexane.
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US9096483B2 (en) 2013-06-28 2015-08-04 Uop Llc Catalytic isomerization of hexanes using ionic liquids
CN104815695B (en) * 2015-05-18 2017-03-08 浙江海洋学院 A kind of method that carbon nanotube loaded ionic-liquid catalyst catalysis prepares diisobutylene
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CN107570182A (en) * 2016-07-04 2018-01-12 中国石油大学(华东) Catalyst for alkane isomerization and preparation method thereof and reaction unit
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101177371A (en) * 2006-11-11 2008-05-14 中国科学院兰州化学物理研究所 Method for alkylation of isoparaffin and olefin catalyzed by ion liquid
CN102492462A (en) * 2011-11-23 2012-06-13 抚顺仁和生物燃料化工科技开发有限公司 Ionic liquid-solid superacid catalysis light hydrocarbon isomerization method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2001130402A (en) * 2001-11-13 2003-08-20 Хальдор Топсеэ А/С (DK) Method of isomerization of C5-C8 paraffin hydrocarbon feed

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101177371A (en) * 2006-11-11 2008-05-14 中国科学院兰州化学物理研究所 Method for alkylation of isoparaffin and olefin catalyzed by ion liquid
CN102492462A (en) * 2011-11-23 2012-06-13 抚顺仁和生物燃料化工科技开发有限公司 Ionic liquid-solid superacid catalysis light hydrocarbon isomerization method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
室温离子液体催化正己烷异构化反应的研究;石振民等;《燃料化学学报》;20081031;第36卷(第5期);第594-600页 *
石振民等.室温离子液体催化正己烷异构化反应的研究.《燃料化学学报》.2008,第36卷(第5期),第594-600页.

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