CN103934023B - For ionic-liquid catalyst and the preparation and application thereof of C5/C6 alkane isomerization - Google Patents

For ionic-liquid catalyst and the preparation and application thereof of C5/C6 alkane isomerization Download PDF

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CN103934023B
CN103934023B CN201410172912.7A CN201410172912A CN103934023B CN 103934023 B CN103934023 B CN 103934023B CN 201410172912 A CN201410172912 A CN 201410172912A CN 103934023 B CN103934023 B CN 103934023B
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liquid catalyst
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catalyst
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CN103934023A (en
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夏道宏
周文博
于建宁
朱丽君
刘咸尚
蔡婷婷
周玉路
项玉芝
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China University of Petroleum East China
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Abstract

The invention provides a kind of ionic-liquid catalyst for C5/C6 alkane isomerization, the chemical structural formula of described catalyst is: wherein, R 1and R 2be respectively in C2-C9 straight chained alkyl any one; X 1and X 2be respectively AlCl 4 -and Al 2cl 7 -in any one, or X 1and X 2be respectively AlCl 3br -and Al 2cl 6br -in any one.Ionic-liquid catalyst of the present invention is when for isomerization reaction, and reaction system is liquid-liquid phase, stable reaction and easily controlling.And when reaction completes, after product is cooled to room temperature, ionic-liquid catalyst condenses into solid-state again, thus is easy to be separated with liquid product.

Description

For ionic-liquid catalyst and the preparation and application thereof of C5/C6 alkane isomerization
Technical field
The invention belongs to light paraffins isomerization field, be specifically related to a kind of dication liquid catalyst for catalysis C5/C6 alkane isomerization and preparation and application thereof.
Background technology
Along with the development of China Petroleum, improving constantly of environmental consciousness, the quality standard of domestic motor petrol is also improving constantly, and under this background, the production technology of development high-octane rating clear gusoline is imperative.At present, the technique for the production of high-knock rating gasoline and component thereof mainly contains catalytic reforming, etherificate, alkylation and isomerization.Wherein, isomerization technique, because have flexible operation, small investment, is polluted low advantage and is widely used.Very excellent gasoline blending component to the light paraffins isomerized oil that especially C5/C6 alkane hydrocarbon isomerisation prepares, the research octane number (RON) (RON) of such as n-hexane is 24.8, and can 91.8 be reached through the RON of 2, the 2-dimethylbutanes that isomerization obtains.
Ionic liquid is a development in recent years class green catalyst rapidly, and isomerization is one of important use of ionic liquid.Be used to isomerized ionic liquid at present and mainly contain alkyl imidazole, pyridine, quaternary ammonium salt etc.As Chinese patent literature CN102492462A discloses the method for a kind of ionic liquid-solid superacid as catalyst light hydrocarbon isomerization, the method first uses triethylamine chloroaluminate ionic liquid to carry out an isomerization to linear paraffin, re-use solid super-strong acid and carry out secondary isomerization to once isomerized product, the volume yield finally preparing isomerization hydrocarbon can reach 100%.Abovementioned alkyl amine salt chlorine aluminium acidic ionic liquids is one of more ionic liquid of research, but its technical problem existed is, what participate in due to above-mentioned ionic liquid is reactive liquid solution, and the product after therefore react is difficult to be separated complete usually.
In order to solve the not segregative problem of this product, prior art brings into use immobilised ionic-liquid catalyst to carry out isomerization reaction, as Chinese patent literature CN103373886A discloses a kind of solid-phase catalyst for normal alkane isomerization, the preparation method of this solid-phase catalyst is: utilize infusion process that acidic ion liquid is impregnated into SiO 2, Al 2o 3, on HZSM-5 or SBA-15; Or utilize chemical grafting by the silicic acid fat of halogenation and methylimidazole reaction, then again with Lewis acid reaction, obtain the Lewis acid ion liquid containing silicic acid fat, silicic acid fat on ionic liquid and the Si-OH base on carrier react, thus by Lewis acid type ion liquid immobilization on carrier.
Above-mentioned prior art by use solid-phase catalyst, the liquid product that isomerization reaction is generated is highly susceptible to being separated with solid-phase catalyst, thus efficiently solve ionic liquid be difficult to separation problem.But the defect of existence is when using solid-phase catalyst to carry out isomerization reaction: much more complicated than liquid--liquid reaction of liquid-solid two alternate courses of reaction, the factors such as the diffusion between liquid-solid phase, absorption all can have an impact to reaction rate, thus cause isomerization reaction unstable and be difficult to control.In current technology, isomerization product distribution situation is also unfavorable for the octane number improving isomerization product.Therefore, how can also realize the good separation of catalyst and isomerization product under the prerequisite ensureing reaction stability, and obtain the isomerized oil with higher octane, be the still unsolved difficult problem of prior art.
Summary of the invention
What the present invention solved is for the not segregative problem that isomerized ionic-liquid catalyst exists in prior art, and then provides a kind of and not only had excellent isomerization effect simultaneously but also be easy to the ionic-liquid catalyst with product separation.Effectively improve the distribution situation of isomerization product simultaneously, improve the octane number of isomerization product further.
The technical scheme of isomerization catalyst described in the present invention and preparation and application thereof is:
For an ionic-liquid catalyst for C5/C6 alkane isomerization, the chemical structural formula of described catalyst is:
Wherein, R 1and R 2be respectively in C2-C9 straight chained alkyl any one; X 1and X 2be respectively AlCl 4 -and Al 2cl 7 -in any one, or X 1and X 2be respectively AlCl 3br -and Al 2cl 6br -in any one.
Described R 1and R 2for identical alkyl.
Described R 1and R 2for normal-butyl, X 1and X 2be respectively AlCl 4 -or Al 2cl 7 -in any one.
Described R 1and R 2for different alkyl.
The preparation method of described ionic-liquid catalyst, comprises the steps:
(1) be that any one in the tetramethylethylenediamine of 1:5-1:1 and C2-C9 straight chain one alkyl halide is dissolved in absolute ethyl alcohol by mol ratio, react under 60-120 DEG C of condition;
(2), after the reaction in step (1) completes, filtration product obtains ionic liquid presoma;
(3) by described ionic liquid presoma and AlCl 3join in closed container and mix, at 60 ~ 120 DEG C, place 6-12h, obtain described ionic-liquid catalyst.
The preparation method of described ionic-liquid catalyst, comprises the steps:
(1) be first that any one in the tetramethylethylenediamine of 1:1 and C2-C9 straight chain one alkyl halide is dissolved in absolute ethyl alcohol by mol ratio, under 60-120 DEG C of condition, carry out reaction prepare single halogeno salt;
Be that another in described single halogeno salt of 1:5-1:1 and C2-C9 straight chain one alkyl halide is dissolved in absolute ethyl alcohol again by mol ratio, react under 60-120 DEG C of condition;
(2), after the reaction in step (1) completes, filtration product obtains ionic liquid presoma;
(3) by described ionic liquid presoma and AlCl 3join in closed container and mix, at 60 ~ 120 DEG C, place 6-12h, obtain described ionic-liquid catalyst.
Described ionic-liquid catalyst is used for the purposes of C5/C6 alkane isomerization.
Described ionic-liquid catalyst is used for the method for C5/C6 alkane isomerization, comprises the steps:
(1) initator, ionic-liquid catalyst and C5/C6 n-alkane are mixed, the volume ratio of wherein said initator and described n-alkane is 1:10-1:100; The mass ratio of described ionic-liquid catalyst and described n-alkane is 2:1-1:3;
(2) described mixture temperature be 60-140 DEG C, pressure reacts under being the condition of 0.1-2Mpa.
The volume ratio of described initator and n-alkane is 1:12.5-1:25; The mass ratio of described ionic-liquid catalyst and n-alkane is 1:3.
Reaction in described step (2) is carried out in nitrogen atmosphere.
Ionic-liquid catalyst for C5/C6 alkane isomerization of the present invention, advantage is:
(1) ionic-liquid catalyst for C5/C6 alkane isomerization of the present invention, a kind of two centers cationic ion liquid catalysts, described catalyst is solid state under normal temperature condition, and be liquid condition under the reaction temperature condition of 60-140 DEG C, therefore ionic-liquid catalyst of the present invention is when for isomerization reaction, reaction system is liquid-liquid phase, stable reaction and easily controlling.And when reaction completes, after product is cooled to room temperature, ionic-liquid catalyst condenses into solid-state again, thus is easy to be separated with liquid product.
Further, ionic-liquid catalyst of the present invention, due to the cationic introducing in two center, makes the acidic site in ionic liquid structure increase, obtains comparatively peracid density, decrease the consumption of ionic liquid; Simultaneously owing to there being higher acid strength, therefore there is reaction speed fast, the advantage that the reaction time is short, reaction condition is gentle.In addition, ionic-liquid catalyst described in the present invention is compared to prior art, also effectively improve the distribution situation of isomerization product, when for C5/C6 alkane isomerization, significantly reduce the content of C4 product in product, when for C6 alkane isomerization, in product, the ratio of C6 isomeric alkane is greatly improved, thus effectively improves the octane number of isomerization product.
(2) ionic-liquid catalyst for C5/C6 alkane isomerization of the present invention, the R also in further preferred described catalyst structure formula is normal-butyl, X 1and X 2be respectively AlCl 4 -or Al 2cl 7 -in any one.Reason is, the ionic-liquid catalyst under this setup has very excellent normal alkane conversion ratio and isoparaffin yield.
Detailed description of the invention
Below in conjunction with embodiment, invention is described in further details.
Embodiment 1
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein: R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 60 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:12.5 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 100 DEG C, reaction 4h.
The concrete operation method that ionic liquid described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:10 takes chloro-normal butane and n-hexane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 100 DEG C, reaction 4h.
Embodiment 2
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein: R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.3molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:100 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 100 DEG C, reaction 4h.
The concrete operation method that ionic liquid described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:100 takes chloro-normal butane and n-hexane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 80 DEG C, reaction 4h.
Embodiment 3
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein: R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.3molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 100 DEG C, reaction 4h.
The method that ionic liquid described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 60 DEG C, reaction 4h.
Embodiment 4
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein: R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.5molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:12.5 takes chloro-normal butane and pentane by volume, is that 2:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 100 DEG C, reaction 4h.
The concrete operation method that ionic liquid described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 1:2 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 100 DEG C, reaction 4h.
Embodiment 5
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.5molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 80 DEG C, reaction 4h.
The concrete operation method that ionic liquid described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 2:3 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 80 DEG C, reaction 4h.
Embodiment 6
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic liquid described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 120 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 2:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 120 DEG C, reaction 4h.
Embodiment 7
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 60 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
Embodiment 8
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.5molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 1:3 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 1:3 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
Embodiment 9
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.5molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 2:3 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 2:3 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
Embodiment 10
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.5molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 5:6 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 5:6 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
Embodiment 11
Ionic-liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein R 1and R 2be respectively ethyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.2mol bromoethane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times, dry 12h in vacuum drying chamber with ethanol, obtain ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.5molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 4:3 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 4:3 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 140 DEG C, reaction 4h.
Embodiment 12
Two centers cationic strong acidic ion liquid catalyst chemical structural formula described in the present embodiment is as follows:
Wherein R 1and R 2be respectively normal-butyl; X 1and X 2be respectively AlCl 4 -or Al 2cl 7 -.The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.5mol chloro-normal butane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 24h, revolve steaming and obtain yellow, viscous liquid, wash 3 times with ethyl acetate, dry 12h in vacuum drying chamber, obtains ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 120 DEG C, place 12h, namely obtain highly acid dication type ionic liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 1:3 takes ionic-liquid catalyst by ionic liquid and pentane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 100 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:12.5 takes chloro-normal butane and n-hexane by volume, is that 1:3 takes ionic-liquid catalyst by ionic liquid and n-hexane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 100 DEG C, reaction 4h.
Embodiment 13
The chemical structural formula of ionic-liquid catalyst described in the present embodiment is as follows:
Wherein R 1and R 2be respectively normal-butyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.5mol bromination of n-butane are dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 24h, revolve steaming and obtain yellow, viscous liquid, wash 3 times with ethyl acetate, dry 12h in vacuum drying chamber, obtains ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 120 DEG C, place 12h, namely obtain highly acid dication type ionic liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:40 takes chloro-normal butane and pentane by volume, is that 1:3 takes ionic-liquid catalyst by ionic liquid and pentane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 100 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:40 takes chloro-normal butane and n-hexane by volume, is that 1:3 takes ionic-liquid catalyst by ionic liquid and n-hexane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 100 DEG C, reaction 4h.
Embodiment 14
The chemical structural formula of ionic-liquid catalyst described in the present embodiment is as follows:
Wherein R 1and R 2be respectively normal-butyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br-.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.5mol bromo n-hexane dissolution are in absolute ethyl alcohol, at 80 DEG C of stirring reaction 24h, revolve steaming and obtain yellow, viscous liquid, wash 3 times with ethyl acetate, dry 12h in vacuum drying chamber, obtains ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 120 DEG C, place 12h, namely obtain highly acid dication type ionic liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:45 takes chloro-normal butane and pentane by volume, is that 1:3 takes ionic-liquid catalyst by ionic liquid and pentane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 120 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:45 takes chloro-normal butane and n-hexane by volume, is that 1:3 takes ionic-liquid catalyst by ionic liquid and n-hexane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 120 DEG C, reaction 4h.
Embodiment 15
The chemical structural formula of ionic-liquid catalyst described in the present embodiment is as follows:
Wherein R 1and R 2be respectively nonyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
(1) 0.1mol tetramethylethylenediamine and 0.5mol bromo n-nonane are dissolved in absolute ethyl alcohol, at 120 DEG C of stirring reaction 24h, revolve steaming and obtain yellow, viscous liquid, wash 3 times with ethyl acetate, dry 12h in vacuum drying chamber, obtains ionic liquid presoma.
(2) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 120 DEG C, place 12h, namely obtain highly acid dication type ionic liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 2:1 takes ionic-liquid catalyst by ionic liquid and pentane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 120 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 2:1 takes ionic-liquid catalyst by ionic liquid and n-hexane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 120 DEG C, reaction 4h.
Embodiment 16
The chemical structural formula of ionic-liquid catalyst described in the present embodiment is as follows:
Wherein R 1for ethyl; R 2for nonyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.1mol bromononane are dissolved in absolute ethyl alcohol, and at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times with ethanol, dry 12h in vacuum drying chamber, obtains single halogeno salt.
(2) single halogeno salt that 0.1mol (1) step obtains is got and 0.1mol bromoethane is dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times with ethanol, dry 12h in vacuum drying chamber, obtains ionic liquid presoma.
(3) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic-liquid catalyst by ionic liquid and pentane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 100 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 1:1 takes ionic-liquid catalyst by ionic liquid and n-hexane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 100 DEG C, reaction 4h.
Embodiment 17
The chemical structural formula of ionic-liquid catalyst described in the present embodiment is as follows:
Wherein R 1for normal-butyl; R 2for nonyl; X 1and X 2be respectively AlCl 3br -or Al 2cl 6br -.
The synthetic method of above-mentioned ionic-liquid catalyst is as follows:
(1) 0.1mol tetramethylethylenediamine and 0.1mol bromononane are dissolved in absolute ethyl alcohol, and at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times with ethanol, dry 12h in vacuum drying chamber, obtains single halogeno salt.
(2) single halogeno salt that 0.1mol (1) step obtains is got and 0.3mol bromination of n-butane is dissolved in absolute ethyl alcohol, at 80 DEG C of stirring reaction 2h, filter and obtain white solid, wash 3 times with ethanol, dry 12h in vacuum drying chamber, obtains ionic liquid presoma.
(3) by 0.1mol ionic liquid presoma and 0.4molAlCl 3join in closed container and mix, at 90 DEG C, place 12h, namely prepare highly acid two centers cationic ion liquid.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C5 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic-liquid catalyst by ionic liquid and pentane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 100 DEG C, reaction 4h.
The concrete operation method that ionic-liquid catalyst described in the present embodiment is used for C6 alkane isomerization is:
(1) ratio of 1:25 takes chloro-normal butane and n-hexane by volume, is that 1:1 takes ionic-liquid catalyst by ionic liquid and n-hexane mass ratio;
(2) reaction system being placed in nitrogen first pressing is 0.5MPa, and reaction temperature controls at 100 DEG C, reaction 4h.
Experimental example
In order to prove the technique effect of technical scheme of the present invention, the present invention is provided with experimental example and evaluates the catalysis n-hexane in each embodiment above-mentioned, n-pentane isomerization reaction, is analyzed by product Agilent6820 gas chromatograph.
The calculating of the selective S of the conversion ratio X of raw material, the yield Y of isoparaffin, product is provided by formula (1-1), (1-2) and (1-3).
S = Y X × 100 % - - - ( 1 - 3 )
In formula:
[A] raw materialfor the ratio shared by n-hexane in raw material (pentane) peak area, %;
[A] productfor the ratio shared by n-hexane in product (pentane) peak area, %;
[B] productfor the ratio shared by isoparaffin peak area sums all in product, %.
In embodiment 1-17, the experimental result of isomerization reaction is as shown in table 1:
Conversion ratio, the isoparaffin yield and selective of the reaction of table 1 embodiment isoversion
Simultaneously, this experimental example is also observed the product of isomerization reaction in embodiment 1-17, result shows that the product of C5/C6 isomerization reaction in embodiment 1-17 is after the cooling period in stratification state, upper strata is the isomeric alkane hydrocarbon layers of liquid phase, lower floor is the catalyst layer in thickness solid phase, and after being tilted by reactor, the isoparaffin of liquid phase is poured out, and the catalyst layer of solid phase is still stayed in described reactor, thus being separated of catalyst and product can be realized very simply.
Comparative example
In order to prove the technique effect of technical scheme of the present invention further, the present invention is also provided with comparative example, and the ionic liquid adopted in this comparative example is 1-butyl-3-methylimidazole chlorine Ion-selective electrod.The preparation method of described 1-butyl-3-methylimidazole chlorine Ion-selective electrod is:
Take 17.47g chlorination (1-butyl-3-methylimidazole) in 100ml round-bottomed flask, then by 26.67gAlCl 3add in round-bottomed flask, mix, obtain brown liquid 44.14g, be 1-butyl-3-methylimidazole chlorine Ion-selective electrod.
The concrete operation method that ionic liquid described in this comparative example is used for C5 alkane isomerization is:
(1) ratio of 1:12.5 takes chloro-normal butane and pentane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and pentane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 100 DEG C, reaction 4h.
The concrete operation method that ionic liquid described in this comparative example is used for C6 alkane isomerization is:
(1) ratio of 1:10 takes chloro-normal butane and n-hexane by volume, is that 1:1 takes ionic liquid by the mass ratio of ionic-liquid catalyst and n-hexane;
(2) controlling the first pressing of autoclave nitrogen is 0.5MPa, and mixing speed controls at 600r/min, and reaction temperature controls at 100 DEG C, reaction 4h.
Measure the result of C5, C6 alkane isomerization reaction in this comparative example, result is as shown in table 2:
Conversion ratio, the isoparaffin yield and selective of the reaction of table 2 comparative example isoversion
The distribution of product in comparative example and embodiment 1 contrasted, result is as shown in table 3, and (i-represents isomerization product; N-represents n-alkane):
The composition situation of product in table 3 comparative example and embodiment 1
Contrast by comparative example and the composition of product in embodiment 1 novel ion liquid adopted in known embodiment 1 to compare with traditional ionic liquid there is significant advantage, which raises the content of C6 in the conversion ratio of raw material and product, reduce C in product 4content, improve product slates.
Known by the result in above-mentioned experimental example and comparative example, ionic-liquid catalyst of the present invention compared with prior art, have higher isomerization reaction conversion ratio and isoparaffin yield, and the selective of product is better than comparative example.And ionic-liquid catalyst of the present invention becomes solid-state after reaction end, cooling, is highly susceptible to being separated with isomerization product.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.

Claims (10)

1. for an ionic-liquid catalyst for C5/C6 alkane isomerization, it is characterized in that, the chemical structural formula of described catalyst is:
Wherein, R 1and R 2be respectively in C2-C9 straight chained alkyl any one; X 1and X 2be respectively AlCl 4 -and Al 2cl 7 -in any one, or X 1and X 2be respectively AlCl 3br -and Al 2cl 6br -in any one.
2. ionic-liquid catalyst according to claim 1, is characterized in that, described R 1and R 2for identical alkyl.
3. ionic-liquid catalyst according to claim 2, is characterized in that, described R 1and R 2for normal-butyl, X 1and X 2be respectively AlCl 4 -and Al 2cl 7 -in any one.
4. ionic-liquid catalyst according to claim 1, is characterized in that, described R 1and R 2for different alkyl.
5. the preparation method of ionic-liquid catalyst described in claim 2, is characterized in that, comprises the steps:
(1) be that any one in the tetramethylethylenediamine of 1:5-1:1 and C2-C9 straight chain one alkyl halide is dissolved in absolute ethyl alcohol by mol ratio, react under 60-120 DEG C of condition;
(2), after the reaction in step (1) completes, filtration product obtains ionic liquid presoma;
(3) by described ionic liquid presoma and AlCl 3join in closed container and mix, at 60 ~ 120 DEG C, place 6-12h, obtain described ionic-liquid catalyst.
6. the preparation method of ionic-liquid catalyst described in claim 4, is characterized in that, comprises the steps:
(1) be first that any one in the tetramethylethylenediamine of 1:1 and C2-C9 straight chain one alkyl halide is dissolved in absolute ethyl alcohol by mol ratio, under 60-120 DEG C of condition, carry out reaction prepare single halogeno salt;
Be that another in described single halogeno salt of 1:5-1:1 and C2-C9 straight chain one alkyl halide is dissolved in absolute ethyl alcohol again by mol ratio, react under 60-120 DEG C of condition;
(2), after the reaction in step (1) completes, filtration product obtains ionic liquid presoma;
(3) by described ionic liquid presoma and AlCl 3join in closed container and mix, at 60 ~ 120 DEG C, place 6-12h, obtain described ionic-liquid catalyst.
7. the ionic-liquid catalyst described in any one of claim 1-4 is used for the purposes of C5/C6 alkane isomerization.
8. purposes according to claim 7, is characterized in that, comprises the steps:
(1) initator, ionic-liquid catalyst and C5/C6 n-alkane are mixed formation mixture, the volume ratio of wherein said initator and described n-alkane is 1:10-1:100; The mass ratio of described ionic-liquid catalyst and described n-alkane is 2:1-1:3;
(2) described mixture temperature be 60-140 DEG C, pressure reacts under being the condition of 0.1-2Mpa.
9. purposes according to claim 8, is characterized in that, the volume ratio of described initator and n-alkane is 1:12.5-1:25; The mass ratio of described ionic-liquid catalyst and n-alkane is 1:3.
10. purposes according to claim 8 or claim 9, it is characterized in that, the reaction in described step (2) is carried out in nitrogen atmosphere.
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CN101993378A (en) * 2010-09-10 2011-03-30 中国石油大学(北京) Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof
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

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WO1996018459A1 (en) * 1994-12-13 1996-06-20 Bp Chemicals Limited Ionic liquids
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CN101993378A (en) * 2010-09-10 2011-03-30 中国石油大学(北京) Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof
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

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