CN105562104A - Light-weight alkane isomerization method using ion-like liquid as catalyst - Google Patents

Light-weight alkane isomerization method using ion-like liquid as catalyst Download PDF

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CN105562104A
CN105562104A CN201510921185.4A CN201510921185A CN105562104A CN 105562104 A CN105562104 A CN 105562104A CN 201510921185 A CN201510921185 A CN 201510921185A CN 105562104 A CN105562104 A CN 105562104A
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ionic liquid
isomerization
light paraffins
class ionic
reaction
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CN105562104B (en
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张睿
胡鹏程
刘植昌
孟祥海
徐春明
刘海燕
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China University of Petroleum Beijing
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2794—Catalytic processes with hydrides or organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper
    • C07C2531/30—Halides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions

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  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a light-weight alkane isomerization method using ion-like liquid as a catalyst. The light-weight alkane isomerization method comprises the following steps that ingredients containing light-weight alkane are in contact with ion-like liquid so that the light-weight alkane takes an isomerization reaction, wherein the ion-like liquid is prepared from an amide compound and more than one kind of metal compound through reaction. The method has the advantages that the ion-like liquid is used as the catalyst; the synthesis raw materials can be easily obtained; the synthesis method is simple; the price is low; in addition, the ion-like liquid has high catalysis activity, high stability and high selectivity; the conversion rate of the light-weight alkane isomerization raw materials catalyzed by the ion-like liquid and the isomerous alkane content in the reaction product are greatly improved.

Description

Light paraffins isomerization method using class ionic liquid as catalyst
Technical field
The present invention relates to a kind of alkane isomerization process, particularly relate to a kind of light paraffins isomerization method using class ionic liquid as catalyst.
Background technology
In recent years, because the requirement of environmental protection is more and more higher, gasoline quality standard is to the future development of low aromatic hydrocarbons, low alkene, low-steam pressure, hyposensitivity, high-octane rating and elevated oxygen level.Light naphthar (such as light straight-run naphtha, hydrogenation plant light naphthar etc.) and light condensate (the light condensation wet goods in such as oil field) are based on C5, C6 alkane, because octane number is lower, thus harmonic proportion is in the oil restricted.By carrying out isomerization reaction to this part light paraffins, effectively can improve the octane number of light paraffins, thus increase the harmonic proportion of light paraffins in gasoline, improve the octane number of gasoline light fraction, make vapour oil fraction and octane number have reasonable layout.Therefore, develop light paraffins isomerization process alkene and the too high tool of arene content in alleviation China gasoline are of great significance.
At present, the Performance of Isomerization Catalysts for Light n-Paraffin generally adopted is noble metal catalyst, can be divided into middle warm type and low form two kinds by the difference of operating temperature.Middle warm type noble metal (Pt or Pd) is carried on bifunctional catalyst obtained on zeolite, and using it as catalyst, the reaction temperature of carrying out needed for light paraffins isomerization is generally 230 ~ 280 DEG C, and isomerization equilibrium conversion ratio is lower; Low form is noble metal halide amorphous catalyst, and compared with middle temperature catalyst, this kind of catalyst is comparatively active, and reaction temperature can be down to 115 ~ 150 DEG C, but the halogen of catalyst cupport easily runs off, and needs to supplement halogen.
In recent years, research for the Performance of Isomerization Catalysts for Light n-Paraffin performance mainly concentrated on by improving carrier improves the activity and selectivity of catalyst, such as US Patent No. 5095169 discloses a kind of isomerization catalyst prepared for carrier with the β zeolite of activation, this patent mainly improves the activation method of β zeolite, and the activity and selectivity of the isomerization catalyst prepared with this carrier increases.In addition, it is also current study hotspot, such as patent US6180555, CN1428197A etc. that solid super-strong acid is used for light paraffins isomerization, but this type of catalyst exists defects such as active component easily runs off, the easy coking and deactivation of catalyst.
The above-mentioned Performance of Isomerization Catalysts for Light n-Paraffin studied and use is mostly solid catalyst, and all there is expensive, process matched therewith needs the shortcomings such as hydrogenation, cost are higher.In addition, the equilibrium conversion of alkane isomerization reaction is by balance controlled, and reaction temperature is lower, and equilibrium conversion is higher, but the process of enforcement isomerization at present still needs higher reaction temperature.Therefore, the low temp isomerizing catalyst that exploitation can overcome above-mentioned shortcoming is an important research topic.
In order to reduce costs, also some are had using base metal as the Performance of Isomerization Catalysts for Light n-Paraffin of active component at present, such as patent CN1314330A, CN85105389A etc., although the price of its active component is 1/4 of noble metal, but performance is inferior to noble metal catalyst.
It is low, acid adjustable, easily and separation of products, cyclic utilization rate advantages of higher that ionic liquid has corrosivity, and the catalyst becoming the alternative solid acid of a class is used for the isomerization reaction of catalysis light paraffins.Publication number is that the Chinese patent of CN1284540A discloses a kind of method being Material synthesis ionic liquid with alkyl pyridine, imidazoles or trimethylamine nitrogen-containing compound and metal or non-metallic halide, and utilizes this ionic liquid for the method for catalyst light paraffins isomerization reaction.But the synthesis of ionic liquid is higher to synthesis ingredient requirement, and synthetic method is comparatively complicated, and price is relatively costly; In addition, the catalytic activity of this ionic liquid and selective limited, in feed stock conversion and product, the content of isoparaffin need further raising.
Summary of the invention
The invention provides a kind of light paraffins isomerization method using class ionic liquid as catalyst, the method adopts class ionic liquid as catalyst, and synthesis material is easy to get, synthetic method simple and low price; In addition, the catalytic activity of such ionic liquid, stability and selective height, all significantly improve with the content of isoparaffin in the light paraffins isomerate feeds conversion ratio of its catalysis and product.
The invention provides a kind of light paraffins isomerization method using class ionic liquid as catalyst, the raw material containing light paraffins is contacted with class ionic liquid, to make described light paraffins generation isomerization reaction; Wherein, described class ionic liquid reacts obtained by amide compound and more than one metallic compounds.
In concrete scheme of the present invention, described amide compound is selected from general formula R 1cONR 2r 3chain acid amides and general formula R 1cONR 2r 3cyclic amide in one or more; General formula R 1cONR 2r 3in, R 1for alkyl or the-NR of hydrogen, carbon number 1-10 2r 3, R 2, R 3independently be selected from hydrogen, the alkyl of carbon number 1-10 or the thiazolinyl of carbon number 1-10 separately.
Further, described amide compound is selected from urea, formamide, N-METHYLFORMAMIDE, N, dinethylformamide, acetamide, N-methylacetamide, N, one or more of N-dimethylacetylamide, acrylamide, 2-Pyrrolidone, 1-METHYLPYRROLIDONE, DMI.
In concrete scheme of the present invention, described metallic compound is the halide of metal, sulfate or nitrate, and described metal is aluminium, copper, iron, zinc, nickel, cobalt, silver, molybdenum or platinum.The present invention does not do strict restriction to the quantity of described metallic compound, such as, can be one or both; In addition, the present invention does not do strict restriction to the valence state of metal in described metallic compound, and the compound of multivalent state metal can be the metallic compound under its various valence state, and the halide of such as copper can be copper or cuprous halide etc.Further, described metallic compound is the halide of metal, and described metal is aluminium or copper.
Any feasible method synthesis that class ionic liquid of the present invention can adopt prior art to record obtains.Common synthetic method is: under protective atmosphere, is mixed by described amide compound with described metallic compound, stirring reaction 2-10 hour, obtains foundation class ionic liquid (it can directly use as Performance of Isomerization Catalysts for Light n-Paraffin); Alternatively, in described foundation class ionic liquid, add another kind of metallic compound further and react, obtain class ionic liquid.
In one embodiment, described class ionic liquid reacts obtained by amide compound and a kind of metallic compound, and adopts and prepare described class ionic liquid with the following method:
Under protective atmosphere, described amide compound is joined in described metallic compound, after stirring at room temperature, is warming up to 80-180 DEG C, continue to be stirred to complete reaction, obtain described class ionic liquid.
Particularly, can inert gas as protective gas thus formed protective atmosphere, inert gas can be such as nitrogen, helium, neon, argon etc.; Consider from economical and practical angle, drying nitrogen can be adopted as protective gas.
In addition, the mol ratio of described amide compound and described metallic compound can be 1:0.1 to 1:10, and being 0.3:1 to 2.5:1 further, is further 0.3:1 to 1:1; The described stirring at room temperature time can be 15-60min; Described continuation mixing time can be 2-6 hour.In this embodiment, metallic compound can be such as alchlor.
In another embodiment, described class ionic liquid reacts obtained by amide compound and two or more metallic compound, and adopts and prepare described class ionic liquid with the following method:
Under protective atmosphere, described amide compound is joined in the first metallic compound, after stirring at room temperature, is warming up to 80-180 DEG C, continue to be stirred to complete reaction, obtain reactant;
Under protective atmosphere, in above-mentioned reactant, add more than one second metallic compounds, keep temperature-resistant or continue to be warming up to being no more than 180 DEG C, continue to be stirred to complete reaction, obtain described class ionic liquid.
Particularly, two or more metallic compound comprises the first metallic compound and the second metallic compound; Wherein, the first metallic compound is the halide of the first metal, sulfate or nitrate, such as halide, and the first metal is aluminium or gallium, such as aluminium; Second metallic compound is bimetallic halide, sulfate or nitrate, such as halide, and the second metal is copper, iron, zinc, nickel, cobalt, silver, molybdenum or platinum, such as copper.
Further, the mol ratio of described amide compound and described first metallic compound can be 1:0.1 to 1:10, and the mol ratio of described first metallic compound and the second metallic compound can be 1:100 to 100:1; In addition, the stirring at room temperature time can be 15-60min; Continuing mixing time can be 2-6 hour.In this embodiment, the first metallic compound can be such as alchlor, and the second metallic compound can be such as stannous chloride or copper chloride.
In the present invention, described raw material can also comprise initator, described initator be selected from alkene, halogenated alkane, alcohol and isoparaffin one or more, and mass percentage≤10% of described initator in described raw material, such as 0.5-10%.Initator is for accelerating the isomerization reaction time, and in concrete scheme of the present invention, initator can be butylene, butyl halide, iso-butane, isopentane, n-butanol, isobutanol etc.
The present invention does not do strict restriction to described light paraffins, and such as can comprise carbon number is one or more in the alkane of 4-7.Particularly, described light paraffins can be light naphthar and/or light condensate; Wherein, light naphthar can be all kinds of light naphtha product that petroleum refining process produces, such as light straight-run naphtha, light naphthar etc. from hydrogenation technique, and hydrogenation technique comprises the common process such as hydrocracking, hydrofinishing.
In isomerization reaction of the present invention, the volume ratio of described light paraffins and class ionic liquid can be 1:50 to 50:1, such as 1:10 to 10:1; The reaction temperature of described isomerization reaction can be 0-100 DEG C, such as room temperature-100 DEG C, is 50-80 DEG C further; Reaction time can be 1-300min, such as 30-150min (intermittent reaction), is 45-120min further.In addition, reaction pressure is to ensure that the reaction raw materials under reaction condition keeps liquid condition for lower limit, and can be such as 0.1 ~ 2.0MPa, be 1-1.5MPa further.
In the present invention, described isomerization reaction can be batch (-type) or continuous reaction; Further, left standstill by the mixture that described isomerization reaction is formed, the isomerization product in mixture and class ionic liquid AUTOMATIC ZONING, upper strata is isomerization product.
In addition, isomerization reaction of the present invention can be carried out in the reactor; Wherein, the reactor used can be the conventional reactor of this area, such as, reactor with agitating device, or other continuous reaction apparatus etc.
Enforcement of the present invention, at least has following advantage:
1, the inventive method is using class ionic liquid as catalyst, and it can be used as a kind of good ionic liquid substitute, not only has the physicochemical characteristic similar to ionic liquid, and synthesis material is easy to get more, synthetic method is more simple and price is relatively cheap; In addition, such ionic liquid has good catalytic activity and stability, uses continuously more than 120 hours activity not subtract, and catalyst consumption amount is low, can be recycled, and has both been conducive to reducing production cost, also can be suitable for continuous reaction operation.
2, method of the present invention does not use any organic solvent, vapour pressure as the class ionic liquid of catalyst is extremely low, free from environmental pollution, be easy to be separated with isomerization product, whole technical process is simple, easy to operate, without the need to hydrogenation, and do not produce the pollutant such as spent solvent, waste water, environmental protection, has good Social benefit and economic benefit.
3, the reaction temperature needed for isomerization reaction of the present invention is low, reaction pressure is little, and reaction condition is gentle; Particularly, isomerization product is all the saturated alkane of C4-C9, single reaction raw materials conversion ratio reaches more than 60%, in product, the ratio of isoparaffin reaches more than 60%, the RON (research octane number (RON)) of the isomerized oil of gained is 80-90, comparatively reaction raw materials (such as pentane RON61.8, n-hexane RON24.8) has and significantly improves.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of alkane isomerization process of the present invention;
Fig. 2 is the chromatogram of the isomerization product of the embodiment of the present invention three;
Fig. 3 is the variation diagram of n-alkane conversion ratio in the continous way isomerization reaction of the embodiment of the present invention three.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with drawings and Examples of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The preparation of embodiment one class ionic liquid
Embodiment 1-1
Under drying nitrogen protection, the acetamide of 0.065 mole (3.84 grams) is slowly added the AlCl of 0.1 mole (13.34 grams) 3in, stir 30 minutes at ambient temperature, be then heated to 80 DEG C, continuation stirring obtains class ionic liquid to make to react completely in 2 hours.
Embodiment 1-2
Under drying nitrogen protection, the N-methylacetamide of 0.055 mole (4.02 grams) is slowly added the AlCl of 0.1 mole (13.34 grams) 3in, stir 30 minutes at ambient temperature, be then heated to 60 DEG C, continuation stirring obtains foundation class ionic liquid to make to react completely in 3 hours.Subsequently, under drying nitrogen protection, in foundation class ionic liquid, add the CuCl of 0.015 mole (1.48 grams) and be warming up to 120 DEG C, continuing to stir to make react completely (being converted into liquid completely), obtain class ionic liquid.
Embodiment 1-3
Under drying nitrogen protection, the DMA of 0.085 mole (7.41 grams) is slowly added the AlCl of 0.1 mole (13.34 grams) 3in, stir 30 minutes at ambient temperature, be then heated to 80 DEG C, continuation stirring obtains class ionic liquid to make to react completely in 4 hours.
Embodiment 1-4
Under drying nitrogen protection, the N-METHYLFORMAMIDE of 0.075 mole (4.43 grams) is slowly added the AlCl of 0.1 mole (13.34 grams) 3in, stir 30 minutes at ambient temperature, be then heated to 60 DEG C, continuation stirring obtains foundation class ionic liquid to make to react completely in 3 hours.Subsequently, under drying nitrogen protection, in foundation class ionic liquid, add the CuCl of 0.015 mole (1.48 grams) 2and be warming up to 120 DEG C, continue to stir to make react completely (being converted into liquid completely), obtain class ionic liquid.
The isomerization reaction of embodiment two batch (-type)
Embodiment 2-1
The class ionic liquid 150ml prepared in above-described embodiment 1-1 is added in the autoclave of band stirring, 1.0MPa is pressurized to nitrogen, high-pressure pump is utilized to squeeze into pentane raw material 150ml containing 1.0wt% n-butanol, simultaneously vigorous stirring, isomerization reaction 60 minutes at 50 DEG C.After question response terminates, cooling, stratification, extract supernatant liquid, obtain isomerization product; After separation, lower floor's class ionic liquid can be recycled.
Adopt the component of chromatography to above-mentioned isomerization product to detect, and adopt following formula (1) and formula (2) to calculate feed stock conversion and isomerization rate:
x = ( 1 - W W f ) × 100 % - - - ( 1 )
s = W p W t × 100 % - - - ( 2 )
In formula: x is feed stock conversion, unit wt%; S is isomerization rate, unit wt%; W is the n-alkane quality do not reacted, unit g; W ffor the quality of the n-alkane before reaction, unit g; W pfor the quality of isoparaffin in product, unit g; W tfor product gross mass, unit g;
In addition, detect the research octane number (RON) RON of isomerization product, testing result is in table 1.
Embodiment 2-2
The class ionic liquid 150ml prepared in above-described embodiment 1-2 is added in the autoclave of band stirring, 1.5MPa is pressurized to nitrogen, high-pressure pump is utilized to squeeze into pentane raw material 20ml containing 10wt% iso-butane, simultaneously vigorous stirring, isomerization reaction 45 minutes at 80 DEG C.After question response terminates, cooling, stratification, extract supernatant liquid, obtain isomerization product; After separation, lower floor's class ionic liquid can be recycled.
Adopt the component of chromatography to above-mentioned isomerization product to detect, and adopt formula (1) and formula (2) to calculate feed stock conversion and isomerization rate; In addition, detect the research octane number (RON) RON of isomerization product, testing result is in table 1.
Embodiment 2-3
The class ionic liquid 100ml prepared in above-described embodiment 1-3 is added in the autoclave of band stirring, 1.0MPa is pressurized to nitrogen, high-pressure pump is utilized to squeeze into n-hexane raw material 50ml containing 1.0wt% chlorobutane, simultaneously vigorous stirring, isomerization reaction 60 minutes at 50 DEG C.After question response terminates, cooling, stratification, extract supernatant liquid, obtain isomerization product; After separation, lower floor's class ionic liquid can be recycled.
Adopt the component of chromatography to above-mentioned isomerization product to detect, and adopt formula (1) and formula (2) to calculate feed stock conversion and isomerization rate; In addition, detect the research octane number (RON) RON of isomerization product, testing result is in table 1.
Embodiment 2-4
The class ionic liquid 200ml prepared in above-described embodiment 1-4 is added in the autoclave of band stirring, 1.0MPa is pressurized to nitrogen, high-pressure pump is utilized to squeeze into light naphthar raw material 1500ml containing 2.0wt% isobutene, simultaneously vigorous stirring, isomerization reaction 120 minutes at 30 DEG C.After question response terminates, cooling, stratification, extract supernatant liquid, obtain isomerization product; After separation, lower floor's class ionic liquid can be recycled.
Adopt the component of chromatography to above-mentioned isomerization product to detect, and adopt formula (1) and formula (2) to calculate feed stock conversion and isomerization rate; In addition, detect the research octane number (RON) RON of isomerization product, testing result is in table 1.
Embodiment 2-5
The class ionic liquid 150ml prepared in above-described embodiment 1-1 is added in the autoclave of band stirring, 1.0MPa is pressurized to nitrogen, high-pressure pump is utilized to squeeze into raw material 700ml containing n-butanol 1.0wt%, pentane 49.5wt% and n-hexane 49.5wt%, vigorous stirring simultaneously, isomerization reaction 60 minutes at 50 DEG C.After question response terminates, cooling, stratification, extract supernatant liquid, obtain isomerization product; After separation, lower floor's class ionic liquid can be recycled.
Adopt the component of chromatography to above-mentioned isomerization product to detect, and adopt formula (1) and formula (2) to calculate feed stock conversion and isomerization rate; In addition, detect the research octane number (RON) RON of isomerization product, testing result is in table 1.
Embodiment 2-6
The class ionic liquid 150ml prepared in above-described embodiment 1-3 is added in the autoclave of band stirring, 1.0MPa is pressurized to nitrogen, high-pressure pump is utilized to squeeze into light condensate raw material 450ml containing 0.5wt% isobutanol, simultaneously vigorous stirring, isomerization reaction 45 minutes at 50 DEG C.After question response terminates, cooling, stratification, extract supernatant liquid, obtain isomerization product; After separation, lower floor's class ionic liquid can be recycled.
Adopt the component of chromatography to above-mentioned isomerization product to detect, and adopt formula (1) and formula (2) to calculate feed stock conversion and isomerization rate; In addition, detect the research octane number (RON) RON of isomerization product, testing result is in table 1.
Embodiment 2-7
Added by the class ionic liquid 150ml prepared in above-described embodiment 1-1 in the autoclave of band stirring, be pressurized to 1.0MPa, utilize high-pressure pump to squeeze into pentane raw material 150ml with nitrogen, simultaneously vigorous stirring, at 50 DEG C, reaction carries out 45 minutes.After question response terminates, cooling, stratification, extract supernatant liquid, obtain isomerization product; After separation, lower floor's class ionic liquid can be recycled.
Adopt the component of chromatography to above-mentioned isomerization product to detect, and adopt formula (1) and formula (2) to calculate feed stock conversion and isomerization rate; In addition, detect the research octane number (RON) RON of isomerization product, testing result is in table 1.
The testing result of the isomerization product of each embodiment of table 1
As shown in Table 1: the isomerization product of various embodiments of the present invention is all the saturated alkane of C4-C9, single reaction raw materials conversion ratio reaches more than 60%, in product, the ratio of isoparaffin reaches more than 60%, the RON (research octane number (RON)) of the isomerized oil of gained is 80-90, comparatively reaction raw materials (such as pentane RON61.8, n-hexane RON24.8) has and significantly improves.
The isomerization reaction of embodiment three continous way
As shown in Figure 1, first, class ionic liquid 200ml prepared by Example 1-1, add in the reactor 1 of band stirring, raw material (raw material composition is in table 2) subsequently in head tank 2 enters continuously in reactor 1 through measuring pump 3 and drying tube 4 successively and carries out isomerization reaction, and isomerization product discharges reactor 1 continuously.Isomerization reaction is carried out at 1.0MPa, at 50 DEG C, and the charging rate of raw material is 200ml/h, successive reaction 120 hours.
Adopt the component of chromatography to above-mentioned isomerization product to detect, the results are shown in Figure 2 and table 2; Meanwhile, detect the research octane number (RON) RON of isomerization product, testing result is in table 2.As shown in Table 2: in isomerization reaction product, the ratio of isoparaffin improves greatly continuously, and research octane number (RON) RON significantly promotes.
In addition, detect the conversion ratio of n-alkane in raw material, the results are shown in Figure 3.As shown in Figure 3, in the continuous isomerization reaction of 120 hours, the conversion ratio of C5, C6 n-alkane is all higher and steady with reaction time variation tendency, illustrates that class ionic liquid of the present invention has good stability as light paraffins isomerization.
The testing result of table 2 continous way isomerization reaction Raw and isomerization product
Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.

Claims (10)

1. the light paraffins isomerization method using class ionic liquid as catalyst, is characterized in that, is contacted by the raw material containing light paraffins with class ionic liquid, to make described light paraffins generation isomerization reaction; Wherein, described class ionic liquid reacts obtained by amide compound and more than one metallic compounds.
2. light paraffins isomerization method according to claim 1, is characterized in that, described amide compound is selected from general formula R 1cONR 2r 3chain acid amides and general formula R 1cONR 2r 3cyclic amide in one or more; General formula R 1cONR 2r 3in, R 1for alkyl or the-NR of hydrogen, carbon number 1-10 2r 3, R 2, R 3independently be selected from hydrogen, the alkyl of carbon number 1-10 or the thiazolinyl of carbon number 1-10 separately.
3. light paraffins isomerization method according to claim 1, is characterized in that, described metallic compound is the halide of metal, sulfate or nitrate, and described metal is aluminium, copper, iron, zinc, nickel, cobalt, silver, molybdenum or platinum.
4. according to the arbitrary described light paraffins isomerization method of claims 1 to 3, it is characterized in that, described class ionic liquid is reacted by amide compound and a kind of metallic compound and obtains, and adopts and prepare described class ionic liquid with the following method:
Under protective atmosphere, described amide compound is joined in described metallic compound, after stirring at room temperature, is warming up to 80-180 DEG C, continue to be stirred to complete reaction, obtain described class ionic liquid.
5. light paraffins isomerization method according to claim 4, is characterized in that, the mol ratio of described amide compound and described metallic compound is 1:0.1 to 1:10.
6. according to the arbitrary described light paraffins isomerization method of claims 1 to 3, it is characterized in that, described class ionic liquid is reacted by amide compound and two or more metallic compound and obtains, and adopts and prepare described class ionic liquid with the following method:
Under protective atmosphere, described amide compound is joined in the first metallic compound, after stirring at room temperature, is warming up to 80-180 DEG C, continue to be stirred to complete reaction, obtain reactant;
Under protective atmosphere, in above-mentioned reactant, add more than one second metallic compounds, keep temperature-resistant or continue to be warming up to being no more than 180 DEG C, continue to be stirred to complete reaction, obtain described class ionic liquid.
7. light paraffins isomerization method according to claim 6, it is characterized in that, the mol ratio of described amide compound and described first metallic compound is 1:0.1 to 1:10, and the mol ratio of described first metallic compound and the second metallic compound is 1:100 to 100:1.
8. according to the arbitrary described light paraffins isomerization method of claim 1 to 7, it is characterized in that, described raw material also comprises initator, described initator be selected from alkene, halogenated alkane, alcohol and isoparaffin one or more, and mass percentage≤10% of described initator in described raw material.
9. the light paraffins isomerization method according to claim 1 or 8, is characterized in that, it is one or more in the alkane of 4-7 that described light paraffins comprises carbon number.
10. the light paraffins isomerization method according to claim 1 or 8, is characterized in that, the volume ratio of described light paraffins and class ionic liquid is 1:50 to 50:1, and the reaction temperature of described isomerization reaction is 0-100 DEG C, and the reaction time is 1-300min.
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CN106964401A (en) * 2017-04-06 2017-07-21 福州大学 A kind of light paraffins isomerization ionic-liquid catalyst and preparation method thereof
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CN113336614A (en) * 2021-05-31 2021-09-03 中国石油大学(北京) Preparation method of alkylbenzene based on catalysis of ionic liquid
CN113336614B (en) * 2021-05-31 2023-03-14 中国石油大学(北京) Preparation method of alkylbenzene based on catalysis of ionic liquid
CN115181585A (en) * 2022-08-09 2022-10-14 中国石油大学(北京) Alkane isomerization method based on ionic liquid catalysis
CN115181585B (en) * 2022-08-09 2023-11-07 中国石油大学(北京) Alkane isomerization method based on ionic liquid catalysis

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