WO2021000685A1 - Method for catalytic preparation of alkylated oil by using functionalized ionic liquid acid coupling system - Google Patents
Method for catalytic preparation of alkylated oil by using functionalized ionic liquid acid coupling system Download PDFInfo
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- WO2021000685A1 WO2021000685A1 PCT/CN2020/094073 CN2020094073W WO2021000685A1 WO 2021000685 A1 WO2021000685 A1 WO 2021000685A1 CN 2020094073 W CN2020094073 W CN 2020094073W WO 2021000685 A1 WO2021000685 A1 WO 2021000685A1
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- Prior art keywords
- formula
- alkylation reaction
- alkyl group
- acid
- catalyst
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Links
- 230000008878 coupling Effects 0.000 title claims abstract description 31
- 238000010168 coupling process Methods 0.000 title claims abstract description 31
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002608 ionic liquid Substances 0.000 title abstract description 22
- 238000000034 method Methods 0.000 title abstract description 13
- 230000003197 catalytic effect Effects 0.000 title abstract description 5
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 63
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 12
- 125000002883 imidazolyl group Chemical group 0.000 claims description 10
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 8
- 239000001282 iso-butane Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical group O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- -1 n-octyl Chemical group 0.000 claims description 3
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229960005181 morphine Drugs 0.000 claims description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000003921 oil Substances 0.000 description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000005457 ice water Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- MMDFSEGJGPURPF-UHFFFAOYSA-N 2-octyl-1h-imidazole Chemical compound CCCCCCCCC1=NC=CN1 MMDFSEGJGPURPF-UHFFFAOYSA-N 0.000 description 1
- VDWDZFIPYQGZHP-UHFFFAOYSA-O CCC[N+](CCC)(CCC)CCCS(O)(=O)=O Chemical compound CCC[N+](CCC)(CCC)CCCS(O)(=O)=O VDWDZFIPYQGZHP-UHFFFAOYSA-O 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 208000037943 overwhelming post-splenectomy infection Diseases 0.000 description 1
- 150000003217 pyrazoles Chemical group 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the invention relates to a method for catalyzing and preparing alkylated oil by a functionalized ionic liquid acid coupling system.
- Alkylated oil is a C 8 component formed by the reaction of isobutane and small molecular olefins under the catalysis of acid. Compared with FCC gasoline and reformed gasoline, it has a higher octane number and contains almost no olefins. , Aromatics, low sulfur content and vapor pressure, so it can be used as a blending component of clean gasoline.
- the catalyst is mainly sulfuric acid, hydrofluoric acid or solid acid method.
- sulfuric acid method the acid consumption is large and the waste acid is difficult to treat, which brings serious environmental pollution
- solid acid method the solid acid is easily deactivated and difficult to regenerate.
- Ionic liquids have been used in isobutane alkylation due to their extremely low vapor pressure and flexible design.
- chloroaluminate ionic liquids have been studied early in the alkylation reaction, and then modified composite ionic liquids have been developed and have obtained relatively ideal catalytic effects.
- chloroaluminate ionic liquids are extremely sensitive to water and air and are very unstable. Therefore, people are Acidic ionic liquids have been studied, but due to their low acid strength, the effect of catalyzing the alkylation reaction of isobutane alone is not ideal.
- the technical problem to be solved by the present invention is to overcome the defects of the prior art alkylation oil preparation method, the catalyst acid consumption is large, the environmental pollution is serious, the toxicity is large, the reproducibility and the catalytic effect are poor, and provide a A method for catalyzing the preparation of alkylated oil by a functionalized ionic liquid acid coupling system.
- the functionalized ionic liquid acid coupling system of the present invention catalyzes the method for preparing alkylated oil, which has good catalytic effect, the catalyst can be reused many times, the reaction temperature is moderate, the reaction time is short, and it is environmentally friendly and simple.
- the present invention solves the above technical problems through the following technical solutions.
- the present invention provides a method for preparing alkylated oil, which comprises the following steps: in the presence of a catalyst, the alkylation reaction of isoparaffins and olefins is performed to obtain alkylated oil; wherein the catalyst is The coupling system formed by the "compound of formula I and/or formula II" and acid;
- n is any integer from 1 to 10;
- a ring is an imidazole ring, an imidazole ring substituted with an NC 1-10 alkyl group, a pyrazole ring, a pyrazole ring substituted with an NC 1-10 alkyl group, a pyridine ring, Pyrrole ring or morphine ring;
- m is any integer from 1 to 10; Q is N or P; R 1a , R 1b and R 1c are independently C 1-10 alkyl.
- the C 1-10 alkyl group in the imidazole ring substituted by the NC 1-10 alkyl group may be a C 4-8 alkyl group.
- the C 4-8 alkyl group is n-butyl or its isomers, n-pentyl or its isomers, n-heptyl or its isomers, or n-octyl or its isomers.
- n is preferably an integer of 1 to 3, for example 3.
- the A ring is preferably an imidazole ring substituted with an NC 1-10 alkyl group.
- m is preferably an integer of 1 to 3, for example 3.
- Q is preferably N.
- R 1a , R 1b and R 1c are independently a C 1-10 alkyl group
- the C 1-10 alkyl group is a C 1-3 alkyl group.
- the C 1-3 alkyl group can be methyl, ethyl, n-propyl or isopropyl, or n-propyl.
- the temperature of the alkylation reaction may be a temperature conventional in the art, preferably 1 to 5°C; preferably 1 to 3°C.
- the time of the alkylation reaction can be a conventional time in the art, preferably 5-20 minutes, more preferably 5-15 minutes, still more preferably 5-12 minutes, such as 10 minutes .
- the pressure of the alkylation reaction may be 0.5MPa-10MP.
- the stirring speed of the alkylation reaction may be a conventional speed of such reactions in the art, preferably 1000-5000 rpm, for example 3000 rpm.
- the amount of the catalyst can be a conventional amount in the art.
- the volume ratio of the catalyst to the "isoparaffin and olefin" is preferably 0.5:1 to 2:1, for example 1.5:1.
- the isoparaffin may be a conventional isoparaffin in the field, preferably isobutane.
- the olefin may be a conventional olefin in the art, preferably butene.
- the volume ratio of the isoparaffin to the olefin may be a conventional volume ratio in the art, preferably 1:1-10:1, for example 6.5:1.
- the acid may be a conventional acid used in such reactions in the art, preferably halogenated sulfonic acid and/or sulfuric acid, and may also preferably be sulfuric acid, such as 98% sulfuric acid.
- the “compound of formula I and/or formula II” and the acid in the alkylation reaction, in the coupling system formed by the "compound of formula I and/or formula II" and the acid, the “compound of formula I and/or formula II" and The weight ratio of the acid can be 0.03:1 to 0.1:1, or 0.03:1 to 0.5:1.
- the catalyst can also be recycled.
- the number of times the catalyst is recycled may be 21 to 23 times, such as 22 times.
- the catalyst is a "coupling system formed by a compound represented by formula I-1 and sulfuric acid", "a coupling system formed by a compound represented by formula I-2 and sulfuric acid", or, " The coupling system formed by the compound represented by formula I-3 and sulfuric acid”; the temperature of the alkylation reaction is 1 to 5°C;
- the catalyst is a "coupling system formed by a compound represented by formula I-1 and sulfuric acid", "a coupling system formed by a compound represented by formula I-2 and sulfuric acid", or, " The coupling system formed by the compound represented by formula I-3 and sulfuric acid”; the temperature of the alkylation reaction is 1 to 5°C; the time of the alkylation reaction is 5 to 20 minutes;
- the catalyst is a "coupling system formed by a compound represented by formula I-2 and sulfuric acid"; the volume ratio of the catalyst to the "isoparaffin and olefin” is 0.5: 1 to 2:1; in the alkylation reaction, the weight ratio of the formula I-2 to the acid may be 0.03:1 to 0.1:1;
- the catalyst is a "coupling system formed by the compound represented by formula I-2 and sulfuric acid"; the temperature of the alkylation reaction is 1 to 3°C; The reaction time is 5-12 minutes; the volume ratio of the catalyst to the "isoparaffin and olefin” is 0.5:1 to 2:1; in the alkylation reaction, the formula I
- the weight ratio of -2 to the acid can be 0.03:1 to 0.1:1;
- C 1-10 alkyl refers to a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms.
- the term "coupling system” means that the ionic liquid and the acid interact and influence each other, thereby forming a system together.
- the reagents and raw materials used in the present invention are all commercially available.
- the positive progress effect of the present invention is that the preparation method of the alkylated oil of the present invention can produce alkylated oils with an octane number as high as 97.67, the reaction temperature is moderate, the reaction time is short, and the catalyst can be repeatedly recycled. Times or more.
- the coupling system of the sulfonic acid functionalized ionic liquid sulfuric acid used in the following examples is self-made, and the preparation method of the alkylated oil of the present invention is also suitable for coupling systems of other sources of sulfonic acid functionalized ionic liquid sulfuric acid as a catalyst.
- the reaction product was washed with ethyl acetate and filtered 3 times to remove unreacted raw materials, and then the reaction product was placed in a vacuum drying oven to dry and the ethyl acetate was removed to obtain 22 g of product.
- the obtained intermediate is acidified by adding an equimolar amount of concentrated sulfuric acid to obtain a sulfonic acid functionalized quaternary ammonium salt ionic liquid [n-Pro 3 N(CH 2 ) 3 SO 3 H] [HSO 4 ] (21 g).
- the reaction After the reaction, it was washed with ethyl acetate three times to remove the incompletely reacted raw materials, and then the reaction product was placed in a vacuum drying oven to dry and the ethyl acetate was removed to obtain 41 g of product.
- the obtained ylide is acidified by adding an equimolar amount (98% concentration) of concentrated sulfuric acid to obtain a sulfonic acid functionalized imidazole ionic liquid [BPSIm][HSO 4 ] (45 g).
- the reaction After the reaction, it was washed with ethyl acetate three times to remove the incompletely reacted raw materials, and then the reaction product was placed in a vacuum drying oven to dry and the ethyl acetate was removed to obtain 137 g of product.
- the obtained ylide is acidified by adding an equimolar amount of concentrated sulfuric acid to obtain a sulfonic acid functionalized imidazole ionic liquid [OPSIm][HSO 4 ] (175 g).
- the product has an octane number of 97.25 after testing.
- the type and content of the sulfonic acid functionalized ionic liquid were replaced with the data in the following table, and the octane number and the number of reuses were tested.
- the dosage of sulfonic acid functionalized ionic liquid in the above table is the weight percentage of sulfonic acid functionalized ionic liquid and sulfuric acid.
- the type and content of the sulfonic acid functionalized ionic liquid and the reaction conditions were replaced with the data in the following table, and the octane number and the number of reuses were tested.
- the dosage of sulfonic acid functionalized ionic liquid in the above table is the weight percentage of sulfonic acid functionalized ionic liquid and sulfuric acid.
- the catalyst was replaced with the data in the following table, and its octane number and repeated use times were tested.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for the catalytic preparation of alkylated oil by using a functionalized ionic liquid acid coupling system, comprising the following step: in the presence of a catalyst, performing an alkylation reaction on an isoparaffin and an olefin to obtain alkylated oil, the catalyst being a coupling system formed by "a compound represented by formula I and/or formula II" and an acid. The obtained alkylated oil has a higher octane number; moreover, the catalyst may be reused many times, the reaction temperature is moderate, reaction time is shorter, and the method is simple and easy to carry out.
Description
本发明涉及一种功能化离子液体酸耦合体系催化制备烷基化油的方法。The invention relates to a method for catalyzing and preparing alkylated oil by a functionalized ionic liquid acid coupling system.
烷基化油是异丁烷和小分子烯烃在酸的催化作用下反应生成的C
8组分，相对于FCC汽油和重整汽油而言，它的辛烷值较高，而且几乎不含烯烃、芳烃，硫含量和蒸气压低，因此可作为清洁汽油的调和组分。
Alkylated oil is a C 8 component formed by the reaction of isobutane and small molecular olefins under the catalysis of acid. Compared with FCC gasoline and reformed gasoline, it has a higher octane number and contains almost no olefins. , Aromatics, low sulfur content and vapor pressure, so it can be used as a blending component of clean gasoline.
目前烷基化油制备工艺，催化剂主要为硫酸、氢氟酸或固体酸法。这些工艺中还存一些缺陷：硫酸法中，酸耗较大且废酸难以处理，带来严重的环境污染；氢氟酸法中，由于氢氟酸的易挥发性和剧毒性存在着严重的安全问题；而且两者都会严重腐蚀设备；固体酸法中，固体酸极易失活而且难以再生。At present, in the preparation process of alkylated oil, the catalyst is mainly sulfuric acid, hydrofluoric acid or solid acid method. There are still some shortcomings in these processes: in the sulfuric acid method, the acid consumption is large and the waste acid is difficult to treat, which brings serious environmental pollution; In the solid acid method, the solid acid is easily deactivated and difficult to regenerate.
离子液体由于极低的蒸汽压以及灵活的可设计性，在异丁烷烷基化中得到应用。其中，氯铝酸类离子液体在烷基化反应中的研究较早，此后发展了改性的复合离子液体并得到了较为理想的催化效果。但是，氯铝酸类离子液体对水和空气极为敏感，很不稳定。因此，人们对
酸性离子液体展开了研究，但是由于其酸强度较低，单独催化异丁烷烷基化反应的效果不理想。
Ionic liquids have been used in isobutane alkylation due to their extremely low vapor pressure and flexible design. Among them, chloroaluminate ionic liquids have been studied early in the alkylation reaction, and then modified composite ionic liquids have been developed and have obtained relatively ideal catalytic effects. However, chloroaluminate ionic liquids are extremely sensitive to water and air and are very unstable. Therefore, people are Acidic ionic liquids have been studied, but due to their low acid strength, the effect of catalyzing the alkylation reaction of isobutane alone is not ideal.
故亟须开发一种功能化离子液体酸耦合体系催化制备烷基化油的方法。Therefore, it is urgent to develop a method for catalyzing the preparation of alkylated oil by functionalized ionic liquid acid coupling system.
发明内容Summary of the invention
本发明所要解决的技术问题在于克服现有技术中烷基化油制备方法中、催化剂酸耗较大、环境污染严重、毒性大、重现性以及催化效果较差的缺陷，而提供了一种功能化离子液体酸耦合体系催化制备烷基化油的方法。本发明的功能化离子液体酸耦合体系催化制备烷基化油的方法，催化效果较好、催化剂可多次重复利用、反应温度适中、反应时间较短、环境友好且简单易行。The technical problem to be solved by the present invention is to overcome the defects of the prior art alkylation oil preparation method, the catalyst acid consumption is large, the environmental pollution is serious, the toxicity is large, the reproducibility and the catalytic effect are poor, and provide a A method for catalyzing the preparation of alkylated oil by a functionalized ionic liquid acid coupling system. The functionalized ionic liquid acid coupling system of the present invention catalyzes the method for preparing alkylated oil, which has good catalytic effect, the catalyst can be reused many times, the reaction temperature is moderate, the reaction time is short, and it is environmentally friendly and simple.
本发明通过以下技术方案解决上述技术问题。The present invention solves the above technical problems through the following technical solutions.
本发明提供了一种烷基化油的制备方法，其包括以下步骤：以在催化剂存在下，将异构烷烃和烯烃进行烷基化反应，得到烷基化油；其中，所述的催化剂为“式I和/或式II所示的化合物”与酸形成的耦合体系；The present invention provides a method for preparing alkylated oil, which comprises the following steps: in the presence of a catalyst, the alkylation reaction of isoparaffins and olefins is performed to obtain alkylated oil; wherein the catalyst is The coupling system formed by the "compound of formula I and/or formula II" and acid;
式I中，n为1～10中任一整数；A环为咪唑环、N-C
1～10烷基取代的咪唑环、吡唑环、N-C
1～10烷基取代的吡唑环、吡啶环、吡咯环或吗啡环；
In formula I, n is any integer from 1 to 10; A ring is an imidazole ring, an imidazole ring substituted with an NC 1-10 alkyl group, a pyrazole ring, a pyrazole ring substituted with an NC 1-10 alkyl group, a pyridine ring, Pyrrole ring or morphine ring;
式II中，m为1～10中任一整数；Q为N或P；R
1a、R
1b和R
1c独立地为C
1～10烷基。
In formula II, m is any integer from 1 to 10; Q is N or P; R 1a , R 1b and R 1c are independently C 1-10 alkyl.
式I中，所述的N-C
1～10烷基取代的咪唑环中的C
1～10烷基可以为C
4～8烷基。所述的C
4～8烷基为正丁基或其异构体、正戊基或其异构体、正庚基或其异构体、或者、正辛基或其异构体。
In formula I, the C 1-10 alkyl group in the imidazole ring substituted by the NC 1-10 alkyl group may be a C 4-8 alkyl group. The C 4-8 alkyl group is n-butyl or its isomers, n-pentyl or its isomers, n-heptyl or its isomers, or n-octyl or its isomers.
式I中，n优选为1～3中任一整数，例如3。In formula I, n is preferably an integer of 1 to 3, for example 3.
式I中，所述的A环优选为N-C
1～10烷基取代的咪唑环。
In formula I, the A ring is preferably an imidazole ring substituted with an NC 1-10 alkyl group.
式II中，m优选为1～3中任一整数，例如3。In formula II, m is preferably an integer of 1 to 3, for example 3.
式II中，Q优选为N。In formula II, Q is preferably N.
式II中，当R
1a、R
1b和R
1c独立地为C
1～10烷基时，所述的C
1～10烷基为C
1～3烷基。所述的C
1～3烷基可为甲基、乙基、正丙基或异丙基，还可以为正丙基。
In Formula II, when R 1a , R 1b and R 1c are independently a C 1-10 alkyl group, the C 1-10 alkyl group is a C 1-3 alkyl group. The C 1-3 alkyl group can be methyl, ethyl, n-propyl or isopropyl, or n-propyl.
本发明中，所述“式I和/或式II所示的化合物”优选以下化合物：In the present invention, the "compounds represented by formula I and/or formula II" are preferably the following compounds:
所述的烷基化反应中，所述的烷基化反应的温度可为本领域常规的温度，优选1～5℃；优选1～3℃。In the alkylation reaction, the temperature of the alkylation reaction may be a temperature conventional in the art, preferably 1 to 5°C; preferably 1 to 3°C.
所述的烷基化反应中，所述的烷基化反应的时间可为本领域常规的时间，优选5～20分钟，更优选5～15分钟，进一步更优选5～12分钟，例如10分钟。In the alkylation reaction, the time of the alkylation reaction can be a conventional time in the art, preferably 5-20 minutes, more preferably 5-15 minutes, still more preferably 5-12 minutes, such as 10 minutes .
所述的烷基化反应中，所述烷基化反应的压力可为0.5MPa-10MP。In the alkylation reaction, the pressure of the alkylation reaction may be 0.5MPa-10MP.
所述的烷基化反应中，所述烷基化反应的搅拌的转速可为本领域此类反应常规的转速，优选1000～5000rmp，例如3000rmp。In the alkylation reaction, the stirring speed of the alkylation reaction may be a conventional speed of such reactions in the art, preferably 1000-5000 rpm, for example 3000 rpm.
所述的烷基化反应中，所述的催化剂的用量可为本领域常规的用量。所述的催化剂与所述“异构烷烃和烯烃”的体积比优选0.5:1～2:1，例如1.5:1。In the alkylation reaction, the amount of the catalyst can be a conventional amount in the art. The volume ratio of the catalyst to the "isoparaffin and olefin" is preferably 0.5:1 to 2:1, for example 1.5:1.
所述的烷基化反应中，所述的异构烷烃可为本领域常规的异构烷烃，优选异丁烷。In the alkylation reaction, the isoparaffin may be a conventional isoparaffin in the field, preferably isobutane.
所述的烷基化反应中，所述的烯烃可为本领域常规的烯烃，优选丁烯。In the alkylation reaction, the olefin may be a conventional olefin in the art, preferably butene.
所述的烷基化反应中，所述的异构烷烃与烯烃的体积比可为本领域常规的体积比，优选为1:1～10:1，例如6.5:1。In the alkylation reaction, the volume ratio of the isoparaffin to the olefin may be a conventional volume ratio in the art, preferably 1:1-10:1, for example 6.5:1.
所述的烷基化反应中，所述酸可为本领域此类反应所用常规的酸，优选卤代磺酸和/或硫酸，还可以优选硫酸，例如98％硫酸。In the alkylation reaction, the acid may be a conventional acid used in such reactions in the art, preferably halogenated sulfonic acid and/or sulfuric acid, and may also preferably be sulfuric acid, such as 98% sulfuric acid.
所述的烷基化反应中，所述的“式I和/或式II所示的化合物”与酸形成的耦合体系中，所述的“式I和/或式II所示的化合物”与所述的酸的重量比可以为0.03:1～0.1:1，还可以为0.03:1～0.5:1。In the alkylation reaction, in the coupling system formed by the "compound of formula I and/or formula II" and the acid, the "compound of formula I and/or formula II" and The weight ratio of the acid can be 0.03:1 to 0.1:1, or 0.03:1 to 0.5:1.
本发明中，所述的催化剂还可以循环使用。所述的催化剂循环使用的次数可以为21～23次，例如22次。In the present invention, the catalyst can also be recycled. The number of times the catalyst is recycled may be 21 to 23 times, such as 22 times.
在本发明一实施方案中，所述的催化剂为“式I-1所示的化合物和硫酸形成的耦合体系”、“式I-2所示的化合物和硫酸形成的耦合体系”、或、“式I-3所示的化合物和硫酸形成的耦合体系”；所述的烷基化反应的温度为1～5℃；In one embodiment of the present invention, the catalyst is a "coupling system formed by a compound represented by formula I-1 and sulfuric acid", "a coupling system formed by a compound represented by formula I-2 and sulfuric acid", or, " The coupling system formed by the compound represented by formula I-3 and sulfuric acid"; the temperature of the alkylation reaction is 1 to 5°C;
在本发明一实施方案中，所述的催化剂为“式I-1所示的化合物和硫酸形成的耦合体系”、“式I-2所示的化合物和硫酸形成的耦合体系”、或、“式I-3所示的化合物和硫酸形成的耦合体系”；所述的烷基化反应的温度为1～5℃；所述的烷基化 反应的时间为5～20分钟；In one embodiment of the present invention, the catalyst is a "coupling system formed by a compound represented by formula I-1 and sulfuric acid", "a coupling system formed by a compound represented by formula I-2 and sulfuric acid", or, " The coupling system formed by the compound represented by formula I-3 and sulfuric acid"; the temperature of the alkylation reaction is 1 to 5°C; the time of the alkylation reaction is 5 to 20 minutes;
在本发明一实施方案中，所述的催化剂为“式I-2所示的化合物和硫酸形成的耦合体系”；所述的催化剂与所述“异构烷烃和烯烃”的体积比为0.5:1～2:1；所述的烷基化反应中，所述的式I-2与所述的酸的重量比可为0.03:1～0.1:1；In one embodiment of the present invention, the catalyst is a "coupling system formed by a compound represented by formula I-2 and sulfuric acid"; the volume ratio of the catalyst to the "isoparaffin and olefin" is 0.5: 1 to 2:1; in the alkylation reaction, the weight ratio of the formula I-2 to the acid may be 0.03:1 to 0.1:1;
在本发明一实施方案中，所述的催化剂为“式I-2所示的化合物和硫酸形成的耦合体系”；所述的烷基化反应的温度为1～3℃；所述的烷基化反应的时间为5～12分钟；所述的催化剂与所述“异构烷烃和烯烃”的体积比为0.5:1～2:1；所述的烷基化反应中，所述的式I-2与所述的酸的重量比可为0.03:1～0.1:1；In one embodiment of the present invention, the catalyst is a "coupling system formed by the compound represented by formula I-2 and sulfuric acid"; the temperature of the alkylation reaction is 1 to 3°C; The reaction time is 5-12 minutes; the volume ratio of the catalyst to the "isoparaffin and olefin" is 0.5:1 to 2:1; in the alkylation reaction, the formula I The weight ratio of -2 to the acid can be 0.03:1 to 0.1:1;
本发明中，术语“C
1～10烷基”是指具有1至10个碳原子的直链或支链的饱和烃基团。
In the present invention, the term "C 1-10 alkyl" refers to a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms.
在本发明中，术语“耦合体系”是指离子液体与酸相互作用又彼此影响，从而联合起来形成一体系。In the present invention, the term "coupling system" means that the ionic liquid and the acid interact and influence each other, thereby forming a system together.
在不违背本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。On the basis of not violating common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain preferred embodiments of the present invention.
本发明所用试剂和原料均市售可得。The reagents and raw materials used in the present invention are all commercially available.
本发明的积极进步效果在于：本发明的烷基化油的制备方法，可制得辛烷值高 达97.67的烷基化油，反应温度适中，反应时间较短，而且该催化剂可重复循环利用23次以上。The positive progress effect of the present invention is that the preparation method of the alkylated oil of the present invention can produce alkylated oils with an octane number as high as 97.67, the reaction temperature is moderate, the reaction time is short, and the catalyst can be repeatedly recycled. Times or more.
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。The present invention will be further explained by way of examples below, but the present invention is not limited to the scope of the described examples. In the following examples, the experimental methods without specific conditions are selected according to conventional methods and conditions, or according to the product specification.
以下实施例中采用的磺酸功能化离子液体硫酸的耦合体系为自制，本发明的烷基化油的制备方法也适用于其它来源的磺酸功能化离子液体硫酸的耦合体系作为催化剂。The coupling system of the sulfonic acid functionalized ionic liquid sulfuric acid used in the following examples is self-made, and the preparation method of the alkylated oil of the present invention is also suitable for coupling systems of other sources of sulfonic acid functionalized ionic liquid sulfuric acid as a catalyst.
辛烷值的检测Detection of octane number
采用气相色谱对实验获得的烷基化油样品进行产物分析：Agilent Technology GC7890B气相色谱，HP-PONA(50m×0.2mm×0.5μm)毛细管色谱柱，定量方法采用面积归一法。Gas chromatography was used to analyze the products of the alkylated oil samples obtained in the experiment: Agilent Technology GC7890B gas chromatography, HP-PONA (50m×0.2mm×0.5μm) capillary column, and the quantitative method used area normalization method.
实施例1Example 1
称取一定质量的1,3-丙磺酸内酯(12.3g，0.1mol)三口烧瓶中，加入乙酸乙酯(200ml)使其溶解。将等摩尔的三丙胺(14.3g，0.1mol)加入至恒压漏斗中。开启机械搅拌，在冰水浴条件下打开恒压漏斗，将三丙胺逐滴滴加至三口烧瓶中。滴加完毕后，70℃下超声反应2小时，反应过程中逐渐生成白色粉末。反应完成后，用乙酸乙酯洗涤抽滤3次，除去未反应完全的原料，然后将反应产物放置于真空干燥箱烘干并除去乙酸乙酯，得到22g产物。反应后所得中间体加入等摩尔量浓硫酸进行酸化，得到磺酸功能化季铵盐类离子液体[n-Pro
3N(CH
2)
3SO
3H][HSO
4](21g)。
Weigh a certain mass of 1,3-propane sultone (12.3g, 0.1mol) into a three-necked flask, add ethyl acetate (200ml) to dissolve it. An equimolar amount of tripropylamine (14.3 g, 0.1 mol) was added to the constant pressure funnel. Turn on the mechanical stirring, open the constant pressure funnel under the ice-water bath condition, and add the tripropylamine dropwise to the three-necked flask. After the dripping was completed, the ultrasonic reaction was carried out at 70°C for 2 hours, and white powder was gradually formed during the reaction. After the completion of the reaction, it was washed with ethyl acetate and filtered 3 times to remove unreacted raw materials, and then the reaction product was placed in a vacuum drying oven to dry and the ethyl acetate was removed to obtain 22 g of product. After the reaction, the obtained intermediate is acidified by adding an equimolar amount of concentrated sulfuric acid to obtain a sulfonic acid functionalized quaternary ammonium salt ionic liquid [n-Pro 3 N(CH 2 ) 3 SO 3 H] [HSO 4 ] (21 g).
实施例2Example 2
称取一定质量的(24.6g，0.2mol)1,3-丙磺酸内酯于三口烧瓶中，加入(300ml)乙酸乙酯使其溶解。将等摩尔量(24.8g，0.2mol)的N-丁基咪唑BPSI加入至恒压漏斗中。开启机械搅拌，在冰水浴的条件下打开恒压漏斗，将烷基取代基咪唑逐滴滴加至三口烧瓶中，滴加完毕后将冰水浴换成油浴，加热至70℃搅拌6h，生成白色粉末。反应结束后用乙酸乙酯洗涤3次，除去未完全反应的原料，然后将反应产物放置于真空干燥箱烘干并除去乙酸乙酯，得到41g产物。反应后所得内鎓盐加入等摩尔量(浓度98％)浓硫酸进行酸化，得到磺酸功能化咪唑类离子液体 [BPSIm][HSO
4](45g)。
Weigh a certain mass (24.6g, 0.2mol) of 1,3-propane sultone into a three-necked flask, add (300ml) ethyl acetate to dissolve it. An equimolar amount (24.8g, 0.2mol) of N-butylimidazole BPSI was added to the constant pressure funnel. Turn on the mechanical stirring, open the constant pressure funnel under the condition of the ice water bath, add the alkyl substituted imidazole dropwise to the three-necked flask, change the ice water bath to an oil bath after the addition is complete, heat to 70°C and stir for 6 hours to produce White powder. After the reaction, it was washed with ethyl acetate three times to remove the incompletely reacted raw materials, and then the reaction product was placed in a vacuum drying oven to dry and the ethyl acetate was removed to obtain 41 g of product. After the reaction, the obtained ylide is acidified by adding an equimolar amount (98% concentration) of concentrated sulfuric acid to obtain a sulfonic acid functionalized imidazole ionic liquid [BPSIm][HSO 4 ] (45 g).
实施例3Example 3
称取一定质量的(61.5g，0.5mol)1,3-丙磺酸内酯于三口烧瓶中，加入(300ml)乙酸乙酯使其溶解。将等摩尔量(90.0g，0.5mol)的N-辛基咪唑OPSI加入至恒压漏斗中。开启机械搅拌，在冰水浴的条件下打开恒压漏斗，将烷基取代基咪唑逐滴滴加至三口烧瓶中，滴加完毕后将冰水浴换成油浴，加热至70℃搅拌6h，生成粘稠液体。反应结束后用乙酸乙酯洗涤3次，除去未完全反应的原料，然后将反应产物放置于真空干燥箱烘干并除去乙酸乙酯，得到137g产物。反应后所得内鎓盐加入等摩尔量浓硫酸进行酸化，得到磺酸功能化咪唑类离子液体[OPSIm][HSO
4](175g)。
Weigh a certain mass (61.5g, 0.5mol) of 1,3-propane sultone into a three-necked flask, add (300ml) ethyl acetate to dissolve it. An equimolar amount (90.0g, 0.5mol) of N-octylimidazole OPSI was added to the constant pressure funnel. Turn on the mechanical stirring, open the constant pressure funnel under the condition of the ice water bath, add the alkyl substituted imidazole dropwise to the three-necked flask, change the ice water bath to an oil bath after the addition is complete, heat to 70°C and stir for 6 hours to produce Viscous liquid. After the reaction, it was washed with ethyl acetate three times to remove the incompletely reacted raw materials, and then the reaction product was placed in a vacuum drying oven to dry and the ethyl acetate was removed to obtain 137 g of product. After the reaction, the obtained ylide is acidified by adding an equimolar amount of concentrated sulfuric acid to obtain a sulfonic acid functionalized imidazole ionic liquid [OPSIm][HSO 4 ] (175 g).
实施例4Example 4
将实施例1得到的[n-Pro
3N(CH
2)
3SO
3H][HSO
4]和H
2SO
4的耦合体系，其中硫酸的量为201.4g，[n-Pro
3N(CH
2)
3SO
3H][HSO
4]为6.042g(添加量为硫酸的3wt％)，加入到1L的玻璃反应釜中，设定釜内压力为0.5MPa，反应温度为3℃。加入140ml原料气(异丁烷和反2-丁烯，其体积比为6.5:1)，搅拌，搅拌转速为3000rpm，反应时间为12分钟。反应结束后，取样检测。待反应结束后，将反应液转移至分液漏斗中，静置分层，其上层为烷基化油，下层为催化剂，分离后分别得到烷基化油产品和催化剂。
The coupling system of [n-Pro 3 N(CH 2 ) 3 SO 3 H][HSO 4 ] and H 2 SO 4 obtained in Example 1, wherein the amount of sulfuric acid is 201.4g, [n-Pro 3 N(CH 2 ) 3 SO 3 H][HSO 4 ] is 6.042g (addition amount is 3wt% of sulfuric acid), added to a 1L glass reaction kettle, set the pressure in the kettle to 0.5MPa, and the reaction temperature to 3°C. Add 140 ml of raw material gas (isobutane and trans-2-butene, the volume ratio of which is 6.5:1), stir, the stirring speed is 3000 rpm, and the reaction time is 12 minutes. After the reaction is over, take samples for testing. After the reaction is over, the reaction liquid is transferred to a separatory funnel and left to stand for stratification. The upper layer is alkylated oil, and the lower layer is catalyst. After separation, the alkylated oil product and the catalyst are obtained respectively.
采用气相色谱分析，经检测，产品的辛烷值为97.25。Analyzed by gas chromatography, the product has an octane number of 97.25 after testing.
将回收后的[n-Pro
3N(CH
2)
3SO
3H][HSO
4]和硫酸的耦合体系进行循环使用，使用22次，其得到的产物的辛烷值为91.12，因此[n-Pro
3N(CH
2)
3SO
3H][HSO
4]和硫酸的耦合体系至少可以重复使用22次。
The recovered coupling system of [n-Pro 3 N(CH 2 ) 3 SO 3 H][HSO 4 ] and sulfuric acid was recycled and used 22 times. The octane value of the product obtained was 91.12, so [n -The coupling system of Pro 3 N(CH 2 ) 3 SO 3 H][HSO 4 ] and sulfuric acid can be reused at least 22 times.
实施例5～7Examples 5-7
按照实施4的制备方法和后处理步骤，将磺酸功能化离子液体的种类及含量替换为下表中的数据，并测试其辛烷值为和重复利用次数。According to the preparation method and post-treatment steps of implementation 4, the type and content of the sulfonic acid functionalized ionic liquid were replaced with the data in the following table, and the octane number and the number of reuses were tested.
备注：上表中磺酸功能化离子液体的用量为磺酸功能化离子液体与硫酸的重量百分比。Remarks: The dosage of sulfonic acid functionalized ionic liquid in the above table is the weight percentage of sulfonic acid functionalized ionic liquid and sulfuric acid.
实施例8～15Examples 8-15
按照实施4的制备方法和后处理步骤，将磺酸功能化离子液体的种类及含量和反应条件替换为下表中的数据，并测试其辛烷值和重复利用次数。According to the preparation method and post-treatment steps of implementation 4, the type and content of the sulfonic acid functionalized ionic liquid and the reaction conditions were replaced with the data in the following table, and the octane number and the number of reuses were tested.
备注：上表中磺酸功能化离子液体的用量为磺酸功能化离子液体与硫酸的重量百分比。Remarks: The dosage of sulfonic acid functionalized ionic liquid in the above table is the weight percentage of sulfonic acid functionalized ionic liquid and sulfuric acid.
对比例1～2Comparative example 1～2
将实施例2中催化剂的阴离子替换为表格中离子。Replace the anion of the catalyst in Example 2 with the ion in the table.
按照实施4的制备方法和后处理步骤，将催化剂替换为下表中的数据，并测试其辛烷值为和重复利用次数。According to the preparation method and post-treatment steps of implementation 4, the catalyst was replaced with the data in the following table, and its octane number and repeated use times were tested.
| 编号Numbering | 催化剂catalyst | 首次辛烷值First octane number | 最后辛烷值Final octane number | 使用次数usage count |
| 对比例1Comparative example 1 | [BPSIm][CF 3SO 3]和硫酸的耦合体系 [BPSIm][CF 3 SO 3 ] and sulfuric acid coupling system | 95.3095.30 | 91.3191.31 | 1919 |
| 对比例2Comparative example 2 | [BPSIm][BF 4]/H 2SO 4和硫酸的耦合体系 [BPSIm][BF 4 ]/H 2 SO 4 and sulfuric acid coupling system | 94.9394.93 | 91.2791.27 | 1818 |
| 对比例3Comparative example 3 | 硫酸sulfuric acid | 93.2193.21 | 89.7489.74 | 55 |
Claims (10)
- 一种烷基化油的制备方法，其特征在于，其包括以下步骤：在催化剂存在下，将异构烷烃和烯烃进行烷基化反应，得到烷基化油；其中，所述的催化剂为“式I和/或式II所示的化合物”与酸形成的耦合体系；A preparation method of alkylated oil, characterized in that it comprises the following steps: in the presence of a catalyst, the isoparaffin and olefin are alkylated to obtain alkylated oil; wherein the catalyst is " A coupling system formed by a compound represented by formula I and/or formula II and an acid;
式I中，n为1～10中任一整数；A环为咪唑环、N-C 1～10烷基取代的咪唑环、吡唑环、N-C 1～10烷基取代的吡唑环、吡啶环、吡咯环或吗啡环； In formula I, n is any integer from 1 to 10; A ring is an imidazole ring, an imidazole ring substituted with an NC 1-10 alkyl group, a pyrazole ring, a pyrazole ring substituted with an NC 1-10 alkyl group, a pyridine ring, Pyrrole ring or morphine ring;式II中，m为1～10中任一整数；Q为N或P；R 1a、R 1b和R 1c独立地为C 1～10烷基。 In formula II, m is any integer from 1 to 10; Q is N or P; R 1a , R 1b and R 1c are independently C 1-10 alkyl. - 如权利要求1所述的制备方法，其特征在于，式I中，所述的N-C 1～10烷基取代的咪唑环中的C 1～10烷基为C 4～8烷基； The preparation method according to claim 1, wherein in formula I, the C 1-10 alkyl group in the imidazole ring substituted by the NC 1-10 alkyl group is a C 4-8 alkyl group;和/或，式II中，当R 1a、R 1b和R 1c独立地为C 1～10烷基时，所述的C 1～10烷基为C 1～3烷基。 And/or, in Formula II, when R 1a , R 1b and R 1c are independently a C 1-10 alkyl group, the C 1-10 alkyl group is a C 1-3 alkyl group.
- 如权利要求2所述的制备方法，其特征在于，式I中，当所述的N-C 1～10烷基取代的咪唑环中的C 1～10烷基为C 4～8烷基时，所述的C 4～8烷基为正丁基或其异构体、正戊基或其异构体、正庚基或其异构体、或者、正辛基或其异构体； The preparation method according to claim 2, wherein in formula I, when the C 1-10 alkyl group in the imidazole ring substituted by the NC 1-10 alkyl group is a C 4-8 alkyl group, The C 4-8 alkyl group is n-butyl or its isomer, n-pentyl or its isomer, n-heptyl or its isomer, or, n-octyl or its isomer;和/或，式II中，当R 1a、R 1b和R 1c独立地为C 1～3烷基时，所述的C 1～3烷基为甲基、乙基、正丙基或异丙基。 And/or, in Formula II, when R 1a , R 1b and R 1c are independently C 1-3 alkyl, the C 1-3 alkyl is methyl, ethyl, n-propyl or isopropyl base.
- 如权利要求3所述的制备方法，其特征在于，式I中，当所述的N-C 1～10烷基取代的咪唑环中的C 1～10烷基为C 4～8烷基时，所述的C 4～8烷基为正丁基或正辛基； The preparation method according to claim 3, wherein, in formula I, when the C 1-10 alkyl group in the imidazole ring substituted by the NC 1-10 alkyl group is a C 4-8 alkyl group, The C 4-8 alkyl group is n-butyl or n-octyl;和/或，式II中，当R 1a、R 1b和R 1c独立地为C 1～3烷基时，所述的C 1～3烷基为正丙基。 And/or, in Formula II, when R 1a , R 1b and R 1c are independently C 1-3 alkyl, the C 1-3 alkyl is n-propyl.
- 如权利要求1所述的制备方法，其特征在于，式I中，n为1～3中任一整数；The preparation method according to claim 1, wherein in formula I, n is any integer from 1 to 3;和/或，式I中，所述的A环为N-C 1～10烷基取代的咪唑环； And/or, in formula I, the A ring is an imidazole ring substituted with an NC 1-10 alkyl group;和/或，式II中，m为1～3中任一整数；And/or, in formula II, m is any integer from 1 to 3;和/或，式II中，Q为N。And/or, in formula II, Q is N.
- 如权利要求1所述的制备方法，其特征在于，所述的烷基化反应中，所述的烷基化反应的温度为1～5℃；The preparation method according to claim 1, wherein in the alkylation reaction, the temperature of the alkylation reaction is 1 to 5°C;和/或，所述的烷基化反应中，所述的烷基化反应的时间为5～20分钟；And/or, in the alkylation reaction, the time of the alkylation reaction is 5-20 minutes;和/或，所述的烷基化反应中，所述烷基化反应的压力为0.5MPa～10MPa；And/or, in the alkylation reaction, the pressure of the alkylation reaction is 0.5 MPa-10 MPa;和/或，所述的烷基化反应中，所述烷基化反应的搅拌的转速为1000～5000rmp；And/or, in the alkylation reaction, the stirring speed of the alkylation reaction is 1000-5000 rpm;和/或，所述的烷基化反应中，所述的异构烷烃为异丁烷；And/or, in the alkylation reaction, the isoparaffin is isobutane;和/或，所述的烷基化反应中，所述的烯烃为丁烯；And/or, in the alkylation reaction, the olefin is butene;和/或，所述的烷基化反应中，所述酸为卤代磺酸和/或硫酸；And/or, in the alkylation reaction, the acid is a halogenated sulfonic acid and/or sulfuric acid;和/或，所述的烷基化反应中，所述的催化剂与所述“异构烷烃和烯烃”的体积比为0.5:1～2:1；And/or, in the alkylation reaction, the volume ratio of the catalyst to the "isoparaffin and olefin" is 0.5:1 to 2:1;和/或，所述的烷基化反应中，所述的异构烷烃与烯烃的体积为1:1～10:1；And/or, in the alkylation reaction, the volume of the isoparaffin and the olefin is 1:1-10:1;和/或，所述的烷基化反应中，所述的“式I和/或式II所示的化合物”与酸形成的耦合体系中，所述的“式I和/或式II所示的化合物”与所述的酸的重量比可以为0.03:1～0.1:1；And/or, in the alkylation reaction, in the coupling system formed by the "compound of formula I and/or formula II" and acid, the "formula I and/or formula II" The weight ratio of the compound" to the acid can be 0.03:1 to 0.1:1;和/或，所述的催化剂循环使用；And/or, said catalyst is recycled;和/或，所述式I和/或式II所示的化合物为以下化合物：And/or, the compound represented by formula I and/or formula II is the following compound:
- 如权利要求6所述的制备方法，其特征在于，所述的烷基化反应中，所述的烷基化反应中，所述的烷基化反应的温度为1～3℃；8. The preparation method of claim 6, wherein in the alkylation reaction, the temperature of the alkylation reaction is 1 to 3°C;和/或，所述的烷基化反应的时间为5～15分钟；And/or, the alkylation reaction time is 5-15 minutes;和/或，所述的烷基化反应中，所述酸为硫酸；And/or, in the alkylation reaction, the acid is sulfuric acid;和/或，所述的“式I和/或式II所示的化合物”与所述的酸的重量比为0.03:1～0.5:1。And/or, the weight ratio of the "compound of formula I and/or formula II" to the acid is 0.03:1 to 0.5:1.
- 如权利要求7所述的制备方法，其特征在于，所述的烷基化反应中，所述的 烷基化反应的时间为5～12分钟。8. The preparation method of claim 7, wherein in the alkylation reaction, the alkylation reaction time is 5-12 minutes.
- 如权利要求1～8任一项所述的制备方法，其特征在于，所述的催化剂为“式I-1所示的化合物和硫酸形成的耦合体系”、“式I-2所示的化合物和硫酸形成的耦合体系”、或、“式I-3所示的化合物和硫酸形成的耦合体系”；所述的烷基化反应的温度为1～5℃；The preparation method according to any one of claims 1 to 8, wherein the catalyst is a "coupling system formed by a compound represented by formula I-1 and sulfuric acid", "a compound represented by formula I-2" "Coupling system formed with sulfuric acid" or "coupling system formed by a compound represented by formula I-3 and sulfuric acid"; the temperature of the alkylation reaction is 1 to 5°C;
- 如权利要求9所述的制备方法，其特征在于，所述的催化剂为“式I-2所示的化合物和硫酸形成的耦合体系”；所述的烷基化反应的温度为1～3℃；所述的催化剂与所述“异构烷烃和烯烃”的体积比为0.5:1～2:1；所述的烷基化反应中，所述的式I-2与所述的酸的重量比可为0.03:1～0.1:1；The preparation method of claim 9, wherein the catalyst is a "coupling system formed by the compound represented by formula I-2 and sulfuric acid"; the temperature of the alkylation reaction is 1 to 3°C The volume ratio of the catalyst and the "isoparaffin and olefin" is 0.5:1 to 2:1; in the alkylation reaction, the weight of the formula 1-2 and the acid The ratio can be 0.03:1～0.1:1;
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