CN108160111A - A kind of alkylation catalyst and its application - Google Patents
A kind of alkylation catalyst and its application Download PDFInfo
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- CN108160111A CN108160111A CN201810064801.2A CN201810064801A CN108160111A CN 108160111 A CN108160111 A CN 108160111A CN 201810064801 A CN201810064801 A CN 201810064801A CN 108160111 A CN108160111 A CN 108160111A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/0279—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 cationic portion being acyclic or nitrogen being a substituent on a ring
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- 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
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- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- 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
- C10G2300/1081—Alkanes
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- 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
- C10G2300/1088—Olefins
- C10G2300/1092—C2-C4 olefins
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- 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
- C10G2300/70—Catalyst aspects
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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The present invention relates to petrochemical industry catalytic fields, provide a kind of alkylation catalyst, the catalyst is organic matter and the mixture of compound ion liquid, the organic matter is at least one of benzene class and amine organic matter, the cation of the compound ion liquid is at least one of quaternary ammonium, imidazoles, amides compound, and anion is aluminium and the halide of copper.And the alkylation catalyst catalysis alkylated methods of C4, include the following steps：Compound ion liquid and organic matter are added in reaction kettle, iso-butane is passed through and C4 alkene is alkylated reaction, obtain alkylate oil；Wherein, the organic matter is at least one of benzene class and amine organic matter, and the cation of the compound ion liquid is at least one of quaternary ammonium, imidazoles, amides compound, and anion is aluminium and the halide of copper.The present invention makes C4 alkylated reactions have higher selectivity, improves the octane number of alkylate oil, also further improves the yield of product；Meanwhile reduce the dosage of catalyst, cost is reduced, production operation is simple, reduces the pollution to environment, conducive to environmental protection.
Description
Technical field
The invention belongs to petrochemical industry catalytic fields, and in particular to a kind of alkylation catalyst and its application.
Background technology
C4 alkylations refer to the process of that iso-butane generates gasoline alkylate with C4 alkene under the catalytic action of acid, gained
Gasoline alkylate has high-octane rating and low Reid vapour pressures, is made of saturation of olefins, aromatic-free, alkene and sulphur, is newly to match
The square optimal blend component of gasoline is referred to as cleaning alkyl gasoline.At present, industrialized alkyl gasoline producing process master
Sulfuric acid and hydrofluoric acid to be used as catalyst, there are spent acid discharge capacity is big, environmental pollution is serious and production equipment is corroded etc. asks
Topic.There is the shortcomings that inactivation is very fast, reaction condition is more harsh in solid acid catalyst such as zeolite, solid super-strong acid etc., it is difficult into
Row industrialized production.
Ionic liquid is a kind of emerging fluent material being made of completely zwitterion, have environmental-friendly, corrosivity is low,
The features such as small toxicity, acidity and physicochemical properties can adjust, be easy to product separation, cyclic utilization rate is high.Acidic ion liquid
Catalytic alkylation, which prepares alkylate oil, has become the main direction of development of advanced liquid acid alkylation techniques in recent years.
In recent years, be alkylated using ionic liquid as catalyst or additive reaction patent and article very
It is more, if Chinese patent CN106939173A is mainly based on classical acid, ionic liquid is added in strong acid, has both been avoided a large amount of
The use of ionic liquid, and improve catalytic effect；United States Patent (USP) US7285698, Chinese patent CN1203032C,
CN102108306A etc. is mainly alkylated reaction using a variety of chloride metals of chlorine aluminic acid ion bluk recombination as catalyst, and
Effect well is obtained, but octane number is still to be improved.
Invention content
The technical problems to be solved by the invention are to overcome traditional liquid acid and the alkylated defects of solid acid catalysis C4,
A kind of alkylation catalyst and its application are provided.
The present invention provides a kind of alkylation catalyst, wherein, the catalyst is mixed for organic matter and compound ion liquid
Object is closed, the organic matter is at least one of benzene class and amine organic matter, and the cation of the compound ion liquid is quaternary amine
At least one of class, imidazoles, amides compound, anion are aluminium and the halide of copper.
The present invention also provides the alkylated methods of abovementioned alkyl catalyst C4, include the following steps：
Compound ion liquid and organic matter are added in reaction kettle, iso-butane is passed through and C4 alkene is alkylated instead
Should, obtain alkylate oil；
Wherein, the organic matter be at least one of benzene class and amine organic matter, the compound ion liquid sun from
Son is at least one of quaternary ammonium, imidazoles, amides compound, and anion is aluminium and the halide of copper.
Alkylation catalyst catalysis C4 alkylations provided by the present invention improve the selectivity of C4 alkylated reactions,
The higher alkylate oil of octane number is obtained, also further improves the yield of product.Heavy constituent content reduces 10-20%, C8 choosings
Selecting property can reach 65-90%, wherein the ratio of high-octane TMP significantly improves, the octane number of gained alkylate oil is compared
The alkylate oil that single ionic liquid obtains greatly improves.At the same time it can also reducing the dosage of catalyst, cost is reduced,
Production operation is simple, reduces the pollution to environment, conducive to environmental protection.
Description of the drawings
Fig. 1 is the octane number of alkylate oil that alkylated reaction obtains under different condition.
Specific embodiment
For clearer displaying the objectives, technical solutions, and advantages of the present invention, in conjunction with the following drawings and embodiment, to this
Invention is further elaborated.The specific embodiments described herein are merely illustrative of the present invention, it is impossible to be interpreted as pair
The restriction of the scope of the present invention.
The embodiment of the present invention provides a kind of alkylation catalyst, wherein, the catalyst is organic matter and compound ion liquid
The mixture of body, the organic matter be at least one of benzene class and amine organic matter, the cation of the compound ion liquid
For at least one of quaternary ammonium, imidazoles, amides compound, anion is aluminium and the halide of copper.
Preferably, the molar ratio of the aluminium and copper is 1:0.01~0.1.It is highly preferred that the molar ratio of the aluminium and copper is
1:0.02~0.05.The organic matter is the 0.1%~10% of compound ion liquid quality.Specifically, the organic matter is first
At least one of benzene, benzene and dimethylbenzene.Preferably, the organic matter is toluene.It is highly preferred that the molar ratio of aluminium and copper is 1:
When 0.02~0.03, the effect that toluene can just have is added in.Moreover, the 0.2%~5% of toluene and compound ion liquid quality most
Good, because the addition of the organic matters such as toluene can generate the heavy constituents such as alkylbenzene, a small amount of alkylbenzene can promote alkylated reaction, and
A large amount of alkylbenzene can reduce the content of TMP.
Further, the preparation method of the compound ion liquid includes the following steps：Nitrogen protection, -10 DEG C -50 DEG C
Under, at least one of quaternary ammonium, imidazoles, amides compound are added in reactor, add the halogenation of aluminium and copper
Object；It is stirred, is warming up to 80-120 DEG C, keep 1-4h, obtain the compound ion liquid.
The organic matters such as the toluene of addition can be with free AlCl3Complexing occurs, forms new complex compound, and can
Promote the activity of Cu, so as to greatly improve the catalytic performance of compound ion liquid.And improve the key of ionic liquid-catalyzed performance
It is the electron supplying capacity of organic matter, due to hyperconjugation, methyl has faint electron repulsive ability, is big pi bond on phenyl ring
Cloud density be increased slightly than benzene, therefore, the effect of toluene is best.
The embodiment of the present invention also provides the alkylated methods of abovementioned alkyl catalyst C4, includes the following steps：
Compound ion liquid and organic matter are added in reaction kettle, iso-butane is passed through and C4 alkene is alkylated instead
Should, obtain alkylate oil；
Wherein, the organic matter be at least one of benzene class and amine organic matter, the compound ion liquid sun from
Son is at least one of quaternary ammonium, imidazoles, amides compound, and anion is aluminium and the halide of copper.
Preferably, the molar ratio of the aluminium and copper is 1:0.01~0.1.It is highly preferred that the molar ratio of the aluminium and copper is
1:0.02~0.05.The organic matter is the 0.1%-10% of compound ion liquid quality.Specifically, the organic matter is first
At least one of benzene, benzene and dimethylbenzene.Preferably, the organic matter is toluene.
Specifically, the condition of the alkylated reaction is：- 10 DEG C -50 DEG C of temperature, pressure 0.1MPa-1.8MPa, during reaction
Between 1-60min.The C4 alkene is at least one of 1- butylene, 2- butylene and isobutene.It is highly preferred that the alkylation is anti-
The condition answered is：10~20 DEG C of temperature, pressure are in 0.8~1.2MPa, and the reaction time is in 1~5min.
The organic matters such as the toluene of addition can be with free AlCl3Complexing occurs, forms new complex compound, and can
Promote the activity of Cu, so as to greatly improve the catalytic performance of compound ion liquid.And improve the key of ionic liquid-catalyzed performance
It is the electron supplying capacity of organic matter, due to hyperconjugation, methyl has faint electron repulsive ability, is big pi bond on phenyl ring
Cloud density be increased slightly than benzene, therefore, the effect of toluene is best.Preferably, the molar ratio of aluminium and copper is 1:0.02~
When 0.03, the effect that toluene can just have is added in.It is highly preferred that the 0.2%~5% of toluene and compound ion liquid quality most
Good, because the addition of the organic matters such as toluene can generate the heavy constituents such as alkylbenzene, a small amount of alkylbenzene can promote alkylated reaction, and
A large amount of alkylbenzene can reduce the content of TMP.
The preparation of alkylation catalyst and its application are illustrated below by way of specific embodiment.In example below
Compound can be directly prepared according to existing method respectively, certainly, can also directly be purchased from the market in other embodiments
, however it is not limited to this.
Embodiment 1：
Under -10 DEG C~50 DEG C, nitrogen protection, 1- butyl -3- methylimidazole villaumites (BmimCl, 0.5mol) are added to
In three-necked flask, aluminum trichloride (anhydrous) (1mol) then is slowly added in constantly stirring, after two kinds of substances are completely dissolved,
Temperature is risen to 80 DEG C, is continuously added into 2h.Then adding in stannous chloride, (molar ratio of aluminium and copper is 1:0.01~0.1), then with
Identical temperature heating 2h is completely dissolved to stannous chloride, obtains compound ion liquid.
Embodiment 2：
Under -10 DEG C~50 DEG C, nitrogen protection, triethylamine hydrochloride (0.5mol) is added in three-necked flask, Ran Hou
Aluminum trichloride (anhydrous) (1mol) is slowly added in constantly stirring, after two kinds of substances are completely dissolved, temperature is risen to 80 DEG C, is held
It is continuous to add in 2h.Then adding in stannous chloride, (molar ratio of aluminium and copper is 1:0.01~0.1), then with identical temperature heating 2h extremely
Stannous chloride is completely dissolved, and obtains compound ion liquid.
Embodiment 3：
Under -10 DEG C~50 DEG C, nitrogen protection, n,N-dimethylacetamide (0.75mol) is added in three-necked flask,
Then aluminum trichloride (anhydrous) (1mol) is slowly added in constantly stirring, after two kinds of substances are completely dissolved, temperature is risen to
80 DEG C, it is continuously added into 2h.Then adding in stannous chloride, (molar ratio of aluminium and copper is 1:0.01~0.1), then with identical temperature
Heating 2h is completely dissolved to stannous chloride, obtains compound ion liquid.
Implementation column 4：
Compound ion liquid obtained in 30mL embodiments 1 and 1% benzene are added in the autoclave of 250mL, used
Nitrogen punching press is stirred with the rotating speed of 1000r/min to 1.0MPa, iso-butane and C4 alkene is squeezed into 500mL/h conducive to duplex plunger pump
Hydrocarbon mixed raw material 60mL, the alkane alkene ratio in raw material are 50:1,1min is reacted at 15 DEG C, is discharged after reaction unreacted different
Butane.Solution is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion liquid
Body catalyst.The alkylate oil on upper strata is by washing to neutrality, you can obtains gasoline alkylate.Through gas chromatographic detection, can obtain
The octane number of alkylate oil is 92.89.
Implementation column 5：
Compound ion liquid obtained in 30mL embodiments 1 and 1% toluene are added in the autoclave of 250mL,
With nitrogen punching press to 1.0MPa, stirred with the rotating speed of 1000r/min, iso-butane and C4 are squeezed into 500mL/h conducive to duplex plunger pump
Olefin raw material 60mL, the alkane alkene ratio in raw material are 50:1,1min is reacted at 15 DEG C, is discharged after reaction unreacted
Iso-butane.Solution is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion
Liquid catalyst.The alkylate oil on upper strata is by washing to neutrality, you can obtains gasoline alkylate.It, can through gas chromatographic detection
The octane number for obtaining alkylate oil is 92.47.
Embodiment 6：
Compound ion liquid obtained in 30mL embodiments 2 and 1% benzene are added in the autoclave of 250mL, used
Nitrogen punching press is stirred with the rotating speed of 1000r/min to 1.0MPa, iso-butane and C4 alkene is squeezed into 500mL/h conducive to duplex plunger pump
Hydrocarbon mixed raw material 60mL, the alkane alkene ratio in raw material are 50:1,1min is reacted at 15 DEG C, is discharged after reaction unreacted different
Butane.Solution is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion liquid
Body catalyst.The alkylate oil on upper strata is by washing to neutrality, you can obtains gasoline alkylate.Through gas chromatographic detection, can obtain
The octane number of alkylate oil is 91.99.
Embodiment 7：
Compound ion liquid obtained in 30mL embodiments 2 and 1% toluene are added in the autoclave of 250mL,
With nitrogen punching press to 1.0MPa, stirred with the rotating speed of 1000r/min, iso-butane and C4 are squeezed into 500mL/h conducive to duplex plunger pump
Olefin raw material 60mL, the alkane alkene ratio in raw material are 50:1,1min is reacted at 15 DEG C, is discharged after reaction unreacted
Iso-butane.Solution is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion
Liquid catalyst.The alkylate oil on upper strata is by washing to neutrality, you can obtains gasoline alkylate.It, can through gas chromatographic detection
The octane number for obtaining alkylate oil is 92.99.
Embodiment 8：
Compound ion liquid obtained in 30mL embodiments 3 and 1% toluene are added in the autoclave of 250mL,
With nitrogen punching press to 1.0MPa, stirred with the rotating speed of 1000r/min, iso-butane and C4 are squeezed into 500mL/h conducive to duplex plunger pump
Olefin raw material 60mL, the alkane alkene ratio in raw material are 50:1,1min is reacted at 15 DEG C, is discharged after reaction unreacted
Iso-butane.Solution is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion
Liquid catalyst.The alkylate oil on upper strata is by washing to neutrality, you can obtains gasoline alkylate.It, can through gas chromatographic detection
The octane number for obtaining alkylate oil is 91.
Embodiment 9：
Compound ion liquid obtained in 30mL embodiments 3 and 1% toluene are added in the autoclave of 250mL,
With nitrogen punching press to 1.0MPa, stirred with the rotating speed of 1000r/min, iso-butane and C4 are squeezed into 500mL/h conducive to duplex plunger pump
Olefin raw material 60mL, the alkane alkene ratio in raw material are 50:1,1min is reacted at 15 DEG C, is discharged after reaction unreacted
Iso-butane.Solution is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion
Liquid catalyst.The alkylate oil on upper strata is by washing to neutrality, you can obtains gasoline alkylate.It, can through gas chromatographic detection
The octane number for obtaining alkylate oil is 94.39.
Comparative example 1：
Compound ion liquid obtained in 30mL embodiments 1 is added in the autoclave of 250mL, with nitrogen punching press extremely
1.0MPa is stirred with the rotating speed of 1000r/min, iso-butane and C4 olefin raw materials is squeezed into 500mL/h conducive to duplex plunger pump
60mL, the alkane alkene ratio in raw material are 9:1,1min is reacted at 15 DEG C, discharges unreacted iso-butane after reaction.By solution
It is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion liquid catalyst.On
The alkylate oil of layer is by washing to neutrality, you can obtains gasoline alkylate.Through gas chromatographic detection, the pungent of alkylate oil can be obtained
Alkane value is 88.54.
Comparative example 2：
Compound ion liquid obtained in 30mL embodiments 2 is added in the autoclave of 250mL, with nitrogen punching press extremely
1.0MPa is stirred with the rotating speed of 1000r/min, iso-butane and C4 olefin raw materials is squeezed into 500mL/h conducive to duplex plunger pump
60mL, the alkane alkene ratio in raw material are 9:1,1min is reacted at 15 DEG C, discharges unreacted iso-butane after reaction.By solution
It is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion liquid catalyst.On
The alkylate oil of layer is by washing to neutrality, you can obtains gasoline alkylate.Through gas chromatographic detection, the pungent of alkylate oil can be obtained
Alkane value is 88.65.
Comparative example 3：
Compound ion liquid obtained in 30mL embodiments 3 is added in the autoclave of 250mL, with nitrogen punching press extremely
1.0MPa is stirred with the rotating speed of 1000r/min, iso-butane and C4 olefin raw materials is squeezed into 500mL/h conducive to duplex plunger pump
60mL, the alkane alkene ratio in raw material are 9:1,1min is reacted at 15 DEG C, discharges unreacted iso-butane after reaction.By solution
It is being stood in separatory funnel, product is divided into two layers up and down, and upper strata is alkylate oil, and lower floor is compound ion liquid catalyst.On
The alkylate oil of layer is by washing to neutrality, you can obtains gasoline alkylate.Through gas chromatographic detection, the pungent of alkylate oil can be obtained
Alkane value is 89.21.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of alkylation catalyst, which is characterized in that mixture of the catalyst for organic matter and compound ion liquid, institute
Organic matter is stated as at least one of benzene class and amine organic matter, the cation of the compound ion liquid is quaternary ammonium, imidazoles
At least one of class, amides compound, anion are aluminium and the halide of copper.
2. alkylation catalyst as described in claim 1, which is characterized in that the organic matter is in benzene, toluene and dimethylbenzene
At least one.
3. alkylation catalyst as claimed in claim 1 or 2, which is characterized in that the organic matter is toluene.
4. alkylation catalyst as described in claim 1, which is characterized in that the preparation method of the compound ion liquid includes
Following steps：At nitrogen protection, -10 DEG C~50 DEG C, at least one of quaternary ammonium, imidazoles, amides compound are added
Enter into reactor, add the halide of aluminium and copper；It is stirred, is warming up to 80~120 DEG C, keep 1~4h, described in acquisition
Compound ion liquid.
5. alkylation catalyst as described in claim 1, which is characterized in that the molar ratio of the aluminium and copper is 1:0.01~
0.1。
6. alkylation catalyst as described in claim 1, which is characterized in that the organic matter is compound ion liquid quality
0.1%~10%.
7. a kind of organic matter and the compound ion liquid catalysis alkylated methods of C4, which is characterized in that include the following steps：
Compound ion liquid and organic matter are added in reaction kettle, iso-butane is passed through and C4 alkene is alkylated reaction, obtain
Obtain alkylate oil；
Wherein, the organic matter is at least one of benzene class and amine organic matter, and the cation of the compound ion liquid is
At least one of quaternary ammonium, imidazoles, amides compound, anion are aluminium and the halide of copper.
8. organic matter as claimed in claim 7 and the compound ion liquid catalysis alkylated methods of C4, which is characterized in that the alkane
The condition of glycosylation reaction is：- 10 DEG C of temperature~50 DEG C, pressure 0.1MPa~1.8MPa, 1~60min of reaction time.
9. organic matter as claimed in claim 7 and the compound ion liquid catalysis alkylated methods of C4, which is characterized in that described
C4 alkene is at least one of 1- butylene, 2- butylene and isobutene.
10. organic matter as claimed in claim 7 or 8 and the compound ion liquid catalysis alkylated methods of C4, which is characterized in that institute
The condition for stating alkylated reaction is：Temperature is in 10~20 DEG C, pressure in 0.8~1.0MPa, and the reaction time is in 1~5min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810064801.2A CN108160111A (en) | 2018-01-23 | 2018-01-23 | A kind of alkylation catalyst and its application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109985611A (en) * | 2019-04-28 | 2019-07-09 | 中国科学院兰州化学物理研究所 | A kind of catalyst and preparation method thereof, a kind of preparation method of N- alkyl imidazole compound |
| 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 |
| CN114014775A (en) * | 2021-11-26 | 2022-02-08 | 华东理工大学 | Functionalized surface active ionic liquid and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2842605A (en) * | 1954-11-24 | 1958-07-08 | Universal Oil Prod Co | Alkylation process and catalyst therefor |
| CN1500764A (en) * | 2002-11-12 | 2004-06-02 | ʯ�ʹ�ѧ(����) | Preparing method for alkylate agent using compound ion as catalyst |
| CN1836780A (en) * | 2005-03-24 | 2006-09-27 | 北京化工大学 | Ion liquid catalyst for producing alkylated oil and its preparation method |
| CN101885655A (en) * | 2010-07-05 | 2010-11-17 | 中国科学院过程工程研究所 | Method for preparing alkylate |
| CN105536866A (en) * | 2015-12-11 | 2016-05-04 | 中国石油大学(北京) | Ionic-like liquid and preparation method and application thereof in preparation of alkylated oil |
| CN106167467A (en) * | 2016-09-27 | 2016-11-30 | 河北科技大学 | The preparation of a kind of polyaza ligand bit function ionic liquid for ATRP reaction and application |
-
2018
- 2018-01-23 CN CN201810064801.2A patent/CN108160111A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2842605A (en) * | 1954-11-24 | 1958-07-08 | Universal Oil Prod Co | Alkylation process and catalyst therefor |
| CN1500764A (en) * | 2002-11-12 | 2004-06-02 | ʯ�ʹ�ѧ(����) | Preparing method for alkylate agent using compound ion as catalyst |
| CN1836780A (en) * | 2005-03-24 | 2006-09-27 | 北京化工大学 | Ion liquid catalyst for producing alkylated oil and its preparation method |
| CN101885655A (en) * | 2010-07-05 | 2010-11-17 | 中国科学院过程工程研究所 | Method for preparing alkylate |
| CN105536866A (en) * | 2015-12-11 | 2016-05-04 | 中国石油大学(北京) | Ionic-like liquid and preparation method and application thereof in preparation of alkylated oil |
| CN106167467A (en) * | 2016-09-27 | 2016-11-30 | 河北科技大学 | The preparation of a kind of polyaza ligand bit function ionic liquid for ATRP reaction and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109985611A (en) * | 2019-04-28 | 2019-07-09 | 中国科学院兰州化学物理研究所 | A kind of catalyst and preparation method thereof, a kind of preparation method of N- alkyl imidazole compound |
| 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 |
| CN114014775A (en) * | 2021-11-26 | 2022-02-08 | 华东理工大学 | Functionalized surface active ionic liquid and preparation method and application thereof |
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