CN109395776A - A kind of alkylated reaction catalyst system and its preparation method and application - Google Patents
A kind of alkylated reaction catalyst system and its preparation method and application Download PDFInfo
- Publication number
- CN109395776A CN109395776A CN201710706949.7A CN201710706949A CN109395776A CN 109395776 A CN109395776 A CN 109395776A CN 201710706949 A CN201710706949 A CN 201710706949A CN 109395776 A CN109395776 A CN 109395776A
- Authority
- CN
- China
- Prior art keywords
- reaction
- preparation
- catalyst system
- reaction catalyst
- alkylated reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- B01J31/0285—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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
-
- 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
Abstract
The invention discloses a kind of alkylated reaction catalyst systems and its preparation method and application.The alkylated reaction catalyst system includes sulfonic acid funtionalized glyoxaline ion liquid and sulfuric acid as shown in formula I, and the content of the sulfonic acid funtionalized glyoxaline ion liquid is 1-30wt%, R C1‑C20Alkyl.The preparation method generates inner salt the following steps are included: alkyl substituted imidazole and 1,3-propane sultone are reacted, and is acidified using the concentrated sulfuric acid, is mixed with the concentrated sulfuric acid later to get the alkylated reaction catalyst system.Alkylated reaction catalyst system of the invention does not use nitric acid, and can be recycled for multiple times, and greatly reduces enterprise's production cost, reduces the pollution to environment.In addition, the ratio that gasoline alkylate octane number prepared by the present invention can reach 96, TMP/DMH improves a lot, hence it is evident that better than the preparation method of existing gasoline alkylate, with good application prospect.
Description
Technical field
The invention belongs to petrochemical industries, and in particular, to a kind of alkylated reaction catalyst system and preparation method thereof
And application.
Background technique
Gasoline alkylate is the C8 component that iso-butane and small-numerator olefin react generation under the catalytic action of strong acid, relatively
In catalytic cracking gasoline alkylate (FCC gasoline alkylate) and for reforming gasoline alkylate, its octane number is higher, Er Qieji
Not olefin-containing, aromatic hydrocarbons, sulfur content and steam force down, therefore can be used as the blend component of clean gasoline.In isobutane alkylation
In the reaction for producing gasoline alkylate, common catalyst mainly has traditional liquid acid catalyst (concentrated sulfuric acid, hydrofluoric acid), solid
Acid catalyst and ionic-liquid catalyst.H2SO4It is most widely used in the industrial production of gasoline alkylate with HF, technology
It is the most mature, but there is some the problem of can not be ignored, and such as cause serious environmental pollution, acid to consume big, spent acid and are difficult to back
Utilization and equipment corrosion etc. are received, especially there is insecurity factors for the effumability of HF.Solid acid catalysis is then developed
Technology, these solid acid catalysts can be divided into molecular sieve type and non-molecular sieve catalyst again, but solid acid catalyst
It is easy to inactivate and be difficult to regeneration issues to limit its application.Ionic liquid has obtained more and more as new research direction
Concern, and good catalytic effect is shown, become the developing direction of isobutane alkylation catalyst research.
Chinese patent CN106010636A discloses a kind of mixed acid system using ionic liquid and nitric acid and catalyzes and synthesizes alkane
The method of base gasoline, but there is no biggish promotions for the gasoline alkylate octane number for using this method to produce, and need to make
With nitric acid and sulfuric acid.
Furthermore Shandong Deyang Chemical Co., Ltd. has been produced using compound ion liquid as catalyst high-octane
Gasoline alkylate, but its compound ion liquid used belongs to lewis acid, it is more sensitive to air and water, it reacts and unstable
It is fixed and unfavorable to the service life of catalyst.
Therefore, this field needs a kind of catalyst system that can produce high-octane gasoline alkylate.
Summary of the invention
The invention aims to solve to lack existing for this field a kind of to produce urging for high-octane rating gasoline alkylate
The problem of change system, and then provide a kind of alkylated reaction catalyst system.The alkylated reaction catalyst system includes sulphur
Acid functionalization glyoxaline ion liquid and sulfuric acid, and nitric acid is not used, and can be recycled for multiple times, it is raw to greatly reduce enterprise
Cost is produced, the pollution to environment is reduced；In addition, can be reached using gasoline alkylate octane number made from technical solution of the present invention
96, TMP/DMH ratio improves a lot, hence it is evident that better than the preparation method of existing gasoline alkylate, has preferable industry
Application prospect.
The present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of alkylated reaction catalyst systems, wherein the alkylated reaction catalyst system includes such as
Sulfonic acid funtionalized glyoxaline ion liquid and sulfuric acid shown in formula I,
The content of the sulfonic acid funtionalized glyoxaline ion liquid is 1-30wt%；
R is C1-C20Alkyl；
The alkylated reaction catalyst system, sulfonic acid funtionalized glyoxaline ion liquid and sulfuric acid as shown in formula I
Composition.
The alkylated reaction catalyst system, wherein
The content preferred 8-15wt%, more preferable 10wt% of the sulfonic acid funtionalized glyoxaline ion liquid.
R is preferably C1-C10Alkyl is more preferably methyl, ethyl, normal-butyl, n-hexyl or n-octyl.
The sulfonic acid funtionalized glyoxaline ion liquid can be
(i.e. [OPSIm] [HSO4])、
(i.e. [HPSIm] [HSO4])、
(i.e. BPSIm] [HSO4])、
(i.e. [EPSIm] [HSO4]) or
(i.e. [MPSIm] [HSO4])。
The present invention also provides the preparation methods of the alkylated reaction catalyst system described in one kind, wherein the preparation side
Method the following steps are included:
Alkyl substituted imidazole shown in A1, Formula II and the reaction of 1,3- propane sultone generate inner salt；
A2, the resulting inner salt of step A1 and the concentrated sulfuric acid are mixed, the sulfonic acid funtionalized imidazole-like ionic is made in acidification
Liquid；
A3, sulfonic acid funtionalized glyoxaline ion liquid made from step A2 is mixed with the concentrated sulfuric acid to get the alkyl
Change catalytic reaction system；
Wherein R1For C1-C20Alkyl.
The preparation method of the alkylated reaction catalyst system, wherein
R1Preferably C1-C10Alkyl is more preferably methyl, ethyl, normal-butyl, n-hexyl or n-octyl.
The alkyl substituted imidazole can be
The preparation method of the alkylated reaction catalyst system, wherein
The reaction condition of step A1 and operation can be conventional for this field, preferably, the following steps are included: to 1,3-N-morpholinopropanesulfonic acid
Alkyl substituted imidazole is added dropwise in lactone, reacts.
In step A1, alkyl substituted imidazole shown in Formula II can be conventional for this field, commercially available, such as can be by An Naiji
Chemistry provides.
In step A1, the 1,3-propane sultone is dissolvable in water in organic solvent, the preferred acetic acid second of organic solvent
Ester.
In step A1, the molar ratio of the alkyl substituted imidazole and 1,3-propane sultone is preferably 1:1-1:2.
In step A1, during the dropwise addition alkyl substituted imidazole, reaction system is preferably placed in ice-water bath.
In step A1, after the completion of the operation that alkyl substituted imidazole is added dropwise, reaction system is rearranged in oil bath and is heated
Stirring, it is more preferably 70 DEG C, mixing time is preferably 5-8 hours, more preferably small for 6 that heating temperature, which is preferably 60-80 DEG C,
When.
In step A1, also product can be further purified by last handling process.The last handling process preferably include as
Lower condition and step:
If in alkyl substituted imidazole shown in Formula II, substituent group is methyl, ethyl or butyl, then by the body after reaction
System's removal liquid, washs obtained solid with ethyl acetate, and dry.The number washed using ethyl acetate can be this field
Conventional, preferably 3-5 times, the drying temperature can be conventional for this field, and preferably 50-70 DEG C, be more preferably 60 DEG C；
If in alkyl substituted imidazole shown in Formula II, substituent group is hexyl or octyl, then the system after reaction is used
Ethyl acetate washing, and it is separated off ethyl acetate phase, products therefrom phase rotary evaporation is removed into remaining ethyl acetate.It is described
The number washed using ethyl acetate can be conventional for this field, and preferably 3-5 times；The temperature of the rotary evaporation can be ability
Domain is conventional, and preferably 65-75 DEG C, be more preferably 70 DEG C.
In step A2, the concentrated sulfuric acid is generally the concentrated sulfuric acid of 98% or more mass content commonly used in the art, city
Selling can obtain.
In step A2, the molar ratio of the concentrated sulfuric acid and inner salt is preferably 1:0.5-1:3, is more preferably 1:1.
In step A3, the mass ratio of the concentrated sulfuric acid and sulfonic acid funtionalized glyoxaline ion liquid can be 1:1-12:1, preferably
It is more preferably 9:1 for 6:1-10:1.
The present invention also provides a kind of preparation methods of gasoline alkylate, and the preparation method comprises the following steps: lazy
Under property atmosphere, under stress, by alkylated reaction catalyst system of the present invention and raw material solid/liquid/gas reactions；Wherein, described
Unstripped gas includes iso-butane and alkene, and the alkene is selected from one of n-butene, isobutene, n- 2- butylene and Trans-2-butene
Or it is a variety of.
The preparation method of the gasoline alkylate, wherein
The unstripped gas can be conventional for this field, commercially available, such as can open Gas Technologies LLC by upper sea God and mention
For；Its pressure value is preferably 1-1.5Mpa, is more preferably 1.2Mpa；It is described when the container inner pressure of reaction is 0.5Mpa
Unstripped gas is preferably liquid condition.
The preferred Trans-2-butene of unstripped gas.
In the unstripped gas, the ratio between volume of iso-butane and alkene can be optional, can be depending on actual reaction requirement.
In a preferred embodiment, the ratio between volume of iso-butane and alkene is 8:1 in the unstripped gas.
The container of the reaction can be conventional for this field, preferably reaction kettle, and preferred reaction kettle is glass reaction kettle
Or metal reaction kettle.
The inert atmosphere can be conventional for this field, preferably nitrogen.
The introducing method of the inert atmosphere can be conventional for this field, and scavenging 3-5 times mode is preferably taken to carry out.
The pressure can be conventional for this field, and preferably 0.1-1Mpa is more preferably 0.2-0.8Mpa, further more preferably
Ground is 0.5Mpa.
The temperature of the reaction can be conventional for this field, and preferably 0-20 DEG C, be more preferably 5-10 DEG C, further more preferably
Ground is 8 DEG C.
The reaction carries out under stiring, and the speed of the stirring can be conventional for this field, preferably 2000-
4000rpm is more preferably 3000rpm.
The time of the reaction can be conventional for this field, and preferably 10-60 minutes, more preferably 20-40 minutes, further
It is more preferably 25 minutes.
The process of the reaction can be monitored by gas-chromatography, end when generally reaching balance with C8 content and octane number
Only react.
It is described after the reaction was completed, may also include and take out reaction system and the step of stratification, the acid after layering is mutually
For alkylated reaction catalyst system of the present invention；Preferably, being layered under resulting alkylated reaction catalyst system can be used for
One step alkylation reaction.
Gasoline alkylate prepared by the preparation method that the present invention also provides a kind of by gasoline alkylate of the present invention,
Wherein, the gasoline alkylate, octane number 92-97.
The gasoline alkylate, the preferred 94-96 of octane number.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
Technical solution of the present invention is using sulfonic acid funtionalized glyoxaline ion liquid and sulfuric acid work unlike the prior art
For the catalyst system of alkylated reaction, the catalyst system does not use nitric acid, and can be recycled for multiple times, and number is recycled
Reach more than 20 times, greatly reduces enterprise's production cost, and reduce the pollution to environment；In addition, using technology of the invention
The ratio that gasoline alkylate octane number can reach 96, TMP/DMH made from scheme improves a lot, hence it is evident that is better than existing alkyl
Change the preparation method of gasoline, therefore industrial application value with higher.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In the present invention, RON refers to research octane number (RON), is also urban road octane number, Chinese common gasoline generally with
Research octane number (RON) label: 93#, 97# etc..
TMP/DMH is the ratio of the dimethylhexane of high-octane trimethylpentane and low octane rating in gasoline alkylate
Value, which represent the selectivity of gasoline alkylate.
In the present invention, 1,3-propane sultone be purchased from be purchased from Aladdin Reagent Company, AR grades.
Unstripped gas opens Gas Technologies LLC, pressure 1.2Mpa purchased from upper sea God；
Remaining raw material and reality are commercially available.
The preparation of 1 gasoline alkylate of embodiment
(1) preparation of sulfonic acid funtionalized glyoxaline ion liquid
Since the fusing point of 1,3-propane sultone is 31 ± 1 DEG C, it is at room temperature acicular crystals, is first added before weighing
Heat is to liquid.The 1,3-propane sultone of certain mass is weighed in three-necked flask, ethyl acetate is added and makes it dissolve.By etc. rub
Alkyl substituted imidazole (respectively N- methylimidazole MPSI, N- ethyl imidazol(e) EPSI, N- butyl imidazole BPSI, N- hexyl of your amount
Imidazoles HPSI or N- octylimidazole OPSI) it is added into constant pressure funnel.Mechanical stirring is opened, is opened under conditions of ice-water bath permanent
Funnel is pressed, alkyl substituent imidazoles is added dropwise in three-necked flask dropwise, changes ice-water bath into oil bath after being added dropwise, is heated to
70 DEG C of stirring 6h.
MPSIm, EPSIm and BPSIm (respectively [MPSIm] [HSO4]、[EPSIm][HSO4] and [BPSIm] [HSO4]
Intermediate) processing: above-mentioned reaction increasingly generates white powder, after the reaction was completed with ethyl acetate wash suction filtration 3 times remove not
Then reaction product is placed and dries in a vacuum drying oven and remove ethyl acetate for 60 DEG C by the raw material of fully reacting.
HPSIm, OPSIm (respectively [HPSIm] [HSO4] and [OPSIm] [HSO4] intermediate) processing: above-mentioned reaction
Rufous thick liquid is increasingly generated, 3 times is washed with ethyl acetate after reaction and removes the raw material not reacted completely, liquid separation leakage
Bucket isolates ethyl acetate phase, and product layer is then removed remaining ethyl acetate in 70 DEG C of at a temperature of rotary evaporation.
Gained inner salt is separately added into the equimolar amounts concentrated sulfuric acid and is acidified after reaction, obtain sulfonic acid funtionalized imidazoles from
Sub- liquid, it is spare.
(2) alkylated reaction
By 210ml alkylated reaction catalyst system, (wherein the additive amount of sulfonic acid funtionalized glyoxaline ion liquid is catalysis
The 10wt% of system) it is added in the glass reaction kettle of 1L, the air in reaction kettle, scavenging three are displaced by high pressure nitrogen
It is secondary, set in kettle that pressure is 0.5MPa, to maintain the liquid phase of unstripped gas.Open cooling back installation and the cooling dress of collet
It sets, makes 8 DEG C of temperature in the kettle.Raw material gas cylinder is opened, 140ml unstripped gas is made to rapidly enter in kettle (wherein iso-butane and alkene
Volume ratio is 8:1).
Agitating device revolving speed is set as 3000rpm, opens stirring, while timing, adjusts cooling device during the reaction
Switch keeps temperature in the kettle stable in the reaction temperature of setting and in determining time sampling, extraction, liquid separation, then uses gas phase color
Spectrum analysis.After 25 minutes, end of reaction closes the devices such as stirring, cooling and opens counterbalance valve pressure release.
1 bright sulfur acid catalysis of comparative example prepares gasoline alkylate
In this comparative example, alkylated reaction catalyst system of the invention is replaced using bright sulfur acid to be catalyzed preparation alkylation
Gasoline.The method for preparing gasoline alkylate is identical as method described in embodiment 1.
It is alkylated effect analysis
In the present invention, alkyl is carried out respectively using bright sulfur acid and using alkylated reaction catalyst system of the present invention
Change the preparation of gasoline, income effect is shown in Table 1.
Table 1
As it can be seen from table 1 using alkylated reaction catalytic body of the present invention compared with only using bright sulfur acid catalysis
The obtained gasoline alkylate of system, the content of C8 component are increased to 75.97% from 50.62%, and percentage value improves 25.35%,
RON value improves 5, TMP/DMH and improves 3.5, therefore is alkylated effect and increases substantially, and improvement effect is obvious, wherein and with
Use [OPSIm] [HSO4] scheme improve it is most obvious.
2 circulation experiment of embodiment
What the purpose of circulation experiment was to investigate alkylated reaction catalyst system of the present invention is used for multiple times effect.Wherein sulfonic acid
Functionalization glyoxaline ion liquid [OPSIm] [HSO4] (10wt%)/H2SO4Preparation and alkylated reaction according in embodiment 1
Condition and method carry out.Material in reactor is taken out after completion of the reaction, and the liquid separation in separatory funnel mutually directly uses gained acid
In next alkylated reaction.
Circulation experiment the result shows that, with [OPSIm] [HSO4] (10wt%)/H2SO4Reaction times increase, alkylation
Quality of gasoline is gradually reduced.The content of the C8 component of the gasoline alkylate of 1st secondary response reaches 75.97%, RON and TMP/
The value of DMH is respectively 96.00 and 9.97, then as reaction times increase and reduce.The alkylates C8 of 22nd secondary response
The content of component is that the value of 61.67%, RON and TMP/DMH is respectively 91.07 and 8.21；And when bright sulfur acid is catalyzed for the first time,
The content of C8 component is that the value of 50.62%, RON and TMP/DMH is respectively 91.07 and 6.54, illustrates [OPSIm] [HSO4]
(10wt%)/H2SO4Still it is not less than the catalytic effect of concentrated sulfuric acid first time using the catalytic effect after 22 times, therefore [OPSIm]
[HSO4] (10wt%)/H2SO4It at least may be reused 22 times.
Claims (10)
1. a kind of alkylated reaction catalyst system, which is characterized in that the alkylated reaction catalyst system includes as shown in formula I
Sulfonic acid funtionalized glyoxaline ion liquid and sulfuric acid,
The content of the sulfonic acid funtionalized glyoxaline ion liquid is 1-30wt%；
R is C1-C20Alkyl；
2. alkylated reaction catalyst system as described in claim 1, which is characterized in that its sulfonic acid funtionalized as shown in formula I
Glyoxaline ion liquid and sulfuric acid composition.
3. alkylated reaction catalyst system as claimed in claim 1 or 2, which is characterized in that
The content of the sulfonic acid funtionalized glyoxaline ion liquid is 8-15wt%, preferably 10wt%；
And/or R C1-C10Alkyl, preferably methyl, ethyl, normal-butyl, n-hexyl or n-octyl.
4. alkylated reaction catalyst system as described in any one of claims 1-3, which is characterized in that the sulfonic acid funtionalized miaow
Azole ionic liquid is
5. a kind of preparation method of alkylated reaction catalyst system according to any one of claims 1-4, which is characterized in that institute
State preparation method the following steps are included:
Alkyl substituted imidazole shown in A1, Formula II and the reaction of 1,3- propane sultone generate inner salt；
A2, the resulting inner salt of step A1 and the concentrated sulfuric acid are mixed, the sulfonic acid funtionalized imidazole-like ionic liquid is made in acidification
Body；
A3, sulfonic acid funtionalized glyoxaline ion liquid made from step A2 is mixed with the concentrated sulfuric acid it is anti-to get the alkylation
Answer catalyst system；
Wherein R1For C1-C20Alkyl.
6. preparation method as claimed in claim 5, which is characterized in that
R1For C1-C10Alkyl, preferably methyl, ethyl, normal-butyl, n-hexyl or n-octyl；
And/or preferred alkyl substituted imidazole is
And/or in step A1, the 1,3-propane sultone is dissolved in organic solvent, the preferred acetic acid second of organic solvent
Ester；
And/or in step A1, the molar ratio of the alkyl substituted imidazole and 1,3-propane sultone is 1:1-1:2；
And/or step A1 reacts the following steps are included: alkyl substituted imidazole is added dropwise into 1,3-propane sultone；Institute
It states during alkyl substituted imidazole is added dropwise, reaction system is placed in ice-water bath；It is added dropwise after the completion of the operation of alkyl substituted imidazole,
Reaction system rearranges in oil bath and heating stirring, and the temperature of the heating is 60-80 DEG C, preferably 70 DEG C, the stirring when
Between be 5-8 hours, preferably 6 hours；
It further include last handling process and/or in step A1, the last handling process includes the following steps:
If in alkyl substituted imidazole shown in Formula II, substituent group is methyl, ethyl or butyl, then the system after reaction is gone
Except liquid, obtained solid is washed with ethyl acetate, and dry；
If in alkyl substituted imidazole shown in Formula II, substituent group is hexyl or octyl, then by the system acetic acid after reaction
Ethyl ester washing, and remove ethyl acetate phase；
And/or in step A2, the molar ratio of the concentrated sulfuric acid and inner salt is 1:0.5-1:3, preferably 1:1；
And/or in step A3, the mass ratio of the concentrated sulfuric acid and sulfonic acid funtionalized glyoxaline ion liquid is 1:1-12:1, excellent
Select 6:1-10:1, more preferable 9:1.
7. a kind of preparation method of gasoline alkylate, which is characterized in that the preparation method comprises the following steps: in inert atmosphere
Under, under stress, by the described in any item alkylated reaction catalyst systems of claim 1-4 and raw material solid/liquid/gas reactions；
Wherein, the unstripped gas includes iso-butane and alkene, and the alkene is selected from n-butene, isobutene, n- 2- butylene and trans-
One of 2- butylene is a variety of.
8. preparation method as claimed in claim 7, which is characterized in that
The material pressure force value is 1-1.5Mpa, preferably 1.2Mpa；
And/or the alkene is Trans-2-butene；
And/or the inert atmosphere is nitrogen；
And/or the introducing method of the inert atmosphere takes scavenging 3-5 times mode to carry out；
And/or the pressure is 0.1-1Mpa, preferably 0.2-0.8Mpa, more preferable 0.5Mpa；When the container inner pressure of reaction is
When 0.5Mpa, the unstripped gas is liquid condition；
And/or the temperature of the reaction is 0-20 DEG C, preferably 5-10 DEG C, more preferable 8 DEG C；
And/or the reaction carries out under stiring, the speed of the stirring is 2000-4000rpm, preferably 3000rpm；
And/or the time of the reaction is 10-60 minutes, preferably 20-40 minutes, more preferable 25 minutes；
And/or it is described further include the steps that taking out reaction system and stratification after the reaction was completed, the acid after layering is mutually
For the described in any item alkylated reaction catalyst systems of claim 1-4.
9. a kind of gasoline alkylate of the preparation of the preparation method as described in claim 7 or 8, which is characterized in that the alkylation
The octane number of gasoline is 92-97.
10. gasoline alkylate as claimed in claim 9, which is characterized in that the gasoline alkylate octane number is 94-96.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710706949.7A CN109395776A (en) | 2017-08-17 | 2017-08-17 | A kind of alkylated reaction catalyst system and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710706949.7A CN109395776A (en) | 2017-08-17 | 2017-08-17 | A kind of alkylated reaction catalyst system and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109395776A true CN109395776A (en) | 2019-03-01 |
Family
ID=65455001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710706949.7A Pending CN109395776A (en) | 2017-08-17 | 2017-08-17 | A kind of alkylated reaction catalyst system and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109395776A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092358A (en) * | 2019-05-24 | 2019-08-06 | 华东理工大学 | A kind of processing method of waste sulfuric acid from alkylation |
| CN110292949A (en) * | 2019-07-02 | 2019-10-01 | 华东理工大学 | The method that functionalized ion liquid acid Fourier Series expansion technique catalysis prepares alkylate oil |
| CN112239405A (en) * | 2019-07-17 | 2021-01-19 | 中国石油化工股份有限公司 | Synthesis method of dimethyl 2, 6-naphthalenedicarboxylate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210192A (en) * | 2006-12-26 | 2008-07-02 | 中国科学院兰州化学物理研究所 | Process for preparing alkylated oil |
| CN102134507A (en) * | 2011-02-15 | 2011-07-27 | 中国科学院过程工程研究所 | Method for preparing alkylate by modifying concentrated sulfuric acid by using trifluoroethanol or ionic liquid as assistant |
| CN102603451A (en) * | 2012-02-28 | 2012-07-25 | 南开大学 | Method for preparing diphenylethane catalyzed by mixed liquid of concentrated sulfuric acid and ion liquid |
| CN106101636A (en) * | 2016-07-11 | 2016-11-09 | 南京捷特普智能科技有限公司 | A kind of war instruction information gathering transmission system |
-
2017
- 2017-08-17 CN CN201710706949.7A patent/CN109395776A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210192A (en) * | 2006-12-26 | 2008-07-02 | 中国科学院兰州化学物理研究所 | Process for preparing alkylated oil |
| CN102134507A (en) * | 2011-02-15 | 2011-07-27 | 中国科学院过程工程研究所 | Method for preparing alkylate by modifying concentrated sulfuric acid by using trifluoroethanol or ionic liquid as assistant |
| CN102603451A (en) * | 2012-02-28 | 2012-07-25 | 南开大学 | Method for preparing diphenylethane catalyzed by mixed liquid of concentrated sulfuric acid and ion liquid |
| CN106101636A (en) * | 2016-07-11 | 2016-11-09 | 南京捷特普智能科技有限公司 | A kind of war instruction information gathering transmission system |
Non-Patent Citations (1)
| Title |
|---|
| 王永红等: "《综合化学实验》", 31 August 2009, 浙江大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092358A (en) * | 2019-05-24 | 2019-08-06 | 华东理工大学 | A kind of processing method of waste sulfuric acid from alkylation |
| CN110292949A (en) * | 2019-07-02 | 2019-10-01 | 华东理工大学 | The method that functionalized ion liquid acid Fourier Series expansion technique catalysis prepares alkylate oil |
| WO2021000685A1 (en) * | 2019-07-02 | 2021-01-07 | 华东理工大学 | Method for catalytic preparation of alkylated oil by using functionalized ionic liquid acid coupling system |
| CN110292949B (en) * | 2019-07-02 | 2023-12-15 | 华东理工大学 | Method for preparing alkylate by catalyzing functionalized ionic liquid acid coupling system |
| CN112239405A (en) * | 2019-07-17 | 2021-01-19 | 中国石油化工股份有限公司 | Synthesis method of dimethyl 2, 6-naphthalenedicarboxylate |
| CN112239405B (en) * | 2019-07-17 | 2023-05-02 | 中国石油化工股份有限公司 | Synthesis method of 2, 6-dimethyl naphthalene dicarboxylate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109395776A (en) | A kind of alkylated reaction catalyst system and its preparation method and application | |
| CN101332432B (en) | Load-type solid acid catalyst with selective oligomerisation for mixed C4 | |
| CN103506150A (en) | Water vapor modified catalyst for preparing gasoline from methanol, and preparation method and application of water vapor modified catalyst | |
| CN103012034A (en) | Method for removing micro-quantity alkene in aromatic hydrocarbon | |
| CN102134507B (en) | Method for preparing alkylate by modifying concentrated sulfuric acid by using trifluoroethanol or ionic liquid as assistant | |
| CN103611571A (en) | Preparation method of nano-pore resin solid acid for alkylation of butane and butylene | |
| CN102553632A (en) | Low carbon alkane dehydrogenation catalyst, preparation method and application thereof | |
| CN105505450B (en) | A kind of gasoline alkylate preparation method based on ionic-liquid catalyst | |
| CN106916237B (en) | A kind of acidity polymeric ionic liquid and its preparation method and application | |
| CN103058814A (en) | Method for producing aromatic hydrocarbon and olefin from liquefied gas | |
| CN103058807B (en) | Method for producing arene by utilizing methanol | |
| CN107754850B (en) | Method for preparing carbon-based acidic material by using alkylated waste acid containing ionic liquid | |
| CN108097303A (en) | A kind of preparation method of catalytic diesel oil cracking producing light olefins catalyst | |
| CN110292949B (en) | Method for preparing alkylate by catalyzing functionalized ionic liquid acid coupling system | |
| CN109485064A (en) | The method of useless MTP catalyst preparation modenite and the application of useless MTP catalyst | |
| CN106608780B (en) | The method of oxygenatedchemicals propylene and aromatic hydrocarbons | |
| CN103664452B (en) | Method for producing ethylene by dehydration of alcohol | |
| CN111072464A (en) | Method for directly introducing aldehyde group on aromatic ring | |
| CN115121282A (en) | Catalyst for preparing ethylbenzene by catalyzing ethanol and benzene and application thereof | |
| CN102319586B (en) | Resin catalyst used in alkylation reaction of isobutene and butylene and preparation method thereof | |
| CN106365941B (en) | A kind of conversion process of lower carbon number hydrocarbons | |
| CN108295896B (en) | Method for catalytically producing alkylated gasoline | |
| CN113680387B (en) | Catalyst for synthesizing isooctane alkylate, and preparation method and application thereof | |
| CN105583008B (en) | Polyoxymethylene dimethyl ethers catalyst and preparation method thereof | |
| CN107286984B (en) | The method of n-butene gasoline component coproduction isobutene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190301 |