CN104447160A - Production method for alkylate oil - Google Patents
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Abstract
The invention relates to a production method for alkylate oil. The method is characterized by: under alkylation reaction conditions, subjecting isobutane and C4 alkene to contact reaction in the presence of concentrated sulfuric acid, sulfonic acid ester and acid-soluble oil, and recovering the obtained alkylate gasoline. In the alkylate oil obtained by the method, the selectivity of C8 and the selectivity of the high octane number component trimethylpentane (TMP) in C8 are high, and the content of C5-7 components and heavy components above C9 is greatly reduced. At the same time, the product octane number is also significantly improved.
Description
Technical field
The present invention relates to a kind of production method of alkylate oil, more particularly the present invention relates to the production method of the alkylate oil of sulfuric acid catalysis.
Background technology
Along with the high speed development of automotive industry and the increasingly stringent of automobile exhaust emission standard, the demand of countries in the world to clean gasoline production constantly increases.By Trimethylmethane and C
4olefin alkylation reaction generates C
8side chain isooctane product, i.e. alkylate oil, have that octane value is high, anti-knocking property good, an advantage that low containing alkene and aromatic hydrocarbons, sulphur content, steam forces down, is the optimal blend component of clean gasoline.
The method of present industrial production alkylate oil mainly contains sulfuric acid process and hydrogen fluoride.But because sulfuric acid process spent acid quantity discharged is large, environmental pollution is serious; Hydrofluoric acid is volatile severe poisonous chemicals, there is the problem such as personnel safety and environmental pollution in operating process.
For many years, drop into the research and development that a large amount of human and material resources are devoted to solid acid alkylation catalysts and technique both at home and abroad, it is desirable to replace current liquid acid alkylation process technology, solve environmental pollution and the equipment corrosion problem of liquid acid.The solid acid catalyst of research and development mainly contains metal halide, molecular sieve, solid super-strong acid and carried heteropoly acid etc.Advantages such as it is low that although solid acid alkylation processes has corrodibility, safety and environmental protection, a set of solid acid alkylation processes is not still had to realize industrialization so far in the world.Reason is that various novel solid acid catalyst all exists a common shortcoming, that is exactly that the initial activity of solid acid catalyst is fine, but inactivation is very fast, several hours even after dozens of minutes, active sites is covered by the macromole unsaturated hydrocarbons compounds that the side reactions such as alkene self-polymerization generate very soon in reaction process, and catalyst regeneration cost is high, its economy still cannot be competed with sulfuric acid and hydrofluoric acid alkylation technique.
Because ionic liquid is a kind of salt at room temperature existed in liquid form, there is much special character, as strong in dissolving power, thermostability is high, vapour pressure is very low, non-corrosiveness, reusable, the advantages such as acid intensity is adjustable, have therefore caused the vast concern of researcher in the research of alkylated reaction as catalyst application with ionic liquid.Chinese Petroleum Univ. adopts the ionic liquid-catalyzed Trimethylmethane of chloro-aluminate type of modification and butylene to carry out alkylated reaction, can obtain close to or reach the alkylating level of industrial sulphuric acid method, but due to its AlCl adopted
3there is defects such as water-content being required to harsh, self stability difference in type ionic liquid, process of industrialization is slow.
RU2114808C1 proposes and adopts tetramethylene sulfone as the additive of sulfuric acid, and it is characterized in that when tetramethylene sulfone addition is 5 ~ 10wt%, in product, trimethylpentane increases by 1.2 ~ 1.3 times, and product octane value increases 4-5 unit, and acid consumption reduces 30-40%.
TW418247B and TW575550 proposes respectively and adopts 2-naphthene sulfonic acid and two-n-methyl isophthalic acid, 4-phenylenediamine makes sulfate additive, it is characterized in that when 2-naphthene sulfonic acid addition is 0.05wt% ~ 1.5wt% and two-n-methyl isophthalic acid, when 4-phenylenediamine addition is 0.01wt% ~ 2wt%, effectively can increase the solubleness of Trimethylmethane in sulfuric acid phase, C in product
8optionally improve, thus improve the octane value of alkylate oil.
US3970721A proposes and adopts trifluoromethanesulfonic acid to make co-catalyst, and when trifluoromethanesulfonic acid addition is 16.6%, RON brings up to 96.6 from 95.8.
US3655807A proposes and adopts Witco 1298 Soft Acid to make sulfate additive, it is characterized in that, when Witco 1298 Soft Acid addition is 0.01wt% ~ 2wt%, effectively to increase the content of trimethylpentane in product, thus improves the quality of alkylate oil.
CN201110038062.8 proposes with trifluoroethanol or ionic liquid as the additive modification vitriol oil prepares the method for alkylate oil, it is characterized in that when the content of trifluoroethanol and ionic liquid is 1.0wt% ~ 10.0wt%, catalytic activity and the stability of catalyzer can be improved, improve C
8selectivity and the quality of trimethylpentane.
Summary of the invention
The present inventor on the lot of experiments basis that sulfuric acid catalysis alkylate oil is produced, unexpected find when with sulphonate, acid-soluble hydrocarbon ils for the vitriol oil co-catalyst time, more efficient Trimethylmethane and C can be formed
4the alkylation catalyst systems of the high-octane alkylate oil of olefin production.Based on this, form the present invention.
Therefore, the object of the invention is, on the basis of the alkylation catalyst system of the existing vitriol oil, to provide a kind of production method of more efficient alkylate oil.
The production method of alkylate oil provided by the invention, is characterized in that, makes Trimethylmethane and C under alkylation reaction condition
4alkene carries out contact reacts and also reclaims the gasoline alkylate obtained under the vitriol oil, sulphonate and acid soluble oil exist.
The production method of alkylate oil provided by the invention, has the following advantages:
(1) be that the catalytic activity of concentrated sulfuric acid catalyst system of co-catalyst is good containing sulphonate and acid soluble oil, C in alkylate oil
8selectivity and C
8in component, high-octane number component trimethylpentane (TMP) selectivity is high; And C
5-7component and C
9above heavy constituent content significantly reduces, and meanwhile, product octane value also significantly improves.
(2) acid consumption is low, low to the corrodibility of equipment, by product growing amount is few, simplify subsequent processes and reduce alkylation process running cost.
Embodiment
The production method of alkylate oil provided by the invention, is characterized in that, makes Trimethylmethane and C under alkylation reaction condition
4alkene carries out contact reacts and also reclaims the gasoline alkylate obtained under the vitriol oil, sulphonate and acid soluble oil exist.
The production method of alkylate oil provided by the invention is the co-catalyst that is the vitriol oil with sulphonate and acid soluble oil, with Trimethylmethane and C
4alkene is raw material, and product is mainly the high octane gasoline component of carbon eight isoparaffin.Said alkylation reaction condition is temperature is-15 ~ 40 DEG C, be preferably-5 ~ 20 DEG C; Pressure is 0.1 ~ 1MPa, is preferably 0.2 ~ 0.5Mpa.
Said sulfuric acid concentration is counted with the mass percent of the sulfuric acid in aqueous sulfuric acid and is more than or equal to 70, be preferably 85-99.8, be more preferably 90-99, in most preferred embodiment of the present invention, said sulfuric acid concentration is 98.3, its density is 1.84g/ml, and its substance withdrawl syndrome is 18.4mol/L.
The general formula of said sulphonate is (R
1sO
2oR
2), said sulphonate can be but be not limited to single sulphonate or their mixtures such as methyl mesylate, ethyl methane sulfonate, 4-methyl tosylate, 4-toluenesulphonic acids ethyl ester, 1.3-propane sultone, 1.4-butyl sultone, 2.4-butyl sultone.In a most preferred embodiment of the present invention, employing 4-toluenesulphonic acids ethyl ester and 1.4-butyl sultone are the co-catalyst of sulfuric acid jointly, and the proportioning of 4-toluenesulphonic acids ethyl ester and 1.4-butyl sultone be 1:0.9 ~ 1.1, the relation of such as 1:1 time can obtain more excellent reaction effect, said more excellent reaction effect is embodied in reaction product alkylate oil, the selectivity of trimethylpentane, C
8selectivity, the data such as research octane number (RON) and motor-method octane number there is larger lifting.Said sulphonate as co-catalyst, its addition be catalyzer vitriol oil weight 0.05 ~ 15%, preferably 0.1 ~ 8%, more preferably 1 ~ 4%.In a preferred embodiment of the present invention, when the type of sulphonate selects the mixture into 4-toluenesulphonic acids ethyl ester and 1.4-butyl sultone, when being co-catalyst with acid soluble oil (such as embodiment 9), compared with pure vitriol oil alkylation result, in product, the selectivity of trimethylpentane improves 10.5 percentage points, research octane number (RON) improves 2.6 units, motor-method octane number improves 1.4 units.
Said acid soluble oil is produced through resetting and be polymerized by alkene and tertiary butyl carbonium ion, these polymkeric substance are highly unsaturated and Ionized, they can continue polymerization with alkene, generate high polymer, because it is highly Ionized, be easy to accept hydride ion from Trimethylmethane, make Trimethylmethane become (C
4h
9)
+, thus cause alkylated reaction.
Said acid soluble oil in the present invention, can obtain through but not limited to following detailed process, comprise 600ml(1104g) vitriol oil pours in reactor, and with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1000r/min, temperature controls at 8 DEG C, pressure-controlling is at 0.4MPa, butane that alkane alkene volume ratio is 1:1 is squeezed into and olefin raw material (be mixed olefins mixed c 4 in other words, specifically consist of Trimethylmethane 40.3%, normal butane 9.7%, 1-butylene 16.1%, anti-2-butylene 18.5%, positive 2-butylene 14.8%, iso-butylene 0.6%) 600ml carries out alkylated reaction 10min with pump.After having reacted, stop stirring, by sulfuric acid static layering after reaction product and reaction, lower floor is sulfuric acid layer, and upper strata is reaction product alkylate oil, obtains sulfuric acid layer after separation.By sulfuric acid layer dilute with water, be separated into aqueous phase (dilute sulphuric acid phase) and acid-soluble oil phase, obtain acid soluble oil.
Said acid soluble oil is as one of co-catalyst, and its addition is 0.5 ~ 10%, preferably 1 ~ 8% of catalyzer vitriol oil weight.
In said raw material, C
4the mixed C that alkene typically refers to
4alkene includes 1-butylene, positive 2-butylene, anti-2-butylene, iso-butylene at interior mixture.
In said raw material, Trimethylmethane and C
4the volume ratio of alkene is 1 ~ 200:1, is preferably 6 ~ 120:1.The vitriol oil and include Trimethylmethane and C
4alkene such as, is 0.5 ~ 2:1 in the volume ratio of interior hydrocarbon mixture (be commonly referred to mixed c 4, a mixed c 4 in a specific embodiment specifically consist of Trimethylmethane 87.4%, normal butane 1.7%, 1-butylene 3.3%, anti-2-butylene 4.1%, positive 2-butylene 3.1%, iso-butylene 0.4%), is preferably 0.8 ~ 1.5:1.
In a preferred embodiment of the present invention, temperature of reaction controls at 4 ~ 10 DEG C, pressure-controlling is at 0.4 ~ 0.5MPa, sulphonate addition be catalyzer vitriol oil weight 1 ~ 5%, acid soluble oil addition is when being 2 ~ 5% of catalyzer vitriol oil weight, the quality product of reaction product is better.
Said alkylated reaction can realize under multiple reactor types, the pressure autoclave type reactor that said reactor types can stir for band, and the time of the reaction of tank reactor is 0.1 ~ 60min, is preferably 1 ~ 20min; Or industrial common sulfuric acid alkylation horizontal reactor continuous production device, as cascade reactor, mixed fillers tower reactor, static mixing reactor, the reaction times can be embodied by air speed at continuous reaction apparatus.
In pressure autoclave type reactor, the vitriol oil and co-catalyst mix by a certain percentage and add in reactor, start and stir and refrigeration, reach after temperature of reaction until temperature, the mixed c 4 pump being made into certain alkane alkene ratio is squeezed into reactor and reacts, after reaction terminates, stop stirring, by reaction product and catalyzer static layering, obtain reaction product alkylate oil after separation, analyze.
For other continuous reaction apparatus, such as cascade reactor is made up of several conversion zones, separate with overflow plate between each conversion zone, each conversion zone is equipped with agitator, and the vitriol oil, Trimethylmethane and mixed c 4 are squeezed in reactor by pump respectively by a certain percentage and reacted; After reaction terminates, reaction product and sulfuric acid enter settling section and are separated, and the sulfuric acid separated uses with being pumped into conversion zone, and reaction product enters product treatment and fractionation stage, finally obtain alkylate, the Trimethylmethane pump after separation is squeezed into conversion zone and is recycled.
Said recovery is well known to those skilled in the art, to be with the pressure autoclave type reactor stirred, normally after said contact reacts completes, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
In embodiment, reaction product adopts the quantitative analysis of GC7890 gas chromatograph, and fid detector, chromatographic column is capillary column.Reaction product octane value near infrared spectroscopy (RON-NIR) measures.
In an embodiment, said acid soluble oil is obtained by following process:
By 600ml(1104g) vitriol oil pours in reactor, and with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1000r/min, temperature controls at 8 DEG C, pressure-controlling is at 0.4MPa, butane that alkane alkene volume ratio is 1:1 is squeezed into and olefin raw material (be mixed olefins mixed c 4 in other words, specifically consist of Trimethylmethane 40.3%, normal butane 9.7%, 1-butylene 16.1%, anti-2-butylene 18.5%, positive 2-butylene 14.8%, iso-butylene 0.6%) 600ml carries out alkylated reaction 10min with pump.After having reacted, stop stirring, by sulfuric acid static layering after reaction product and reaction, lower floor is sulfuric acid layer, and upper strata is reaction product alkylate oil, obtains sulfuric acid layer after separation.By sulfuric acid layer dilute with water, be separated into aqueous phase (dilute sulphuric acid phase) and acid-soluble hydrocarbon ils phase, obtain acid-soluble hydrocarbon ils 65g, for subsequent use.
Comparative example
By 100ml(184g) vitriol oil pours in reactor, and with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, temperature controls at 8 DEG C, pressure-controlling is at 0.4MPa, Trimethylmethane that alkane alkene volume ratio is 8:1 is squeezed into and olefin raw material (is mixed olefins mixed c 4 in other words with pump, specifically consist of Trimethylmethane 87.4%, normal butane 1.7%, 1-butylene 3.3%, anti-2-butylene 4.1%, positive 2-butylene 3.1%, iso-butylene 0.4%, in following examples, alkene is identical therewith) 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 1
By 100ml(184g) vitriol oil pours in reactor, then adds ethyl methane sulfonate 3ml(3.6g) and acid soluble oil 1.8g, with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 8 DEG C, and pressure-controlling, at 0.4MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 2
By 100ml(184g) vitriol oil pours in reactor, then adds ethyl methane sulfonate 3ml(3.6g) and acid soluble oil 3.7g, with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 8 DEG C, and pressure-controlling, at 0.4MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 3
By 100ml(184g) vitriol oil pours in reactor, then adds 4-methyl tosylate 3.7g and acid soluble oil 3.7g, and with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 8 DEG C, and pressure-controlling, at 0.4MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 4
By 100ml(184g) vitriol oil pours in reactor, then adds 4-toluenesulphonic acids ethyl ester 3.7g and acid soluble oil 5.5g, and with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 4 DEG C, and pressure-controlling, at 0.45MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 5
By 100ml(184g) vitriol oil pours in reactor, then adds 1.3-propane sultone 3.7g and acid soluble oil 5.5g, and with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 8 DEG C, and pressure-controlling, at 0.45MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 6
By 100ml(184g) vitriol oil pours in reactor, then adds 1.3-propane sultone 3.7g and acid soluble oil 9.2g, and with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 8 DEG C, and pressure-controlling, at 0.45MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 7
By 100ml(184g) vitriol oil pours in reactor, then adds 1.4-butyl sultone 4ml(5.3g) and acid soluble oil 3.7g, with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 6 DEG C, and pressure-controlling, at 0.4MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 8
By 100ml(184g) vitriol oil pours in reactor, then adds 1.4-butyl sultone 4ml(5.3g) and acid soluble oil 7.4g, with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 6 DEG C, and pressure-controlling, at 0.4MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 15min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Embodiment 9
By 100ml(184g) vitriol oil pours in reactor, then adds 4-toluenesulphonic acids ethyl ester 2.8g, 1.4-butyl sultone 2ml(2.7g) and acid soluble oil 5.5g, with the air in nitrogen replacement reactor, start and stir and refrigeration.Mixing speed is adjusted to 1200r/min, and temperature controls at 8 DEG C, and pressure-controlling, at 0.4MPa, squeezes into pump Trimethylmethane that alkane alkene volume ratio is 8:1 and olefin raw material 100ml carries out alkylated reaction 10min.After having reacted, stop stirring, by reaction product and catalyzer static layering, lower floor is catalyzer, and upper strata is reaction product alkylate oil, obtains reaction product alkylate oil after separation.The analytical results of reaction product alkylate oil is in table 1.
Table 1
(note: DMH is dimethylhexane, and octane value own is very low, and the quality of TMP/DMH ratio higher explanation reaction product oil product is better.）
As can be seen from Table 1, compared to adopting the comparative example that is catalyzer with the pure vitriol oil, when with sulphonate and acid soluble oil for the vitriol oil co-catalyst time, significantly improve selectivity and the quality product of reaction product.Trimethylpentane (TMP) and C in reaction product
8content significantly improve, and C
5-7component and C
9above heavy constituent content significantly reduces, and meanwhile, product octane value also significantly improves.When temperature of reaction controls at 4 ~ 10 DEG C, pressure-controlling is at 0.4 ~ 0.5MPa, and sulphonate addition is 1 ~ 5%, and during acid soluble oil addition 2 ~ 5%, the quality product of reaction product is best.As can be seen from table 1 data also, when with 4-toluenesulphonic acids ethyl ester, 1.4-butyl sultone and acid soluble oil for (embodiment 9) during co-catalyst, this proportioning type is optimum, compared with pure vitriol oil alkylation result, in product, the selectivity of trimethylpentane reaches 78.01%, improves 10.5 percentage points, research octane number (RON) improves 2.6 units, motor-method octane number improves 1.4 units.
Claims (17)
1. a production method for alkylate oil, is characterized in that, makes Trimethylmethane and C under alkylation reaction condition
4alkene carries out contact reacts and also reclaims the gasoline alkylate obtained under the vitriol oil, sulphonate and acid soluble oil exist.
2., according to the process of claim 1 wherein, in said alkylation reaction condition, temperature is-15 ~ 40 DEG C, pressure is 0.1 ~ 1MPa.
3. according to the process of claim 1 wherein, in said alkylation reaction condition, temperature is-5 ~ 20 DEG C, pressure is 0.2 ~ 0.5Mpa.
4. according to the process of claim 1 wherein, in said raw material, Trimethylmethane and C
4the volume ratio of alkene is 1 ~ 200:1.
5. according to the process of claim 1 wherein, in said raw material, Trimethylmethane and C
4the volume ratio of alkene is 6 ~ 120:1.
6. according to the method for claim 1,4 or 5, wherein, said C
4alkene is a kind of in 1-butylene, positive 2-butylene, anti-2-butylene, iso-butylene or their mixture.
7. according to the method for claim 1, wherein, said sulphonate is single sulphonate or their mixtures such as methyl mesylate, ethyl methane sulfonate, 4-methyl tosylate, 4-toluenesulphonic acids ethyl ester, 1.3-propane sultone, 1.4-butyl sultone, 2.4-butyl sultone.
8., according to the process of claim 1 wherein, said sulphonate is 4-toluenesulphonic acids ethyl ester and 1.4-butyl sultone.
9. according to the method for claim 8, wherein, the proportioning of said 4-toluenesulphonic acids ethyl ester and 1.4-butyl sultone is 1:0.9 ~ 1.1.
10. according to the method for one of claim 1,7 ~ 9, wherein, said sulphonate, its addition is 0.05 ~ 15% of vitriol oil weight.
11. according to the method for claim 10, and wherein, said addition is 0.1 ~ 8% of vitriol oil weight.
12. according to the process of claim 1 wherein, said acid soluble oil, its addition be vitriol oil weight 0.5 ~ 10%.
13. according to the method for claim 12, and wherein, said addition is 1 ~ 8% of vitriol oil weight.
14. according to the process of claim 1 wherein, the volume ratio of the said vitriol oil and raw material hydro carbons is 0.5 ~ 2:1.
15. according to the method for claim 14, and wherein, said volume ratio is 0.8 ~ 1.5:1.
16., according to the method for claim 1, is characterized in that temperature of reaction controls at 4 ~ 10 DEG C, pressure-controlling at 0.4 ~ 0.5MPa, sulphonate addition be catalyzer vitriol oil weight 1 ~ 5%, acid soluble oil addition is 2 ~ 5% of catalyzer vitriol oil weight.
17., according to the method for claim 1, is characterized in that, add in the vitriol oil by sulphonate and acid soluble oil, stir at the reaction temperatures and make it mix.
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| CN105688986A (en) * | 2016-03-08 | 2016-06-22 | 抚顺美精石化添加剂有限公司 | Additive for improving catalytic activity of alkylation reaction |
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| CN113122312A (en) * | 2019-12-30 | 2021-07-16 | 中国石油大学(北京) | Method for co-catalytic production of alkylated gasoline by taking cycloalkane as co-catalyst |
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| CN107532088A (en) * | 2015-04-06 | 2018-01-02 | 道达尔销售服务公司 | The method that isoparaffin is obtained from alkylates bottoms |
| CN105688986A (en) * | 2016-03-08 | 2016-06-22 | 抚顺美精石化添加剂有限公司 | Additive for improving catalytic activity of alkylation reaction |
| CN105688986B (en) * | 2016-03-08 | 2018-01-09 | 抚顺美精石化添加剂有限公司 | A kind of additive for being used to improve alkylated reaction catalytic activity |
| CN106076411B (en) * | 2016-07-07 | 2018-05-29 | 清华大学 | A kind of sulfuric acid catalysis compound and the application in gasoline alkylate is produced |
| CN109305872A (en) * | 2018-10-25 | 2019-02-05 | 中国石油大学(北京) | A kind of experimental provision and method of carbon tetra-alkylation |
| CN113122312A (en) * | 2019-12-30 | 2021-07-16 | 中国石油大学(北京) | Method for co-catalytic production of alkylated gasoline by taking cycloalkane as co-catalyst |
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| CN104447160B (en) | 2016-05-25 |
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