A kind of preparation method of gasoline alkylate
Technical field
The present invention relates to a kind of preparation method of gasoline alkylate, in particular to a kind of polyetheramine ionic liquid is urged
The method that change prepares gasoline alkylate.
Background technique
Gasoline alkylate is by certain alkane alkene by iso-butane and C4 alkene than alkylated reaction occurs under the catalysis of acid
Be prepared, its main component is the mixture of C8 isoparaffin, mainly include trimethylpentane (TMP) and dimethyl oneself
Alkane (DMH), wherein the content of TMP is more, and the capability of antidetonance of gasoline alkylate is better.Gasoline alkylate has octane number high, steams
Air pressure is low, and arene content is lower, and the hardly series of advantages such as sulfur-bearing.This makes gasoline alkylate can be used as an ideal
Mixed composition and gasoline arrange in pairs or groups, then obtain that there is high-octane environmentally friendly gasoline.Currently, the alkylation vapour in the whole world
The yield of oil is 102,000,000 tons/year, but is only able to satisfy the whole world the desired amount of 10% or so, and produces the technology of gasoline alkylate
Still remain larger defect.Therefore, the clearer production technology of gasoline alkylate is each major company, the world and researchers weight
The project of point research.
Alkylated reaction usually along with polymerization reaction and cracking reaction, reduces the selectivity of C8 alkylate oil, higher
Alkane alkene than being the key that alkylated reaction is gone on smoothly with suitable acidity.Due to solubility of the iso-butane in acid system
It is extremely low, and alkene is soluble in acid system, the polymerization of alkene in order to prevent, alkylated reaction is usually required in high alkane/alkene ratio
Lower progress.It is just industrial as the gasoline alkylate production technology of catalyst using the concentrated sulfuric acid or hydrofluoric acid from the thirties in last century
Change and uses till today.Although technique is very mature, there are still many inevitable drawbacks for these strong acid catalysts.Example
Such as sour consumption is big, equipment seriously corroded, spent acid are difficult to handle, environmental pollution is serious.Solid acid catalyst can to equipment because of it
The corrosivity and hypotoxicity ignored, and excellent catalytic performance and higher selectivity are shown, cause the extensive of people
Concern.But the fatal defects of solid acid catalyst easy in inactivation in successive reaction, so that it is anti-in iso-butane/butene alkylated
Application pause in answering stays in laboratory stage.Therefore, a kind of efficient, environmental protection, safety, and alkylation can be recycled are found
Catalyst becomes the emphasis of contemporary scientific research.
In numerous catalyst for alkylation reaction, ionic-liquid catalyst is undoubtedly one of great potential.Due to its tool
There is steam to force down, nonflammable, thermal stability is high, and numerous inherent advantages, the people such as acidity is adjustable have been widely used in electricity
Chemistry, liquid/liquid extraction, numerous reactions such as catalysis and polymerization simultaneously achieve good effect.Then people make ionic liquid
It is applied in iso-butane/butene alkylation for catalyst and is filled with expectation.From 1994, Chauvin etc. first will
[C4mim]Cl–AlCl3] ionic liquid be used for catalyzing iso-butane alkane/butene alkylation, achieve better catalytic effect
Later, constantly to the type of ionic liquid, structure is designed and optimizes to reaction condition people, to reach more
Excellent effect.Studying more is metal chloride type Lewis acidic ionic liquid catalysts, although such catalyst is used for
Alkylated reaction has obtained preferable catalytic effect, but since it easily causes the irreversible inactivation of catalyst to water sensitive, therefore limits
Its industrialized development is made.
Summary of the invention
The present invention provides the new methods that a kind of catalysis prepares gasoline alkylate.Using polyetheramine cheap and easy to get as parent,
Pass through a kind of double-core of one-step synthesis methodAcid polyetheramine ionic liquid, the alkane for catalyzing iso-butane alkane and isobutene
Glycosylation reaction realizes high C8 selectivity of product and high TMP selectivity, and polyetheramine ionic liquid at normal temperatures and pressures
Body can efficiently be recycled and repeatable regeneration.
The inventive method mainly has the characteristic of following several respects: (1) preparation of catalyst passes through simple one step of one kettle way
It synthesizes, in reaction process, no coupling product is generated, and atom utilization reaches 100%, the requirement of composite green chemistry.(2) pass through choosing
Different polyoxyalkyl structures is selected, the hydrophilic and hydrophobic of polyetheramine ionic liquid is adjusted.Design synthesizes with hydrophobic
Polyetheramine ionic liquid can effectively increase dissolubility of the unstripped gas especially iso-butane in catalyst phase, to significantly drop
Alkane needed for low reaction/alkene ratio, substantially reduces cost of material.(3) by selecting different polyethers chain lengths, polyetheramine is adjusted
The viscosity of ionic liquid.The viscosity for adjusting ionic liquid is unlikely to excessive, has both kept also ensuring that the good solubilising of unstripped gas
Reaction is gone on smoothly;In addition it is important that, also to realize that the alkylate oil of generation is separated with ionic liquid automatically, is not required to
Want special processing step.(4) new catalyst system catalytic performance is superior, and reaction can be catalyzed under normal temperature and pressure, is wanted to equipment
It asks low, is advantageously implemented industrialized production.(5) ionic liquid and alkylate oil split-phase are good, and ionic-liquid catalyst can be efficient
It is recycled multiple.(6) hydrophobicity for utilizing polyetheramine ionic liquid, can also realize polyetheramine ionic liquid it is simple again
It is raw.A certain amount of water only need to be added into the ionic liquid being used for multiple times, the acid soluble oil in ionic liquid can be removed, it is real
The regeneration of existing ionic liquid.And in the regeneration of conventional ionic liquid, to use a large amount of organic solvent as extractant, water
Replace conventional organic solvent, not only significantly reduces operating cost, but also avoid environmental pollution.
The technical scheme of the present invention is realized as follows:
Using polyetheramine ionic liquid as catalyst, a certain amount of trifluoromethayl sulfonic acid, catalyzing iso-butane alkane and isobutene are added
Alkylated reaction, prepare gasoline alkylate;The structural formula of the polyetheramine ionic liquid is as follows:
After reaction, alkylate oil is automatically separated the preparation method of gasoline alkylate provided by the invention with catalyst.
Preferably, a kind of preparation method of gasoline alkylate particularly into stainless steel machinery stirred tank, is added
10mL polyetheramine ionic liquid and 3mL trifluoromethayl sulfonic acid are then pumped into 20mL alkane/alkene than the iso-butane and isobutene for 10:1
Mixing liquid, the mechanic whirl-nett reaction 20min at 25 DEG C, after reaction, collect upper layer alkylate oil phase, the ion of lower layer
Liquid direct reuse.
In the preparation method of gasoline alkylate provided by the invention, the preparation method of the polyetheramine ionic-liquid catalyst
To be prepared using one kettle way using polyetheramine D-2000,1,3-propane sultone and trifluoromethayl sulfonic acid as raw material.
Preferably, 20g polyetheramine D-2000 is particularly dissolved in 30mL first by the preparation method of the catalyst
It in methylene chloride, stirring evenly, 2.44g 1,3-propane sultone is then added dropwise thereto, is added dropwise, temperature rises to 50 DEG C,
It is condensed back reaction 2h.Later, it is added dropwise 3.01g trifluoromethayl sulfonic acid again thereto, is kept for 50 DEG C the reaction was continued 4h, stop anti-
It answers.Revolving removes methylene chloride, and products therefrom is dried in vacuo to get polyetheramine ionic-liquid catalyst.
The present invention compared with traditional method, its main feature is that: (1) catalyst preparation simple, at low cost, atom utilization
100%, the requirement of composite green chemistry;(2) reaction condition is mild, easily realizes industrialization;(3) catalytic activity is high, alkylate oil
Selectivity is good;(4) catalyst separates simply with product, and catalyst circulation service efficiency is high;(5) catalyst can simply regenerate
Reuse.
Specific implementation method
Method of the invention is described further below with reference to embodiment, but is not limitation of the invention.
(1) synthesis step of polyetheramine ionic-liquid catalyst
Embodiment 1: the synthesis of polyetheramine ionic liquid uses one kettle way, and 20g polyetheramine D-2000 is dissolved in 30mL first
It in methylene chloride, stirring evenly, 2.44g 1,3-propane sultone is then added dropwise thereto, is added dropwise, temperature rises to 50 DEG C,
It is condensed back reaction 2h.Later, it is added dropwise 3.01g trifluoromethayl sulfonic acid again thereto, is kept for 50 DEG C the reaction was continued 4h, stop anti-
It answers.Revolving removes methylene chloride, and products therefrom is dried in vacuo to get polyetheramine ionic-liquid catalyst.Polyetheramine ion
The synthetic route of liquid is as follows:
(2) preparation of gasoline alkylate
Embodiment 2: into stainless steel machinery stirred autoclave, 10mL polyetheramine ionic liquid and 3mL fluoroform is added
Sulfonic acid seals kettle, with air 3 times in 4MPa high pure nitrogen displacement kettle.20mL alkane/alkene is then pumped into than iso-butane for 10:1 and different
The mixing liquid of butylene, the mechanic whirl-nett reaction 20min at 25 DEG C open kettle after reaction, collect upper layer alkylate oil phase,
Quantitative analysis is carried out with gas-chromatography.The conversion ratio of isobutene is 99%, and the selectivity of C8 product reaches 87% in alkylate oil,
Wherein the ratio of trimethylpentane accounts for 98%.
(3) reuse of catalyst
Embodiment 3-15: to be catalyzed the ionic liquid after primary first-order equation in embodiment 2 mutually for catalyst, without adding trifluoro
Loprazolam directly seals kettle after isolating alkylate oil, after air in nitrogen displacement kettle, is pumped into fresh 20mL alkane/alkene ratio
For the iso-butane of 10:1 and the mixing liquid of isobutene, catalysis reaction is carried out, experiment condition is the same as embodiment 2.So reuse
Ionic liquid phase catalyst, after carrying out 13 repetition experiments, the conversion ratio of isobutene C8 still in 95% or more, alkylate oil is produced
The selectivity of object is still 84% or more.
(4) regeneration of catalyst
Embodiment 16: being by the ionic liquid after catalysis reaction in embodiment 15 by the ionic liquid after being recycled 13
20mL water is added from taking out and being transferred in beaker in reaction kettle in (dissolved with a large amount of acid soluble oils), and stirring forms white " milky " liquid,
It is then heated to boiling and keeps 5min, stop heating, stand natural cooling, final emulsion can be divided into three layers, and upper layer is drift
Floating acid soluble oil, middle layer are water layer, and lowest level is the ionic liquid lived again.Separate acid soluble oil and water, ionic liquid
It is rotated at 40 DEG C, removes moisture.It is dried in vacuo 4h at 60 DEG C again later, further removes remaining minor amount of water.Ionic liquid
The regeneration of body is completed, and catalytic cycle reaction can be continued on for.
(5) reuse of regenerated catalyst
Embodiment 17: ionic liquid is only changed to after regenerating in embodiment 16 by experiment condition and step with embodiment 2
Ionic liquid, the conversion ratio of isobutene are 97%, and the selectivity of C8 product is 84% in alkylate oil.
(6) compared with other polyethers ionic-liquid catalysts
Embodiment 18: using the polyethers ionic liquid in patent CN106398742A as catalyst, at optimum conditions into
Row experiment, experiment condition and step are with the embodiment 5 in patent CN106398742A, and the conversion ratio of isobutene is only 78%, alkane
The selectivity of base carburetion C8 product is 81%.
In contrast, polyetheramine ionic liquid has apparent advantage, simple one-step synthesis, atom in synthesis
Utilization rate reaches 100%;Polyetheramine ionic liquid catalyst systems catalytic activity is high, realizes the catalysis reaction under room temperature, and alkane
The selectivity of C8 product is up to 87% in base carburetion;The recycling of polyetheramine ionic liquid is high-efficient, and reuse number may be up to 13
It is secondary;In addition, polyetheramine ionic liquid can also utilize the hydrophobicity of itself, environmental-friendly regeneration is realized.Therefore this skill
Art has significant progress compared with patent CN106398742A.