CN1135260C - Additive compsn. for raising octane number of gasoline and its preparing process - Google Patents

Abstract

The present invention relates to an additive component of gasoline for increasing ocane number and a preparing method thereof. The additive component contains 60 to 80% of mixed ether, 15 to 35% of xylene and 5% of octane number improver. 1. The mixed ether is prepared by that a. the bipolymer of olefin is obtained by the catalytic polyreaction of C2 to C4 olefin in liquefied gas which is not separated; b. the bipolymer of olefin reacts with methanol and ethanol in an etherification mode for forming mixed ether alcohol; c. alcohol is separated by dealcoholization; then, the mixed ether is obtained. 2. The mixed ether is mixed with the xylene and the octane number improver to obtain the additive component. The additive component is added in gasoline, which causes the octane number of gasoline to greatly rise; the stability of gasoline products is high; CO discharged by tail gas is reduced by 20%; HC is reduced by 10.3%.

Description

The dopes for gasoline composition and method of making the same

External at present for preventing the environmental pollution that motor vehicle exhaust causes, to vehicle exhaust---each emission of harmful substances amount has all been made strict regulation in the discharging, banned low octane value gasoline simultaneously, promote the use of high-octane fine clean gasoline, can make gasoline combustion abundant like this, reduce the discharging of CO in the tail gas, HC greatly.

1999 the end of the year China issued the national standard of GB 17930-1999 unleaded gasoline for vehicle, sulphur content (massfraction) and lead content reduced to respectively be not more than 0.1% and be not more than 0.005g/l, increased benzene, aromatic hydrocarbons, olefin(e) centent test, and stipulated that its volume fraction is not more than 2.5%, 40%, 35% respectively; If add organic oxygen-containing compound, stipulate that then its massfraction is not more than 2.7%.Because the enforcement of new standard means 70 ^#Motor spirit will be superseded fully, can not produce so the domestic middle-size and small-size petroleum chemical plant of China uses atmospheric and vacuum distillation unit to produce gasoline, be faced with the raising gasoline label, use quality of gasoline to reach the difficult problem of new standard fully.In the face of each middle-size and small-size refinery, make it adjust it and produce product structure, for adapting to the appearance of new standard, eliminate 70 ^#Gasoline products, the present method of taking are to reach the lifting of low grade gasoline by the raising gasoline octane rating and be 90-93 ^#The purpose of gasoline.The approach that improves gasoline octane rating has two classes: the one, process the purpose that reaches boosting of octane rating by apparatus and process, as catalytic cracking, catalytic reforming, alkylation, isomerization etc.; The 2nd, by in gasoline, adding octane promoter (as the tetraethyllead of now having forbidden) or in gasoline, adding the purpose that blending agents composition (be MTBE) reaches boosting of octane rating.The production of MTBE is main raw material with iso-butylene and methyl alcohol mainly in the prior art, under the effect of catalyzer, generate methyl tertiary butyl ether, resulting blender composition (being compositions of additives) is little for the scope of boosting of octane rating, so the burning of gasoline is insufficient, the quantity discharged of tail gas CO, HC is big.In addition, because major part be the dimerization or the trimer of alkene in the polymer gasoline, destabilization during storage, its is general only uses with the blending of other agent compositions as the agent composition of stop bracket gasoline, if will add antigum inhibitor when independent storage or use.

The purpose of this invention is to provide a kind of dopes for gasoline composition and method of making the same, polymer gasoline and methyl alcohol are carried out etherification reaction jointly, under the strongly acidic catalyst effect, obtaining corresponding ethers mixture, and further improve its labile factor.

Purpose of the present invention realizes like this: the dopes for gasoline composition, it is formulated in proportion by mixed ether, dimethylbenzene and aniline, said mixed ether is formulated in proportion by methyl tertiary butyl ether, methyl amylether, Ethyl Tertisry Butyl Ether, and their percentage composition is respectively:

Mixed ether 60-80%

Dimethylbenzene 15-35%

Aniline 5%

The best blending ratio of this compositions of additives is respectively: mixed ether 65%, dimethylbenzene 30%, aniline 5%.

Methyl tertiary butyl ether 10-35%, methyl amylether 40-60%, Ethyl Tertisry Butyl Ether 5-50% in the wherein said mixed ether.

This dopes for gasoline preparation of compositions method mainly contains following steps:

1) producing of mixed ether:

C in a, the not separated liquefied gas ₃-C ₄Alkene, reaction obtains the dipolymer of superimposed alkene through catalytic polymerization, and operational condition: 350 ℃ of temperature, pressure 0.5MPa, weight space velocity are 1.5h ^-1

The dipolymer of b, superimposed alkene and methyl alcohol, ethanol obtain the ether alcohol mixture, operational condition by 3: 1: 1 material proportion through etherification reaction: 200 ℃ of temperature, pressure 15Mpa;

C, ether alcohol mixture obtain mixed ether after the washing dealcoholysis,

2) producing of compositions of additives:

After mixing, mixed ether, dimethylbenzene, aniline obtains the compositions of additives of stop bracket gasoline.

The present invention has mainly adopted catalytic polymerization reaction and etherification reaction process.Referring to Fig. 1, the main technique flow process: lighter hydrocarbons are so incensed that not separated liquefied gas (putting forward the gas process) through carrying, alkene reacts through catalytic polymerization in the not separated liquefied gas, form superimposed product (catalytic polymerization reaction process) methyl alcohol and small amount of ethanol and superimposed product and carry out etherification reaction (etherification procedure) jointly, unreacted methanol, alcoholic acid Separation and Recovery five processes such as (sepn processes).1), put forward the gas process: lighter hydrocarbons are 100 ℃ temperature, and carrying atmospheric pressure is 5kg/cm ²Condition under pull out gas, cat head is isolated not separated liquefied petroleum gas (LPG), enters surge tank through stabilizer tower, isolates lightweight oil at the bottom of the tower.2), catalytic polymerization: without the C in the parting liquid gasification ₃～C ₄Alkene enter superposition reactor, at 350 ℃ temperature, 0.5MP _aPressure, weight space velocity is 1.5h ^-1Condition under, building-up reactions takes place under the effect of SKP-1 type molecular sieve catalyst.Its reaction product is isolated wherein unreacted liquefied petroleum gas (LPG) through filter and separator, has both obtained the superimposed product dipolymer or the trimer of alkene.3), etherification reaction: with methyl alcohol, ethanol and superimposed product with 1: 1: 3 mixed after, after the process charging is heated to 40～50 ℃, enter the purification methyltertiarvbutyl ether reactor from top, scavenging agent is the strongly-acid ion exchange resin, cleaner purifies and a spot of etherification raw material, and the enol mixture enters methyltertiarvbutyl ether reactor then.At 200 ℃ temperature, 15MP _aPressure condition under, as catalyzer, etherification reaction takes place with the strongly-acid ion exchange resin.4), sepn process: in the reaction product of coming out by methyltertiarvbutyl ether reactor, unreacted alkene, remaining methyl alcohol, small amount of ethanol, and a spot of side reaction product are arranged still.Because alcohols has bigger influence to composite additive for gasoline, so need through sepn process.The present invention adopts the way of washing that alcohols is separated from mixed ether, and repeatedly the raffinate after the washing proposes alcohols continuation use after fractionation, has both obtained mixed ether.5), blending process: mixed ether, dimethylbenzene, aniline obtain composite additive for gasoline after mixing in tempering tank with 65: 35: 5 ratio.

Its principal reaction equation is:

The main raw material of catalytic polymerization reaction is the C that utilizes without the parting liquid gasification ₃-C ₄Alkene, under certain temperature and pressure condition, on catalyzer, react, but product remains alkene, also can continue to be overlapped into high molecular weight products, only wish to obtain dimer or tripolymer but produce polymer gasoline, do not wish to have too much superpolymer to produce, therefore want suitable control reaction conditions.When building-up reactions carries out, also can follow some side reactions, as isomerization, cyclisation etc.The present invention has selected the skp-1 type molecular sieve building-up reactions catalyzer by the development of Sinopec research institute for use, and this catalyzer has good activity, selectivity and stability, to the raw material unconditional request.

Etherification reaction is that dipolymer or trimeric alkene with methyl alcohol and building-up reactions are main raw material among the present invention, forms the mixed methyl ethers under the effect of strongly-acid ion exchange resin, is the reversible thermopositive reaction in its reaction process, and temperature of reaction low-conversion more is high more.So selecting appropriate catalyst and control reaction conditions also is key of the present invention.In the etherification reaction process, might follow corresponding side reaction, but what influence this compositions of additives is not had.Generate dme as methanol dehydration, further polymerization forms polymer alkene in the alkene; Water reaction in alkene and the raw material forms alcohol etc.Because adopt the way of washing that alcohols is separated from mixed ether among the present invention, repeatedly the raffinate after the washing proposes alcohols and continues to use after fractionation.

Following is the accompanying drawing of this specification sheets:

Fig. 1 is the compositions of additives of preparation stop bracket gasoline and the process flow sheet of stop bracket gasoline.

Fig. 2 is to use the continuous gear shift ramp characteristic of the automobile of this gasoline.

Fig. 3 is to use the direct gear shift ramp characteristic of the automobile of this gasoline.

Fig. 4 is the graph of a relation of aromaticity content and gasoline octane rating.

Enforcement of the present invention and result of use thereof are described in detail in detail in conjunction with the accompanying drawings:

Consider to use a spot of aromatic hydrocarbons such as toluene, dimethylbenzene in the present invention.Its reason is: aromatic hydrocarbons is compared with alkane, and under identical carbon containing said conditions, the carbon content of aromatic hydrocarbons, density, boiling point, octane value and heat of gasification are equivalent all high.But high and low calorific value, hydrogen content, chemically correct fuel, theoretical mixture gas calorific value etc. are all than low with carbon number alkane.

Be that aromaticity content is to 70 below ^#The influence of gasoline octane rating: with commercially available 70 ^#Gasoline is reference oil, to wherein adding aromatic hydrocarbons, its test-results: see Table and Fig. 4

Sequence number	Aromaticity content (%) v/v	Octane value (RON)
			1	12.5	79.2
2	18	82
			3	22.5	92.8
4	25	94.3

As seen from Figure 4,70 ^#Increase aromaticity content in the gasoline, can make octane value 70 ^#The octane value of gasoline increases, but its volume percent dosage is not obvious in 18% scope, after addition surpasses 18%, octane value (RON) just has obvious ascendant trend, but aromaticity content is excessive, the incomplete possibility of gasoline combustion is just big, so the amount that adds aromatic hydrocarbons in the compositions of additives of the present invention must strict control.It has adopted orthogonal experiment, has determined the optimal addn of each material: get mixed ether 65%, dimethylbenzene 30%, aniline 5%.

Its compound method and process are: (is example with blending 10kg composite additive for gasoline)

1, producing of mixed ether:

1) lighter hydrocarbons with 120kg pass through distillation tower, at 100 ℃ temperature, 5kg/cm ²Pressure condition under pull out gas, overhead gas is through entering surge tank, the C in the not separated liquefied petroleum gas (LPG) behind the stabilizer tower ₃-C ₄Alkene is at pressure, the weight space velocity 1.5h of 350 ℃ temperature, 0.5Mpa ^-1Condition under, building-up reactions takes place under the katalysis of SKP-1 type molecular sieve, obtain superimposed product (dipolymer or trimer) 10.8Kg;

2) with methyl alcohol, ethanol and superimposed product (dipolymer or trimer) with after 1: 1: 3 the mixed, under the pressure condition of 200 ℃ temperature, 15Mpa, as catalyzer, etherification reaction takes place with the strongly-acid ion exchange resin;

3) with etherificate product process water wash column, flush away is unreacted methanol, ethanol wherein, obtains mixed ether 6.5Kg.

2, get the aniline mixing and stirring of the dimethylbenzene of mixed ether, 3.0Kg of 6.5Kg and 0.5Kg after, obtain the compositions of additives 10Kg. (aniline is provided by western An Haili petrochemical industry Science and Technology Ltd.) of stop bracket gasoline.

The new compositions of additives that will obtain below is mixed in the situation in the low octane value gasoline:

After the 1 new compositions of additives with the catalytic gasoline of 8.5Kg and 1.5Kg mixes, both obtained 93 of 10Kg ^#Agent composition gasoline.

2 with catalytic gasoline and the straight-run spirit ratio furnishing base oil (70 with 1.3: 1 ^#), form 90 of 10Kg after getting the base oil of 7.3Kg and the new compositions of additives mixing and stirring of 2.7kg ^#Agent composition gasoline.

3 with catalytic gasoline and the straight-run spirit ratio furnishing base oil (70 with 1.5: 1 ^#), get and form 90 of 10Kg after the new compositions of additives mixing and stirring of 7.5Kg base oil and 2.5kg ^#Agent composition gasoline.

The technology quality index of product sees table: (examine through Shaanxi Province's petroleum products quality testing station

Survey)

Project	Quality index	Measured data	Experimental technique	The individual event evaluation
					Anti-knocking property:
Research octane number (RON) (RON) is not less than	93	93.9	GB/T	Qualified

Often: urge=1: 1.5	25％	90
			Often: urge=1: 1.3	27％	90.3

Bench testing:

After the HH368Q petrol motor uses No. 93 agent composition gasoline (gained gasoline of the present invention), compare with using RON93 gasoline, the external characteristics peak power has increased 0.7kw; Effective specific fuel consumption on average descends 2.3%; CO in the discharging has descended 20.0%, and HC has descended 10.3%.

Actual road test: (shown in Fig. 2,3)

A, Santana's 330k88lolTD2 automobile use No. 93 agent composition gasoline and compare with using RON93 gasoline, and the 0-90km/h gear shift pick-up period shortens 0.9 second, and the 25-90km/h direct high pick-up period shortens 1.0 seconds.

B, Santana's 330k88lolTDL2 automobile use No. 93 agent composition gasoline and compare with using RON93 gasoline, and a fuel consumption per hundred kilometers descends 6.5%;

C, Santana's 330k88lolTDL2 automobile use No. 93 agent composition gasoline and compare with using RON93 gasoline, and minimum stabilizing speed reduces 2.4km/h.

Claims (3)

1, a kind of dopes for gasoline composition, it is characterized in that it is formulated in proportion by mixed ether, dimethylbenzene and aniline, said mixed ether is formulated in proportion by methyl tertiary butyl ether, methyl amylether, Ethyl Tertisry Butyl Ether, and their percentage composition is respectively:

Mixed ether 60-80%

Dimethylbenzene 15-35%

Aniline 5%

Wherein methyl tertiary butyl ether 10-35%, methyl amylether 40-60%, Ethyl Tertisry Butyl Ether 5-50% in the mixed ether,

2, dopes for gasoline composition according to claim 1 is characterized in that the blending ratio of said composition is respectively: mixed ether 65%, dimethylbenzene 30%, aniline 5%.

3, a kind of dopes for gasoline preparation of compositions method is characterized in that it has following steps to finish:

1) producing of mixed ether:

C in a, the not separated liquefied gas ₃-C ₄Alkene, reaction obtains the dipolymer of superimposed alkene through catalytic polymerization, and operational condition: 350 ℃ of temperature, pressure 0.5MPa, weight space velocity are 1.5h ^-1

The dipolymer of b, superimposed alkene and methyl alcohol, ethanol obtain the ether alcohol mixture, operational condition by 3: 1: 1 material proportion through etherification reaction: 200 ℃ of temperature, pressure 15Mpa;

C, ether alcohol mixture obtain mixed ether after the washing dealcoholysis,

2) producing of compositions of additives:

After mixing, mixed ether, dimethylbenzene, aniline obtains the interpolation composition of stop bracket gasoline.

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