CN102627985B - Gasoline and diesel oil additive composition and preparation method and application thereof - Google Patents
Gasoline and diesel oil additive composition and preparation method and application thereof Download PDFInfo
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- CN102627985B CN102627985B CN201210096253.4A CN201210096253A CN102627985B CN 102627985 B CN102627985 B CN 102627985B CN 201210096253 A CN201210096253 A CN 201210096253A CN 102627985 B CN102627985 B CN 102627985B
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- 239000003502 gasoline Substances 0.000 title claims abstract description 108
- 239000000654 additive Substances 0.000 title claims abstract description 103
- 230000000996 additive effect Effects 0.000 title claims abstract description 101
- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 153
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000002131 composite material Substances 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000009835 boiling Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007259 addition reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 34
- -1 glycol dimethyl ethers Chemical class 0.000 claims description 20
- 238000010306 acid treatment Methods 0.000 claims description 9
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 9
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- AHJWSRRHTXRLAQ-UHFFFAOYSA-N tetramethoxymethane Chemical compound COC(OC)(OC)OC AHJWSRRHTXRLAQ-UHFFFAOYSA-N 0.000 claims description 5
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 63
- 239000000446 fuel Substances 0.000 abstract description 27
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000003254 gasoline additive Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 25
- 239000003921 oil Substances 0.000 description 22
- 239000002994 raw material Substances 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 18
- 238000005520 cutting process Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- QFNSAOSWJSCHID-UHFFFAOYSA-N 2-butylbenzenesulfonic acid Chemical compound CCCCC1=CC=CC=C1S(O)(=O)=O QFNSAOSWJSCHID-UHFFFAOYSA-N 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000002828 fuel tank Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 0 *c(nc1)ccc1S(O)(=O)=O Chemical compound *c(nc1)ccc1S(O)(=O)=O 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention provides a method for preparing a gasoline and diesel oil additive composition. The method comprises the following steps of: performing addition and dehydration reaction on glycol, trioxymethylene and methanol in the mole ratio of 1: (0.5-3.5): (1.0-6.0) under the action of an acidic ionic liquid catalyst for 2 to 8 hours at the temperature of 65 to 140 DEG C to generate a mixture containing dimethoxymethane and bidimethoxyethane; and separating the mixture, wherein the dimethoxymethane-containing product with low boiling point is a gasoline additive composition, and the bidimethoxyethane-containing product with high boiling point is a diesel oil additive composition. The reaction process is high in controllability, reaction equipment is readily available, the operation is simple, the applicability of the reaction products is relatively good in distribution, the total yield of the products is high, and the economic benefit is good. The invention also provides a composite oil product prepared from the gasoline and diesel oil additive composition, and the performance of the composite oil product meets the quality index requirement on commoditization of automotive fuels.
Description
Technical field
The present invention relates to clean oxygen containing vehicle fuel field, relate in particular to vapour, composition of additive for diesel oil, the Preparation Method And The Use by ethylene glycol, methyl alcohol, paraformaldehyde, prepared.
Background technology
Along with social progress, rolling up of automobile, bring oil-fired a large amount of consumption and cause the severe contamination of environment, so research and development are with raw material such as the methyl alcohol of coal production, formaldehyde etc., it is further changed into the interpolation component of alternative vehicle fuel, so both can increase vehicle fuel source, can reduce again the pollution of environment.
Methylal(dimethoxymethane) (claiming again methylal), two glycol dimethyl ether, polymethoxy methylal are that the ideal of novel fuel for cleaning vehicle is added component, and containing widespread use in the vehicle fuel of methyl alcohol, itself can promote oil product burning containing oxygen, reduces NO
x, the discharge of CO and the phenomenon of tail gas over-emitting black exhaust, reduced the pollution to environment, the desirable performance of adding component of above-mentioned novel vehicle fuel shows again with gasoline, diesel oil has the good stability of dissolving each other.If the physical and chemical performance index of adding the compound oil product obtaining in vapour, diesel oil to by certain amount all meets the requirement of vehicle fuel oil product, can reduce the production cost of vehicle fuel.
The various reports about Methylal(dimethoxymethane) synthetic method have recently been there are, comprising: adopting methyl alcohol and trioxymethylene (or highly concentrated formaldehyde solution) is raw material, and method and the Methylal(dimethoxymethane) of under the existence that is catalyzer at sulfuric acid, alkyl pyridine sulfonic acid, alkyl benzene sulphonate (ABS), ion exchange resin, preparing Methylal(dimethoxymethane) add the purposes of component as gasoline; Adopting methyl alcohol, methylal, trioxymethylene is raw material, and under the effect of ionic-liquid catalyst, method and the polymethoxy methylal of through the compressive reaction of heating, preparing polymethoxy methylal add the purposes of component as diesel oil.Chinese patent application 200810116763.7 discloses a kind of method that methyl alcohol and paraformaldehyde be raw material production Methylal(dimethoxymethane) of take, but the transformation efficiency of this reaction raw materials is lower.Therefore, need to find a kind of more effective preparation to be suitable as vapour, the vapour of diesel oil ideal composition, the method for diesel-dope, and meet the commercial quality index requirement of vehicle fuel.
Summary of the invention
The present inventor has now found that, in methyl alcohol and paraformaldehyde, introduce ethylene glycol, choosing acidic ion liquid is catalyzer, under suitable reaction conditions and separation condition, can obtain vapour, composition of additive for diesel oil, reaction raw materials utilization ratio is high, reaction product performance profile is better, and the compositions of additives making can meet the requirement as ideal composition in vapour, diesel oil vehicle fuel completely.
Therefore, it is a kind of by methyl alcohol that one of object of the present invention is to provide, paraformaldehyde and ethylene glycol are prepared the method for composite additive for gasoline and composition of additive for diesel oil, described method comprises: ethylene glycol, trioxymethylene and methyl alcohol carry out addition and dehydration reaction under the effect of acidic ionic liquid catalysts, ethylene glycol wherein: trioxymethylene: the mol ratio of methyl alcohol is 1: 0.5-3.5: 1.0-6.0, temperature of reaction is 65-140 ℃, under normal pressure, react 2-8 hour, the mixture that generation contains two glycol dimethyl ethers and Methylal(dimethoxymethane), described mixture is carried out to separation and obtain two cut section products, the low-boiling products that wherein contains Methylal(dimethoxymethane) is composite additive for gasoline, the high boiling point product that contains two glycol dimethyl ethers is composition of additive for diesel oil.
According to a preferred implementation of the inventive method, described acidic ionic liquid catalysts is selected from sulfuric acid, pyridine-sulfonic acid, alkyl pyridine sulfonic acid, Phenylsulfonic acid or alkyl benzene sulphonate (ABS).
According to another preferred implementation of the inventive method, the consumption of described acidic ionic liquid catalysts is the 0.1-10 quality % of ethylene glycol, trioxymethylene and the total consumption of methyl alcohol, is preferably 5-10 quality %.
In a preferred implementation of the inventive method, described acidic ionic liquid catalysts is that pyridine-sulfonic acid or structural formula are
alkyl pyridine sulfonic acid, wherein R is C
1-C
4alkyl.
In another preferred implementation of the inventive method, described acidic ionic liquid catalysts is that Phenylsulfonic acid or structural formula are
alkyl benzene sulphonate (ABS), wherein R ' is C
1-C
12alkyl.Described Phenylsulfonic acid or alkyl benzene sulphonate (ABS) can be prepared according to conventional sulfonation reaction,, take aromatic hydrocarbon and the vitriol oil as raw material that is, under the temperature of reaction of 40-60 ℃, sulfonation reaction occur, and generate Phenylsulfonic acid required for the present invention or alkyl benzene sulphonate (ABS).In the present invention, described Phenylsulfonic acid or alkyl benzene sulphonate (ABS) preferably make as follows: in the reaction system that contains ethylene glycol, trioxymethylene and methyl alcohol, add in advance aromatic hydrocarbon and the vitriol oil, under the reaction conditions of 40-60 ℃, carry out in advance sulfonation reaction, making the Phenylsulfonic acid of generation or the amount of alkyl benzene sulphonate (ABS) is the 0.1-10 quality % of ethylene glycol in reaction system, trioxymethylene and methyl alcohol total amount, is preferably 5-10 quality %.
In the present invention, the mixture that can adopt routine techniques to generate reaction carries out separation, preferably adopts distillation technique to carry out separation.
According to a preferred embodiment of the present invention, the mixture that reaction is generated carries out fractionation by distillation, obtain two cut section products, wherein, the low-boiling products that contains Methylal(dimethoxymethane) is composite additive for gasoline, the high boiling point product that contains two glycol dimethyl ethers is composition of additive for diesel oil, and the yield of described composite additive for gasoline is 45-50%, and the yield of described composition of additive for diesel oil is 40-45%.
According to another preferred embodiment of the present invention, the described method of preparing composite additive for gasoline and composition of additive for diesel oil comprises: ethylene glycol, trioxymethylene and methyl alcohol carry out addition and dehydration reaction under the effect of acidic ionic liquid catalysts, ethylene glycol wherein: trioxymethylene: the mol ratio of methyl alcohol is 1: 0.5-3.5: 1.0-6.0, temperature of reaction is 65-140 ℃, under normal pressure, react 2-8 hour, the mixture that generation contains two glycol dimethyl ethers and Methylal(dimethoxymethane), according to the difference of boiling range, described mixture is carried out to fractionation by distillation, cut out two cut section products of initial boiling point to 125 ℃ and 125 ℃ to 180 ℃, wherein, using the cut from initial boiling point to 125 ℃ as the described low-boiling products that contains Methylal(dimethoxymethane), then dewater except acid treatment, obtain described composite additive for gasoline, using the cut from 125 ℃ to 180 ℃ as the described high boiling point product that contains two glycol dimethyl ethers, then dewater except acid treatment, obtain described composition of additive for diesel oil.
According to further preferred embodiment of the present invention, in the described low-boiling products that contains Methylal(dimethoxymethane), also comprise 1,2-glycol dimethyl ether, dimethoxy methylal and DOX, described in contain two glycol dimethyl ethers high boiling point product in also comprise polymethoxy methylal.
In method provided by the present invention, ethylene glycol, trioxymethylene and methyl alcohol carry out addition and dehydration reaction under the effect of acidic ionic liquid catalysts, and reaction mechanism is as follows:
(1) formaldehyde and methyl alcohol generate Methylal(dimethoxymethane) (claiming again methylal) by nucleophilic addition(Adn), intermolecular dehydration reaction, and reaction formula is:
H-CHO+2CH
3-OH->CH
3-O-CH
2-O-CH
3+H
2O
(2) ethylene glycol and formaldehyde generation addition reaction generate hemiacetal, then with methyl alcohol, the two glycol dimethyl ethers of intermolecular dehydration reaction generation occur, and reaction formula is:
HO-CH
2-CH
2-OH+2H-CHO->HO-CH
2-O-CH
2-CH
2-O-CH
2-OH
HO-CH
2-O-CH
2-CH
2-O-CH
2-OH+2CH
3-OH
->CH
3-O-CH
2-O-CH
2-CH
2-O-CH
2-O-CH
3+2H
2O
(3) there is intermolecular dehydration generation 1,2-glycol dimethyl ether in ethylene glycol and methyl alcohol, and reaction formula is:
HO-CH
2-CH
2-OH+2CH
3-OH->CH
3-O-CH
2-CH
2-O-CH
3+2H
2O
(4) formaldehyde and methyl alcohol generate dimethoxy methylal by nucleophilic addition(Adn), intermolecular dehydration reaction, and reaction formula is:
2H-CHO+2CH
3-OH->CH
3-O-CH
2-O-CH
2-O-CH
3+H
2O
(5) there is intermolecular dehydration generating glycol methyl ether in ethylene glycol and methyl alcohol, and reaction formula is:
HO-CH
2-CH
2-OH+H-CHO->CH
3-O-CH
2-CH
2-OH+H
2O
(6) ethylene glycol and formaldehyde generate DOX by addition cyclodehydration, and reaction formula is:
(7) there is intermolecular dehydration generation dme in methyl alcohol, and reaction formula is:
CH
3-OH+CH
3-OH->CH
3-O-CH
3+H
2O
(8) formaldehyde and methyl alcohol generate polymethoxy methylal by addition, polymerization, intermolecular dehydration, and reaction formula is:
nH-CHO+2CH
3-OH->CH
3-O-(CH
2-O)
n-CH
3+H
2O，n＝3～7
Wherein, reaction (1) and (2) belongs to main reaction, generates principal product: Methylal(dimethoxymethane) and two glycol dimethyl ether; Reaction (3)-(7) belong to side reaction, generate by product: dimethoxy methylal, ethylene glycol monomethyl ether, DOX, polymethoxy methylal, 1,2-glycol dimethyl ether and dme.
As can be seen here, the major and minor product generating in reaction is more, and generate 1, the mutual solubility of 2-glycol dimethyl ether, dimethoxy methylal and DOX and gasoline is good, is all suitable as gasoline ideal composition; Flash-point and the cetane value of described polymethoxy methylal are high, good with the mutual solubility of diesel oil, are suitable as diesel oil ideal composition.Therefore, adopt and provided by the present inventionly take ethylene glycol, trioxymethylene and methyl alcohol and prepare the method for vapour, composition of additive for diesel oil as raw material, can be by controlling mol ratio, temperature of reaction and the reaction times of reactant feed, make major and minor reaction that reaction raw materials ethylene glycol, trioxymethylene and methyl alcohol occurs under the effect of acidic ionic liquid catalysts all more (alcohol aldehyde addition, condensation and dehydration reaction mainly occur), and the major and minor product being generated by above-mentioned major and minor reaction is all suitable as the binder component of oxygen containing vehicle fuel.
And, adopt preparation method provided by the present invention, the mixture that only need to generate reaction be taked suitable separating step and purifying treatment, the composite additive for gasoline that is suitable as gasoline ideal composition that just mixture of generation can be cut into component distribution is suitable, the excellent property that is mixed, yield is relatively high and be suitable as the composition of additive for diesel oil of diesel oil ideal composition.In the present invention, described separating step can adopt routine techniques, preferably adopts distillation technique to carry out separation; Described purifying treatment comprises dehydration and removes acid treatment.
In the present invention, the yield of described composite additive for gasoline=(total mass of the reaction raw materials of the quality/input of composite additive for gasoline) * 100%; The yield of described composition of additive for diesel oil=(total mass of the reaction raw materials of the quality/input of composition of additive for diesel oil) * 100%.
Another object of the present invention is to provide the composite additive for gasoline and the composition of additive for diesel oil that by aforesaid method, make.Described composition can meet the requirement as ideal composition in vapour, diesel oil vehicle fuel completely.
A further object of the present invention is to provide the purposes that above-mentioned composite additive for gasoline and composition of additive for diesel oil are respectively used to prepare compound vapour, diesel product, with the 10-30% based on described compound vapour, diesel product quality, the preferred ratio of 10-20%, described composite additive for gasoline and composition of additive for diesel oil are added into respectively and in vapour, diesel oil, prepare composite gasoline product and compound diesel product.Adopt vapour of the present invention, composition of additive for diesel oil, can directly add to and in vapour, diesel oil, prepare composite fuel product, composite additive for gasoline of the present invention can also with methanol mixed after as additive, add to and in gasoline, prepare composite gasoline product.
Therefore, another object of the present invention is to provide a kind of composite gasoline product and compound diesel product, in described composite gasoline product, contain the 10-30 quality % of the total mass based on this composite gasoline product, the composite additive for gasoline that preferably 10-20 quality % is prepared according to aforesaid method, in described compound diesel product, contain the 10-30 quality % of the total mass based on this compound diesel product, the composition of additive for diesel oil that preferably 10-20 quality % is prepared according to aforesaid method.
With respect to prior art, the present invention has following beneficial effect:
(1) the present invention introduces ethylene glycol in raw material, make the component of the product mixtures of reaction generation that variation occur, after suitable separating treatment, can obtain two cut section products, be suitable as respectively the ideal composition of gasoline, diesel oil allotment, the physical and chemical performance that is added to the composite fuel product making in vapour, diesel oil according to certain amount meets the commercial quality index requirement of vehicle fuel, can directly as vehicle fuel, use.
(2) the present invention has selected suitable preparation method and processing condition, impel reaction raw materials to be almost all converted into object product, the total recovery of object product can reach 95%, raw material availability is high, good in economic efficiency, and the major and minor product generating in reaction is all suitable as the ideal composition of oxygen containing vehicle fuel, to reaction mixture carry out suitably separatedly just can obtaining that component distribution is suitable, the excellent property that is mixed, two cut section products that yield is relatively high.In the present invention, utilize ethylene glycol, trioxymethylene, the addition of methyl alcohol, condensation, polymerization, the reaction principles such as dehydration, select suitable preparation method and processing condition, make to be applicable to doing the product generation increase of vehicle fuel ideal composition, unfavorable component (ethylene glycol for example, formaldehyde) transform completely as much as possible, impel ethylene glycol and formaldehyde in reaction raw materials to be almost all converted into object product, the principal product that reaction generates (Methylal(dimethoxymethane) and two glycol dimethyl ether), by product (dme, 1, 2-glycol dimethyl ether, ethylene glycol monomethyl ether, 1, 3-dioxolane, polymethoxy methylal) be all suitable as the ideal composition of oxygen containing vehicle fuel, Methylal(dimethoxymethane) wherein, 1, 1-glycol dimethyl ether, ethylene glycol monomethyl ether, 1, the mutual solubility of 3-dioxolane and gasoline is good, be applicable to doing gasoline dope component, flash-point and the cetane value of two glycol dimethyl ethers and polymethoxy methylal are high, good with the mutual solubility of diesel oil, are applicable to doing diesel-dope component.
(3) the inventive method operates under the temperature of reaction of normal pressure and 65-140 ℃, and reaction conditions is gentle, and the controllability of reaction process is strong, conversion unit is easy to get, simple to operate, and reaction raw materials is all from Coal Chemical Industry, source is abundant, and raw material is easy to get, and greatly reduces the production cost of vehicle fuel.
(4) composite additive for gasoline the present invention being made adds formed composite gasoline in gasoline to the ratio of the 10-30% based on composite gasoline quality, outward appearance is limpid stable, water tolerance better (adds the water of 0.5-1.0 quality % to keep not stratified), and at-30 ℃, place 48 hours, there is not muddy separation phenomenon, can be mixed arbitrarily; Car examination directly perceived, easily light a fire winter, do not produce vapour lock summer, and dynamic property, accelerating ability, startability, oil consumption and commercial gasoline are suitable; The composition of additive for diesel oil that the present invention is made adds the compound diesel forming in diesel oil to the ratio of the 10-30% based on compound diesel quality, flash-point, condensation point, compatibility all meet the requirement of commercial Dissel oil.
(5) to adopt acidic ion liquid be catalyzer in the present invention, and catalyzer is easy to get and catalytic activity is high, consumption is few, and the consumption of described catalyzer is only the 0.1-10 quality % of the total consumption of raw material.
Embodiment
Below in conjunction with specific embodiment, further describe content of the present invention, but scope of the present invention is not subject to the restriction of these embodiment.
The reactor of conventional heating, thermometric, stirring and reflux dewatering device is equipped with in employing, throw in wherein ethylene glycol, trioxymethylene, methyl alcohol and acidic ionic liquid catalysts, ethylene glycol wherein: trioxymethylene: mol ratio=1 of methyl alcohol: 0.5-3.5: 1.0-6.0, the amount of described acidic ionic liquid catalysts is the 0.1-10wt% of ethylene glycol, trioxymethylene and methyl alcohol total amount.Under the reaction conditions of normal pressure and 65-140 ℃, carry out addition and dehydration reaction, wait discharging water, approach after theoretical value, stopped reaction, use water distilling apparatus instead reaction mixture is separated into two cut section products, the high boiling point product that obtains the low-boiling products that contains Methylal(dimethoxymethane) and contain two glycol dimethyl ethers, using described low-boiling products and high boiling point product respectively as composite additive for gasoline and composition of additive for diesel oil with based on compound vapour, the ratio of the 10-20 quality % of diesel product quality is added into commercial gasoline, in diesel oil, obtain compound vapour, diesel product.
Embodiment 1:
Get 60 grams of ethylene glycol, 30 grams of trioxymethylenes, 80 grams of methyl alcohol, 8 grams of toluene sulfonic acides, temperature of reaction is controlled at 100 ℃, reacts after 4 hours, the reaction mixture obtaining is carried out to cutting and separating, and wherein the yield of composite additive for gasoline is 46%, and the yield of composition of additive for diesel oil is 45%.
Embodiment 2:
Get 45 grams of ethylene glycol, 45 grams of trioxymethylenes, 80 grams of methyl alcohol, 8 grams of toluene sulfonic acides, temperature of reaction is controlled at 125 ℃, reacts after 4 hours, the reaction mixture obtaining is carried out to cutting and separating, and wherein the yield of composite additive for gasoline is 46%, and the yield of composition of additive for diesel oil is 43%.
Embodiment 3:
Get 45 grams of ethylene glycol, 45 grams of trioxymethylenes, 100 grams of methyl alcohol, 8 grams of toluene sulfonic acides, temperature of reaction is controlled at 125 ℃, reacts after 4 hours, the reaction mixture obtaining is carried out to cutting and separating, and wherein the yield of composite additive for gasoline is 50%, and the yield of composition of additive for diesel oil is 42%.
Embodiment 4:
Get 45 grams of ethylene glycol, 60 grams of trioxymethylenes, 120 grams of methyl alcohol, 8 grams of toluene sulfonic acides, temperature of reaction is controlled at 125 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 50%, and the yield of composition of additive for diesel oil is 45%.
Embodiment 5:
Get 30 grams of ethylene glycol, 60 grams of trioxymethylenes, 80 grams of methyl alcohol, 8 grams of toluene sulfonic acides, temperature of reaction is controlled at 125 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 46%, and the yield of composition of additive for diesel oil is 45%.
Embodiment 6:
Get 30 grams of ethylene glycol, 60 grams of trioxymethylenes, 100 grams of methyl alcohol, 8 grams of isopropyl benzene sulfonic acid, temperature of reaction is controlled at 125 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 46%, and the yield of composition of additive for diesel oil is 42%.
Embodiment 7:
Get 30 grams of ethylene glycol, 60 grams of trioxymethylenes, 100 grams of methyl alcohol, 8 grams of isopropyl benzene sulfonic acid, temperature of reaction is controlled at 135 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 50%, and the yield of composition of additive for diesel oil is 40%.
Embodiment 8:
Get 30 grams of ethylene glycol, 45 grams of trioxymethylenes, 80 grams of methyl alcohol, 8 grams of isopropyl benzene sulfonic acid, temperature of reaction is controlled at 120 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 45%, and the yield of composition of additive for diesel oil is 40%.
Embodiment 9:
Get 30 grams of ethylene glycol, 45 grams of trioxymethylenes, 80 grams of methyl alcohol, 8 grams of isopropyl benzene sulfonic acid, temperature of reaction is controlled at 135 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 50%, and the yield of composition of additive for diesel oil is 43%.
Embodiment 10:
Get 60 grams of ethylene glycol, 45 grams of trioxymethylenes, 80 grams of methyl alcohol, 5 grams of n-butylbenzene sulfonic acid, temperature of reaction is controlled at 135 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 46%, and the yield of composition of additive for diesel oil is 45%.
Embodiment 11:
Get 30 grams of ethylene glycol, 45 grams of trioxymethylenes, 80 grams of methyl alcohol, 5 grams of n-butylbenzene sulfonic acid, temperature of reaction is controlled at 110 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 46%, and the yield of composition of additive for diesel oil is 41%.
Embodiment 12:
Get 30 grams of ethylene glycol, 45 grams of trioxymethylenes, 100 grams of methyl alcohol, 5 grams of n-butylbenzene sulfonic acid, temperature of reaction is controlled at 110 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 46%, and the yield of composition of additive for diesel oil is 42%.
Embodiment 13:
Get 30 grams of ethylene glycol, 45 grams of trioxymethylenes, 80 grams of methyl alcohol, 5 grams of n-butylbenzene sulfonic acid, temperature of reaction is controlled at 120 ℃, reacts after 4 hours, by the reaction mixture cutting and separating obtaining, wherein the yield of composite additive for gasoline is 46%, and the yield of composition of additive for diesel oil is 45%.
Embodiment 14:
In the there-necked flask with thermometric, stirring and reflux dewatering device, add 60 grams of ethylene glycol, 90 grams of trioxymethylenes, 64 grams of methyl alcohol, 15 grams of n-butylbenzene sulfonic acid, temperature of reaction is controlled at 80 ℃, react after 8 hours, by the reaction mixture cutting and separating obtaining, wherein, the mixture distillating in the temperature range of initial boiling point to 125 ℃ through dehydration except after acid treatment, as composite additive for gasoline, yield is 45%; At the mixture distillating in the temperature range of 125 ℃ to 180 ℃, after dehydration removes acid treatment, as composition of additive for diesel oil, yield is 40%.
Embodiment 15:
In the there-necked flask with thermometric, stirring and reflux dewatering device, add 62 grams of ethylene glycol, 180 grams of trioxymethylenes, 96 grams of methyl alcohol, 20 grams of n-butylbenzene sulfonic acid, temperature of reaction is controlled at 100 ℃, react after 3 hours, by the reaction mixture cutting and separating obtaining, wherein, the mixture distillating in the temperature range of initial boiling point to 125 ℃ through dehydration except after acid treatment, as composite additive for gasoline, yield is 46%; At the mixture distillating in the temperature range of 125 ℃ to 180 ℃, after dehydration removes acid treatment, as composition of additive for diesel oil, yield is 41%.
Embodiment 16:
In the there-necked flask with thermometric, stirring and reflux dewatering device, add 62 grams of ethylene glycol, 240 grams of trioxymethylenes, 128 grams of methyl alcohol, 20 grams of n-butylbenzene sulfonic acid, temperature of reaction is controlled at 140 ℃, react after 5 hours, by the reaction mixture cutting and separating obtaining, wherein, the mixture distillating in the temperature range of initial boiling point to 125 ℃ is after purifying treatment, as composite additive for gasoline, yield is 50%; The mixture distillating in the temperature range of 125 ℃ to 180 ℃ is after purifying treatment, and as composition of additive for diesel oil, yield is 45%.
The Preparation Example 1-13 of composite fuel product
Getting the composite additive for gasoline that makes in above-described embodiment 1-13 and composition of additive for diesel oil adds to respectively in commercial Dissel oil and gasoline and is mixed, obtain compound diesel product 1-13 and composite gasoline product 1-13, its outward appearance is the liquid of transparent and stable, and wherein the addition of two kinds of compositions of additives is respectively the 10-20 quality % of composite fuel product.After testing, the boiling range of the composite gasoline product obtaining, vapour pressure, water tolerance, being mixed property, low temperature resisting phase separation all meet the requirement of commercial gasoline, and discharge index during actual use meets environmental requirement; The flash-point of the compound diesel product obtaining, CN value (cetane value), condensation point and calorific value all meet the requirement of commercial Dissel oil, and discharge index during actual use meets environmental requirement.
The Preparation Example 14 of composite fuel product
Get the composite additive for gasoline after purifying treatment that 1.5 mass parts are made by embodiment 14, be placed in flask, in flask, add No. 93 gasoline of 8.5 mass parts, fully rock flask it is mixed, result forms the composite gasoline 14 of transparent and stable.Through actual performance, detect, the boiling range of composite gasoline 14, vapour pressure and former commercial gasoline are basically identical, and discharge index meets the emission request of national III stage vehicular pollutant.
The composition of additive for diesel oil after purifying treatment being made by embodiment 14 of separately getting 2 mass parts, is placed in flask, adds No. 0 diesel oil of 8 mass parts in flask, fully rocks flask it is mixed, and result forms the compound diesel 14 of transparent and stable.Through actual performance, detect, the flash-point of compound diesel 14, CN value (cetane value), condensation point and calorific value and former commercial Dissel oil are basically identical, and discharge index meets the emission request of national III stage vehicular pollutant.
The Preparation Example 15 of composite fuel product
Get the composite additive for gasoline after purifying treatment that 1 mass parts is made by embodiment 15, be placed in flask, add No. 93 gasoline of 9 mass parts in flask, fully rock flask it is mixed, result forms the composite gasoline 15 of transparent and stable.Through actual performance, detect, the boiling range of composite gasoline 15, vapour pressure and former commercial gasoline are basically identical, and discharge index meets the emission request of national III stage vehicular pollutant.
The composition of additive for diesel oil after purifying treatment being made by embodiment 15 of separately getting 2 mass parts, is placed in flask, adds No. 0 diesel oil of 8 mass parts in flask, fully rocks flask it is mixed, and result forms the compound diesel 15 of transparent and stable.Through actual performance, detect, the flash-point of compound diesel 15, CN value (cetane value), condensation point and calorific value and former commercial Dissel oil are basically identical, and discharge index meets the emission request of national III stage vehicular pollutant.
The Preparation Example 16 of composite fuel product
Get the composite additive for gasoline after purifying treatment that 1.5 mass parts are made by embodiment 16, be placed in flask, in flask, add No. 93 gasoline of 8.5 mass parts, fully rock flask it is mixed, result forms the composite gasoline 16 of transparent and stable.Through actual performance, detect, the boiling range of composite gasoline 16, vapour pressure and former commercial gasoline are basically identical, and discharge index meets the emission request of national III stage vehicular pollutant.
The composition of additive for diesel oil after purifying being made by embodiment 16 of separately getting 3 mass parts, is placed in flask, adds No. 0 diesel oil of 7 mass parts in flask, fully rocks flask it is mixed, and result forms the compound diesel 16 of transparent and stable.Through actual performance, detect, the flash-point of compound diesel 16, CN value (cetane value), condensation point and calorific value and former commercial Dissel oil are basically identical, and discharge index meets the emission request of national III stage vehicular pollutant.
The commercial gasoline adopting in above-described embodiment, commercial Dissel oil are respectively No. 93 gasoline and No. 0 diesel oil purchased from PetroChina Company Limited.'s Company Shanxi Branch.No. 93 gasoline and No. 0 diesel oil for above-described embodiment meet respectively state III motor spirit quality index and state III derv fuel oil quality index, and its physicochemical property parameter is listed in table 1 and table 2 respectively.In addition, compound diesel 1-10, the 14-16 making by above-described embodiment and the physicochemical property parameter of composite gasoline 1-10,14-16 are listed in table 1 and table 2 respectively.
The oil consumption of composite fuel product and the test of dynamic property road travel
Testing method:
First the excess oil in test vehicle fuel tank is drained only, and clean fuel tank, oil filter, then fill it up with composite gasoline, certain mileage number (more than 100 kilometers) travels, and the stability of testing dynamic property, accelerating ability, running at high speed, after test finishes, fuel tank metering is filled, institute's complement amount is exactly the Actual Burnoff amount of test actual service life again, and method of calculation are: hundred kilometers of oil consumption=(Actual Burnoff amount/actual travel mileage number) * 100.
Test vehicle: gasoline version Jetta and diesel oil version Jetta
Test oil product: composite gasoline 1-10,14-16 and compound diesel 1-10,14-16
Test-results: composite gasoline 1-10,14-16 are through the road travel test of gasoline version Jetta, and the stability of engine idle, dynamic property, accelerating ability, high-speed cruising etc. are functional, there is no notable difference.And as shown in table 4, the oil consumption of the oil consumption of composite gasoline 1-10,14-16 and No. 93 gasoline is basic identical, therefore, above-mentioned composite gasoline can replace commercial gasoline to use completely.In addition, as shown in table 2, composite gasoline 1-10,14-16 all meet state III motor spirit standard, and its tail gas discharging pollutant meets the emission request of national III stage vehicular pollutant completely.
In addition, compound diesel 1-10,14-16 are through the road travel test of diesel oil version Jetta, and the stability of engine idle, dynamic property, accelerating ability, high-speed cruising etc. are functional, there is no notable difference; And as shown in table 3, the oil consumption of the oil consumption of compound diesel 1-10,14-16 and No. 0 diesel oil is basic identical, therefore, above-mentioned compound diesel can replace commercial Dissel oil to use completely.In addition, as shown in table 1, compound diesel 1-10,14-16 all meet state III derv fuel oil standard, and its tail gas discharging pollutant meets the emission request of national III stage vehicular pollutant.
As can be seen here, the production cost of the composite fuel product that the composite additive for gasoline being obtained by the inventive method and composition of additive for diesel oil make is low, and profit margin is large, good in economic efficiency, and discharge index meets environmental requirement.
Claims (13)
1. a method of preparing composite additive for gasoline and composition of additive for diesel oil, it is characterized in that, described method comprises: ethylene glycol, trioxymethylene and methyl alcohol carry out addition and dehydration reaction under the effect of acidic ionic liquid catalysts, ethylene glycol wherein: trioxymethylene: the mol ratio of methyl alcohol is 1:0.5-3.5:1.0-6.0, temperature of reaction is 65-140 ℃, under normal pressure, react 2-8 hour, the mixture that generation contains two glycol dimethyl ethers and Methylal(dimethoxymethane), described mixture is carried out to separation and obtain two cut section products, the low-boiling products that wherein contains Methylal(dimethoxymethane) is composite additive for gasoline, the high boiling point product that contains two glycol dimethyl ethers is composition of additive for diesel oil, the wherein said low-boiling products that contains Methylal(dimethoxymethane) is the cut from initial boiling point to 125 ℃, the described high boiling point product that contains two glycol dimethyl ethers is the cut from 125 ℃ to 180 ℃.
2. method according to claim 1, is characterized in that, described acidic ionic liquid catalysts is selected from pyridine-sulfonic acid, alkyl pyridine sulfonic acid, Phenylsulfonic acid or alkyl benzene sulphonate (ABS).
3. method according to claim 2, is characterized in that, the consumption of described acidic ionic liquid catalysts is the 0.1-10 quality % of ethylene glycol, trioxymethylene and the total consumption of methyl alcohol.
4. method according to claim 3, is characterized in that, the consumption of described acidic ionic liquid catalysts is the 5-10 quality % of ethylene glycol, trioxymethylene and the total consumption of methyl alcohol.
5. method according to claim 3, is characterized in that, described acidic ionic liquid catalysts is that pyridine-sulfonic acid or structural formula are
alkyl pyridine sulfonic acid, wherein R is C
1-C
4alkyl.
6. method according to claim 3, is characterized in that, described acidic ionic liquid catalysts is that Phenylsulfonic acid or structural formula are
alkyl benzene sulphonate (ABS), wherein R ' is C
1-C
12alkyl.
7. method according to claim 1, it is characterized in that, according to the difference of boiling range, described mixture is carried out to fractionation by distillation, cut out two cut section products of initial boiling point to 125 ℃ and 125 ℃ to 180 ℃, wherein, using the cut from initial boiling point to 125 ℃ as the described low-boiling products that contains Methylal(dimethoxymethane), then dewater except acid treatment, obtain described composite additive for gasoline; Using the cut from 125 ℃ to 180 ℃ as the described high boiling point product that contains two glycol dimethyl ethers, then dewater except acid treatment, obtain described composition of additive for diesel oil.
8. method according to claim 7, it is characterized in that, in the described low-boiling products that contains Methylal(dimethoxymethane), also comprise 1,2-glycol dimethyl ether, dimethoxy methylal and 1,3-dioxolane, described in contain two glycol dimethyl ethers high boiling point product in also comprise polymethoxy methylal.
9. the method as described in any one in claim 1-8 makes composite additive for gasoline and composition of additive for diesel oil.
10. composite additive for gasoline as claimed in claim 9 and composition of additive for diesel oil are for the preparation of the purposes of compound vapour, diesel product, it is characterized in that, with the 10-30% based on described composite gasoline quality product, described composite additive for gasoline is added into and in gasoline, prepares composite gasoline product, with the 10-30% based on described compound diesel quality product, described composition of additive for diesel oil is added into and in diesel oil, prepares compound diesel product.
11. purposes as claimed in claim 10, it is characterized in that, with the 10-20% based on described composite gasoline quality product, described composite additive for gasoline is added into and in gasoline, prepares composite gasoline product, with the 10-20% based on described compound diesel quality product, described composition of additive for diesel oil is added into and in diesel oil, prepares compound diesel product.
12. 1 kinds of composite gasoline products and compound diesel product, it is characterized in that, the composite additive for gasoline as claimed in claim 9 that contains 10-30 quality % in described composite gasoline product, contains the composition of additive for diesel oil as claimed in claim 9 of 10-30 quality % in described compound diesel product.
13. composite gasoline product as claimed in claim 12 and compound diesel products, it is characterized in that, the composite additive for gasoline as claimed in claim 9 that contains 10-20 quality % in described composite gasoline product, contains the composition of additive for diesel oil as claimed in claim 9 of 10-20 quality % in described compound diesel product.
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| CN109721582B (en) * | 2017-10-30 | 2020-11-13 | 中国石油化工股份有限公司 | Preparation method of 1, 3-oxacycloalkane |
| CN110643398A (en) * | 2019-09-29 | 2020-01-03 | 上海金山廊林实业有限公司 | Gasoline cleaning synergistic oil-saving agent |
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