CN107384490A

CN107384490A - A kind of biogasoline containing additive and its preparation method and application

Info

Publication number: CN107384490A
Application number: CN201710780951.9A
Authority: CN
Inventors: 于仰坤; 时登民
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-09-01
Filing date: 2017-09-01
Publication date: 2017-11-24

Abstract

The invention discloses a kind of biogasoline containing additive and its preparation method and application, belong to clean fuel technical field.The biogasoline raw material of the present invention includes methanol, ferrocene, Tween 80, triethanolamine, n-butanol, oleic acid, ethylene glycol and gasoline, the biogasoline powerful of the present invention, low-carbon environment-friendly, and preparation method is relatively simple, cost is relatively low, the cost of every liter of biogasoline is well below regular gasoline, without transform the engine of vehicles equipped with gasoline engine during application.

Description

A kind of biogasoline containing additive and its preparation method and application

Technical field

The invention belongs to clean fuel technical field, more specifically to a kind of biogasoline containing additive and Its preparation method and application.

Background technology

The expense caused by fossil fuel and environmental problem are growing day by day, and regenerative resource becomes more and more important, opens Hair recyclable fuel can reduce the dependence to fossil fuel, and therefore, current techniques personnel are just in every field to renewable combustion Material is explored and developed.

It is more urgent to find fungible energy source, and methanol is as a kind of low-carbon energy, have abundance, octane number it is high, The advantages that small is polluted, if methanol can be used as into fuel, there is good hair under global energy crisis and the background of environmental pollution Exhibition prospect.For at present, the raw material for producing methanol is mainly coal, natural gas, coal bed gas, oven gas etc., in particular with high-sulfur Colm and oven gas production methanol, can not only improve comprehensive utilization of resources but also can reduce environmental pollution.For production at present, first Alcohol production is the mature industry in China's chemical industry, and simple production process, investment and production cost are all relatively low.China in 2012 Methanol annual capacity is 50,740,000 tons, and about 26,400,000 tons of annual production, production capacity surplus situation is serious.Development of Coal methanol fuel, mend Fill and part substitutes petroleum fuel, China's energy shortage situation can be alleviated, improve comprehensive utilization of resources.But methanol there is no method at present Big content directly applies to vehicles equipped with gasoline engine, because it has severe corrosive, to the anti-corrosion of engine and automobile component metal material Elastomeric material requires very high, and methanol gasoline has Swelling to foam, generally requires to transform engine, So methanol is used as a small amount of additive of motor vehicle fuel at present, the example of widespread adoption is there is no, if so energy Solve methanol high-volume replacing gasoline or substitute ethanol petrol, then future prospect is very wide.

The content of the invention

1. to solve the problems, such as

Vehicles equipped with gasoline engine, and if the content of methanol can not be directly widely used in for methanol fuel in the prior art Higher, the problem of needing to transform engine, present invention offer is a kind of to contain the biogasoline of additive and its preparation side Method and application, biogasoline of the invention can largely using methanol in the case of engine need not be transformed, while institute The petrol power made is powerful, and calorific value is higher, low-carbon environment-friendly, and preparation method is relatively simple, and cost is relatively low, every liter of biogasoline Cost is well below regular gasoline.

2. technical scheme

In order to solve the above problems, the technical solution adopted in the present invention is as follows：

A kind of methanol gasoline additive, by methanol, ferrocene, Tween 80, triethanolamine, n-butanol, oleic acid and ethylene glycol Composition, the mass fraction of wherein each component are：

Methanol 1000

Ferrocene 8-18

Tween 80 60-80

Triethanolamine 10-40

N-butanol 100-200

Oleic acid 15-45

Ethylene glycol 20-45.

Preferably, the mass fraction of each component is：

Methanol 1000

Ferrocene 15

Tween 80 72

Triethanolamine 34

N-butanol 160

Oleic acid 28

Ethylene glycol 36.

Wherein, the purity of methanol is more than 99%.

A kind of preparation method of methanol gasoline additive, its step are：The methanol of 500 mass fractions is added into reaction to hold In device, the ferrocene of 8-18 mass fractions, the Tween 80 of 60-80 mass fractions, the three of 10-40 mass fractions are then sequentially added Monoethanolamine, the n-butanol of 100-200 mass fractions, the oleic acid of 15-45 mass fractions, the ethylene glycol of 20-45 mass fractions and 500 The methanol of mass fraction.

Preferably, all it is stirred after often adding a kind of material, preferable mixing speed is 45 turns per minute.

Above-mentioned methanol gasoline additive can be applied to methanol gasoline.

A kind of biogasoline containing additive, above-mentioned methanol gasoline additive is mixed with methanol and gasoline； Described methanol gasoline additive, methanol and quality of gasoline ratio be：(1213-1428):(495000):(450000- 550000)。

Preferably, the methanol gasoline additive of brand-new stands more than 1h and mixed again with methanol and gasoline.Be herein for Methanol gasoline additive sufficiently mix and react.

Preferably, described gasoline is 93# gasoline (state's V standards are 92#).

Preferably, the mass ratio of described methanol gasoline additive, methanol and 93# gasoline (state's V standards are 92#) is： 1345:495000:50000。

The above-mentioned biogasoline containing additive can be applied on petrol engine.

3. beneficial effect

Compared to prior art, beneficial effects of the present invention are：

(1) the biogasoline powerful of the invention containing additive, performance is excellent compared with national standard gasoline substantially quite More, smaller to engine corrosion, calorific value is also higher, and every gram of calorific value is in more than 7500cal；Present invention employs it is many everybody Conventional gasoline additive, it is minimum to engine damage, such as our material ferrocene, Tween 80 and triethanolamines for taking It is Deng, it has been found that Chinese Patent Application No.：201710045088.2 publication date is：The patent document on May 31st, 2017 is public Opened a kind of automobile nutrient, its component according to percent by weight, including：Ferrocene 8%-12%, triethanolamine 8%- 15%, tween 80 6%-12%, cosolvent 20%-30%, higher alcohols 30%-40%.As can be seen here, the present invention uses material Influence and security to engine are by test of many times mistake, and still, at first sight, some of the staff may think that the skill of the present invention The technical scheme of art scheme and documents carefully analyzes that can to find that both are present huge something like, material especially used Substantive difference：

1) first, from the point of view of technical problems to be solved, documents provide a kind of automobile nutrient, it is intended to solve vapour Car engine can produce the sediments such as colloid and carbon distribution when running, and cause inlet channel sectional area to reduce, and intake efficiency reduces, work( Rate declines, and can make valve operation slow when serious, be not closed completely, and atomizer carbon distribution makes oil spout not smooth, fuel-oil atmozation Quality Down, Fuel oil is caused to be difficult to completely burned after entering combustion chamber, so as to cause engine start difficult, unstable idle speed, and oil consumption add Greatly, the problem of exhaust emissions deterioration etc.；It is heavy equal to the purpose is to reduce colloid and carbon distribution etc. caused by automobile engine operation Starch, and the purpose of the present invention be by modified methanol, can be direct after it is mixed with 93# gasoline (state's V standards are 92#) Applied to vehicles equipped with gasoline engine, without transforming engine, so as to realize that part substitutes petroleum fuel, effect is completely not Together；

2) from the technical scheme of use, the present invention has carried out a large amount of realities in the case where breaking through existing common knowledge Test, find to carry out the proportion of each raw material after significantly adjusting, can apply to methanol gasoline, and be no longer conduct The additive of gasoline, the present invention is by rectifying and improving raw material and ratio, it is therefore an objective to methanol is modified, realizes methanol gasoline Feasibility；It is because methanol gasoline can not fully burn, and can be produced after imperfect combustion that originally methanol, which can not be widely applied, Formaldehyde, formic acid etc., more serious corrosion and effect of attrition are produced to engine, and methanol gasoline is to automobile oil supply system The swelling action of rubber components is larger, and the tartan of sealing and miscellaneous part to oil pump mostly has burn into swelling, soft Change or cracking acts on, or even also have corrosiveness to resin filter element and metal filtering core, the gasoline particularly containing 10% methanol is to each The swelling rate of kind rubber is all bigger, so this, which is also everybody, is only applied to methanol the additive of gasoline, nothing all the time Method is largely added the reason for methanol, and by our proportioning, is able to the calorific value of gasoline after mixing to still remain in In more than 7500cal/g higher level, the purpose of methanol extensive application is realized.

(2) low-carbon environment-friendly when biogasoline of the present invention containing additive uses, carbon monoxide emission is averagely less than common Gasoline 50%；

(3) preparation method of the biogasoline of the invention containing additive is simpler, and preparation cost is relatively low, and price is just Preferably, the cost of every liter of biogasoline is far below regular gasoline；

(4) it is easy to use when biogasoline of the present invention containing additive is applied, it can be suitably used for various gasoline vehicles, nothing Engine need to be made any change；

Embodiment

The present invention is further described below with reference to specific embodiment.

Embodiment 1

A kind of biogasoline containing additive, smart alcohol (purity methanol more than 99%) of its raw material including 496kg, 15g ferrocene, 72g Tween 80,34g triethanolamine, 160g n-butanol, 28g oleic acid, 36g ethylene glycol and 500kg 93# gasoline (state's V standards are 92#).

Its prepare the step of be：500g smart alcohol is added in reaction vessel, then sequentially add 15g ferrocene, 72g Tween 80,34g triethanolamine, 160g n-butanol, 28g oleic acid, 36g ethylene glycol and 500g smart alcohol, often plus All it is stirred after entering a kind of material, speed is 45 turns per minute.495kg essence alcohol is added after standing 1h afterwards, stirs 15min Addition 500kg sinopec 93# gasoline (state's V standards are 92#) is well mixed afterwards obtains finished product.

Gained finished product send third party testing agency to detect, and examining report numbering is W0516-118A, and examining report data are such as Shown in table 1 below：

Biogasoline examining report one of the table 1 containing additive

Detection project	Testing result	Detect foundation
			Calorific value, cal/g	8478	GB 384-81
Flash-point (is remained silent), DEG C	14	GB/T 261-2008
			Condensation point, DEG C	＜ -60	GB/T 510-1983
Carbon residue, %	0.01	GB 268-87
			50% recovered (distilled) temperature, DEG C	75	GB/T 6536-1997
Copper corrosion (50 DEG C, 3h), level	1a	GB/T 5096-1985
			pH	7.04	GB 16663-1996
Density (19 DEG C), g/mL	0.755	GB/T 611-2006

Using the biogasoline containing additive made from above-mentioned preparation method, powerful, with 93# gasoline (state's V standards For 92#) compared to substantially quite, calorific value is still higher after mixing a large amount of methanol, is maintained at 8478cal/g, far above the heat of smart alcohol Value (about 5000cal/g), from 50 DEG C of series to copper corrosion 3h, its corrosivity to engine is smaller, but uses The proportioning and preparation method of the present invention, the cost for preparing biogasoline are far below common 93# gasoline (state's V standards are 92#), carbon residue Only 0.01%, experiment measures carbon monoxide emission and is less than 93# gasoline (state's V standards are 92#) 53%, and without to hair during use Motivation carries out any transformation, is applicable to various gasoline vehicles.Cost is relatively low, and oil price is only 2/5ths of 93# gasoline. The precedent of a large amount of replacing gasolines of methanol is especially realized, is of coursed, by retrieval, was also attempted before someone big using methanol The replacing gasoline of amount, such as in Chinese Patent Application No. be 201010284989.5, publication date is：The patent on April 4th, 2012 There is use in file, it discloses a kind of high-cleaness methanol gasoline, and it includes the raw material of following parts by weight：Methanol 33 parts~53 Part, 40 parts~65 parts of gasoline, 5.8 parts~8 parts of additive, 0.1 part~0.5 part of cleaning agent, 0.1 part~0.5 part of preservative.It is described Additive is n-butanol, acetone, methyl tertiary butyl ether(MTBE), dodecyl sodium sulfate, surfactant, dimethylbenzene, ethyl acetate, carbon Any three kinds or more in dimethyl phthalate, ferrocene is mixed to prepare in any proportion；The surfactant is by tween 80 and span 20 composition；The cleaning agent is NPE, triethanolamine, any one in isopropanol；It is described Preservative is BHT, any one in alkaline barium mahogany sulfonate.And it is as follows to disclose its preparation method： At normal temperatures and pressures, by the raw material of above-mentioned parts by weight, it is sequentially added into reactor, with the scattered stirring of high-shearing dispersion emulsifying machine 20 minutes~30 minutes, above-mentioned raw materials are well mixed, are got product.

We are in the original plan contrasted the effect of the effect of this patent embodiment 1 and the documents, unfortunately, We are tested once, and engine is damaged, and does not dare to test again, we are by technically being analyzed, the contrast Still there is larger substantive difference in file, the calorific value very little of documents 1 with the present invention, be also easy to pinking during use.This Field those of ordinary skill knows, the calorific value of 93# gasoline (state's V standards are 92#) is in more than 10000cal/g, and the one of methanol As the calorific value of burning of situation be only its half or so, if proportioning is unreasonable obviously to cause mixed gasoline heat value significantly Decline, use simultaneously, engine can produce very big vibrations, less effective, this estimation and our laboratory engines The reason for there occurs damaging, but the mixed calorific value of the present invention is big, and anti-seismic performance is good.The present inventor has been surprisingly found that：Will The additive proportion such as n-butanol, ferrocene, Tween 80 is greatly decreased and then by reasonably matching, but can be unexpected So that the performance of miscella greatly improves, especially in terms of power, reach 93# gasoline (the use mark of (state's V standards are 92#) Standard, its cost can also be reduced during large-scale production.Of course, the present invention relative to this application, also with it is certain the defects of, this hair It is bright that in 93# gasoline, (using effect is good in (state's V standards are 92#), but is used in the gasoline of other labels, less effective, reaches The gasoline that can substitute a variety of labels declared less than each embodiment of documents.

Gasoline prepared by the present embodiment, we are tested to different vehicles, as a result as follows：

Embodiment 2

A kind of biogasoline containing additive, the quality of each component are：

Smart alcohol 496kg, ferrocene 8g, Tween 80 60g, triethanolamine 10g, n-butanol 100g, oleic acid 15g, ethylene glycol 20g and petrochina 93# gasoline (state's V standards are 92#) 450kg.

Methanol gasoline additive is prepared first, and step is as follows：500g methanol is added in reaction vessel, then successively Add 8g ferrocene, 60g Tween 80,10g triethanolamine, 100g n-butanol, 15g oleic acid, 20g ethylene glycol and 500g methanol, often add a kind of material and be all stirred.

Then by the methanol gasoline additive being prepared and 450kg petrochina 93# gasoline (state's V standards are 92#) and 495kg smart alcohol is well mixed to can obtain biogasoline finished product.

Sample detection is reported as follows shown in table 2：

Biogasoline examining report two of the table 2 containing additive

Detection project	Testing result	Detect foundation
			Calorific value, cal/g	7864	GB 384-81
Flash-point (is remained silent), DEG C	15.5	GB/T 261-2008
			Condensation point, DEG C	＜ -60	GB/T 510-1983
Carbon residue, %	0.06	GB 268-87
			50% recovered (distilled) temperature, DEG C	75	GB/T 6536-1997
Copper corrosion (50 DEG C, 3h), level	1a	GB/T 5096-1985
			pH	7.06	GB 16663-1996
Density (19 DEG C), g/mL	0.743	GB/T 611-2006

Biogasoline carbon residue containing additive made from the present embodiment is 0.06%, and it is low that experiment measures carbon monoxide emission In 93# gasoline (state's V standards are 92#) 47% or so, its calorific value is 7864cal/g as seen from the above table.

Embodiment 3

A kind of biogasoline containing additive, its raw material are：496kg smart alcohol, 13g ferrocene, 75g tween 80th, 27g triethanolamine, 140g n-butanol, 33g oleic acid, 28g ethylene glycol and 510kg petrochina 93# gasoline (state's V standards are 92#).

A kind of preparation method of the biogasoline containing additive, step are：500g smart alcohol is added to reaction vessel In, then sequentially add 13g ferrocene, 75g Tween 80,27g triethanolamine, 140g n-butanol, 33g oleic acid, 28g ethylene glycol and 500g smart alcohol, are all stirred after often adding a kind of material, and speed is 45 turns per minute.Stand afterwards Add 495kg essence alcohol after 1h, stir add after 15min 510kg 93# gasoline (state's V standards be 92#) it is well mixed be to obtain Finished product.

Sample detection is reported as follows shown in table 3：

Biogasoline examining report three of the table 3 containing additive

Detection project	Testing result	Detect foundation
			Calorific value, cal/g	8185	GB 384-81
Flash-point (is remained silent), DEG C	14.65	GB/T 261-2008
			Condensation point, DEG C	＜ -60	GB/T 510-1983
Carbon residue, %	0.02	GB 268-87
			50% recovered (distilled) temperature, DEG C	75	GB/T 6536-1997
Copper corrosion (50 DEG C, 3h), level	1a	GB/T 5096-1985
			pH	7.05	GB 16663-1996
Density (19 DEG C), g/mL	0.745	GB/T 611-2006

Biogasoline carbon residue containing additive made from the present embodiment is only 0.02%, and experiment measures carbon monoxide emission Less than 93# gasoline (state's V standards are 92#) 50% or so, its calorific value is also higher as seen from the above table, has reached 8185cal/g.

Embodiment 4

A kind of biogasoline containing additive, the quality of each component are：

Smart alcohol 496kg, ferrocene 18g, Tween 80 80g, triethanolamine 40g, n-butanol 200g, oleic acid 45g, ethylene glycol 45g and 93# gasoline (state's V standards are 92#) 550kg.

Its preparation method is as follows：500g smart alcohol is added in reaction vessel, then sequentially add 18g ferrocene, 80g Tween 80,40g triethanolamine, 200g n-butanol, 45g oleic acid, 45g ethylene glycol and 500g smart alcohol, often plus All it is stirred after entering a kind of material, speed is 45 turns per minute.495kg essence alcohol is added after standing 1h afterwards, stirs 15min Addition 550kg 93# gasoline (state's V standards are 92#) is well mixed afterwards obtains finished product.

Sample detection is reported as follows shown in table 4：

Biogasoline examining report four of the table 4 containing additive

Detection project	Testing result	Detect foundation
			Calorific value, cal/g	7974	GB 384-81
Flash-point (is remained silent), DEG C	15	GB/T 261-2008
			Condensation point, DEG C	＜ -60	GB/T 510-1983
Carbon residue, %	0.03	GB 268-87
			50% recovered (distilled) temperature, DEG C	75	GB/T 6536-1997
Copper corrosion (50 DEG C, 3h), level	1a	GB/T 5096-1985
			pH	7.06	GB 16663-1996
Density (19 DEG C), g/mL	0.747	GB/T 611-2006

The biogasoline carbon residue containing additive is 0.03% made from the present embodiment, and carbon monoxide emission is less than 93# vapour Oily (state's V standards are 92#) 51% or so, its calorific value is 7974cal/g as seen from the above table.

Claims

A kind of 1. methanol gasoline additive, by methanol, ferrocene, Tween 80, triethanolamine, n-butanol, oleic acid and ethylene glycol group Into the mass fraction of wherein each component is：

Methanol 1000

Ferrocene 8-18

Tween 80 60-80

Triethanolamine 10-40

N-butanol 100-200

Oleic acid 15-45

Ethylene glycol 20-45.
2. methanol gasoline additive according to claim 1, it is characterised in that the mass fraction of each component is：

Methanol 1000

Ferrocene 15

Tween 80 72

Triethanolamine 34

N-butanol 160

Oleic acid 28

Ethylene glycol 36.
3. a kind of preparation method of methanol gasoline additive, its step are：The methanol of 500 mass fractions is added to reaction vessel In, then sequentially add the ferrocene of 8-18 mass fractions, the Tween 80 of 60-80 mass fractions, three second of 10-40 mass fractions Hydramine, the n-butanol of 100-200 mass fractions, the oleic acid of 15-45 mass fractions, the ethylene glycol of 20-45 mass fractions and 500 matter Measure the methanol of number.
4. the preparation method of methanol gasoline additive according to claim 3, it is characterised in that：After often adding a kind of material All it is stirred；Preferably 45 turns per minute of mixing speed.
5. methanol gasoline addition prepared by the method in the methanol gasoline additive or claim 3 described in claim 1 or 2 Application of the agent in methanol gasoline.
A kind of 6. biogasoline containing additive, it is characterised in that：By the methanol gasoline additive described in claim 1 or 2 Mixed with methanol and gasoline；Described methanol gasoline additive, methanol and quality of gasoline ratio be：(1213-1428): (495000):(450000-550000)。
7. the biogasoline according to claim 6 containing additive, it is characterised in that：The methanol gasoline additive of brand-new Standing more than 1h is needed to be mixed again with methanol and gasoline.
8. a kind of biogasoline containing additive according to claim 6 or 7, it is characterised in that described gasoline is 93# gasoline (state's V standards are 92#).
9. a kind of biogasoline containing additive according to claim 8, it is characterised in that described methanol gasoline adds The mass ratio for adding agent, methanol and 93# gasoline (state's V standards are 92#) is：1345:495000:50000.
10. application of the biogasoline containing additive on petrol engine described in claim 9.