CN111303950A

CN111303950A - High-oxygen-content ethanol fuel oil additive and preparation method thereof

Info

Publication number: CN111303950A
Application number: CN202010211870.9A
Authority: CN
Inventors: 陈庆; 廖健淞; 杨洁; 曾军堂; 何方
Original assignee: Chengdu New Keli Chemical Science Co Ltd
Current assignee: Zhejiang Ruizhi Fuel Co ltd
Priority date: 2020-03-24
Filing date: 2020-03-24
Publication date: 2020-06-19
Anticipated expiration: 2040-03-24
Also published as: CN111303950B

Abstract

The invention relates to the field of ethanol fuel oil, in particular to an ethanol fuel oil auxiliary agent with high oxygen content and a preparation method thereof. The ethanol fuel oil additive with high oxygen content is prepared by the following method: dissolving 1,2, 3-trihydroxybenzene in absolute ethyl alcohol to obtain a 1,2, 3-trihydroxybenzene ethanol solution; adding potassium hydroxide powder into the 1,2, 3-trihydroxybenzene ethanol solution to obtain a solution A; sealing the solution A, and then introducing excessive pure oxygen into the solution A to enable the solution A to be fully adsorbed to obtain a solution B; adding calcium oxide into the solution B, dehydrating for 24-30 hours, and filtering to obtain an ethanol fuel oil additive; the 1,2, 3-trihydroxybenzene is used for absorbing oxygen to form high-oxygen-concentration liquid, so that aerobic combustion of gasoline can be effectively promoted in the combustion process, and carbonization of organic matters in the gasoline is inhibited.

Description

High-oxygen-content ethanol fuel oil additive and preparation method thereof

Technical Field

The invention relates to the field of ethanol, in particular to an ethanol fuel oil additive with high oxygen content and a preparation method thereof.

Background

With the continuous development of economy, the consumption of fossil energy such as gasoline rises year by year, and the reduction and elimination of the dependence on non-renewable energy are essential factors for establishing a continuously developing society. The ethanol gasoline is prepared by adding 10% of ethanol into the traditional gasoline as fuel oil for automobiles, so that the dependence on petroleum resources can be relieved, a large amount of aged grains can be digested, and the development of agriculture is promoted. The use of the ethanol gasoline can greatly reduce the emission of CO in the automobile exhaust, improve the atmospheric quality and relieve the environmental pollution.

Ethanol gasoline also has many disadvantages, such as low calorific value of combustion, swelling of rubber, corrosion of pipelines by products, and the like. One of the key problems is that the heat value of combustion is low, because the latent heat of evaporation of ethanol is large, heat absorption is obvious in the early stage atomization process, the temperature of fuel gas conveyed into an engine is low, the air intake is small, incomplete combustion is easily caused due to insufficient oxygen content, and meanwhile, the ethanol can cause the viscosity modifier to be separated out, so that carbon deposition in a cylinder is serious.

The patent application with application number 2004100000173 proposes ethanol gasoline for gasoline engine, which is formed by mixing ethanol, gasoline, emulsifier and catalyst, and by means of the catalyst comprising RE element particle, the mixed fuel is made to interact with each other to reform fuel inside the cylinder in the process of burning. The preparation method of the mixed fuel comprises the steps of determining the water content and the possible water absorption capacity of the ethanol and the gasoline, determining the content of the ethanol, determining the content of an emulsifier, determining the addition amount of a catalyst, mixing the emulsifier with the determined content with the ethanol, mixing the catalyst with the gasoline, and mixing the two mixtures to form the ethanol gasoline. The defects that the power of an engine is reduced and the oil consumption is increased after ethanol is added into gasoline in a traditional mode, particularly after the ethanol absorbs moisture, are overcome, the phenomenon that the high pressure in an air cylinder is delayed is automatically compensated, and the pollutant discharge amount is greatly reduced. The ethanol gasoline used by the gasoline engine and the preparation method thereof improve the combustion heat value by taking rare earth metal as a catalyst for combustion supporting, but the used raw materials are harsh, thereby being not beneficial to industrialized application. Therefore, the method has very important practical significance for the research and development of the combustion-supporting effect of the ethanol gasoline.

The patent application with the application number of 2006101135124 discloses a civil synthetic fuel, which is prepared from methanol, gasoline, light oil, ethanol, carbon 5, ethane, acetone, potassium nitrate and potassium permanganate according to the following weight percentage ranges: 14-55% of methanol, 4-45% of gasoline, 5-48% of light oil, 1-49% of ethanol, 51-39% of carbon, 2-45% of ethane, 8-37% of acetone, 2-49% of potassium nitrate and 2-38% of potassium permanganate, wherein the preparation method comprises the following steps: mixing light oil, methanol, carbon 5, ethane, acetone and potassium nitrate to obtain a semi-finished product; mixing ethanol, gasoline and potassium permanganate into a semi-finished product; and mixing the two semi-finished products to obtain the finished product. Compared with the traditional civil fuel, the fuel has high heat value, is more complete in combustion, is free of smoke and PM, is more energy-saving and environment-friendly, and is safe to use and convenient to carry.

The patent application with the application number of 2017112506060 discloses ethanol gasoline and a preparation method thereof, wherein the ethanol gasoline comprises the following raw materials in parts by weight: 60-70 parts of main fuel oil, 1-3 parts of alcohol additives, 20-30 parts of MTBE components and 10-15 parts of ethanol; the main fuel oil comprises aromatized oil and/or isomeric oil, and the alcohol additive comprises isobutyl alcohol and/or tertiary butyl alcohol. The ethanol gasoline has the advantages of sufficient raw materials, low cost, no three wastes generated during combustion, environmental protection, better volatility, more thorough combustion, high octane number (92-95), and greatly increased antiknock index, and better safety, and the calorific value reaches 46000 KJ/kg.

The patent application with the application number of 2017111361952 discloses an ethanol gasoline combustion enhancer and a preparation method thereof, belonging to the technical field of fuel additives. The invention aims to provide a preparation method of an ethanol gasoline combustion enhancer. The method comprises the following steps: a. dissolving xanthan gum in water to form a wall material solution; dissolving nitrocotton and tween 80 in ethyl acetate to form a core material solution; b. adding the core material solution into the wall material solution at the temperature of 0-4 ℃, and stirring at a high speed to obtain an emulsion; c. freeze-drying the emulsion to obtain nitrocotton capsules; d. uniformly mixing the nitrocotton capsule, the castor oil, the dicyclopentadienyl iron, the normal hexane, the amyl nitrate and the surfactant to obtain the ethanol gasoline combustion enhancer. The preparation method provided by the invention is simple in process and low in cost, and the prepared ethanol gasoline combustion enhancer is good in stability, strong in dynamic property and good in intersolubility, and can increase the combustion value of ethanol gasoline during combustion and solve the problems of low heat value and insufficient dynamic property of the ethanol gasoline.

The patent application No. 200710154478X discloses an ethanol gasoline, which is prepared by mixing ethanol added with a biological additive and common gasoline according to a certain proportion (ethanol mass: gasoline mass = 50%: 50%), wherein the main component of the added additive is degreased 100% castor oil, and the ethanol gasoline is mainly used for solving three problems, namely, ① ethanol and gasoline layering problem, ② improves the combustion heat value of ethanol, ③ reduces the corrosion of the mixed fuel to automobile parts, and the additive is extracted from plants and does not belong to a chemical additive, so the additive is called as the biological additive, and the 50% ethanol gasoline containing the biological additive is used as a substitute fuel of the gasoline and has the advantages that (1) compared with the gasoline, the power is reduced by less than 7%, (2) compared with the gasoline, the oil consumption of the automobile is not obviously increased, (3) compared with the gasoline, the harmful emissions of the automobile are obviously reduced, (4) compared with the gasoline, the automobile parts are not corroded, and the key parts of the automobile are lubricated, (5) the production process is simple and the production cost is low.

Patent application No. 2015110131530 discloses a fuel for vehicles. The vehicle fuel consists of fuel ethanol, gasoline, methanol and a combustion improver, wherein the components in parts by weight are as follows: 1-20 parts of fuel ethanol, 50-90 parts of gasoline, 10-20 parts of methanol and 1-10 parts of combustion improver; the combustion improver is prepared from: 1-10 parts of antioxidant, 1-3 parts of ferrocene, 2-10 parts of dimethyl carbonate, 3-9 parts of dimethylbenzene and 8-20 parts of ethylene glycol monoethyl ether. The vehicle fuel has the characteristics of cleanness, environmental protection, full combustion and high heat value, the adopted combustion improver can enhance the stability and cleanness of the gasoline, effectively inhibits the corrosion of the gasoline to an engine combustion system, and has high combustion efficiency, strong power and environment-friendly tail gas emission.

Disclosure of Invention

Aiming at the problem of incomplete combustion of the prior ethanol gasoline, the invention provides an ethanol fuel oil additive with high oxygen content and a preparation method thereof.

In order to solve the technical problems, the ethanol fuel oil additive with high oxygen content is prepared by the following method:

(1) dissolving 1,2, 3-trihydroxybenzene in absolute ethyl alcohol to obtain a 1,2, 3-trihydroxybenzene ethanol solution;

(2) adding potassium hydroxide powder into the 1,2, 3-trihydroxybenzene ethanol solution in the step (1) to obtain a solution A;

(3) sealing the solution A obtained in the step (2), and then introducing excessive pure oxygen into the solution A to enable the solution A to be fully adsorbed to obtain a solution B;

(4) and (4) adding calcium oxide into the solution B obtained in the step (3) to dehydrate for 24-30 hours, and filtering to obtain the ethanol fuel oil additive.

(5) Compounding the dehydration product obtained in the step (4) with gasoline and a cosolvent to obtain ethanol gasoline with high oxygen concentration;

the weight ratio of the 1,2, 3-trihydroxybenzene to the potassium hydroxide is 10-15: 2-6;

in the step (1), 1,2, 3-trihydroxybenzene generates autoxidation reaction in an alkaline environment to release superoxide anion free radical (. O)^2-) And the oxygen is fully adsorbed.

1,2, 3-trihydroxybenzene is also known as 1,2, 3-benzenetriol, pyrogallol, etc. The 1,2, 3-trihydroxybenzene sold on the market can be adopted, the higher the purity is, the better the purity is, but the purity is high, the cost is generally higher, and the influence of the purity of the 1,2, 3-trihydroxybenzene of more than 98% on the product is small.

The potassium hydroxide solid is white powder or flake solid, and in order to fully react with the 1,2, 3-trihydroxybenzene, the potassium hydroxide in a white powder state is required to be adopted in the invention.

More preferably, the weight ratio of the 1,2, 3-trihydroxybenzene to the absolute ethyl alcohol in the step (1) is 5-15: 90-100, and the weight ratio of the 1,2, 3-trihydroxybenzene to the absolute ethyl alcohol is 5-10: 90-95.

The pure oxygen is introduced too little to achieve the purpose of excess, the obtained ethanol gasoline still has more incomplete combustion residues after combustion, and the excessive pure oxygen is introduced to cause certain waste. Preferably, the purpose of excess pure oxygen can be achieved by introducing pure oxygen of more than 5ml into every 100ml of the solution A, 5-8 ml of pure oxygen into every 100ml of the solution A cannot be wasted, the safety problem of overlarge air pressure cannot be caused, the purpose of excess pure oxygen can be achieved, and the obtained incomplete combustion residues of the ethanol gasoline after combustion are few.

Therefore, it is further preferred that the introducing excess pure oxygen in step (3) is: introducing pure oxygen of more than 5ml into every 100ml of the solution A; the step (5) of introducing excess pure oxygen is preferably as follows: and introducing 5-8 ml of pure oxygen into every 100ml of the solution A.

Further preferably, the weight ratio of the calcium oxide to the 1,2, 3-trihydroxybenzene in the step (4) is 25-50: 50-150.

The invention further provides a preparation method of the ethanol fuel oil additive with high oxygen content, which comprises the following steps:

Aiming at the problems that the ethanol gasoline is easy to combust incompletely and cause carbon deposition, the invention dissolves 1,2, 3-trihydroxybenzene in absolute ethyl alcohol, adds potassium hydroxide powder and then seals, and then introduces excessive pure oxygen into liquid to dehydrate the liquid after the excessive pure oxygen is fully absorbed, compared with the prior art, the ethanol gasoline has the outstanding characteristics and excellent effects that: by using the 1,2, 3-trihydroxybenzene to absorb oxygen to form high-oxygen-concentration liquid, the aerobic combustion of gasoline can be effectively promoted in the combustion process, and the carbonization of organic matters in the gasoline is inhibited.

In principle, the ethanol fuel oil additive is directly used as an additive of gasoline. Typical methods of use that may be referred to in the specific use are as follows:

the ethanol fuel oil additive is compounded with gasoline and cosolvent to obtain ethanol gasoline with high oxygen concentration; the cosolvent is one of isopropanol, n-butanol, isobutanol, isoamylol, octanol or fusel; the ethanol fuel oil additive, the gasoline and the cosolvent respectively account for 9-11 parts by weight, 88-95 parts by weight and 3-5 parts by weight.

When the alcohol gasoline additive is used, the ratio of the alcohol fuel additive, the gasoline and the cosolvent has great influence on the quality of the alcohol gasoline, the adding amount of the alcohol fuel additive is too small, the incomplete combustion residues of the obtained alcohol gasoline after combustion are still more, and the adding amount of the alcohol fuel additive is too large, the incomplete combustion residues of the obtained alcohol gasoline after combustion are also more.

Drawings

FIG. 1 is a graph showing the residue after combustion in a container of the ethanol gasoline prepared in example 1.

Fig. 2 is a graph showing the residue after combustion in a container of the ethanol gasoline prepared in comparative example 1.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.

Example 1

Preparing the ethanol fuel oil additive with high oxygen content:

step 1: dissolving 1 g, 2, 3-trihydroxybenzene in 900g absolute ethanol to obtain 1,2, 3-trihydroxybenzene ethanol solution;

step 2: adding 20g of potassium hydroxide powder into the 1,2, 3-trihydroxybenzene ethanol solution prepared in the step 1 to obtain a solution A;

and step 3: and (3) sealing the solution A prepared in the step (2), and then introducing 80ml of pure oxygen into the solution A to enable the pure oxygen to be fully adsorbed to obtain a solution B.

And 4, step 4: adding 50g of calcium oxide into the solution B prepared in the step 3, dehydrating for 24 hours, and filtering to obtain an ethanol fuel oil additive;

50g of ethanol fuel oil additive, 450g of gasoline and 25g of cosolvent n-butyl alcohol are compounded to obtain the ethanol gasoline with high oxygen concentration.

The related detection method comprises the following steps:

100ml of the ethanol gasoline sample prepared in example 1 was placed in a container, after ignition of the gasoline and combustion, the container was cooled to room temperature, the weight of the container was measured, and the initial volumetric weight was subtracted, which was the weight of the residue after combustion of the ethanol gasoline, and the results are shown in Table 1. The residue after combustion in the container of the ethanol gasoline prepared in example 1 is shown in fig. 1.

Example 2

Preparing the ethanol fuel oil additive with high oxygen content:

step 2: adding 30g of potassium hydroxide powder into the 1,2, 3-trihydroxybenzene ethanol solution prepared in the step 1 to obtain a solution A;

100ml of the ethanol gasoline sample prepared in example 2 was placed in the same container, after ignition of the gasoline and combustion, and after cooling to room temperature, the weight of the container was measured, and the initial volumetric weight was subtracted, which was the weight of the residue after combustion of the ethanol gasoline, and the results are shown in Table 1.

Example 3

Preparing the ethanol fuel oil additive with high oxygen content:

50g of ethanol fuel oil additive, 450g of gasoline and 25g of cosolvent isoamylol are compounded to obtain the ethanol gasoline with high oxygen concentration.

100ml of the ethanol gasoline sample prepared in example 3 was placed in the same container, after ignition of the gasoline and combustion, and after cooling to room temperature, the weight of the container was measured, and the initial volumetric weight was subtracted, which was the weight of the residue after combustion of the ethanol gasoline, and the results are shown in Table 1.

Example 4

Preparing the ethanol fuel oil additive with high oxygen content:

step 1: dissolving 140g of 1,2, 3-trihydroxybenzene in 900g of absolute ethanol to obtain a 1,2, 3-trihydroxybenzene ethanol solution;

100ml of the ethanol gasoline sample prepared in example 4 was placed in the same container, after ignition of the gasoline and combustion, and after cooling to room temperature, the weight of the container was measured, and the initial volumetric weight was subtracted, which was the weight of the residue after combustion of the ethanol gasoline, and the results are shown in Table 1.

Example 5

Preparing the ethanol fuel oil additive with high oxygen content:

step 1: dissolving 150g of 1,2, 3-trihydroxybenzene in 900g of absolute ethanol to obtain a 1,2, 3-trihydroxybenzene ethanol solution;

50g of ethanol fuel oil additive, 450g of gasoline and 25g of cosolvent isobutanol are compounded to obtain the ethanol gasoline with high oxygen concentration.

100ml of the ethanol gasoline sample prepared in example 5 was placed in the same container, after ignition of the gasoline and combustion, and after cooling to room temperature, the weight of the container was measured, and the initial volumetric weight was subtracted, which was the weight of the residue after combustion of the ethanol gasoline, and the results are shown in Table 1.

Example 6

Preparing the ethanol fuel oil additive with high oxygen content:

step 2: adding 40g of potassium hydroxide powder into the 1,2, 3-trihydroxybenzene ethanol solution prepared in the step 1 to obtain a solution A;

50g of ethanol fuel oil additive, 450g of gasoline and 25g of cosolvent isopropanol are compounded to obtain the ethanol gasoline with high oxygen concentration.

100ml of the ethanol gasoline sample prepared in example 6 was placed in the same container, after ignition of the gasoline and combustion, and after cooling to room temperature, the weight of the container was measured, and the initial volumetric weight was subtracted, which was the weight of the residue after combustion of the ethanol gasoline, and the results are shown in Table 1.

Comparative example 1

Preparing ethanol gasoline:

100g of ethanol, 900g of gasoline and 50g of isopropanol are mixed and compounded to obtain the ethanol gasoline.

100ml of the ethanol gasoline sample prepared in comparative example 1 was placed in the same container as in example, after ignition of the gasoline and combustion, the container was cooled to room temperature, and the weight of the container was measured, and the initial volume weight was subtracted, which was the weight of the residue after combustion of the ethanol gasoline, and the results were shown in Table 1. The residue of ethanol gasoline prepared in comparative example 1 after combustion in the container is shown in fig. 2.

TABLE 1 weight of residue after combustion of ethanol gasolines of examples and comparative examples

Test sample	Residue/g
		Example 1	1.26
Example 2	1.38
		Example 3	1.29
Example 4	1.34
		Example 5	1.21
Example 6	1.32
		Comparative example 1	4.22

Through detection, as can be seen from the weight of the residue after the ethanol gasoline of the example and the comparative example in table 1 is combusted, the combustion product left in the example is less than that of the combustion product of the comparative example 1 after the ethanol gasoline is combusted, and in addition, as can be seen from fig. 1 and fig. 2, the combustion product left in the example 1 is less than that of the comparative example 1, which indicates that the ethanol gasoline of the example is combusted more fully, because the 1,2, 3-trihydroxybenzene added in the example is dissolved in ethanol and then fully adsorbs oxygen, and the obtained high oxygen content product is compounded with gasoline, so that the oxygen content of the gasoline is effectively increased, and the ethanol gasoline is combusted more fully.

Claims

1. An ethanol fuel oil additive with high oxygen content is characterized in that: the ethanol fuel oil additive with high oxygen content is prepared by the following method:

(4) adding calcium oxide into the solution B obtained in the step (3), dehydrating for 24-30 hours, and filtering to obtain an ethanol fuel oil additive;

the weight ratio of the 1,2, 3-trihydroxybenzene to the potassium hydroxide is 10-15: 2-6.

2. The high oxygen content ethanol fuel oil adjuvant according to claim 1, characterized in that: the weight ratio of the 1,2, 3-trihydroxybenzene to the absolute ethyl alcohol in the step (1) is 5-10: 90-95.

3. The high oxygen content ethanol fuel oil adjuvant according to claim 1, characterized in that: the step (3) of introducing excessive pure oxygen is as follows: every 100ml of the solution A is filled with more than 5ml of pure oxygen.

4. The high oxygen content ethanol fuel oil adjuvant according to claim 1, characterized in that: the weight ratio of the calcium oxide to the 1,2, 3-trihydroxybenzene in the step (4) is 25-50: 50-150.

5. The preparation method of the high-oxygen-content ethanol fuel oil additive as claimed in any one of claims 1 to 4, which is characterized in that: the preparation method comprises the following steps:

6. The method for preparing the ethanol fuel oil additive with high oxygen content according to claim 5, is characterized in that: the weight ratio of the 1,2, 3-trihydroxybenzene to the potassium hydroxide in the step (1) is 10-15: 2-6.

7. The method for preparing the ethanol fuel oil additive with high oxygen content according to claim 5, is characterized in that: the weight ratio of the 1,2, 3-trihydroxybenzene to the absolute ethyl alcohol in the step (1) is 5-10: 90-95.