CN113897228A - Micro-emulsified methanol diesel oil dispersant and application thereof - Google Patents

Micro-emulsified methanol diesel oil dispersant and application thereof Download PDF

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CN113897228A
CN113897228A CN202111083662.6A CN202111083662A CN113897228A CN 113897228 A CN113897228 A CN 113897228A CN 202111083662 A CN202111083662 A CN 202111083662A CN 113897228 A CN113897228 A CN 113897228A
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diesel oil
methanol
micro
acid
methanol diesel
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夏道宏
李子涵
朱丽君
杨朝合
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China University of Petroleum East China
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Abstract

The invention provides a micro-emulsified methanol diesel oil dispersant, which mainly comprises an emulsifier, a solubilizer and a stabilizer. The emulsifier is one or two of Span80 and Tween80, and the solubilizer is C10‑C20One or two of the long-chain fatty acids are compounded with C6‑C14The stabilizer is C8‑C9And one of dicarboxylic acid monoester, glycol ether and propylene glycol ether. When the content of the emulsifier is 0.05-1 w%, the content of the solubilizer is 4-25 w% and the content of the stabilizer is 0.05-1 w%, the micro-emulsified methanol diesel oil mixed fuel with the methanol content of 5-50 w% can be prepared. The dispersing process of the micro-emulsified methanol diesel oil dispersing agent is simple and convenient, is easy to operate, has the characteristics of wide additive source, relatively low price and simple preparation process, and is favorable for popularization and application. Compared with the traditional dispersant, the microemulsion has good micro-emulsification effect, is environment-friendly and green, and belongs to an environment-friendly methanol diesel dispersant.

Description

Micro-emulsified methanol diesel oil dispersant and application thereof
Technical Field
The invention relates to the technical field of petrochemical industry, and particularly relates to a micro-emulsified methanol diesel oil dispersant and application thereof.
Background
The basic condition of energy in China is 'rich coal, poor oil and little gas', and in the face of severe energy situation and environmental pollution problems, the dependence on petroleum fuel is reduced as much as possible, and new energy-saving fuel is developed. The methanol has low price and wide sources, and the technology for preparing the methanol from the coal is developed and matured in China. The yield of methanol is very high every year in China, and the productivity is surplus, so if the methanol and diesel oil can be used for preparing mixed fuel to replace part of petroleum diesel oil, good economic and social benefits can be generated. However, as is known, the polarity difference between methanol and diesel oil is very large, so that the methanol and diesel oil are difficult to be mutually dissolved without adding other additives, the main route for preparing the methanol diesel oil fuel at present comprises methanol diesel oil emulsification and micro emulsification, although the addition amount of the additives is small, the prepared emulsified methanol diesel oil belongs to a thermodynamically unstable system, the phenomenon of emulsion breaking and layering is easy to occur, the storage time is short, and the generally stable non-layering time is several hours to several days. The methanol diesel oil prepared by the micro-emulsification route is a thermodynamic stable system, so that the micro-emulsified methanol diesel oil has long storage time, for example, the micro-emulsified methanol diesel oil can be stable for 1-2 months in the case, and the appearance is clear and transparent, so that the methanol diesel oil is more easily accepted by users and has better development prospect. The methanol diesel oil additive is the core for solving the mutual solubility problem of methanol diesel oil no matter methanol diesel oil emulsion or microemulsion, and the invention patents surrounding the methanol diesel oil additive in the last two decades have many patents, but are not perfect enough, for example: the patent CN113088345A discloses methanol diesel, the types of the added additives are as many as 7, and most of the additives are high in cost and difficult to popularize; the patent CN108913231A discloses methanol diesel, wherein the used auxiliary agent comprises 0.04-0.06 part of ferric chloride and 0.003-0.005 part of sodium carboxymethyl cellulose, and the metal salts can generate adverse effects on the service life of a diesel engine; in addition, there are patents using biodiesel as a main additive, including CN112725042A and CN107880950, etc., but biodiesel has a low calorific value and a high preparation cost, which phase change increases the cost of methanol diesel fuel. The problems lead the prior methanol diesel fuel to be difficult to popularize and apply. Hair brushThe auxiliary agent added into the methanol diesel mainly comprises emulsifiers of Span80 and Tween80 and a solubilizer C10-C20Long chain fatty acids and C6-C14The stabilizer is C8-C9The dicarboxylic acid monoester, the glycol ether and the propylene glycol ether. The mainly used long-chain fatty acid is used as a large amount of chemical products, has large global annual yield, rich sources, easily obtained raw materials and low cost, can be used as a main solubilizer and is supplemented with a small amount of C6-C14The fatty alcohol has better effect, and the environment-friendly methanol diesel oil can be prepared. In the micro-emulsified methanol diesel fuel, the addition amount of methanol can be adjusted according to actual needs, the addition range of the methanol can be as wide as 5-50 w%, and the micro-emulsified methanol diesel fuel has high flexibility.
Disclosure of Invention
Aiming at some problems of the existing methanol diesel fuel, the invention takes straight-run diesel, hydrogenated diesel and methanol as main raw materials, uses Span80 and Tween80 as emulsifiers and C10-C20One or two of the long-chain fatty acids are compounded with C6- C14As solubilizer, C8-C9One of dicarboxylic acid monoester, ethylene glycol monoether and propylene glycol monoether is used as a stabilizer to prepare the methanol diesel oil microemulsion. Wherein, C10-C20Long chain fatty acids of (a) include: capric acid (n-decanoic acid), myristic acid (myristic acid), palmitic acid (palmitic acid), linoleic acid (octadecadienoic acid), linolenic acid (octadecatrienoic acid) and eicosanoic acid. C6-C14The fatty alcohols of (a) include: isohexanol, n-heptanol, isoheptanol, and n-tetradecanol. Stabilizer C8-C9The dicarboxylic acid monoesters and glycol ethers and propylene glycol ethers of (a) include: monomethyl suberate, monoethyl suberate, monopropyl suberate, monomethyl azelate, monoethyl azelate, monopropyl azelate and ethylene glycol monomethyl ether, ethylene glycol monobutyl ether and propylene glycol monomethyl ether. The raw materials are prepared according to the following mass fraction:
5-50 w% of methanol;
95-50 w% of diesel oil;
one or two of Span80 and Tween80 account for 0.05-1 w%;
the total solubilizer content is 4-25 w%;
the total stabilizing dose is 0.05-1 w%.
Note: the addition of the emulsifier, the solubilizer and the stabilizer is the operation steps of the preparation process of the total weight percentage of the methanol and the diesel oil respectively: the emulsifier, the solubilizer and the stabilizer are all liquid at normal temperature, and the methanol, the diesel oil, the emulsifier, the solubilizer and the stabilizer in the weight ratio are stirred and mixed vigorously at room temperature until the mixture is clear and transparent; and for the emulsifier, the solubilizer and the stabilizer which contain solids at normal temperature, heating the solid additive to be completely melted, adding the solid additive into the methanol, the diesel oil, the emulsifier, the solubilizer and the stabilizer in the weight ratio while the solid additive is hot, fully mixing, and violently stirring until the mixture is clear and transparent.
Compared with the prior art, the invention mainly has the following advantages:
1. the prepared micro-emulsified methanol diesel oil mixed fuel has high stability and can be stably stored for more than 30 days at room temperature;
2. the used dispersing agent has wide source and lower cost;
3. the preparation process is simple to operate, and complex equipment is not needed;
4. the weight proportion range of the added methanol is wide and is flexibly adjustable between 5 and 50w percent.
Drawings
FIG. 1 is a graph comparing the stabilization time of micro-emulsified and emulsified methanol diesel fuel blend fuels.
Detailed Description
The indexes for evaluating the stability of the microemulsified methanol diesel mainly include the lowest critical temperature of turbidity and delamination of the microemulsified methanol diesel and the storage time at a certain temperature. The microemulsion of the methanol diesel oil is greatly influenced by the environmental temperature, and the lower the temperature is in a certain temperature range, the more easily the microemulsion methanol diesel oil is turbid and layered, so that the lower the critical temperature of the prepared microemulsion methanol diesel oil which is turbid and layered is, the more stable the microemulsion methanol diesel oil is proved to be and the less easily the microemulsion is influenced by the environmental temperature. The storage time at a certain temperature refers to the longest time for keeping the prepared micro-emulsified methanol diesel oil in a stable and non-layering state at room temperature above the critical temperature in a sealed manner.
The stability influencing factors of the prepared micro-emulsified methanol diesel fuel mainly comprise the environmental temperature and the dispersant, wherein the influence of the dispersant is mainly expressed by the relative addition amount (relative methanol diesel content) and the type of various additives. For a system with a certain methanol content, the stability of the micro-emulsified methanol diesel oil prepared by the invention is improved along with the increase of the addition amount of the dispersing agent, and the addition amount of the required dispersing agent is correspondingly increased when the methanol content in the micro-emulsified methanol diesel oil is increased.
The invention further concretely describes a micro-emulsified methanol diesel oil dispersant and an application technical scheme thereof by examples.
Example 1
Heating 0.03kg of capric acid to be completely melted, adding the heated capric acid into 0.95kg of hydrogenated diesel oil, 0.05kg of methanol, 0.0005kg of Span80, 0.01kg of isohexanol and 0.0005kg of monomethyl suberate, and uniformly stirring until the mixture is clear and transparent, thereby obtaining the micro-emulsified methanol diesel oil with the methanol weight fraction of 5 w%. The minimum critical temperature is 20 ℃, and the product can be stored at normal temperature for more than 45 days.
Example 2
Heating 0.06kg of myristic acid to be completely melted, adding the myristic acid into 0.90kg of straight-run diesel oil, 0.10kg of methanol, 0.0005kg of Tween80, 0.01kg of isohexanol and 0.0005kg of ethyl suberate, and uniformly stirring until the myristic acid is clear and transparent, thereby obtaining the micro-emulsified methanol diesel oil with the methanol weight fraction of 10 w%. The minimum critical temperature is 9 ℃, and the product can be stored at normal temperature for more than 45 days.
Example 3
Heating 0.04kg of linolenic acid to be completely melted, adding the linolenic acid into 0.85kg of hydrogenated diesel oil, 0.15kg of methanol, 0.0003kg of Span80, 0.0003kg of Tween80, 0.04kg of linoleic acid, 0.01kg of n-heptanol and 0.0006kg of monopropyl suberate, and uniformly stirring until the mixture is clear and transparent, thereby obtaining the micro-emulsified methanol diesel oil with the methanol weight fraction of 15w percent. The minimum critical temperature is 8 deg.C, and can be stored at room temperature for more than 40 days.
Example 4
Heating 0.11kg of palmitic acid to be completely melted, adding the palmitic acid into 0.80kg of hydrogenated diesel oil, 0.20kg of methanol, 0.0003kg of Span80, 0.0003kg of Tween80, 0.01kg of isoheptanol and 0.0006kg of monomethyl azelate, and uniformly stirring until the mixture is clear and transparent, thereby obtaining the micro-emulsified methanol diesel oil with the methanol weight fraction of 20 w%. The minimum critical temperature is 18 ℃, and the product can be stored for more than 42 days at normal temperature.
Example 5
Heating 0.07kg of eicosanoic acid to be completely melted, adding the eicosanoic acid into 0.75kg of hydrogenated diesel oil, 0.25kg of methanol, 0.0007kg of Span80, 0.06kg of linoleic acid, 0.01kg of n-tetradecanol and 0.0007kg of ethyl azelate, and uniformly stirring until the mixture is clear and transparent, thereby obtaining the microemulsified methanol diesel oil with the methanol weight fraction of 25w percent. The minimum critical temperature is 9 deg.C, and can be stored at room temperature for more than 40 days.
Example 6
Heating 0.07kg of capric acid and 0.07kg of myristic acid to be completely melted, adding the heated materials into 0.70kg of straight-run diesel oil, 0.30kg of methanol, 0.0004kg of Span80, 0.0004kg of Tween80, 0.02kg of n-tetradecanol and 0.0007kg of monopropyl azelate, and uniformly stirring the materials until the materials are clear and transparent, thereby obtaining the micro-emulsified methanol diesel oil with the methanol weight fraction of 30w percent. The minimum critical temperature is 16 deg.C, and can be stored at room temperature for more than 50 days.
Example 7
Heating 0.08kg of linolenic acid to be completely melted, adding the linolenic acid into 0.65kg of hydrogenated diesel oil, 0.35kg of methanol, 0.0004kg of Span80, 0.0004kg of Tween80, 0.09kg of linoleic acid, 0.01kg of isohexanol and 0.0008kg of ethylene glycol monomethyl ether, and uniformly stirring until the mixture is clear and transparent, thereby preparing the micro-emulsified methanol diesel oil with the methanol weight fraction of 35 w%. The minimum critical temperature is 22 deg.C, and can be stored at room temperature for more than 55 days.
Example 8
Heating 0.10kg of myristic acid to be completely melted, adding the myristic acid into 0.60kg of hydrogenated diesel oil, 0.40kg of methanol, 0.0008kg of Span80, 0.10kg of linoleic acid, 0.01kg of n-heptanol and 0.0008kg of ethylene glycol monobutyl ether, and uniformly stirring until the myristic acid is clear and transparent to obtain the micro-emulsified methanol diesel oil with the methanol weight fraction of 40w percent. The minimum critical temperature is 12 deg.C, and can be stored at room temperature for more than 40 days.
Example 9
Heating 0.11kg of palmitic acid to be completely melted, adding the palmitic acid into 0.55kg of hydrogenated diesel oil, 0.45kg of methanol, 0.0009kg of Tween80, 0.11kg of linolenic acid, 0.01kg of isoheptanol and 0.0009kg of ethylene glycol monobutyl ether, and uniformly stirring until the mixture is clear and transparent, thereby obtaining the micro-emulsified methanol diesel oil with the methanol weight fraction of 45w percent. The minimum critical temperature is 20 deg.C, and can be stored at room temperature for more than 50 days.
Example 10
Heating 0.12kg of eicosanoic acid to be completely melted, adding the eicosanoic acid into 0.50kg of hydrogenated diesel oil, 0.50kg of methanol, 0.0005kg of Span80, 0.0005kg of Tween80, 0.12kg of linoleic acid, 0.01kg of n-tetradecanol and 0.0010kg of propylene glycol monomethyl ether, and uniformly stirring until the mixture is clear and transparent, thereby obtaining the micro-emulsified methanol diesel oil with the methanol weight fraction of 50 w%. The minimum critical temperature is 10 ℃, and the product can be stored for more than 45 days at normal temperature.
Comparative example 1
A methanol diesel oil emulsion having a methanol weight fraction of 45 w% was prepared. The used compound emulsifier comprises the following components in percentage by weight: adding 0.09kg of the compound emulsifier into 0.55kg of hydrogenated diesel oil and 0.45kg of methanol, and then carrying out ultrasonic dispersion uniformly, wherein the ratio of the ultrasonic dispersion parameters is as follows: the power is 400W, the time is 10min, and the prepared emulsified methanol diesel oil can be stored for 1 day at normal temperature (25 ℃).
Comparative example 2
A methanol diesel oil emulsion having a methanol weight fraction of 45 w% was prepared. The used compound emulsifier comprises the following components in percentage by weight: tween20, oleic acid, sodium carboxymethylcellulose and n-amyl alcohol in a ratio of 1:3:2:3, 0.09kg of the compound emulsifier is added into 0.55kg of hydrogenated diesel oil and 0.45kg of methanol, and then ultrasonic dispersion is carried out uniformly, wherein the ultrasonic dispersion parameters are as follows: the power is 350W, the time is 15min, and the prepared emulsified methanol diesel oil can be stored for 2 days at normal temperature (25 ℃).
FIG. 1 is a graph comparing the stabilization times of comparative example 1, comparative example 2 and the methanol diesel fuel blend fuel prepared in example 9 of the present invention. As can be seen from FIG. 1, the stabilization time of the micro-emulsified methanol diesel fuel mixture fuel of the invention is obviously longer than that of the emulsified methanol diesel fuel.
Obviously, the above examples are only for clearly illustrating a micro-emulsified methanol diesel fuel dispersant and its application, and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (6)

1. A micro-emulsified methanol diesel oil dispersant is characterized by comprising an emulsifier, a solubilizer and a stabilizer, wherein the emulsifier is compounded by one or two of Span80 and Tween80, and the solubilizer is C10-C20One or two of the long-chain fatty acids are compounded with C6-C14The stabilizer is C8-C9And one of dicarboxylic acid monoester, glycol ether and propylene glycol ether.
2. A micro-emulsified methanol diesel oil dispersant according to claim 1, characterized in that when the emulsifiers Span80 and Tween80 are compounded, they are added in equal weight.
3. A microemulsified methanol diesel oil dispersant according to claim 1, characterized in that solubilizer C10-C20The long-chain fatty acids of (a) include capric acid (n-capric acid), myristic acid (myristic acid), palmitic acid (palmitic acid), linoleic acid (octadecadienoic acid), linolenic acid (octadecatrienoic acid), and eicosanoic acid.
4. A microemulsified methanol diesel oil dispersant according to claim 1, characterized in that solubilizer C6-C14The fatty alcohols of (a) include isohexanol, n-heptanol, isoheptanol and n-tetradecanol.
5. According to claimThe micro-emulsified methanol diesel oil dispersant as claimed in claim 1, wherein the stabilizer is C8-C9The dicarboxylic acid monoesters and glycol ethers, propylene glycol ethers of (a) include monomethyl suberate, monoethyl suberate, monopropyl suberate, monomethyl azelate, monoethyl azelate, monopropyl azelate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether.
6. A micro-emulsified methanol diesel oil dispersant according to claim 1, wherein when the content of the emulsifier is 0.05-1 w%, the content of the solubilizer is 4-25 w% and the content of the stabilizer is 0.05-1 w%, the micro-emulsified methanol diesel oil fuel mixture with the methanol content of 5-50 w% can be prepared.
CN202111083662.6A 2021-09-16 2021-09-16 Micro-emulsified methanol diesel oil dispersant and application thereof Pending CN113897228A (en)

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