WO2017096680A1

WO2017096680A1 - Environment-friendly antistatic agent for oil product and use method thereof

Info

Publication number: WO2017096680A1
Application number: PCT/CN2016/070037
Authority: WO
Inventors: 熊靓; 严斌; 张捷
Original assignee: 深圳市广昌达实业有限公司; 深圳市广昌达石油添加剂有限公司
Priority date: 2015-12-11
Filing date: 2016-01-04
Publication date: 2017-06-15
Also published as: CN105400555B; CN105400555A

Abstract

A compound environment-friendly antistatic agent for oil products and a use method thereof. The formulation of the antistatic agent consists of a polyamine, an organic acid or an amide copolymer, an amphoteric quaternary ammonium carboxylate inner salt, a polyol fatty acid ester or an amide, and a solvent. The antistatic agent is directly added to oil products for use. The antistatic agent is free of heavy metals and elements such as sulfur and phosphorus, safe, environment-friendly, small in addition amount, high in antistatic efficiency, and capable of effectively eliminating potential safety hazards caused by static during oil product storage and transportation.

Description

Environmentally friendly oil antistatic agent and using method thereof

Technical field

The invention belongs to the field of chemistry and chemical industry, and in particular relates to a composite environmental protection oil antistatic agent.

Background technique

The main components of gasoline, diesel, aviation kerosene and other fuels are hydrocarbon compounds, and the conductivity is very low. In recent years, with the upgrading of the quality of finished products, diesel, the control of sulfur content in oil products has become more and more strict, steam, Diesel hydrorefining solves the problem of sulfur content in oil products, and also removes natural polar substances (such as sulfur, nitrogen compounds and carboxylic acids) in oils, making the conductivity of fuels worse. . During the production, storage, refueling and use of these fuels, the interface friction with the filter medium, the container, the pipe wall, etc. is very easy to generate static charge. When the charge accumulates to a certain extent, it will generate static sparks, which is easy to ignite explosive mixture. Gas caused a major disaster. Therefore, eliminating the electrostatic hazard of oil products and improving the safety of oil use are necessary measures in the field of oil application.

Commonly used measures to eliminate static electricity of oil are: 1) Grounding discharge static electricity, that is, static electricity is introduced into the earth through the connecting device, reducing the possibility of discharge to the ground, but the static charge in the container cannot be changed, which has great limitations. ; 2) change the storage conditions, mainly to change the air humidity, because the object is charged and the humidity of the environment is closely related; 3) use the process control to reduce the speed of the oil delivery process; 4) the conductive coating, the inner wall coating can guide Some nano or other conductive substances of static electricity to conduct static charge; 5) use static eliminator to neutralize the ions of the object itself by using ions generated by the static eliminator; 6) add antistatic agent, use the pole of antistatic agent Sexual characteristics, reduce the thickness of the galvanic layer until it disappears to reduce the static electricity of the oil. Among all these measures to eliminate static electricity, the addition of antistatic agents is the most convenient and effective method and the most widely used method.

Antistatic agents are usually ionic, nonionic or amphoteric surfactants with strong adsorptivity, Ionicity and surface activity prevent the accumulation of static charge and accelerate the leakage rate of static charge. The research and application of antistatic agents abroad started earlier, and there are many patent reports. However, there are still many shortcomings in the practical and theoretical aspects of oil antistatic agents in China. At present, the antistatic agents for oils sold in the domestic market mainly include ASA-3. STD-450, T1501, T1502, etc., with fewer varieties and mainly foreign brands. Antistatic additives are broadly classified into gray type and ashless type. Gray type antistatic additives have problems such as high toxicity, poor production process conditions, serious environmental pollution, easy emulsification of oil products and unacceptable water separation index. At home and abroad, production and use have been discontinued around 2000 years ago; The additive has the advantages of high conductivity, good water separation property, no chromium pollution after combustion and multiple additions, but the main components of the ashless antistatic agent currently marketed are polysulfone and polyamine, and polysulfone production process. Complex, and due to sulfur-containing elements, combustion will produce sulfides, which are likely to cause environmental pollution. Therefore, the development of a cheap and efficient environmentally-friendly antistatic agent is an urgent and arduous task in the field of research and development of antistatic agents for oils.

Summary of the invention

In view of the current situation of China's oil antistatic agent type, poor effect, serious environmental pollution, etc., the present invention provides a composite ring oil product antistatic agent. The product of the invention has small dosage, good antistatic effect and can reduce pollutant discharge at the same time.

The specific scheme of the invention is as follows:

An environmentally friendly oil antistatic agent characterized by comprising 20 to 80% polyamine, 20 to 80% organic acid or amide copolymer, 0 to 20% amphoteric quaternary ammonium carboxylate inner salt, 0 parts by weight ～20% fatty acid polyol ester or amide and 10-30% solvent composition.

An environmentally friendly oil antistatic agent characterized by comprising 30 to 45% polyamine, 30 to 45% organic acid or amide copolymer, 5 to 10% amphoteric quaternary ammonium carboxylate internal salt, 5 parts by weight ～10% fatty acid polyol ester or amide and 15 to 25% solvent composition.

Further, the polyamine is a mixture of one or more of dodecylamine, octadecylamine, and aniline polyamine, preferably dodecylamine.

Further, the organic acid or amide copolymer is a mixture of one or more of an acrylic acid-methyl acrylate copolymer, an acrylamide-ethylene copolymer, a maleimide-styrene copolymer, preferably Malay. Imide-styrene copolymer.

Further, the amphoteric quaternary ammonium carboxylate inner salt is a betaine or an imidazoline quaternary ammonium salt, preferably an imidazoline quaternary ammonium salt.

Further, the fatty acid polyol ester or amide is one of glyceryl oleate, sorbitan oleate and oleic acid diethanolamide, preferably oleic acid glyceride.

Further, the solvent is a mixture of one or more of toluene, xylene, gasoline, diesel and kerosene, preferably xylene.

Further, the antistatic agent may be directly added to the oil for use in an amount of 1 to 10 ppm, preferably 2 to 5 ppm.

The above components are mixed and stirred at 50 ° C for 0.5 to 2 hours to obtain the finished antistatic agent of the present invention. The antistatic agent of the present invention can be used for various oils such as gasoline, diesel, aviation kerosene, naphtha, etc., and the recommended addition amount is 1 to 10 ppm, preferably 2 to 5 ppm.

Mechanism of action: In the antistatic additive of the present invention, the main component polyamine can obtain protons and be partially positively charged, while the organic acid/amide copolymer can lose protons and partially negatively charge, thereby easily forming dipole ion pairs. When an external electric field is present, the dipole ion pairs are aligned, one end of the positively charged polyamine is turned to the negative electrode of the external electric field, and one end of the negatively charged organic acid/amide copolymer is turned to the external electrostatic field positive electrode to form an external electrostatic field pole. The opposite "polarized electric field", which reduces the external electrostatic field strength and acts as an antistatic. If the external electrostatic field is strong, the dipole ion pair can finally be separated into positively and negatively charged ions under strong inducing force, showing stronger conductivity; in the case of low external electric field, the conductivity is mainly By betaine or imidazoline The quaternary ammonium carboxylic acid inner salt is provided to compensate for the lack of conductivity of the low main agent polyamine and the organic acid/amide copolymer, thereby enhancing the susceptibility of the product of the present invention to different oil environments. The fatty acid polyol ester or amide nonionic surfactant also provides the functions of solubilization, anti-wear and fuel economy while providing antistatic function.

The invention has the advantages that: 1) the addition amount is small, the operation is simple, the cost is low, and the antistatic effect is remarkable; 2) the compatibility with other oil additives is good, the oil property is not affected, and the solubilization, antiwear and energy saving are also provided. And other functions; 3) non-toxic, free of heavy metals, sulfur, phosphorus and other elements, reducing the pollution of the atmosphere.

Specific embodiment

The invention will be further described below in conjunction with specific embodiments. However, the technical content described in this embodiment is illustrative and not limiting, and the scope of the present invention should not be limited thereto.

Raw material oil: 93# gasoline and O# diesel produced by a petrochemical company in Northwest China (both without antistatic agent). The conductivity data of steam and diesel are shown in Table 1.

Table 1 Conductivity of steam and diesel

样品sample	93#汽油93# gasoline	0#柴油0# diesel
电导率，pS·m^-1 Conductivity, pS·m ^-1	3～53~5	1～31 to 3

Antistatic agent: The components are mixed and stirred at a certain ratio of 50 ° C for 1 hour to obtain an antistatic agent sample to be tested.

Test instrument: MAIHAK MLA 900 (digital) conductivity tester; test method: GB/T6539 "Aeronautical fuel and distillate fuel conductivity measurement method".

Table 2 Effect of polyamines on antistatic effect

Note: 1) Antistatic agent sample component polyamine: acrylic acid-methyl acrylate copolymer: xylene = 2: 2: 1 (weight ratio); 2) dosage 5 ppm.

From the data in the table, the dodecylamine polyamine effect is better.

Table 3 Effect of organic acid or amide copolymer on antistatic effect

Note: 1) Anti-static agent sample component dodecamine polyamine: organic acid or amide copolymer: kerosene = 2:2:1 (weight ratio); 2) dosage of 5ppm.

From the data in the table, the maleimide-styrene copolymer works well. In addition, the data in Tables 2-3 also show that the antistatic effect of using kerosene as solvent is not as good as that of xylene, which may be due to the different strength of the polarizing action of different solvents against the electrostatic agent. The aromatic hydrocarbon solvent has a strong polarization against the electrostatic agent molecules, and the antistatic agent is liable to form charged ions, and the electrical conductivity is high. Therefore, xylene is preferred as the solvent.

Table 4 Effect of anti-static effect of amphoteric quaternary ammonium carboxylate/salt fatty acid polyol ester or amide

Note: 1) Antistatic agent sample component dodecamine polyamine: maleimide-styrene copolymer: amphoteric quaternary ammonium carboxylate inner salt / fatty acid polyol ester or amide: xylene = 3:3: 2:2 (weight ratio); 2) Dosing 5 ppm.

From the data in the table, it is better to add a mixture of imidazoline quaternary ammonium salt and oleic acid glyceride in a weight ratio of 1:1.

Table 5 Effect of compounding ratio on antistatic effect

Note: The dosage is 5ppm.

According to the data in the table, in combination with cost considerations, the components of the composite oil antistatic agent of the present invention are dodecylamine polyamine, maleimide-styrene copolymer, imidazoline quaternary ammonium salt, oleic acid glyceride and two The optimum levels of toluene are 35%, 35%, 5%, 5% and 20%, respectively.

Table 6 Effect of dosage on antistatic effect

Note: The content of the dodecylamine polyamine, maleimide-styrene copolymer, imidazoline quaternary ammonium salt, oleic acid glyceride and xylene in the antistatic agent sample is 35%, 35%, 5 respectively. %, 5% and 20%.

From the data in the table, the antistatic effect of the antistatic agent of the composite oil of the invention is equivalent to that of the imported product STADIS-450, and the dosage of 2 ppm can meet the antistatic requirement of the oil.

Claims

An environmentally friendly oil antistatic agent characterized by comprising 20 to 80% polyamine, 20 to 80% organic acid or amide copolymer, 0 to 20% amphoteric quaternary ammonium carboxylate inner salt, 0 parts by weight ～20% fatty acid polyol ester or amide and 10-30% solvent composition.
An environmentally friendly oil antistatic agent characterized by comprising 30 to 45% polyamine, 30 to 45% organic acid or amide copolymer, 5 to 10% amphoteric quaternary ammonium carboxylate internal salt, 5 parts by weight ～10% fatty acid polyol ester or amide and 15 to 25% solvent composition.
The environmentally-friendly oil antistatic agent according to claim 1 or 2, wherein the polyamine is one or more of dodecylamine, octadecylamine and aniline polyamine. mixture.
The environmentally-friendly oil antistatic agent according to claim 1 or 2, wherein the organic acid or amide copolymer is an acrylic acid-methyl acrylate copolymer, an acrylamide-ethylene copolymer, and a Malay. A mixture of one or more of an imide-styrene copolymer.
An environmentally friendly oil antistatic agent according to claim 1 or 2, wherein the amphoteric quaternary ammonium carboxylate internal salt is a betaine or an imidazoline quaternary ammonium salt.
The environmentally-friendly oil antistatic agent according to claim 1 or 2, wherein the fatty acid polyol ester or amide is oleic acid glyceride, sorbitan oleate and oleic acid diethanol. a type of amide.
An environmentally friendly oil antistatic agent according to claim 1 or 2, wherein the solvent is one or a mixture of toluene, xylene, gasoline, diesel oil and kerosene.
A method for using an environmentally-friendly oil antistatic agent, characterized in that the antistatic agent is directly added to an oil, and the amount of addition is from 1 to 10 ppm.