CN111303702B - Method for improving oxidation resistance stability of biological fuel oil - Google Patents

Method for improving oxidation resistance stability of biological fuel oil Download PDF

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Publication number
CN111303702B
CN111303702B CN202010327681.8A CN202010327681A CN111303702B CN 111303702 B CN111303702 B CN 111303702B CN 202010327681 A CN202010327681 A CN 202010327681A CN 111303702 B CN111303702 B CN 111303702B
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oil
antioxidant
fuel oil
biological fuel
coating
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CN111303702A (en
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盖景刚
邹倩
盖洪波
杨光
闫葳
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Panjin Lanhai Petrochemical Co ltd
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Panjin Lanhai Petrochemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Abstract

The invention discloses a method for improving the oxidation resistance stability of biological fuel oil, belonging to the technical field of fuel oil, and the method comprises the following steps: adding an antioxidant into the high polymer coating, coating the antioxidant coating on the inner wall of a biological fuel oil storage container, and drying to directly store the biological fuel oil. The antioxidant is added into the high polymer coating, the high polymer coating is uniformly coated on the inner surface of the storage container, and one or more layers of films are formed on the inner surface of the storage container through bonding, so that some surface functions of the storage container can be improved, the antioxidant function is endowed, and the oxidation induction period of the biofuel oil is effectively prolonged.

Description

Method for improving oxidation resistance stability of biological fuel oil
Technical Field
The invention belongs to the technical field of fuel oil, and particularly relates to a method for improving the oxidation resistance stability of biological fuel oil.
Background
The biofuel oil is a typical 'green energy source', and compared with fossil energy, the biofuel oil has important functions and development potentials for promoting economic sustainable development, promoting energy substitution, reducing environmental pressure and controlling urban atmospheric pollution. However, the biofuel oil is susceptible to the influence of light, oxygen, temperature, moisture, trace metal ions and other factors during storage and transportation, and is inevitably oxidized. Along with the extension of the oxidation time, indexes such as viscosity, density and the like of the biological fuel oil are increased, the discharged HC, smoke intensity and particle number are increased due to the oxidized biological fuel oil, the nitrogen oxide is reduced, the combustion efficiency is reduced, and the effective fuel consumption rate is increased. The secondary oxidation product causes phenomena such as odor, biological fuel oil layering and the like, can cause engine corrosion in the using process, generates macromolecular colloidal substances by polymerization in an oil way, causes a series of problems such as fuel system gel formation, difficult filtration, oil way and oil nozzle blockage and unstable power and the like. Thus, oxidation affects not only the quality of the biofuel oil, but also the operation of the various systems of the motor vehicle, shortening the service life of the vehicle. The poor oxidation resistance and stability of the biofuel oil severely restricts the development and commercial application of the biofuel oil. The oxidation stability of the biological fuel oil is not less than 6h, which is specified by China national standard for biological fuel oil, and the performance of most biological fuel oils is difficult to reach the standard. Therefore, optimizing the oxidation stability of biofuel oil is one of the problems that must be faced and solved during the research and development of biofuel oils.
At present, the method which is most researched and widely applied is to add an antioxidant into the biofuel oil to improve the antioxidant performance of the biofuel oil. The conventional antioxidant has good antioxidant effect, but the dissolving capacity of the antioxidant in the biofuel oil is small, so that the antioxidant effect of the antioxidant in the biofuel oil is influenced. How to economically and effectively improve the oxidation stability of the biofuel oil is always a research focus, and solving the problem is undoubtedly of great significance for improving the use efficiency of the biofuel oil, better utilizing the clean alternative energy and promoting the development of the biofuel oil industry.
Disclosure of Invention
The invention aims to provide a method for improving the oxidation resistance stability of biological fuel oil, which comprises the following steps: adding an antioxidant into the high polymer coating, coating the antioxidant coating on the inner wall of a biological fuel oil storage container, and directly storing the biological fuel oil after drying.
According to the method for improving the oxidation resistance stability of the biological fuel oil, the antioxidant is directly added into the high polymer coating and mixed uniformly.
According to the method for improving the oxidation resistance stability of the biological fuel oil, the antioxidant is grafted to the polymer in the polymer coating in an adding mode.
According to the method for improving the oxidation resistance stability of the biological fuel oil, the addition amount of the antioxidant is 0.01-5 wt% of the mass of the high polymer coating; preferably, the addition amount of the antioxidant is 1-3 wt% of the mass of the high polymer coating.
In the method for improving the oxidation resistance stability of the biofuel oil, the antioxidant is selected from more than one of natural antioxidants or artificially synthesized antioxidants;
preferably, the natural antioxidant is selected from more than one of propyl gallate, protocatechinic acid, tea polyphenol, vitamin or chitosan; the synthetic antioxidant is selected from more than one of butyl hydroxy anisol, dibutyl hydroxy toluene, propyl gallate, di-tert-butyl hydroquinone or tert-butyl hydroquinone.
In the method for improving the oxidation resistance stability of the biological fuel oil, the solid content of the high polymer coating is 1-60%.
In the method for improving the oxidation resistance stability of the biological fuel oil, the base material of the high polymer coating is a natural high polymer material or an artificially synthesized high polymer material; preferably, the natural polymer material is selected from starch, cellulose, chitin or chitosan; the artificially synthesized high polymer material is selected from polyvinyl alcohol, polylactic acid, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, nylon, polycarbonate, polyurethane or polyethylene terephthalate.
The method for improving the oxidation resistance stability of the biofuel oil comprises the step of coating, wherein the coating mode is airless spraying, air spraying, electrostatic spraying or mechanical dip coating.
According to the method for improving the oxidation resistance stability of the biological fuel oil, the biological fuel oil storage container is a stainless steel container or a plastic container.
According to the method for improving the oxidation resistance stability of the biological fuel oil, the biological fuel oil is prepared from one or more of soybean oil, corn oil, peanut oil, rapeseed oil, palm oil, sesame oil, sunflower seed oil, linseed oil, cottonseed oil, linseed oil, safflower seed oil, hemp seed oil, linseed oil, camellia seed oil, peony seed oil, walnut oil, coconut oil and olive oil.
Compared with the prior art, the invention has the beneficial effects that:
the antioxidant is added into the high molecular paint, the high molecular compound paint is uniformly coated on the inner surface of the storage container, and one or more layers of films are formed on the inner surface of the storage container through bonding, so that some surface functions of the storage container can be improved, the antioxidant function is endowed, and the oxidation induction period of the biofuel oil is effectively prolonged.
Detailed Description
A method for improving the oxidation resistance stability of biological fuel oil comprises the following steps: adding an antioxidant into the high polymer coating, coating the antioxidant coating on the inner wall of a biological fuel oil storage container, and directly storing the biological fuel oil after drying.
In the method, two adding modes of the antioxidant are provided, wherein one mode is to directly add the antioxidant into the high-molecular coating and mix the antioxidant uniformly; the other is to graft an antioxidant to a polymer in a polymer coating. Wherein, the antioxidant with the same dosage is added into the high molecular paint in a grafting way, so that the antioxidant effect on the biological fuel oil is better.
In the method, the addition amount of the antioxidant is increased, the induction period is prolonged, but the addition amount is controlled to be less than 5 wt%, the effect of the antioxidant can be achieved, and if the addition amount of the antioxidant is too high, the fluidity, the spraying property, the film forming property and the like of the coating liquid are influenced. Therefore, the addition amount of the antioxidant is 0.01-5 wt% of the mass of the high polymer coating; preferably, the addition amount of the antioxidant is 1-3 wt% of the mass of the high polymer coating.
The antioxidant used in the invention is selected from more than one of natural antioxidant or artificial synthetic antioxidant; preferably, the natural antioxidant is selected from more than one of propyl gallate, protocatechinic acid, tea polyphenol, vitamin or chitosan; the synthetic antioxidant is selected from more than one of butyl hydroxy anisol, dibutyl hydroxy toluene, propyl gallate, di-tert-butyl hydroquinone or tert-butyl hydroquinone. In the method of the invention, the effect of the synergistic effect of the two antioxidants is better than that of a single antioxidant.
The high molecular coating in the method is only a carrier of the antioxidant, so the solid content of the high molecular coating has no influence on the improvement of the oxidation resistance stability of the biofuel oil, and the high molecular coating can be uniformly coated on the surface of a container to form a film. Preferably, the solid content of the high molecular coating in the method is 1-60%.
The antioxidant is added into the polymer coating and coated on the inner wall of the biofuel oil storage container, so that the oxidation stability of the biofuel oil is optimized. Different from the traditional biological fuel oil antioxidant research method, the antioxidant is innovatively coated on the inner wall of the container instead of being directly added into the biological fuel oil, so that the problem of poor solubility of the antioxidant in the biological fuel oil can be avoided.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Adding 3 wt% of propyl gallate into the polytetrafluoroethylene coating liquid (the solid content is 40%) at room temperature, stirring for 2h, uniformly mixing, and performing ultrasonic defoaming treatment for later use. Deoiling and roughening the inner wall of a biofuel oil stainless steel container, spraying the antioxidant polytetrafluoroethylene coating liquid on the surface of the inner wall through air spraying, sending the inner wall into an oven at 80 ℃, and heating for 1h at the temperature of 250 ℃ after drying moisture. The resulting container is used for biofuel oil storage made from soybean oil.
The induction period of the biofuel oil stored in this example was extended to 30.17 h.
Example 2
Adding 1.5 wt% of propyl gallate and 1.5 wt% of butyl hydroxy anisol into polytetrafluoroethylene coating liquid (the solid content is 40%) at room temperature, continuously stirring for 2h, uniformly mixing, and performing ultrasonic treatment and defoaming treatment for later use. Deoiling and roughening the inner wall of a biofuel oil stainless steel container, spraying the antioxidant polytetrafluoroethylene coating liquid on the surface of the inner wall through air spraying, sending the inner wall into an oven at 80 ℃, and heating for 1h at the temperature of 250 ℃ after drying moisture. The resulting container is used for biofuel oil storage made from soybean oil.
The induction period of the biofuel oil stored in this example was extended to 33.87 h.
Example 3
Placing polyvinyl alcohol in distilled water, stirring and swelling for 3.5h at 50 ℃, heating to 85 ℃, and stirring until PVA is completely dissolved to obtain 4 wt% polyvinyl alcohol solution; cooling to 50 ℃, then slowly adding 3 wt% of tea polyphenol into the polyvinyl alcohol solution, carrying out ultrasonic treatment for 1 hour, uniformly mixing, standing and defoaming for later use. Wiping the inner wall of a plastic container of the biofuel oil, spraying the antioxidant polyvinyl alcohol coating liquid on the surface of the inner wall in an electrostatic spraying mode, and drying in a drying oven at the temperature of 80 ℃. The resulting container is used for biofuel oil storage from palm oil.
The induction period of the biofuel oil stored in this example was extended to 51.32 h.
Example 4
Dissolving polylactic acid in dichloromethane at normal temperature, carrying out ultrasonic 200W homogenization until the polylactic acid is completely dissolved to prepare a 4 wt% polylactic acid solution, then adding 3 wt% dibutyl hydroxy toluene, continuing ultrasonic treatment for 2h, uniformly mixing, standing and defoaming for later use. Wiping the inner wall of a plastic container of the biological fuel oil, spraying the antioxidant polylactic acid coating liquid on the surface of the inner wall through electrostatic spraying, and forming a uniform antioxidant film on the inner wall at room temperature after the solvent naturally volatilizes in a ventilation position. The resulting container is used for the storage of biofuel oil made from peanut oil.
The induction period of the biofuel oil stored in this example was extended to 19.99 h.
Example 5
Dissolving chitosan in 2 wt% acetic acid water solution, and stirring at room temperature for 4h to obtain 4 wt% chitosan solution; and then adding 3 wt% of vitamin E into the chitosan solution, carrying out ultrasonic treatment for 1 hour, uniformly mixing, standing and defoaming for later use. Wiping the inner wall of a plastic container for biological fuel oil, coating the anti-oxidation chitosan coating liquid on the surface of the inner wall in a mechanical dip-coating mode, and drying in a 50 ℃ oven to form a uniform anti-oxidation film on the inner wall. The resulting container is used for biofuel oil storage from illegal cooking oil.
The induction period of the biofuel oil stored in this example was extended to 7.43 h.
Example 6
Dissolving chitosan in 2 wt% acetic acid water solution, and stirring at room temperature for 4h to obtain 4 wt% chitosan solution; 100mL of the chitosan solution was taken in a 150mL three-necked flask, and 1.68g of adenine (vitamin B4) powder was added at 90 ℃ until the adenine was completely dissolved, and the molar ratio of adenine to chitosan units was 1: 1. Then 0.5mL of formaldehyde solution was slowly added dropwise with stirring at 90 ℃ to react for 72 hours, and adenine was grafted onto chitosan. Wiping the inner wall of a plastic container for biological fuel oil, coating the anti-oxidation chitosan coating liquid on the surface of the inner wall in a mechanical dip-coating mode, and drying in a 50 ℃ oven to form a uniform anti-oxidation film on the inner wall. The resulting container was used for biofuel oil storage from rapeseed oil.
The induction period of the biofuel oil stored in this example was extended to 27.51 h.

Claims (1)

1. The method for improving the oxidation resistance stability of the biological fuel oil is characterized by comprising the following steps:
dissolving chitosan in 2 wt% acetic acid water solution, and stirring at room temperature for 4h to obtain 4 wt% chitosan solution; 100mL of the chitosan solution is weighed in a 150mL three-neck flask, 1.68g of adenine powder is added at 90 ℃ until adenine is completely dissolved, and the molar ratio of adenine to chitosan units is 1: 1; then slowly dropwise adding 0.5mL of formaldehyde solution under stirring at 90 ℃, reacting for 72 hours, and grafting adenine onto chitosan; wiping the inner wall of a plastic container for biological fuel oil, coating the anti-oxidation chitosan coating liquid on the surface of the inner wall in a mechanical dip-coating mode, and drying in a 50 ℃ drying oven to form a uniform anti-oxidation film on the inner wall; the resulting container was used for biofuel oil storage from rapeseed oil.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101475760A (en) * 2009-01-16 2009-07-08 上海瓷龙化工有限公司 Oil product antioxidant material and preparation thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9953739B2 (en) * 2011-08-31 2018-04-24 Tesla Nanocoatings, Inc. Composition for corrosion prevention

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101475760A (en) * 2009-01-16 2009-07-08 上海瓷龙化工有限公司 Oil product antioxidant material and preparation thereof

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