CN106811242A - A kind of environmentally friendly low-carbon (LC) high heating value New Marine fuel oil - Google Patents

Abstract

The invention discloses an environment-friendly, low-carbon and high calorific value marine fuel oil. The formula composition is calculated in parts by weight, including 600-750 kg of main raw materials of marine fuel oil, 250-350 kg of soft water, and 80-120 kg of hexadecane emulsion Value enhancer 1-3kg, biphenyl 0.05-0.15kg, polyisobutylamine 0.15-0.3kg, benzotriazole 0.005-0.015kg, ferrocene: 0.3kg-0.5kg. After 500kHz high-frequency, 25KW high-power ultrasonic microemulsifier and homogeneous high-speed shearing machine are mixed into marine fuel oil, marine distillate fuel oil is clear and transparent, does not change color for 3 years, and does not separate oil and water. The product of the invention is suitable for marine diesel engine main engines and generators, and has the advantages of environmental protection, low carbon, energy saving, high calorific value, low cost, rust prevention, corrosion prevention and the like.

Description

A new type of marine fuel oil with low carbon and high calorific value, which is environmentally friendly

technical field

The invention relates to an environment-friendly, low-carbon and high-calorific-value marine fuel oil, which belongs to the technical field of modified fuel oil.

Background technique

In order to save energy, reduce sulfur emissions, and reduce operating costs, the GB17411-2015 standard for marine fuel oil is a mandatory standard; the sulfur content is less than 0.5%, and the calorific value is more than 39.8MJ/kg.

The Ministry of Environmental Protection and the General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China have revised GB/T15097-2008 Ship Engine Exhaust Pollutant Emission Limits and Measurement Methods (China's first and second phases). It is stipulated that the GB17411-2015 marine fuel oil standard will be implemented from July 1, 2016.

According to the new standard requirements: the cost of blending bunker fuel oil with traditional technology will be high.

In view of this, the present inventor has completed the present invention through many years of experiments. Through practical tests, the marine distillate fuel oil of the present invention does not change color for 3 years, is clear and transparent, and has no oil-water layering. All technical indicators meet the requirements of the GB17411-2015 standard.

Contents of the invention

The purpose of the present invention is to provide an environment-friendly, low-carbon, high-calorific-value marine fuel oil. It can solve the defects of the existing emulsified fuel oil, such as low cetane number, poor cold car startability, insufficient power, high fuel consumption, engine damage due to long-term use, etc., and meets the needs of marine fuel oil standards.

The characteristics of marine fuel oil of the present invention are as follows:

or:

The technical problems to be solved by the present invention can be realized through the following technical solutions.

Use 200-350Kg of soft water by weight, use 500KHZ ultrasonic emulsification technology to denature water molecules, then add the following components (except soft water), and use high-speed shearing machine to mix and micro-emulsify. It is characterized in that the components are in parts by weight, including as follows:

The main raw material of the marine fuel oil described in the present invention must meet the marine distillate fuel oil and marine residual fuel oil or biodiesel in the GB17411-2015 standard. It can also be used as a raw material or mixed with marine distillate fuel oil and marine residual fuel oil.

The soft water described in the present invention is the soft water treated by active carbon or soft water equipment.

The ratio by weight of marine distillate fuel oil and/or marine residual fuel oil and water in the formulation composition of the present invention is preferably 700kg:300kg.

The cetane number improving agent of the present invention is isooctyl nitrate, density: 0.963kg/liter, molecular weight: 175.22788, molecular formula: (C8H17)NO2; Spontaneous ignition point: 250 ℃; Closed flash point: 76 ℃; Acid value : (KOH) 36mg/g. Good compatibility with diesel and bunker fuel oil. The usage amount of the cetane number improving agent in the formula composition of the present invention is 2-4 kg by weight. Preferably it is 3 parts by weight.

The biphenyl described in the present invention has a molecular formula: C12H10 and a molecular weight of 154.21. It is a preservative, a high-energy fuel and a heat carrier. It is a low toxicity chemical. In the formula composition of the present invention, the biphenyl used in the marine fuel oil is used in an amount of 0.05-0.15 parts by weight. Preferably it is 0.1 part by weight.

The diesel detergent described in the present invention is polyisobutylene amine (PIBA), which is a surfactant and has the functions of cleaning, dispersing and demulsifying. It can disperse the sediment formed in the engine oil circuit system and prevent the sediment from depositing on the fuel injector, combustion chamber, etc. The deposits that have formed in these parts can be peeled off from the metal surface, dispersed, and peptized in marine fuel oil, so that these parts can restore the technical parameters of the new car. In the formula composition of the present invention, the amount of polyisobutene amine used in marine fuel oil is 0.1-0.3 parts by weight. It is preferably 0.2 parts by weight.

The anti-corrosion and anti-rust agent used in the present invention is benzotriazole, which is a kind of chemical, which is sheet-like, dissolves in water, forms a layer of film on the metal surface, and is a kind of anti-corrosion, anti-rust agent. The anti-corrosion and anti-rust agent used in marine fuel oil is used in an amount of 0.005-0.015 parts by weight, preferably 0.01 parts by weight.

The energy-saving and smoke-eliminating combustion accelerator used in the present invention is ferrocene, which is an organic transition metal compound with aromatic properties. It is an orange-yellow powder at room temperature, with a boiling point of 250 ° C. It is soluble in diesel oil, aromatic hydrocarbons, etc. Organic solvents. It has stable chemical properties and does not decompose within 400°C. It is a superior energy-saving combustion accelerator. The amount of ferrocene used in marine fuel oil is 0.5-1.5 parts by weight, and the best effect is 1 part by weight.

Emulsion is a compound liquid, main ingredient 1: Span 80 (Spah80); Chinese name; sorbitan monooleate, molecular weight: 429, is a nonionic surfactant, mainly used as w/o Emulsion, the addition amount is 0.48 parts by weight. Main agent 2: cetyltrimethylammonium ammonium (CTMAB), chemical formula: C19H42BrN; it is a quaternary ammonium salt, which has good coordination with anionic, nonionic and amphoteric surfactants, and is an excellent w /o emulsion, the addition amount is 0.52 parts by weight. 3: Octanol raffinate can be used as an additive, (containing 30% octanol, 20% butanol, and 50% C6-C10 fatty alcohol), density: (20°C), 0.87kg/liter, calorific value: 8500kcaI/ kg, can also replace octanol raffinate with pentanol, the amount added; 50 parts by weight.

Above-mentioned isooctyl nitrate, biphenyl, polyisobutenylamine, benzotriazole, ferrocene etc. are all commercially available chemical products. Span 80 and CTMAB are products of Jiangsu Haian Petrochemical Plant. Octanol raffinate was produced by Shandong Zibo Yuqiang Technology Co., Ltd.

Environmental protection, low carbon, high calorific value marine fuel oil of the present invention, its preparation method is a kind of physical mixing method, first soft water is used 500kHz ultrasonic emulsification technology, makes water molecular denaturation and formula composition of marine fuel oil (except soft water) , heated to 50°C±5°C, put into a high-speed shear mixer and stirred evenly, and precipitated for 24 hours to 48 hours. After filtering with a 400 mesh diesel fine filter, it becomes usable marine fuel oil.

Biofuel refers to fuel ethanol, biofuel and aviation biofuel produced from biological resources, which can replace gasoline and diesel produced from petroleum, and is an important direction for the development and utilization of renewable energy. The so-called biological resources refer to various organisms produced through photosynthesis by using the atmosphere, water, and land, that is, all living organic substances that can grow. It includes plants, animals, and microorganisms. Different from traditional fuels such as petroleum, coal, and nuclear energy, these emerging fuels are renewable fuels.

At present, biofuel has been studied more as a fuel that can replace diesel. Biofuel, namely fatty acid methyl ester, is a kind of oxygen-containing clean fuel. It has attracted people's attention because of its advantages of high combustion rate, less pollution, and regeneration. At present, biofuels are mainly produced by chemical methods, that is, animal and vegetable oils and low-carbon alcohols such as methanol or ethanol are used for transesterification under acid or alkaline catalysts and high temperatures (230-250°C) to generate corresponding fatty acid formaldehyde ester or ethyl ester.

The invention also provides a production method of bio-fuel, which can effectively increase the oil production rate and reduce the reaction temperature through biological pre-fermentation and then extraction, and meets the requirements of the new generation of energy saving and environmental protection.

Advantages of the present invention:

The invention provides an environmentally friendly, low-carbon, high calorific value marine fuel oil, the main raw material of which is 4 types of marine distillate fuel oil, DMX, DMA, DMZ, DMB and 6 types of marine residual fuel oil that meet the GB17411-2015 standard RMA10, RMB30, RMD80, RME180, RMG380, RMG500 and biodiesel. Use 700kg of marine distillate fuel oil and/or marine residual fuel oil, add 300kg of soft water, use 500kHz ultrasonic emulsification technology to denature water molecules, add 3kg of cetane number improver, 0.1kg of calorific value improver, and 0.2kg of diesel detergent , 0.01kg of anti-corrosion, anti-rust agent and 1kg of energy-saving, combustion accelerator, the main technical requirements of the obtained product: pour point: 0--6 ℃, closed flash point: not less than 62 ℃, cetane number index: Not less than 40, calorific value: not less than 39.8MJ/kg. Sulfur content: less than 0.5%, carbon aromaticity index: not more than 850.

detailed description

The embodiments of the present invention are described in detail below, and the embodiments are only used to explain the present invention, and should not be construed as limiting the present invention.

Specific examples of the present invention are described below.

Example 1

The concrete formula composition of a kind of environmental protection, low carbon, high calorific value marine fuel oil of the present invention is as follows:

In the above-mentioned embodiment 1, the main raw material is marine distillate fuel oil.

Cut distillate fuel oil, emulsion and soft water at room temperature, use 500kHz high-frequency, 25KW high-power ultrasonic microemulsion technology to cut the particle size of oil molecules and water molecules to <50 nanometers, and stir them evenly through a homogeneous high-speed shearing machine. After filtering with a 400-mesh diesel fine filter, the marine fuel oil product is obtained.

Example 2:

Another specific formula of the present invention's environmental protection, low carbon, high calorific value marine fuel oil is composed as follows, and its preparation method is as described in embodiment 1:

In the above-mentioned embodiment 2, the indicators of the marine residual fuel oil must meet the standards of GB17411-2015.

In the above-mentioned embodiment 2, di-tert-butyl peroxide can also be used as the cetane number improver, and the addition amount is 0.3% by weight, which can increase the cetane number by 8-9 units and increase the calorific value by 10%.

In the above-mentioned embodiment 2, biphenyl is a kind of high-energy fuel, and the addition amount of 0.01% by weight can increase the calorific value by 8%.

In the above example 2, benzotriazole is a kind of anticorrosion and antirust agent dissolved in water, and the addition amount is 0.001% by weight.

The ferrocene in the above-mentioned embodiment 2 is an energy-saving combustion accelerator, and the addition amount is 0.1% by weight, which can increase the calorific value by 10-14%.

The inventor found that when carrying out small-scale tests, the main raw material of marine fuel oil used 700kg when adding soft water 300kg, the added cetane number enhancer, biphenyl, ferrocene, first they were uniformly mixed in marine fuel oil Among the main raw materials, after mixing benzotriazole and water, ultrasonic technology is used to denature water molecules into microemulsions, which can be mixed with hydrocarbon diesel and marine fuel oil without oil-water separation.

Add cetane number enhancers including isooctyl nitrate and di-tert-butyl peroxide, biphenyl, polyisobutene amine, benzotriazole, ferrocene, which can reduce the spontaneous ignition point of fuel and increase the cetane number , Improve fuel combustion characteristics, increase fuel combustion efficiency, promote combustion, increase engine power, reduce engine wear, avoid carbon deposits in diesel engine cylinders, and reduce fuel consumption and exhaust emissions. It is an environmentally friendly, low-carbon, high calorific value marine fuel oil.

Example 3

Another specific formula of the present invention's environmental protection, low carbon, high calorific value marine fuel oil is composed as follows, and its preparation method is as described in embodiment 1:

In the above-mentioned embodiment 3, di-tert-butyl peroxide can also be used as the cetane number improver, and the addition amount is 0.3% by weight, which can increase the cetane number by 8-9 units and increase the calorific value by 10%.

In the above-mentioned embodiment 3, biphenyl is a kind of high-energy fuel, and the addition amount of 0.01% by weight can increase the calorific value by 8%.

In the above example 3, benzotriazole is a kind of anti-corrosion and anti-rust agent dissolved in water, and the addition amount is 0.001% by weight.

The ferrocene in the above-mentioned embodiment 3 is an energy-saving combustion accelerator, and the addition amount is 0.1% by weight, which can increase the calorific value by 10-14%.

The preparation method of described biodiesel is:

Oil yield (%) of cyanobacteria extracted oil=weight of cyanobacteria extracted oil/cyanobacteria weight×100%.

(1) Pre-fermented Spirulina:

Mix the cyanobacteria with 0.3 times the dry weight of water, inoculate the strain according to the inoculum amount of 0.5%, and ferment for 5-8 hours at 37 degrees Celsius;

The bacterial strain for inoculation is: Mesophilic Sphingobacterium;

The Mesophilic Sphingobacterium was purchased from Guangdong Microbial Culture Collection Center, its number is JCM 21153, ATCC43320, DSM 11723, NBRC 14963;

(2) After the cyanobacteria after fermentation is broken, it is mixed with ethanol with a mass fraction of 75% according to the solid-to-liquid ratio (g/ml) of 1:10 and placed in the reactor, and ammonium phosphate trihydrate and manganese sulfate are added for catalysis, and the trihydrate The addition of ammonium phosphate is 0.5% of the weight of blue-green algae, and the addition of manganese sulfate is 0.1% of the weight of blue-green algae;

(3) Heating: the reaction conditions are: the temperature is 200°C, the pressure is 12MPa, and the reaction time is 20min; the reaction solution is obtained;

(4) adding absolute ethanol to extract the reaction solution, suction filtration to separate the solid residue, and the liquid phase to stand and stratify into an organic phase and an aqueous ethanol phase;

(5) Distill the organic phase under reduced pressure. The reduced-pressure distillation condition is: 0.09MPa, the temperature is 20°C, and the obtained oily liquid is cyanobacteria extract oil, the oil yield of cyanobacteria extract oil is 30.2%, and the calorific value is 6619 kcal /kg.

Under the condition of heating to 50°C, mix the proportions of the formula components described in the examples, undergo ultrasonic emulsification at 500kHz, stir and mix evenly, store for 24 hours, and filter with a 400 mesh (mesh) diesel oil refining filter Then get the finished product.

Example 4

Another specific formula of the present invention's environmental protection, low carbon, high calorific value marine fuel oil is composed as follows, and its preparation method is as described in embodiment 1:

Other conditions are with embodiment 3, and the bacterial strain of inoculation becomes Aspergillus niger;

Results: The obtained oily liquid was cyanobacteria extract oil, the oil yield of cyanobacteria extract oil was 30.9%, and the heat value was 6672 kcal/kg.

Example 5

Another specific formula of the present invention's environmental protection, low carbon, high calorific value marine fuel oil is composed as follows, and its preparation method is as described in embodiment 1:

Other conditions are the same as in Example 3, the inoculated strain becomes Aspergillus niger; result: the obtained oily liquid is cyanobacteria extract oil, the oil yield of cyanobacteria extract oil is 45.3%, and the calorific value is 10052.3 kcal/kg.

As a comparative experiment, with embodiment 3, but do not carry out microbial pre-fermentation, use conventional temperature to extract;

The preparation method of described biodiesel is:

Oil yield (%) of cyanobacteria extracted oil=weight of cyanobacteria extracted oil/cyanobacteria weight×100%.

Cyanobacteria and ethanol with a mass fraction of 75% are mixed according to the solid-to-liquid ratio (g/ml) of 1:10 and placed in a reaction kettle, and ammonium phosphate trihydrate and manganese sulfate are added for catalysis, and the addition of the ammonium phosphate trihydrate is the weight of blue algae 0.5% of manganese sulfate, the addition of manganese sulfate is 0.1% of blue-green algae weight;

Heating: the reaction conditions are: temperature is 320°C, pressure is 12MPa, reaction time is 30min; the reaction liquid is obtained;

Add anhydrous ethanol to extract the reaction solution, filter and separate the solid residue, and separate the liquid phase into an organic phase and an aqueous ethanol phase;

The organic phase was distilled under reduced pressure under the conditions of 0.09MPa and 20°C, and the obtained oily liquid was cyanobacteria extract oil. The oil yield of cyanobacteria extract oil was 26.82%, and the calorific value was 6256.1 kcal/kg.

It can be seen that microbial fermentation can significantly reduce the reaction temperature, increase the oil production rate, and increase the calorific value.

Example 6

The product of the embodiment of the present invention 1, after testing, the result is as follows:

The product of the embodiment of the present invention 2 is tested:

The product of embodiment 5 of the present invention, through sending detection, result is as follows:

It should be noted that the above descriptions are only preferred specific embodiments of the present invention,

If changes are made according to the conception of the present invention, the functions produced by them shall all fall within the scope of the present invention as long as they do not exceed the spirit covered by the description.

In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or feature is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

Although the embodiments of the present invention have been shown and described, those skilled in the art can understand that various changes, modifications, substitutions and modifications can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the invention is defined by the claims and their equivalents.

Claims (10)

1. A marine fuel oil with environmental protection, low carbon and high calorific value is characterized in that: the components are calculated in parts by weight and include the following: . 2. An environmentally friendly, low-carbon, high-calorific-value marine fuel oil, characterized in that: the components are calculated in parts by weight and include the following; . 3. The marine fuel oil according to claim 1 or 2, characterized in that: said soft water is water filtered by water softening equipment from well water, river water and tap water. 4. according to the described marine fuel oil of claim 1 or 2, it is characterized in that: described cetane number improving agent is isooctyl nitrate or di-tert-butyl peroxide. 5. The marine fuel oil according to claim 1 or 2, characterized in that: said diesel oil detergent is polyisobutene amine. 6. According to the described marine fuel oil of claim 1 or 2, it is characterized in that: the described anti-corrosion and anti-rust agent is benzotriazole. 7. The marine fuel oil according to claim 1 or 2, characterized in that: the energy-saving combustion accelerator is ferrocene. 8. The fuel oil according to claim 1, wherein the preparation method of the biodiesel is: (1) Pre-fermented Spirulina: Mix the cyanobacteria with 0.3 times the dry weight of water, inoculate the strain according to the inoculum amount of 0.5%, and ferment for 5-8 hours at 37 degrees Celsius; (2) After the cyanobacteria after fermentation is broken, it is mixed with ethanol with a mass fraction of 75% according to the solid-to-liquid ratio (g/ml) of 1:10 and placed in the reactor, and ammonium phosphate trihydrate and manganese sulfate are added for catalysis, and the trihydrate The addition of ammonium phosphate is 0.5% of the weight of blue-green algae, and the addition of manganese sulfate is 0.1% of the weight of blue-green algae; (3) Heating: the reaction conditions are: the temperature is 200°C, the pressure is 12MPa, and the reaction time is 20min; the reaction solution is obtained; (4) adding absolute ethanol to extract the reaction solution, suction filtration to separate the solid residue, and the liquid phase to stand and stratify into an organic phase and an aqueous ethanol phase; (5) The organic phase is distilled under reduced pressure, the conditions of the reduced pressure distillation are: 0.09 MPa, the temperature is 20° C., and the obtained oily liquid is cyanobacteria extract oil. The inoculated strain is: Mesophilic Sphingobacterium. 9. The fuel oil according to claim 8, wherein the bacterial strain to be inoculated is: Mesophilic Sphingobacterium or Aspergillus niger, and a mixed bacterial agent of Mesophilic Sphingobacterium and Aspergillus niger. 10. The fuel oil according to claim 9, wherein the mixing ratio of the mesophilic Sphingobacterium and Aspergillus niger is 1:1 according to the quantitative ratio.