CN113265279B - Composite additive containing modifier and heat value agent for modified methanol and application thereof - Google Patents

Abstract

The invention discloses a composite additive containing a modifier and a heat value agent for modified methanol and application thereof, wherein the composite additive comprises the following raw materials in percentage by mass: 5-90% of modifier and the balance of heat value agent. The invention aims at the modification of the methanol, solves the problem of low heat value of the methanol in the application process, simultaneously relieves the corrosion of the methanol to pipelines and equipment to a great extent, ensures that the modified methanol is more stable and is convenient to store for a long time without layering, and the application method adopted by the invention has the advantages of convenient operation, low requirement on the equipment, convenient control of product quality and suitability for large-scale industrial production.

Description

Composite additive containing modifier and heat value agent for modified methanol and application thereof

Technical Field

The invention relates to the technical field of fuel energy, in particular to a composite additive containing a modifier and a heat value agent for modified methanol and application thereof.

Background

China is the first major energy consuming country in the world, has the characteristics of fossil energy, oil shortage, gas shortage, coal enrichment and renewable wind and light resource enrichment, oil is imported 4.6 hundred million tons in 2018, the external dependence degree is 70.6%, about half of the oil is imported from middle east high risk areas such as Iran and the like, the oil faces the supply interruption risk at any time, the oil becomes a soft rib for economic and social development, and the implementation of an alternative oil strategy is a necessary choice and is also a great matter for the safety of the concerned countries.

Currently, methanol is the inevitable alternative to petroleum. The path of oil substitution is multiple: methanol, ethanol, electricity and hydrogen and coal-made oil can be selected. Ethanol is extracted from grains or plants, and the characteristics of competing with people for grains and competing with grains for land limit large-scale application. The development of electric and hydrogen energy vehicles has great working force at present, but the cost is high, and the industrialized popularization is still in the future. The coal-to-liquids has the problem of higher cost no matter direct liquefaction or indirect liquefaction. The methanol raw material has wide source and guaranteed resources, can be produced by taking coal, rural straws, coal bed gas and chemical waste gas as raw materials at present, and can be used for producing hydrogen by wind-light energy and synthesizing the methanol with atmospheric carbon dioxide in future. Therefore, methanol is a more viable alternative to petroleum.

However, the technical obstacles presented by the popularization of methanol fuel limit the scale application. At present, methanol as fuel has many defects in the application process of vehicle fuel, industrial boiler fuel, civil fuel and the like: in the aspect of vehicle fuel, methanol can be prepared into methanol gasoline and methanol diesel, but the two have lower heat values, great corrosion to an oil way system of a vehicle and great damage to an engine, and the engine is generally modified in the prior art to be suitable for the methanol gasoline and the methanol diesel, so that the application cost of the methanol gasoline and the methanol diesel is high, and the application effect is not ideal; in the aspect of industrial boiler fuel, methanol is used as fuel, the heat value is low, and the difference exists between part of physical and chemical properties and fuel oil, so that the popularization and application of the methanol in the industrial field are influenced; in the aspect of civil fuel, methanol also has low heat value and can cause corrosion to burners and pipeline system equipment. In view of the above, how to modify methanol to be a reliable fuel source remains a problem to be solved by those skilled in the art.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a composite additive containing a modifier and a calorific value agent for modified methanol and application thereof, so as to solve the problems of low calorific value, strong corrosivity to used equipment and high application cost of methanol as a fuel in the prior art.

In order to solve the technical problems, the invention adopts the following technical scheme:

a composite additive containing a modifier and a heat value agent for modified methanol comprises the following raw materials in percentage by mass: 5 to 90 percent of modifier and the balance of heat value agent.

Preferably, the modifier comprises the following raw materials in percentage by mass: 10 to 30 percent of isopropanol, 10 to 20 percent of isobutanol, 10 to 20 percent of tertiary butanol, 10 to 42 percent of methyl propionate, 10 to 25 percent of diethanolamine, 0.1 to 1 percent of benzamide, 0.1 to 1 percent of sodium petroleum sulfonate, 0.1 to 1 percent of octylphenol ether, 0.1 to 1 percent of maleic acid, 0.1 to 1 percent of 4-aminophenol, 0.1 to 1 percent of benzotriazole and 0.1 to 1 percent of pyrazolone; the heat value agent comprises the following raw materials in percentage by mass: 1-20% of petroleum ether, 20-65% of fuel oil, 1-20% of heavy naphtha, 1-20% of solvent oil, 10-20% of octane and 1-10% of methanolamine solution.

Preferably, the modifier comprises the following raw materials in percentage by mass: 10 to 25 percent of isopropanol, 10 to 18 percent of isobutanol, 10 to 18 percent of tertiary butanol, 20 to 40 percent of methyl propionate, 10 to 20 percent of diethanolamine, 0.2 to 0.4 percent of benzamide, 0.2 to 0.4 percent of sodium petroleum sulfonate, 0.1 to 0.3 percent of octylphenol ether, 0.1 to 0.3 percent of maleic acid, 0.1 to 2 percent of 4-aminophenol, 0.1 to 0.2 percent of benzotriazole and 0.1 to 0.2 percent of pyrazolone.

Preferably, the heat value agent comprises the following raw materials in percentage by mass: 5-18% of petroleum ether, 25-40% of fuel oil, 5-18% of heavy naphtha, 10-20% of solvent oil, 10-18% of octane and 5-8% of methanolamine solution.

Preferably, the modifier comprises the following raw materials in percentage by mass: 10 to 30 percent of isopropanol, 10 to 20 percent of isobutanol, 10 to 20 percent of tertiary butanol, 10 to 42 percent of methyl propionate, 10 to 25 percent of diethanolamine, 0.1 to 1 percent of sodium petroleum sulfonate, 0.1 to 1 percent of octylphenol ether, 0.1 to 1 percent of maleic acid, 0.1 to 1 percent of 4-aminophenol, 0.1 to 1 percent of benzotriazole and 0.1 to 1 percent of pyrazolone; the heat value agent comprises the following raw materials in percentage by mass: 80 to 90 percent of petroleum ether, 1 to 10 percent of benzamide, 1 to 10 percent of 4-aminophenol and 0.1 to 1 percent of benzotriazole.

Preferably, the fuel oil comprises one of No. 1 fuel oil, no. 2 fuel oil, or No. 4 fuel oil.

Preferably, the mineral spirits include one of mineral spirits No. 6, mineral spirits No. 120, or mineral spirits No. 200.

Preferably, the sodium petroleum sulfonate comprises C _14～18 One or more of alkyl sodium sulfonate.

Preferably, the pyrazolone is 5-pyrazolone.

The invention discloses an application of a composite additive containing a modifier and a heat value agent for modified methanol, which is prepared according to any component of the invention, and specifically comprises the following steps:

1) Preparing a modifier: sequentially adding raw materials of the modifier into a reaction kettle, uniformly stirring, and standing for at least 24 hours to obtain the modifier;

2) Preparing a heat value agent: adding the raw material of the heat value agent into another reaction kettle, uniformly stirring, and standing for at least 24 hours to obtain the heat value agent;

3) Preparing modified methanol fuel: putting the modifier prepared in the step 1) and methanol into a reaction kettle according to a ratio, mixing and stirring, standing for at least 24 hours to obtain a product, uniformly mixing with the heat value agent prepared in the step 2) according to a ratio, and standing for at least 24 hours to obtain a product.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention selects the raw material of the modifier, modifies the alcohol through the modifier, converts the property of the methanol to the fuel methanol, and improves the heat value of the methanol by matching with the use of the heat value agent, so that the methanol becomes the fuel methanol with excellent performance.

2. The addition of the modifier and the heat value agent greatly improves the condition of methanol as fuel application: when the methanol fuel is used for a vehicle with a spark-ignition engine, the methanol fuel modified by the modifier and the heat value agent can be used by the vehicle independently, and can also be used by the vehicle after being mixed with national standard gasoline in any proportion; when the methanol fuel is used for a vehicle of a compression ignition engine, the methanol fuel modified by adding the modifier and the heat value agent can be used with national standard diesel oil in a certain proportion; in both cases, the fuel injection system of the vehicle is not required to be cleaned and can be directly used, the oil circuit system and the engine of the vehicle are not required to be modified, the oil pump, the oil circuit system and the fuel injection nozzle are not corroded, the swelling effect on plastic parts is equivalent to that of gasoline and diesel oil, and smooth fuel supply can be well kept in the long-term use process, so that the application cost of methanol in the field of vehicle fuel is greatly reduced; when the additive is used for industrial boiler fuel and civil fuel, the additive has a very obvious modification effect on methanol, the calorific value of the modified methanol is obviously improved, meanwhile, the modified methanol has a corrosion effect on metal and rubber equivalent to that of other fossil fuels in the using process, and the modified methanol is very stable, cannot generate a layering phenomenon after being stored for a long time and can still be used continuously.

3. The additive is applied by firstly modifying the methanol by the modifier, then mixing the modified methanol with the heat value agent and modifying the methanol by a fractional method, and is safe, reliable, easy to operate, simple in process flow, low in requirement on equipment, easy to control the product quality and suitable for large-scale industrial production.

Detailed Description

The present invention will be further described with reference to the following examples.

1. Composite additive containing modifier and heat value agent for modified methanol

The composite additive containing the modifier and the heat value agent for the modified methanol comprises the following raw materials in percentage by mass: 5 to 90 percent of modifier and the balance of heat value agent. Wherein the additive comprises the following raw materials in percentage by mass: 15 to 90 percent of modifier and the balance of heat value agent.

In specific implementation, the components of the additive need to be adjusted according to the application of the modified methanol, the methanol is modified by adopting the additive, and the modified methanol can be used as automobile fuel, industrial boiler fuel and civil stove fuel. When the modified methanol is used as the fuel of ignition engines, vehicles, industrial boilers and civil cooking utensils, the following formula can be adopted:

the modifier comprises the following raw materials in percentage by mass: 10 to 30 percent of isopropanol, 10 to 20 percent of isobutanol, 10 to 20 percent of tertiary butanol, 10 to 42 percent of methyl propionate, 10 to 25 percent of diethanolamine, 0.1 to 1 percent of benzamide, 0.1 to 1 percent of sodium petroleum sulfonate, 0.1 to 1 percent of octylphenol ether, 0.1 to 1 percent of maleic acid, 0.1 to 1 percent of 4-aminophenol, 0.1 to 1 percent of benzotriazole and 0.1 to 1 percent of pyrazolone; the heat value agent comprises the following raw materials in percentage by mass: 1-20% of petroleum ether, 20-65% of fuel oil, 1-20% of heavy naphtha, 1-20% of solvent oil, 10-20% of octane and 1-10% of methanolamine solution.

Preferably, the modifier comprises the following raw materials in percentage by mass: 10 to 25 percent of isopropanol, 10 to 18 percent of isobutanol, 10 to 18 percent of tertiary butanol, 20 to 40 percent of methyl propionate, 10 to 20 percent of diethanolamine, 0.2 to 0.4 percent of benzamide, 0.2 to 0.4 percent of sodium petroleum sulfonate, 0.1 to 0.3 percent of octylphenol ether, 0.1 to 0.3 percent of maleic acid, 0.1 to 2 percent of 4-aminophenol, 0.1 to 0.2 percent of benzotriazole and 0.1 to 0.2 percent of pyrazolone. 5-18% of petroleum ether, 25-40% of fuel oil, 5-18% of heavy naphtha, 10-20% of solvent oil, 10-18% of octane and 5-8% of methanolamine solution.

When the modified methanol is used as a fuel of a compression ignition engine vehicle, the following component formula can be adopted:

the modifier comprises the following raw materials in percentage by mass: 10 to 30 percent of isopropanol, 10 to 20 percent of isobutanol, 10 to 20 percent of tertiary butanol, 10 to 42 percent of methyl propionate, 10 to 25 percent of diethanolamine, 0.1 to 1 percent of sodium petroleum sulfonate, 0.1 to 1 percent of octylphenol ether, 0.1 to 1 percent of maleic acid, 0.1 to 1 percent of 4-aminophenol, 0.1 to 1 percent of benzotriazole and 0.1 to 1 percent of pyrazolone; the heat value agent comprises the following raw materials in percentage by mass: 80 to 90 percent of petroleum ether, 1 to 10 percent of benzamide, 1 to 10 percent of 4-aminophenol and 0.1 to 1 percent of benzotriazole.

In practical use, the octylphenol ether is octylphenol polyoxyethylene (10) ether, is a partial product in alkylphenol polyoxyethylene ethers, also called emulsifier OPE-10, and the chemical structural general formula of the alkylphenol polyoxyethylene ether compound is as follows:

OPE series products, such as: OPE-7 to OPE-15 can be used in the present invention, and OPE-7, OPE-8, OPE-9, OPE-12, OPE-13, OPE-14, OPE-15 and the like can be used in the present invention.

In the invention, the fuel oil comprises one of No. 1 fuel oil, no. 2 fuel oil or No. 4 fuel oil, the fuel oils can be used as raw materials of the heat value agent, and the type of the fuel oil is adjusted according to the application of the modified methanol fuel. When the modified methanol fuel is used as the vehicle fuel, the fuel oil is No. 1 fuel oil; when the modified methanol fuel is used as industrial boiler fuel or civil fuel, the fuel oil can be No. 2 fuel oil or No. 4 fuel oil. The same applies to the solvent oil, which includes one of No. 6 solvent oil, no. 120 solvent oil or No. 200 solvent oil, and the solvent oils can be used as raw materials of the heat value agent, and the type of the solvent oil is adjusted according to the application of the modified methanol fuel. When the modified methanol fuel is used as the vehicle fuel, the solvent oil is No. 6 solvent oil; when the modified methanol fuel is used as industrial boiler fuel or civil fuel, the solvent oil can be No. 120 solvent oil or No. 200 solvent oil. The petroleum sodium sulfonate comprises C _14～18 One or more of alkyl sodium sulfonate. The pyrazolone is 5-pyrazolone.

Because the calorific value of methanol is low, the methanol fuel needs to be mixed with fuel oil for use, and the calorific value of the methanol fuel is increased by increasing the hydrocarbon content of the methanol. The methanol fuel in the current market cannot be well dissolved with the additive for improving the hydrocarbon content, the quality guarantee period of the product is short, the product is unstable in property, and the layering phenomenon is easy to occur. The invention combines experiments and practical application to discover that isopropanol, isobutanol, tert-butanol, methyl propionate, diethanolamine, benzamide, sodium petroleum sulfonate, octylphenol ether, maleic acid, 4-aminophenol, benzotriazole and pyrazolone are selected to prepare the modifier, wherein alcohol compounds, octylphenol ether and the like are adopted to effectively solve the problems of corrosion, air resistance, swelling, washing, high-temperature lubrication damage and the like of methanol, benzotriazole and other compounds are adopted to act together, so that the corrosion effect of the modified methanol fuel on an oil-way system and an engine of a vehicle is equivalent to that of gasoline and diesel oil, and the compounds such as alcohol, ether and ester in the modifier can ensure that the methanol and hydrocarbon compounds in a heat value agent are stably compatible and combined.

2. Examples of the embodiments

Example 1

1. Composite additive containing modifier and heat value agent for modified methanol

The composite material comprises the following raw materials in percentage by mass: 33.3 percent of modifier and 66.7 percent of heat value agent.

Wherein the modifier comprises the following raw materials in percentage by mass: 20% of isopropanol, 15% of isobutanol, 15% of tert-butyl alcohol, 30% of methyl propionate, 18.6% of diethanolamine, 0.3% of benzamide, 0.3% of sodium petroleum sulfonate, 0.2% of octylphenol ether, 0.2% of maleic acid, 0.15% of 4-aminophenol, 0.15% of benzotriazole and 0.1% of pyrazolone.

The heat value agent comprises the following raw materials in percentage by mass: 15% of petroleum ether, 34% of fuel oil, 15% of heavy naphtha, 15% of solvent oil, 15% of octane and 6% of methanolamine solution. Wherein the fuel oil is No. 1 fuel oil, and the solvent oil is No. 6 solvent oil.

2. Application of composite additive containing modifier and heat value agent for modified methanol

The ingredients of example 1 were mixed and mixed with methanol to give a product. The composite material comprises the following raw materials in percentage by mass: 85% of methanol, 5% of modifier and 10% of heat value agent. The method specifically comprises the following steps:

1) Preparing a modifier: sequentially adding raw materials of the modifier into a reaction kettle, uniformly stirring, and standing for at least 24 hours to obtain the modifier;

2) Preparing a heat value agent: adding the raw material of the heat value agent into another reaction kettle, uniformly stirring, and standing for at least 24 hours to obtain the heat value agent;

3) Preparing modified methanol fuel: and (3) putting the modifier prepared in the step 1) and methanol into a reaction kettle according to a ratio, mixing and stirring, standing for at least 24 hours to obtain a product, uniformly mixing with the heat value agent prepared in the step 2) according to a ratio, and standing for at least 24 hours to obtain a product.

During specific implementation, prepared raw materials are added into a reaction kettle, and the raw materials are circulated in a pipeline repeatedly by a pump, so that the effect of uniform mixing is achieved.

Example 2

The composite material comprises the following raw materials in percentage by mass: 16.7 percent of modifier and 83.3 percent of heat value agent.

Wherein the modifier comprises the following raw materials in percentage by mass: 15% of isopropanol, 12% of isobutanol, 12% of tert-butyl alcohol, 40% of methyl propionate, 20% of diethanolamine, 0.3% of benzamide, 0.2% of sodium petroleum sulfonate, 0.1% of octylphenol ether, 0.1% of maleic acid, 0.1% of 4-aminophenol, 0.1% of benzotriazole and 0.1% of pyrazolone.

The heat value agent comprises the following raw materials in percentage by mass: 5% of petroleum ether, 65% of fuel oil, 8% of heavy naphtha, 5% of solvent oil, 12% of octane and 5% of methanolamine solution. Wherein the fuel oil is No. 2 fuel oil, and the solvent oil is No. 120 solvent oil.

The ingredients of example 2 were mixed with methanol and used as the product. The composite material comprises the following raw materials in percentage by mass: 82% of methanol, 3% of modifier and 15% of heat value agent. The specific implementation steps are the same as those of example 1, including the following examples, all implemented according to the procedure of example 1.

Example 3

The composite material comprises the following raw materials in percentage by mass: 20% of modifier and 80% of heat value agent.

Wherein the modifier comprises the following raw materials in percentage by mass: 16% of isopropanol, 13% of isobutanol, 14% of tert-butyl alcohol, 38% of methyl propionate, 18% of diethanolamine, 0.2% of benzamide, 0.2% of sodium petroleum sulfonate, 0.15% of octylphenol ether, 0.1% of maleic acid, 0.15% of 4-aminophenol, 0.1% of benzotriazole and 0.1% of pyrazolone.

The heat value agent comprises the following raw materials in percentage by mass: 10% of petroleum ether, 60% of fuel oil, 10% of heavy naphtha, 7% of solvent oil, 8% of octane and 5% of methanolamine solution. Wherein the fuel oil is No. 4 fuel oil, and the solvent oil is No. 200 solvent oil.

The ingredients of example 3 were mixed and then used as a product after mixing with methanol. The composite material comprises the following raw materials in percentage by mass: 90% of methanol, 2% of modifier and 8% of heat value agent.

Example 4

The composite material comprises the following raw materials in percentage by mass: 90% of modifier and 10% of heat value agent.

The modifier comprises the following raw materials in percentage by mass: 30% of isopropanol, 19.2% of isobutanol, 20% of tert-butanol, 20% of methyl propionate, 10% of diethanolamine, 0.2% of sodium petroleum sulfonate, 0.15% of octylphenol ether, 0.1% of maleic acid, 0.15% of 4-aminophenol, 0.1% of benzotriazole and 0.1% of pyrazolone.

The heat value agent comprises the following raw materials in percentage by mass: 9% of petroleum ether, 0.5% of benzamide, 0.4% of 4-aminophenol and 0.1% of benzotriazole.

The ingredients of example 4 were mixed and then used as a product after mixing with methanol. The composite material comprises the following raw materials in percentage by mass: 50% of methanol, 45% of modifier and 5% of heat value agent.

3. Comparison of Fuel Properties

1. Example 1 comparison of Performance with gasoline

Example 1 can be used in combination with gasoline or alone. The gasoline of example 1 and 92# are mixed and used, and the mass ratio of the gasoline of example 1 to the gasoline of example 92 is as follows: gasoline = 2. Three cars with the same model are selected, and the gasoline mixture of the embodiment 1, the embodiment 1 and the 92# gasoline are respectively used as vehicle fuel for the cars to use practically. After one year of operation, the fuel usage was compared. See table below:

TABLE 1 comparison of amounts

Fuel and its production method	92# gasoline	EXAMPLE 1 use alone	Example 1 was used in combination with No. 92 gasoline
				Operating mileage (Km)	26093.1	23022.9	24947.1
Fuel quantity (L)	1850	2000	1900
				Specific fuel consumption (L/100 km)	7.090	8.687	7.610
Energy consumption ratio	/	1.225：1	1.073：1

As can be seen from Table 1, the energy consumption ratio of the embodiment 1 used alone is slightly higher than that of the 92# gasoline, but the energy consumption ratio of the embodiment 1 and the 92# gasoline used in a mixed mode is very close to that of the 92# gasoline, the use cost of the embodiment 1 is far lower than that of the 92# gasoline in actual use, the embodiment 1 is directly used in the running process of the passenger cars, the cleaning of an oil injection system of the passenger cars is not needed, after the passenger cars run for one year, oil pumps, oil line systems and oil nozzles of the three passenger cars are observed, faults caused by corrosion do not occur, and the oil pumps, the oil line systems and the oil nozzles of the three passenger cars have no corrosion marks from the appearance. It can be seen that the corrosion effect of example 1 on metal and rubber is comparable to that of other fossil fuels during use.

The emission performance of the gasoline mixture of example 1 and No. 92 and the gasoline mixture of No. 92 is tested, and the results are shown in the following table:

TABLE 2 comparison of emissions Performance

Fuel and its production method	Example 1	Example 1 was used in combination with No. 92 gasoline	92# gasoline
				Rotating speed (y/min)	780	768	754
HC(ppm)	21	69	155
				CO(％)	0.01	0.16	0.37
NOx(ppm)	5	35	136

As can be seen from Table 2, the emission performance of example 1 is very excellent in the case where the difference in the rotational speed is not large, and HC, CO and NO are contained in the emission when example 1 is used alone _x The amounts of HC, CO and NOx in the emissions were significantly reduced compared to gasoline 92 even when example 1 was used in combination with gasoline 92, which also demonstrates that example 1, whether used alone or in combination with gasoline, had significantly reduced adverse environmental effects.

2. Example 4 comparison with the Performance of Diesel

Example 4 can be used with national standard diesel oil, and can be with the adaptation of each type of national standard diesel oil, find in the practical application, can also use normally after storing for a year after example 4 is mixed with each type of national standard diesel oil, the phenomenon of layering does not appear after a year.

Taking No. 10 diesel oil as an example, mixing the diesel oil of the example 4 with No. 10 diesel oil, wherein the mass ratio of the diesel oil of the example 4 to the No. 10 diesel oil is 1:

TABLE 3 comparison of amounts

In practical use, the example 4 and the national diesel can be mixed with the national diesel according to the ratio of 1. Since diesel oil has a high calorific value, the types of the raw materials of the calorific value agent are adjusted in example 4, the amount of the calorific value agent is reduced, and the amount of the modifier is increased greatly, so that methanol and diesel oil are dissolved with each other well. Because through a large amount of experimental research findings, because diesel oil and methanol self physical and chemical properties exist the difference, make mutual solubility effect after both mix very poor, if do not use the modifier only to mix both can't realize fine mutual solubility, and the quantity of modifier can produce the important influence to mutual solubility situation between them and the stability after mutually soluble, the modifier of lower quantity can lead to the mutual solubility effect of methanol and diesel oil not good, the layering phenomenon appears easily, both unable normal use, also do not be favorable to long-term storage.

The mixture of the No. 4 and the No. 10 diesel oil is applied to a vehicle of the same vehicle type with the No. 10 diesel oil, and the dosage is shown in the table 3, so that the energy consumption of the mixture of the No. 4 and the No. 10 diesel oil is not much different from that of the No. 10 diesel oil, the mixture can be used for replacing part of the diesel oil, and the use cost is far lower than that of the diesel oil only using the No. 10 diesel oil. The vehicle using the mixture of example 4 and-10 diesel fuel did not modify the engine system of the vehicle in any way during the running of the vehicle, and no failure due to methanol corrosion occurred during the whole running process, and the vehicle was still in normal use until now.

Comparison of the emissions performance of the engine for the mixture of example 4 and diesel No. 10:

TABLE 4 emission Performance comparison

Fuel and its production method	No. 10 diesel oil	Example 4 was used in admixture with No. 10 diesel fuel
			Rotating speed (y/min)	2000	2000
HC(g/kw·h)	0.021	0.009
			CO(g/kw·h)	0.19	0.04
NO x (g/kw·h)	0.135	0.01

After comparing the emission performance, it is obvious that the addition of the embodiment 4 can greatly reduce HC, CO and NO under the condition of the same rotating speed after the embodiment 4 is used for replacing part of No. 10 diesel oil _x And the discharge amount of substances greatly relieves the influence of using diesel oil on the environment.

3. Example 2 comparison of Performance with Industrial boiler Fuel

The calorific values of the natural gas and the coal in the embodiment 2 are detected by a calorimeter, and then the natural gas and the coal in the embodiment 2 are used for burning in boilers of the same type, and the consumption of the steam with the same quantity generated by the natural gas, the natural gas and the coal is compared.

TABLE 5 Fuel consumption and Performance Explanation

Examples and comparative examples	Heat value of	Fuel consumption for 1 ton steam generation
			Natural gas	33500kj/m 3	90m 3
Coal (coal)	21000kj/kg	220kg
			Example 2	29300kj/kg	95

As can be seen from Table 5, the heating value of example 2 is greatly increased compared to methanol (the heating value of normal methanol is 1111 kj/kg), although lower than that of natural gas, it is already significantly higher than that of coal, and the consumption of steam for generating 1 ton is also much lower than that of coal, close to that of natural gas. When the boiler is actually used, the boiler normally operates, and the whole pipeline system is not blocked due to corrosion. After the boiler is operated for a long time, the boiler is checked, and the long-term application of the fuel of the boiler in the embodiment 2 has small corrosiveness to equipment, and compared with the boiler using natural gas and coal as fuel, the corrosion state difference between the boiler and the equipment is not large.

The emissions of example 2, when natural gas and coal were used in the combustion of a boiler of the same model were tested as follows:

TABLE 6 comparison of the emissions content after combustion (unit: mg/m) ³ )

Compared with the existing boiler fuel natural gas, after the example 2 is adopted as the boiler fuel, the emission of the boiler is completely free of sulfide, particulate matters, nitrogen oxides and CO ₂ Coefficient of emission (CO emission per kg fuel burned) ₂ Amount) of the additive, which also indicates that the modified methanol can be used as fuel for boiler combustion after the additive is used for modifying the methanol, and the adverse effect on the environment is greatly reduced.

4. Example 3 comparison of Performance with domestic Fuel

The methanol fuel used for civil gas appliances in the current market is industrial methanol with the mass fraction of 99%, and example 3 is compared with the methanol fuel of the existing civil gas appliances, and the methanol fuel are applied to the civil gas appliances with the same model, and the specific conditions are as follows:

TABLE 7 comparative test Table for energy consumption

It can be seen from table 7 that, in the process of heating 10kg of water to 60 ℃, the civil gas appliance using example 3 as fuel takes shorter time and consumes less fuel, which indicates that the additive of the present invention modifies methanol, so that the thermal efficiency of the modified methanol fuel is significantly improved, and the consumption of fuel is reduced while obtaining the same amount of heat. In addition, in the use process, the fact that the example 3 as the fuel has small corrosion effect on the civil gas appliance, has the corrosion effect equivalent to that of the fossil fuel used by the existing civil gas appliance, and does not cause the gas appliance pipeline to be blocked due to corrosion after being used for a long time for one year.

The embodiment 3 is used for operating a wall-held furnace of a certain type, and because the current alcohol fuel heating water heater does not have an executable national standard, the operation process is detected by adopting an industry standard, and the detection result is as follows:

TABLE 8

As can be seen from Table 8, when the embodiment 3 is applied to the operation of a wall-held furnace of a certain type, and the operation lasts for a period of time, the concentrations of carbon monoxide and nitrogen oxides in the emissions of the wall-held furnace are obviously lower than the standard of fossil fuels, which indicates that the civil modified methanol fuel completely meets the national standard requirements in the application process, and has excellent performance, especially in the aspect of environmental protection, good environment and no serious pollution to the environment.

5. Stability of examples 1 to 4

Removing the modifier in the embodiments 1 to 4, directly stirring and mixing the heat value agent and the methanol, and then putting the mixture into a container for standing and storage; the modifier in the examples 1 to 4 is replaced by the octylphenol ether with the same mass; the samples 1 to 4 were placed in containers of the same material and the same volume and stored by standing. Wherein, the three are stored for more than one year at room temperature under the same environmental conditions, and the appearance, whether layering, whether deterioration and continuous use of the product in the container after one year of storage are compared.

TABLE 9

In a container without a modifier, obvious layering can occur when the container is stored for less than one month, the container is generally divided into two layers, layering between substances can be more obvious along with the passage of time, the layering is reflected in color, the colors of upper and lower layers of liquid can be very obviously different, part of layered liquid is darker in color and is turbid, substances in the container can be mixed again to form a turbid state if the part of liquid is slightly shaken, the layering can occur again after the container is kept for a period of time, the liquid in the container can be very obviously layered after the container is stored for one year, the color of the previous layer with the darker color can be further deepened, and coagula begins to appear, so that the container without the modifier has very poor mixing effect of a heat value agent and methanol, the layering can occur even if the container is stored for a short time, the liquid in the container can be easily deteriorated after the layering occurs, and the substances in the container can not be used as vehicle fuel, industrial boiler and fuel for kitchen range.

In the container in which the modifier is replaced by emulsifier octylphenol ether with the same mass, no layering occurs after half a year of storage, so that the emulsifier can actually make methanol and a heat value agent mutually soluble, but the mutual soluble state is unstable, and substances in the container begin to layer after half a year of storage.

In the embodiments 1 to 4, after being stored for one year, the state of the substances in the container is very stable, the substances are kept in a clear and transparent state all the time, and the substances can still be applied to automobile fuel, industrial boiler fuel and civil stove fuel after being stored for one year without causing corrosion to the used equipment.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.

Claims (7)

1. The composite additive containing the modifier and the heat value agent for the modified methanol is characterized by comprising the following raw materials in percentage by mass: 5-90% of modifier and the balance of heat value agent;

when the modified methanol is used as ignition engine vehicle fuel, industrial boiler fuel and civil kitchen range fuel, the modifier is composed of the following raw materials in percentage by mass: 10-30% of isopropanol, 10-20% of isobutanol, 10-20% of tert-butanol, 10-42% of methyl propionate, 10-25% of diethanolamine, 0.1-1% of benzamide, 0.1-1% of petroleum sodium sulfonate, 0.1-1% of octylphenol ether, 0.1-1% of maleic acid, 0.1-1% of 4-aminophenol, 0.1-1% of benzotriazole and 0.1-1% of pyrazolone;

the heat value agent is composed of the following raw materials in percentage by mass: 1-20% of petroleum ether, 20-65% of fuel oil, 1-20% of heavy naphtha, 1-20% of solvent oil, 10-20% of octane and 1-10% of methanolamine solution;

or when the modified methanol is used as a compression ignition engine vehicle fuel, the modifier consists of the following raw materials in percentage by mass: 10-30% of isopropanol, 10-20% of isobutanol, 10-20% of tert-butanol, 10-42% of methyl propionate, 10-25% of diethanolamine, 0.1-1% of sodium petroleum sulfonate, 0.1-1% of octylphenol ether, 0.1-1% of maleic acid, 0.1-1% of 4-aminophenol, 0.1-1% of benzotriazole and 0.1-1% of pyrazolone;

the heat value agent is composed of the following raw materials in percentage by mass: 80-90% of petroleum ether, 1-10% of benzamide, 1-10% of 4-aminophenol and 0.1-1% of benzotriazole;

the fuel oil comprises one of No. 1 fuel oil, no. 2 fuel oil or No. 4 fuel oil.

2. The compound additive containing the modifier and the heat value agent for modified methanol as claimed in claim 1, wherein when the modified methanol is used as ignition engine vehicle fuel, industrial boiler fuel and civil kitchen range fuel, the modifier is composed of the following raw materials in percentage by mass: 10-25% of isopropanol, 10-18% of isobutanol, 10-18% of tert-butanol, 20-40% of methyl propionate, 10-20% of diethanolamine, 0.2-0.4% of benzamide, 0.2-0.4% of sodium petroleum sulfonate, 0.1-0.3% of octylphenol ether, 0.1-0.3% of maleic acid, 0.1-2% of 4-aminophenol, 0.1-0.2% of benzotriazole and 0.1-0.2% of pyrazolone.

3. The compound additive containing the modifier and the heat value agent for modified methanol as claimed in claim 1, wherein when the modified methanol is used as ignition engine vehicle fuel, industrial boiler fuel and civil kitchen range fuel, the heat value agent is composed of the following raw materials in percentage by mass: 5-18% of petroleum ether, 25-40% of fuel oil, 5-18% of heavy naphtha, 10-20% of solvent oil, 10-18% of octane and 5-8% of methanolamine solution.

4. The complex additive for modified methanol containing a modifier and a heating value agent according to claim 1, wherein the mineral spirits comprise one of mineral spirits No. 6, mineral spirits No. 120, or mineral spirits No. 200.

5. The complex additive for modified methanol containing a modifier and a heating value agent as claimed in claim 1, wherein the sodium petroleum sulfonate comprises C _14~18 One or more of alkyl sodium sulfonate.

6. The complex additive for modified methanol containing a modifier and a heating value agent as defined in claim 1, wherein said pyrazolone is 5-pyrazolone.

7. The application of the composite additive containing the modifier and the heat value agent for modified methanol is characterized in that the composite additive containing the modifier and the heat value agent for modified methanol is prepared according to any one of claims 1 to 6, and specifically comprises the following steps:

1) Preparing a modifier: sequentially adding raw materials of the modifier into a reaction kettle, uniformly stirring, and standing for at least 24 hours to obtain the modifier;

2) Preparing a heat value agent: adding the raw material of the heat value agent into another reaction kettle, uniformly stirring, and standing for at least 24 hours to obtain the heat value agent;

3) Preparing modified methanol fuel: and (3) putting the modifier prepared in the step 1) and methanol into a reaction kettle according to a ratio, mixing and stirring, standing for at least 24 hours to obtain a product, uniformly mixing with the heat value agent prepared in the step 2) according to a ratio, and standing for at least 24 hours to obtain a product.