A modified methanol fuel for civil use and a preparation method thereof

Abstract

The invention discloses a modified methanol fuel for civilian use and a preparation method thereof, comprising the following raw materials in parts by weight: 80-95 parts of methanol, 1-5 parts of modifiers, and 1-20 parts of calorific value agents; wherein the improver comprises the following raw materials in parts by weight: 25-45 parts of n-butanol, 25-45 parts of ethylene glycol, 20-30 parts of methyl oleate, 20-35 parts of dimethoxymethane, 1-8 parts of cyclohexylamine, 0.1-1 parts of NPE‑9, and 0.01-1 parts of toluene triazole; the calorific value agent comprises the following raw materials in parts by weight: 25-50 parts of 1# paint and solvent oil for cleaning, 20-45 parts of naphtha, and 30-60 parts of kerosene. The present invention modifies methanol, solves the problem of low calorific value when industrial methanol is used as fuel, and at the same time, greatly alleviates its corrosion to burners and pipeline systems, making the modified methanol fuel more stable, and no stratification phenomenon will occur when stored for a long time. The preparation method adopted by the invention is easy to operate, has a simple process flow, has low requirements on equipment, is easy to control product quality, and is suitable for large-scale industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of fuel energy, and in particular to a modified methanol fuel for civilian use and a preparation method thereof. Background Art

[0002] At present, methanol is the inevitable choice to replace oil. There are many ways to replace oil: methanol, ethanol, electricity and hydrogen, and coal-to-oil are all available. Ethanol is extracted from grain or plants, and its characteristics of competing with people for grain and grain for land limit its large-scale application. The development of electric and hydrogen vehicles is currently very intensive, but the cost is high and industrial promotion is still a long way to go. Coal-to-oil, whether direct liquefaction or indirect liquefaction, has the problem of high cost. Methanol raw materials are widely available and resources are guaranteed. At present, it can be produced from coal, rural straw, coalbed methane, and chemical waste gas. In the future, it can also be produced by using wind and solar energy to produce hydrogen and atmospheric carbon dioxide to synthesize methanol. Therefore, methanol is a more feasible way to replace oil.

[0003] At present, the standard of civil methanol fuel is GB16663-1996, while industrial refined methanol is often used as fuel for heating boilers in northern China. Although both fuels can be used, there are still some technical problems. The existing alcohol-based liquid fuel and industrial refined methanol both have low calorific value. In addition, methanol has not been modified, so the use effect is not ideal. Moreover, due to its inherent physical and chemical properties, methanol will corrode the gas appliances and pipeline system equipment during use. At the same time, in actual use, users reported that there is a problem of "burning eyes" when using high fire. This is also due to the high concentration of by-products such as formaldehyde formed by incomplete combustion of methanol. This series of problems have limited the application of civil methanol fuel. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a modified methanol fuel for civilian use and a preparation method thereof, so as to solve the problems of the existing alcohol-based fuel having a slightly low calorific value, insufficient fuel combustion, insufficient combustion thermal efficiency, and the generated by-products affecting human health.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A modified methanol fuel for civilian use, comprising the following raw materials in parts by weight: 80-95 parts of methanol, 1-5 parts of a modifier, and 1-20 parts of a calorific value agent. The modifier comprises the following raw materials in parts by weight: 25-45 parts of n-butanol, 25-45 parts of ethylene glycol, 20-30 parts of methyl oleate, 20-35 parts of dimethoxymethane, 1-8 parts of cyclohexylamine, 0.1-1 parts of NPE-9, and 0.01-1 parts of toluene triazole. The calorific value agent comprises the following raw materials in parts by weight: 25-50 parts of 1# paint and cleaning solvent oil, 20-45 parts of naphtha, and 30-60 parts of kerosene.

[0007] Preferably, the improver comprises the following raw materials in parts by weight: 25-45 parts of n-butanol, 25-45 parts of ethylene glycol, 20-30 parts of methyl oleate, 20-35 parts of dimethoxymethane, 1-8 parts of cyclohexylamine, 0.1-1 parts of NPE-9, and 0.01-1 parts of tolutriazole.

[0008] Preferably, the calorific value agent comprises the following raw materials in parts by weight: 25 to 50 parts of 1# paint and cleaning solvent oil, 20 to 45 parts of naphtha, and 30 to 60 parts of kerosene.

[0009] Preferably, the methanol is selected from methanol with a mass fraction of not less than 99%.

[0010] Preferably, the solvent oil is 1# paint and cleaning solvent oil.

[0011] Preferably, the naphtha is heavy naphtha, with a fraction of 70 to 180°C.

[0012] The present invention also provides a method for preparing a modified methanol fuel for civil use, and the method for preparing the modified methanol fuel for civil use comprises the following steps:

[0013] 1) preparing the modifier: preparing the raw materials of the modifier, adding the raw materials into a reaction kettle, stirring evenly, and standing for at least 24 hours to obtain the modifier;

[0014] 2) preparing a calorific value agent: preparing the raw material of the calorific value agent, adding the raw material into another reaction kettle, stirring evenly, and standing for at least 24 hours to obtain a modifier;

[0015] 3) adding the modifier prepared in step 1) and methanol into a reactor, mixing and stirring evenly, and standing for at least 24 hours, then adding the calorific value agent prepared in step 2) into the reactor, mixing and stirring evenly, and standing for at least 24 hours to obtain the product.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. The present invention utilizes a modifier and a calorific value agent to modify methanol, so that the calorific value of the modified methanol is improved, and good results are achieved in practical applications, solving the problem of low calorific value when industrial methanol is used as fuel; at the same time, the modifier and the calorific value agent are used to improve the combustion efficiency of methanol, so that the methanol is burned as fully as possible, avoiding the formation of by-products caused by incomplete combustion.

[0018] 2. After the present invention modifies methanol through a modifier, the corrosion of methanol to the burners and pipeline systems is greatly alleviated, so that the corrosion of the modified methanol fuel to the burners and pipeline systems is equivalent to that of other petrochemical fuels. The modified methanol fuel is more stable, and the modifier made of several raw materials is preferably selected to make methanol more compatible with other fuels, and there will be no stratification phenomenon during long-term storage; at the same time, the combined use of the modifier and the calorific value agent improves the combustion efficiency of the methanol fuel, and even when the stove is at the lowest flame, it can continue to burn stably.

[0019] 3. The present invention adopts a step-by-step preparation method, which is safe and reliable, has a simple process flow, does not require high equipment, is easy to control product quality, and is suitable for large-scale industrial production. DETAILED DESCRIPTION

[0020] The present invention will be further described below in conjunction with embodiments.

[0021] 1. A modified methanol fuel for civil use

[0022] The modified methanol fuel for civil use comprises the following raw materials by weight: 80-95 parts of methanol, 1-5 parts of modifier, and 1-20 parts of calorific value agent. The methanol is selected with a percentage concentration of not less than 99%, and can be industrially produced methanol or recycled and refined methanol.

[0023] The improver comprises the following raw materials in parts by weight: 25-45 parts of n-butanol, 25-45 parts of ethylene glycol, 20-30 parts of methyl oleate, 20-35 parts of dimethoxymethane, 1-8 parts of cyclohexylamine, 0.1-1 parts of NPE-9, and 0.01-1 parts of methylbenzotriazole. NPE-9 is nonylphenol polyoxyethylene (9) ether.

[0024] The calorific value agent comprises the following raw materials in parts by weight: 25 to 50 parts of 1# paint and solvent oil for cleaning, 20 to 45 parts of heavy naphtha, and 30 to 60 parts of kerosene.

[0025] In a specific implementation, the improver includes the following raw materials in parts by weight: 25-45 parts of n-butanol, 25-45 parts of ethylene glycol, 20-30 parts of methyl oleate, 20-35 parts of dimethoxymethane, 1-8 parts of cyclohexylamine, 0.1-1 parts of NPE-9, and 0.01-1 parts of toluene triazole.

[0026] The calorific value agent includes the following raw materials by weight: 25-50 parts of 1# paint and cleaning solvent oil, 20-45 parts of naphtha, and 30-60 parts of kerosene. The naphtha is a fraction of 70-180°C naphtha, and the solvent oil is 1# paint and cleaning solvent oil.

[0027] Table 1 (unit: parts)

[0028] Example Methanol Modifier Calorific value agent 1 95 1 4 2 90 1.5 8.5 3 80 2.5 17.5 4 85 2 13 5 92 1.2 6.8

[0029] Table 2 Modifiers used in Examples 1 to 5 (unit: part)

[0030] Example n-Butanol Ethylene glycol Methyl oleate Dimethoxymethane Cyclohexylamine NPE-9 Methylbenzotriazole 1 25 30 18 21.7 5 0.25 0.05 2 26 31 19 20.6 3 0.35 0.05 3 27 31 20 19.6 2 0.38 0.02 4 20 38 15 23 3.5 0.48 0.02 5 35 25 16 18 5.5 0.45 0.05

[0031] Table 3 Calorific value agent used in Examples 1 to 5 (unit: part)

[0032]

[0033]

[0034] Taking Example 1 as an example, the following method is used to prepare modified methanol fuel for civilian use:

[0035] 1) preparing the modifier: preparing the raw materials of the modifier, adding them into a reaction kettle in order, stirring them evenly, and leaving them to stand for at least 24 hours to obtain the modifier;

[0036] 2) preparing the calorific value agent: preparing the raw materials of the calorific value agent, adding them into another reaction kettle in sequence, stirring evenly, and standing for at least 24 hours to obtain the modifier;

[0037] 3) adding the modifier prepared in step 1) and methanol into a reactor, mixing and stirring evenly for 1 hour, and standing for at least 24 hours, then adding the calorific value agent prepared in step 2) into the reactor, mixing and stirring evenly for 1 hour, and standing for at least 24 hours to obtain the product.

[0038] In the specific implementation, the prepared raw materials are added to the reactor, and the raw materials are circulated in the pipeline for multiple times by using a pump, so as to achieve a uniform mixing effect. Among them, the raw materials of the modifier and the calorific value agent are put in as much as possible according to the raw material sequence described in the present invention, that is, according to 25-45 parts of n-butanol, 25-45 parts of ethylene glycol, 20-30 parts of methyl oleate, 20-35 parts of dimethoxymethane, 1-8 parts of cyclohexylamine, 0.1-1 parts of NPE-9, and 0.01-1 parts of toluene triazole.

[0039] Add the calorific value agent raw materials in the following order: 25-50 parts of 1# paint and cleaning solvent oil, 20-45 parts of heavy naphtha, and 30-60 parts of kerosene.

[0040] In Examples 2 to 5, materials were prepared according to Tables 1 to 3, and the modified methanol fuel for civilian use was prepared by the above-mentioned preparation method.

[0041] The product obtained by directly mixing the calorific value agent and methanol in Example 1 is used as Comparative Example 1; the modifier in Example 1 is replaced by an emulsifier (AEO4) of equal weight as Comparative Example 2; the product obtained by directly mixing the modifier and methanol in Example 1 is used as Comparative Example 3; at the same time, industrial methanol purchased directly on the market is used as Comparative Example 4.

[0042] 2. Comparison of fuel combustion performance

[0043] The modified methanol fuels for civil use prepared in Examples 1 to 5 were compared with Comparative Examples 1 to 4. Both the examples and the comparative examples were used on the same type of civil fuel appliances. 10 kg of water at 0° C. was heated to 50° C. The specific conditions are shown in the following table:

[0044] Table 1 Comparison of energy consumption between the embodiment and the comparative example

[0045]

[0046]

[0047] As can be seen from Table 1, the modifier is removed from Comparative Example 1, and the calorific value decreases compared with Example 1, which indicates that the modifier of the present invention enhances the effect of the calorific value agent on the calorific value of methanol; Comparative Example 2 uses other emulsifiers, which obviously cannot enhance the effect of the calorific value agent on the calorific value of methanol; Comparative Example 4 produces obvious irritating gas during combustion, and the operator's eyes have obvious irritating sensations, which indicates that Comparative Example 4 will produce formaldehyde that is irritating to the human eye during the combustion process. The compounds produced after the combustion of the embodiments and comparative examples are collected and tested, and formaldehyde is detected in all Comparative Examples 1 to 4, which indicates that the combustion of the fuel described in the comparative example is not sufficient, and irritating by-products are produced; No formaldehyde is detected in the products after the combustion of the embodiments, which indicates that the fuel of the present invention can be fully burned and no irritating by-products are produced; and, under the condition of heating 10kg of water at 0°C to 50°C, the fuel consumption of the comparative example is significantly higher than that of the embodiment, that is, the comparative example needs to burn more fuel to provide the same amount of heat as the embodiment, which also indicates that the combustion efficiency of the fuel described in the comparative example is lower than that of the present invention.

[0048] The embodiment and the comparative example were used continuously for half a year on the same type of burner. After the burner was disassembled and the internal structure of the burner was observed, in the burner using the embodiment, there was no swelling in the rubber pipe for transporting fuel, no corrosion or foreign matter blockage occurred inside each component, no deposits were found at the burner nozzle, and the internal structure of the burner was in good condition;

[0049] The rubber pipe of the burner of Comparative Example 1 has a very serious swelling phenomenon, and the metal pipe has obvious corrosion phenomenon. A large amount of foreign matter has formed at the nozzle of the burner. Although it has not been blocked, it can be inferred that it will be blocked if it continues to be used.

[0050] In the burner of Comparative Example 2, obvious swelling occurred in the rubber pipe, corrosion also occurred inside the metal pipe, and foreign matter was also formed at the burner nozzle, but the amount of foreign matter was less than that of Comparative Example 1.

[0051] The internal condition of the rubber pipe for transporting fuel of the burner of Comparative Example 3 is similar to that of Comparative Example 2. The internal corrosion of the metal pipe is also observed, and foreign matter is also formed at the burner nozzle, but the amount of foreign matter is less than that of Comparative Example 1.

[0052] When using the burner of Comparative Example 4, the rubber pipe for transporting fuel has a more serious swelling phenomenon than that of Comparative Example 1, and there is also obvious corrosion inside the metal structure of the pipe, and some of the nozzles of the burner have been blocked. After long-term use, when the flame of the burner of Comparative Example 3 is adjusted to the minimum, the flame will go out.

[0053] This shows that after the present invention modifies methanol through a modifier, its corrosion to the burners and pipeline systems is greatly alleviated, and the corrosion effect of the modified methanol fuel on the burners and pipeline systems is equivalent to that of other petrochemical fuels. The modified methanol fuel is more stable, and the modifier made of several raw materials is preferably used to make methanol more compatible with other fuels, and no stratification will occur during long-term storage; at the same time, the combined use of the modifier and the calorific value agent improves the combustion efficiency of the methanol fuel, and even when the stove is at the lowest flame, it can continue to burn stably.

[0054] The modified methanol fuels for civil use prepared in Examples 1 to 5 were compared with Comparative Examples 1 to 3. The examples and comparative examples were used on the same type of fireplaces to heat the same area and consistent internal layout of the house space. The fireplace outlet temperature was set to 60° C. and the operation lasted for 18 days. The specific results are shown in the following table:

[0055] Table 2 Comparison of heating energy consumption of embodiment and comparative example

[0056]

[0057] During the long-term heating process, the energy consumption of the comparative example is much higher than that of the embodiment, while the consumption of comparative examples 1 to 3 is lower than that of comparative example 4, which indicates that the addition of a calorific value agent or a modifier alone or the replacement of the modifier with an emulsifier can indeed increase the calorific value of methanol to a certain extent; however, the modifier used in the embodiment can enhance the effect of the calorific value agent on the calorific value of methanol, and has lower energy consumption than the simple mixing of the two in comparative example 1; at the same time, it can be seen from comparative example 2 that a single emulsifier cannot replace the modifier described in the present invention, and the emulsifier does not play the same role as the modifier described in the present invention, namely: enhancing the effect of the calorific value agent on the calorific value of methanol.

[0058] The examples and comparative examples were placed in containers of the same material and volume, and placed at -30°C and under exactly the same environmental conditions for long-term static storage. After one week, one month, and one year of storage, the appearance of the products in the containers was observed, and the ability to continue to be used and the combustion performance when continued to be used were compared.

[0059] Table 3

[0060]

[0061] As time goes by, the product in the container where the examples are stored remains clear and transparent. After one year of storage, there is no stratification phenomenon. Even after two years of storage, it remains clear and transparent. In the comparative examples, after one month of storage, comparative example 1 begins to stratify first. At this time, the container is shaken, and the substances in the container will be re-mixed to form a short-term homogeneous state. After continued standing, stratification will occur again. After one year of storage, comparative examples 1 to 3 all show very obvious stratification. Although comparative example 4 does not show stratification, the concentration of methanol in the container has decreased.

[0062] The examples and comparative examples were taken out after being stored for one year, and the combustion performance was compared, see Table 4.

[0063] Table 4 Comparison of emission content of each product after combustion after one year of storage (unit: mg / m 3 )

[0064] Examples and Comparative Examples Nitrogen oxides Sulfide Particles <![CDATA[CO2 emission factor (kg-CO2 / kg)]]> Example 0～60 0 0 1.56～1.65 Comparative Example 1 270～390 0 More 1.98～2.14 Comparative Example 2 160～260 0 Small amount 1.67～1.84 Comparative Example 3 250～380 0 More 1.94～2.21 Comparative Example 4 60～100 0 0 2.75～2.84

[0065] The embodiment and comparative example after being stored for one year were used in the same type of civil fuel appliances, and all were used for half a year. During the use period, combustion comparison was performed. Comparative Example 1 and Comparative Example 3 both needed to be shaken and mixed to form a homogeneous state before they could be used; ignition was relatively difficult, and the ignition operation was performed more than 10 times before ignition, and it could continue to burn for a period of time. The formation of formaldehyde was detected by detecting the products after combustion, and then the flame was extinguished, and it could not be ignited; after half a year, the fuel appliance was inspected, and it was found that deposits were formed in the fuel delivery pipeline, and the nozzle of the fuel appliance was seriously blocked; Comparative Example 2 also needed to be shaken to mix, and ignition was relatively difficult. The ignition operation was performed about 5 times to achieve ignition, and it could continue to burn stably for a long time, but the formation of formaldehyde could be detected during the combustion process, indicating that a large amount of by-products were formed during the combustion process of Comparative Example 2; Comparative Example 4 was difficult to ignite due to the significant decrease in its methanol concentration. The ignition operation was performed more than 6 times before ignition, and it could burn, but the flame flickered and was unstable during combustion. At the same time, the formation of formaldehyde could also be detected by detecting the products after combustion. The embodiment does not require shaking and mixing, can be ignited after one ignition operation, can burn stably and continuously, and the flame is bright and does not flicker. The products after combustion are tested and no formaldehyde is detected.

[0066] This shows that being in storage for a long time may cause abnormal conditions in comparative examples 1 to 3. It may be that the effect of unmodified protected methanol and calorific value agent substances in the natural environment causes the product to deteriorate. The unmodified protected methanol and calorific value agent substances are fully miscible, and hydrocarbon substances are not fully burned, resulting in an increase in particulate matter. However, ordinary single emulsifiers cannot keep methanol and calorific value agents in a stable state for a long time. Long-term storage (more than six months) will still cause product deterioration, and the combustion effect is also poor. Only the product of modifier and methanol is stored for a long time. Although there is no calorific value agent, the system with only the two is also difficult to maintain stability for a long time. After long-term storage (more than six months), deterioration also occurs. Although industrial methanol can be stored for a long time, methanol is volatile. After long-term storage, its concentration has dropped significantly, and incomplete combustion will produce substances with irritating odors. The state of Examples 1 to 5 after being stored for one year is very stable, and they remain clear and transparent, and can be used as civilian fuels. At the same time, even after being stored for one year, after Examples 1 to 5 were used as civilian fuels for half a year, the internal structure of the fuel appliances was observed after the fuel appliances were disassembled. In the fuel appliances using the embodiments, there was no swelling in the rubber pipes for transporting fuel, and there was no corrosion or foreign matter blockage inside the various components. No deposits were found at the nozzle of the fuel appliance, and the internal structure of the fuel appliance was in good condition.

[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the technical solution. Those skilled in the art should understand that those modifications or equivalent substitutions of the technical solution of the present invention that do not depart from the purpose and scope of the technical solution should be included in the scope of the claims of the present invention.

Claims

1. A modified methanol fuel for civil use, characterized in that: The method is composed of the following raw materials in parts by weight: 80-95 parts of methanol, 1-5 parts of a modifier, and 1-20 parts of a calorific value agent; The improver is composed of the following raw materials in parts by weight: 25-45 parts of n-butanol, 25-45 parts of ethylene glycol, 20-30 parts of methyl oleate, 20-35 parts of dimethoxymethane, 1-8 parts of cyclohexylamine, 0.1-1 parts of NPE-9, and 0.01-1 parts of tolutriazole; The calorific value agent is composed of the following raw materials in parts by weight: 25-50 parts of 1# paint and cleaning solvent oil, 20-45 parts of naphtha, and 30-60 parts of kerosene.

2. The modified methanol fuel for civilian use according to claim 1, characterized in that: The methanol is selected from methanol with a mass fraction of not less than 99%.

3. The modified methanol fuel for civilian use according to claim 1, characterized in that: The naphtha is heavy naphtha with a distillation range of 70-180°C.

4. A method for preparing modified methanol fuel for civilian use, characterized in that: The preparation of the modified methanol fuel for civilian use as claimed in any one of claims 1 to 3 comprises the following steps: 1) Preparation of the modifier: prepare the raw materials of the modifier, add them into a reaction kettle, stir evenly, and let stand for at least 24 hours to obtain the modifier; 2) Preparation of calorific value agent: prepare the raw materials of the calorific value agent, add them into another reaction kettle, stir evenly, and let stand for at least 24 hours to obtain the calorific value agent; 3) The modifier prepared in step 1) and methanol are added to a reactor, mixed and stirred evenly, and then allowed to stand for at least 24 hours. Then, the calorific value agent prepared in step 2) is added to the reactor, mixed and stirred evenly, and allowed to stand for at least 24 hours to obtain the product.

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