A modified methanol fuel for industrial use and preparation method thereof

Abstract

The invention discloses a modified methanol fuel for industrial use, which includes the following raw materials by weight: 60-90 parts of industrial methanol, 2-5 parts of modifiers and 6-38 parts of calorific value agents; the modifier includes the following raw materials by mass percentage: 5%-35% of ethanol, 5%-35% of propanol, 5%-25% of n-hexanol, 5%-25% of ethyl formate, 5%-25% of dimethyl carbonate, 1%-10% of triethanolamine, and 0.1%-10% of OP-10; the calorific value agent includes the following raw materials by mass percentage: 5%-55% of hexane, 25%-75% of solvent oil, and 15%-55% of fatty acid methyl ester. The present invention modifies methanol by a modifier and a calorific value agent, so that the calorific value of the modified methanol fuel is improved, pollutant emissions are reduced, storage and transportation are convenient, and use costs are reduced, and the preparation method has a simple process flow, low requirements on equipment, easy control of 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 industrial use and a preparation method thereof. Background Art

[0002] my country is the world's largest methanol production country, with an annual production capacity of nearly 100 million tons, and the capacity is expected to increase in the future. Methanol can be used directly as fuel, but the effect is not optimal. If tens to hundreds of millions of tons of industrial methanol are modified and formulated into modified methanol fuel, it will play a beneficial role in my country's development of a multi-energy strategy.

[0003] At present, the fuels used in industry and kilns are mainly coal, oil and gas. As a liquid fuel, the composition and properties of oil are related to the crude oil and processing method. 18 Sulfur and other impurities in hydrocarbons and crude oil cause the fuel to produce a large amount of atmospheric pollutants such as flue gas nitrogen oxides and sulfur dioxide after combustion. Although alcohol-based liquid fuel can also be used as a substitute for fuel oil, its calorific value is low, and there is a gap between some physical and chemical properties and fuel oil, which makes it difficult to promote and apply it in the industrial field. Especially in the Northeast region, due to the low temperature in winter, poor quality alcohol-based fuels are prone to stratification in low temperature environments, making these alcohol-based fuels unusable, which in turn limits the promotion and application of alcohol-based fuels. 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 industrial use and a preparation method thereof, so as to solve the problems of the prior art alcohol-based liquid fuel having low calorific value, high use cost, and easy stratification in low temperature environment, resulting in unusable.

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

[0006] A modified methanol fuel for industrial use, comprising the following raw materials by weight: 60-90 parts of industrial methanol, 2-5 parts of a modifier and 6-38 parts of a calorific value agent;

[0007] The modifier comprises the following raw materials calculated by mass percentage: 5% to 35% ethanol, 5% to 35% propanol, 5% to 25% n-hexanol, 5% to 25% ethyl formate, 5% to 25% dimethyl carbonate, 1% to 10% triethanolamine, and 0.1% to 10% OP-10;

[0008] The calorific value agent comprises the following raw materials calculated by mass percentage: 5% to 55% hexane, 25% to 75% solvent oil, and 15% to 55% fatty acid methyl ester. The industrial methanol meets the GB338 qualified product standard.

[0009] Preferably, the modifier comprises the following raw materials calculated by mass percentage: 10% to 30% ethanol, 10% to 30% propanol, 10% to 20% n-hexanol, 8% to 20% ethyl formate, 10% to 20% dimethyl carbonate, 4% to 10% triethanolamine, and 0.1% to 5% OP-10.

[0010] Preferably, the calorific value agent comprises the following raw materials calculated by mass percentage: 6% to 50% hexane, 30% to 70% solvent oil, and 20% to 50% fatty acid methyl ester.

[0011] Preferably, the solvent oil is rubber solvent oil.

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

[0013] 1) Industrial methanol preparation;

[0014] 2) 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;

[0015] 3) preparing a calorific value agent: preparing the raw materials of the calorific value agent, adding the raw materials into another reaction kettle, stirring evenly, and standing for at least 24 hours to obtain the calorific value agent;

[0016] 4) Preparing industrial modified methanol fuel: putting the modifier obtained in step 2) and the prepared industrial methanol into a reactor, mixing and stirring evenly, standing for at least 24 hours, then adding the calorific value agent prepared in step 3) and mixing and stirring evenly, standing for at least 24 hours to obtain the modified methanol fuel for industrial use.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] 1. The present invention modifies industrial methanol by adding a modifier and a calorific value agent to industrial methanol, thereby improving the calorific value of the modified methanol. At the same time, the modifier can reduce the corrosion of industrial modified methanol fuel on metals and rubbers during use, so that the corrosion of industrial modified methanol fuel on metals and rubbers is equivalent to that of other petrochemical fuels; and the modifier can also improve the stability of industrial modified methanol fuel. Several alcohols, ethers, esters, etc. are specially selected as additives, so that industrial methanol can be better compatible with the calorific value agent, and will not be stratified or deteriorated during long-term storage at a temperature of -30°C, and can continue to be used after storage.

[0019] 2. The present invention adopts a step-by-step method for preparation, which is safe and reliable, 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. DETAILED DESCRIPTION

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

[0021] 1. Examples and Comparative Examples

[0022] Table 1: Raw material components of the modified methanol fuel (unit: part)

[0023] Example Industrial Methanol Modifier Calorific value agent 1 90 2.5 7.5 2 82 2 16 3 70 4 26 4 85 3 12 5 80 3.5 16.5

[0024] Table 2 Raw material components of modifier (unit: %)

[0025] Example Ethanol Propanol n-Hexyl alcohol Ethyl formate Dimethyl carbonate Triethanolamine OP-10 1 30 25 12 10 15 7.8 0.2 2 28 30 13 9 13 6.5 0.5 3 26 28 15 12 14 4.9 0.1 4 16 25 18 16 20 5.6 0.4 5 11 25 20 17 18 6.7 2.3

[0026] Table 3 Raw material components of the calorific value agent (unit: %)

[0027] Example Hexane Rubber solvent oil Fatty acid methyl esters 1 25 35 40 2 10 60 30 3 40 35 25 4 23 32 45 5 50 30 20

[0028] Taking Example 1 as an example, the composition ratios in Tables 1 to 3 are used to obtain the methanol fuel for industrial use by the following method:

[0029] 1) Industrial methanol preparation;

[0030] 2) 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;

[0031] 3) preparing a calorific value agent: preparing the raw materials of the calorific value agent, adding the raw materials into another reaction kettle, stirring evenly, and standing for at least 24 hours to obtain the calorific value agent;

[0032] 4) Preparing industrial modified methanol fuel: putting the modifier obtained in step 2) and the prepared industrial methanol into a reactor, mixing and stirring evenly, standing for at least 24 hours, then adding the calorific value agent prepared in step 3) and mixing and stirring evenly, standing for at least 24 hours to obtain the modified methanol fuel for industrial use.

[0033] Examples 2 to 5 also use the component ratios in Tables 1 to 3 to obtain the modified methanol fuel for industrial use through the above method.

[0034] All components and preparation methods of Comparative Examples 1 to 5 are exactly the same as those of Example 1, except that: in Comparative Example 1, ethanol is used to replace an equal mass of a mixture of ethanol, propanol and n-hexanol; in Comparative Example 2, butyl propionate is used to replace an equal mass of a mixture of ethyl formate and dimethyl carbonate; in Comparative Example 3, emulsifier TX-6 is used to replace an equal mass of OP-10; in Comparative Example 4, naphtha is used to replace an equal mass of hexane; and in Comparative Example 5, No. 1 fuel oil is used to replace an equal mass of rubber solvent oil.

[0035] 2. Performance Comparison

[0036] The above embodiments and comparative examples were used for boiler combustion, and their emissions were tested according to the national standard GB13271-2014. The test results are shown in the following table:

[0037] Table 4

[0038]

[0039]

[0040] It can be seen from Table 1 that after the industrial modified methanol fuel of the present invention is burned in a boiler, no particulate matter, sulfur dioxide, mercury and their compounds are generated, the generated flue gas is colorless or white, without blackness, and the amount of nitrogen oxides generated is much lower than that of coal-fired, oil-fired and gas-fired boilers. This shows that during the application process of the industrial modified methanol fuel of the present invention, its emissions fully meet the requirements of national standards and have excellent performance, especially in terms of environmental protection, it is good to the environment and will not cause excessive pollution to the environment.

[0041] Examples 1 to 5 without modifiers and directly mixing calorific value agent with methanol, emulsifiers (e.g. TX-21) of equal mass replaced by modifiers, comparative examples and examples were placed in containers of the same material and volume and stored. The above products were stored for a long time at -30°C and under the same environmental conditions, and the appearance, delamination, deterioration, whether the products could be used continuously, and the combustion performance after continued use of the products in the containers after storage for ten days, one month and three months were compared.

[0042] Table 5

[0043]

[0044] After ten days of storage, a portion of all the above products were taken out for combustion experiments, and the post-combustion emission content was tested. When ignited, the embodiment without modifier, calorific value agent and methanol directly mixed, the product needs to be stirred several times, and it is difficult to ignite; the embodiment in which the modifier is replaced with TX-21 of equal quality, no stirring is required, and it can be directly ignited; Examples 1 to 5 do not need to be stirred and can be directly ignited; Comparative Examples 1 to 5 do not need to be stirred and can be directly ignited. Specific combustion emissions are as follows:

[0045] Table 6 Comparison of emission content of each product after combustion after storage for ten days (unit: mg / m 3 )

[0046]

[0047] After one month of storage, a part of all the above products was taken out, a combustion experiment was carried out, and the emission content after combustion was detected. When ignited, the embodiment that does not contain modifiers and the calorific value agent is directly mixed with methanol needs to add functional additives to the product to make it a single-phase liquid before ignition operation, but the functional additives of the non-modifiers of the present invention are not easy to select. If the selection is not good, the product will be turbid. After repeated stirring, it is still difficult to ignite, and it is necessary to ignite and burn through other combustion aids (such as gasoline). After the product is burned for a period of time, its emission content is detected again to avoid the added combustion aid affecting the test results. At the same time, after use, the boiler equipment is blocked. The embodiment that the modifier is replaced with the same quality TX-21 needs to add an emulsifier to the product to make the two phases become a single-phase liquid. The technical effect brought by the emulsifier after such treatment is still not good, and the liquid product will be relatively turbid. After stirring evenly, it is difficult to ignite, but no combustion aid is needed, and it can be ignited and burned by itself. Examples 1 to 5 do not need to be stirred and can be ignited smoothly at one time without multiple ignition operations; Comparative Examples 1 to 5 need to be stirred evenly and can only be ignited after more than 3 ignition operations. Specific combustion emissions are as follows:

[0048] Table 7 Comparison of emission content of each product after combustion after storage for one month (unit: mg / m 3 )

[0049]

[0050] Comparing Table 6 and Table 7, it can be seen that after being stored in a low temperature environment for a long time, the container without a modifier begins to stratify after ten days of storage. As time goes by, the stratification phenomenon becomes more obvious. At this time, if the container is slightly shaken, the substances in the container will be re-mixed to form a homogeneous state. After standing for a period of time, stratification will occur again; after three months of storage, the solution is divided into upper and lower layers, and simple oscillation and stirring cannot restore it to a single-phase state. At the same time, after three months of storage, the mixed phase product in the container cannot be ignited in the combustion equipment, and additional combustion aids need to be added, such as a certain amount of gasoline needs to be added to ignite it and continue to burn. More importantly, the particulate matter in the combustion emissions begins to increase significantly, which indicates that the product has been abnormal due to being in a low temperature environment for a long time. It may be that the unmodified protective methanol and the calorific value agent material in the natural environment cause the product to deteriorate, and there is no sufficient miscibility of methanol and calorific value agent material, and the hydrocarbon material is not fully burned, resulting in an increase in particulate matter.

[0051] In the container where the modifier is replaced with TX-21 of the same quality, after ten days of storage, it can still remain clear and no stratification occurs. It can be seen that the emulsifier can indeed make methanol and the calorific value agent more miscible at low temperature, but this miscible effect is not lasting. After one month of storage at low temperature, the material in the container begins to stratify, which also proves that the ordinary single emulsifier cannot keep methanol and the calorific value agent in a stable state for a long time at low temperature. Moreover, the combustion effect is getting worse and worse. In the first ten days, it can be ignited smoothly, but after one month, due to the appearance of paste after the product is stratified, the same problem as the previous product without the modifier occurs. It is necessary to add functional additives to it before it can become a homogeneous liquid fuel. The liquid obtained after treatment, although it can burn by itself without a combustion aid, needs to be ignited multiple times. Similarly, the particulate matter in the combustion emissions has increased significantly compared with before, and the flame formed during combustion is obviously not as bright as when Examples 1 to 5 are burned. After three months of storage, it is also necessary to add functional additives to it before it can become a homogeneous liquid fuel, and it also needs to be ignited with the help of a combustion aid.

[0052] The same situation also exists in Comparative Examples 1 to 5, which all need the help of combustion aids to ignite in the end. Although other compounds of the same type can be used as replacements and good results are indeed achieved in the short term, in the long run, other compounds of the same type still have an adverse effect on the stability of the entire system, so the technical effect achieved by the embodiments of the present invention cannot be obtained.

[0053] However, the state of Examples 1 to 5 is still very stable even after being stored for three months under low temperature conditions, and remains clear and transparent, and can be used as fuel in the industrial field. In addition, after using the examples, the equipment does not become blocked, which also proves that the industrial methanol fuel of the present invention can still be used normally after being stored for a long time under low temperature conditions.

[0054] The calorific value of the embodiment and the existing boiler fuel natural gas and coal after being stored in a low temperature environment for one month was tested by a calorimeter, and the energy consumption performance of the embodiments 1 to 5, the comparative examples 1 to 5, the natural gas and the coal was compared, as shown in the following table:

[0055] Table 8 Fuel consumption and performance description

[0056]

[0057]

[0058] The calorific value of ordinary methanol is 20000 kj / kg. As can be seen from Table 8, after the modified methanol fuel of the present invention is stored in a low temperature environment for one month, its calorific value is still improved to a certain extent compared with the unmodified methanol. The calorific value of modified methanol is lower than that of natural gas and slightly higher than that of coal, but the thermal efficiency of the combustion system is higher than that of coal. From the consumption of fuel per ton of steam generated, the consumption of the embodiment is much lower than that of coal and slightly higher than that of natural gas. The calorific value of comparative examples 1 to 2 has decreased because of the influence of its stability, and the energy consumption has increased significantly.

[0059] In actual use, the existing alcohol-based fuel has poor solubility due to the poor mutual solubility of alcohol and other additives, which makes the modified existing alcohol-based fuel poor in solubility, and is prone to stratification, so that the flame of the fuel is prone to extinguishing when burning, which is very unstable. The industrial modified methanol fuel of the present invention has good stability, and will not have stratification during use. The flame is very bright and stable during combustion, and the industrial modified methanol fuel of the present invention has low corrosiveness to the pipeline system, which is comparable to ordinary fuels such as gasoline and diesel, and will not cause the pipeline system to be blocked due to corrosion. Moreover, even after being stored for a long time under low temperature conditions, it can still be used continuously, and has excellent stability under low temperature environment.

[0060] 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 industrial use, characterized in that: The raw materials are as follows: 60-90 parts of industrial methanol, 2-5 parts of modifier and 6-38 parts of calorific value agent; The modifier is composed of the following raw materials calculated by mass percentage: 10% to 30% ethanol, 10% to 30% propanol, 10% to 20% n-hexanol, 8% to 20% ethyl formate, 10% to 20% dimethyl carbonate, 4% to 10% triethanolamine, and 0.1% to 5% OP-10; The calorific value agent is composed of the following raw materials calculated according to mass percentage: 6% to 50% hexane, 30% to 70% solvent oil, and 20% to 50% fatty acid methyl ester; wherein the solvent oil is rubber solvent oil.

2. A method for preparing modified methanol fuel for industrial use, characterized in that: The preparation of the modified methanol fuel for industrial use as claimed in claim 1 comprises the following steps: 1) Industrial methanol preparation; 2) preparing the modifier: preparing the raw materials of the modifier, adding them into a reaction kettle, stirring evenly, and leaving them to stand for at least 24 hours to obtain the modifier; 3) 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; 4) Preparation of industrial modified methanol fuel: the modifier obtained in step 2) and the prepared industrial methanol are placed in a reactor and mixed and stirred evenly, and after standing for at least 24 hours, the calorific value agent prepared in step 3) is added and mixed and stirred evenly, and after standing for at least 24 hours, the modified methanol fuel for industrial use is obtained.

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