Method for producing oil mixture by using methanol

Abstract

The invention belongs to the technical field of organic compounds, and provides a method for producing an oil mixture by using methanol. According to the present invention, the methanol and the light hydrocarbon auxiliary agent are adopted as the raw materials, the hydrogenation synthesis reaction is performed in the presence of the hydrogen and the catalyst to prepare the oil mixture, the product contains rich oxygen-containing organic compounds and alkanes, the product value is improved, and the prepared oil mixture has characteristics of high octane number, low cost, and easy industrial production. The method can be directly used as efficient and clean high-quality fuel oil, can also be used as an auxiliary agent to be added into the existing fuel to improve the octane number of the fuel, can also separate the components and be independently used as a solvent, and is simple, convenient, easy to operate and environment-friendly, and meets the requirement of carbon reduction.

Description

Technical Field

[0001] The present invention relates to the technical field of organic compounds, and more particularly to a method for producing an oil mixture by utilizing methanol. Background Art

[0002] Methanol is a simple and inexpensive organic compound with a wide range of uses. Methanol can be used directly as a raw material, and its combustion products are mainly carbon dioxide and water, making it a clean energy source.

[0003] However, due to the low calorific value of methanol itself (about 19.6MJ / kg), which is much lower than the calorific value of gasoline (about 43.1MJ / kg), the value of methanol as a fuel is low, which limits the application of methanol. However, there is no method for preparing high-quality fuel oil using methanol in the prior art. Therefore, it is urgent to develop a method for producing fuel oil using methanol, improve the utilization value of methanol, and expand the use of methanol. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for producing an oil mixture using methanol. The present invention prepares an oil mixture from methanol through a hydrogenation synthesis reaction. The oil mixture contains abundant oxygen-containing organic compounds (such as alcohols, ethers) and paraffins, which can not only be used as high-quality fuel oil, but also can be added to existing conventional fuels to improve their performance (such as improving the octane number of conventional fuels). The various components in the oil mixture can also be separated and used as a solvent. The oil mixture prepared by the present invention using methanol has a wide range of uses, which greatly improves the utilization value of methanol.

[0005] A first aspect of the present invention provides a method for producing an oil mixture using methanol.

[0006] Specifically, a method for producing an oil mixture using methanol comprises the following steps:

[0007] Methanol, light hydrocarbon additives and catalysts are mixed and placed in a hydrogen atmosphere for hydrogenation synthesis reaction to obtain the oil mixture, which contains oxygen-containing organic compounds and chain alkanes.

[0008] The present invention uses methanol and light hydrocarbon additives as raw materials, and produces an oil mixture through a hydrogenation synthesis reaction in the presence of a catalyst and hydrogen conditions. The product contains rich oxygen-containing organic compounds (such as alcohol compounds, ether compounds) and chain alkanes. The method provided by the present invention can convert methanol, an alcohol compound with only a single carbon, into substances such as polyols and ethers. The molecular weight and structure of the products before and after the reaction are changed, and the utilization value is improved. For example, the oil compound can be directly used as fuel oil, and can also be added to other fuel oils as an additive. Different types of substances in the product can also be separated and used as a solvent, and the product value is significantly improved (the market price of methanol is about 2,500 yuan / ton, while the market price of fuel oil is about 8,000 yuan / ton. After the fuel oil is made from methanol, the product value is greatly improved).

[0009] Preferably, the weight ratio of the methanol to the light hydrocarbon additive is (60-99):(1-40).

[0010] Preferably, the light hydrocarbon additive is a C4-C11 hydrocarbon compound.

[0011] Further preferably, the light hydrocarbon additive is naphtha and C5-C8 olefins.

[0012] Preferably, the purity of the methanol, light hydrocarbon additive and hydrogen is ≥99%.

[0013] Preferably, the pressure of the hydrogenation synthesis reaction is ≤1.2Mpa, and / or the temperature of the hydrogenation synthesis reaction is 200-400°C, and / or the time of the hydrogenation synthesis reaction is 10-300s. The higher the reaction temperature, the shorter the required reaction time.

[0014] Further preferably, the pressure of the hydrogenation synthesis reaction is 0.2-1.5 MPa, and / or the temperature of the hydrogenation synthesis reaction is 300-360° C., and / or the time of the hydrogenation synthesis reaction is 120-130 s.

[0015] Preferably, the weight of the hydrogen is ≤1% of the total weight of the raw materials, and the total weight of the raw materials is the total weight of methanol, light hydrocarbon additive and hydrogen.

[0016] The present invention produces and prepares an oil mixture under hydrogen-presence and low-pressure conditions, requiring low reaction pressure, low reaction temperature, and small amount of hydrogen (hydrogen accounts for ≤1% of the total weight of the raw materials, for example, the total weight of methanol+light hydrocarbons+hydrogen is 100kg, and the amount of hydrogen used is 1kg).

[0017] Preferably, the catalyst contains at least one of platinum, palladium, rhodium, silver and ruthenium.

[0018] More preferably, the catalyst is a platinum-rhenium-palladium-rhodium catalyst and / or a platinum-rhodium-palladium catalyst. The noble metal in the catalyst is distributed in the form of a compound.

[0019] Preferably, the pressurized methanol, light hydrocarbon additive and hydrogen are mixed, heat exchanged to 150-200°C, then heated to 200-400°C, and subjected to hydrogenation synthesis reaction under the action of a catalyst. After heat exchange again, the mixture is cooled to 20-30°C, and the liquid phase is collected to obtain the oil mixture.

[0020] Further preferably, the methanol and light hydrocarbon additive are mixed, pressurized by a pump, and passed into a mixer; the hydrogen is pressurized by a hydrogen compressor and passed into the mixer; the pressurized methanol, light hydrocarbon additive and hydrogen are mixed in the mixer, and then enter a heat exchanger for heat exchange to 150-200°C, and then enter a heating furnace to be heated to 200-400°C, and then enter a reactor to carry out a hydrogenation synthesis reaction under the action of a catalyst, and then heat exchange again through a heat exchanger, and cool to 20-30°C in a cooler, and the liquid phase is collected and enters a separator tank to obtain the oil mixture.

[0021] The present invention adopts the above-mentioned continuous production process, uses methanol as a raw material, and prepares an oil mixture. The entire production process runs continuously to form a stable production process, which can realize automation and large-scale production, and is conducive to ensuring the stability of product quality.

[0022] A second aspect of the present invention provides an oil mixture.

[0023] An oil mixture is prepared by the above preparation method.

[0024] Preferably, the oxygen-containing organic compound includes alcohol compounds and / or ether compounds.

[0025] Preferably, the alcohol compound is a C1-C5 alcohol compound, and / or the ether compound is a C2-C5 ether compound.

[0026] Preferably, the alcohol compound is at least one of methanol, isopropanol, n-propanol, tert-butanol and ethanol.

[0027] Preferably, the ether compound is at least one of methyl tert-butyl ether (MTBE), dimethyl ether (DME), and diethyl ether.

[0028] Preferably, the chain alkane is octane and / or C5-C10 isoalkane.

[0029] Preferably, the octane number of the oil mixture is ≥90.

[0030] More preferably, the octane number of the oil mixture is greater than 110.

[0031] Octane number: Determined by comparison with a standard fuel mixture consisting of n-heptane (high tendency to deflagration) and isooctane (good resistance to deflagration). Octane number is an indicator of the resistance of fuel (gasoline) used in vehicles to knock. The higher the octane number, the better the resistance to knock and the higher its value as a fuel.

[0032] Preferably, the density of the oil mixture is 0.785-0.8 g / cm 3 .

[0033] A third aspect of the present invention provides a use of an oil mixture.

[0034] The invention discloses an application of an oil mixture as fuel oil, fuel additive or in preparing a solvent.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] The present invention utilizes methanol and light hydrocarbon additives as raw materials, and a hydrogenation synthesis reaction occurs under the conditions of hydrogen and a catalyst to produce an oil mixture, which contains rich oxygen-containing organic compounds (such as alcohol compounds, ether compounds) and chain alkanes, thereby improving the product value. In addition, the oil mixture prepared by the present invention has a high octane number and can be directly used as efficient and clean high-quality fuel oil, or can be added as an additive to existing fuels to improve their octane number. In addition, the product can be separated and used alone as a solvent. In addition, the method of the present invention is simple and easy to operate, environmentally friendly, and meets the requirements of carbon reduction. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic diagram of a reaction device for preparing an oil mixture using methanol in Example 1 of the present invention;

[0038] Figure 2 is a chromatogram of the oil mixture prepared in Example 1 of the present invention;

[0039] Figure 3 The chromatogram of the oil mixture prepared in Example 2 of the present invention. DETAILED DESCRIPTION

[0040] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0041] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0042] The purity of the methanol, light hydrocarbon auxiliary agent and hydrogen used in the present invention is ≥99%.

[0043] Example 1

[0044] A method for producing an oil mixture using methanol comprises the following steps:

[0045] Use Figure 1 The reaction system shown in the figure is used for production. Methanol and naphtha (light hydrocarbon auxiliary agent) with a weight ratio of 60:40 are mixed, pressurized by a pump, and then enter the mixer; hydrogen is pressurized by a hydrogen compressor and passed into the mixer, and the weight of the hydrogen is 1% of the total weight of methanol, naphtha, and hydrogen; the above pressurized methanol, light hydrocarbon auxiliary agent, and hydrogen are mixed in the mixer, and then enter the heat exchanger, heat exchanged to 240°C, and then enter the heating furnace to be heated to 380±10°C, and then enter the reactor to carry out hydrogenation synthesis reaction under the action of platinum rhenium palladium rhodium catalyst, the reaction pressure is 1.2-1.5Mpa, the reaction time is 120s, and the heat is exchanged again by the heat exchanger, and then enters the cooler to be cooled to 25°C, and enters the separator to obtain an oil mixture, which is a light yellow liquid with a density of 0.781g / cm 3 .

[0046] Example 2

[0047] A method for producing an oil mixture using methanol comprises the following steps:

[0048] Methanol and C5-C8 olefins (light hydrocarbon additives) with a weight ratio of 99:1 are mixed, pumped and pressurized, and then enter the mixer. The weight of hydrogen is 1% of the total weight of methanol, C5-C8 olefins and hydrogen. The hydrogen is pressurized by a hydrogen compressor and then introduced into the mixer. The pressurized methanol, light hydrocarbon additives and hydrogen are mixed in the mixer and then enter the heat exchanger to exchange heat to 200°C, then enter the heating furnace to be heated to 350±10°C, and then enter the reactor to carry out hydrogenation synthesis reaction under the action of platinum, rhodium and palladium catalysts, exchange heat again through the heat exchanger, then enter the cooler to be cooled to 25°C, and enter the separator to obtain an oil mixture, which is a light yellow liquid with a density of 0.780g / cm 3 .

[0049] Example 3

[0050] A method for producing an oil mixture using methanol, which differs from Example 1 in that the platinum-rhenium-palladium-rhodium catalyst is replaced by a platinum catalyst.

[0051] Comparative Example 1

[0052] A method for producing an oil mixture using methanol, which differs from Example 1 in that naphtha (light hydrocarbon additive) is replaced by an equal weight of olefin tar.

[0053] Product effect testing

[0054] 1. Ingredient testing

[0055] (1) Detection of hydrocarbon composition, oxides and benzene

[0056] Test method: ASTM D6839-21a (Part A).

[0057] The test results of the oil compounds prepared in Example 1 are shown in Table 1 below.

[0058] Table 1 Test results of oil compounds obtained in Example 1

[0059] Ingredient name Content (wt%) Aromatics 11.7 Cycloalkanes 33.5 Olefins 1.9 Alkanes 52.8 Total Oxide 0.2

[0060] (2) Octane number detection

[0061] Test method: GB / T 5487-2015 and XG1-2017.

[0062] The test results show that the octane number of the oil compound prepared in Example 1 is greater than 110. The octane number of the oil compound prepared in Example 1 is higher than that of the 92, 95, and 98 gasoline commonly used on the market, indicating that the oil compound of the present invention can be directly used as a high-quality fuel, and can also be used as an additive to be added to conventional fuels to improve the quality of existing fuels.

[0063] (3) Detection of oxygen content of certain alcohols and ethers in products (gas chromatography)

[0064] Test method: NB / SH / T 0663-2014.

[0065] The test results show that the oxygen content of alcohols and ethers in the oil mixture prepared in Example 1 is 37.71%.

[0066] (4) Chromatographic detection

[0067] like Figure 2 and Figure 3 As shown, the results show that the oil mixture prepared in Example 1 of the present invention mainly contains methanol, ethanol, isopropanol, tert-butanol, n-propanol, methyl tert-butyl ether (MTBE), and dimethyl ether (DME), and these substances can be separated and used as solvents.

[0068] The oil mixtures prepared in Example 1 and Example 2 contain similar main components. Example 3 uses a platinum catalyst, and the product conversion rate is about 20% lower than that of Example 1 and Example 2.

[0069] 2. Application performance testing

[0070] Six Mercedes-Benz Maybachs of the same model were prepared as test vehicles, and the oil compound prepared in Example 1 of the present invention was used as fuel to drive in the urban area. The test results show that the fuel of Example 1 is powerful, fuel-efficient and durable, with a cumulative test drive of more than 500 days and a mileage of more than 10,000 kilometers. Compared with the commercially available No. 98 gasoline, each tank of oil can travel about 100 kilometers more. The oil mixtures of Example 1 and Example 2 have similar application performances.

Claims

1. A method for producing an oil mixture using methanol, characterized in that: The steps include: Methanol, light hydrocarbon additives and catalysts are mixed and placed in a hydrogen atmosphere for hydrogenation synthesis reaction to obtain the oil mixture, which contains oxygen-containing organic compounds and chain alkanes.

2. The method according to claim 1, characterized in that The weight ratio of the methanol to the light hydrocarbon additive is (60-99):(1-40).

3. The method according to claim 2, characterized in that The light hydrocarbon additive is a C4-C11 hydrocarbon compound.

4. The method according to claim 1, characterized in that The pressure of the hydrogenation synthesis reaction is ≤1.2Mpa, and / or the temperature of the hydrogenation synthesis reaction is 200-400°C, and / or the time of the hydrogenation synthesis reaction is 10-300s.

5. The method according to claim 1, characterized in that The catalyst contains at least one of platinum, palladium, rhodium, silver and ruthenium.

6. The method according to claim 1, characterized in that The pressurized methanol, light hydrocarbon additive and hydrogen are mixed, heat exchanged to 150-200°C, then heated to 200-400°C, and subjected to hydrogenation synthesis reaction under the action of a catalyst. After heat exchange again, the mixture is cooled to 20-30°C, and the liquid phase is collected to obtain the oil mixture.

7. An oil mixture, characterized in that: Prepared by the method according to any one of claims 1 to 6, the oil mixture comprises oxygen-containing organic compounds and paraffins.

8. The oil mixture according to claim 7, characterized in that: The oxygen-containing organic compound includes alcohol compounds and / or ether compounds.

9. The oil mixture according to claim 8, characterized in that The alcohol compound is a C1-C5 alcohol compound, and / or the ether compound is a C2-C5 ether compound.

10. The oil mixture according to claim 7, characterized in that: The chain alkane is octane and / or C5-C10 isoalkane.

11. The oil mixture according to claim 10, characterized in that The octane number of the oil mixture is ≥90.

12. Use of the oil mixture according to any one of claims 7 to 11 as fuel oil, fuel additive or in the preparation of solvent.

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