CN114891543A - Method for synthesizing methanol diesel oil - Google Patents
Method for synthesizing methanol diesel oil Download PDFInfo
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- CN114891543A CN114891543A CN202210534765.8A CN202210534765A CN114891543A CN 114891543 A CN114891543 A CN 114891543A CN 202210534765 A CN202210534765 A CN 202210534765A CN 114891543 A CN114891543 A CN 114891543A
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- methanol
- propylene glycol
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- kerosene
- coal tar
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000003350 kerosene Substances 0.000 claims abstract description 45
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 239000011280 coal tar Substances 0.000 claims abstract description 26
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 21
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 5
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229940055577 oleyl alcohol Drugs 0.000 description 4
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carboxyl carbon Chemical compound 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
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- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
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Abstract
The invention discloses a formula and a method for synthesizing methanol diesel oil, wherein the formula comprises light coal tar, methanol, aviation kerosene, ethyl acetate, ferrocene, isobutanol, propylene glycol, dimethyl carbonate and propylene glycol methyl ether; the synthesis method comprises the steps of adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol; adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 150-225 ℃ and under the pressure of 1-1.5 Mpa; then adding ethyl acetate and dimethyl carbonate into the light coal tar; and finally, mixing the products obtained in the second step and the third step, adding ferrocene, and uniformly stirring at 50-90 ℃ and 1-1.5 Mpa. The method has the advantages of cheap and easily-obtained raw materials, low cost, simple process, mild reaction conditions, low energy consumption, no post-treatment, greenness and environmental protection, high yield of the product up to 99.9 percent, high yield and good quality.
Description
Technical Field
The invention belongs to the technical field of fuels, and particularly relates to methanol diesel oil and a synthesis method thereof.
Background
With the development of economy, the problem of insufficient petroleum backup resources is fully developed, the large consumption of petroleum fuels and the air pollution caused by the petroleum fuels are problems which need to be solved urgently, the solution is to partially replace the traditional fuels by alternative fuels, and the development of coal-based fuels is an important way for solving the problems. Among the existing alternative energy sources, compared with diesel oil, the methanol is the only methanol which has the advantages of wide resources, easy availability, convenient transportation and acceptable cost, and is also a world-recognized clean fuel. From the characteristics, the methanol diesel oil has great physical property advantages as a substitute environment-friendly fuel at the present stage.
Some alcohol-based fuels are available on the market at present, but the fuels cannot be stored for a long time, are insufficient in stability, particularly cannot allow water to be added, are emulsified and layered during storage, transportation and use even if a trace amount of water enters, are not easy to ignite and have corrosiveness. The synthesis process of the alcohol-based fuel usually needs a large amount of additives, so that the inherent cost is increased, the process is complicated, the dosage of the additives is required to be very accurate, and the target product cannot be obtained if deviation exists.
Disclosure of Invention
The invention aims to provide a formula and a method for synthesizing methanol diesel oil, which aim to solve the problems and provide the methanol diesel oil with simple process, mild reaction conditions, high reaction efficiency, low energy consumption, economy and environmental protection and a synthesis method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the methanol diesel oil is composed of the following raw materials in percentage by volume: 40-70% of light coal tar, 5-18% of methanol and the balance of auxiliary agent; the auxiliary agent consists of the following raw materials in percentage by volume: 3 to 20 percent of aviation kerosene, 2 to 20 percent of kerosene, 5 to 35 percent of ethyl acetate, 0.1 to 3 percent of ferrocene, 0.2 to 9 percent of isobutanol, 0.3 to 9 percent of propylene glycol, 0.5 to 10 percent of dimethyl carbonate and 1 to 5 percent of propylene glycol methyl ether.
The method for synthesizing the methanol diesel comprises the following steps:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 150-225 ℃ and under the pressure of 1-1.5 Mpa; when the temperature exceeds 150 ℃, the solubility of the denatured methanol and the aviation kerosene is greatly improved, and because the flash point of alcohol substances is usually lower than 20 ℃ and happens to be higher than the flash point of diesel oil, the safety performance of the alcohol substances and the diesel oil is improved and the problem of insufficient combustion liquid power is also enhanced by mixing the alcohol substances and the diesel oil, but when the temperature exceeds 150 ℃, the oleyl alcohol mixture does not contain flame retardant components and is extremely easy to ignite; when the temperature reaches 225 ℃, the limit is reached, and the oleyl alcohol mixed solution has a surface film-forming flame-retardant component and is not easy to ignite; no obvious change is caused when the temperature exceeds 225 ℃; when the pressure exceeds 1Mpa, the solubility of the denatured methanol and the aviation kerosene is greatly improved, when the temperature is 150 ℃ and the pressure exceeds 1MP, the methanol vapor pressure is 1385KPa, the impurities in the oleyl alcohol mixed solution are gradually reduced, the purity is slowly improved, and the anticorrosion technology is in a semi-solved state; the limit is reached when the pressure reaches 1.5MPa, when the temperature is 225 ℃ and the pressure is 1.5MPa, the methanol steam pressure is 4036KPa, the oleyl alcohol mixed solution has no obvious impurity, the purity reaches the experimental standard purity, and the anticorrosion technology is completely solved.
Adding ethyl acetate and dimethyl carbonate into the light coal tar;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and stirring uniformly at 50-90 ℃ and 1-1.5 Mpa. At 50-90 ℃, the solubility is better, the mutual solubility is faster, and the solution is not separated into segregation after being cooled, the aldehydic acid is effectively inhibited, and the problem of colloid dispersion is solved; under the pressure of 1-1.5Mpa, the solubility is better, the mutual dissolving speed is faster, the solution can not be separated after being cooled, and the condition that the oil-alcohol mixed solution does not denature again and the like is ensured.
In order to further realize the invention, the first step and the third step are both carried out at normal temperature and normal pressure.
In order to further realize the invention, the stirring rotating speed in the second step and the fourth step is 30-60 r/min. Too high a rotational speed may emulsify the solution, producing the opposite effect.
Compared with the prior art, the invention has the beneficial effects that:
the methanol has low cost, high octane number, wide ignition limit, oxygen content of over 50 percent and full combustion, and is a recognized clean fuel in the world. But the methanol has strong toxicity to human bodies, lower heat value, poor antiknock property, low self-ignition point and flash point, is insoluble in oil and has certain corrosivity to nonferrous metals and rubber products. But the coal mine reserves in China are large, so the alcohol resources are very rich.
The diesel oil has the advantages of high heat value, high flash point, no toxicity and no corrosion, but the cost is high, and most of our country's dependence on the finished oil comes from import and is limited by people.
Before the additive is added, the methanol cannot be mutually dissolved with the oil, and after the additive is added, the methanol generates freeness and is mutually dissolved with the kerosene, and the methanol has polarity and stronger hydrophilicity and can be infinitely dissolved in water; diesel oil belongs to petroleum fuel and has hydrophobicity. When methanol is denatured, the hydrophilicity is reduced, the carboxylic acid group and hydroxyl group are combined to generate condensation reaction, the reaction principle is that electron cloud on carboxyl carbon is biased to carbon oxygen and is positively charged, and the oxygen of alcohol initiates nucleophilic attack on carbon to obtain ester. Amphiphilic molecules are adopted to form micelles with solubilizing capability on methanol in diesel oil, and mutual solubility is realized through the solubilizing effect of the micelles. Thereby greatly improving the solubility with oil substances. As the content of other substances in the methanol is increased, the solubility of the methanol and oil substances is increased.
From the problem of cost, in a common solvent, the price of methanol is the lowest, the price of propylene glycol methyl ether is the highest, the cost is increased along with the increase of carbon content, and the improvement of the solubility of methanol and oil substances on the premise of reducing the cost as much as possible is a primary problem.
Aviation kerosene is often used as an additive in diesel fuel to lower the pour point of the produced oil, but is miscible with denatured methanol in step two to increase the flash point of alcohols. The alcohol substance has a flash point below 20 ℃ generally, so that the alcohol substance is high in danger, and the diesel oil has a flash point above 60 ℃ and is safe. On the premise of realizing mutual solubility of methanol and diesel oil, the flash point of the diesel oil cannot be reduced, and the danger is increased. At present, the main processing mode of diesel oil is hydrogenation of light coal tar to reduce the sulfur content and the nitrogen oxide content of the coal tar, so that the sulfur content and the nitrogen oxide content can reach the national VI emission standard, and the methanol is added into the light coal tar to reduce the sulfur content and the nitrogen oxide content in a phase-changing manner, but the safety and the combustibility of the coal tar cannot be reduced while the emission requirement is met, so that the step 3 is to improve the combustibility of the coal tar, and the step four is the content required to be completed in the last step. This sequence cannot be disturbed, otherwise mutual dissolution cannot be achieved.
The method has the advantages of cheap and easily-obtained raw materials, low cost, simple process, mild reaction conditions, low energy consumption, no post-treatment, greenness and environmental protection, high yield of the product up to 99.9 percent, high yield and good quality.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The methanol diesel oil is composed of the following raw materials in percentage by volume: 40-70% of light coal tar, 5-18% of methanol and the balance of auxiliary agent; the auxiliary agent comprises the following raw materials in percentage by volume: 3 to 20 percent of aviation kerosene, 2 to 20 percent of kerosene, 5 to 35 percent of ethyl acetate, 0.1 to 3 percent of ferrocene, 0.2 to 9 percent of isobutanol, 0.3 to 9 percent of propylene glycol, 0.5 to 10 percent of dimethyl carbonate and 1 to 5 percent of propylene glycol methyl ether.
The method for synthesizing the methanol diesel comprises the following steps:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol at normal temperature and normal pressure;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 150-225 ℃ and the pressure of 1-1.5Mpa, wherein the stirring speed is 30-60 r/min;
step three, adding ethyl acetate and dimethyl carbonate into the light coal tar at normal temperature and normal pressure;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and uniformly stirring at the temperature of between 50 and 90 ℃ and under the pressure of between 1 and 1.5Mpa at the stirring speed of between 30 and 60 r/min.
Example 1:
the methanol diesel oil is composed of the following raw materials in percentage by volume: 70% of light coal tar, 5% of methanol, 5% of aviation kerosene, 5% of kerosene, 8% of ethyl acetate, 0.1% of ferrocene, 1% of isobutanol, 1.9% of propylene glycol, 3% of dimethyl carbonate and 1% of propylene glycol methyl ether.
The method for synthesizing the methanol diesel comprises the following steps:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol at normal temperature and normal pressure;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 150 ℃ and the pressure of 1Mpa at the stirring speed of 30 r/min;
step three, adding ethyl acetate and dimethyl carbonate into the light coal tar at normal temperature and normal pressure;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and stirring uniformly at the temperature of 50 ℃ and the pressure of 1MPa, wherein the stirring speed is 30 r/min.
The methanol diesel produced in this example was reported in table 1.
Example 2:
the methanol diesel oil is composed of the following raw materials in percentage by volume: 70% of light coal tar, 5% of methanol, 3% of aviation kerosene, 2% of kerosene, 28% of ethyl acetate, 2% of ferrocene, 2% of isobutanol, 2% of propylene glycol, 6% of dimethyl carbonate and 5% of propylene glycol methyl ether.
The method for synthesizing the methanol diesel comprises the following steps:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol at normal temperature and normal pressure;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 150 ℃ and the pressure of 1Mpa at the stirring speed of 30 r/min;
step three, adding ethyl acetate and dimethyl carbonate into the light coal tar at normal temperature and normal pressure;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and stirring uniformly at the temperature of 50 ℃ and the pressure of 1MPa, wherein the stirring speed is 30 r/min.
Example 3:
the methanol diesel oil is composed of the following raw materials in percentage by volume: 40% of light coal tar, 10% of methanol, 3% of aviation kerosene, 2% of kerosene, 28% of ethyl acetate, 2% of ferrocene, 2% of isobutanol, 2% of propylene glycol, 6% of dimethyl carbonate and 5% of propylene glycol methyl ether.
The method for synthesizing the methanol diesel comprises the following steps:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol at normal temperature and normal pressure;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 150-225 ℃ and the pressure of 1-1.5Mpa, wherein the stirring speed is 30-60 r/min;
step three, adding ethyl acetate and dimethyl carbonate into the light coal tar at normal temperature and normal pressure;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and uniformly stirring at the temperature of between 50 and 90 ℃ and under the pressure of between 1 and 1.5Mpa at the stirring speed of between 30 and 60 r/min.
Example 4:
the methanol diesel oil is composed of the following raw materials in percentage by volume: 55% of light coal tar, 9% of methanol, 4% of aviation kerosene, 3% of kerosene, 18% of ethyl acetate, 1% of ferrocene, 1% of isobutanol, 1% of propylene glycol, 5% of dimethyl carbonate and 3% of propylene glycol methyl ether.
The method for synthesizing the methanol diesel comprises the following steps:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol at normal temperature and normal pressure;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 150 ℃ and the pressure of 1Mpa at the stirring speed of 30 r/min;
step three, adding ethyl acetate and dimethyl carbonate into the light coal tar at normal temperature and normal pressure;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and stirring uniformly at the temperature of 50 ℃ and the pressure of 1MPa, wherein the stirring speed is 30 r/min.
Example 5:
the methanol diesel oil is composed of the following raw materials in percentage by volume: 60% of light coal tar, 18% of methanol, 20% of aviation kerosene, 20% of kerosene, 5% of ethyl acetate, 3% of ferrocene, 0.2% of isobutanol, 0.3% of propylene glycol, 0.5% of dimethyl carbonate and 3% of propylene glycol methyl ether.
The method for synthesizing the methanol diesel comprises the following steps:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol at normal temperature and normal pressure;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at 225 ℃ and 1.5Mpa at the stirring speed of 60 r/min;
step three, adding ethyl acetate and dimethyl carbonate into the light coal tar at normal temperature and normal pressure;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and stirring uniformly at the temperature of 90 ℃ and the pressure of 1.5Mpa at the stirring speed of 60 r/min.
Example 6:
the methanol diesel oil is composed of the following raw materials in percentage by volume: 65% of light coal tar, 18% of methanol, 15% of aviation kerosene, 20% of kerosene, 35% of ethyl acetate, 3% of ferrocene, 9% of isobutanol, 9% of propylene glycol, 10% of dimethyl carbonate and 5% of propylene glycol methyl ether.
The method for synthesizing the methanol diesel comprises the following steps:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol at normal temperature and normal pressure;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 180 ℃ and the pressure of 1.3Mpa, wherein the stirring speed is 50 r/min;
step three, adding ethyl acetate and dimethyl carbonate into the light coal tar at normal temperature and normal pressure;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and stirring uniformly at 75 ℃ and 1.3Mpa at the stirring speed of 45 r/min.
Comparative example:
the same formulation as in example 1 was used: the methanol diesel oil is composed of the following raw materials in percentage by volume: 70% of light coal tar, 5% of methanol, 5% of aviation kerosene, 5% of kerosene, 8% of ethyl acetate, 0.1% of ferrocene, 1% of isobutanol, 1.9% of propylene glycol, 3% of dimethyl carbonate and 1% of propylene glycol methyl ether, and directly mixing the above raw materials.
The test report of the methanol diesel oil prepared in this example is shown in Table 2.
As can be seen from the data and conclusions in tables 1 and 2, the methanol diesel fuel conforming to GB19147-2016 (VI) can be obtained only by mixing the formulation in example 1 according to the corresponding procedure, while in the comparative example, the methanol diesel fuel obtained by direct mixing has the same formulation as in example 1, and the fatty acid methanol 5 and cetane number do not conform to GB19147-2016 (VI) in the test item.
Claims (4)
1. The methanol diesel oil is characterized by comprising the following raw materials in percentage by volume: 40-70% of light coal tar, 5-18% of methanol and the balance of auxiliary agent; the auxiliary agent consists of the following raw materials in percentage by volume: 3 to 20 percent of aviation kerosene, 2 to 20 percent of kerosene, 5 to 35 percent of ethyl acetate, 0.1 to 3 percent of ferrocene, 0.2 to 9 percent of isobutanol, 0.3 to 9 percent of propylene glycol, 0.5 to 10 percent of dimethyl carbonate and 1 to 5 percent of propylene glycol methyl ether.
2. A method for synthesizing methanol diesel fuel according to claim 1, comprising the steps of:
adding isobutanol, propylene glycol and propylene glycol methyl ether into methanol;
step two, adding the mixed solution of aviation kerosene and kerosene into the denatured methanol obtained in the step one, and uniformly stirring at the temperature of 150-225 ℃ and under the pressure of 1-1.5 Mpa;
adding ethyl acetate and dimethyl carbonate into the light coal tar;
and step four, mixing the products obtained in the step two and the step three, adding ferrocene, and stirring uniformly at 50-90 ℃ and 1-1.5 Mpa.
3. The method for synthesizing methanol diesel fuel according to claim 2, characterized in that: and the first step and the third step are both carried out at normal temperature and normal pressure.
4. The method for synthesizing methanol diesel as claimed in claim 3, wherein: the stirring rotating speed in the second step and the fourth step is 30-60 r/min.
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