CN114350418A - Low-volatility methanol gasoline and preparation method thereof - Google Patents
Low-volatility methanol gasoline and preparation method thereof Download PDFInfo
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- CN114350418A CN114350418A CN202111416726.XA CN202111416726A CN114350418A CN 114350418 A CN114350418 A CN 114350418A CN 202111416726 A CN202111416726 A CN 202111416726A CN 114350418 A CN114350418 A CN 114350418A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 285
- 239000003502 gasoline Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 239000000654 additive Substances 0.000 claims abstract description 35
- 230000000996 additive effect Effects 0.000 claims abstract description 35
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 24
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 24
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002199 base oil Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002096 quantum dot Substances 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000009924 canning Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001718 carbodiimides Chemical class 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229910021404 metallic carbon Inorganic materials 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005457 optimization Methods 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 4
- 229940106681 chloroacetic acid Drugs 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 210000002249 digestive system Anatomy 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 210000000653 nervous system Anatomy 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 210000002345 respiratory system Anatomy 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 208000004756 Respiratory Insufficiency Diseases 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 208000004998 Abdominal Pain Diseases 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 208000012671 Gastrointestinal haemorrhages Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 206010038678 Respiratory depression Diseases 0.000 description 1
- 208000009205 Tinnitus Diseases 0.000 description 1
- 208000012886 Vertigo Diseases 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 208000030304 gastrointestinal bleeding Diseases 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 206010027175 memory impairment Diseases 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 210000001034 respiratory center Anatomy 0.000 description 1
- 201000004193 respiratory failure Diseases 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000886 tinnitus Toxicity 0.000 description 1
- 231100000889 vertigo Toxicity 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses low-volatility methanol gasoline and a preparation method thereof, and relates to the technical field of new energy. When the low-volatility methanol gasoline is prepared, ferric chloride and terephthalic acid are reacted to prepare a metal organic framework, the metal organic framework is carbonized to prepare metal carbon nanodots, the metal carbon nanodots are modified to ensure that anthranilic acid and 2, 6-dicarboxylpyridine are polymerized on the modified metal carbon nanodots to prepare an additive, the additive and methanol are uniformly mixed to prepare a methanol mixed solution, and finally the methanol mixed solution and base oil are uniformly mixed and canned to prepare the low-volatility methanol gasoline. The low-volatility methanol gasoline prepared by the invention has good stability, is not easy to volatilize and is convenient to store.
Description
Technical Field
The invention relates to the technical field of new energy, in particular to low-volatility methanol gasoline and a preparation method thereof.
Background
With the rapid development of the world economy, the automobile holding amount is rising year by year, the automobile holding amount in China is more than 7000 thousands at present, the demand of automobile fuel is continuously increasing, the environmental problem is increasingly serious, and the situation that the petroleum resources are increasingly exhausted is more severe as the world energy reserves are gradually in shortage. China's economy is developing at a high rate, and most of the petroleum consumed every year needs to be imported. Energy and environmental problems restrict the rapid development of economy in China. Therefore, the search for new clean alternative energy has become a key topic for promoting the economic development of China.
The methanol is a colorless and transparent volatile liquid, has high octane value, good antiknock property and high oxygen content, has combustion performance similar to that of gasoline, and has lower emission of HC, CO and NOx after combustion than that of the gasoline. From the viewpoints of energy conservation, reduction of dependence on petroleum fuels and environmental protection, the methanol is proved to be a good automobile alternative fuel, and has great development value and application prospect. The methanol gasoline is prepared by adding methanol in a certain proportion into gasoline. The methanol can be converted from raw materials such as petroleum, coal, natural gas, wood fiber and the like, so that the source is wide, the production process is mature, and the cost is lower. However, methanol has a small molecular weight and is volatile, and methanol has great damage to human bodies, can cause serious problems in respiratory systems and nervous systems of human bodies, and can also be accumulated in digestive systems. The nervous system and respiratory system are the systems most prone to accumulation and the earliest symptoms, like dizziness, headache, tinnitus, visual disturbances and vertigo, memory disturbances, and confusion of the nervous system. The accumulation of respiratory system can lead to respiratory depression, and severe patients can lead to paralysis of respiratory center and even respiratory failure and death. Nausea, vomiting, abdominal pain, diarrhea, etc. may occur when the digestive system is accumulated, and gastrointestinal bleeding may occur when the digestive system is severe. Therefore, the problem of volatility of methanol gasoline needs to be solved urgently.
Disclosure of Invention
The invention aims to provide low-volatility methanol gasoline and a preparation method thereof, which are used for solving the problems in the prior art.
The low-volatility methanol gasoline is characterized by mainly comprising the following components in parts by weight: 14-20 parts of base oil, 8-12 parts of methanol and 2-4 parts of additive.
As optimization, one or more of national standard gasoline of No. 90, No. 93 and No. 97 of the base oil are mixed for use.
The additive is prepared by reacting ferric chloride with terephthalic acid to prepare a metal organic framework, carbonizing the metal organic framework to prepare metal carbon nanodots, and modifying the metal carbon nanodots to polymerize anthranilic acid and 2, 6-dicarboxylpyridine on the modified metal carbon nanodots.
A preparation method of low-volatility methanol gasoline mainly comprises the following preparation steps:
(1) reacting ferric chloride and terephthalic acid to prepare a metal organic framework, carbonizing the metal organic framework to prepare metal carbon nanodots, modifying the metal carbon nanodots to polymerize anthranilic acid and 2, 6-dicarboxylpyridine on the modified metal carbon nanodots to prepare an additive;
(2) uniformly mixing the additive and the methanol to prepare a methanol mixed solution;
(3) and uniformly mixing the methanol mixed solution and the base oil, and canning to obtain the low-volatility methanol gasoline.
As optimization, the preparation method of the low-volatility methanol gasoline mainly comprises the following preparation steps:
(1) mixing ferric chloride and pure water according to a mass ratio of 1: 10-1: 15, uniformly mixing, adding terephthalic acid with the mass of 0.9-1.1 times of that of ferric chloride, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.05-0.08 times of that of the ferric chloride, stirring at 20-30 ℃ and 800-1000 r/min for 30-40 min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting at 200-250 ℃ for 7-9 h, cooling to 20-30 ℃, performing centrifugal separation, washing with N, N-dimethylformamide and absolute ethyl alcohol for 3-5 times respectively, soaking in absolute ethyl alcohol with the temperature of 60-70 ℃ for 20-24 h, cooling to 20-30 ℃, filtering, drying at-10 to-1 ℃ and 5-10 Pa for 6-8 h to prepare a metal organic framework, placing the metal organic framework in a muffle furnace, carbonizing at the temperature of 700-900 ℃ in a nitrogen atmosphere for 10-12 h to prepare a metal carbon nanodot, modifying the metal carbon nanodot to prepare the modified metal carbon nanodot, mixing 2, 6-dicarboxy pyridine, anthranilic acid, modified metal carbon nanodots, dimethyl sulfoxide and pure water according to a mass ratio of 1: 3: 4: 5: 5-1: 3: 4: 7: 7, uniformly mixing, adding carbodiimide with the mass of 0.01-0.03 time of that of 2, 6-dicarboxylpyridine, reacting for 2-3 h at 20-30 ℃, filtering, washing for 3-5 times by using absolute ethyl alcohol, and drying for 6-8 h at-10-1 ℃ and 5-10 Pa to obtain the additive;
(2) mixing methanol and an additive according to a mass ratio of 3: 1-4: 1, placing the mixture into a container, and stirring the mixture for 20 to 30min at the temperature of between 20 and 30 ℃ at 1500 to 2000r/min to prepare a methanol mixed solution;
(3) mixing the methanol mixed solution and the base oil according to the mass ratio of 5: 4-7: 5, placing the mixture into a container, stirring the mixture for 30 to 40min at the temperature of 50 to 60 ℃ and the pressure of 1.1 to 1.3MPa at 1500 to 2000r/min, cooling the mixture to 10 to 20 ℃, and canning the cooled mixture to obtain the low-volatility methanol gasoline.
As optimization, the preparation method of the modified metal carbon nanodots in the step (1) comprises the following steps: mixing metal carbon nano-dots with 98% concentrated sulfuric acid according to a mass ratio of 1: 10, uniformly mixing, adding potassium permanganate with the mass of 1 time that of the metal carbon nanodots, reacting for 4-6 hours under the condition of ultrasonic oscillation at 50-60 ℃ and 30-40 kHz, controlling the temperature at 1-5 ℃, adding hydrogen peroxide with the mass of 0.1-0.3 time that of the metal carbon nanodots, stirring for 10-15 minutes at the rotating speed of 800-1000 r/min, putting into a centrifuge, centrifuging at the rotating speed of 6000-8000 r/min to obtain oxidized metal carbon nanodots, washing the oxidized metal carbon nanodots with pure water for 3-5 times, uniformly mixing with pure water with the mass of 100 times that of the oxidized metal carbon nanodots, adding sodium hydroxide with the mass of 20-30 times that of the oxidized metal carbon nanodots and monochloroacetic acid with the mass of 15-25 times that of the oxidized metal carbon nanodots, reacting for 3-4 hours under the condition of ultrasonic oscillation at 50-60 ℃ and 30-40 kHz, filtering at 60-70 ℃, and washing for 3-5 times with pure water, drying for 4-6 h at the temperature of-10 to-5 ℃ and under the pressure of 5-10 Pa to prepare the nano-silver.
And (3) as optimization, the container in the steps (2) and (3) is a high-pressure stirring kettle, the highest working temperature is 300 ℃, the volume is 5L, and the highest working pressure is 10 MPa.
As an optimization, the canning method in the step (3) comprises the following steps: and vacuumizing the tank body, filling nitrogen, adding low-volatility methanol gasoline to 75-85% of the volume of the tank body, and filling nitrogen to enable the pressure of the tank body to be 0.13-0.15 MPa.
Compared with the prior art, the invention has the following beneficial effects:
when the low-volatility methanol gasoline is prepared, the additive is prepared firstly, and the additive is mixed with the methanol and then mixed with the base oil to prepare the low-volatility methanol gasoline.
Firstly, the raw materials are easy to obtain, the operation steps are simple, and the industrial production is easy to realize; reacting ferric chloride and terephthalic acid to prepare a metal organic framework, carbonizing the metal organic framework to prepare a metal carbon nanodot, modifying the metal carbon nanodot to polymerize anthranilic acid and 2, 6-dicarboxylpyridine on the modified metal carbon nanodot to prepare an additive, wherein a porous channel structure group of the metal carbon nanodot and a metal center in a channel can adsorb and complex methanol gasoline, so that volatility is reduced, and hydrogen atoms connected with nitrogen atoms on an amide group between the 2, 6-dicarboxylpyridine and anthranilic acid can respectively form a conjugated hydrogen bond chelating ring with nitrogen atoms in a pyridine ring of the 2, 6-dicarboxylpyridine and oxygen atoms on an acyl group of the anthranilic acid, so that the additive is folded under the coplanar trend; when the temperature is too high, the methanol gasoline is volatile, the additive can absorb heat to enable the conjugated hydrogen bond chelating ring to open, the rise of heat is slowed down, the folded state is released, the molecules of the additive are unfolded to form a long chain structure, the long chain structure can increase the flow resistance and the winding degree of the molecules in the methanol gasoline, the nitrogen unfolded inside can generate hydrogen bond action with the methanol, the volatility of the methanol gasoline is further reduced, when the temperature is too low, the additive can release heat to enable the conjugated hydrogen bond chelating ring to close, the folded state with small molecular length is formed, the mobility of the methanol gasoline is increased, and the methanol gasoline is not easy to solidify at low temperature and is convenient to use.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe the method for testing each index of the low volatile methanol gasoline prepared in the following examples as follows:
volatility: the low-volatility methanol gasoline obtained in each example and the comparative example material are put in beakers of the same type, are placed for the same time under the conditions of the same pressure and 50 ℃, are subjected to quality test, and are calculated and recorded as initial quality-test quality.
Example 1
A low-volatility methanol gasoline mainly comprises the following components in parts by weight: 20 parts of base oil, 12 parts of methanol and 4 parts of additive.
A preparation method of low-volatility methanol gasoline mainly comprises the following preparation steps:
(1) mixing ferric chloride and pure water according to a mass ratio of 1: 10, uniformly mixing, adding terephthalic acid with the mass of 0.9 time that of ferric chloride, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.05 time that of the ferric chloride, stirring for 30min at 20 ℃ at 800r/min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting for 7h at 200 ℃, cooling to 20 ℃, performing centrifugal separation, washing 3 times with N, N-dimethylformamide and absolute ethyl alcohol respectively, soaking in absolute ethyl alcohol at 60 ℃ for 24h, cooling to 20 ℃, filtering, drying for 6h at-10 ℃ and 5Pa to prepare a metal organic framework, placing the metal organic framework in a muffle furnace, carbonizing for 12h at 700 ℃ in a nitrogen atmosphere to prepare a metal carbon nanodot, and mixing the metal carbon nanodot with concentrated sulfuric acid with the mass fraction of 98% according to a mass ratio of 1: 10, uniformly mixing, adding potassium permanganate with the mass of 1 time that of the metallic carbon nanodots, reacting for 6 hours under the ultrasonic oscillation condition of 50 ℃ and 30kHz, controlling the temperature to be 1 ℃, adding hydrogen peroxide with the mass of 0.1 time that of the metallic carbon nanodots, stirring for 15 minutes at the rotating speed of 800r/min, putting into a centrifugal machine, centrifuging at the rotating speed of 6000r/min to obtain oxidized metallic carbon nanodots, washing the oxidized metallic carbon nanodots with pure water for 3 times, uniformly mixing with the pure water with the mass of 100 times that of the oxidized metallic carbon nanodots, adding sodium hydroxide with the mass of 20 times that of the oxidized metallic carbon nanodots and chloroacetic acid with the mass of 15 times that of the oxidized metallic carbon nanodots, reacting for 4 hours under the ultrasonic oscillation condition of 50 ℃ and 30kHz, filtering at 60 ℃, washing for 3 times with the pure water, drying for 6 hours at the temperature of-10 ℃ and the pressure of 5Pa to obtain modified carbon nanodots, mixing 2, 6-dicarboxy pyridine, anthranilic acid, modified metal carbon nanodots, dimethyl sulfoxide and pure water according to a mass ratio of 1: 3: 4: 5: 5, uniformly mixing, adding carbodiimide with the mass of 0.01 time of that of 2, 6-dicarboxylpyridine, reacting for 2 hours at 20 ℃, filtering, washing for 3 times by using absolute ethyl alcohol, and drying for 6 hours at-10 ℃ under 5Pa to obtain an additive;
(2) mixing methanol and an additive according to a mass ratio of 3: 1, placing the mixture in a container, and stirring the mixture for 30min at the temperature of 20 ℃ and 1500r/min to prepare a methanol mixed solution;
(3) mixing the methanol mixed solution and the base oil according to the mass ratio of 5: 4, placing the mixture into a container, stirring the mixture for 30min at the temperature of 50 ℃, the pressure of 1.1MPa and the speed of 1500r/min, cooling the mixture to 10 ℃, and canning the cooled mixture to obtain the low-volatility methanol gasoline.
Example 2
A low-volatility methanol gasoline mainly comprises the following components in parts by weight: 17 parts of base oil, 10 parts of methanol and 3 parts of additive.
A preparation method of low-volatility methanol gasoline mainly comprises the following preparation steps:
(1) mixing ferric chloride and pure water according to a mass ratio of 1: 12, uniformly mixing, adding terephthalic acid with the mass of 1 time of that of ferric chloride, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.06 time of that of the ferric chloride, stirring for 35min at 25 ℃ and 900r/min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting for 8h at 230 ℃, cooling to 25 ℃, performing centrifugal separation, washing for 4 times respectively with N, N-dimethylformamide and absolute ethyl alcohol, soaking in absolute ethyl alcohol at 65 ℃ for 22h, cooling to 25 ℃, filtering, drying for 7h at-5 ℃ and 8Pa to prepare a metal organic framework, placing the metal organic framework in a muffle furnace, carbonizing for 11h at 800 ℃ in a nitrogen atmosphere to prepare metal carbon nanodots, and mixing the metal carbon nanodots with concentrated sulfuric acid with the mass fraction of 98% according to a mass ratio of 1: 10, uniformly mixing, adding potassium permanganate with the mass of 1 time that of the metallic carbon nanodots, reacting for 5 hours under the ultrasonic oscillation condition of 55 ℃ and 35kHz, controlling the temperature to be 3 ℃, adding hydrogen peroxide with the mass of 0.2 time that of the metallic carbon nanodots, stirring for 12 minutes at the rotating speed of 900r/min, putting into a centrifugal machine, centrifuging at the rotating speed of 7000r/min to obtain oxidized metallic carbon nanodots, washing the oxidized metallic carbon nanodots with pure water for 4 times, uniformly mixing with the pure water with the mass of 100 times that of the oxidized metallic carbon nanodots, adding sodium hydroxide with the mass of 25 times that of the oxidized metallic carbon nanodots and chloroacetic acid with the mass of 20 times that of the oxidized metallic carbon nanodots, reacting for 3 hours under the ultrasonic oscillation condition of 55 ℃ and 35kHz, filtering at 65 ℃, washing for 4 times with the pure water, drying for 5 hours at the temperature of-8 ℃ and the pressure of 8Pa to obtain modified carbon nanodots, mixing 2, 6-dicarboxy pyridine, anthranilic acid, modified metal carbon nanodots, dimethyl sulfoxide and pure water according to a mass ratio of 1: 3: 4: 6: 6, uniformly mixing, adding carbodiimide with the mass of 0.02 time of that of 2, 6-dicarboxylpyridine, reacting for 2.5 hours at 25 ℃, filtering, washing for 4 times by using absolute ethyl alcohol, and drying for 7 hours at-5 ℃ under 8Pa to obtain the additive;
(2) mixing methanol and an additive according to a mass ratio of 3.5: 1, placing the mixture in a container, and stirring the mixture at a temperature of 25 ℃ and a speed of 1800r/min for 25min to prepare a methanol mixed solution;
(3) mixing the methanol mixed solution and the base oil according to the mass ratio of 6: 4.5 placing the mixture into a container, stirring the mixture for 35min at the temperature of 55 ℃, the pressure of 1.2MPa and the pressure of 1800r/min, cooling the mixture to 15 ℃, and canning the cooled mixture to obtain the low-volatility methanol gasoline.
Example 3
A low-volatility methanol gasoline mainly comprises the following components in parts by weight: 14 parts of base oil, 8 parts of methanol and 2 parts of additive.
A preparation method of low-volatility methanol gasoline mainly comprises the following preparation steps:
(1) mixing ferric chloride and pure water according to a mass ratio of 1: 15, uniformly mixing, adding terephthalic acid with the mass of 1.1 times that of ferric chloride, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.08 times that of the ferric chloride, stirring for 30min at 30 ℃ and 1000r/min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting for 7h at 250 ℃, cooling to 30 ℃, performing centrifugal separation, washing for 5 times by using N, N-dimethylformamide and absolute ethyl alcohol respectively, soaking in 70 ℃ absolute ethyl alcohol for 20h, cooling to 30 ℃, filtering, drying for 6h at-1 ℃ and 10Pa to prepare a metal organic framework, placing the metal organic framework in a muffle furnace, carbonizing for 10h at 900 ℃ in a nitrogen atmosphere to prepare a metal carbon nanodot, and mixing the metal carbon nanodot with concentrated sulfuric acid with the mass fraction of 98% according to a mass ratio of 1: 10, uniformly mixing, adding potassium permanganate with the mass of 1 time that of the metallic carbon nanodots, reacting for 4 hours under the condition of ultrasonic oscillation at 60 ℃ and 40kHz, controlling the temperature to be 5 ℃, adding hydrogen peroxide with the mass of 0.3 time that of the metallic carbon nanodots, stirring for 10 hours at the rotating speed of 1000r/min, putting into a centrifugal machine, centrifuging at the rotating speed of 8000r/min to obtain oxidized metallic carbon nanodots, washing the oxidized metallic carbon nanodots with pure water for 5 times, uniformly mixing with pure water with the mass of 100 times that of the oxidized metallic carbon nanodots, adding sodium hydroxide with the mass of 30 times that of the oxidized metallic carbon nanodots and chloroacetic acid with the mass of 25 times that of the oxidized metallic carbon nanodots, reacting for 3 hours under the condition of ultrasonic oscillation at 60 ℃ and 40kHz, filtering at 70 ℃, washing for 5 times with the pure water, drying for 4 hours at the temperature of-5 ℃ and under the pressure of 10Pa to obtain modified carbon nanodots, mixing 2, 6-dicarboxy pyridine, anthranilic acid, modified metal carbon nanodots, dimethyl sulfoxide and pure water according to a mass ratio of 1: 3: 4: 7: 7, uniformly mixing, adding carbodiimide with the mass of 0.03 time of that of 2, 6-dicarboxylpyridine, reacting for 2 hours at 30 ℃, filtering, washing for 5 times by using absolute ethyl alcohol, and drying for 6 hours at-1 ℃ under 10Pa to obtain an additive;
(2) methanol and an additive are mixed according to a mass ratio of 4: 1, placing the mixture in a container, and stirring the mixture for 20min at the temperature of 30 ℃ and at the speed of 2000r/min to prepare a methanol mixed solution;
(3) mixing the methanol mixed solution and the base oil according to the mass ratio of 7: 5, placing the mixture into a container, stirring the mixture for 30min at the temperature of 60 ℃ and the pressure of 1.3MPa at a speed of 2000r/min, cooling the mixture to 20 ℃, and canning the cooled mixture to obtain the low-volatility methanol gasoline.
Comparative example 1
A low-volatility methanol gasoline mainly comprises the following components in parts by weight: 17 parts of base oil, 10 parts of methanol and 3 parts of additive.
A preparation method of low-volatility methanol gasoline mainly comprises the following preparation steps:
(1) mixing ferric chloride and pure water according to a mass ratio of 1: 12, uniformly mixing, adding terephthalic acid with the mass of 1 time of that of ferric chloride, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.06 time of that of the ferric chloride, stirring for 35min at 25 ℃ and 900r/min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting for 8h at 230 ℃, cooling to 25 ℃, performing centrifugal separation, washing for 4 times respectively with N, N-dimethylformamide and absolute ethyl alcohol, soaking in absolute ethyl alcohol at 65 ℃ for 22h, cooling to 25 ℃, filtering, drying for 7h at-5 ℃ and 8Pa to prepare a metal organic framework, placing the metal organic framework in a muffle furnace, carbonizing for 11h at 800 ℃ in a nitrogen atmosphere to prepare metal carbon nanodots, and mixing the metal carbon nanodots with concentrated sulfuric acid with the mass fraction of 98% according to a mass ratio of 1: 10, uniformly mixing, adding potassium permanganate with the mass of 1 time that of the metallic carbon nanodots, reacting for 5 hours under the ultrasonic oscillation condition of 55 ℃ and 35kHz, controlling the temperature to be 3 ℃, adding hydrogen peroxide with the mass of 0.2 time that of the metallic carbon nanodots, stirring for 12 minutes at the rotating speed of 900r/min, putting into a centrifugal machine, centrifuging at the rotating speed of 7000r/min to obtain oxidized metallic carbon nanodots, washing the oxidized metallic carbon nanodots with pure water for 4 times, uniformly mixing with the pure water with the mass of 100 times that of the oxidized metallic carbon nanodots, adding sodium hydroxide with the mass of 25 times that of the oxidized metallic carbon nanodots and chloroacetic acid with the mass of 20 times that of the oxidized metallic carbon nanodots, reacting for 3 hours under the ultrasonic oscillation condition of 55 ℃ and 35kHz, filtering at 65 ℃, washing for 4 times with the pure water, drying for 5 hours at the temperature of-8 ℃ and the pressure of 8Pa to obtain modified carbon nanodots, 2, 6-dicarboxy pyridine, o-aminobenzoic acid and modified metal carbon nanodots are mixed according to the mass ratio of 1: 3: 4, mixing uniformly to prepare an additive;
(2) mixing methanol and an additive according to a mass ratio of 3.5: 1, placing the mixture in a container, and stirring the mixture at a temperature of 25 ℃ and a speed of 1800r/min for 25min to prepare a methanol mixed solution;
(3) mixing the methanol mixed solution and the base oil according to the mass ratio of 6: 4.5 placing the mixture into a container, stirring the mixture for 35min at the temperature of 55 ℃, the pressure of 1.2MPa and the pressure of 1800r/min, cooling the mixture to 15 ℃, and canning the cooled mixture to obtain the low-volatility methanol gasoline.
Examples of effects
Table 1 below gives the results of performance analysis of volatility of low-volatility methanol gasoline using examples 1 to 3 of the present invention and comparative example 1.
TABLE 1
| Amount of volatilization | Amount of volatilization | ||
| Example 1 | 0.15g | Example 3 | 0.16g |
| Example 2 | 0.13g | Comparative example 1 | 1.32g |
From the comparison of the experimental data of examples 1, 2 and 3 and comparative example 1 in table 1, it can be seen that the volatilization amount of examples 1, 2 and 3 is large compared with that of comparative example 1, which shows that the additive prepared by polymerizing 2, 6-dicarboxylpyridine and anthranilic acid on modified metal carbon nanodots can absorb heat to open the conjugated hydrogen bond chelating ring, slow down the rise of heat, relieve the folded state, enable the additive molecule to unfold and form a long-chain structure, enable the internal nitrogen and oxygen atoms to unfold, enable the long-chain structure to increase the flow resistance and entanglement of the molecules in the methanol gasoline, enable the internally unfolded nitrogen and oxygen atoms to generate hydrogen bonding with methanol, and reduce the volatility of the methanol gasoline.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (8)
1. A low-volatility methanol gasoline mainly comprises the following components in parts by weight: 14-20 parts of base oil, 8-12 parts of methanol and 2-4 parts of additive.
2. The low-volatility methanol gasoline of claim 1, wherein one or more of national standard gasoline of base oil No. 90, No. 93 and No. 97 is/are used in combination.
3. The low-volatility methanol gasoline of claim 2, wherein the additive is prepared by reacting ferric chloride with terephthalic acid to obtain a metal-organic framework, carbonizing the metal-organic framework to obtain metal carbon nanodots, modifying the metal carbon nanodots, and polymerizing anthranilic acid and 2, 6-dicarboxylpyridine on the modified metal carbon nanodots.
4. A preparation method of low-volatility methanol gasoline mainly comprises the following preparation steps:
(1) reacting ferric chloride and terephthalic acid to prepare a metal organic framework, carbonizing the metal organic framework to prepare metal carbon nanodots, modifying the metal carbon nanodots to polymerize anthranilic acid and 2, 6-dicarboxylpyridine on the modified metal carbon nanodots to prepare an additive;
(2) uniformly mixing the additive and methanol to prepare a methanol mixed solution;
(3) and uniformly mixing the methanol mixed solution and the base oil, and canning to obtain the low-volatility methanol gasoline.
5. The method for preparing the low-volatility methanol gasoline according to claim 4, wherein the method for preparing the low-volatility methanol gasoline mainly comprises the following steps:
(1) mixing ferric chloride and pure water according to a mass ratio of 1: 10-1: 15, uniformly mixing, adding terephthalic acid with the mass of 0.9-1.1 times of that of ferric chloride, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.05-0.08 times of that of the ferric chloride, stirring at 20-30 ℃ and 800-1000 r/min for 30-40 min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting at 200-250 ℃ for 7-9 h, cooling to 20-30 ℃, performing centrifugal separation, washing with N, N-dimethylformamide and absolute ethyl alcohol for 3-5 times respectively, soaking in absolute ethyl alcohol with the temperature of 60-70 ℃ for 20-24 h, cooling to 20-30 ℃, filtering, drying at-10 to-1 ℃ and 5-10 Pa for 6-8 h to prepare a metal organic framework, placing the metal organic framework in a muffle furnace, carbonizing at the temperature of 700-900 ℃ in a nitrogen atmosphere for 10-12 h to prepare a metal carbon nanodot, modifying the metal carbon nanodot to prepare the modified metal carbon nanodot, mixing 2, 6-dicarboxy pyridine, anthranilic acid, modified metal carbon nanodots, dimethyl sulfoxide and pure water according to a mass ratio of 1: 3: 4: 5: 5-1: 3: 4: 7: 7, uniformly mixing, adding carbodiimide with the mass of 0.01-0.03 time of that of 2, 6-dicarboxylpyridine, reacting for 2-3 h at 20-30 ℃, filtering, washing for 3-5 times by using absolute ethyl alcohol, and drying for 6-8 h at-10-1 ℃ and 5-10 Pa to obtain the additive;
(2) mixing methanol and an additive according to a mass ratio of 3: 1-4: 1, placing the mixture into a container, and stirring the mixture for 20 to 30min at the temperature of between 20 and 30 ℃ at 1500 to 2000r/min to prepare a methanol mixed solution;
(3) mixing the methanol mixed solution and the base oil according to the mass ratio of 5: 4-7: 5, placing the mixture into a container, stirring the mixture for 30 to 40min at the temperature of 50 to 60 ℃ and the pressure of 1.1 to 1.3MPa at 1500 to 2000r/min, cooling the mixture to 10 to 20 ℃, and canning the cooled mixture to obtain the low-volatility methanol gasoline.
6. The method for preparing low-volatility methanol gasoline according to claim 5, wherein the modified metal carbon nanodots prepared in the step (1) are prepared by the following steps: mixing metal carbon nano-dots with 98% concentrated sulfuric acid according to a mass ratio of 1: 10, uniformly mixing, adding potassium permanganate with the mass of 1 time that of the metal carbon nanodots, reacting for 4-6 hours under the condition of ultrasonic oscillation at 50-60 ℃ and 30-40 kHz, controlling the temperature at 1-5 ℃, adding hydrogen peroxide with the mass of 0.1-0.3 time that of the metal carbon nanodots, stirring for 10-15 minutes at the rotating speed of 800-1000 r/min, putting into a centrifuge, centrifuging at the rotating speed of 6000-8000 r/min to obtain oxidized metal carbon nanodots, washing the oxidized metal carbon nanodots with pure water for 3-5 times, uniformly mixing with pure water with the mass of 100 times that of the oxidized metal carbon nanodots, adding sodium hydroxide with the mass of 20-30 times that of the oxidized metal carbon nanodots and monochloroacetic acid with the mass of 15-25 times that of the oxidized metal carbon nanodots, reacting for 3-4 hours under the condition of ultrasonic oscillation at 50-60 ℃ and 30-40 kHz, filtering at 60-70 ℃, and washing for 3-5 times with pure water, drying for 4-6 h at the temperature of-10 to-5 ℃ and under the pressure of 5-10 Pa to prepare the nano-silver.
7. The method for preparing the low-volatility methanol gasoline according to claim 6, wherein the containers in the steps (2) and (3) are high-pressure stirred tanks, the maximum working temperature is 300 ℃, the volume is 5L, and the maximum working pressure is 10 MPa.
8. The method for preparing low-volatility methanol gasoline according to claim 7, wherein the canning method in the step (3) comprises the following steps: and vacuumizing the tank body, filling nitrogen, adding low-volatility methanol gasoline to 75-85% of the volume of the tank body, and filling nitrogen to enable the pressure of the tank body to be 0.13-0.15 MPa.
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