CN115322815A - Bio-based methanol gasoline and preparation method thereof - Google Patents
Bio-based methanol gasoline and preparation method thereof Download PDFInfo
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- CN115322815A CN115322815A CN202210844269.2A CN202210844269A CN115322815A CN 115322815 A CN115322815 A CN 115322815A CN 202210844269 A CN202210844269 A CN 202210844269A CN 115322815 A CN115322815 A CN 115322815A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000012075 bio-oil Substances 0.000 claims abstract description 48
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 26
- 239000002028 Biomass Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000000855 fermentation Methods 0.000 claims description 28
- 230000004151 fermentation Effects 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002504 physiological saline solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 11
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 241001337994 Cryptococcus <scale insect> Species 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 238000012258 culturing Methods 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 244000005700 microbiome Species 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 241000199914 Dinophyceae Species 0.000 claims description 2
- 241000907999 Mortierella alpina Species 0.000 claims description 2
- 235000008708 Morus alba Nutrition 0.000 claims description 2
- 240000000249 Morus alba Species 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000004071 soot Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Classifications
-
- 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
- C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses bio-based methanol gasoline and a preparation method thereof, and relates to the technical field of methanol gasoline. When the bio-based methanol gasoline is prepared, leaves are pretreated to prepare biomass powder, the biomass powder is inoculated and fermented and then extracted to obtain bio-oil, the bio-oil is catalyzed and hydrogenated to prepare saturated bio-oil, and the methanol, the saturated bio-oil and the gasoline are mixed to prepare the bio-based methanol gasoline. The bio-based methanol gasoline prepared by the invention has excellent low pollution.
Description
Technical Field
The invention relates to the technical field of methanol gasoline, in particular to bio-based methanol gasoline and a preparation method thereof.
Background
The methanol gasoline is a novel environment-friendly fuel prepared by national standard gasoline, methanol and an additive according to a certain volume (mass) ratio through a strict flow, is a fuel substitute for automobiles, and is an important component of new energy. Crude oil is the most major primary energy source in the world, and the essence of current energy shortage is crude oil shortage.
With the rapid development of the world economy, the automobile holding capacity is rising year by year, the demand of automobile fuel is increasing, the environmental problem is becoming more serious, and the situation of increasingly exhausted petroleum resources is more severe as the world energy storage is 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 sources has become a key topic for promoting the economic development of China.
Disclosure of Invention
The invention aims to provide bio-based methanol gasoline and a preparation method thereof, which are used for solving the problems in the prior art.
A bio-based methanol gasoline and a preparation method thereof are characterized by mainly comprising the following components in parts by weight: 7-9 parts of methanol, 12-16 parts of saturated bio-oil and 24-30 parts of gasoline.
Preferably, the saturated bio-oil is prepared from bio-oil by catalytic hydrogenation.
Preferably, the bio-oil is obtained by inoculating and fermenting biomass powder and then extracting.
Preferably, the biomass powder is prepared by grinding leaves, performing hydrothermal treatment and alkali treatment.
As optimization, the preparation method of the bio-based methanol gasoline mainly comprises the following preparation steps:
(1) Pretreatment: crushing the leaves to particles smaller than 9mm at the environment temperature of-10 to-5 ℃, then placing the crushed leaves into a pulverizer, grinding the crushed leaves to particles smaller than 1mm at the environment temperature of-10 to-5 ℃, and then mixing the pulverized leaves with deionized water according to the mass ratio of 1: 8-1: 10, uniformly mixing, placing in a high-pressure reaction kettle, reacting at 180-200 ℃ for 20-24 h, cooling, taking out, washing with pure water for 3-5 times, drying at 70-80 ℃ for 4-6 h, and mixing with a sodium hydroxide solution with the mass fraction of 6-8% according to the mass ratio of 1:20 to 1:25, mixing, performing ultrasonic treatment at 50-60 ℃ and 30-40 kHz for 40-50 min, performing centrifugal separation, washing to be neutral by pure water, drying for 6-8 h at 60-70 ℃, and grinding at-10 to-5 ℃ until the particle size is less than 0.5mm to prepare biomass powder;
(2) Inoculating and fermenting: mixing biomass powder, glucose and physiological saline according to a mass ratio of 5:1: 80-6: 1:100, uniformly mixing, inoculating oil-producing microorganisms, controlling the pH value to be 6-8 by using hydrochloric acid with the mass fraction of 3-5% and a sodium hydroxide solution with the mass fraction of 3-5%, adjusting the fermentation temperature to be 20-30 ℃, enabling the air flow per minute to be 6-10 times of the volume of physiological saline, and culturing for 140-200 h to obtain fermentation liquor;
(3) Extraction: adjusting the pH value of the fermentation liquor to 3.5-4.5, heating to 40-60 ℃, stirring for 10-12 h at 800-1000 r/min, adding an extraction solvent with the mass of 1.2-1.8 times of that of the fermentation liquor, keeping the temperature unchanged, continuously stirring for 40-50 min, standing for 4-6 h, layering to obtain an oil phase, and standing for 8-10 h at 20-30 ℃ under 1-2 kPa to obtain biological oil;
(4) Catalytic hydrogenation: preheating bio-oil at 130-140 ℃ under the condition of 60-100 Pa for 40-50 min, adding metal nickel with the mass of 0.002-0.004 times of that of the bio-oil, stirring at 800-1000 r/min for 20-30 min, placing in a hydrogenation tank, introducing hydrogen to ensure that the pressure reaches and maintains 1.1-1.5 MPa, reacting at 180-220 ℃ for 3-4 h, cooling to room temperature, and filtering to prepare saturated bio-oil;
(5) Mixing materials: methanol, saturated bio-oil and gasoline are mixed according to the mass ratio of 7:12:24 to 9:16:30, and mixing uniformly to obtain the bio-based methanol gasoline.
As optimization, the leaves in the step (1) are mulberry leaves which are cleaned and then air-dried.
Preferably, the oleaginous microorganism in the step (2) is Cryptococcus, mortierella alpina or dinoflagellate.
Preferably, the extraction solvent in step (3) is hexane.
Preferably, the purity of the metallic nickel in the step (4) is more than 99.9%, and the particle size is less than 0.1mm.
And (3) as an optimization, the gasoline in the step (5) is 93# gasoline.
Compared with the prior art, the invention has the following beneficial effects:
when the bio-based methanol gasoline is prepared, leaves are pretreated to prepare biomass powder, the biomass powder is inoculated and fermented and then extracted to obtain bio-oil, the bio-oil is catalyzed and hydrogenated to prepare saturated bio-oil, and the methanol, the saturated bio-oil and the gasoline are mixed to prepare the bio-based methanol gasoline.
Firstly, the invention recycles the resources of the leaves, has low cost, is green and environment-friendly, is easy for industrial production and has good economic benefit; the pretreatment comprises grinding, hydrothermal treatment and sodium hydroxide alkali treatment, so that the surface protection structure of the biomass powder is primarily destroyed, impurities are further removed, the adhesion and decomposition of subsequent inoculated oil-producing microorganisms are increased, more purer oil phases are obtained, and the pollution of the bio-based methanol gasoline is reduced.
Secondly, catalytic hydrogenation is carried out to convert unsaturated bonds in the bio-oil into saturated bonds, so that combustion can be more sufficient, and the pollution of the bio-based methanol gasoline is reduced.
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 illustrate the method for testing each index of bio-based methanol gasoline prepared in the following examples as follows:
pollution property: the bio-based methanol gasoline obtained in each example was weighed to be the same as the comparative example material, a combustion experiment was performed under the same conditions, and the deposited combustion carbon particles were collected on the top of a glass plate, and the amount of soot was weighed and recorded.
Example 1
A bio-based methanol gasoline mainly comprises the following components in parts by weight: 7 parts of methanol, 12 parts of saturated bio-oil and 24 parts of gasoline.
A preparation method of bio-based methanol gasoline mainly comprises the following preparation steps:
(1) Pretreatment: crushing the leaves at the environment temperature of-10 ℃ until the particles are smaller than 9mm, then placing the crushed leaves into a pulverizer, pulverizing the crushed leaves at the environment temperature of-10 ℃ until the particles are smaller than 1mm, and mixing the pulverized leaves with deionized water according to the mass ratio of 1:8, uniformly mixing, placing in a high-pressure reaction kettle, reacting at 180 ℃ for 24 hours, cooling, taking out, washing with pure water for 3 times, drying at 70 ℃ for 6 hours, and mixing with a sodium hydroxide solution with the mass fraction of 6% according to the mass ratio of 1:20, performing ultrasonic treatment at 50 ℃ and 30kHz for 50min, performing centrifugal separation, washing with pure water to be neutral, drying at 60 ℃ for 8h, and grinding at-10 ℃ until the particle size is less than 0.5mm to obtain biomass powder;
(2) Inoculating and fermenting: mixing biomass powder, glucose and physiological saline according to a mass ratio of 5:1:80, uniformly mixing, inoculating cryptococcus, controlling the pH value to be 8 by using hydrochloric acid with the mass fraction of 3% and a sodium hydroxide solution with the mass fraction of 3%, adjusting the fermentation temperature to be 20 ℃, adjusting the air flow per minute to be 6 times of the volume of physiological saline, and culturing for 140 hours to obtain fermentation liquor;
(3) Extraction: adjusting the pH value of the fermentation liquor to 3.5, heating to 40 ℃, stirring for 12h at 800r/min, adding hexane which is 1.2 times of the mass of the fermentation liquor, keeping the temperature unchanged, continuously stirring for 40min, standing for 4h, layering to obtain an oil phase, and standing for 10h at 20 ℃ under 1kPa to obtain biological oil;
(4) Catalytic hydrogenation: preheating bio-oil for 50min at 130 ℃ under 60Pa, adding metallic nickel with the quality 0.002 times of that of the bio-oil, stirring for 30min at 800r/min, placing in a hydrogenation tank, introducing hydrogen to ensure that the pressure reaches and is maintained at 1.1MPa, reacting for 4h at 180 ℃, cooling to room temperature, and filtering to obtain saturated bio-oil;
(5) Mixing materials: methanol, saturated bio-oil and 93# gasoline are mixed according to the mass ratio of 7:12:24, uniformly mixing to obtain the bio-based methanol gasoline.
Example 2
A bio-based methanol gasoline mainly comprises the following components in parts by weight: 8 parts of methanol, 14 parts of saturated bio-oil and 27 parts of gasoline.
A preparation method of bio-based methanol gasoline mainly comprises the following preparation steps:
(1) Pretreatment: crushing the leaves at the ambient temperature of-8 ℃ until the particles are smaller than 9mm, then placing the crushed leaves in a pulverizer, pulverizing the crushed leaves at the ambient temperature of-8 ℃ until the particles are smaller than 1mm, and mixing the pulverized leaves with deionized water according to the mass ratio of 1:9, uniformly mixing, placing in a high-pressure reaction kettle, reacting at 190 ℃ for 22h, cooling, taking out, washing with pure water for 4 times, drying at 75 ℃ for 5h, and mixing with a sodium hydroxide solution with the mass fraction of 7% according to a mass ratio of 1:22, performing ultrasonic treatment at 55 ℃ and 35kHz for 45min, performing centrifugal separation, washing with pure water to be neutral, drying at 65 ℃ for 7h, and grinding at-8 ℃ until the particle size is less than 0.5mm to obtain biomass powder;
(2) Inoculating and fermenting: mixing biomass powder, glucose and physiological saline according to a mass ratio of 5.5:1:90, uniformly mixing, inoculating cryptococcus, controlling the pH value to be 7 by using hydrochloric acid with the mass fraction of 4% and a sodium hydroxide solution with the mass fraction of 4%, adjusting the fermentation temperature to be 25 ℃, culturing for 170h, wherein the air flow per minute is 7 times of the volume of physiological saline, and obtaining fermentation liquor;
(3) Extraction: adjusting the pH value of the fermentation liquor to 4, heating to 50 ℃, stirring for 11h at 900r/min, adding hexane which is 1.5 times of the mass of the fermentation liquor, keeping the temperature unchanged, continuously stirring for 45min, standing for 5h, layering to obtain an oil phase, and standing for 9h at 25 ℃ under 1.5kPa to obtain biological oil;
(4) Catalytic hydrogenation: preheating bio-oil at 135 deg.C under 80Pa for 45min, adding metal nickel 0.003 times of the bio-oil, stirring at 900r/min for 25min, placing in hydrogenation tank, introducing hydrogen gas to make the pressure reach and maintain 1.3MPa, reacting at 200 deg.C for 3.5h, cooling to room temperature, and filtering to obtain saturated bio-oil;
(5) Mixing materials: methanol, saturated bio-oil and 93# gasoline are mixed according to the mass ratio of 8:14:27 are mixed evenly to prepare the bio-based methanol gasoline.
Example 3
A bio-based methanol gasoline mainly comprises the following components in parts by weight: 9 parts of methanol, 16 parts of saturated bio-oil and 30 parts of gasoline.
A preparation method of bio-based methanol gasoline mainly comprises the following preparation steps:
(1) Pretreatment: crushing the leaves at the ambient temperature of-5 ℃ until the particles are smaller than 9mm, then placing the crushed leaves in a pulverizer, pulverizing the crushed leaves at the ambient temperature of-5 ℃ until the particles are smaller than 1mm, and mixing the pulverized leaves with deionized water according to the mass ratio of 1:10, uniformly mixing, placing in a high-pressure reaction kettle, reacting for 20h at 200 ℃, taking out after cooling, washing for 5 times by pure water, drying for 4h at 80 ℃, and mixing with a sodium hydroxide solution with the mass fraction of 8% according to the mass ratio of 1:25, mixing, performing ultrasonic treatment at 60 ℃ and 40kHz for 40min, performing centrifugal separation, washing with pure water to be neutral, drying at 70 ℃ for 6h, and grinding at-5 ℃ until the particle size is less than 0.5mm to obtain biomass powder;
(2) Inoculating and fermenting: mixing biomass powder, glucose and physiological saline according to a mass ratio of 6:1:100, uniformly mixing, inoculating cryptococcus, controlling the pH value to be 8 by using hydrochloric acid with the mass fraction of 5% and a sodium hydroxide solution with the mass fraction of 5%, adjusting the fermentation temperature to be 30 ℃, enabling the air flow per minute to be 10 times of the volume of physiological saline, and culturing for 200 hours to obtain fermentation liquor;
(3) Extraction: adjusting the pH value of the fermentation liquor to 4.5, heating to 60 ℃, stirring for 10h at 1000r/min, adding hexane which is 1.8 times of the mass of the fermentation liquor, keeping the temperature unchanged, continuously stirring for 50min, standing for 6h for layering to obtain an oil phase, and standing for 8h at 30 ℃ and 2kPa to obtain biological oil;
(4) Catalytic hydrogenation: preheating bio-oil at 140 ℃ under 100Pa for 40min, adding metallic nickel with the weight 0.004 times of that of the bio-oil, stirring at 1000r/min for 20min, placing in a hydrogenation tank, introducing hydrogen to make the pressure reach and maintain at 1.5MPa, reacting at 220 ℃ for 3h, cooling to room temperature, and filtering to obtain saturated bio-oil;
(5) Mixing materials: methanol, saturated bio-oil and 93# gasoline are mixed according to the mass ratio of 9:16:30, and mixing uniformly to obtain the bio-based methanol gasoline.
Comparative example 1
A bio-based methanol gasoline mainly comprises the following components in parts by weight: 8 parts of methanol, 14 parts of saturated bio-oil and 27 parts of gasoline.
A preparation method of bio-based methanol gasoline mainly comprises the following preparation steps:
(1) Grinding: crushing leaves at-8 ℃ to particles smaller than 9mm, then placing the crushed leaves in a pulverizer, and pulverizing at-8 ℃ until the particles are smaller than 0.5mm to obtain biomass powder;
(2) Inoculating and fermenting: mixing biomass powder, glucose and physiological saline according to a mass ratio of 5.5:1:90, uniformly mixing, inoculating cryptococcus, controlling the pH value to be 7 by using hydrochloric acid with the mass fraction of 4% and a sodium hydroxide solution with the mass fraction of 4%, adjusting the fermentation temperature to be 25 ℃, enabling the air flow per minute to be 7 times of the volume of physiological saline, and culturing for 170 hours to obtain fermentation liquor;
(3) Extraction: adjusting the pH value of the fermentation liquor to 4, heating to 50 ℃, stirring at 900r/min for 11h, adding hexane with the mass of 1.5 times of that of the fermentation liquor, keeping the temperature unchanged, continuing stirring for 45min, standing for 5h, layering to obtain an oil phase, and standing for 9h at 25 ℃ and 1.5kPa to obtain biological oil;
(4) Catalytic hydrogenation: preheating bio-oil at 135 deg.C under 80Pa for 45min, adding metal nickel 0.003 times of the bio-oil, stirring at 900r/min for 25min, placing in hydrogenation tank, introducing hydrogen gas to make the pressure reach and maintain 1.3MPa, reacting at 200 deg.C for 3.5h, cooling to room temperature, and filtering to obtain saturated bio-oil;
(5) Mixing materials: methanol, saturated bio-oil and 93# gasoline are mixed according to the mass ratio of 8:14:27 are mixed evenly to prepare the bio-based methanol gasoline.
Comparative example 2
A bio-based methanol gasoline mainly comprises the following components in parts by weight: 8 parts of methanol, 14 parts of bio-oil and 27 parts of gasoline.
A preparation method of bio-based methanol gasoline mainly comprises the following preparation steps:
(1) Pretreatment: crushing the leaves at the ambient temperature of-8 ℃ until the particles are smaller than 9mm, then placing the crushed leaves in a pulverizer, pulverizing the crushed leaves at the ambient temperature of-8 ℃ until the particles are smaller than 1mm, and mixing the pulverized leaves with deionized water according to the mass ratio of 1:9, uniformly mixing, placing in a high-pressure reaction kettle, reacting at 190 ℃ for 22h, cooling, taking out, washing with pure water for 4 times, drying at 75 ℃ for 5h, and mixing with a sodium hydroxide solution with the mass fraction of 7% according to the mass ratio of 1:22, performing ultrasonic treatment at 55 ℃ and 35kHz for 45min, performing centrifugal separation, washing with pure water to be neutral, drying at 65 ℃ for 7h, and grinding at-8 ℃ until the particle size is less than 0.5mm to obtain biomass powder;
(2) Inoculating and fermenting: mixing biomass powder, glucose and physiological saline according to a mass ratio of 5.5:1:90, uniformly mixing, inoculating cryptococcus, controlling the pH value to be 7 by using hydrochloric acid with the mass fraction of 4% and a sodium hydroxide solution with the mass fraction of 4%, adjusting the fermentation temperature to be 25 ℃, enabling the air flow per minute to be 7 times of the volume of physiological saline, and culturing for 170 hours to obtain fermentation liquor;
(3) Extraction: adjusting the pH value of the fermentation liquor to 4, heating to 50 ℃, stirring at 900r/min for 11h, adding hexane with the mass of 1.5 times of that of the fermentation liquor, keeping the temperature unchanged, continuing stirring for 45min, standing for 5h, layering to obtain an oil phase, and standing for 9h at 25 ℃ and 1.5kPa to obtain biological oil;
(4) Mixing materials: methanol, bio-oil and 93# gasoline are mixed according to the mass ratio of 8:14:27 to obtain the bio-based methanol gasoline.
Effects of the invention
The following table 1 shows the results of performance analysis of the contamination property of bio-based methanol gasoline using examples 1 to 3 of the present invention and comparative examples 1 to 4.
| Amount of soot | Amount of soot | ||
| Example 1 | 0.04g | Comparative example 1 | 0.53g |
| Example 2 | 0.04g | Comparative example 2 | 0.45g |
| Example 3 | 0.06g |
TABLE 1
The experimental data comparison of examples 1, 2 and 3 and comparative column 1 in table 1 shows that the soot amount of examples 1, 2 and 3 and comparative column 1 is low, which indicates that hydrothermal and sodium hydroxide treatment is performed in the pretreatment process, so that the surface protection structure of biomass powder is primarily destroyed, impurities are further removed, the adhesion and decomposition of subsequent inoculated oil-producing microorganisms are increased, more purer oil phase is obtained, and the pollution of bio-based methanol gasoline is reduced; from the comparison of the experimental data of examples 1, 2, 3 and comparative example 2, it can be seen that the low soot levels of examples 1, 2, 3 and comparative example 2 indicate that catalytic hydrogenation is performed to convert unsaturated bonds in bio-oil to saturated bonds, so that combustion can be more complete, thereby reducing the pollution of bio-based 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 (10)
1. The bio-based methanol gasoline is characterized by mainly comprising the following components in parts by weight: 7-9 parts of methanol, 12-16 parts of saturated bio-oil and 24-30 parts of gasoline.
2. The bio-based methanol gasoline as claimed in claim 1, wherein said saturated bio-oil is produced from bio-oil by catalytic hydrogenation.
3. The bio-based methanol gasoline as claimed in claim 2, wherein the bio-oil is obtained by inoculating and fermenting biomass powder and then extracting.
4. The bio-based methanol gasoline as claimed in claim 3, wherein the biomass powder is prepared by grinding leaves, hydrothermal treatment and alkali treatment.
5. A preparation method of bio-based methanol gasoline is characterized by mainly comprising the following preparation steps:
(1) Pretreatment: crushing the leaves to particles smaller than 9mm at the environment temperature of-10 to-5 ℃, then placing the crushed leaves into a pulverizer, grinding the crushed leaves to particles smaller than 1mm at the environment temperature of-10 to-5 ℃, and then mixing the pulverized leaves with deionized water according to the mass ratio of 1: 8-1: 10, uniformly mixing, placing in a high-pressure reaction kettle, reacting at 180-200 ℃ for 20-24 h, cooling, taking out, washing with pure water for 3-5 times, drying at 70-80 ℃ for 4-6 h, and mixing with a sodium hydroxide solution with the mass fraction of 6-8% according to the mass ratio of 1:20 to 1:25, mixing, performing ultrasonic treatment at 50-60 ℃ and 30-40 kHz for 40-50 min, performing centrifugal separation, washing to be neutral by pure water, drying for 6-8 h at 60-70 ℃, and grinding at-10 to-5 ℃ until the particle size is less than 0.5mm to prepare biomass powder;
(2) Inoculating and fermenting: mixing biomass powder, glucose and physiological saline according to a mass ratio of 5:1: 80-6: 1:100, uniformly mixing, inoculating oil-producing microorganisms, controlling the pH value to be 6-8 by using hydrochloric acid with the mass fraction of 3-5% and a sodium hydroxide solution with the mass fraction of 3-5%, adjusting the fermentation temperature to be 20-30 ℃, enabling the air flow per minute to be 6-10 times of the volume of physiological saline, and culturing for 140-200 h to obtain fermentation liquor;
(3) Extraction: adjusting the pH value of the fermentation liquor to 3.5-4.5, heating to 40-60 ℃, stirring for 10-12 h at 800-1000 r/min, adding an extraction solvent with the mass of 1.2-1.8 times of that of the fermentation liquor, keeping the temperature unchanged, continuously stirring for 40-50 min, standing for 4-6 h, layering to obtain an oil phase, and standing for 8-10 h at 20-30 ℃ under 1-2 kPa to obtain biological oil;
(4) Catalytic hydrogenation: preheating bio-oil for 40-50 min at 130-140 ℃ under the condition of 60-100 Pa, adding metallic nickel with the mass of 0.002-0.004 times of that of the bio-oil, stirring for 20-30 min at 800-1000 r/min, placing the mixture into a hydrogenation tank, introducing hydrogen to ensure that the pressure reaches and is kept at 1.1-1.5 MPa, reacting for 3-4 h at 180-220 ℃, cooling to room temperature, and filtering to prepare saturated bio-oil;
(5) Mixing materials: methanol, saturated bio-oil and gasoline are mixed according to the mass ratio of 7:12: 24-9: 16:30, and mixing uniformly to obtain the bio-based methanol gasoline.
6. The method for preparing bio-based methanol gasoline according to claim 5, wherein the leaves in step (1) are cleaned and air-dried mulberry leaves.
7. The method according to claim 5, wherein the oleaginous microorganism of step (2) is Cryptococcus, mortierella alpina or dinoflagellate.
8. The method for preparing bio-based methanol gasoline as claimed in claim 5, wherein the extraction solvent of step (3) is hexane.
9. The method for preparing bio-based methanol gasoline according to claim 5, wherein the purity of the metallic nickel in step (4) is more than 99.9%, and the particle size is less than 0.1mm.
10. The method for preparing bio-based methanol gasoline according to claim 5, wherein the gasoline of step (5) is 93# gasoline.
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