CN109694758A - A kind of high heating value alcohol radical liquid fuel and preparation method thereof - Google Patents
A kind of high heating value alcohol radical liquid fuel and preparation method thereof Download PDFInfo
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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
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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
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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
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
- C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
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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
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
- C10L1/1258—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof hydrogen peroxide, oxygenated water
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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
- C10L1/16—Hydrocarbons
- C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
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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
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1857—Aldehydes; Ketones
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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
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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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
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
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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
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- 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 belongs to alcohol-based fuel technical fields, it is related to a kind of high heating value alcohol radical liquid fuel and preparation method thereof, which is made of the raw material of following weight parts: 70 ~ 90 parts of methanol, 5 ~ 10 parts of water, 0.01 ~ 1 part of nonionic surfactant, 15 ~ 20 parts of acetone, 10 ~ 30 parts of condensate, 10 ~ 30 parts of naphtha, 1 ~ 3 part of cyclohexyl nitrate, hydrogen peroxidase 10 .1 ~ 0.5 part and 2 ~ 5 parts of potassium tert-butoxide.The present invention solves the problems such as low calorific value existing for existing alcohol radical liquid fuel, unstable quality, and the indices of alcohol-based fuel are better than national alcohol-group fuel oil relevant criterion.
Description
Technical field
The invention belongs to alcohol-based fuel technical field, it is related to a kind of high heating value alcohol radical liquid fuel and preparation method thereof.
Background technique
With economic rapid development, the benefit of subsisting of the demand to the energy increases, but due to shortage of resources, price occupy it is high not
Under, energy shortage problem has become the chronic stress for restricting development of world economy, and the petroleum of fossil resources, can make atmosphere
The middle a large amount of harmful substance of discharge, causes air pollution, ecology and human health is influenced, in order to which the supply for alleviating petroleum resources is tight
, mitigate environmental pollution, recycle resource preferably, benefit the next generation, various countries start to carry out replacing for novel environment friendly economy
Replacing fuel, wherein alcohol-based fuel is paid attention to because of its environmentally friendly characteristic by every country.
Alcohol-based fuel is usually to be mixed with the liquid fuel of other polyalcohols and hydro carbons, it is also one based on methanol
Kind biomass energy and nuclear energy, solar energy, wind power energy, water conservancy can be the same, be the environment protection clean energy that national governments widely popularize at present
Source；And coal, diesel oil are compared, most complete, the thermal conversion efficiency highest of alcohol-based fuel burning discharges based on water and carbon dioxide, is
Future is most cleaned, most environmentally friendly, most there is the fuel of development potentiality, but most of alcohol-based fuel high production cost, and calorific value at present
Low, methanol flash-point is low, dangerous, limits its extensive use, it is therefore necessary to improve to existing alcohol-based fuel.
Summary of the invention
The purpose of the present invention is to provide a kind of high heating value alcohol radical liquid fuels and preparation method thereof, solve existing alcohol radical
The problems such as calorific value existing for liquid fuel is low, unstable quality, the indices of alcohol-based fuel are better than national alcohol-group fuel oil
Relevant criterion.
To achieve the above object, the invention adopts the following technical scheme:
The present invention provides a kind of high heating value alcohol radical liquid fuel, is made of the raw material of following weight parts: 70~90 parts of methanol, water 5
~10 parts, 0.01~1 part of nonionic surfactant, 15~20 parts of acetone, 10~30 parts of condensate, 10~30 parts of naphtha,
1~3 part of cyclohexyl nitrate, hydrogen peroxidase 10 .1~0.5 part and 2~5 parts of potassium tert-butoxide.
Preferably, the purity of the methanol is 95~99%.
Preferably, the concentration of the hydrogen peroxide is 30%.
Preferably, the nonionic surfactant be polyoxyethylene non-ionic surfactant or polyol type it is non-from
Sub- surfactant.
Preferably, the polyoxyethylene non-ionic surfactant is alkyl phenol polyoxyethylene ether.
Preferably, the polyol-based non-ionic surfactant is fatty acid glyceride.
The present invention also provides a kind of preparation methods of high heating value alcohol radical liquid fuel, comprising the following steps:
The methanol, water, nonionic surfactant of above-mentioned parts by weight are mixed, with the speed of 300r/min stir evenly A is molten
Liquid, then the acetone of above-mentioned parts by weight, condensate, cyclohexyl nitrate, naphtha mixing are stirred evenly with the speed of 300r/min
B solution is obtained, solution A and B solution are then mixed to obtain C solution, then potassium tert-butoxide and hydrogen peroxide addition C above-mentioned parts by weight
In solution, at 30 DEG C with the speed stirring half an hour of 300r/min to obtain the final product.
Condensate in the present invention refers to the liquid phase component come out from gas condensate field or oil field associated natural gas condensation, again
Claim natural gasoline, main component is C5To C11The mixture of hydro carbons is light brown liquid, density and gasoline phase under condensate room temperature
Imitative, flash-point is low, belongs to flammable liquid, and Light Hydrocarbons for Condensate Oil constituent content is high, and it is as the good raw material of solvent naphtha that volatility is high.
Naphtha also known as raw gasoline are a kind of colourless transparent liquids, are one of petroleum distillates.Generally containing alkane 55.4%,
Monocycle alkane 30.3%, bicyclic alkane 2.4%, alkylbenzene 11.7%, benzene 0.1%, indane and tetralin 0.1%.Density is
0.76g/cm3, explosion limit 1.2%~6.0%.Its fraction is light, and alkane, naphthene content are high, and roadholding is good, and heavy metal contains
Measure low, sulfur content is low, and toxicity is smaller, and modulates cost far below all types of petrochemical industry auxiliary agents on the market, can substitute MMT (first completely
Butylcyclopentadiene manganese tricarbonyl), all kinds of metallic anti-knock agent such as ferrocene, it is not soluble in water, be dissolved in most organic solvents.
Potassium tert-butoxide is a kind of important organic base, and alkalinity is greater than potassium hydroxide.Due to (CH3)3There are three methyl by CO-
Inductive effect makes it have stronger alkalinity and activity than other potassium alcoholates, therefore is a kind of good catalyst.
Cyclohexyl nitrate is as cetane number improver, and generally addition 1.5%, and about 20 lists can be improved in Cetane number
Position, gets well than the additive effect of isooctyl ester nitrate, is a potential cetane number improver.
Compared with prior art, the beneficial effects of the present invention are:
On the one hand 1. the present invention improves the combustion heat value of alcohol-based fuel using naphtha as calorific value enhancer and anti-knock agent,
On the other hand the anti-knock properties of fuel also can be improved, it is safer, convenient for storage.It is smaller than water density additionally, due to naphtha and solidifying
Condensate oil and water contact highly volatile, so naphtha is also used as the stability of volatilization prevention agent protection liquid fuel.
2. using nonionic surfactant as emulsifier in the present invention, there is stable property, acid and alkali-resistance and at low cost
Etc. features, methanol can be made, water and condensate dissolve each other.
3. the present invention makes the alcohol radical liquid fuel of preparation using cyclohexyl nitrate as high-octane rating additive and anti-knock agent
With excellent anti-knock properties, and compared to methyl tertiary butyl ether(MTBE) and other additives, the additive usage amount is few, but effect is bright
It is aobvious.
4. the present invention is used as catalyst using organic base potassium tert-butoxide, than inorganic base potassium hydroxide it is alkaline by force, it is high-efficient.
Specific embodiment
The following examples are intended to illustrate the invention, but is not used to limit the scope of protection of the present invention.Unless otherwise specified, real
Apply the conventional means that technological means used in example is well known to those skilled in the art.Test method in following embodiments, such as
It is conventional method without special instruction.
Embodiment 1
A kind of high heating value alcohol radical liquid fuel, is made of the raw material of following weight parts: methanol 70 part, water 10 of the purity for 95%
Part, 0.01 part of alkyl phenol polyoxyethylene ether, 20 parts of acetone, 15 parts of condensate, 15 parts of naphtha, 1.5 parts of cyclohexyl nitrate, concentration
For .3 parts and 3 parts of potassium tert-butoxide of hydrogen peroxidase 10 of 30%.
The preparation method of above-mentioned high heating value alcohol radical liquid fuel is the following steps are included: by the methanol of above-mentioned parts by weight, water, non-
Ionic surface active agent mixing, stirs evenly to obtain solution A, then the acetone above-mentioned parts by weight, condensation with the speed of 300r/min
Oil, cyclohexyl nitrate, naphtha mixing stir evenly to obtain B solution with the speed of 300r/min, and then solution A and B solution are mixed
C solution is closed to obtain, then in the potassium tert-butoxide and hydrogen peroxide addition C solution above-mentioned parts by weight, with 300r/min's at 30 DEG C
Speed stirs half an hour to obtain the final product.
Embodiment 2
A kind of high heating value alcohol radical liquid fuel, is made of the raw material of following weight parts: purity be 98% 75 parts of methanol, 5 parts of water,
1 part of alkyl phenol polyoxyethylene ether, 15 parts of acetone, 10 parts of condensate, 10 parts of naphtha, 2 parts of cyclohexyl nitrate, concentration are 30%
.5 parts and 5 parts of potassium tert-butoxide of hydrogen peroxidase 10.
Embodiment 3
A kind of high heating value alcohol radical liquid fuel, is made of the raw material of following weight parts: purity be 99% 80 parts of methanol, 8 parts of water,
0.03 part of alkyl phenol polyoxyethylene ether, 18 parts of acetone, 20 parts of condensate, 20 parts of naphtha, 3 parts of cyclohexyl nitrate, concentration are
.2 parts and 2 parts of potassium tert-butoxide of 30% hydrogen peroxidase 10.
Embodiment 4
A kind of high heating value alcohol radical liquid fuel, is made of the raw material of following weight parts: purity be 96% 90 parts of methanol, 5 parts of water,
0.01 part of fatty acid glyceride, 18 parts of acetone, 30 parts of condensate, 30 parts of naphtha, 1 part of cyclohexyl nitrate, concentration are 30%
.1 parts and 2 parts of potassium tert-butoxide of hydrogen peroxidase 10.
Alcohol radical liquid fuel made from above-described embodiment 1~3 is tested for the property by GB16663-1996, as a result such as table
Shown in 1.
Alcohol radical liquid fuel the performance test results made from 1 Examples 1 to 3 of table
As can be seen from Table 1, all meet national alcohol radical by the indices of the alcohol-based fuel of the present invention for being formulated and obtaining
Fuel oil relevant criterion.
The embodiment of the above, only presently preferred embodiments of the present invention, is only used to explain the present invention, not limit
The scope of the present invention processed to those of ordinary skill in the art certainly can be according to skill disclosed in this specification
Art content makes other embodiments easily by way of replacing or changing, therefore all made in the principle of the present invention
Changes and improvements etc., should be included in scope of the present invention patent.
Claims (7)
1. a kind of high heating value alcohol radical liquid fuel, which is characterized in that be made of the raw material of following weight parts: 70 ~ 90 parts of methanol, water
5 ~ 10 parts, 0.01 ~ 1 part of nonionic surfactant, 15 ~ 20 parts of acetone, 10 ~ 30 parts of condensate, 10 ~ 30 parts of naphtha, nitric acid
1 ~ 3 part of cyclohexyl, hydrogen peroxidase 10 .1 ~ 0.5 part and 2 ~ 5 parts of potassium tert-butoxide.
2. a kind of high heating value alcohol radical liquid fuel according to claim 1, which is characterized in that the purity of the methanol is 95
~ 99%.
3. a kind of high heating value alcohol radical liquid fuel according to claim 1, which is characterized in that the concentration of the hydrogen peroxide
It is 30%.
4. a kind of high heating value alcohol radical liquid fuel according to claim 1, which is characterized in that the non-ionic surface active
Agent is polyoxyethylene non-ionic surfactant or polyol-based non-ionic surfactant.
5. a kind of high heating value alcohol radical liquid fuel according to claim 4, which is characterized in that the polyoxyethylene-type it is non-from
Sub- surfactant is alkyl phenol polyoxyethylene ether.
6. a kind of high heating value alcohol radical liquid fuel according to claim 4, which is characterized in that the polyol type nonionic
Surfactant is fatty acid glyceride.
7. a kind of described in any item preparation methods of high heating value alcohol radical liquid fuel of claim 1 ~ 6, which is characterized in that including
Following steps:
The methanol, water, nonionic surfactant of parts by weight described in claim 1 are mixed, stirred with the speed of 300r/min
Mix uniform solution A, then the acetone of parts by weight described in claim 1, condensate, cyclohexyl nitrate, naphtha mixing with
The speed of 300r/min stirs evenly to obtain B solution, solution A and B solution is then mixed to obtain C solution, then institute in claim 1
The potassium tert-butoxide and hydrogen peroxide for stating parts by weight are added in C solution, are with the speed stirring half an hour of 300r/min at 30 DEG C
?.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791335A (en) * | 2019-11-14 | 2020-02-14 | 陕西祥火环保新能源股份有限公司 | High-calorific-value alcohol-based liquid fuel and preparation method thereof |
| CN111763541A (en) * | 2020-03-12 | 2020-10-13 | 榆林碳氢研究院股份有限公司 | High-calorific-value clean fuel for industrial boiler and preparation method thereof |
| CN114381307A (en) * | 2022-03-22 | 2022-04-22 | 玉门祥天新能源产业发展有限公司 | Alcohol-based fuel for ignition type internal combustion engine and preparation method thereof |
| CN116463153A (en) * | 2023-03-07 | 2023-07-21 | 重庆鸿邦科技有限公司 | Modified methanol fuel for industrial kiln and preparation method thereof |
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| CN110791335A (en) * | 2019-11-14 | 2020-02-14 | 陕西祥火环保新能源股份有限公司 | High-calorific-value alcohol-based liquid fuel and preparation method thereof |
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| CN114381307A (en) * | 2022-03-22 | 2022-04-22 | 玉门祥天新能源产业发展有限公司 | Alcohol-based fuel for ignition type internal combustion engine and preparation method thereof |
| CN116463153A (en) * | 2023-03-07 | 2023-07-21 | 重庆鸿邦科技有限公司 | Modified methanol fuel for industrial kiln and preparation method thereof |
| CN116463153B (en) * | 2023-03-07 | 2024-03-19 | 重庆鸿邦科技有限公司 | Modified methanol fuel for industrial kiln and preparation method thereof |
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