CN112029546A - Non-metal anti-knock additive and preparation method thereof - Google Patents

Non-metal anti-knock additive and preparation method thereof Download PDF

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Publication number
CN112029546A
CN112029546A CN202010892705.4A CN202010892705A CN112029546A CN 112029546 A CN112029546 A CN 112029546A CN 202010892705 A CN202010892705 A CN 202010892705A CN 112029546 A CN112029546 A CN 112029546A
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parts
inhibitor
methyl
additive
methylformamide
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郭银亮
崔秋生
胡君
郑应坚
李清
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Yangpu Aoli Petrochemical Co ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/143Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/10Use of additives to fuels or fires for particular purposes for improving the octane number
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1608Well defined compounds, e.g. hexane, benzene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/185Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852Ethers; Acetals; Ketals; Orthoesters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/19Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224Amides; Imides carboxylic acid amides, imides

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

The invention provides a non-metal anti-knock additive and a preparation method thereof, wherein the anti-knock additive comprises the following components in parts by weight: the feed comprises the following raw materials in parts by weight: 50-120 parts of N-methylformamide, 1-5 parts of methyl tert-butyl ether, 2-15 parts of dimethyl carbonate, 5-20 parts of methyl p-hydroxybenzoate, 3-18 parts of glycerol stearate and 2-8 parts of an inhibitor; the prepared antiknock agent blended gasoline has good stability, is not layered after being placed for two months, has no octane value attenuation, does not change the original property of the gasoline, can provide technical support for blending commercial gasoline with naphtha in a large amount of oil refining gas-liquid, and can create more economic benefits for enterprises.

Description

Non-metal anti-knock additive and preparation method thereof
Technical Field
The invention relates to the field of petrochemical industry, in particular to a non-metal anti-knock additive and a preparation method thereof.
Background
Since the advent of Methylcyclopentadienyl Manganese Tricarbonyl (MMT), the manganese tricarbonyl (MMT) has been popularized and used in most countries in the world as an antiknock agent with excellent performance. However, because there are some disputes about the use of MMT, and governments in various countries have adopted restrictive measures for MMT use, with limited additions to gasoline, the effect of MMT in increasing gasoline octane is limited (2-3 units) in a policy setting. On the other hand, as the MMT addition increases, the increase amplitude of the gasoline octane number gradually attenuates, and the advantages are gradually lost; in the nonmetal antiknock agent produced at present, the MTBE commonly used in oil refineries has large addition amount and has certain influence on the environment. Therefore, for the demand of greatly improving the octane number of gasoline, the market is urgently required to provide the antiknock agent which can meet the demand.
Disclosure of Invention
In view of the above, the present invention provides a non-metallic anti-knock additive and a preparation method thereof, which solve the above problems.
The technical scheme of the invention is realized as follows: a non-metallic antiknock additive: the feed comprises the following raw materials in parts by weight: 50-120 parts of N-methylformamide, 1-5 parts of methyl tert-butyl ether, 2-15 parts of dimethyl carbonate, 5-20 parts of methyl p-hydroxybenzoate, 3-18 parts of glycerol stearate and 2-8 parts of an inhibitor.
Further, the non-metal anti-knock additive comprises the following raw materials in parts by weight: 80 parts of N-methylformamide, 3 parts of methyl tert-butyl ether, 8 parts of dimethyl carbonate, 12 parts of methyl p-hydroxybenzoate, 11 parts of glycerol stearate and 6 parts of inhibitor.
Further, the inhibitor comprises polyethylene glycol, carboxymethyl cellulose and limonene.
Further, the nonmetal antiknock additive is characterized in that: the inhibitor is polyethylene glycol, carboxymethyl cellulose and limonene in a weight ratio of 1-3: 0.2-0.9: 0.1-0.6.
Further, the preparation method of the non-metal anti-knock additive comprises the following steps:
s1, heating N-methylformamide, methyl tert-butyl ether and dimethyl carbonate to 50-80 ℃, preserving heat, mixing for 20-60 min, and then performing ultrasonic treatment for 20-40 min under the conditions of ultrasonic frequency of 1200-2000 MHz and power of 600-800W to obtain a material A;
s2, adding methyl p-hydroxybenzoate and glycerol stearate into ethanol, soaking for 15-30 min, and performing ultrasonic treatment for 10-30 min at an ultrasonic frequency of 1800-2400 MHz and a power of 500-700W to obtain a material B;
and S3, mixing the material A and the material B, adding an inhibitor, and fully stirring at a stirring speed of 80-150 rpm to obtain the anti-knock additive.
Further, the soaking temperature in the step S2 is 40-60 ℃.
Further, the stirring time in the step S3 is 20-40 min.
Compared with the prior art, the invention has the beneficial effects that:
the antiknock agent does not contain heavy metal, can not be limited by adding amount when blending gasoline, does not have the problem that the content of the heavy metal exceeds the standard, wherein, all the components play a role in synergy, the components such as inhibitor and the like are added, the addition amount of the methyl tert-butyl ether is reduced, the environmental pollution is avoided, the defect that the increase of the octane value is gradually attenuated along with the increase of the adding amount of MMT is overcome, the antiknock agent has the characteristics that the octane value is improved more when the adding amount is larger, the blended gasoline has good stability, the antiknock agent is not layered after being placed for two months, the octane value is not attenuated, the original property of the gasoline is not changed, the antiknock agent can provide technical support for blending the petroleum gas liquid with naphtha for blending.
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
Example 1
A non-metallic antiknock additive: the feed comprises the following raw materials in parts by weight: 50 parts of N-methylformamide, 1 part of methyl tert-butyl ether, 2 parts of dimethyl carbonate, 5 parts of methyl p-hydroxybenzoate, 3 parts of glycerol stearate and 2 parts of inhibitor.
The inhibitor is polyethylene glycol, carboxymethyl cellulose and limonene in a weight ratio of 1:0.2: 0.1.
Example 2
A non-metallic antiknock additive: the feed comprises the following raw materials in parts by weight: 120 parts of N-methylformamide, 5 parts of methyl tert-butyl ether, 15 parts of dimethyl carbonate, 20 parts of methyl p-hydroxybenzoate, 18 parts of glycerol stearate and 8 parts of inhibitor.
The inhibitor is polyethylene glycol, carboxymethyl cellulose and limonene in a weight ratio of 3:0.9: 0.6.
Example 3
A non-metal anti-knock additive comprises the following raw materials in parts by weight: 80 parts of N-methylformamide, 3 parts of methyl tert-butyl ether, 8 parts of dimethyl carbonate, 12 parts of methyl p-hydroxybenzoate, 11 parts of glycerol stearate and 6 parts of inhibitor.
The inhibitor is polyethylene glycol, carboxymethyl cellulose and limonene in a weight ratio of 2:0.5:0.4, and the following preparation method is used in the above examples 1-3:
s1, heating N-methylformamide, methyl tert-butyl ether and dimethyl carbonate to 70 ℃, preserving heat, mixing for 40min, and then performing ultrasonic treatment for 30min under the ultrasonic frequency of 1600MHz and the power of 700W to obtain a material A;
s2, adding methyl p-hydroxybenzoate and glycerol stearate into ethanol, soaking at 50 ℃ for 22min, and performing ultrasonic treatment at ultrasonic frequency of 2000MHz and power of 600W for 20min to obtain a material B;
and S3, mixing the material A and the material B, adding an inhibitor, and fully stirring for 30min at a stirring speed of 120rpm to obtain the anti-knock additive.
Example 4
The difference between this example and example 3 is that the preparation method of the non-metallic antiknock additive is as follows:
s1, heating N-methylformamide, methyl tert-butyl ether and dimethyl carbonate to 50 ℃, preserving heat, mixing for 20min, and then performing ultrasonic treatment for 20-40 min at the ultrasonic frequency of 1200MHz and the power of 600W to obtain a material A;
s2, adding methyl p-hydroxybenzoate and glycerol stearate into ethanol, soaking for 15min at 40 ℃, and performing ultrasonic treatment for 10min at an ultrasonic frequency of 1800MHz and a power of 500W to obtain a material B;
and S3, mixing the material A and the material B, adding an inhibitor, and fully stirring at the stirring speed of 80rpm for 20min to obtain the anti-knock additive.
Example 5
The difference between this example and example 3 is that the preparation method of the non-metallic antiknock additive is as follows:
s1, heating N-methylformamide, methyl tert-butyl ether and dimethyl carbonate to 50-80 ℃, preserving heat, mixing for 60min, and then performing ultrasonic treatment for 40min under the ultrasonic frequency of 2000MHz and the power of 800W to obtain a material A;
s2, adding methyl p-hydroxybenzoate and glycerol stearate into ethanol, soaking for 30min at 40-60 ℃, and performing ultrasonic treatment for 30min at the ultrasonic frequency of 2400MHz and the power of 700W to obtain a material B;
and S3, mixing the material A and the material B, adding an inhibitor, and fully stirring for 40min at the stirring speed of 150rpm to obtain the anti-knock additive.
Example 6
This example differs from example 3 in that the inhibitor is polyethylene glycol, carboxymethyl cellulose, limonene in a 4:1:0.1 weight part ratio.
Comparative example 1
The difference between the comparative example and the example 3 is that the nonmetal antiknock additive comprises the following raw materials in parts by weight: 130 parts of N-methylformamide, 8 parts of methyl tert-butyl ether, 18 parts of dimethyl carbonate, 22 parts of methyl p-hydroxybenzoate, 20 parts of glycerol stearate and 10 parts of inhibitor.
Comparative example 2
This comparative example differs from example 3 in that the inhibitor is a polyethylene glycol, carboxymethyl cellulose, in a 1:1 weight part ratio.
Comparative example 3
This comparative example differs from example 3 in that the non-metallic antiknock additive does not contain an inhibitor.
Octane Number (RON) determination
Adding the antiknock agents obtained in the examples 1-6 and the comparative examples 1-3 into No. 88 catalytic cracking gasoline, and determining the octane number increase value of the gasoline under the following experimental conditions: temperature 20 ℃, atmospheric pressure 101.2kPa, mixer temperature 50.6 ℃, the following measurements:
Figure BDA0002657359540000041
Figure BDA0002657359540000051
the above table shows that the nonmetal antiknock agent can improve the octane number of gasoline, wherein examples 1-6 can improve the octane number by 5-6 units, and compared with comparative examples 1-3, the proportion of each component of the antiknock agent forms an excellent synergistic effect, the prepared antiknock agent has good performance of improving the octane number, and the inhibitor can be combined with other components in the antiknock agent to achieve better antiknock performance.
Second, the actual data of the sensitivity of the antiknock agent to the oil product of the oil refinery
The antiknock agent obtained in example 3 was added to base oil, and the octane number (RON) of the oil sample was measured according to the method of GB/T5487, and the experimental conditions were as follows: temperature 20 ℃, atmospheric pressure 101.2kPa, mixer temperature 50.6 ℃, the following measurements:
Figure BDA0002657359540000052
Figure BDA0002657359540000061
as can be seen from the above table, the antiknock agent overcomes the defect that the increase of the octane number gradually attenuates along with the increase of the addition amount of MMT, and has the characteristics that the larger the addition amount is, the more the octane number is improved, and the blended gasoline has good stability and does not attenuate the octane number.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A non-metal antiknock additive is characterized in that: the feed comprises the following raw materials in parts by weight: 50-120 parts of N-methylformamide, 1-5 parts of methyl tert-butyl ether, 2-15 parts of dimethyl carbonate, 5-20 parts of methyl p-hydroxybenzoate, 3-18 parts of glycerol stearate and 2-8 parts of an inhibitor.
2. The non-metallic antiknock additive of claim 1, wherein: the feed comprises the following raw materials in parts by weight: 80 parts of N-methylformamide, 3 parts of methyl tert-butyl ether, 8 parts of dimethyl carbonate, 12 parts of methyl p-hydroxybenzoate, 11 parts of glycerol stearate and 6 parts of inhibitor.
3. The non-metallic antiknock additive of claim 1, wherein: the inhibitor comprises polyethylene glycol, carboxymethyl cellulose, limonene.
4. The non-metallic antiknock additive of claim 1, wherein: the inhibitor is polyethylene glycol, carboxymethyl cellulose and limonene in a weight ratio of 1-3: 0.2-0.9: 0.1-0.6.
5. The method for preparing the non-metallic antiknock additive as claimed in claim 1, wherein: the method comprises the following steps:
s1, heating N-methylformamide, methyl tert-butyl ether and dimethyl carbonate to 50-80 ℃, preserving heat, mixing for 20-60 min, and then performing ultrasonic treatment for 20-40 min under the conditions of ultrasonic frequency of 1200-2000 MHz and power of 600-800W to obtain a material A;
s2, adding methyl p-hydroxybenzoate and glycerol stearate into ethanol, soaking for 15-30 min, and performing ultrasonic treatment for 10-30 min at an ultrasonic frequency of 1800-2400 MHz and a power of 500-700W to obtain a material B;
and S3, mixing the material A and the material B, adding an inhibitor, and fully stirring at a stirring speed of 80-150 rpm to obtain the anti-knock additive.
6. The method for preparing the non-metallic antiknock additive as claimed in claim 5, wherein: and the soaking temperature in the step S2 is 40-60 ℃.
7. The method for preparing the non-metallic antiknock additive as claimed in claim 5, wherein: and the stirring time in the step S3 is 20-40 min.
CN202010892705.4A 2020-08-31 2020-08-31 Non-metal anti-knock additive and preparation method thereof Pending CN112029546A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117965213A (en) * 2024-03-05 2024-05-03 洋浦傲立石化有限公司 Preparation method and application of compound gasoline antiknock agent and gasoline
CN117965213B (en) * 2024-03-05 2024-10-22 洋浦傲立石化有限公司 Preparation method and application of compound gasoline antiknock agent and gasoline

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101548000A (en) * 2006-11-08 2009-09-30 创新溶液现代公司 Fuel or fuel additive composition and method for its manufacture and use
CN104711049A (en) * 2015-03-06 2015-06-17 黄河三角洲京博化工研究院有限公司 Nonmetallic gasoline antiknock
CN105296016A (en) * 2015-10-09 2016-02-03 玉溪健坤生物药业有限公司 High-cost performance automotive methanol fuel (M70) and preparation method
CN107201253A (en) * 2017-05-08 2017-09-26 安徽海德石油化工有限公司 A kind of oil anti-knock agent
CN108587705A (en) * 2018-04-14 2018-09-28 张宝臣 A kind of nonmetallic gasoline anti-knock agent and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101548000A (en) * 2006-11-08 2009-09-30 创新溶液现代公司 Fuel or fuel additive composition and method for its manufacture and use
CN104711049A (en) * 2015-03-06 2015-06-17 黄河三角洲京博化工研究院有限公司 Nonmetallic gasoline antiknock
CN105296016A (en) * 2015-10-09 2016-02-03 玉溪健坤生物药业有限公司 High-cost performance automotive methanol fuel (M70) and preparation method
CN107201253A (en) * 2017-05-08 2017-09-26 安徽海德石油化工有限公司 A kind of oil anti-knock agent
CN108587705A (en) * 2018-04-14 2018-09-28 张宝臣 A kind of nonmetallic gasoline anti-knock agent and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117965213A (en) * 2024-03-05 2024-05-03 洋浦傲立石化有限公司 Preparation method and application of compound gasoline antiknock agent and gasoline
CN117965213B (en) * 2024-03-05 2024-10-22 洋浦傲立石化有限公司 Preparation method and application of compound gasoline antiknock agent and gasoline

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