This article was born from a casual conversation with a colleague, when a phrase was heard that, according to representatives of foreign auto-building companies, with the sulfur content that Russian fuel differs in, not a single diesel engine can travel more than 600 thousand km. But they do go! We thought about it and realized that everything here is not as simple as our colleague would like. And in order not to produce conjectures and legends, they turned to specialists: Viktor Davidovich Reznikov, already well known to our readers, and his colleague at the VNII NP, specializing in fuel, Arkady Mironovich Bakaleinik.
Sulfur and its compounds as a natural component are included in the composition of crude oil in the form of elemental sulfur, hydrogen sulfide and various organic compounds (mercaptans, sulfides, disulfides, etc.), while heavier distillates of oil contain more sulfur and sulfur compounds than lungs. Elemental sulfur, hydrogen sulfide, mercaptans are highly corrosive, therefore, their presence in gasoline and diesel fuels was not allowed (sulfur and hydrogen sulfide) or strictly limited (mercaptans). The total content of the remaining sulfur compounds in the fuel is limited by the limit of the “mass fraction of sulfur” indicator. Tightening the standards for this indicator requires deepening the removal of sulfur and, accordingly, additional costs for the production of fuel, increases its cost, and reduces resources. Therefore, some amount of sulfur is present in all commercial fuels.
Recall that the current standard divides diesel fuel into "sulphurous" and "low-sulphurous". These terms have had different meanings at different times. When equipment manufacturers did not have or had minimal restrictions on emissions of harmful substances, the sulfur content was normalized based on the possibility of ensuring reliable operation of the engine without a significant reduction in its resource, but in such a way that this did not reduce fuel yield and did not increase its cost.
At this stage, i.e. in the 50s - 70s, diesel fuel with a sulfur content of about 1.0% was referred to as "sulphurous", and fuel with a sulfur content of not more than 0.2% was considered "low-sulphurous". The main problem with the use of sulphurous fuels was an increase in the wear of parts of the cylinder-piston group of diesel engines and an increase in the amount of deposits on them under the influence of sulfur combustion products. Most of these products (SO2 and SO3) are emitted with exhaust gases into the atmosphere, but the amount of SO2 and SO3 that forms sulfurous and sulfuric acids with water vapor significantly increases the corrosive wear of cylinders, piston rings and other parts, contributes to carbon formation, which disrupts heat removal from the piston, the mobility of the piston rings, which reduces compression.
To solve these problems, diesel oils have been given neutralizing power with the help of alkaline detergent additives. Additives almost completely prevent corrosive wear of engine parts and increased carbon formation. With sufficient alkalinity of the oil (about 8 - 10 mg KOH / g), wear of a set of piston rings when operating on fuels with a sulfur content of 1.0; 0.5 and 0.2% are almost the same if the oil change is done in a timely manner. When operating on fuels with a high sulfur content, the base number of the oil decreases faster and the oil change interval is reduced.
Today the situation has changed. Now "sulphurous" is called fuel containing 0.2% sulfur, and in "low sulfur" it can be only 0.035% or less. What is the reason for such drastic changes?
In recent years, due to the severity of the problem of environmental pollution from the operation of a rapidly growing multimillion-dollar fleet of vehicles, increasingly stringent standards have been introduced for vehicle emissions of toxic compounds, particulate matter, and other air pollutants. Compliance with these standards required from vehicle manufacturers the use of various emission control systems (afterburners, catalytic converters, filters, etc.) in the design of vehicles, as well as changes in the organization of the combustion process, the introduction of exhaust gas recirculation, and new fuel injection systems.
The presence of sulfur compounds in the fuel increases the toxicity of exhaust gases not only directly - by increasing the concentration of sulfur oxides and particulate matter in them, but also indirectly - by reducing the efficiency and reliability of modern exhaust gas composition control systems. Therefore, at present, along with the development and production of equipment that meets the new standards for emissions of harmful substances, more stringent restrictions on the sulfur content in automotive fuels are being gradually introduced.
Diesel fuels in Russia are currently produced in accordance with GOST 305-82 and more than thirty technical conditions (TU). According to these documents, diesel fuels are produced not only for vehicles, but also for agricultural machinery, construction and road machines, diesel locomotives, ships, etc. In accordance with GOST 305-82, 80 - 85% is now produced in Russia, i.e. the bulk of diesel fuel. The level of sulfur content of 0.2% can be considered basic for Russia. In diesel fuel of type 2, according to this standard, even a sulfur content of up to 0.5% is allowed. However, this norm is being revised in the direction of tightening in relation to the sulfur content, and fuel with a maximum content of 0.05% is also introduced.
For use in large cities or regions with difficult environmental conditions, technical specifications have been developed for diesel fuel with improved environmental properties - urban (TU 38.401-58-170-96) with a sulfur content of not more than 0.05% and "environmentally friendly" fuels (TU 38.1011348 -99), providing for, among other restrictions, the release of fuel with a sulfur content of not more than 0.035%.
On November 1, 2001, TU 38.401-58-296-2001 “Diesel automotive fuel. Specifications”, developed on the basis of an authentic translation of EN-590-2000 with a sulfur content of not more than 0.035%, for cars that meet Euro-3 requirements. By 2003 - 2005 it is planned to harmonize domestic standards for gasoline and diesel fuel with European requirements for Euro-3 vehicles. This means limiting the sulfur content in gasolines to 0.015% and in diesel fuel to 0.035%. But the introduction of such standards will not mean a simultaneous transition to new requirements: the process will continue for at least 5 years. During this period, the "old" and "new" requirements will operate simultaneously.
Diesel fuels with a sulfur content of less than 0.035% have poorer lubricating properties. Their use leads to a significant increase in the wear of the high-pressure pump plungers and a decrease in the uptime of other units of the fuel equipment. It became necessary to introduce additives into fuels that improve their lubricating properties. In Russia, such additives are not yet mass-produced. And this is not the only problem associated with the transition to new standards.
Unfortunately, our gas stations have not yet organized separate sales of diesel fuels of different grades that differ in their sulfur content and other indicators that characterize their environmental friendliness. This urgent task must be solved, since the mixing of fuels in one gas station tank leads to a deterioration in the quality of environmentally friendly varieties. But this is already a matter of reforming the infrastructure, which will require considerable time.
GOST 305-2013
INTERSTATE STANDARD
FUEL DIESEL
Specifications
diesel fuel. Specifications
MKS 75.160.20
Introduction date 2015-01-01
Foreword
The goals, basic principles and procedure for carrying out work on interstate standardization are established by GOST 1.0-92 "Interstate standardization system. Basic provisions" and GOST 1.2-2009 "Interstate standardization system. Interstate standards, rules and recommendations for interstate standardization. Rules for the development, adoption, application , updates and cancellations"
About the standard
1 DEVELOPED by the Open Joint Stock Company "All-Russian Scientific Research Institute for Oil Refining" (JSC "VNII NP"), the Technical Committee for Standardization TC 31 "Petroleum Fuels and Lubricants"
2 INTRODUCED by the Federal Agency for Technical Regulation and Metrology
3 ADOPTED by the Interstate Council for Standardization, Metrology and Certification (Minutes of November 14, 2013 N 44)
Voted to accept:
Short name of the country according to MK (ISO 3166) 004-97 | Abbreviated name of the national standards body |
|
Armenia | Ministry of Economy of the Republic of Armenia |
|
Kyrgyzstan | Kyrgyzstandart |
|
Russia | Rosstandart |
|
Uzbekistan | Uzstandard |
4 By order of the Federal Agency for Technical Regulation and Metrology of November 22, 2013 N 1871-st, the interstate standard GOST 305-2013 was put into effect as the national standard of the Russian Federation from January 1, 2015.
5 INSTEAD OF GOST 305-82
Information about changes to this standard is published in the annual information index "National Standards", and the text of changes and amendments - in the monthly information index "National Standards". In case of revision (replacement) or cancellation of this standard, a corresponding notice will be published in the monthly information index "National Standards". Relevant information, notification and texts are also posted in the public information system - on the official website of the Federal Agency for Technical Regulation and Metrology on the Internet
1 area of use
1 area of use
This standard applies to diesel fuel (hereinafter referred to as fuel) for high-speed diesel and gas turbine engines of land and ship equipment, obtained during the processing of oils and gas condensates, as well as for export.
Fuel with a sulfur content of 2000 mg/kg is supplied under the state defense order and for export.
This fuel is not allowed to be sold through public filling stations.
The classification of product groups on the territory of the Russian Federation according to the All-Russian Product Classifier (OKP), designed to ensure the reliability, comparability and automated processing of product information, is given in Appendix A.
2 Normative references
This standard uses normative references to the following interstate standards:
GOST 12.1.005-88 System of labor safety standards. General sanitary and hygienic requirements for the air of the working area
GOST 12.1.007-76 Occupational safety standards system. Harmful substances. Classification and general safety requirements
GOST 12.1.018-93 Occupational safety standards system. Fire and explosion safety of static electricity. General requirements
GOST 12.1.044-89 (ISO 4589-84) Occupational safety standards system. Fire and explosion hazard of substances and materials. Nomenclature of indicators and methods for their determination
GOST 12.4.010-75 Occupational safety standards system. Individual protection means. Mittens are special. Specifications
GOST 12.4.011-89 System of labor safety standards. Means of protection for workers. General requirements and classification
GOST 12.4.020-82 Occupational safety standards system. Personal protective equipment for hands. Nomenclature of quality indicators
GOST 12.4.021-75 System of labor safety standards. Ventilation systems. General requirements
GOST 12.4.034-2001 (EN 133-90) Occupational safety standards system. Personal respiratory protection. Classification and labeling
GOST 12.4.068-79 System of labor safety standards. Dermatological personal protective equipment. Classification and general requirements
GOST 12.4.103-83 Occupational safety standards system. Special protective clothing, personal protective equipment for legs and arms. Classification
GOST 12.4.111-82 System of labor safety standards. Man's suits for protection against oil and oil products. Specifications
GOST 12.4.112-82 Occupational safety standards system. Women's suits for protection against oil and oil products. Specifications
GOST 17.2.3.02-78 Nature protection. Atmosphere. Rules for establishing permissible emissions of harmful substances by industrial enterprises
GOST 33-2000 (ISO 3104-94) Oil products. Transparent and opaque liquids. Determination of kinematic viscosity and calculation of dynamic viscosity
GOST EN 116-2013 Domestic diesel and furnace fuels. Method for determining the limiting filterability temperature
GOST 1461-75 Oil and oil products. Method for determining the ash content
GOST 1510-84 Oil and oil products. Marking, packaging, transportation and storage
GOST 2070-82 Light petroleum products. Methods for determining iodine numbers and the content of unsaturated hydrocarbons
GOST ISO 2160-2013
GOST 2177-99 (ISO 3405-88) Oil products. Methods for determining the fractional composition
GOST 2517-2012 Oil and oil products. Sampling methods
GOST ISO 2719-2013 Oil products. Methods for determining the flash point in a Pensky-Martens closed cup
GOST 3122-67 Diesel fuels. Method for determining the cetane number
GOST ISO 3405-2013 Oil products. Method for determining the fractional composition at atmospheric pressure
GOST 5985-79 Petroleum products. Method for determining acidity and acid number
GOST 6307-75 Petroleum products. Method for determining the presence of water-soluble acids and alkalis
GOST 6321-92 (ISO 2160-85) Fuel for engines. Copper strip test method
GOST 6356-75 Petroleum products. Method for determining the flash point in a closed cup
GOST 17323-71 Fuel for engines. Method for determination of mercaptan and hydrogen sulfide sulfur by potentiometric titration
GOST 19121-73 Petroleum products. Method for determining the sulfur content by burning in a lamp
GOST 19433-88 Dangerous goods. Classification and labeling
GOST 19932-99 (ISO 6615-93) Oil products. Determination of coking by the Conradson method
GOST ISO 20846-2012 Oil products. Determination of sulfur content by ultraviolet fluorescence
GOST 22254-92 Diesel fuel. Method for determining the limiting filterability temperature on a cold filter
GOST 32139-2013 Oil and oil products. Determination of sulfur content by energy dispersive X-ray fluorescence spectrometry
GOST 32329-2013 Oil products. Determination of the corrosive effect on a copper plate
GOST 32392-2013 Petroleum products. Determination of coke residue by micromethod
GOST 32508-2013 Diesel fuels. Determination of cetane number
Note - When using this standard, it is advisable to check the validity of reference standards in the public information system - on the official website of the Federal Agency for Technical Regulation and Metrology on the Internet or according to the annual information index "National Standards", which was published as of January 1 of the current year, and on issues of the monthly information index "National Standards" for the current year. If the reference standard is replaced (modified), then when using this standard, you should be guided by the replacing (modified) standard. If the referenced standard is canceled without replacement, the provision in which the reference to it is given applies to the extent that this reference is not affected.
3 Classification
3.1 Depending on the conditions of use, fuel is divided into grades:
- L - summer, recommended for operation at an ambient temperature of minus 5 °C and above;
- E - off-season, recommended for operation at an ambient temperature of minus 15 ° C and above:
- Z - winter, recommended for operation at ambient temperatures up to minus 25 °С (limiting filterability temperature - not higher than minus 25 °С) and up to minus 35 °С (limiting filterability temperature - not higher than minus 35 °С);
- A - arctic, recommended for operation at an ambient temperature of minus 45 ° C and above.
4 Conventions
4.1 In the symbol of the fuel indicate:
- for brand L - flash point and ecological class of fuel.
An example of a symbol for diesel fuel grade L, with a flash point of 40 ° C, environmental class K2, according to GOST 305-2013:
DT-L-40-K2 GOST 305-2013 ;
For grade E - the maximum filterability temperature and the environmental class of the fuel.
An example of a symbol for diesel fuel grade E, with a filtering temperature of minus 15, environmental class K2, according to GOST 305-2013:
DT-E-minus 15-K2 GOST 305-2013 ;
For brand Z - the maximum filterability temperature and the environmental class of the fuel.
An example of a symbol for diesel fuel grade Z, with a filtering temperature of minus 25, environmental class K2, according to GOST 305-2013:
DT-Z-minus 25-K2 GOST 305-2013 ;
For brand A - ecological class of fuel.
An example of a symbol for diesel fuel grade A, environmental class K2, according to GOST 305-2013:
DT-A-K2 by GOST 305-2013 .
5 Technical requirements
5.1 Fuel must comply with the requirements of this standard and be produced according to an approved technology. Fuels must be produced according to the technology and with additives that were used in the manufacture of pilot industrial samples and were tested with positive results.
5.2 In terms of physicochemical and performance indicators, the fuel must meet the requirements specified in Table 1.
Table 1 - Fuel Requirements
Name of indicator | Brand value | Test method |
|||
1 Cetane number, not less than | |||||
2 Fractional composition: | |||||
for locomotive and marine diesel engines and gas turbines | |||||
for general purpose diesels | |||||
5 Mass fraction of sulfur, mg/kg, no more | |||||
6 Mass fraction of mercaptan sulfur, %, no more | |||||
7 Mass fraction of hydrogen sulfide | Absence | ||||
8 Copper strip test | Withstands. Class 1 | ||||
Absence | |||||
10 Acidity, mg KOH per 100 cm of fuel, not more than | |||||
11 Iodine number, g of iodine per 100 g of fuel, not more than | |||||
12 Ash content, %, no more | |||||
14 Total contamination, mg/kg, no more | According to the standard |
||||
According to the standard |
|||||
16 Density at 15 °С, kg/m, no more | |||||
17 Limiting filterability temperature, °С, not higher | Minus 5 | ||||
Minus 45 | |||||
Notes |
|||||
5.3 Fuel may contain dyes (except for green and blue colors) and labeling substances.
5.4 Fuel may contain additives that do not harm the life and health of citizens, the environment, the property of individuals and legal entities, the life and health of animals and plants.
The fuel must not contain metal-containing additives, with the exception of anti-static additives.
6 Precision of test methods
6.1 Precision is specified in the test methods referenced in this International Standard. In case of disagreement in evaluating test results, standards and should be used.
7 Safety requirements
7.1 Fuel is a low-hazard liquid and, according to the degree of impact on the human body, it belongs to the 4th hazard class in accordance with GOST 12.1.007.
7.2 Fuel irritates the mucous membrane and skin of a person, causing damage to it and the occurrence of skin diseases. Constant contact with fuel can cause acute inflammation and chronic eczema.
7.3 The maximum permissible concentration of vapors of aliphatic hydrocarbons in the air of the working area is 300 mg / m in accordance with the requirements of GOST 12.1.005.
Requirements for the maximum permissible concentrations (MPC) of fuel in the atmospheric air of populated areas, in the water of water bodies for drinking and domestic water use, in the soil and control of the concentration of harmful substances in the air of the working area are established in accordance with approved regulatory documents.
7.4 In accordance with GOST 12.1.044, fuel is a flammable liquid.
Explosive concentration of fuel vapors in a mixture with air - 2% vol. - 3% vol.
Self-ignition temperature of fuel grades L, E - 300 °C, grade Z - 310 °C, grade A - 330 °C; temperature limits of ignition:
- L, E - lower 69 °С, upper 119 °С.
- З - lower 62 °С, upper 105 °С;
- A - lower 57 °С, upper 100 °С.
7.5 When fuel ignites, the following fire extinguishing agents are used: sprayed water, foam; for volumetric quenching - carbon dioxide, compositions of SZhB and "3.5", superheated steam.
7.6 It is forbidden to use open fire in the premises for storage and use of fuel; electrical networks and artificial lighting must be explosion-proof.
When working with fuel, it is not allowed to use tools that give a spark when struck.
7.7 Tanks and pipelines intended for storage and transportation of fuel must be protected from static electricity in accordance with GOST 12.1.018.
7.8 When spilling fuel, it is necessary to collect it in a separate container, and wipe the spill site with a dry cloth; in case of a spill in an open area, the spill site must be filled with sand, followed by its removal and neutralization in accordance with the sanitary standards approved in the prescribed manner.
7.9 Premises for work with fuel must be equipped with mechanically actuated general exchange ventilation that meets the requirements of GOST 12.4.021. Places of intensive emission of fuel vapors must be equipped with local exhausts.
It is not allowed to store acids, oxygen cylinders and other oxidizers in fuel storage rooms.
7.10 When working with fuel, personal protective equipment is used in accordance with GOST 12.4.011, GOST 12.4.103, GOST 12.4.111, GOST 12.4.112 and standard industry standards approved in the prescribed manner.
In places with a concentration of fuel vapors exceeding the MPC, it is necessary to use filtering gas masks of the PFMG brand with a BKF box and hose gas masks of the PSh-1 brand or similar ones specified in GOST 12.4.034.
7.11 When working with fuel, it is necessary to observe the rules of personal hygiene.
7.12 If fuel gets into open areas of the body, remove it and wash the skin with plenty of warm soapy water; in case of contact with the mucous membrane of the eyes, it is necessary to rinse the eyes with plenty of warm water.
To protect the skin of the hands, special protective gloves are used according to GOST 12.4.010, ointments and pastes according to GOST 12.4.068, as well as personal protective equipment for hands according to GOST 12.4.020.
7.13 All those working with fuel must, in accordance with the established procedure, undergo preliminary (when hiring) and periodic medical examinations in accordance with established requirements.
8 Environmental requirements
8.1 In order to protect the atmospheric air from pollution by emissions of harmful substances, control over the content of maximum permissible emissions should be organized in accordance with GOST 17.2.3.02.
8.2 The main means of protecting the environment from the harmful effects of fuel are the use of sealed equipment in technological processes and operations related to the production, transportation, use and storage of fuel, as well as strict adherence to the technological regime.
8.3 During the production, storage and use of fuel, measures must be taken to prevent its entry into domestic and storm sewer systems, as well as into open water bodies and soil.
9 Acceptance rules
9.1 Fuel is accepted in batches. A batch is considered to be any quantity of a product manufactured in the course of a continuous technological process, according to the same technological documentation, homogeneous in terms of component composition and quality indicators, accompanied by one quality document (product passport) issued upon acceptance based on the test of the combined sample. The mass of the combined sample is 2 dm of fuel.
9.2 The product passport issued by the manufacturer must contain:
- name and brand of products;
- name of the manufacturer (person authorized by the manufacturer) or importer or seller, their location (indicating the country);
- the designation of this standard;
- normative values and actual test results confirming the compliance of the fuel with the requirements of this standard and technical regulations *;
_______________
- date of issue and passport number;
- signature of the person who issued the passport;
- information about the declaration of conformity (if any);
- information about the presence of additives in the fuel.
9.3 Accompanying documentation for a batch of fuel put into circulation is carried out in Russian and in the state language of the state - a member of the Customs Union, on the territory of which this batch will be in circulation.
9.4 When selling fuel, the seller is obliged to provide information about the name and brand of fuel, its compliance with the requirements of the technical regulation *.
_______________
* Valid on the territory of the countries - members of the Customs Union.
When retailing fuel, it is necessary to provide information on the name, brand of fuel, including the environmental class, which must be placed in places accessible to consumers, on fuel dispensing equipment, and also reflected in cash receipts.
At the request of the consumer, the seller is obliged to present a copy of the quality document (product passport) for fuel.
9.5 Upon receipt of unsatisfactory results of acceptance tests for at least one of the indicators given in Table 1, repeated tests are carried out on a sample again taken from the same batch. The retest results are final and apply to the entire lot.
9.6 Indicators 9-13 of Table 1 are guaranteed by the production technology and are determined once a quarter.
Upon receipt of unsatisfactory results of periodic tests for at least one of the indicated indicators, the tests are transferred to the acceptance category and tests are carried out for this indicator until positive results are obtained on at least two batches in a row.
10 Test methods
10.1 Sampling - according to GOST 2517 or according to standards,.
10.2 In case of disagreement in assessing the quality of the fuel, the test method given in Table 1 first should be used.
11 Marking, transport and storage
11.1 Marking, transportation and storage of fuel - in accordance with GOST 1510.
11.2 The consignor applies a marking characterizing the transport hazard of fuels, according to the rules - and GOST 19433: class - 3; subclass - 3.3; danger sign - 3; classification code - 3313; UN number - 1202, emergency card - 315.
11.3 Transportation is carried out by rail and road tanks or tankers.
11.4 Fuel storage - according to GOST 1510.
12 Manufacturer's warranties
12.1 The manufacturer guarantees that the fuel meets the requirements of this standard, subject to the conditions of transportation and storage.
12.2 Guaranteed shelf life of diesel fuel - 5 years from the date of manufacture.
Annex A (informative). Classification of product groups on the territory of the Russian Federation according to the All-Russian Classification of Products (OKP)
Annex A
(reference)
Table A.1
Fuel grade | OKP for fuel with sulfur content not more than | ||||
500 mg/kg | |||||
L (summer) | |||||
E (off-season) | |||||
W (winter) | |||||
A (Arctic) | |||||
Notes | |||||
Bibliography
Petroleum products are liquid. Medium distillate fuels. Method for Determination of Ignition Delay and Produced Cetane Number (DCN) by Constant Volume Combustion | ||||||
Oil products. Determination of the flammability of diesel fuel. Determination of cetane number by motor method | ||||||
EN ISO 5165:1998* | Oil products. Determination of the flammability of diesel fuels. Cetane number method using engine | |||||
(EN ISO 5165:1998) | (Petroleum products - Determination of the ignition quality of diesel fuels - Cetane engine method) | |||||
________________ | ||||||
Liquid petroleum products. Determination of Ignition Delay and Derived Cetane Number (DCN) of Middle Distillates by Constant Volume Combustion | ||||||
(Liquid petroleum products - Determination of ignition delay and derived cetane number (DCN) of middle distillate fuels by combustion in a constant volume chamber) | ||||||
EN ISO 3104:1996 | Oil products. Transparent and opaque liquids. Determination of kinematic viscosity and calculation of dynamic viscosity | |||||
(EN ISO 3104:1996) | (Petroleum products - Transparent and opaque liquids - Determination of kinematic viscosity and calculation of dynamic viscosity) | |||||
ASTM D 445-12 | Standard Method for Determining the Kinematic Viscosity of Transparent and Opaque Liquids (Dynamic Viscosity Calculation) | |||||
Oil and oil products. Determination of sulfur by energy dispersive X-ray fluorescence spectrometry | ||||||
Oil products. Determination of sulfur content by wavelength dispersive X-ray fluorescence spectrometry | ||||||
ST RK ISO 8754:2003* | ||||||
________________ | ||||||
EN ISO 8754:2003 | Oil products. Determination of sulfur content. X-ray fluorescence spectrometry based on the energy dispersion method | |||||
(EN ISO 8754:2003) | (Petroleum products - Determination of sulfur content - Energy-dispersive X-ray fluorescence spectrometry) | |||||
EN ISO 14596:2007 | Oil products. Determination of sulfur content. Method of long-wavelength dispersive X-ray fluorescence spectrometry | |||||
(EN ISO 14596:2007) | (Petroleum products - Determination of sulfur content - Wavelength-dispersive X-ray fluorescence spectrometry) | |||||
Oil products. Determination of sulfur content in automotive fuels by X-ray fluorescence energy dispersive spectrometry | ||||||
EN ISO 20847:2004 | Oil products. Determination of sulfur content in fuels for internal combustion engines. X-ray fluorescence spectrometry method with energy dispersion | |||||
(EN ISO 20847:2004) | (Petroleum products - Determination of sulfur content of automotive fuels - Energy-dispersive X-ray fluorescence spectrometry) | |||||
EN ISO 6245:2002 | Oil products. Determination of ash content | |||||
(EN ISO 6245:2002) | (Petroleum products - Determination of ash) | |||||
ASTM D 482-13 | Standard Test Method for Ash Content in Petroleum Products | |||||
(Standard test method for ash from petroleum products) | ||||||
Liquid petroleum products. Determination of impurities in middle distillates | ||||||
(Liquid petroleum products - Determination of contamination in middle distillates) | ||||||
EN ISO 12937:2000 | Oil products. Definition of water. Coulometric Karl Fischer titration method | |||||
(EN ISO 12937:2000) | (Petroleum products - Determination of water - Coulometric Karl Fischer titration method) | Crude oil and liquid petroleum products. Laboratory method for determining density using a hydrometer | ||||
EH ISO 12185:1996 | Crude oil and oil products. Determination of density. Oscillatory method in a U-tube | |||||
(EN ISO 12185:1996) | (Crude petroleum and petroleum products - Determination of density - Oscillating U-tube method) | |||||
ASTM D 1298-12 | Standard Test Method for Density, Relative Density (Specific Gravity), or API Density of Crude Petroleum and Liquid Petroleum Products by Hydrometer | |||||
(ASTM D 1298-12) | (Standard test method for density, relative density or API gravity of crude petroleum and liquid petroleum products by hydrometer method) | |||||
Standard Method for Determining Density and Relative Density Using a Digital Density Meter | ||||||
(ASTM D 4052-11) | (Standard test method for density, relative density, and API gravity of liquids by digital density meter) | |||||
State system for ensuring the uniformity of measurements. Definition and application of indicators of precision of test methods for petroleum products | ||||||
EH ISO 4259:2006 | Oil products. Definition and application of test method precision measures | |||||
(EN ISO 4259:2006) | (Petroleum products - Determination and application of precision data in relation to methods of test) | |||||
Technical regulation of the Customs Union TR CU 013/2011 | On requirements for automobile and aviation gasoline, diesel and marine fuel, jet fuel and fuel oil (approved by the decision of the Customs Union Commission dated October 18, 2011 N 826) | |||||
ISO 3170:2004 | Petroleum products are liquid. Manual sampling | |||||
(ISO 3170:2004) | (Petroleum liquids - Manual sampling) | |||||
EN ISO 3171:1999 | Petroleum products are liquid. Automatic sampling from the pipeline | |||||
(EN ISO 3171:1999) | (Petroleum liquids - Automatic pipeline sampling) | |||||
UDC 665.753.4:006.354 MKS 75.160.20
Keywords: diesel fuel, specifications
____________________________________________________________________________________
Electronic text of the document
prepared by Kodeks JSC and verified against:
official publication
M.: Standartinform, 2014
(No. 8 for 2010)
Vladimir SHLYAKHOVOY
Sulfur
Diesel fuel is characterized by a number of rather important parameters, and one of the main among them is the sulfur content. Theoretically, the presence of sulfur improves the lubricity of the fuel, but this is nothing compared to the problems that arise when it is burned during engine operation. The resulting sulfur oxides react with water vapor to form sulfuric and sulphurous acids, which in one quantity or another necessarily enter the engine lubrication system. But, besides, what kind of "Euro" can we talk about if sulfuric acid vapors are pouring out of the exhaust pipe? Yes, and exhaust gas aftertreatment systems, and particulate filters, when using sulphurous fuel, quickly fail. Therefore, along with the growth of requirements for the purity of exhaust gases, the requirements for fuel quality also naturally grow. Including the content of sulfur in it.
For example, in accordance with the current standards, the type of fuel must be indicated depending on the sulfur content in it. In Russia, since 2005, the GOST R 52368-2005 (EN 590:2004) standard has been in force. Fuel diesel EURO. Specifications”, and in Ukraine from January 1, 2008 a similar standard DSTU 4840:2007 “Diesel fuel of improved quality. Specifications”, corresponding to the same standard EN 590:2004. However, DSTU 3858-99 “Diesel fuel. Specifications”, which replaced GOST 305-82 in Ukraine from September 1, 1999, has not yet been canceled, it will operate along with DSTU 4840:2007 until the end of 2010.
Table 1. Cetane number and maximum sulfur content in diesel fuels of various types, mg/kg, depending on the standard
|
Characteristic |
DSTU 3868-99 |
GOST R 52368-2005 |
DSTU 4840:2007 |
|
cetane number |
|||
*Fuel with a sulfur content of not more than 10 mg / kg in the accompanying documents may be designated as "sulfur-free" .
Table. 2 Cetane number and maximum sulfur content in diesel fuels of various environmental norms and standards
|
cetane number |
Sulfur, mg/kg |
|
|
DSTU 3868-99** |
||
|
GOST R 52368-2005* |
||
|
EN 590 (up to 1.01.2005) |
||
|
DSTU 4840:2007** |
||
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EN 590 (from 1.01.2005) |
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*Standard valid in Russia.
**Standards in force in Ukraine.
Thus, in Ukraine it is now possible to refuel with equal success both with diesel fuel of the Euro-5 level, containing sulfur in an amount of 10 mg / kg, and with “Soviet” diesel fuel, in which the concentration of sulfur is 500 (!) times higher.
Frost resistance
Perhaps the second most important parameter of diesel fuel is its frost resistance, which is inversely proportional to the amount of paraffins in it. When the temperature drops, paraffins tend to crystallize, as a result of which diesel fuel first becomes cloudy, then turns into “jelly”, and then completely freezes. Therefore, the integral characteristics of diesel fuel are its parameters such as cloud point and limiting filterability temperature, which are specific for each type of diesel fuel and are separated from each other by about 10 ºС.
At the same time, both of the above parameters are rather conditional, and therefore one should not think that cloudy fuel can be used painlessly. Especially if the fuel filters are not heated. Indeed, in this case, their filter elements will very quickly become tightly clogged with paraffin, which cannot be removed by anything. We will keep silent about the fact that in such a case further operation of the engine is in principle impossible. And to solve the problem, you will have to change very expensive filter elements.
The reason for the cloudiness of diesel fuel is the appearance of groups of oriented paraffin molecules, which become centers for the formation of crystals. At the same time, the minimum allowable temperature for the use of diesel fuel, at which its normal pumpability through the fuel system through the filter elements is ensured, is at least 2 ºС higher than its cloud point.
As for such a concept as "limiting diesel fuel filterability temperature", it means the limit at which cooled diesel fuel is able to pass through a standard filter element at a certain speed. This indicator is used only to determine the possibility of starting the engine. But if unheated fuel filters are used in this case, they will immediately be blocked by paraffin.
To this we can add that such a parameter as the “pour point of diesel fuel” is also normalized, the cause of which is the coalescence of hydrocarbon crystals to each other into a rigid crystal lattice. The pour point determines the possibility of transporting, refueling, draining and pouring diesel fuel into tanks and has no practical significance for determining the possibility of starting the engine or its operation.
And in order to be able to easily determine in what temperature ranges one or another diesel fuel can be used, according to the requirements of the standards, its symbol must indicate the grade (depending on the values of the limiting filterability temperature, or class), determined by both the filterability temperature and the temperature turbidity.
In this case, the grade is set for fuel intended for use in areas with a temperate climate, and the grade is set for the arctic zones.
Table 3. Requirements for low-temperature properties of diesel fuel (GOST R 52368-2005)
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Name of indicator |
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Limiting filterability temperature, ºС, not higher |
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Cloud point, ºС, not higher |
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Cetane number, not less than |
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* N / N - not standardized.
At the same time, Ukrainian DSTU 4840:2007 provides for the same six grades (A-F), but only two classes (0-1) of diesel fuel, as GOST R 52368-2005, regulates a lower sulfur content and a higher cetane number (at least 51 ). Whereas DSTU 3868-99, which will be valid in Ukraine until 01/01/2011, provides for only two grades of diesel fuel: L - summer and Z - winter.
Table 4. Requirements of DSTU 3868-99 for low-temperature properties of diesel fuel
In this regard, diesel fuel can be labeled as follows:
- "Diesel fuel EURO according to GOST R 52368-2005 (EN 590:2004), grade A, type I";
- "Diesel fuel of high quality (Euro) class 1, type II in accordance with DSTU 4840:2007".
In a word, it is quite difficult to understand all this variety of varieties, classes and types of diesel fuel. Theoretically, kerosene can be used as a substitute for winter and arctic diesel fuel for diesel engines. But in practice this cannot be done, since kerosene has two significant drawbacks. Firstly, its cetane number is about 40, which is too low for normal engine operation. And secondly, kerosene, unlike diesel fuel, does not have lubricating properties, so all rubbing parts in the fuel system (high-pressure fuel pump, plunger pairs, etc.) will quickly become unusable.
This is allowed only in exceptional cases and only as a temporary remedy, especially on older engines with a mechanical injection pump. But even in this case, it is necessary to introduce anti-wear and cetane-boosting additives. It is believed that without damage to the engine, up to 20% of kerosene can be added to summer diesel fuel to reduce its pour point. But this, too, should be considered only as an extreme measure, unacceptable on modern engines with high injection pressure.
cetane number
An important indicator for diesel fuel is the cetane number (CN), which characterizes the flammability rate of the fuel - from the moment it is injected into the cylinder to the start of combustion (the self-ignition delay period). And the higher the CC, the faster the diesel fuel ignites.
The numerical value of the CN is equal to the percentage of cetane (C16H34, the CN of which is taken as 100) in its mixture with α-methylnaphthalene (its cetane number is 0), the flammability of which is equivalent to the tested diesel fuel. In this case, the CC is determined by testing on a motor installation.
With a cetane number of less than 40, due to the long ignition delay period, the fuel in the cylinder has time to warm up well, so the ignition is explosive, the pressure in the cylinder rises sharply, which leads to knocks in the engine. This operation of a diesel engine is called rigid, since it causes shock loads on the piston and crankshaft bearings, which leads to their accelerated wear.
The higher the cetane number, the shorter the ignition delay, the smoother the fuel mixture burns, the smoother the engine runs and the more environmentally friendly the exhaust. But it's good up to certain limits. Diesel fuel with a CC above 55, which has a short self-ignition delay period, having entered the cylinder, does not have time to warm up well, so the pressure in the cylinder increases evenly and the engine runs smoothly. However, in this case, the mixture formation process deteriorates, since the fuel does not have time to mix well with air, which leads to incomplete combustion of the fuel, a decrease in engine power and efficiency, and an increase in exhaust smoke. In addition, diesel fuel with a high CN is much more expensive. Therefore, unlike the octane number, which the higher the better, the cetane number has its own operating range of 40 - 55 units, the optimum of which is 51 - 53 units.
At the same time, standard diesel fuel is characterized by a cetane number of 40 - 45, and top-quality fuel has a cetane number of 51 - 55. According to modern standards, the CN of summer and winter diesel fuel should be at least 49 units. (According to the EN 590:2004 standard, the CN must be at least 51, and the cetane index (the same, but determined by calculation) must be at least 46.)
To this we can add that the cetane number indirectly indicates the low-temperature characteristics of the fuel - the lower it is, the lower the pour point. Therefore, summer and winter diesel fuels usually have different CNs, and for Arctic diesel fuel, it is completely on the verge of hard engine operation. But here the soft work of a diesel engine is often deliberately sacrificed in order to ensure its normal start-up and fuel pumpability through filters in severe frosts. At the same time, high quality diesel fuel is lighter, contains more flammable light fractions and is therefore more suitable for starting the engine in cold weather. In addition, the ratio of hydrogen to carbon in light fractions is higher, so less smoke is generated during the combustion of such diesel fuel.
Coking capacity, ash content and others…
Other standardized parameters of diesel fuel include its coking capacity, which contributes to the formation of deposits in the combustion chamber and on piston rings, and the ash content, which determines the non-combustible fuel residue. Thus, the coking capacity of the ten percent residue remaining after distillation of the volatile fractions of diesel fuel should be within 0.3%, and the ash content should not exceed 0.01%, while according to the previous standards, this value was ten times higher.
As for various additives, they are usually added industrially only to special grades of diesel fuel, primarily to the Arctic. Although sometimes manufacturers throw special grades of fuel onto the market.
These include, for example, Shell V-Power Diesel.
For the first time this fuel was presented in Italy in 2002. And now it has appeared in Ukraine. At the same time, neither Russian nor Belarusian drivers can yet refuel with such fuel, despite the fact that Shell came to Russia much earlier than to Ukraine. In Belarus, there are no Shell gas stations at all.
The new fuel is produced on the basis of Eurodiesel, which meets Euro-4 (type II) standards, with the addition of a special detergent additive NEMO 2010. At the same time, as the manufacturer declares, the composition of Shell V-Power Diesel helps to remove existing deposits and prevents the formation of new deposits in combustion chamber of the engine, which contributes to the extension of its resource, stable power and improvement of environmental parameters. This fuel contains no more than 0.05% (50 mg / kg) of sulfur, but it also costs the same as AI-95.
According to Shell representatives, a run of 2400 km on Shell V-Power Diesel fuel is enough to almost completely clean the combustion chamber and injector. Naturally, the benefits of this fuel can be most pronounced when used on used cars, while on new cars the difference will not be noticeable.
diesel fuel divided into the following brands:- summer- used at an air temperature not lower than 0°C and has in its designation the amount of sulfur and the flash point, for example, L-0.2-40;
- winter- it is used at temperatures not lower than -20°C and has in the designation the amount of sulfur and the pour point, for example, Z-0.05 (-25°C);
- arctic- it is used up to -50°С, has in the designation the amount of sulfur and the pour point, for example, A-0.05 (-50°С).
At present, the above USSR standard is outdated, but the old diesel fuel designations can still be found in consumer requests.
In the European Union in 1993, the EN 590 standard (originally Euro-1) was introduced, which has undergone 4 modifications. Currently, the European standard EN 590-2009, aka EURO-5, is in effect. These standards classify diesel fuel according to temperature and climatic zones of application: Class A - F for temperatures from +5 to -20 °С, Class 0 - 4 for temperatures from -20 to -44 °С.
In Russia when leaving the Soviet standard, they initially decided to switch to the European classification system. Since 2005, a new state standard for diesel fuel has been in force in the Russian Federation - GOST R 52368-2005. It fully complies with the EN 590 specification. According to the new standard, the sulfur content in diesel fuel is limited, namely:
- species I- sulfur content is not more than 350 mg/kg;
- view II- sulfur content is not more than 50 mg/kg;
- view III- sulfur content is not more than 10 mg/kg.
The new GOST considers diesel fuel separately, depending on the climatic conditions of the area where it is used. For temperate regions diesel fuel is divided into grades, which indicate the limiting filterability temperature:
- Grade A(+5 °C)
- Grade B(0 °C)
- Grade C(-5 °C)
- Grade D(-10 °C)
- Grade E(-15 °C)
- Grade F(-20 °С)
And for cold climates diesel fuel is divided into classes with limiting filterability temperature:
- Class 0(-20 °С)
- Class 1(-26 °C)
- Class 2(-32 °С)
- Class 3(-38 °C)
- Class 4(-44 °C)
It should be noted that at present (2014) the use of diesel fuel of environmental class K2, starting from January 01, 2015, class K3 fuel is being withdrawn from circulation, and from January 1, 2016, the production and circulation of diesel fuel of an environmental class of at least K5 is allowed in the Russian Federation.
From July 1, 2014, GOST R 55475-2013 "Dewaxed Winter and Arctic Diesel Fuel" will be put into effect in Russia. This fuel is produced using a modern method of catalytic dewaxing. In accordance with GOST, diesel fuel for regions with a cold climate is designated as follows:
- DT-Z-K3(K4, K5) minus 32;
- DT-Z-K3(K4, K5) minus 38;
- DT-A-K3(K4, K5) minus 44;
- DT-A-K3(K4, K5) minus 48;
- DT-A-K3(K4, K5) minus 52.
At the same time, the production and use of diesel fuel in accordance with GOST R 52368-2005 is not limited.
As can be seen, at diesel fuel classification 2 main parameters of diesel fuel are used: sulfur content and filterability temperature. Meanwhile, diesel fuel is characterized by a large number of indicators, some of which are given in quality certificates for the released batch of fuel.
The constant improvement of technology and the tightening of environmental standards lead to increased requirements for fuel quality . Much attention is paid sulfur content in petroleum products and oil. This parameter is necessarily reflected in the quality passport.
Sulfur impurities are present in any grade of oil and in all oil products, ranging from 0,05 before 6% from the total mass. Sulfur compounds are unevenly distributed over all fractions, being present even in deeply purified distillates. High sulfur content in fuel is undesirable for many reasons:
- sulfur is toxic and causes an unpleasant smell of petroleum products,
- reduces the resistance of gasoline to detonation,
- provokes increased resin formation during cracking,
- increases corrosivity,
- vapors of sulfur compounds irritate the human respiratory tract and worsen the condition of plants.
However, it is not yet possible to completely eliminate sulfur from fuel. For example, if the sulfur content in diesel fuel is below 0.035%, then its lubricity significantly deteriorates, which leads to accelerated wear of the elements of the fuel system of the car. To prevent this, additives are added to diesel fuel that improve lubricating properties. But they are still inaccessible, since mass production has not yet been established. The only way out is to reduce the amount of sulfur in oil products by setting strict standards.
Sulfur oil classification
GOST R 51858-2002 determines oil classes by sulfur content:
- Class 1 - low sulfur - sulfur in the total mass of 0.6%.
- Class 2 - sulfurous - sulfur in the total mass up to 1.8%.
- Class 3 - high sulfur - sulfur in the total mass up to 3.5%.
- Class 4 - especially high sulfur - sulfur in the total mass is above 3.5%.
Oil usually contains pure sulfur (not much) and its derivatives. IN quality passport the proportion of total sulfur is indicated (pure sulfur + sulfur-containing impurities). The higher the sulfur content in oil, the lower its cost.
The main share of sulfur compounds (50-80%) in oil products are almost neutral sulfides and disulfides. The most "unpleasant" of the sulfur derivatives are mercaptans. It is they who cause a pungent odor and more than others provoke corrosion and the formation of resins. The content of mercaptans is limited to a few hundredths of a percent depending on the type of fuel and is indicated separately in the quality certificate.
Sulfur content standards for different types of fuel
Sulfur content standards are set for all types of fuel. The most stringent requirements apply to motor gasoline And jet fuel. Permissible sulfur content in them is from 0.02 to 0.1%. The same requirements apply to gasoline-solvents.
Diesel fuel in terms of sulfur content is divided into environmental classes. Today in Russia it is allowed to issue and use only Euro-5 diesel fuel with sulfur content less than 10 mg/kg.
How to reduce sulfur
Sulfur removal from fuel is carried out at refineries in two ways:
Previously, oil is passed through filters to free it from mechanical impurities. And then it is processed by catalytic hydrogenation at high temperature. The cost of sweet oil is about twice as high as the cost of the initial raw material, but in this way it is possible to obtain oil with a sulfur content of up to 1%.
The second method involves the removal of sulfur from part of the heavy oil fractions using vacuum distillation. These fractions are then subjected to hydrogenation with hydrogen. The obtained sulfur-free raw material is mixed with the bulk, and the total sulfur content is reduced by 80-95%.
