1、BSI Standards PublicationPD CEN/TR 16680:2014Liquid petroleum products Investigation on internaldiesel injector sticking depositsmechanisms and the impacts ofcorrosion inhibitorsPD CEN/TR 16680:2014 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation of CEN/TR16680:20
2、14.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/2, Liquid Fuels.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are respon
3、sible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 84015 9ICS 75.160.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under the authority of theStandards
4、 Policy and Strategy Committee on 30 April 2014.Amendments issued since publicationDate Text affectedPD CEN/TR 16680:2014TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 16680 February 2014 ICS 75.160.20 English Version Liquid petroleum products - Investigation on internal diesel inject
5、or sticking deposits mechanisms and the impacts of corrosion inhibitors Flssige Minerallerzeugnisse - Untersuchung der Mechanismen fr die Bildung von Ablagerungen in Dieselinjektionsvorrichtungen und der Auswirkung von Korrosionsinhibitoren This Technical Report was approved by CEN on 23 December 20
6、13. It has been drawn up by the Technical Committee CEN/TC 19. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, La
7、tvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Ma
8、rnix 17, B-1000 Brussels 2014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 16680:2014 EPD CEN/TR 16680:2014CEN/TR 16680:2014 (E) 2 Contents page Foreword 3 1 Scope 4 2 Normative references 4 3 Symbols and abbreviations 4 4 S
9、ummary . 5 5 Description of injector sticking problems . 5 6 FIEM/OEM experience . 6 7 Changes influencing internal injector deposits . 7 8 Deposit forming mechanism 7 9 Potential sources of sodium in diesel fuel 8 10 Corrosion inhibitors 9 11 Investigations in France 9 12 Investigations in Spain 12
10、 13 Investigations in Denmark 14 14 Conclusions . 15 15 Future work 16 Bibliography 17 PD CEN/TR 16680:2014CEN/TR 16680:2014 (E) 3 Foreword This document (CEN/TR 16680:2014) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, sy
11、nthetic and biological origin”, the secretariat of which is held by NEN. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. PD CEN/TR 166
12、80:2014CEN/TR 16680:2014 (E) 4 1 Scope This Technical Report describes the investigation into diesel vehicle common rail fuel injector sticking problems in a number of countries across Europe since 2005/2006, carried out by the CEN/TC 19/WG 24/IDID Task Force. It provides conclusions following this
13、work that have been adopted by CEN. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the refe
14、renced document (including any amendments) applies. EN 590, Automotive fuels - Diesel - Requirements and test methods 3 Symbols and abbreviations For the purposes of this document, the following symbols and abbreviations apply. Abbreviation Meaning AGQM Arbeitsgemeinschaft Qualitatsmanagement Biodie
15、sel ACEA Association des Constructeurs Europens dAutomobiles (European Automobile Manufacturers Association) BNPe Bureau de Normalization au service des metiers du Petrole B7 7 % (V/V) blend of biodiesel (FAME) with diesel fuel meeting the requirements of EN 590 B30 30 % (V/V) blend of biodiesel (FA
16、ME) with diesel fuel meeting the requirements of EN 590 CEC Coordinating European Council CEN Comit Europen de Normalization (European Committee for Standardization) CONCAWE CONservation of Clean Air and Water in Europe CRC Coordinating Research Council DDSA Dodecenyls Succinic Acid EN European Norm
17、 FAME Fatty Acid Methyl Ester FIEM Fuel Injection Equipment Manufacturer FTIR Fourier Transform Infra-Red HDSA Hexadecenyl Succinic Acid ICP-AES Inductively Coupled Plasma Atomic Emission Spectroscopy ICP-OES Inductively Coupled Plasma Optical Emission Spectroscopy ICP-MS Inductively Coupled Plasma
18、Mass Spectroscopy IDID Internal Diesel Injector Deposits MIL Malfunction Indicator Light Na Sodium OEM Original Equipment Manufacturer SPMR Societe du Pipeline Mediterranee Rhone TRAPIL Societe Des Transports Petroliers Par Pipeline UFIP Union Francaise des Industries Petrolieres PD CEN/TR 16680:201
19、4CEN/TR 16680:2014 (E) 5 Abbreviation Meaning WDXRF Wavelength-Dispersive X-Ray Fluorescence WG Working Group 4 Summary At the CEN/TC 19/WG 24, Distillate fuels, meeting on 24 May 2011 in Krakow, Poland there were strong technical representations from the Vehicle Manufacturers (ACEA) and Fuel Inject
20、ion Equipment suppliers describing serious vehicle fuel injector sticking problems in a number of countries across Europe since 2005/2006. The worst affected country was France although sporadic problems had been reported in Denmark, Germany and Spain in recent years. As a result of these diesel veh
21、icle common rail injector sticking field problems WG 24 recommended and CEN/TC 19 endorsed the formation of an ad hoc task force under the leadership of the WG 24 convenor to urgently investigate the injector sticking issue and provide feedback to WG 24 on a monthly basis. 5 Description of injector
22、sticking problems Traditional external “coking” deposits form inside and around nozzle fuel flow holes on the outside tip of injector and are caused by combustion heat and gases, interacting with diesel fuel and engine lubricant components. These deposits can affect the fuel spray pattern and volume
23、 of fuel delivered to each cylinder. In the injector sticking case, two new types of internal injector deposits have been reported by vehicle manufacturers and FIE manufacturers, these two new types of internal injector deposits can also be found together (salt crystals inside a polymeric matrix), s
24、ee Figure 1: Carboxylate soaps and salt deposits - typically soft, white/tan crystalline deposit; Organic amide deposits - lacquer, polymeric in nature, typically hard, tan/orange/brown deposit. Deposits form on inner component surfaces of the injector restricting fuel flow by reducing armature lift
25、 and affecting injection timing and fuel volume delivery by armature and injector needle sluggishness and sticking (see also Figure 2). Both Solenoid and Piezo actuated injectors were affected. Smaller component clearances due to increasing injection pressure and highly sophisticated injection profi
26、les required to meet increasingly challenging emission targets make injection technologies more sensitive to IDID formation than previous generations of direct injectors. Figure 1 Types of injector deposits (courtesy PSA) PD CEN/TR 16680:2014CEN/TR 16680:2014 (E) 6 An increased rate of injector stic
27、king cases was reported in wintertime. Fuel Injection Equipment Manufacturers (FIEM) manufacturers believe the formation of the soaps continues all year round but that deterioration of fuel injector performance is likely to be more apparent to vehicle drivers under cold starting and operating condit
28、ions where deviations in precise control of the fuel injection becomes much a more perceptible phenomenon . The IDID Task Force agreed to focus on the carboxylate soap deposits initially as these appeared to be the most serious and independent of the Amide deposit issue which was thought to be relat
29、ed to performance additive detergent (PIBSI). It should be noted however that the amide deposits contribute to the overall level of deposits increasing the likelihood of an injector malfunction or even sticking failure. Key injector needle (left):- aubern and white crystalline deposits armature/sole
30、noid (middle and right): golden brown paste like deposit Figure 2 Example of caboxylate injector deposits (courtesy Daimler) 6 FIEM/OEM experience Problems with injector sticking reported in specific geographic areas: France was the most affected country followed by Denmark and Spain, with occasiona
31、l issues in Germany. A higher number of injector sticking cases were reported in the northern part of France. The injector sticking issues in Denmark were however believed to be related to the use of a specific corrosion inhibitor additive - Dodecenyl Succinic Acid (DDSA). Prior to 2003, no injector
32、 sticking problems had been reported in France. ACEA experts reported that all OEMs are affected to some extent and that injector sticking failures are not just restricted to Europe as most major US manufacturers of both on and off highway equipment applications with common rail systems have also re
33、ported injector sticking failures. The US failures were primarily with heavy duty engines as there are relatively few light duty diesel vehicles in the US vehicle parc. The Coordinating Research Council (CRC) Diesel Performance Committee diesel deposits panel have formed a technical group to investi
34、gate injector sticking in cooperation with the Engine Manufacturers Association (EMA). In general vehicles covering higher mileages such as taxis and delivery vans are affected the most. Reported injector sticking symptoms include: loss of power and acceleration poor idle stability increased diesel
35、knock misfire - especially during cold condition difficulty in starting particularly in cold conditions rough running PD CEN/TR 16680:2014CEN/TR 16680:2014 (E) 7 Malfunction Indicator Light (MIL) illuminated in some cases major drivability concern and in extreme cases - no engine start emission dete
36、rioration and non-compliance with long-term emission requirements Problems seem to increase with higher biodiesel content but are not always restricted to biodiesel blends. However fleets running B30 in France have not experienced any problems although this could be due to the increased solvency of
37、the B30 from the higher level of FAME. Problems have also occurred under high load/high rpm conditions on engine test benches but only with EN 590 diesel fuel with a biodiesel content of at least 5 % v/v. The first indications of similar problems under real driving conditions for passenger cars and
38、medium/heavy duty vehicles driving more frequently at the high load/high rpm conditions occur after a mileage of 50.000 km to 100.000 km. Injectors retrieved from field vehicles show an accumulation of deposits over time exceeding a tolerable level, particularly when additional deposit material from
39、 fuel contamination or by additive compatibility issues is also taken into account. Problems were experienced with light commercial vans in France during 2010/11 timeframe, with a regional distribution of cases (Alsace Lorraine) in western France and also cases of taxi vehicles in Denmark 2010/2011.
40、 A large number of technical papers have been published by the industry describing research into injector sticking and references are provided in the Bibliography of this report. 7 Changes influencing internal injector deposits A number of changes in vehicle and fuel quality requirements are believe
41、d to be responsible for internal injector deposits: More stringent Euro IV and V vehicle emissions standards requiring high pressure (1800 bar) fuel injection pressures and hence very small internal injector clearances, increased operating temperatures and more sophisticated injection profile; Sulfu
42、r free diesel with lower aromatic levels, resulting in reduced natural fuel solvency for polar compounds; Increased biodiesel blending up to 7 % FAME provides an additional source of sodium and weak acids (fatty acids). 8 Deposit forming mechanism Common rail internal injector deposit analysis condu
43、cted by FIEM/OEM and fuel/additive companies confirmed the presence of carboxylate soap/salts and organic amide (see Figures 3 and 4). Figure 3 shows a typical spectrum from FTIR analysis of the deposits detected carboxylate (major peaks) and organic amide functionality on injectors returned to Ford
44、 from the French market. PD CEN/TR 16680:2014CEN/TR 16680:2014 (E) 8 Figure 3 FTIR analysis of injector deposits from the French market (data courtesy Ford) Figure 4 FTIR analysis of injector deposits (data courtesy Afton Chemical Ltd) There are a number of mechanisms that can result in the formatio
45、n of carboxylate salts and soaps as well as organic amide deposits: a) Carboxylates can be sodium salts of DDS acid (Dodecenyl Succinic) and HDS acid (Hexadecenyl Succinic) corrosion inhibitors. b) Carboxylates can be sodium salts of fatty acids. c) Carboxylates can be sodium salts of low molecular
46、weight PIBSA/PIBSI based materials. d) Sodium hydroxide (caustic, NaOH) can react with fatty acids in biodiesel and acidic lubricity additives to form fatty acid salts. Also corrosion inhibitors can contain sodium e.g. sodium nitrite/sodium hydroxide. Caustic is very aggressive, forming insoluble sa
47、lts with biodiesel and most lubricity additives, including ester types. It is very likely that the carboxylate sodium soap deposits are formed by a reaction between sodium in the fuel and weak acids from biodiesel and/or corrosion inhibitors. 9 Potential sources of sodium in diesel fuel There are a
48、number of potential sources of sodium in diesel fuel: refinery salt driers (sodium chloride); PD CEN/TR 16680:2014CEN/TR 16680:2014 (E) 9 biodiesel blending (sodium hydroxide catalyst, sodium methanolate, neutralization with hydrochloric acid forming sodium chloride), although controlled by limit se
49、tting in EN 14214; refinery processing units (Merox desulphurisation process in the refinery with sodium hydroxide); refinery process additives (corrosion inhibitors); import terminal salt driers; contamination from sea water due to logistics systems (ballast water, sea water); airborne sodium in coastal locations (sea salt); pipeline corrosion inhibitors such as sodium nitrite, caustic (sodium hydroxide), soda; other additives - biocide? Oil industry experience reported by Concawe experts confirms that sodium levels
