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M85、M100车用甲醇燃料1范围本标准规定了用于装有甲醇发动机的汽车、甲醇／汽油灵活燃料汽车或经过一定改装的汽车的M85、M100车用甲醇燃料的术语和定义、要求、试验方法、检验规则及标志、包装、运输、贮存和安全。
本标准适用于山西省内M85、M100车用甲醇燃料的生产和检验。
2规范性引用文件下列文件中的条款通过本标准的引用而成为本标准的条款。
凡是注日期的引用文件，其随后所有的修改单（不包括勘误的内容）或修订版均不适用于本标准，然而，鼓励根据本标准达成协议的各方研究是否可使用这些文件的最新版本。
凡是不注日期的引用文件，其最新版本适用于本标准。
GB190危险货物包装标志GB338工业用甲醇GB/T380石油产品硫含量测定法（燃灯法）GB/T4472化工产品密度、相对密度测定通则GB/T6283化工产品中水分含量的测定卡尔·费休法（通用方法）〔GB/T6283-1986，eqv ISO 760:1978〕GB/T6682分析实验室用水规格和试验方法GB/T6680液体化工产品采样通则GB/T8017石油产品蒸气压测定法（雷德法）GB/T8019车用汽油和航空燃料实际胶质测定法（喷射蒸发法）GB/T8020汽油铅含量测定法（原子吸收光谱法）GB/T11140石油产品硫含量测定法（X射线光谱法）GB/T17476使用过的润滑油中添加剂元素、磨损金属和污染物以及基础油中某些元素测定法（电感耦合等离子体发射光谱法）GB17930车用汽油GB/T18612原油中有机氯含量的测定（微库仑计法）SH/T0164石油产品包装、贮运及交货验收规则SH/T0253轻质石油产品中总硫含量测定法（电量法）SH/T0663汽油中某些醇类和醚类测定法（气相色谱法）SH/T0689轻质烃及发动机燃料和其他油品的总硫含量测定法（紫外荧光法）SH/T0794石油产品蒸气压的测定（微量法）3术语和定义下列术语和定义适用于本标准。
首例车用甲醇汽油（M85）经权威检验达到国家标准首例车用甲醇汽油（M85）经权威检验达到国家标准：由海南省海洋油气研究所占小玲教授经长达24年之久研究的甲醇汽油，在通过各种检验、鉴定及列入国家重大科技成果一系列工作后，又迎来了2009年5月1日发布的车用甲醇汽油（M85）国家标准。
恰逢该标准2009年12月1日正式实施的前夕，也就是2009年9月29日又一次通过了国家有关石油产品监督检验中心检验，全部指标符合刚颁布的GB/T23799-2009车用甲醇汽油（M85）国家标准的要求。
这是继2005年6月在交通部汽车运输行业能源利用检测中心进行汽车道路检验后的又一次进行质量标准检验，这在国内尚属首例。
中华人民共和国车用甲醇汽油（M85）国家标准，由国家标准化管理委员会、中华人民共和国国家质量监督检验检疫总局于2009年5月1日正式批准发布，2009年12日1日实施，这是甲醇汽油的首个产品标准。
《车用甲醇汽油（M85）标准》的制定，参考和总结了美国M75、M85标准存在的问题和取得的经验，同时结合国内实际情况。
该标准有两大特点：一是对易造成腐蚀的非金属元素含量进行严格控制；二是在检验方法上对质量指标进行从严控制。
此前出台的《车用燃料甲醇标准》是中间产品标准，即是车用甲醇汽油（M85）的原料，而《车用甲醇汽油（M85）标准》是产品标准，按照此标准生产出的合格产品可以直接使用。
由于是终端产品，因此技术要求十分严格，指标多达十多项。
一、技术概况甲醇汽油项目是1985年1月8日由占小玲教授立课题开始研制的，1987年4月25日通过技术鉴定，1987年获得市级新产品证书，证书编号：870029。
1988年6月17日由国家科委科技成果管理办公室发函申报国家级重大成果进行登记，1989年3月30日由国家科委成果管理办公室《公报》，并列入予以正式登记的国家级重大科技成果；分类号：TE626。
21，登记号：882147，国家科委于1989年6月颁发了《国家科技成果证书》，证书编号：002850，占教授本人获得国家科技成果完成者证书，证书编号：009387。
M5、M15车用甲醇汽油1范围本标准规定了用于点燃式内燃机的M5、M15车用甲醇汽油的术语和定义、分类和标识、要求、试验方法、检验规则以及标志、包装、运输、贮存、安全。
本标准适用于山西省内M5、M15车用甲醇汽油的生产和检验。
2规范性引用文件下列文件对于本文件的应用是必不可少的。
凡是注日期的引用文件，仅所注日期的版本适用于本文件。
凡是不注日期的引用文件，其最新版本（包括所有的修改单）适用于本文件。
GB190危险货物包装标志GB/T259石油产品水溶性酸及碱测定法GB/T503汽油辛烷值测定法（马达法）GB/T511石油和石油产品及添加剂机械杂质测定法GB/T1792馏分燃料中硫醇硫测定法（电位滴定法）GB/T4756石油液体手工取样法GB/T5096石油产品铜片腐蚀试验法GB/T5487汽油辛烷值测定法（研究法）GB/T6536石油产品常压蒸馏特性测定法GB/T8017石油产品蒸气压的测定雷德法GB/T8018汽油氧化安定性测定法（诱导期法）GB/T8019燃料胶质含量的测定喷射蒸发法GB/T8020汽油铅含量测定方法（原子吸收光谱法）GB/T11132液体石油产品烃类的测定荧光指示剂吸附法GB/T11140石油产品硫含量测定法波长色散X射线荧光光谱法GB17930车用汽油SH/T0164石油产品包装、贮运及交货验收规则SH/T0174芳烃和轻质石油产品硫醇定性试验法（博士实验法）SH/T0246轻质石油产品中水含量测定法（电量法）SH/T0253轻质石油产品中总硫含量测定法（电量法）SH/T0689轻质烃及发动机燃料和其他油品的总硫含量测定法（紫外荧光法）SH/T0693汽油中芳烃含量测定法（气相色谱法）SH/T0711汽油中锰含量测定法（原子吸收光谱法）SH/T0712汽油中铁含量测定法（原子吸收光谱法）SH/T0713车用汽油和航空汽油中苯和甲苯含量的测定（气相色谱法）NB/SH/T0741汽油中烃族组成的测定多维气相色谱法SH/T0794石油产品蒸气压的测定微量法DB14/T177车用甲醇汽油变性醇DB14/T178车用甲醇汽油组分油3术语和定义下列术语和定义适用于本文件。
M85甲醇汽油有关建设甲醇汽油项目的相关调研与开发建议甲醇是：无色、无味、易流动，易挥发的可燃性液体，甲醇汽油是：（国标汽油+甲醇+甲醇汽油添加剂）按一定量的比例勾兑后的混合物产物。
甲醇掺入量一般为5％～20％。
以掺入15％者为最多，称M15 甲醇汽油。
如：M85甲醇汽油= 15%汽油+ 85%甲醇油（甲醇+0.5%添加剂）甲醇汽油优点是：特点（一）：通用性好1、在以汽油93#、97#、以按任意比例与国标90”、93、”98”车用汽油互溶，且不影响汽车发动机正常工作。
使用甲醇汽油无论是电喷式和化油器式的任何一款汽油发动机，无须作任何改造即可正常使用。
特点（二）：无腐蚀性高清洁甲醇汽油经过单车行使20万公里，经上海内燃机研究所等权威检测证明，特点（三）：互溶性优特点（四）：动力性强高清洁甲醇汽油能有效地预防和消除汽车部件的积炭形成，有利疏通油路，延长车辆发动机寿命，抗爆性好，降低油耗噪音，具有高效动力节省燃油，可提高发动机的效率，增强动力。
特点（五）：替代性好高清洁甲醇汽油将工业原料一甲醇，经高科技改性后，大比例加入汽油中，替代车用能源，可节约替代大量石油资源，符合国家政策导向，有助于缓解因石油资源枯竭造成的紧张局面。
特点（六）：环保性好高清洁甲醇汽油由于含氧量高，燃烧充分，能有效地减少50%以上的有害气体排放，其中CO 、HC 和NOx排放降低90%以上，经国家权威机构的多项检测，各项指标均已达到欧IV标准，减少排放，满足环保需求，大大改善生态环境。
特点（七）：便捷推广高清洁甲醇汽油常温下存放，品质有效期可达到2年之久，有效的解决了贮存、运输和销售各环节所需的时间。
特点（八）：品质稳定高清洁甲醇汽油在35℃高温气候条件下使用，汽车油路不会发生气阻现象，同时在气候零下35℃的低温条件下，不分层，不乳化，发动机可正常起动，特别适应高寒地区规模化生产和使用，低温易启动、高温无气阻。
特点（九）：经济实惠高清洁甲醇汽油燃烧完全，动力性强，可提高发动机的效率，与普通汽油相比，节能效果明显，加速性能优良，车用甲醇汽油在发动机中热效率高，低速时动力性接近于传统汽油，高速时动力性优于传统汽油，消费者使用经济效益显著。
M85甲醇汽油有关建设甲醇汽油项目的相关调研与开发建议甲醇是:无色、无味、易流动，易挥发的可燃性液体，甲醇汽油是:(国标汽油+甲醇+甲醇汽油添加剂)按一定量的比例勾兑后的混合物产物。
甲醇掺入量一般为5,,20,。
以掺入15,者为最多，称M15 甲醇汽油。
如:M85甲醇汽油 = 15%汽油 + 85%甲醇油(甲醇+0.5%添加剂) 甲醇汽油优点是: 特点(一):通用性好1、高清洁甲醇汽油方便普及与推广使用，无须改动加油站的机器设备，更无须改动车辆发动机即可直接添加交叉使用。
在以汽油为燃料的汽车上使用，可直接替代国标93#、97#、98#汽油使用;可以按任意比例与国标90”、93、”98”车用汽油互溶，且不影响汽车发动机正常工作。
使用甲醇汽油无论是电喷式和化油器式的任何一款汽油发动机，无须作任何改造即可正常使用。
特点(二):无腐蚀性高清洁甲醇汽油经过单车行使20万公里，经上海内燃机研究所等权威检测证明，其腐蚀性与普通汽油类同，未发现对汽车发动机有腐蚀现象。
特点(三):互溶性优高清洁甲醇汽油专利配方中的添加剂，变性剂可以使甲醇和汽油的互溶性增强，可与普通汽油任意混合或交叉使用。
1特点(四):动力性强高清洁甲醇汽油能有效地预防和消除汽车部件的积炭形成，有利疏通油路，延长车辆发动机寿命，抗爆性好，降低油耗噪音，具有高效动力节省燃油，可提高发动机的效率，增强动力。
特点(五):替代性好高清洁甲醇汽油将工业原料一甲醇，经高科技改性后，大比例加入汽油中，替代车用能源，可节约替代大量石油资源，符合国家政策导向，有助于缓解因石油资源枯竭造成的紧张局面。
特点(六):环保性好高清洁甲醇汽油由于含氧量高，燃烧充分，能有效地减少50%以上的有害气体排放，其中CO 、HC 和NOx排放降低90%以上，经国家权威机构的多项检测，各项指标均已达到欧IV标准，减少排放，满足环保需求，大大改善生态环境。
特点(七):便捷推广高清洁甲醇汽油常温下存放，品质有效期可达到2年之久，有效的解决了贮存、运输和销售各环节所需的时间。
EQ6100汽油机应用M85甲醇时化油器的适应性及其改进张华;刘峰
【期刊名称】《小型内燃机》
【年(卷),期】1991(000)005
【摘要】本文着重介绍 EQ6100汽油机应用 M85甲醇时,在不改变原机化油器整体结构的条件下对化油器的适应性进行改进、试验的情况。
改进的结果使整机性能达到和超过合同规定的要求,并且具有良好的怠速稳定性。
同时还对供油系的易溶件进行溶胀试验,提出长期使用中应注意的问题。
【总页数】9页(P5-13)
【作者】张华;刘峰
【作者单位】不详;不详
【正文语种】中文
【中图分类】TK413.81
【相关文献】
1.喷油脉宽对电控汽油机燃用M85甲醇汽油的影响 [J], 宋建桐;朱清江
2.495Q汽油机燃用M85甲醇时化油器的改造 [J], 张峻霞;岳东鹏
3.495Q汽油机燃用M85甲醇时预热系统的研究 [J], 岳东鹏
4.M85甲醇燃料在EQ6100发动机上应用的试验研究 [J], 胡真
5.M5甲醇汽油在EQ6100—1型汽油机上的应用研究 [J], 王贺武;马志义
因版权原因，仅展示原文概要，查看原文内容请购买。
专利名称：M15－M85车用醇醚燃料及其配制方法专利类型：发明专利
发明人：齐洪元,蒋文清,何志文
申请号：CN200910050859.2
申请日：20090508
公开号：CN101544918A
公开日：
20090930
专利内容由知识产权出版社提供
摘要：本发明涉及M15－M85车用醇醚燃料及其配制方法，该燃料包括汽油、甲醇、助溶剂、防腐剂和改性复合剂，其重量组成百分比如下：组分：重量百分比(％)；汽油：10～85；甲醇：10～85；助溶剂：0.1～1.5；改性复合剂：1.5～3.0。
本发明的宽范围配比的车用醇醚燃料油燃烧完全，动力性强，节能效果明显，加速性能优良，且辛烷值高，动力强，适用于高压缩比发动机，可提高发动机的效率，一般比普通汽油节油率提高为15－21％。
申请人：上海鑫赛孚能源科技有限公司
地址：200072 上海市普陀区西康路1288弄6号401室
国籍：CN
代理机构：上海新天专利代理有限公司
代理人：周涛
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甲醇汽油混合物的国际标准和规范随着国际社会对环保问题的重视，新能源汽车及其相关技术在全球范围内得到了快速发展。
其中，甲醇汽油混合物作为一种低碳燃料，具有环保、经济、安全等众多优点，得到了越来越广泛的应用。
然而，由于国家标准和质量检验体系的不完善，导致了甲醇汽油混合物的管理和规范有待提高。
本篇文章将从世界范围内的甲醇汽油混合物标准、技术及应用等方面进行探讨。
一、甲醇汽油混合物的国际标准目前，世界范围内的甲醇汽油混合物标准主要有美国ASTM标准、欧洲EN标准、中国GB标准等。
这些标准主要是对甲醇汽油混合物的许用成分含量、物理化学性质、质量控制等进行了规范。
1. 美国ASTM标准美国ASTM标准（American Society for Testing and Materials）是一种国际性的标准组织，制定了许多和燃料有关的标准。
其中ASTM D5798就是用于规范乙醇汽油混合物的标准。
该标准规定了甲醇汽油混合物所允许的成分含量、物理化学性质、以及质量控制。
在甲醇含量不超过4%时，可以依照ASTM D4814进行规范。
2. 欧洲EN标准欧洲EN标准（European Standard）是欧洲对各种商品和服务的标准化体系，包括燃料标准等方面。
EN15376是欧洲对甲醇汽油混合物的标准，主要规定了甲醇含量不超过3%的甲醇汽油混合物的生产、质量控制以及安全规范。
3. 中国GB标准中国GB标准（Guo Biao标准）是中国国家标准化工作的中心文件。
GB18351规定了甲醇汽油混合物的规范，对甲醇汽油混合物的含量、质量、生产、销售等方面进行了规定。
二、甲醇汽油混合物的技术和应用1. 技术甲醇汽油混合物的技术主要有甲醇清洗马达技术、甲醇加裂解重馏技术、甲醇加氢改质技术等。
其中甲醇清洗马达技术是最常用的一种技术。
这种技术建立在“先甲醇，后汽油”的原则基础上，按照特定比例混合甲醇和汽油，来给马达提供动力。
这种技术能够减少尾气污染，但使用过程中需要注意甲醇的腐蚀性和易挥发性。
甲醇汽车的优缺点和解决方案一、产品优势：1)经济节能环保。
可为用户节省40%左右的燃油费用。
早在2007年时，经山西省汽车产品质量监督检验站和北京理工大学动力研究所排放中心检测，使用93#国标汽油与M85甲醇汽油相比，替代比为1：1.4。
按油耗10L车辆计算，若燃用M85甲醇汽油，每1百公里就可以节省32元，每1万公里就可以节省3200元，以车辆终身行驶40万公里计算，就可以节省128000元。
下表是M85与93#汽油燃油费用比较：2)由于甲醇具有清洁作用，可以大幅度清洁发动机积碳和油路中的油垢。
3)安装费用低廉。
按目前市场行情，安装价格在1200-1500元之间。
相对天然气车的5000-6000元的安装价格，要低廉的多，一辆车安装后行驶一个月，即可将安装成本节省回来。
4)低排放，低污染，绿色环保，符合国家环保和节能减排的政策要求。
M85与93#汽油相比较，CO排放下降39%，HC下降47%。
5)全国缺油多醇，符合产业发展政策。
并且山西省政府也给予了1000元/辆车的补贴的政策支持。
6)由于甲醇分子式中含有大量的氧，甲醇汽油是F1赛车和模型飞机、军工动力产品的配方燃料，是高辛烷值、高标号的高等级燃料。
二、产品缺憾和常见解决方案，以及对解决方案的得失分析使用M100甲醇燃料时的产品缺憾：1)由于甲醇对橡胶的融胀作用和对个别金属（铅、铝）的轻微腐蚀作用，造成使用M100甲醇燃料对汽车燃油泵、油表、油路有损伤，增加了汽车维修次数和费用。
2)增加了燃油泵的工作负荷，使燃油泵的工作寿命缩短。
3)冬天冷启动困难。
针对以上缺憾市场上的解决方案：a)安装燃油泵保护器和油表保护器，以延缓甲醇对燃油泵、油表的损伤问题。
b)安装一个小汽油箱，在冬天冷启动时，先使用小汽油箱点火，点火后再切换到大油箱燃烧甲醇。
c)调制符合国家标准的M85甲醇汽油。
同时解决腐蚀和冷启动的问题。
三种解决方案的得失分析1)安装保护器和安装小汽油箱都能延缓、解决相应的问题。
Designation:D5797–07An American National Standard Standard Specification forFuel Methanol(M70-M85)for Automotive Spark-IgnitionEngines1This standard is issued under thefixed designation D5797;the number immediately following the designation indicates the year oforiginal adoption or,in the case of revision,the year of last revision.A number in parentheses indicates the year of last reapproval.Asuperscript epsilon(e)indicates an editorial change since the last revision or reapproval.1.Scope1.1This specification covers a fuel blend,nominally70to 85volume%methanol and30to14volume%hydrocarbons for use in ground vehicles with automotive spark-ignition engines.Appendix X1discusses the significance of the prop-erties specified.Appendix X2presents the current status in the development of a luminosity test procedure for M70-M85. 1.2The values stated in SI units are to be regarded as the standard.The values given in parentheses are for information only.1.3The following precautionary caveat pertains only to the test method portions–Annex A1,Annex A2,Annex A3,and Appendix X2of this specification.This standard does not purport to address all of the safety concerns,if any,associated with its use.It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.2.Referenced Documents2.1ASTM Standards:2,3D86Test Method for Distillation of Petroleum Products at Atmospheric PressureD130Test Method for Corrosiveness to Copper from Petroleum Products by Copper Strip TestD381Test Method for Gum Content in Fuels by Jet EvaporationD512Test Methods for Chloride Ion In WaterD525Test Method for Oxidation Stability of Gasoline (Induction Period Method)D872Method of Test for Sulfonation Index of Road Tars4 D1193Specification for Reagent WaterD1266Test Method for Sulfur in Petroleum Products (Lamp Method)D1613Test Method for Acidity in V olatile Solvents and Chemical Intermediates Used in Paint,Varnish,Lacquer, and Related ProductsD2622Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescence Spectrometry D3120Test Method for Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcou-lometryD3231Test Method for Phosphorus in GasolineD4057Practice for Manual Sampling of Petroleum and Petroleum ProductsD4177Practice for Automatic Sampling of Petroleum and Petroleum ProductsD4306Practice for Aviation Fuel Sample Containers for Tests Affected by Trace ContaminationD4307Practice for Preparation of Liquid Blends for Use as Analytical StandardsD4626Practice for Calculation of Gas Chromatographic Response FactorsD4814Specification for Automotive Spark-Ignition Engine FuelD4815Test Method for Determination of MTBE,ETBE, TAME,DIPE,tertiary-Amyl Alcohol and C1to C4Alco-hols in Gasoline by Gas ChromatographyD4929Test Methods for Determination of Organic Chlo-ride Content in Crude OilD4953Test Method for Vapor Pressure of Gasoline and Gasoline-Oxygenate Blends(Dry Method)D5059Test Methods for Lead in Gasoline by X-Ray SpectroscopyD5190Test Method for Vapor Pressure of Petroleum Prod-ucts(Automatic Method)D5191Test Method for Vapor Pressure of Petroleum Prod-ucts(Mini Method)1This specification is under the jurisdiction of ASTM Committee D02onPetroleum Products and Lubricants and is under the direct responsibility ofSubcommittee D02.A0.01on Gasoline and Gasoline-Oxygenate Blends.Current edition approved May1,2007.Published June2007.Originallyapproved in1995as D5797–st previous edition approved in2006asD5797–06.2Reference to the following documents is to be the latest issue unless otherwisespecified.3For referenced ASTM standards,visit the ASTM website,,orcontact ASTM Customer Service at service@.For Annual Book of ASTMStandards volume information,refer to the standard’s Document Summary page onthe ASTM website.4Withdrawn. Copyright©ASTM International,100Barr Harbor Drive,PO Box C700,West Conshohocken,PA19428-2959,United States.--` , , ` ` ` , , , , ` ` ` ` -` -` , , ` , , ` , ` , , ` ---D5453Test Method for Determination of Total Sulfur in Light Hydrocarbons,Spark Ignition Engine Fuel,Diesel Engine Fuel,and Engine Oil by Ultraviolet Fluorescence D5854Practice for Mixing and Handling of Liquid Samples of Petroleum and Petroleum ProductsE203Test Method for Water Using V olumetric Karl Fischer TitrationE355Practice for Gas Chromatography Terms and Rela-tionshipsE1145Specification for Denatured Ethyl Alcohol,Formula 3A43.Terminology3.1Definitions:3.1.1methanol,n—methyl alcohol,the chemical compound CH3OH.3.2Definitions of Terms Specific to This Standard:3.2.1aliphatic ether—an oxygen-containing,ashless,or-ganic compound in which the oxygen atom is interposed between two carbon atoms(organic groups),has the general formula C n H2n+2O with n being5to8,and in which the carbon atoms are connected in open chains and not closed rings. 3.2.1.1Discussion—Aliphatic compounds can be straight or branched chains and saturated or unsaturated.The term ali-phatic ether,as used in this specification,refers only to the saturated compounds.3.2.2fuel methanol(M70-M85)—a blend of methanol and hydrocarbons of which the methanol portion is nominally70to 85volume%.3.2.3higher alcohols—aliphatic alcohols of the general formula C n H2n+1OH with n being2to8.3.2.4hydrocarbon—those components in a methanol-hydrocarbon blend that contain only hydrogen and carbon.4.Fuel Methanol(M70-M85)Performance Requirements 4.1Fuel methanol(M70-M85)shall conform to the require-ments in Table1.N OTE1—Most of the requirements cited in Table1are based on the best technical information currently available regarding the performance of these fuels in current technology vehicles.Requirements for sulfur, phosphorus,and lead are based on the use of gasoline defined in Specification D4814understanding that control of these elements will affect catalyst lifetime.The lead maximum is limited for Class1and Class 2fuels to the lower limit of the test method.As greater experience is gained fromfield use of M70-M85vehicles,and further vehicle hardware developments for the use of higher methanol content fuels occurs,it is expected that many of these requirements will change.4.1.1Vapor pressure is varied for seasonal and climatic changes by providing three vapor pressure classes for M70-M85.The seasonal and geographic distribution for the three vapor pressure classes is shown in Table2.Class1encom-passes geographical areas with6-h tenth-percentile minimum ambient temperature of greater than5°C(41°F).Class2 encompasses geographical areas with6-h tenth-percentile minimum temperatures of greater than−5°C(23°F)but less than+5°C.Class3encompasses geographical areas with6-h tenth-percentile minimum ambient temperature less than or equal to−5°C.4.1.2The hydrocarbons used shall have afinal maximum boiling point of225°C(437°F)by Test Method D86,oxidation stability of240-min minimum by Test Method D525,and No. 1maximum copper strip corrosion by Test Method D130.The hydrocarbons may contain aliphatic ethers as blending compo-nents as are customarily used for automotive fuel.4.1.3Use of unprotected aluminum in fuel methanol(M70-M85)distribution and dispensing equipment will introduce insoluble aluminum compounds into the fuel causing plugged vehicle fuelfilters.Furthermore,this effect can be exaggerated even with protected aluminum by elevated fuel conductivity caused by contact with a nitrile rubber dispensing hose. Therefore,unprotected aluminum and an unlined nitrile rubber dispensing hose should be avoided in fuel methanol(M70-M85)distribution and dispensing systems.55.Sampling,Containers,and Sample Handling5.1The reader is strongly advised to review all intended test methods prior to sampling to better understand the importance and effects of sampling technique,proper containers,and special handling required for each test method.5.2Correct sampling procedures are critical to obtain a sample representative of the lot intended to be e appropriate procedures in Practice D4057for manual method sampling and in Practice D4177for automatic sampling as applicable.5American Automobile Manufacturers Association,“Fuel Methanol Compatibil-ity Standards and Dispensing Equipment List for M85Fueled Vehicles,”October 1994.TABLE1Requirements for Fuel Methanol(M70-M85) Properties Class1A Class2Class3 Methanol+higher alcohols,min,volume%848070Hydrocarbon/aliphatic ether,volume%14–1614–2014–30Vapor pressure,kPa48–6262–8383–103(psi)7.0–9.09.0–12.012.0–15.0 Lead,max,mg/L 2.6 2.6 3.9 Phosphorus,max,mg/L0.20.30.4Sulfur,max,mg/kg160200300All ClassesHigher alcohols(C2–C8),max,volume%2Acidity,as acetic acid,max,mg/kg50Solvent washed gum content,max,mg/100mL5Unwashed gum content,max,mg/100mL20Total chlorine as chlorides,max,mg/kg2Inorganic chloride,max,mg/kg1Water,max,mass%0.5Appearance This product shall be visibly free ofsuspended or precipitated contaminants(clearand bright).This shall be determined atindoor ambient temperatures unless otherwiseagreed upon between the supplier and thepurchaser.A See4.1.1for volatility classcriteria. --`,,```,,,,````-`-`,,`,,`,`,,`---TABLE2Seasonal and Geographical Volatility Specifications for Fuel Methanol(M70-M85)N OTE—This schedule is subject to agreement between the purchaser and the seller denotes the vapor pressure class of the fuel at the time and place of bulk delivery to fuel dispensing facilities for the end user.Shipments should anticipate this schedule.State January February March April May June July August September October November December Alabama22222/111111/222 AlaskaSouthern Region33333/22/111/22/3333 South Mainland33333/22/11/222/3333 ArizonaN of34°Latitude3333/222/1111/22/333 S of34°Latitude2222/1111111/222 Arkansas333/22/111111/222/33 California ANorth Coast222222/11111/222 South Coast3/22222/111111/22/33 Southeast33/2222/11111/222/33 Interior222222/11111/222 ColoradoE of105°Longitude3333/222/1111/22/333W of105°Longitude33333/222/11/22/3333 Connecticut3333/222/1111/222/33 Delaware333/222/11111/222/33 District of Columbia333/222/11111/222/33 FloridaN of29°Latitude2222/1111111/222 S of29°Latitude22/1111111111/22 Georgia33/222/1111111/222/3 Hawaii111111111111 Idaho3333/2222/11/222/333 IllinoisN of40°Latitude3333/222/1111/22/333 S of40°Latitude3333/22/11111/22/333 Indiana3333/22/11111/22/333 Iowa3333/222/1111/22/333 Kansas3333/222/1111/22/333 Kentucky333/222/11111/222/33 Louisiana2222/1111111/222 Maine3333/222/111/222/333 Maryland333/222/11111/222/33 Massachusetts3333/222/1111/222/33 MichiganLower Michigan3333/222/111/222/333 Upper Michigan33333/22/111/222/333 Minnesota33333/22/111/222/333 Mississippi2222/1111111/222 Missouri3333/22/11111/22/333 Montana33333/222/11/22/3333 Nebraska3333/222/111/222/333 NevadaN of38°Latitude3333/2222/11/222/333 S of38°Latitude333/222/11111/222/33 New Hampshire3333/222/111/222/333 New Jersey333/222/11111/222/33 New MexicoN of34°Latitude3333/222/1111/22/333 S of34°Latitude333/22/1111111/22/33 New YorkN of42°Latitude3333/222/111/222/333 S of42°Latitude3333/22/11111/222/33 North Carolina333/222/11111/22/333 North Dakota33333/22/111/222/333 Ohio3333/22/11111/22/333 Oklahoma3333/22/11111/222/33 OregonE of122°Longitude3333/2222/11/222/333W of122°Longitude33/22222/1111/2222/3 PennsylvaniaN of41°Latitude3333/222/111/222/333 S of41°Latitude3333/222/1111/222/33 Rhode Island3333/22/11111/222/33 South Carolina2222/1111111/222 South Dakota3333/222/111/222/333 Tennessee333/222/11111/222/33 TexasN of31°Latitude333/222/11111/222/335.3The correct sample volume and appropriate container selection are important decisions that can impact test results.Refer to Practice D 4306for aviation fuel container selection for tests sensitive to trace contamination.Refer to Practice D 5854for procedures on container selection and sample mixing and handling.Where practical,M70–M85should be sampled in glass containers.If samples must be collected in metal containers,do not use soldered metal containers.This is because the soldering flux in the containers and the lead in the solder can contaminate the sample.Plastic containers should be avoided.5.4A minimum sample size of about 1L (1qt)is recom-mended.6.Test Methods6.1Determine the requirements enumerated in this specifi-cation in accordance with the following test methods:N OTE 2—The appropriateness of ASTM test methods cited has not been demonstrated for use with M70-M85.In addition,test methods contained in the annexes and appendixes are in the developmental stages or lack precision and bias determinations.6.1.1Methanol —A procedure for a test method for metha-nol content of fuel methanol (M70-M85)is included as Annex A1.Verification of the appropriateness of this test method has indicated that the precision of this method may not be adequate.As work continues to develop a method,this proce-dure remains the best available.6.1.2Hydrocarbon/Aliphatic Ether —Use Test Method D 4815to determine higher alcohols,methyl tert -butyl ether (MTBE),and other ethers.Water may also be determined if the gas chromatograph is equipped with a thermal conductivity detector.As an alternative,water can be determined by the Karl Fischer test method (see 6.1.9).The concentration of methanol,other alcohols,and water can be added,and the sum subtracted from 100to get the percent of hydrocarbons/aliphatic ethers.An alternative test method is contained in Annex A2.6.1.3Vapor Pressure —Test Methods D 4953,D 5190,or D 5191.6.1.4Acidity —Test Method D 1613.6.1.5Gum Content,Solvent Washed and Unwashed —Test Method D 381.6.1.6Total Chlorine as Chloride —Test Methods D 4929,Method B.6.1.7Lead —Test Method D 5059.With Test Method D 5059,prepare the calibration standards using methanol (reagent grade)as the solvent to prevent errors caused by large differences in carbon-hydrogen ratios.6.1.8Phosphorus —Test Method D 3231.6.1.9Water —Test Method E 203.6.1.10Sulfur —Test Methods D 1266,D 2622,D 3120,or D 5453.With Test Method D 2622,prepare the calibration standards using methanol (reagent grade)as the solvent to prevent errors caused by large differences in carbon-hydrogen ratios.6.1.11Inorganic Chloride —Inorganic chloride can be de-termined by Test Methods D 512–81(1985)e 1(Method C).Also,see the test method in Annex A3.Another test method is under development.7.Keywords7.1acidity;alcohol;automotive spark-ignition engine fuel;chloride;copper corrosion;ether;fuel methanol (M70-M85)for automotive spark-ignition engines;gum content;hydrocar-bon;inorganic chloride;lead;MTBE;M70-M85;methanol;oxidation stability;oxygenates;phosphorus;solvent washed;sulfur;total chlorine;vapor pressure;volatility;waterTABLE 2ContinuedStateJanuary FebruaryMarch April May June July August SeptemberOctober November DecemberS of 31°Latitude 2222/1111111/222Utah 3333/222/1111/22/333Vermont 3333/222/111/222/333Virginia 333/222/11111/222/33WashingtonE of 122°Longitude 333/2222/1111/22/333W of 122°Longitude 33/22222/1111/2222/3West Virginia 3333/222/111/222/333Wisconsin 3333/222/111/222/333Wyoming33333/222/11/222/333ADetails of State Climatological Division by county as indicated:California,North Coast—Alameda,Contra Costa,Del Norte,Humbolt,Lake,Marin,Mendocino,Monterey,Napa,San Benito,San Francisco,San Mateo,Santa Clara,Santa Cruz,Solano,Sonoma,TrinityCalifornia,Interior—Lassen,Modoc,Plumas,Sierra,Siskiyou,Alpine,Amador,Butte,Calaveras,Colusa,El Dorado,Fresno,Glenn,Kern (except that portion lying east of Los Angeles County Aqueduct),Kings,Madera,Mariposa,Marced,Placer,Sacramento,San Joaquin,Shasta,Stanislaus,Sutter,Tehama,Tulare,Tuolumne,Yolo,Yuba,NevadaCalifornia,South Coast—Orange,San Diego,San Luis Obispo,Santa Barbara,Ventura,Los Angeles (except that portion north of the San Gabriel Mountain range and east of the Los Angeles County Aqueduct)California,Southeast—Imperial,Riverside,San Bernadino,Los Angeles (that portion north of the San Gabriel Mountain range and east of the Los Angeles County Aqueduct),Mono,Inyo,Kern (that portion lying east of the Los Angeles CountyAqueduct)--`,,```,,,,````-`-`,,`,,`,`,,`---ANNEXES(Mandatory Information)A1.TEST METHOD FOR DETERMINATION OF METHANOL IN FUEL METHANOL(M70-M85)FORAUTOMOTIVE SPARK-IGNITION ENGINESA1.1ScopeA1.1.1This test method covers a procedure for determina-tion of methanol in fuel methanol(M70-M85)by gas chroma-tography.This test method is appropriate for fuels containing 70to95volume%methanol.A1.1.2The values stated in SI units are to be regarded as the standard.The values given in parentheses are for information only.A1.2Referenced DocumentsA1.2.1ASTM Standards2,3:D4057Practice for Manual Sampling of Petroleum and Petroleum ProductsD4177Practice for Automatic Sampling of Petroleum and Petroleum ProductsD4307Practice for Preparation of Liquid Blends for Use as Analytical StandardsD4626Practice for Calculation of Gas Chromatographic Response FactorsE355Practice for Gas Chromatography Terms and Rela-tionshipsA1.3TerminologyA1.3.1Definitions of Terms Specific to This Standard:A1.3.1.1low-volume connector—special union for connect-ing two lengths of tubing1.6mm inside diameter and smaller. Also referred to as a zero dead-volume union.A1.3.1.2split ratio—in gas chromatography using capillary columns the ratio of the totalflow of the carrier gas to the sample inlet versus theflow of carrier gas to the capillary column.A1.3.1.3TCEP—1,2,3-tris-2-cyanoethoxypropane.A gas chromatographic liquid phase.A1.3.1.4WCOT—abbreviation for a type of capillary col-umn,wall-coated open tubular,used in gas chromatography. This type of column is prepared by coating the inside of the capillary with a thinfilm of stationary phaseA1.4Summary of Test MethodA1.4.1An internal standard,tert-amyl alcohol,is added to the sample that is then introduced into a gas chromatograph equipped with two columns and a column switching valve.The sample passes into thefirst column,a polar TCEP column that elutes lighter hydrocarbons to vent and retains the oxygenated and heavier hydrocarbons.A1.4.2After methylcyclopentane,but before methanol elutes from the polar column,the valve is switched to back-flush the oxygenates onto a WCOT nonpolar column.The methanol and internal standard elute from the nonpolar column in boiling point order,before elution of any major hydrocarbon constituents.A1.4.3After the internal standard elutes from the non-polar column,the column switching valve is switched back to its original position to backflush the heavy hydrocarbons.The eluted components are detected by aflame ionization or thermal conductivity detector.The detector response,propor-tional to the component concentration,is recorded;the peak areas are measured;and the concentration of methanol is calculated with reference to the internal standard.A1.5Significance and UseA1.5.1The production of fuel methanol(M70-M85)re-quires knowledge of the methanol content to ensure acceptable commercial fuel quality.The methanol content of fuel metha-nol(M70-M85)affects the performance of an automobile designed to run on such fuel.A1.5.2This test method is applicable to both quality control in the production of fuel methanol(M70-M85)and for the determination of fuel contamination.A1.6ApparatusA1.6.1Chromatograph—See Practice E355for specific descriptions and definitions.A1.6.1.1Gas Chromatographic Instrument,operable at the conditions given in Table A1.1and having a column switching and backflushing system equivalent to Fig.A1.1.Carrier gas flow controllers must be designed for use at the requiredflow rates(see Table A1.1).Pressure control devices and gages must be designed for use at the pressures required.A1.6.1.2Detector,either a thermal conductivity detector (TCD)orflame ionization detector(FID)may be used.The system must have sufficient sensitivity and stability to sense absolute concentration changes of0.01volume%of methanol or internal standard at the50volume%level.A1.6.1.3Switching and Backflushing Valve,a ten-port valve,to be located within the gas chromatographic column oven,capable of performing the functions described in A1.10 TABLE A1.1Chromatographic Operating ConditionsTemperatures,°C Flows mL/min Column Oven60to injector75Injector200column5Detector auxiliary3TCD200makeup18FID250Valve60Carrier Gas—HeliumSample size,µL1Split ratio15:1Backflush,min0.2–0.3Valve reset time,min8–10Total analysis time,min18–20 --`,,```,,,,````-`-`,,`,,`,`,,`---and illustrated in Fig.A1.1.The valve must be of low volume design and not contribute significantly to chromatographic deterioration.6A1.6.1.4Automatic Valve Switching Device ,(strongly rec-ommended to ensure repeatable switching times)a device synchronized with injection and data collection times.If no such device is available,a stopwatch,started at the time of injection,should be used to indicate the proper valve switching time.A1.6.1.5Injection System ,a splitting-type inlet device.Split injection is necessary to maintain the actual chromatographed sample size within the limits of column and detector optimum efficiency and linearity.A1.6.1.6Sample Introduction System ,any system capable of introducing a representative sample into the split inlet device.N OTE A1.1—Microlitre syringes,automatic syringe injectors,and liq-uid sampling valves have been used successfully.A1.6.2Data Presentation or Calculation System :A1.6.2.1Recorder ,a recording potentiometer or equivalent with a full-scale deflection of 1mV or less,and full-scale response time of 1s or less,with sufficient sensitivity and stability to meet the requirements of A1.6.1.2.A1.6.2.2Integrator or Computer Devices ,capable of meet-ing the requirements of A1.6.1.2,and providing graphic and digital presentation of the chromatographic data.Peak heights or areas can be measured by computer,electronic integration,or manual techniques.A1.6.3Columns —Two columns are used as follows:A1.6.3.1Polar Column —Any column with equivalent or better chromatographic efficiency and selectivity to that de-scribed in A1.6.3.1(1)can be used.The column must perform at the same temperature as required for the column in A1.6.3.2.This column performs a pre-separation of the oxygenates from volatile hydrocarbons in the same boiling point range.The oxygenates and remaining hydrocarbons are backflushed onto the nonpolar column in A1.6.3.2.(1)TCEP Micro-Packed Column ,7560-mm (22-in.)by 1.6-mm (1⁄16-in.)outside diameter by 0.38-mm (0.015-in.)inside diameter stainless steel tube packed with 0.14to 0.15g of 20%by mass TCEP on 80/100mesh Chromosorb P(AW).This column is being used to develop precision and bias data for A1.15.A1.6.3.2Nonpolar (Analytical)Column —Any column with equivalent or better chromatographic efficiency and selectivity to that described in (1)and illustrated in Fig.A1.2can be used.(1)WCOT Methyl Silicone Column ,30-mm (1.181-in.)long by 0.53-mm (0.021-in.)inside diameter fused silica WCOT column with a 2.65-µm film thickness of crosslinked methyl siloxane.This column is being used to develop preci-sion and bias data for A1.15.A1.7Reagents and MaterialsA1.7.1Carrier Gas ,carrier gas appropriate to the type of detector used.The minimum purity of the carrier gas shall be 99.995mol %.N OTE A1.2—Helium has been used successfully.A1.7.2Methanol,99.9%Purity ,required to establish iden-tification by retention time and for calibration.Shall be of known purity and free of the other components to be analyzed.(Warning —Flammable.Health hazard.)A1.7.3Methylene Chloride ,used for column preparation.Reagent grade,free of nonvolatile residue.(Warning —Health hazard.)6A Valco Model No.CM-VSV-10-HT valve with 1.6-mm (1⁄16-in.)fittings has been found satisfactory for this purpose.This is the valve being used in the majority of the analyses for the development of the data for A1.15.A Valco Model No.C10W with 0.8-mm (1⁄31-in.)fittings is recommended for use with columns of 0.32-mm inside diameter and smaller.The sole source of supply of the apparatus known to the committee at this time is VICI Valco,7806Bobbitt,Houston,TX 77055.If you are aware of alternative suppliers,please provide this information to ASTM Interna-tional Headquarters.Your comments will receive careful consideration at a meeting of the responsible technical committee,1which you may attend.7The sole source of supply of the apparatus known to the committee at this time is Hewlett-Packard Company,Wilmington,DE 19808.If you are aware of alternative suppliers,please provide this information to ASTM International Headquarters.Your comments will receive careful consideration at a meeting of the responsible technical committee,1which you mayattend.FIG.A1.1Schematic of Chromatographic SystemTABLE A1.2Retention Characteristics for TCEP/WCOT ColumnSet Conditions as in Table A1.1Component Retention Time,minRelative Retention Time (t -Amyl Alcohol =1.00)Methanol3.210.44t -Amyl Alcohol7.301.00A1.7.4Nitrogen,99.998mol%,used to prepare tubing for the micro-packed TCEP column.(Warning—Gas under pressure.)A1.7.5Tert-Amyl Alcohol(2-Methyl-2-Butanol),99%Pu-rity,used as the internal standard.(Warning—Flammable. Health hazard.)A1.8Preparation of Column PackingA1.8.1Preparation of TCEP Column Packing:A1.8.1.1Any satisfactory method,used in the practice of the art that will produce a column capable of retaining methanol and tert-amyl alcohol(internal standard)from hy-drocarbon components of the same boiling point range in a fuel methanol(M70-M85)sample,may be used.The following procedure has been used successfully.A1.8.1.2Completely dissolve10g of TCEP in100mL of methylene chloride.Next add40g of80/100mesh Chro-mosorb P(AW)to the TCEP solution.Quickly transfer this mixture to an evaporating dish,in a fume hood,without scraping any of the residual packing from the sides of the container.Constantly,but gently,stir the packing until all of the solvent has evaporated.This column packing can be used immediately to prepare the TCEP column.A1.8.2Packing of Micro-Packed TCEP Column:A1.8.2.1Wash a straight560-mm length of1.6-mm outside diameter(0.38-mm inside diameter)stainless steel tubing with methanol and dry with compressed nitrogen.A1.8.2.2Insert six to twelve strands of silvered wire,a small mesh screen,or stainless steel frit inside one end of the tube.Slowly add0.14to0.15g of packing material to the column and gently vibrate to settle the packing inside the column.When strands of wire are used to retain the packing material inside the column,leave6.4mm(0.25in.)of space at the top of the column.Place wire or screen in the column to retain packing.A1.8.2.3Column Conditioning—Both the TCEP and WCOT columns are to be briefly conditioned before use. Connect the columns to the valve(see A1.10.1)in the chromatographic oven.Adjust the carrier gasflows as in A1.10.3and place the valve in the RESET position.After several minutes,increase the column oven temperature to 120°C and maintain these conditions for5to10min.Cool the columns below60°C before shutting off the carrierflow.A1.9SamplingA1.9.1To obtain samples for this test method,use the procedures outlined in Practice D4057or Practice D4177 except that water displacement(see section10.3.1.8of Practice D4057)shall not be used.A1.9.2Fuel samples shall be stored under refrigeration until the laboratory subsample is taken for analysis.Any laboratory subsamples shall also be refrigerated if they are not to be analyzed immediately.A1.9.3Thoroughly shake the sample container prior to withdrawing any subsample for analysis.Allow any particulate matter to settle to the bottom of the subsample container. Inspect the subsample for evidence of phase separation.If phase separation is detected,the sample is invalid and a new sample shall be requested.A1.10Preparation of Apparatus and Establishment of ConditionsA1.10.1Assembly—Connect the WCOT column to the valve system using low-volume connectors and narrow bore tubing.It is important to minimize the volume of the chro-matographic system that comes in contact with the sample, otherwise peak broadening will occur.A1.10.2Adjust the operating conditions to those listed in Table A1.1.(If a TCD is being used,do not turn on the detector circuits.)Check the system for leaks before proceeding further. A1.10.3Flow Rate Adjustment—See Fig.A1.1.A1.10.3.1Attach aflow-measuring device to the column vent with the valve in the RESET position and adjust the pressure to the injection port to give5.0-mL/minflow(14 psig).N OTE A1.3—Soap-bubbleflowmeters are suitable.A1.10.3.2Attach aflow-measuring device to the split injec-tor vent and adjust theflow from the split vent using the A Flow Controller to give aflow of70mL/min.Recheck the column ventflow set in A1.10.3.1and adjust,if necessary.A1.10.3.3Switch the valve to the BACKFLUSH position and adjust the variable restrictor to give the same column vent flow set in A1.10.3.1.This is necessary to minimizeflow changes when the valve is switched.A1.10.3.4Switch the valve to the inject position RESET and adjust the B Flow Controller to give aflow of3.0to3.2 mL/min at the detector exit.When required for the particularFIG.A1.2Example of ChromatographicResults--`,,```,,,,````-`-`,,`,,`,`,,`---。
