🔥 Determination of the methanol content of fatty acid methyl esters (FAME) for diesel and heating fuel by headspace gas chromatography with flame ionization detection (HS-GC-FID) — specimen heated in a hermetically sealed vial at 80 °C to equilibrium, injection of part of the gas phase, internal calibration with 2-propanol (procedure A) or external calibration (procedure B) on three solutions of methanol in reference FAME, required methanol/2-propanol resolution of at least 1,5, range 0,01–0,5 % (m/m), PN-EN 14110

Petrochemistry PN-EN 14110

Overview

WHAT THE STANDARD COVERS. We read the text of the standard in the iTeh sample of SIST EN 14110:2019 (text of EN 14110:2019, English): from the title page through the contents, European foreword and Clauses 1–9 to 10.2.1 (procedure A — general) on page 7 inclusive. Outside the sample remain the internal calibration, analysis and calculation of procedure A (10.2.2–10.2.3), procedure B with external calibration (10.3), precision (11), test report (12) and Annexes A (results of an interlaboratory study) and B (example chromatogram).

ACCORDING TO THE TEXT OF EN 14110:2019 (foreword, Clauses 1–10.2.1). The standard was prepared by CEN/TC 307 “Oilseeds, vegetable and animal fats and oils and their by-products — Methods of sampling and analysis” (secretariat AFNOR) under mandate M/245 on FAME; it superseded EN 14110:2003; changes: Formula (1) for the resolution between methanol and 2-propanol was added, the formula for the methanol content with external calibration was corrected, Clause 2 (normative references) and Clause 7 (sampling) were added. Scope (1): determination of methanol in FAME used as diesel fuel and domestic heating fuel, for contents of 0,01–0,5 % (m/m); the method is not applicable to mixtures of FAME containing other low-boiling components. Normative references (2): EN ISO 3170 (manual sampling of petroleum liquids) and EN ISO 3171 (automatic pipeline sampling). Principle (4): the sample is heated at 80 °C in a hermetically sealed vial to allow desorption of methanol into the gas phase; when equilibrium is reached a defined part of the gas phase is injected into a gas chromatograph with a flame ionization detector; the amount of methanol is determined by internal calibration (procedure A) or external calibration (procedure B), and if only manual equipment is available only internal standard calibration should be used. Reagents (5): methanol of purity greater than 99,5 %, 2-propanol of purity greater than 99,5 % (internal standard in procedure A), reference FAME with a methanol content below 0,001 % (m/m) — commercial or washed 3–5 times with distilled water in a separating funnel and dried at 90 °C with stirring under reduced pressure — and carrier gas: nitrogen, helium or hydrogen of purity greater than 99 %. Apparatus (6): 20 ml headspace vials, inert septa (e.g. TFE or Viton) and metal caps, 10 µl syringe accurate to 0,1 µl, 500 µl gas syringe with valve (manual procedure), crimping pliers, 1, 2 and 5 ml pipettes, 10 and 25 ml volumetric flasks, gas chromatograph with capillary column, suitable injector (automatic headspace or split/splitless) and FID; the column shall elute methanol as a symmetrical peak — methylpolysiloxane (e.g. DB1, SE30) or polyethylene glycol (e.g. DBWAX, CARBOWAX) phases, a film of at least 0,5 µm recommended, a packed column also permitted; automatic headspace equipment with an accuracy of 1 % or better for equilibrium temperature, heating times and sampling volume (recommended, because of better repeatability and fast analysis with external calibration; with manual sampling of gas — extreme care); analytical balance ± 0,1 mg; bath or oven up to 80 °C and oven up to 60 °C — the exact temperature has no influence on the result as long as it is the same for calibration and samples, and it is verified indirectly, e.g. by measuring a control sample. Sampling (7): according to EN ISO 3170 or EN ISO 3171 or national regulations. Conditions (8): GC conditions are chosen so that the resolution between the methanol and 2-propanol peaks is at least 1,5, Rs = 1,18 (tB − tA)/(wA + wB), where t — retention times, w — peak widths at half height; example: DB1 column 30 m × 0,32 mm, film 3 µm, split flow 50 ml/min, injector and detector 150 °C, oven 50 °C, hydrogen 40 kPa, injection 500 µl; headspace example: equilibrium at 80 °C for 45 min, volume 500 µl; the chromatograph is operated according to the manufacturer’s instructions. Calibration solutions (9): three solutions of methanol in reference FAME, masses determined by weighing, thorough mixing by vigorous shaking; A — 0,5 % (m/m): 25 ml FAME in a 25 ml flask and (112 ± 0,1) mg (142 µl) methanol added by syringe into the liquid; B — 0,1 % (m/m): 5 ml of solution A made up to 25 ml with FAME; C — 0,01 % (m/m): 1 ml of solution B made up to 10 ml with FAME; three solutions suffice in practice for the scope of the method, other solutions may be chosen for other ranges. Procedure (10.1–10.2.1): two alternatives — internal (10.2) and external (10.3) calibration; procedure A is preferred for a small number of samples and when automatic headspace equipment is not available.

STATUS (as of 03.10.2026). The PKN search (term “PN-EN 14110”, 03.10.2026) shows PN-EN 14110:2019-05 (English version, “Introduces: EN 14110:2019 [IDT]”) without a withdrawal note and PN-EN 14110:2004 (Polish version) withdrawn and replaced by PN-EN 14110:2019-05; the third item, PN-EN 141101:2002, concerns potentiometers — a different document. In the iTeh catalogue (read on 03.10.2026) EN 14110:2019 has the status “Published”, stage 90.93 (decision to confirm) since 03.12.2024. The acid value of FAME is described in a separate entry on PN-EN 14104.

HOW MANY LABORATORIES AND IN WHAT FORM (copy of the accreditation scope database, load up to 17.09.2026, read on 03.10.2026). The number 14110 appears in 6 records at 5 laboratories: AB 009, AB 391, AB 484 (2), AB 1668, AB 1679. In the current PCA documents (read on 03.10.2026, issues from 19.09.2025 to 30.07.2026) the number appears in 6 rows of the same laboratories (AB 484 — 2, the others 1 each); in each of the five documents the number of page markers equals the number of PDF pages, without repetitions. The form “PN-EN 14110:2019-05” (AB 391, AB 484, AB 1679), “PN-EN 14110:2019-05 Procedura A” (procedure A; AB 1668), “PN-EN 14110:2019-05 z wyłączeniem procedury A” (excluding procedure A; AB 484, second row) and “PN-EN 14110” without year (AB 009). At AB 009 the row with PN-EN 14110 is set in bold italics, and the footnote of the document says: “Akredytacja zawieszona na wniosek podmiotu w części zakresu oznaczonego pogrubioną kursywą od 03.06.2026 r. do 30.11.2026 r.” (accreditation suspended at the request of the body for the part of the scope marked in bold italics from 03.06.2026 to 30.11.2026) — this item is therefore temporarily suspended. The AB 484 document also has a suspension footnote, but its rows with PN-EN 14110 are not in bold italics. The “Laboratories” tab (term “PN-EN 14110”) shows all 5 laboratories, including AB 009 with the suspended item — checked with a tab query on the production server labcoda.pl on 03.10.2026.

WHAT THE LABORATORIES TEST (items in PCA). Liquid fuels and liquid biofuels: fatty acid methyl esters (FAME) (all five). Characteristic: methanol content (at AB 484 “methyl alcohol”). Ranges: (0,01–0,50) % (m/m) (AB 009, AB 391, AB 1668), (0,01–0,5) % (m/m) and (0,01–0,10) % (m/m) (AB 484), (0,02–0,50) % (m/m) (AB 1679). Technique: HS-GC-FID (AB 391, AB 484, AB 1679), GC-FID (AB 009, AB 1668 — at AB 1668 with procedure A).

WHERE A SEEMINGLY CORRECT RESULT IS EASY TO GET. With the sample: the method does not apply to FAME with other low-boiling components (1). With resolution: methanol and 2-propanol peaks must have Rs ≥ 1,5 (8.1). With equilibrium temperature: it need not be exactly 80 °C, but must be the same for calibration and samples (6.12). With reference FAME: methanol below 0,001 % (m/m) (5.3). With solutions: methanol masses determined by weighing, not only by volume, and vigorous mixing (9.1). With manual equipment: internal calibration only is recommended (4). With the range: 0,01–0,5 % (m/m); a result outside it requires other calibration solutions (1, 9.1). With accreditation: the AB 009 item is suspended until 30.11.2026.

WHAT WE DO NOT GIVE. We did not read the course of calibration and calculation in procedures A and B (including the corrected formula for external calibration), repeatability and reproducibility, the interlaboratory study results or the report form (10.2.2–12, Annexes A–B). Nor do we give requirements for the maximum methanol content of FAME from product standards.

Method principle

A FAME sample is heated in a hermetically sealed vial at 80 °C until methanol reaches equilibrium between the liquid and gas phase; a defined volume of the gas phase is introduced into a gas chromatograph with a capillary column and a flame ionization detector. The methanol content is determined from internal calibration with 2-propanol (procedure A) or external calibration (procedure B), on solutions of 0,5, 0,1 and 0,01 % (m/m) methanol in practically methanol-free FAME.

Applications

• Fatty acid methyl esters (FAME) used as diesel fuel and heating fuel, methanol 0,01–0,5 % (m/m) (1)
• Control of residual methanol after biodiesel production (1, 4)
• Liquid fuels and biofuels FAME — methanol content in the accreditation scopes of 5 laboratories in PCA

Key parameters

Standard

Standard number

PN-EN 14110:2019-05

Title (PL)

Produkty przetwarzania olejów i tłuszczów — Estry metylowe kwasów tłuszczowych — Oznaczanie zawartości metanolu

Title (EN)

Fat and oil derivatives — Fatty Acid Methyl Esters — Determination of methanol content

Step-by-step procedure

1. Sample

   Taken according to EN ISO 3170 or EN ISO 3171 (7). PN-EN 14110:2019-05 without a withdrawal note (03.10.2026).

2. Calibration solutions

   A 0,5 % — 25 ml FAME + (112 ± 0,1) mg methanol; B 0,1 % — 5 ml A to 25 ml; C 0,01 % — 1 ml B to 10 ml; masses weighed (9).

3. GC conditions

   Chosen so that Rs of methanol and 2-propanol ≥ 1,5 (8.1).

4. Headspace

   Vial hermetically sealed, heated at 80 °C to equilibrium, injection of a defined volume of the gas phase (4).

5. Calibration and result

   Procedure A (internal, 2-propanol) for few samples or manual equipment, procedure B (external) with automatic headspace; calculations according to 10.2–10.3 (not read).

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Methanol — toxic and flammable; work in a fume hood, avoid skin contact
• Hydrogen as carrier gas — explosion risk, leak checking
• Heated vials under pressure — open carefully after cooling

Frequently asked questions