Jones D.S.J., Pujado P.R. Handbook of Petroleum Processing

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704 CHAPTER 15

High expansion foam concentrates

High expansion foam concentrates are based on combination of hydrocarbon surfac-

tants and solvents. They are used with foam generators for applying foam to large

areas in total ﬂooding and three-dimensional applications such as warehouses, ship

cargo holds, and mine shafts. They are especially useful on fuels such as liqueﬁed

natural gas (cryogenic fuels) for vapor dispersion and control. In certain concentra-

tions, high expansion foams are effective on hydrocarbon spill ﬁres of most types and

in conﬁned areas.

Class A ﬁre foams

Class A foams are typically formulated from a combination of specialty hydrocarbon

surfactants, stabilizers, inhibitors, and solvents. They reduce the surface tension of

water for improved wetting and penetrating characteristics and create a clinging foam

blanket that suppresses combustible vapors while cooling the fuel. Class A foams

can be applied using a variety of proportioning/discharge devices and have proven

to be highly effective for use in structural and forest ﬁreﬁghting, coal mines, tire,

and rubber manufacturing, lumber mills, coal bunkers, paper warehouses, and other

hazards involving ordinary combustible materials. Please note that Class B foams

are acceptable for use on Class A ﬁres, however they are not designed for use on

Class A ﬁres as such. The foam concentrate percentage refers to the amount of

concentrate that is proportioned or pre-mixed with water to give the resulting foam

solutions.

Environmental impact and toxicity. Most foam concentrates are formulated to maxi-

mize performance and minimize environmental impact and human exposure hazards.

All concentrates are readily biodegradable—both in the natural environment and in

sewage treatment facilities. However, all foam agents should be metered into the fa-

cility to prevent overloading the plant due to foam formation. They are not considered

skin irritants; however, prolonged contact may cause some dryness of the skin. For

this reason, we recommend that areas of the skin which have come in contact with

the foam concentrate be ﬂushed with fresh water.

Shelf life. Shelf life is the length of time over which foam concentrates remain sta-

ble without signiﬁcant changes in performance characteristics. Many AFFF, high-

expansion and Class A foam concentrates—if stored in accordance with recommended

guidelines—have a normal shelf life of 20–25 years. Other foam agents—those which

are not totally synthetic—have a normal shelf life of 7–10 years.

Chapter 16

Quality control of products in petroleum reﬁning

D.S.J. Jones

Introduction

This chapter is concerned mostly with the laboratory testing for the control of

petroleum products. It will be concerned with those tests that establish the quality

of reﬁnery streams and in some ﬁnished and saleable products. What is not covered

are those specialized tests such as Mass Spectrometry, motor road tests and the like.

Where possible sketches of test apparatus are included. Most of these tests are per-

formed in the reﬁnery laboratory, and generally follow the methods provided by the

respective ASTM numbered tests.

The most common tests to check the quality of ﬁnished products cover the fol-

lowing:

Speciﬁc gravity

ASTM distillations

Pensky Marten closed cup ﬂash point

Kinematic viscosities

Octane numbers

Sulfur content tests

LPG weathering tests

Reid vapor pressure

Bromine number

The chapter begins with some details of typical product speciﬁcations. More discus-

sion and description of modern day trends in product quality (such as the effect of

Reformulated Gasoline) are given in Chapter 2 of this book.

705

706 CHAPTER 16

16.1 Speciﬁcations for some common ﬁnished products

This chapter is concerned only with those energy products that are common to ev-

eryday living. They include, the LPGs, gasolines, burning oil (including kerosene),

diesel fuel, jet fuels, and the black oils including fuel oil and marine diesel.

The LPG products

This category includes the normal speciﬁcation for propane and butane LPG. They

are given in Table 16.1.

The gasolines

Two grades of gasoline are given here. They represent present day and near future qual-

ity requirements meeting the environmental parameters already discussed in Chapter 2

of this volume. The two grades are:

Table 16.1. Speciﬁcations covering saleable LPG

Propane LPG (Note 1.0) Method of test

Vapor pressure at 113

◦

F, psig 255 max IP 161

Hydrocarbons, mol% 0.1 max ASTM 2163

Hydrocarbons, mol% 5.0 max ASTM 2163

Hydrocarbons, mol% 95.0 min ASTM 2163

and heavier hydrocarbons, mol% 4.0 max ASTM 2163

Total unsaturated hydrocarbons, mol% 1.0 max ASTM 2163

Total sulfur content, wt% 0.1 max ASTM D1266

Mercaptan sulfur grains per 100 cuft @ STP 3.0 max IP 104

S content Absent IP 103

Butane LPG (Note 1.0)

Vapor pressure at 113

◦

F, psig 70–85 IP 161

Hydrocarbons, mol% Nil ASTM 2163

Hydrocarbons, mol% 0.5 max ASTM 2163

Hydrocarbons (as nC

), mol% 2.0 max ASTM 2163

Total sulfur content, wt% 0.01 max ASTM D1266

Mercaptan sulfur grains per 100 cuft @ STP 2.0 max IP 104

S content Absent IP 103

Note 1.0. The above products shall not contain harmful quantities of toxic or nauseating substances and

shall be free from entrained water. The odor of the gases shall be distinctive, unpleasant and non persistent,

and shall indicate the presence of the gas at concentrations in air down to 1/5th of the lower limit of

inﬂammability.

QUALITY CONTROL OF PRODUCTS IN PETROLEUM REFINING 707

Regular grade

Premium grade (100 octane)

The speciﬁcations given in Table 16.2 cover present day quality requirements. Note

only the major quality items and tests are listed here.

Table 16.2. Gasoline quality requirements

Regular gasoline Premium gasoline

Effective date: September 2002

Research octane number

(RON)

91.0 minimum 100 minimum ASTM D2699

Motor octane number

(MON)

82.0 minimum 91.0 minimum ASTM D2700

Color Off white Orange Visual

Distillation:

vol% distilled @ 70

◦

Minimum 20 22 ASTM D86

vol% distilled @ 100

◦

Maximum

Minimum

vol% distilled

@ 180

◦

Not applicable

ASTM D86

Minimum 90 90

End point

◦

C 220

◦

C maximum 210 maximum ASTM D86

Residue vol% 2 maximum 2 maximum ASTM D86

Vapor pressures

Psig @ 100

◦

䉳

←−−−−−−−−−−−−Summer 10 max 7.0 min−−−−−−−−→

䉴

ASTM D323

䉳

←−−−−−−−−−−−−Winter 13.5 max 8.5 min−−−−−−−−→

䉴

Copper strip corrosion

(3 hr at 50

◦

䉳

←−−−−−−−−−−−−−−−Class 1 maximum−−−−−−−−−−→

䉴

ASTM D130

Sulfur wt%

䉳

←−−−−−−−−−−−−−−−−−0.035 max−−−−−−−−−−−−−→

䉴

IP 336 or

ASTM D5453

Existent gum (solvent

washed) (mg/100 ml)

䉳

←−−−−−−−−−−−−−−−−4 maximum−−−−−−−−−−−−−→

䉴

ASTM D381

Oxidation stability

induction period

(minutes)

䉳

←−−−−−−−−−−−−−−−360 minimum−−−−−−−−−−−−→

䉴

ASTM D525

Other speciﬁcations for regular and premium grade gasoline are:

Lead, mg ms/litre 5 maximum IP 224

Benzene, vol% 4 maximum ASTM D5580

Total aromatics 42 maximum (regular) ASTM D 5580

48 maximum (premium)

Oxygenates, vol% 1 maximum (except

ethanol)

ASTM D 4815

Ethanol, vol% 10% maximum

Oleﬁns, vol% 18 maximum ASTM D 1319

708 CHAPTER 16

Table 16.3. Speciﬁcations for kerosene products

Odorless

kerosene Regular grade Premium grade Test methods

Speciﬁc gravity @ 15 0.820 max 0.820 max 0.820 max ASTM D 4052

Appearance @ 15

◦

䉳

←−−−−−−− Clear & Bright −−−−−−−→

䉴

Visual

Color saybolt

䉳

←−−−−−−− + 20 −−−−−−−→

䉴

ASTM D156

Odor Merchantable N/A N/A

Distillation IBP

◦

䉳

←−−−−−−− 175 −−−−−−−→

䉴

ASTM D86

50% 240 max 235 max N/A

90% 210 min N/A N/A

FBP 280 max N/A 280 max

Residue vol% N/A 2.0 max N/A

Flash point

◦

C 75 min (PMCC) 20 min (Abel) 43 min (Abel)

Smoke point mm N/A 20 min 35 min IP 57

Sulfur content Wt% 0.01 max 0.2 max 0.04 max IP 336

Copper 3 hrs 100

◦

C 1 max 1 max 1 max ASTM D 130

Aromatics vol% 1 max N/A N/A

Doctor test

䉳

←−−−−−−− Negative −−−−−−−→

䉴

IP 30

Burning test mg/kg N/A N/A 10 max

The kerosenes

There are three grades of kerosenes which are common in most reﬁneries. These are:

Odorless kerosene

Regular grade kerosene

Premium kerosene

Speciﬁcations for each of these are given in Table 16.3.

Aviation turbine gasoline (ATG) and jet fuels

This product is among the most important item produced in a reﬁnery. Its quality

must conform with stringent requirements particularly for use in commercial aircraft.

In this chapter the description and discussion on ATG will be conﬁned mainly to that

for civil purposes, although reference will be made to the military grades of ATG.

The speciﬁcation that sets the standard for commercial jet fuel quality is the ASTM D

1655. A summary of the speciﬁcation is given in Table 16.4.

IATA (International Air Transport Association) publishes a document for the guidance

of international users of ATG. This document is titled Guidance Material for Aviation

Turbine Fuels Speciﬁcations. This guidance contains speciﬁcations for four aviation

turbine fuel types. Three of these are Kerosene type fuels (Jet A, Jet A1, and TS1)

QUALITY CONTROL OF PRODUCTS IN PETROLEUM REFINING 709

and one wide cut fuel Jet B. Jet A meets the ASTM requirements, Jet A1 meets the

Joint Checklist requirements, TS1 meets the Russian GOST requirements, and Jet

B meets the Canadian CGSB requirements. These speciﬁcations are summarized in

Table 16.5. Jet A1 is listed as the Defense Standard 91–91 which is close to the UK

JetA1 standard.

Table 16.4. Commercial jet fuel speciﬁcation

Composition

Acidity, total, mg KOH/g, max 0.10 – D 3242

Aromatics, vol%, max 25 25 D 1319

Sulfur, mercaptan, % mass, max 0.003 0.003 D 3227

Sulfur, total, % mass, max 0.30 0.3 D 1266, D 1552, D 2622

D 4294, or D 5453

Volatility

Distillation,

◦

CD86

Volume percent recovered

10, max 205 –

20, max – 145

50, max Report 190

90, max Report 245

Final boiling point, max 300 −

Distillation yields, vol%:

Residue, max 1.5 1.5

Loss, max 1.5 1.5

Flash point,

◦

C, min 38 − D 56 or D 3828

Density, 15

◦

C, kg/m

775 to 840 751 to 802 D 1298 or D 4052

Vapor pressure at 38

◦

C, kPa, max − 21 D 323 or D 5191

Fluidity

Freezing point,

◦

C, max −40 (Jet A)

−47 (Jet A-1)

−50 D 2386, D 4305, D 5501, or

D 5972

Viscosity at −20

◦

C, mm

/sec max 8.0 − D 445

Combustion

Net heat of combustion, MJ/kg, min 42.8 42.8 D 4529, D 3338, or D 4809

One of the following requirements:

1. Luminometer number, min 45 45 D 1740

2. Smoke point, mm, min 25 25 D 1322

3. Smoke point, mm, min and 18 18 D 1322

Naphthalenes, vol%, max 3.0 3.0 D 1840

Corrosion

Copper strip, 2 hr. at 100

◦

C, max No. 1 No. 1 D 130

Stability

Thermal stability, 2.5 hr. at 260

◦

Filter pressure drop, mm Hg, max 25 25 D 3241

Tube deposit, less than Contaminants Code 3 Code 3

Existent gum, mg/100 ml, max 7 7 D 381

Water reaction, interface rating, max 1b 1b D 1094

Jet A or A1 Jet B

710 CHAPTER 16

Table 16.5. Summary of speciﬁcations for civil jet fuels

DEF STAN

Speciﬁcation ASTM D 1655 91–91 GOST 10227* CGSB-3.22

Aromatics, vol%, max 25 25.0 22 (% mass) 25.0

Distillation,

◦

Initial boiling point – Report 150 Report

10% recovered, max 205 205 165 Report

50% recovered, max Report Report 195 Min 110; max 190

90% recovered, max Report Report 230 245

End point 300 300 250 Report

Vapor pressure, kPa, max – – – 21

Flash point,

◦

C, min 38 38.0 28 –

Density, 15

◦

C, kg/m

775–840 775–840 – 750–801

Density, 20

◦

C, kg/m

, min – – 775 –

Freezing point,

◦

C, max −40 −47.0– −51

Chilling point,

◦

C, max – – −50 –

Viscosity, −20

◦

C, mm

/sec, max 8 8.0 – –

Viscosity, 20

◦

C, mm

/sec, min – – 1.25 –

Viscosity, −40

◦

C, mm

/sec, max – – 8.0 –

*Some of the GOST test methods are signiﬁcantly different from those used in other speciﬁcations, so

values for these properties may not agree.

Military jet fuel. The governments of the United States and many other countries

maintain separate speciﬁcations for jet fuel for military use. The reasons for separate

speciﬁcations include the operational and logistical differences between the military

and civilian systems and the additional demands high performance jet ﬁghter engines

place on the fuel.

There are currently two fuels in widespread use by the US military. They are JP-5

used by the Navy, and JP-8 used by the Air Force. Both are kerosene type fuels and the

major difference between them is their ﬂash point temperature. The minimum ﬂash

point for JP-8 is 38

◦

C while that for JP-5 is 60

◦

C. The higher ﬂash point for JP-5 is

for safer handling of the fuel on aircraft carriers.

The gas oils

Three grades of gas oils are considered here. They are:

Heating oil (regular grade gas oil)

Automotive grade (diesel fuel)

Marine diesel

QUALITY CONTROL OF PRODUCTS IN PETROLEUM REFINING 711

Table 16.6. General speciﬁcation for regular grade gas oil

Properties Method of test

Speciﬁc gravity @ 60

◦

F 0.820–0.845 ASTM D 1298

Color NPA 1

ASTM D 155

Pour point ASTM D 97

Summer,

◦

F14

Winter,

◦

Cloud point ASTM D 97

Summer,

◦

F25

Winter,

◦

F20

Sulfur, wt% 0.5 ASTM D 129

Diesel index 57 min IP 21

Cetane number 50 min ASTM D 613

Distillation: ASTM D 158

Recovered at 230

◦

C, vol% 10 min

Recovered at 240

◦

C, vol% 50 max

Recovered at 300

◦

C, vol% 70 min

Recovered at 357

◦

C, vol% 90 max

FBP,

◦

C 385 max

Flash point (PM),

◦

F 150 min ASTM D 93

Copper strip (3 hr @ 100

◦

C) 1 A ASTM D 130

Viscosity @ 100

◦

F SUS 37.5 max ASTM D 88

Carbon residue

(Condradson) on 10%

Btms, wt%

0.1 max ASTM D 189

Ash, wt% 0.01 max ASTM D 482

Water by distillation, wt% 0.05 max ASTM D 95

Sediment by extraction, wt% 0.01 max ASTM D 473

Caloriﬁc value (Gross),

Btu/lb

19,300 min ASTM D 240

Heating oil is used predominately as domestic heating oil in many countries. Its most

important properties are the pour point and sulfur content, A full speciﬁcation of the

gas oil is given as Table 16.6.

The speciﬁcation for automotive grade gas oil (Diesel fuel) is given as Table 16.7.

Certain properties of this product are more stringent than those for the heating oil to

meet the present environmental requirements and the present design features of the

diesel engine. The one item that stands out as being very stringent is the sulfur content

of the diesel. This speciﬁcation became effective in 2002. All indications are that it

will be even more stringent in 2006 (see Chapter 2 for more details).

The third gas oil product is really a blend of the gas oil distillate and atmospheric

residuum. It’s color is black and has the following, much smaller speciﬁcation. This

is given as Table 16.8.

712 CHAPTER 16

Table 16.7. The speciﬁcation for diesel fuel

Properties Method of test

Speciﬁc gravity @ 60

◦

F 0.820–0.860 ASTM D 1298

Color NPA 3 max ASTM D 155

Pour point ASTM D 97

Summer,

◦

F15

Winter,

◦

Cloud point ASTM D 97

Summer,

◦

F N/A

Winter,

◦

F N/A

Sulfur, wt% 0.1

∗

ASTM D 129

Diesel index 54 min IP 21

Cetane number 47 min ASTM D 613

Distillation:

Recovered at 230

◦

C, vol% 10 min ASTM D 158

Recovered at 240

◦

C, vol% 50 max

Recovered at 347

◦

C, vol% 50 min

Recovered at 370

◦

C, vol% 95 max

FBP,

◦

C 385 max

Flash point (PM),

◦

F 14 0 min ASTM D 93

Copper strip (3 hr @ 100

◦

C) 1 max ASTM D 130

Viscosity @ 100

◦

F, SUS 35.9 max ASTM D 88

Carbon residue (Condradson)

on 10% Btms, wt%

0.25 max ASTM D 189

Ash, wt% 0.1 max ASTM D 482

Water by distillation, wt% 0.02 max ASTM D 95

Sediment by extraction, wt% 0.005 max ASTM D 473

Caloriﬁc value (Gross), Btu/lb Not speciﬁed ASTM D 240

(*) Down to 50 wt-ppm (0.005 wt%) for ultra.low.sulfur diesel

The fuel oil products

The single most common fuel oil marketed today is the No 6 grade. Of the lighter

grades No 1, 2, 3 were distillate fuels (mostly regular grade kerosene and gas oil

Table 16.8. The speciﬁcation for marine diesel fuel

Properties Method of test

Speciﬁc gravity @ 60

◦

F 0.840 min ASTM D 1298

Pour point—Winter,

◦

F 15 max ASTM D 97

Sulfur, wt% N/A ASTM D 129

Diesel index 50 min IP 21

Flash point (PM),

◦

F 150 min ASTM D 93

Viscosity @ 100

◦

F SUS 32.0–43.9 ASTM D 88

Carbon residue (Condradson) on 10% Btms, wt% 0.2 max ASTM D 189

QUALITY CONTROL OF PRODUCTS IN PETROLEUM REFINING 713

Table 16.9. Speciﬁcation for No 6 fuel oil product

Properties Method of test

Speciﬁc gravity @ 60

◦

F 0.990 max ASTM D 1298

Pour point,

◦

F 65 max ASTM D 97

Sulfur, wt% 2.0 max* ASTM D 129

Viscosity kinematic @ 122

◦

F, Cs 370 max ASTM D 445

Flash point (PM),

◦

F 160 min ASTM D 93

Ash, wt% 0.1 max ASTM D 482

Water (by distillation), vol% 1.0 max ASTM D 95

Sediment (by extraction), wt% 0.1 max ASTM D 473

*Sulfur content is probably closer to 1.5% wt for most areas now.

types). These pretty much disappeared from the markets during the 1980s. No 5 fuel

was a light residual fuel used mostly in the steel industry. It is no longer widely used.

No 6 fuel is a heavy residual fuel normally a mixture of atmospheric and vacuum

distillation residues cut back to adjust for viscosity with kerosene or gas oil cutter

stock. This fuel oil product is almost entirely used as ship bunker oil, with some

market outlet to stationary power plants in producing steam for their turbines. For the

last 20 years or so these markets have been in decline. Power plants are converting to

the use of coal or natural gas, and ships are leaning more to the use of marine diesel

or just diesel fuel. Environmental restrictions are calling for a continual decrease in

the sulfur content of this particular product. As a result no 6 fuel is the least valued

reﬁnery product and is worth less than the crude feed itself. Reﬁners are now installing

processes (such as ‘deep oil cracking’, and residue hydrocracking) to upgrade this

product to the more valued distillates such as gasoline and the middle distillates. The

speciﬁcation for a No 6 fuel oil is given as Table 16.9.

The lube oils

Most marketable lube oils produced in a reﬁnery are graded by their viscosity. Pro-

prietary brands of these lube oil grades will contain additives as provided by their

particular marketing outlets. These basic grades and their speciﬁcation are given in

Table 16.10. Other speciﬁcations apply for multi-grade lube oils

These grades and their processing are described in some detail in Chapter 12.

The asphalts

The production of the asphalt grades and their speciﬁcation has been described and

discussed in Chapter 12 of this book.