COLD FLOW

IMPROVERS

Paul McIntosh
CONTENT

 Introduction
 Temperature Effects
 Flow Improver mechanisms
 Paraffin distribution
 Monitoring tests

2
DIFFERENT FUEL COLD FLOW TEMPERATURES

As diesel start to cool down in temperature the first wax crystals start to form

- Cloud Point is the temperature at which the first wax crystals start to form

- Cold Filter Plugging Point (CFPP) is the temperature at which fuel filters block with
wax - affecting engine operability. This is considered to be a more relevant test over
the basic pour point

- Pour Point (ASTM D97) measurement is the temperature at which diesel stops
flowing completely

CFPP is the most prevalent cold flow specification on diesel or mid distillate fuels that
needs to be met

*
COLD FLOW TEMPERATURES
• linear, branched, or cyclic hydrocarbons typically
WAX
containing from 8 up to 60 carbon atoms

• The temperature that crystallized wax becomes visible

Cloud
Point

• The lowest temperature at which fuel remains operability

CFPP
through a standardized test filter*

• The lowest temperature at which fuel remains in the liquid

state
Pour Point • just prior to gelation
*
there is currently a new phenomenon called Wax Drop Out (WDO) where under periods of extended
“Cold Soak” (+ 48 hours) the wax in the fuel suddenly drops out of the fuel can happen at temperatures
that can be above the CP: this problem appears at this time to be independent of CP or CFPP.
MORE ON CLOUD POINT AKA WAX APPEARANCE TEMPERATURE

WAT is not a fixed value, consider method and also effect of temperature & pressure

The wax appearance temperature (WAT) is the temperature at which paraffin first begins to crystallize in a crude oil of
distillation fraction.

Several methods are available to determine the WAT, most commonly used are:

- Differential Scanning Calorimetry (DSC) – need ~100ppm wax out of solution

- Cross Polar Microscopy (CPM) – first crystal or change in transmitted light
- Filter Plugging from ΔP measured across a fine mesh filter

Each method has its limitations, with significant variation observed between
procedures

*
CFPP SPECIFICATIONS

CFPP specification varies with season and climate

Region/Country Summer Winter

South Africa +3ºC -4ºC
India +18ºC +6ºC
Artic Countries +5ºC -44ºC
United Kingdom -5ºC -15ºC

Region/Country Spec
Saudi Arabia Export -6ºC -15ºC
CFPP MEASUREMENT

A variety of manual and automatic Cold Filter Plugging Point analysers are
available on the market.

- Cold Filter Plugging Point assessed using ASTM D 6371 (equivalent to

EN116) test method.

- Repeatability of method +/- 1.76°C.

*
CFPP (MDFI) ADDITIVES

CFPP improvers are added to diesel streams to minimise cold weather handling problems and to meet country specifications.

CFPP ADDITIVE MECHANISM

- CFPP Additives improve the low temperature properties of gas oils by changing the way the wax crystals grow.

- CFP Additives are polymers which contain “crystallisable” paraffin character within the molecule, functioning in two ways:

1. Nucleation - additive itself starts to crystallise from solution at or near the wax appearance point of the gas oil. This
creates additional nucleation sites which promotes the formation of many small irregular crystals rather than larger
crystals

2. Co-crystallization - additive co-crystallises with wax altering the size/shape of wax crystals. Co-crystallization
of the additive with wax inhibits wax crystal cohesion
*
CFPP (MDFI) ADDITIVES OR WAX CRYSTAL MODIFIERS

▪ Additives which improve the low temperature properties of crude or middle distillates by changing
the way the wax crystals grow

▪ Typical WCM characteristics:

✓ a paraffinic component composed of linear alkane chains 8 to 32 carbons in length
- interacts with the diesel wax
- hydrocarbon soluble
✓ a polar component (an acrylate or acetate) O CH3
✓ Polymeric
H O
H H
*
n ran
H H *
H H

Examples of the chemistries* in WCMs include polyethylene vinyl acetate copolymers, vinyl acetate alpha
olefin copolymers, alkyl esters of styrene-maleic anhydride copolymers, polyalkyl acrylates, polyalkyl
methacrylate and alkyl esters of unsaturated carboxylic acid and alpha olefin copolymers
MECHANISM OF WAX CRYSTAL MODIFICATION

Mechanism of nucleation with crystals

Visualization of CFA Effect on Wax Crystal Formation

EFFECT OF COLD FLOW ADDITIVES ON FUEL

The CFPP injection improves the Pour Point and CFPP but doesn’t impact the Cloud
Point
IMPACT ON THE FUEL’S WAX DISTRIBUTION
PARAFFIN RATIO / WAX DISTRIBUTION IN DIESEL
FUELS
PARAFFIN DISTRIBUTION IN DIESEL FUELS
(DISTILLATION DIFFERENCES)
SELECTING OF CFPP ADDITIVES
Typical dosage rates range between 100-800 ppm.
- CFPP requirements are known to vary with the base crudes, diesel cut point and target specifications.
- Strongly recommend that CFPP test work be carried out to establish the correct additive and treat rate for a particular diesel blend.
- CFPP’s may require taylor made products.

Selection of correct CFPP Changing fuel blend at same customer

6

CFPP result (ºC)

0 200 400 600 800 1000 1200 1400
-2 TSR 6821
-4 TSR 08174
TSR 0497
-6
TSR 04587
-8

-10

-12

-14
EC5941A Dosage (ppm)
SERVICE SUPPORT - DIFFERENTIATION
An effective CFPP additive alone does not guarantee success of the treatment programm. Of equal
importance is application, monitoring and reaction to CFPP results.

- Depending on customer requirements Nalco can at the basic level advise on suitable application points and
carryout simple pump and stock checks on an agreed frequency. Alternatively we can monitor and report on
a much greater frequency factors effecting results and take a much more proactive role in the control of
CFPP additive and other treatment programs.

- At some sites Nalco personnel act as a link between Production Planning, Blending and the Site
Laboratory
to ensure that all program dosage rates are quickly adjusted as and when required.

- Diesel additive spend represents in the case of most refineries their biggest chemical expenditure and
consequently the one in which the greatest savings may be possible
BEST PRACTICE INJECTION
- Inject at least 10 degrees C above the cloud point
- Inject continuously rather than batch wise
CFPP PSR