U.S. patent number 3,776,248 [Application Number 05/170,563] was granted by the patent office on 1973-12-04 for pipeline transportation of waxy products.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to Paul E. Titus.
United States Patent |
3,776,248 |
Titus |
December 4, 1973 |
PIPELINE TRANSPORTATION OF WAXY PRODUCTS
Abstract
An improved method of pipeline transporting highly waxy crude
oil in pumpable slurry form with the aid of a particular class of
non-ionic surfactants.
Inventors: |
Titus; Paul E. (Houston,
TX) |
Assignee: |
Shell Oil Company (Houston,
TX)
|
Family
ID: |
22620372 |
Appl.
No.: |
05/170,563 |
Filed: |
August 10, 1971 |
Current U.S.
Class: |
406/49; 137/13;
507/90; 208/370 |
Current CPC
Class: |
C10L
1/106 (20130101); C10L 1/10 (20130101); C10L
1/1985 (20130101); C10L 1/125 (20130101); Y10T
137/0391 (20150401) |
Current International
Class: |
C10L
1/10 (20060101); C10L 1/18 (20060101); C10L
1/12 (20060101); F17d 001/16 (); B65g 053/04 () |
Field of
Search: |
;252/8.3,8.55R ;302/66
;137/13 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Guynn; Herbert B.
Claims
We claim as our invention:
1. A method of pipeline transporting waxy crude oil without causing
plugging or clogging of the pipeline, the steps comprising:
a. adding to the waxy crude oil from about 0.1%v to about 5%v of an
oil-soluble, water insoluble non-ionic surfactant having the
formula ##SPC3## wherein n is an integer of 2 to 7 and R is an
alkyl radical having from four to 20 carbon atoms;
b. adding an aqueous liquid to (a) to form a slurry of the
oil-soluble non-ionic surfactant containing waxy crude oil with the
aqueous liquid; and
c. injecting slurry (b) into a pipeline.
2. The method of claim 1 wherein the aqueous liquid is water.
3. The method of claim 2 wherein the surfactant is
nonylphenoxytetraethyleneoxyethanol.
4. The method of claim 3 wherein the amount of water used to form
the slurry is between 5 and 40 percent.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to an improved process of
pipeline transporting highly waxy crude oil and fractions thereof,
which under normal conditions are difficult or impossible to pump
through a pipeline primarily because of the tendency of such crudes
to plug and clog the pipeline with wax deposits, by treating said
waxy crude oil with an oil-soluble non-ionic surfactant containing
hydrophobic-hydrophilic constituents capable of fragmenting the wax
constituents in the molecule in the crude into small particles on
being contacted with an aqueous liquid such as water and forming an
easy to handle pumpable slurry.
2. Description of the Prior Art
Various methods have been proposed for transporting waxy crude oil
and fractions thereof as evidenced by reference to U. S. Pats.
2,533,878, 2,927,978, 3,067,134, 3,076,757, 3,096,777, 3,244,188
and 3,249,535. A serious defect of these methods of handling and
transporting such materials is their short effectiveness life, the
tendency of the treating or improving composition to form emulsions
causing viscosity increase resulting in increased pumping cost and
handling, separation difficulties, and the general ineffectiveness
of such methods to solve the problems under discussion when
handling highly waxy hydrocarbon liquids. The method of the present
invention overcomes these defects and results in a process which
prevents, inhibits, and solves in general the problem of
accumulation of waxy hydrocarbon materials on contacting
surfaces.
To summarize present conventional methods used to modify waxy
materials for pipeline transport include: (1) diluting the material
with a low-viscosity, low pour point oil, (2) thermally treating
the material to alter composition (visbreak, etc.), (3) addition of
materials to lower the pour point (pour point depressants), and/or
(4) heating the pipeline to maintain the temperature above the pour
point. These steps, while technically feasible, are uneconomical or
the value of the product is depreciated and the material cannot be
fully utilized.
OBJECTS OF THE INVENTION
It is an object of this invention to prevent and inhibit the
formation, deposition and accumulation of hydrocarbonaceous
materials on interior surfaces of pipelines having waxy
hydrocarbons by treating said hydrocarbons with a novel non-ionic
surfactant and slurrying said treated hydrocarbons with an aqueous
liquid.
Still another object of the present invention is to facilitate the
handling and transportation of waxy crude oil and fractions thereof
through pipelines by treating the oil with a
hydrophobic-hydrophilic containing non-ionic surfactant and
slurrying said treated waxy crude oil with water.
Still another object of this invention is to provide an improved
method of handling and transporting highly waxy crude oil at low
pumping costs and under reduced friction conditions.
Other objects will be apparent from the following description and
claims.
Now, in accordance with this invention, it has been found that waxy
crude oil and fractions thereof can be effectively and efficiently
transported through pipelines over great distances without the
danger of clogging, plugging or shutdown by treating or modifying
waxy hydrocarbons such as waxy crude oil with an oil-soluble
non-ionic surfactant having hydrophobic-hydrophilic constituents in
the molecule and having the formula ##SPC1##
wherein R is an alkyl radical having from four to 20 carbon atoms
and n is an integer of from 2 to 7, which treated oil on being
contacted with an aqueous liquid such as water effects
fragmentation of waxy components into small particles of from about
10 to about 10,000 microns, resulting in a slurry formation of waxy
particles in hydrocarbon dispersed in an aqueous liquid which is
easily pumpable and transportable in pipelines over long distances
without causing plugging or clogging of the lines which lines can
be readily restarted after shutdown.
The oil-soluble non-ionic surfactant used in fragmenting and
dispersing wax into small particles which are readily slurried in
an aqueous liquid such as water is an alkyl phenol-ethylene oxide
reaction product in which the final product contains from 3 to 8,
preferably 4-7, ethylene oxide units in the molecule and can be
represented by the formula: ##SPC2##
where n is an integer of 2 to 7 and R is an alkyl radical having
from four to 20 carbon atoms preferably six-10 carbon atoms.
Surfactants of this class are available under the trade names of
Triton X-45, Triton N-57 (Rohm-Haas); Tergitol NP-14 (Union
Carbide) or Igepal CO430 or 530 (GAF Corporation) of which
preferred is Triton X-45 or nonylphenoxytetraethyleneoxyethanol.
The amount of this class of surfactant which is added to a waxy
hydrocarbon or wax per se can vary from about 0.1 percent to about
10 percent by weight.
A typical waxy hydrocarbon which is extremely difficult to
transport through pipelines or through tubing string of well bores
used in oil recovery of such crudes and which on treatment by the
process of this invention are easily pumped and transferred are
Unitah crudes which are high gravity, waxy oils described in the
October 1970 issue of World Oil, pages 113-117 and a typical Unitah
crude has the following properties:
TABLE I
Crude Properties Value API GRAVITY 38.6 RE ID VAPOR PRESS, PSI Z .0
FLASH POINT, COC, .degree.F Z 0. SULFUR CONTENT, PCT W .05 WATER,
BY DIST, PCT V .0 BS-W, BY CENTRIFUGE, .0 PCT V SALT, LBS PER 1000
BBLS 2.0 COLOR 2. SQUALANE NUMBER Z .0 POUR POINT, .degree.F 120.
VISC, SSU AT 40.degree.F Z .0 VISC, SSU AT 100.degree.F Z .0 VISC,
SSU AT 140.degree.F 51.8 VISC, SSU AT 210.degree.F 33.7
these crudes pose a special problem in that below a particular
temperature (pour point, or melting point) these crudes become
solid, or semi-solid and are difficult to handle and pump. When
this temperature occurs above the normal ambient temperature of the
pipeline, these crudes cannot be readily transported as such alone,
but must be modified in some manner to reduce the high pressure
drops associated with the pumping of a viscous semi-solid.
PREFERRED EMBODIMENT OF THE INVENTION
The invention is directed to a method for modifying waxy-containing
hydrocarbons so as to put it in a form of low viscosity, easily
movable, water-continuous slurry as illustrated by the attached
FIG. 1. This is accomplished by adding to or admixing with certain
types or classes of non-ionic oil-soluble surfactants to the waxy
material (when liquid) and then combining the liquid wax (or wax
cooled to the semi-solid state) with an aqueous liquid such as
water, brine, etc., to form the slurry. The most effective
surfactant is an alkylaryl polyether alcohol containing 5 ethylene
oxide groups such as Triton X-45 (Rohm and Haas Company). This
material when added to Unitah crude (about 0.2%v) causes the waxy
crude to form a pumpable slurry when combined with 1-40% water.
Thus, from the figure, the invention is practical as follows:
waxy crude 10 such as Unitah crude oil recovered from an
underground formation is contacted with about 0.2-0.5%v of Triton
X-45 via 11 and thereafter water is added (1-60%, preferably
between 20% and 40%v) via 12 to form a slurry mixture which is
pumped through pump or mixer 13 into a pipeline 14 for
transportation to a terminal station where it is conduced into a
separator 15 such as a filter, settler, cyclone, etc., where the
oil is recovered in pipe 16 for further handling and the water
disposed or recycled through line 17. Thus, at the pipeline
terminal the waxy hydrocarbon can be readily separated from the
water phase of the slurry by filtering or heating and settling.
The essence of the invention is that it causes the formation of a
modified waxy material that can be easily transported by pipeline,
and not be degraded as a result of the process. The additive is
easy to mix with the waxy material, and the mix is easy to slurry
in an aqueous liquid carrier such as a water carrier. The resultant
slurry is readily separated at the terminus either by filtration or
heating and settling. Since the surfactant is not water soluble,
the recovered water does not become a disposal problem.
In addition to waxy hydrocarbons such as waxy crude oil, waxes per
se can be fragmented into small particles by the process of this
invention for easy handling, packaging, molding, etc. In such cases
the wax, e.g., petroleum wax is diluted with or dissolved in a low
boiling point hydrocarbon or polar solvent such as cyclohexane,
hexane, benzene; ketones, ethers, etc., and a small amount
(0.1-5%v) of surfactant such as Triton X-45 or Tergitol NP-14 added
thereto. Water is then added in amount (5-40%) sufficient to form a
slurry. Wax particles (1-1,000 microns) are recovered by separating
the water phase from the wax particles-solvent phase by filtering
and the solvent removed by flashing it off leaving behind
non-agglomerating wax particles.
The foregoing description of the invention is merely intended to be
explanatory thereof. Various changes in the details of the
described method may be made, within the scope of the appended
claims, without departing from the spirit of the invention.
* * * * *