PROCESS TECHNOLOGY

Pluses and minuses of

caustic treating
Proper use and spent solution
Table 1. Comparison of capital and operating costs
management ensure the safest and for a 10,000-bpsd jet fuel caustic treater and a
most cost-effective operations comparable hydrotreater

Caustic treating Hydrotreating

F. J. Suarez, Merichem Co., Houston, Texas
Capital costs, U.S.$/bbl 150 to 200 1,500 to 2,500

I
n recent years, refineries and petrochemical plants Operating costs, U.S.$/bbl
worldwide have faced stricter controls on liquid Catalyst and chemicals .0172 .380
and gas effluent dicharge streams that could cause Utilities .0005 .025
air or water pollution. Spent caustic (NaOH) solutions
Labor .0060 .012
are liquid effluents that must be properly managed to
maintain the plant discharge’s quality. Since there are Total .0237 .417
different types of spent caustic streams, refiners must
correctly categorize them to use the most effective dis-
posal or treating method.
The hydrocarbon processing industry (HPI) has his- 0.16
torically used caustic solutions to extract or treat acidic
0.14
impurities such as hydrogen sulfide (H2S), mercaptans
and organic acids in hydrocarbon streams. Today, caus- 0.12
tic solutions continue to be the primary reagents used in
U.S.$/lb

these treating operations because they have been proven 0.10

safe, economical, effective and, above all, environmentally
0.08
acceptable. When properly recycled or treated, used caustic
streams do not constitute damaging, hazardous waste. 0.06
Over 50 U.S. refineries and 10 outside the U.S. ship
caustic solutions to U.S. chemical plants. Yet these streams 0.04
are not classified as RCRA waste by EPA because they 1986 ’87 ’88 ’89 ’90 ’91 ’92 ’93 ’94 1995
are processed for beneficial reuse. Much of the concern Year
expressed today about caustic use in HPI operations can
be attributed to the following: Fig. 1. Average caustic prices (U.S. Gulf Coast).
• Many plant operators are unaware of options for in-
plant processing or recycling of spent caustic. tic is primarily used to remove sulfur compounds from
• Poorly designed caustic treaters can cause operating light streams and oxidize mercaptans in heavier streams.
problems. The pluses and minuses of caustic treating are presented
• Spent caustic can be turned into hazardous waste by to help refiners and other petrochemical plant operators
outside disposal companies. make careful, intelligent economic choices. Although the
• Unfounded concerns about caustic use, such as these focus is on refinery treating operations, the information
recent inaccurate statements: “Spent caustic will be regu- presented applies equally well to many other petrochemi-
lated as hazardous waste by EPA” and “Spent caustic cal operations.
disposal costs are as high as U.S.$3.00/gal.”
Based on the economic benefits, caustic is still the best Removing sulfur compounds from light refinery
treating reagent available to the HPI. In refineries, caus- streams. The sulfur content of many refinery streams

HYDROCARBON PROCESSING / OCTOBER 1996 117


Table 2. Characteristics of a typical refinery
sulfidic caustic stream
Free NaOH, wt% 2 to 10
Na2S, NaHS as S–, wt% 0.5 to 4
Mercaptides as S, wt% 0.1 to 4
Carbonate as CO3, wt% 0 to 4
pH 13 to 14
Total Na+, wt% 4 to 10
Ammonia Traces
must be reduced. Refinery gases, liquefied petroleum
gases and light naphthas contain sulfur primarily as H2S,
carbonyl sulfide (COS) and mercaptans that can easily
be extracted with caustic solutions. These streams are
almost universally treated with caustic (downstream of an
amine extraction system for bulk H2S removal) because
capital and operating costs are 80% to 95% lower than
hydrotreating costs. When compared to molecular sieves,
caustic treating is not only cheaper, but also far more reli-
able in meeting product specifications.
Used mercaptide rich caustic from these processes can
be regenerated in a catalytic treating system. Sulfidic
caustic solutions rich in Na2S/NaHS can easily be sold,
recycled or treated in situ while maintaining the attrac-
tive economics of caustic treating processes.
Oxidizing mercaptans to sweeten heavier streams.
Unfortunately, sulfur compounds in heavy fractions like
heavy naphtha, jet fuel and diesel are not caustic extract-
able. However, caustic solutions are widely used to convert
odorous and corrosive mercaptans to acceptable disulfide
oil via an air/catalyst oxidation (sweetening) process. If
the total sulfur content is already within product require-
ments, most gasoline, jet fuel, kerosine and diesel frac-
tions can be satisfactorily sweetened with caustic.
Hydrotreating, the most widely used alternative to
caustic sweetening, is very effective. However, hydro-
treating cannot compete with caustic treating in capital
and operating costs. Table 1 compares capital and oper-
ating costs of a 10,000-bpsd jet fuel caustic treater and
a comparable hydrotreater.
Caustic sweetening processes produce organic
byproducts (phenolic caustic and naphthenic caustic
solutions) that must be accounted for when designing
a treating plant. Cracked gasolines contain phenols, a
portion of which are incidentally extracted by the caus-
tic treating solution. For jet fuel, kerosine and diesel
streams, the sweetening process usually uses a caustic
prewash to remove all corrosive naphthenic acids, which
cannot be allowed into the final products. Phenolic and
naphthenic caustic solutions can either be sold or prop-
erly managed in the plant.
In recent years, an old wet sweetening process using
ammonia instead of caustic has been offered as a way
to eliminate coproduct caustic solutions. However, since
ammonia is hydrocarbon soluble and a weak base com-
pared to caustic, extra product cleanup steps and expen-
sive catalytic additives must be used, substantially
increasing treating costs.
118 HYDROCARBON PROCESSING / OCTOBER 1996
In addition, the aqueous ammonia byproduct solution
and the ammonia-laden wash water can be even more dif-
ficult to manage than caustic treating byproducts. Ammo-
nia wastes cannot be recycled either in-plant or outside,
leaving only the option of in-plant waste processing.
If an organic ammonium salt solution is processed in
a refinery sour water stripper, organic acids remain in
the treated sour water and must then be oxidized in the
biological wastewater treating plant. The organic-rich
treated sour water should not be recycled to the crude
desalters, because the acids will eventually end up in the
distillates, to be treated again.
Advantages of caustic as a treating reagent. As
previously stated, aqueous caustic is a proven, safe and
economical chemical treating agent well-adapted for the
HPI and many other industries, including paper, alumi-
num and edible oil.
Economics. Fig. 1 shows caustic prices on the U.S.
Gulf Coast over the last 10 years. Caustic prices fluctu-
ate primarily due to demand for its coproduct, chlorine.
But over the long term, caustic’s price has increased at a
slightly lower rate than inflation. Refiners can dampen
price fluctuations by entering into long-term contracts as
opposed to buying caustic on the spot market. Caustic is,
and will continue to be, one of the lowest priced inorganic
bases available to the HPI.
Safety. Caustic is also safer than many other chemi-
cals used in the HPI. Storage, handling and personnel
protection requirements for caustic solutions are much
less rigorous than those for sulfuric acid, hydrofluoric
acid, gaseous ammonia, H 2S, amines and many other
refinery chemicals.
Performance. In process units, caustic is easy to pump
and control. At operating temperatures below 200°F, the
metallurgical requirement is typically low-cost carbon
steel.
Since caustic is not soluble in hydrocarbons, complete
phase separation can be achieved in a properly designed
treating unit. Some process designs use vigorous mixing
systems that tend to emulsify the caustic and hydro-
carbon phases. In these cases, a sand filter or water
wash will remove any entrained aqueous material from
the hydrocarbon product. Other modern processes can
affect contact between phases without mixing, result-
ing in clean phase separation without resorting to such
cleanup steps.
Spent caustic management. In comparing caustic
treating to alternative processes, the most critical issue,
after hydrocarbon product specifications and process eco-
nomics, is the management of byproduct spent caustic
solutions. Operating companies often choose a treating
process based on spent caustic disposal rather than the
favorable economics of caustic treating.
Spent caustic disposition, like any other refinery opera-
tion, requires careful evaluation. Unfortunately, many
engineering and technology firms that advise refiners
and design spent caustic handling systems do not have
the knowledge to optimize these systems. Errors made
early in the design process are compounded, resulting in
extremely costly economical and environmental mistakes.
These errors include:

• Mixing all types of spent Table 3. Characteristics of typical refinery cresylic
caustic in the same storage caustic streams
vessel, rendering the entire
Strong caustic
mixture unsalable caustic
• Designing caustic stor-
age systems that are too
NaOH (at pH 7), wt%
small to allow for the lowest
possible transportation costs Sulfide as S–, wt%
• Processing a mixture of Mercaptide as S–, wt%
all types of caustics in a sin-
gle treating plant designed Cresylic acids, wt%
for only one type =
• Controlling the pH Carbonates as CO3 , wt%
inadequately in the neu- pH
tralizers, which reduces the
effectiveness of contaminant
removal.
One of the most critical errors is assuming that all
refinery spent caustic streams—sulfidic, cresylic and
naphthenic—are alike and can be mixed and handled
together, either by an outside company or an internal
processing plant. Although this scenario might work in a
few cases, mixing spent caustic streams generally results
in higher disposition costs. For example, a refiner could
receive $0.05/gal for selling phenolic caustic while paying
$0.20/gal for removal of sulfidic caustic, but would not find
a market for the mixed caustic stream. Furthermore, the
refiner would pay a hazardous waste processor at least
$1.00/gal in disposal fees and would have to manifest the
mixed caustic as RCRA waste.
Alternatives for managing each type of spent
caustic. Sulfidic caustic. The composition of a typi-
cal refinery sulfidic caustic stream is in Table 2. The
key potential pollutants are sodium sulfide and sodium
mercaptide. These contribute to chemical and biological
oxygen demand (COD and BOD) in wastewater treating
plants, and produce odors and dangerous gases when
neutralized.
Sulfidic caustic solutions can be sold as treat-
ing agents to pulp and paper plants or to the mining
industry for purifying certain metal ores. Since these
end users require consistent quality, sulfidic caustic
is usually sold to intermediate companies that blend
the required product quality while providing just-in-
time transportation and delivery service. The total
sodium content of these streams is important as well as
the sodium-to-sulfur ratio. Although sulfidic caustic
solutions are valuable to the industries that use them,
in actual practice, transportation and handling
costs usually exceed product value. The refiner must
subsidize the operation with fees that can range from
$0.20/gal to $0.60/gal.
When production of sulfidic caustic is high or potential
end users are far away, resulting in high transportation
costs, in-plant processing may be the most economical
option. Here again, know-how is extremely important to
ensure that the treated caustic will not become an envi-
ronmental liability. Refiners have several options:
• Deep neutralization to a pH below 4, coupled with
acid-gas handling to prevent transfer of pollutants from
the water to air. Neutralization to a pH of 7 does not
120 HYDROCARBON PROCESSING / OCTOBER 1996
significantly reduce con-
taminants in these streams
and has been improperly
applied by many refiners
Dilute
without much environmen-
operation operation tal benefit.
10 to 15 1 to 4
• Partial oxidation of
sodium sulfide to sodium
0 to 1 0 to 0.2 thiosulfate. This allows
0 to 4 0 to 0.5
oxidation to be completed
in the wastewater treating
10 to 25 2 to 5 plant to avoid the risk of
releasing unsafe, odorous
0 to 0.5 0 to 0.1
H2S and mercaptans. Since
12 to 14 12 to 14 caustic is partially regen-
erated in the oxidation pro-
cess, it can also be used as
an alternative to fresh caustic in other plant processes.
• Total oxidation of sodium sulfide to sodium sulfate
for maximum removal of COD and BOD before the waste-
water treating plant
• Thermal incineration
• Cascading to other treating systems for streams like
cracked gasoline while converting the caustic byproduct
to a more valuable product such as cresylic caustic.
Other options used by refiners like sending spent caus-
tic to the crude unit or the sour water stripper are not
considered reliable.
One option refiners try to avoid but often cannot is
outside disposal of sulfidic caustic as hazardous waste.
This can be economically avoided in most cases. The key
is to use high caustic strengths (>20°Be) and segregate
the sulfidic product from other spent caustics.
Cresylic caustic. Cresylic acids are, in effect, part of
gasoline and do not reduce its quality. However, extract-
ing these acids from gasoline is sometimes more profit-
able than leaving them in. Cresylic caustic solutions
produced from treating cracked gasolines generally come
from two sources: 1) extraction or oxidation systems
using strong caustic; and 2) oxidation systems using
weak caustic. Table 3 shows typical characteristics of
cresylic caustics.
The first type of byproduct cresylic caustic solution
can be sold at fairly attractive prices, often covering the
value of the hydrocarbon content even after deducting
transportation costs. These streams typically contain at
least 10 wt% of phenolic compounds (average content
is 15 wt%) in addition to sulfur compounds like sodium
sulfide and mercaptans. Cresylic caustic processors
recover phenolic compounds for the production of valu-
able chemicals. When the refinery is far away from the
caustic processor, railroad or barge transportation costs
exceed the cresylic caustic stream’s value.
The second type of cresylic caustic byproduct contains
less than 5 wt% phenolics. The low acid oil content drasti-
cally increases transportation and processing costs. For
these reasons, this type of byproduct may be more eco-
nomical for in-plant processing. Cresylic caustic solutions
processed in-plant should be segregated from other spent
caustics and neutralized with a mineral acid or acid gas to
a pH of 7. Additional facilities are needed to solvent extract
the neutralized caustic to reduce levels of soluble phenol
and cresols in the water phase. The biological wastewater

Table 4. Characteristics of typical refinery
naphthenic caustic streams
Jet fuel/Kerosine Diesel
NaOH, wt% 1 to 4 1 to 4
Sulfide as S–, wt% 0 to 0.1 Trace
Mercaptide as S=, wt% 0 to 0.5 0 to 0.5
Naphthenic acids, wt% 2 to 10 2 to 15
Phenolics, wt% 1 to 3 0 to 1
pH 12 to 14 12 to 14
treating plant may remove remaining phenolics, provided
the biological mass receives a steady diet of these com-
pounds without abrupt fluctuations in concentration or
total weight. Recovered acid oils can be sold or recycled to
refinery processes that tolerate the oils’ sodium content.
Naphthenic caustic. These solutions typically con-
tain 5 wt% to 15 wt% naphthenic acids, depending on the
caustic concentration, caustic spending target and acidity
of the jet fuel, kerosine or diesel stock being processed.
Table 4 shows typical characteristics of naphthenate
streams derived from kerosine and diesel stocks.
Naphthenic caustic solutions can be sold, often
resulting in positive value to the refiner, if distance or
low acid concentrations do not result in high freight
costs. Outside processors neutralize these solutions to
recover the naphthenic acids, then refine them for sale
to producers of naphthenate metal salts. Acids derived
from jet fuel/kerosine provide a high acidity in the 240
to 250 mg KOH/g range, while acids from diesel are on
the order of 180 to 200 mg KOH/g. Typically, the higher
acidity products are worth more in the marketplace. Net
return can be as much as two to four times the value of
an equivalent amount of diesel fuel.
For refiners whose treaters produce high volumes
of low-concentration naphthenic caustic solutions, in-
122 HYDROCARBON PROCESSING / OCTOBER 1996
plant processing may be the most economical option.
Naphthenic solutions cannot be mixed and oxidized with
sulfidic caustic since sodium naphthenate creates vigor-
ous foaming during air injection.
Refiners should use a process that: 1) neutralizes
the caustic solution with a mineral acid to a pH of 3
to 4; 2) recovers the sprung acid oils and cleans up the
remaining organics; then 3) brings the pH up to the
range required for final treatment in the wastewater
treating plant. Sprung acid oils can be sold or recycled in
the refinery wherever sodium can be tolerated.
As mentioned earlier, one of the root causes of prob-
lems with caustic treating operations is lack of know-
how by both engineering companies and plant operat-
ing groups that design treaters and manage byproduct
caustic solutions. Poor design and management result
in processing and environmental problems, and finally,
in bad economic decisions.
With few exceptions, caustic treating processes are
extremely cost-effective and environmentally sound.
When sold or transferred as chemical feedstocks to out-
side chemical processors, none of these caustic solutions
are labeled hazardous waste by EPA, nor is such labeling
expected in the foreseeable future.
However, when quality specifications are ignored or
when spent caustic management is left to outside dis-
posal companies, spent caustic solutions can easily be
transformed into hazardous wastes. 
The author
Felipe J. Suarez is vice president and general manager of
the process technology division of Merichem Co., Houston,
Texas. He has served as special projects manager, technical
services manager, raw materials technical services manager,
proprietary technology group manager, assistant sales
manager and assistant general manager. From 1969 to
1980, he worked for Murphy Oil, Meraux, Louisiana, with
experience in refinery process design and operations. He
holds a BS degree in chemical engineering from Louisiana
State University in Baton Rouge, Louisiana.
HYDROCARBON PROCESSING / OCTOBER 1996 123