Spent Caustic Treatment:

The Merits of PRETREAT™ Technology

Applications for the
Refinery/Petrochemical Industries
Joseph M. Gondolfe and Sabah A. Kurukchi, PhD

Copyright © All Rights Reserved

Shaw Stone & Webster
Joseph M. Gondolfe and Sabah A. Kurukchi
 Intentionally Blank

Originally prepared for presentation at the

Eleventh Ethylene Forum
May 14-16, 1997
The Woodlands, Texas

Shaw Stone & Webster Shaw Stone & Webster 13

 Spent Caustic Treatment:
The Merits Of PRETREAT™ Technology
Applications for the Refinery/Petrochemical Industries
Today's refiner and petrochemical producer is forced by more stringent
environmental regulations to better monitor and control their wastewater
to/from biological treatment. One of the key contributors to relatively
high chemical oxygen demand (COD) and biological oxygen demand
(BOD) is from the acid gas (both CO2 and H2S) removal system(s)
Intentionally Blank
typically using dilute caustic soda (NaOH) as the active reagent – the
resultant waste stream is otherwise known as spent caustic.
Typical sulfidic spent caustic derived from acid gas removal in either a
petrochemical or refinery facility can contain significant contaminants
comprised of dissolved hydrocarbon, polymers and active polymer
precursors in addition to the well defined levels of sodium salts and free
caustic. These lesser known contaminants can grossly inhibit the
conversion level of sodium sulfide to its highest oxidation state –
sodium sulfate.
A unique approach to (pre)treat these aforementioned contaminants
has been developed, otherwise known as PRETREAT™ Technology¹,
which now allows a cost effective method of achieving virtually
complete oxidation of spent caustic using the following steps:
(1) (Pre)Treatment
(2) Bulk Wet Air Oxidation
(3) Advanced Chemical Oxidation
(4) Post-Treatment
Extensive pilot plant tests have confirmed that the process configuration
illustrated in Figure 1 affords high flexibility to address the specific
demands of today's petrochemical/ refinery facility including upgrading
existing treatment units to better satisfy current (or future) federal and
state regulatory requirements. This unique approach to spent caustic
treatment includes innovations never before applied in the manner
prescribed.
Moreover, the use of PRETREAT™ Technology can now be used as a
singular method to condition raw spent caustic for virtually complete
removal of all oligomers and organics from solution to yield a value-
added “product” for sale to the pulp & paper industry as sulfidic/alkali
make-up (i.e. Na2O equivalency).

Process Configuration

(Pre)Treatment Oxidation Post-Treatment

Bulk Wet Air

Oxidation
Polymer &
Hydrocarbon Advanced Neutralization
Removal Chemical
Oxidation

Figure 1: Process Configuration

12 Shaw Stone & Webster Shaw Stone & Webster 1

1. Patent Pending
Fundamentals of Acid Gas Removal
In ethylene plants, hydrocarbon feedstock and steam are pyrolyzed at
elevated temperatures to produce the desired primary olefinic products,
Ref.1,2
ethylene and propylene . Also produced are a series of other
aliphatic, aromatic, and, to a much lesser extent, oxygenated
hydrocarbon compounds. H2S is produced as a result of sulfur-
hydrogen reaction; CO2 is also produced by water-gas reactions and
reforming.
The steam cracker effluents are cooled, then quenched and
compressed from near atmospheric conditions to high pressure (400-
500 psia) in a multi-stage gas compressor. The acid gases (CO2 and
H2S) are removed from the gas phase in an absorber typically located
between the compression stages as shown in Figure 2. The absorber
removes the CO2 and H2S from up to a few hundred ppm to < 1ppm in
order to satisfy the ethylene and propylene product specifications and
to prevent both poisoning of the downstream hydrogenation catalyst
with H2S and solidification of CO2 in the cryogenic section of the
ethylene train.
Basic Ethylene Unit Diagram
Figure 2: Basic Ethylene Unit Diagram
2 Shaw Stone & Webster
The stoichiometric reactions that are fast and irreversible between CO2
and H2S with excess NaOH are:
CO2 + 2NaOH → Na2CO3 + H2O
H2S + 2NaOH → Na2S + 2H2O
When the caustic tower operates under conditions of NaOH deficiency,
the following reversible reactions also occur:
CO2 + NaOH ↔ NaHCO3
H2S + NaOH ↔ NaHS + H2O
Na2S + H2S ↔ 2NaHS
Because the above reactions are reversible, and in order to insure the
removal of acid gases from the cracked gas stream, the caustic tower is
operated with excess NaOH.
The caustic tower can remove other gases such as hydrogen cyanide
(HCN) and mercaptans (RSH) to the limit of their solubility in the caustic
solution due to the reversible nature of the reaction:
RSH + NaOH ↔ RSNa + H2O
Also absorbed in the caustic tower are the oxygenates formed during
steam cracking, including, but not limited to, the carbonyls, ketones,
and organic acids, which are all soluble in the caustic solution.
Conclusions References
A unique new spent caustic (pre)treatment process known as (1) Hallee, L.P., Zdonik, S.B. & Green, E. J. “Ethylene Worldwide
PRETREAT™ is now available through Shaw Stone & Webster which #18”, The Oil & Gas Journal November 24, P. 96 (1970)
affords a powerful solution for essentially complete removal of all
(2) Hallee, L.P., Zdonik, S.B. & Green, E. J. “Ethylene Worldwide
dissolved organics. PRETREAT™ Technology includes treating the raw
#19”, The Oil & Gas Journal April 27, P. 94 (1971)
spent caustic with hydrogenated aromatic rich gasoline in a liquid-liquid
extractor followed by (indirect) steam stripping. The (pre)treated spent (3) Asomaning, S., Watkinson, A. P., The Canadian Journal of
caustic is environmentally safe and can be sold for its sulfidic-alkali Chemical Engineering, Volume 70, 444 – 451, June 1992
content. (4) Georgeiff, K.K., The Canadian Journal of Chemical Engineering,
There are synergistic effects between industries -refinery/petrochemical Volume 62, 367-373 June 1984
and pulp & paper -wherein industrial waste (as spent caustic) can now (5) Handy, C.T. and Rothrock, H.S., J. Am. Chem. Soc., 80,
be (pre) treated to provide a value-added “product” sold for its sulfidic- 5306-8, 1958
alkali content. The use of PRETREAT™ in this context truly represents
a unique cross-cutting technology. (6) Small, K., “Performance of Low Pressure Wet Air Oxidation
Unit” AIChE Spring National meeting, Houston, TX,
Other obvious benefits are:
April 17 – 21, 1994
• (Pre)treatment of spent caustic enhances simple wet air oxidation by
(7) Matthews, R.W., AIChE 8th Ethylene Producers Conference;
20-40% compared with the oxidation of the untreated spent caustic;
New Orleans, Louisiana; February 27, 1996
and,
• Any oxidation chemistry using ozone-only can be enhanced by 10- (8) Kirk – Othmer, “Encyclopedia of Chemical Technology” 3rd edn,
20% conversion of sulfide to sulfate; and, Volume 19, P. 402, 1982
• Refinery waste caustic may be (pre)treated then neutralized to
liberate H2S for elemental sulfur recovery and further stripped for
ultimate hydrocarbon removal before biological treatment; thus,
enhancing final wastewater quality.
Shaw Stone & Webster 11
Removal of Residual Hydrocarbons
The raffinate (treated spent caustic) from the liquid-liquid extractor is
saturated with the components from the extracting solvent; the
dissolved hydrocarbons in the raffinate would require removal if the
spent caustic is to be sold for its alkali content, or if it is to be oxidized
by simple wet air chemistry or other methods.
The dissolved hydrocarbons can be steam stripped. The stripper is
operated at such a pressure and temperature that ensures the removal
of the hydrocarbons to the desired low levels. The extracting solvent
should be chosen to be free of any heavy residual hydrocarbon tail that
prevents simple stripping as an effective removal step of these residual
organics.
The overhead of the stripper is essentially water vapor with residual
hydrocarbon; this stream is purged. The bottom of the hydrocarbon
stripper is now fully (pre)treated spent caustic. The (pre)treatment unit,
including the Liquid-Liquid Extractor and the Hydrocarbon Stripper, is
shown in Figure 7.

(Pre)Treatment

Spent Caustic Speciation Polymer Formation

To better comprehend those compounds present in typical spent To fully appreciate the positive impact of PRETREAT™ Technology,
caustic from an ethylene plant or refinery, an effort has been made to one must revisit the fundamental sources of polymer formation within
speciate this waste stream to qualitatively and quantitatively define the the acid gas removal system itself.
constituents that may negatively effect oxidation of the principal
Two distinct types of polymers are formed: Aldol Condensation
compound of interest, sodium sulfide. The results of this analytical work
Polymers and Free Radical Addition Polymers.
are shown in Table 1.1 and 1.2.
Aldol Condensation
Spent caustic composition is variable and depends on the type of
feedstock, cracking severity, sulfur content in the feed and caustic Oxygenated compounds, including carbonyl compounds, are formed
utilization. Typical spent caustic composition ranges are: during steam cracking. The amount of carbonyls formed, such as
aldehydes and ketones, can vary widely from 50 to 500 ppm in the
Figure 7: (Pre) Treatment Unit NaOH 1 – 2 wt%
cracked gas stream depending on the type of feedstock and severity of
Na2S 0.5 – 5 wt% cracking.
Na2CO3 1 – 10 wt%
In the caustic tower most of the carbonyls are absorbed in caustic
NaRS 0 – 0.2 wt%
solution. These oxygenates, specially acetaldehyde, will undergo Aldol
Cyanides 0 – 0.05 wt%
Condensation Polymerization in the presence of the strong alkali
Dissolved H/C 0.1 – 0.3 wt%
(NaOH) and at the temperature and pressure conditions in the caustic
COD 20,000 – 50,000 mg/l
tower.
BOD 5,000 – 15,000 mg/l
pH 13.5 – 14

10 Shaw Stone & Webster Shaw Stone & Webster 3

 NaOH Free Radical Addition Optional Solvent Regeneration stream. The light volatile contaminants are purged with the overhead
CH3CH(OH)CH2CHO vapor product and the heavy polymeric materials are removed with the
2CH3CHO Highly unsaturated compounds in the cracked gas, such as acetylenes The solvent from the liquid-liquid extractor is contaminated with all
→ B-hydroxyaldehyde net bottoms.
acetaldehyde and dienes, are appreciably soluble in the caustic solution, and at the components in the spent caustic stream including light hydrocarbons,
(formed but not isolated) polymers, polymer precursors and heavy hydrocarbons. Small make-up solvent is added to replace the solvent lost in the net
temperature and pressure conditions in the caustic tower would
- H2O undergo polymerization by free radical addition mechanism as shown in overhead and bottoms.
The solvent regenerator is a simple distillation column with partial
CH3CH(OH)CH2CHO → CH3CH = CHCHO Figure 3. condenser; the regenerated solvent is withdrawn as a heart-cut side
B-hydroxyaldehyde 2-Butenal
At an appropriate temperature, a peroxide decomposes to yield free
NaOH radicals. In the presence of monomer, the free radicals add to the
CH3CH = CHCHO + CH3CHO → CH3CH = CHCH(OH)CH2CHO monomer and thereby initiate chain growth that can extend in three
-H2O dimensions and eventually result in a high molecular weight, insoluble
polymer that drops out of the solution and causes fouling and plugging
CH3CH = CHCH(OH)CH2CHO → CH3CH = CHCH = CHCHO
of the equipment.
Solvent Recovery – Closed Loop
Among the possible polymeric reaction free radicals (initiators) are
The Aldol Condensation Polymer (Red Oil) formed is partially soluble in peroxides, azo compounds, oxygen, and metal oxides, all of which may
the caustic solution and insoluble in water. be present in the caustic tower and equipment handling and processing
In the caustic tower, the resulting polymer typically settles on tower the spent caustic.
internals, leading to fouling and plugging, unless measures are taken to
remove the polymer from the system at a rate equal to its rate of
formation.
It is estimated that some 70% of the carbonyls in the cracked gas are
absorbed by the caustic solution in the tower. The amount and extent of
polymer formation in the caustic tower depends upon the temperature
and pressure conditions in the tower.

Figure 6b: Solvent Recovery – Closed Loop

Diolefin Polymerization Mechanism

Initiation R• +

Polymer Growth R

Figure 3: Diolefin Polymerization Mechanism

4 Shaw Stone & Webster Shaw Stone & Webster 9

The concentrated Black Liquor is directed to a recovery furnace
operated at 1250°C where the organics are burned and the inorganic
salts are recovered in the form Na2CO3 and Na2S. Make-up sodium
sulfate is added to the furnace feed to compensate for the loss of alkali
in the recovery cycle written as:
Na2SO4 + 2C → Na2S + 2CO2
The flue gas effluent from the furnace is utilized to generate steam
while the inorganic (Na2CO3 and Na2S) residue smelt at 1000°C runs
out of the furnace to a water quench dissolver to form the Green Liquor.
The Green Liquor is causticized with slacked lime as follows:
Na2CO3 + Ca(OH)2 → 2NaOH + CaCO3
The mixture is clarified to separate the insoluble CaCO3. The clarified
solution is the desired White Liquor.
The spent caustic generated in ethylene plants can be used in the pulp
& paper mills as make-up alkali in the Kraft Recovery System, but
environmental regulations and both public and management awareness
of the hazardous nature of aromatic hydrocarbons as well as the
presence of polymers and polymer precursors tend to inhibit this
practice. The use of PRETREAT™ Technology as prescribed herein
frees all hydrocarbons, polymers and polymer precursors to < 10 ppm
Solvent Recovery – Open Loop
Figure 6a: Solvent Recovery – Open Loop
8 Shaw Stone & Webster
in the spent caustic; thus, spent caustic now becomes very attractive for
use in pulp & paper mills while converting a hazardous waste in the
ethylene plants to a valuable byproduct. Other similar use of (pre)
treated spent caustic is found in noble metal catalyst manufacture and
metal treatment processes.
Intimate Contact With a Selective Solvent
Pilot plant tests have demonstrated that these polymer precursors and
their monomers in the spent caustic can be removed by extraction with
organic solvents. The solvent of choice must exhibit favorable
distribution coefficients for the removal of polymer precursors and
monomers. Suitable extracting solvent would be a hydrogenated
aromatic rich stream that may be available at the plant site. The liquid-
liquid extraction is carried out in a multistage countercurrent extractor
sized and operated at conditions and rates that are effective in
removing these polymer precursors and monomers to negligible
concentration levels.
The solvent or extract from the extractor is sent for purification by
solvent regeneration and simply recycled (as new) to the liquid-liquid
extraction. The solvent can be either returned to the primary process of
interest (Figure 6a) or properly conditioned in a dedicated solvent
regenerator (Figure 6b).
Infiltration of Air (as Oxygen) Within the Acid Gas
Removal System
Ref.3,4
As is known in ethylene plant service for deethanizer and
depropanizer columns, pyrophoric polymer formation has been well
proven. Reactive compounds such as butadiene and other conjugated
dienes in the presence of small quantities of air react with oxygen to
Ref.5
form trans-1,4 and 1,2 butadiene polyperoxides .
CH2 = CHCH = CH2 + O2 → [-CH2CH = CHCH2OO-]χ + CHCH200-
γ
CH = CH2
2trans – 1,4 form
Polymerization in The Spent Caustic by Other
Initiators
The spent caustic stream leaving the tower will contain both the
condensation and addition types of polymers formed, as well as the
unreacted monomers and precursors that would continue to polymerize
and cause fouling of equipment handling the spent caustic if the
temperature and pressure conditions in this equipment are conducive to
polymer formation. Ingress of oxygen to the spent caustic will
accelerate polymerization of spent caustic.
Still other known polymer precursors such as methyl
acetylene/propadiene and vinyl/ethyl acetylene are highly solubilized in
this alkaline solution; therefore, at elevated temperatures these alkyne
and allene compounds only aid in the overall polymerization.
The quality of any fresh caustic soda can be paramount to the
concentration and rate of formation of the aforementioned polymers.
These unwanted compounds include heavy metals and other known
initiators such as mercury, iron, nickel, magnesium, silica, calcium,
lead, copper and still others.
These metallic elements react directly with sulfur and give rise to
compounds referred to as metal chalconides and act as polymer
promoters or initiators. To avoid potential formation of metal
chalconides within the spent caustic, a (fresh) caustic soda with the
minimum of initiators is obviously most preferred. If logistically
accessible and economically justifiable, the preferred choice of (fresh)
caustic soda (50% aqueous solution) is Rayon Grade as opposed to
Diaphragm Grade. It is well known that Rayon Grade caustic soda
typically has about half the carbonates, chlorides and heavy metals as
compared to Diaphragm Grade caustic soda.
The qualitative conclusion of importance is that the selection of Rayon
Grade with low chlorates and metals content as opposed to Diaphragm
Grade is the preferred choice to be used in caustic tower services.
Positive Impact of PRETREAT™ Technology
The spent caustic from the absorber is generated as a result of the
intimate countercurrent liquid/vapor contact of the dilute caustic solution
with the Cracked Gas (CG) in the tower. The acid gases react with the
sodium hydroxide to form sodium salts; the spent caustic
simultaneously becomes saturated with an array of hydrocarbon
components in the CG including heat sensitive polymer precursors and
monomers such as carbonyls, dienes and styrenics.
The polymerization rate of polymer precursors and their monomers
increases with increasing temperature. Polymerization of the carbonyls
by aldol condensation reactions is catalyzed by free sodium hydroxide
in solution.
Polymers continue to form within the spent caustic solution as long as
the solution contains dissolved polymer precursors at elevated
temperature. The presence of these species and other organics in the
spent caustic proper act as a poison to appreciably retard the preferred
oxidation chemistry to produce sodium sulfate. The presence of
organics in the spent caustic makes the solution environmentally
hazardous and limits its use for integration within the pulp & paper
industry and other metal treatment processes.
Therefore, it is essential to free the spent caustic from dissolved
polymer precursors and their monomers if polymer formation is to be
avoided prior to any oxidation reaction or if the spent caustic is to be
used for its alkali content.
Proper (pre)treatment of spent caustic, as well as heavy organic
compounds, in the manner prescribed herein offers a unique solution to
removing known polymers and their polymer precursors with relative
ease and simple operation. Although these polymers and their
precursors are present in relatively low concentrations, nonetheless,
they remain as heat sensitive gums in solution that cause fouling and
plugging thus rendering simple distillation impractical.
Shaw Stone & Webster 5
Through the use of liquid/liquid extraction, the transfer of the solute
from one liquid phase (spent caustic) into a second liquid phase
(extracting solvent) allows transfer of the solutes from the spent caustic
to the solvent due to the inherently higher solubility in the extracting
solvent. The preferred attributes of the “solvent of choice” are:
• ready availability within the overall plant configuration at a
reasonable cost; and,
• good selectivity in extracting the solutes from the caustic solution;
and,
• a relatively small density difference and interfacial tension between
the spent caustic and solvent of choice to allow successive ease of
mixing with minimum shear between liquid phases thus facilitating
good separation of the phases subsequent to intimate contacting.
The extracted spent caustic becomes saturated with the components
present in the extracting solvent and these can be removed by
stripping. The stripped spent caustic with <10 ppm total hydrocarbon
content becomes suitable to:
(a) enhance oxidation rates through simple wet air chemistry, as the
presence of hydrocarbon contaminants has been shown by pilot
Ref.6
testing and plotted in Figure 4, to grossly inhibit the conversion level
of sodium sulfide to its highest oxidation state --- sodium sulfate.
(b) sell to the pulp & paper mills and other industrial users for its alkali
salts content without having an environmentally unacceptable
hydrocarbon content.
Industrial Waste to Value-Added “Product”
To fully appreciate the significance of PRETREAT™ Technology, a
proper understanding of this processing scheme as a cross-cutting
technology between the refinery/ petrochemical producer and the pulp
& paper industry is necessary; therefore, for the purpose of
demonstrating to the reader the synergism between industries, a broad
overview of the fundamentals of the Kraft Recovery Process as applied
to the pulp & paper industry is briefly described hereinafter.
In a typical pulp & paper mill, NaOH/Na2S solution (White Liquor) is
Ref.8
used in the Kraft Recovery System (Figure 5) to digest steamed
wood added in a ratio of liquor/wood ≈ 4/1 in a continuous digester
operated at 170°C and 150 psig; this White Liquor has the following
typical specifications:
• 18% Na2O (equivalent NaOH & Na2S)
• 25% Sulfidity (% Na2S/Na2O)
The pulp is washed with water and separated. The spent liquor (Black
Liquor) is drained and now has 12-15 wt% solids.
In order to prevent the loss of the volatile sodium bisulfide and
mercaptides, the Black Liquor is oxidized with air for the stoichiometry
as written:
2NaHS + 2O2 → Na2S2O3 + H2O
2CH3SNa + O2 + 2H2O → CH3SSCH3 + 2NaOH + ½O2 + H2O
The oxidized Black Liquor is evaporated in a multi-effect evaporator to
40-50 wt% solution. The solution is further concentrated to 65-70 wt%
solid in a forced circulation concentrator.

Effect of Organics on Sulfate Yield in LPWAO

Schematic of Kraft Recovery System
Steamed
Wood

Wash
Water
Black Liquor
White Liquor Digester and pulp
Lime Mud CaCO3 and Blow
Tank Pulp
White- NaOH/
Liquor Na2S 150 psig Washer
Clarifier 170°C
Weak Black Liquor
Ca(OH) Na2S, NaOH, (12-15 wt% solids)
CaCO3

(Pre) Treated Slaker and

Spent Caustic Oxidation Air
Causticizer
Addition
Green Liquor
(Na2S, Na2CO3)
Makeup Na2SO4
Dissolving Multiple-effect
Figure 4: Effect of Organics on Sulfate Yield in LPWAO (Low Pressure Wet Air Oxidation) Tank Evaporator /
1250°C Concentrator
Water Smelt
Vapor
Recovery Concentrated
1000°C Furnace Black Liquor,
65 wt% solids

Flue gas for

heat recovery

Figure 5: Schematic of Kraft Recovery System

6 Shaw Stone & Webster Shaw Stone & Webster 7

Through the use of liquid/liquid extraction, the transfer of the solute
from one liquid phase (spent caustic) into a second liquid phase
(extracting solvent) allows transfer of the solutes from the spent caustic
to the solvent due to the inherently higher solubility in the extracting
solvent. The preferred attributes of the “solvent of choice” are:
• ready availability within the overall plant configuration at a
reasonable cost; and,
• good selectivity in extracting the solutes from the caustic solution;
and,
• a relatively small density difference and interfacial tension between
the spent caustic and solvent of choice to allow successive ease of
mixing with minimum shear between liquid phases thus facilitating
good separation of the phases subsequent to intimate contacting.
The extracted spent caustic becomes saturated with the components
present in the extracting solvent and these can be removed by
stripping. The stripped spent caustic with <10 ppm total hydrocarbon
content becomes suitable to:
(a) enhance oxidation rates through simple wet air chemistry, as the
presence of hydrocarbon contaminants has been shown by pilot
Ref.6
testing and plotted in Figure 4, to grossly inhibit the conversion level
of sodium sulfide to its highest oxidation state --- sodium sulfate.
(b) sell to the pulp & paper mills and other industrial users for its alkali
salts content without having an environmentally unacceptable
hydrocarbon content.
Industrial Waste to Value-Added “Product”
To fully appreciate the significance of PRETREAT™ Technology, a
proper understanding of this processing scheme as a cross-cutting
technology between the refinery/ petrochemical producer and the pulp
& paper industry is necessary; therefore, for the purpose of
demonstrating to the reader the synergism between industries, a broad
overview of the fundamentals of the Kraft Recovery Process as applied
to the pulp & paper industry is briefly described hereinafter.
In a typical pulp & paper mill, NaOH/Na2S solution (White Liquor) is
Ref.8
used in the Kraft Recovery System (Figure 5) to digest steamed
wood added in a ratio of liquor/wood ≈ 4/1 in a continuous digester
operated at 170°C and 150 psig; this White Liquor has the following
typical specifications:
• 18% Na2O (equivalent NaOH & Na2S)
• 25% Sulfidity (% Na2S/Na2O)
The pulp is washed with water and separated. The spent liquor (Black
Liquor) is drained and now has 12-15 wt% solids.
In order to prevent the loss of the volatile sodium bisulfide and
mercaptides, the Black Liquor is oxidized with air for the stoichiometry
as written:
2NaHS + 2O2 → Na2S2O3 + H2O
2CH3SNa + O2 + 2H2O → CH3SSCH3 + 2NaOH + ½O2 + H2O
The oxidized Black Liquor is evaporated in a multi-effect evaporator to
40-50 wt% solution. The solution is further concentrated to 65-70 wt%
solid in a forced circulation concentrator.

Effect of Organics on Sulfate Yield in LPWAO

Schematic of Kraft Recovery System
Steamed
Wood

Wash
Water
Black Liquor
White Liquor Digester and pulp
Lime Mud CaCO3 and Blow
Tank Pulp
White- NaOH/
Liquor Na2S 150 psig Washer
Clarifier 170°C
Weak Black Liquor
Ca(OH) Na2S, NaOH, (12-15 wt% solids)
CaCO3

(Pre) Treated Slaker and

Spent Caustic Oxidation Air
Causticizer
Addition
Green Liquor
(Na2S, Na2CO3)
Makeup Na2SO4
Dissolving Multiple-effect
Figure 4: Effect of Organics on Sulfate Yield in LPWAO (Low Pressure Wet Air Oxidation) Tank Evaporator /
1250°C Concentrator
Water Smelt
Vapor
Recovery Concentrated
1000°C Furnace Black Liquor,
65 wt% solids

Flue gas for

heat recovery

Figure 5: Schematic of Kraft Recovery System

6 Shaw Stone & Webster Shaw Stone & Webster 7

The concentrated Black Liquor is directed to a recovery furnace
operated at 1250°C where the organics are burned and the inorganic
salts are recovered in the form Na2CO3 and Na2S. Make-up sodium
sulfate is added to the furnace feed to compensate for the loss of alkali
in the recovery cycle written as:
Na2SO4 + 2C → Na2S + 2CO2
The flue gas effluent from the furnace is utilized to generate steam
while the inorganic (Na2CO3 and Na2S) residue smelt at 1000°C runs
out of the furnace to a water quench dissolver to form the Green Liquor.
The Green Liquor is causticized with slacked lime as follows:
Na2CO3 + Ca(OH)2 → 2NaOH + CaCO3
The mixture is clarified to separate the insoluble CaCO3. The clarified
solution is the desired White Liquor.
The spent caustic generated in ethylene plants can be used in the pulp
& paper mills as make-up alkali in the Kraft Recovery System, but
environmental regulations and both public and management awareness
of the hazardous nature of aromatic hydrocarbons as well as the
presence of polymers and polymer precursors tend to inhibit this
practice. The use of PRETREAT™ Technology as prescribed herein
frees all hydrocarbons, polymers and polymer precursors to < 10 ppm
Solvent Recovery – Open Loop
Figure 6a: Solvent Recovery – Open Loop
8 Shaw Stone & Webster
in the spent caustic; thus, spent caustic now becomes very attractive for
use in pulp & paper mills while converting a hazardous waste in the
ethylene plants to a valuable byproduct. Other similar use of (pre)
treated spent caustic is found in noble metal catalyst manufacture and
metal treatment processes.
Intimate Contact With a Selective Solvent
Pilot plant tests have demonstrated that these polymer precursors and
their monomers in the spent caustic can be removed by extraction with
organic solvents. The solvent of choice must exhibit favorable
distribution coefficients for the removal of polymer precursors and
monomers. Suitable extracting solvent would be a hydrogenated
aromatic rich stream that may be available at the plant site. The liquid-
liquid extraction is carried out in a multistage countercurrent extractor
sized and operated at conditions and rates that are effective in
removing these polymer precursors and monomers to negligible
concentration levels.
The solvent or extract from the extractor is sent for purification by
solvent regeneration and simply recycled (as new) to the liquid-liquid
extraction. The solvent can be either returned to the primary process of
interest (Figure 6a) or properly conditioned in a dedicated solvent
regenerator (Figure 6b).
Infiltration of Air (as Oxygen) Within the Acid Gas
Removal System
Ref.3,4
As is known in ethylene plant service for deethanizer and
depropanizer columns, pyrophoric polymer formation has been well
proven. Reactive compounds such as butadiene and other conjugated
dienes in the presence of small quantities of air react with oxygen to
Ref.5
form trans-1,4 and 1,2 butadiene polyperoxides .
CH2 = CHCH = CH2 + O2 → [-CH2CH = CHCH2OO-]χ + CHCH200-
γ
CH = CH2
2trans – 1,4 form
Polymerization in The Spent Caustic by Other
Initiators
The spent caustic stream leaving the tower will contain both the
condensation and addition types of polymers formed, as well as the
unreacted monomers and precursors that would continue to polymerize
and cause fouling of equipment handling the spent caustic if the
temperature and pressure conditions in this equipment are conducive to
polymer formation. Ingress of oxygen to the spent caustic will
accelerate polymerization of spent caustic.
Still other known polymer precursors such as methyl
acetylene/propadiene and vinyl/ethyl acetylene are highly solubilized in
this alkaline solution; therefore, at elevated temperatures these alkyne
and allene compounds only aid in the overall polymerization.
The quality of any fresh caustic soda can be paramount to the
concentration and rate of formation of the aforementioned polymers.
These unwanted compounds include heavy metals and other known
initiators such as mercury, iron, nickel, magnesium, silica, calcium,
lead, copper and still others.
These metallic elements react directly with sulfur and give rise to
compounds referred to as metal chalconides and act as polymer
promoters or initiators. To avoid potential formation of metal
chalconides within the spent caustic, a (fresh) caustic soda with the
minimum of initiators is obviously most preferred. If logistically
accessible and economically justifiable, the preferred choice of (fresh)
caustic soda (50% aqueous solution) is Rayon Grade as opposed to
Diaphragm Grade. It is well known that Rayon Grade caustic soda
typically has about half the carbonates, chlorides and heavy metals as
compared to Diaphragm Grade caustic soda.
The qualitative conclusion of importance is that the selection of Rayon
Grade with low chlorates and metals content as opposed to Diaphragm
Grade is the preferred choice to be used in caustic tower services.
Positive Impact of PRETREAT™ Technology
The spent caustic from the absorber is generated as a result of the
intimate countercurrent liquid/vapor contact of the dilute caustic solution
with the Cracked Gas (CG) in the tower. The acid gases react with the
sodium hydroxide to form sodium salts; the spent caustic
simultaneously becomes saturated with an array of hydrocarbon
components in the CG including heat sensitive polymer precursors and
monomers such as carbonyls, dienes and styrenics.
The polymerization rate of polymer precursors and their monomers
increases with increasing temperature. Polymerization of the carbonyls
by aldol condensation reactions is catalyzed by free sodium hydroxide
in solution.
Polymers continue to form within the spent caustic solution as long as
the solution contains dissolved polymer precursors at elevated
temperature. The presence of these species and other organics in the
spent caustic proper act as a poison to appreciably retard the preferred
oxidation chemistry to produce sodium sulfate. The presence of
organics in the spent caustic makes the solution environmentally
hazardous and limits its use for integration within the pulp & paper
industry and other metal treatment processes.
Therefore, it is essential to free the spent caustic from dissolved
polymer precursors and their monomers if polymer formation is to be
avoided prior to any oxidation reaction or if the spent caustic is to be
used for its alkali content.
Proper (pre)treatment of spent caustic, as well as heavy organic
compounds, in the manner prescribed herein offers a unique solution to
removing known polymers and their polymer precursors with relative
ease and simple operation. Although these polymers and their
precursors are present in relatively low concentrations, nonetheless,
they remain as heat sensitive gums in solution that cause fouling and
plugging thus rendering simple distillation impractical.
Shaw Stone & Webster 5
 NaOH Free Radical Addition Optional Solvent Regeneration stream. The light volatile contaminants are purged with the overhead
CH3CH(OH)CH2CHO vapor product and the heavy polymeric materials are removed with the
2CH3CHO Highly unsaturated compounds in the cracked gas, such as acetylenes The solvent from the liquid-liquid extractor is contaminated with all
→ B-hydroxyaldehyde net bottoms.
acetaldehyde and dienes, are appreciably soluble in the caustic solution, and at the components in the spent caustic stream including light hydrocarbons,
(formed but not isolated) polymers, polymer precursors and heavy hydrocarbons. Small make-up solvent is added to replace the solvent lost in the net
temperature and pressure conditions in the caustic tower would
- H2O undergo polymerization by free radical addition mechanism as shown in overhead and bottoms.
The solvent regenerator is a simple distillation column with partial
CH3CH(OH)CH2CHO → CH3CH = CHCHO Figure 3. condenser; the regenerated solvent is withdrawn as a heart-cut side
B-hydroxyaldehyde 2-Butenal
At an appropriate temperature, a peroxide decomposes to yield free
NaOH radicals. In the presence of monomer, the free radicals add to the
CH3CH = CHCHO + CH3CHO → CH3CH = CHCH(OH)CH2CHO monomer and thereby initiate chain growth that can extend in three
-H2O dimensions and eventually result in a high molecular weight, insoluble
polymer that drops out of the solution and causes fouling and plugging
CH3CH = CHCH(OH)CH2CHO → CH3CH = CHCH = CHCHO
of the equipment.
Solvent Recovery – Closed Loop
Among the possible polymeric reaction free radicals (initiators) are
The Aldol Condensation Polymer (Red Oil) formed is partially soluble in peroxides, azo compounds, oxygen, and metal oxides, all of which may
the caustic solution and insoluble in water. be present in the caustic tower and equipment handling and processing
In the caustic tower, the resulting polymer typically settles on tower the spent caustic.
internals, leading to fouling and plugging, unless measures are taken to
remove the polymer from the system at a rate equal to its rate of
formation.
It is estimated that some 70% of the carbonyls in the cracked gas are
absorbed by the caustic solution in the tower. The amount and extent of
polymer formation in the caustic tower depends upon the temperature
and pressure conditions in the tower.

Figure 6b: Solvent Recovery – Closed Loop

Diolefin Polymerization Mechanism

Initiation R• +

Polymer Growth R

Figure 3: Diolefin Polymerization Mechanism

4 Shaw Stone & Webster Shaw Stone & Webster 9

Removal of Residual Hydrocarbons
The raffinate (treated spent caustic) from the liquid-liquid extractor is
saturated with the components from the extracting solvent; the
dissolved hydrocarbons in the raffinate would require removal if the
spent caustic is to be sold for its alkali content, or if it is to be oxidized
by simple wet air chemistry or other methods.
The dissolved hydrocarbons can be steam stripped. The stripper is
operated at such a pressure and temperature that ensures the removal
of the hydrocarbons to the desired low levels. The extracting solvent
should be chosen to be free of any heavy residual hydrocarbon tail that
prevents simple stripping as an effective removal step of these residual
organics.
The overhead of the stripper is essentially water vapor with residual
hydrocarbon; this stream is purged. The bottom of the hydrocarbon
stripper is now fully (pre)treated spent caustic. The (pre)treatment unit,
including the Liquid-Liquid Extractor and the Hydrocarbon Stripper, is
shown in Figure 7.

(Pre)Treatment

Spent Caustic Speciation Polymer Formation

To better comprehend those compounds present in typical spent To fully appreciate the positive impact of PRETREAT™ Technology,
caustic from an ethylene plant or refinery, an effort has been made to one must revisit the fundamental sources of polymer formation within
speciate this waste stream to qualitatively and quantitatively define the the acid gas removal system itself.
constituents that may negatively effect oxidation of the principal
Two distinct types of polymers are formed: Aldol Condensation
compound of interest, sodium sulfide. The results of this analytical work
Polymers and Free Radical Addition Polymers.
are shown in Table 1.1 and 1.2.
Aldol Condensation
Spent caustic composition is variable and depends on the type of
feedstock, cracking severity, sulfur content in the feed and caustic Oxygenated compounds, including carbonyl compounds, are formed
utilization. Typical spent caustic composition ranges are: during steam cracking. The amount of carbonyls formed, such as
aldehydes and ketones, can vary widely from 50 to 500 ppm in the
Figure 7: (Pre) Treatment Unit NaOH 1 – 2 wt%
cracked gas stream depending on the type of feedstock and severity of
Na2S 0.5 – 5 wt% cracking.
Na2CO3 1 – 10 wt%
In the caustic tower most of the carbonyls are absorbed in caustic
NaRS 0 – 0.2 wt%
solution. These oxygenates, specially acetaldehyde, will undergo Aldol
Cyanides 0 – 0.05 wt%
Condensation Polymerization in the presence of the strong alkali
Dissolved H/C 0.1 – 0.3 wt%
(NaOH) and at the temperature and pressure conditions in the caustic
COD 20,000 – 50,000 mg/l
tower.
BOD 5,000 – 15,000 mg/l
pH 13.5 – 14

10 Shaw Stone & Webster Shaw Stone & Webster 3

Fundamentals of Acid Gas Removal
In ethylene plants, hydrocarbon feedstock and steam are pyrolyzed at
elevated temperatures to produce the desired primary olefinic products,
Ref.1,2
ethylene and propylene . Also produced are a series of other
aliphatic, aromatic, and, to a much lesser extent, oxygenated
hydrocarbon compounds. H2S is produced as a result of sulfur-
hydrogen reaction; CO2 is also produced by water-gas reactions and
reforming.
The steam cracker effluents are cooled, then quenched and
compressed from near atmospheric conditions to high pressure (400-
500 psia) in a multi-stage gas compressor. The acid gases (CO2 and
H2S) are removed from the gas phase in an absorber typically located
between the compression stages as shown in Figure 2. The absorber
removes the CO2 and H2S from up to a few hundred ppm to < 1ppm in
order to satisfy the ethylene and propylene product specifications and
to prevent both poisoning of the downstream hydrogenation catalyst
with H2S and solidification of CO2 in the cryogenic section of the
ethylene train.
Basic Ethylene Unit Diagram
Figure 2: Basic Ethylene Unit Diagram
2 Shaw Stone & Webster
The stoichiometric reactions that are fast and irreversible between CO2
and H2S with excess NaOH are:
CO2 + 2NaOH → Na2CO3 + H2O
H2S + 2NaOH → Na2S + 2H2O
When the caustic tower operates under conditions of NaOH deficiency,
the following reversible reactions also occur:
CO2 + NaOH ↔ NaHCO3
H2S + NaOH ↔ NaHS + H2O
Na2S + H2S ↔ 2NaHS
Because the above reactions are reversible, and in order to insure the
removal of acid gases from the cracked gas stream, the caustic tower is
operated with excess NaOH.
The caustic tower can remove other gases such as hydrogen cyanide
(HCN) and mercaptans (RSH) to the limit of their solubility in the caustic
solution due to the reversible nature of the reaction:
RSH + NaOH ↔ RSNa + H2O
Also absorbed in the caustic tower are the oxygenates formed during
steam cracking, including, but not limited to, the carbonyls, ketones,
and organic acids, which are all soluble in the caustic solution.
Conclusions References
A unique new spent caustic (pre)treatment process known as (1) Hallee, L.P., Zdonik, S.B. & Green, E. J. “Ethylene Worldwide
PRETREAT™ is now available through Shaw Stone & Webster which #18”, The Oil & Gas Journal November 24, P. 96 (1970)
affords a powerful solution for essentially complete removal of all
(2) Hallee, L.P., Zdonik, S.B. & Green, E. J. “Ethylene Worldwide
dissolved organics. PRETREAT™ Technology includes treating the raw
#19”, The Oil & Gas Journal April 27, P. 94 (1971)
spent caustic with hydrogenated aromatic rich gasoline in a liquid-liquid
extractor followed by (indirect) steam stripping. The (pre)treated spent (3) Asomaning, S., Watkinson, A. P., The Canadian Journal of
caustic is environmentally safe and can be sold for its sulfidic-alkali Chemical Engineering, Volume 70, 444 – 451, June 1992
content. (4) Georgeiff, K.K., The Canadian Journal of Chemical Engineering,
There are synergistic effects between industries -refinery/petrochemical Volume 62, 367-373 June 1984
and pulp & paper -wherein industrial waste (as spent caustic) can now (5) Handy, C.T. and Rothrock, H.S., J. Am. Chem. Soc., 80,
be (pre) treated to provide a value-added “product” sold for its sulfidic- 5306-8, 1958
alkali content. The use of PRETREAT™ in this context truly represents
a unique cross-cutting technology. (6) Small, K., “Performance of Low Pressure Wet Air Oxidation
Unit” AIChE Spring National meeting, Houston, TX,
Other obvious benefits are:
April 17 – 21, 1994
• (Pre)treatment of spent caustic enhances simple wet air oxidation by
(7) Matthews, R.W., AIChE 8th Ethylene Producers Conference;
20-40% compared with the oxidation of the untreated spent caustic;
New Orleans, Louisiana; February 27, 1996
and,
• Any oxidation chemistry using ozone-only can be enhanced by 10- (8) Kirk – Othmer, “Encyclopedia of Chemical Technology” 3rd edn,
20% conversion of sulfide to sulfate; and, Volume 19, P. 402, 1982
• Refinery waste caustic may be (pre)treated then neutralized to
liberate H2S for elemental sulfur recovery and further stripped for
ultimate hydrocarbon removal before biological treatment; thus,
enhancing final wastewater quality.
Shaw Stone & Webster 11
 Spent Caustic Treatment:
The Merits Of PRETREAT™ Technology
Applications for the Refinery/Petrochemical Industries
Today's refiner and petrochemical producer is forced by more stringent
environmental regulations to better monitor and control their wastewater
to/from biological treatment. One of the key contributors to relatively
high chemical oxygen demand (COD) and biological oxygen demand
(BOD) is from the acid gas (both CO2 and H2S) removal system(s)
Intentionally Blank
typically using dilute caustic soda (NaOH) as the active reagent – the
resultant waste stream is otherwise known as spent caustic.
Typical sulfidic spent caustic derived from acid gas removal in either a
petrochemical or refinery facility can contain significant contaminants
comprised of dissolved hydrocarbon, polymers and active polymer
precursors in addition to the well defined levels of sodium salts and free
caustic. These lesser known contaminants can grossly inhibit the
conversion level of sodium sulfide to its highest oxidation state –
sodium sulfate.
A unique approach to (pre)treat these aforementioned contaminants
has been developed, otherwise known as PRETREAT™ Technology¹,
which now allows a cost effective method of achieving virtually
complete oxidation of spent caustic using the following steps:
(1) (Pre)Treatment
(2) Bulk Wet Air Oxidation
(3) Advanced Chemical Oxidation
(4) Post-Treatment
Extensive pilot plant tests have confirmed that the process configuration
illustrated in Figure 1 affords high flexibility to address the specific
demands of today's petrochemical/ refinery facility including upgrading
existing treatment units to better satisfy current (or future) federal and
state regulatory requirements. This unique approach to spent caustic
treatment includes innovations never before applied in the manner
prescribed.
Moreover, the use of PRETREAT™ Technology can now be used as a
singular method to condition raw spent caustic for virtually complete
removal of all oligomers and organics from solution to yield a value-
added “product” for sale to the pulp & paper industry as sulfidic/alkali
make-up (i.e. Na2O equivalency).

Process Configuration

(Pre)Treatment Oxidation Post-Treatment

Bulk Wet Air

Oxidation
Polymer &
Hydrocarbon Advanced Neutralization
Removal Chemical
Oxidation

Figure 1: Process Configuration

12 Shaw Stone & Webster Shaw Stone & Webster 1

1. Patent Pending
 Intentionally Blank

Originally prepared for presentation at the

Eleventh Ethylene Forum
May 14-16, 1997
The Woodlands, Texas

Shaw Stone & Webster Shaw Stone & Webster 13

 Spent Caustic Treatment:
The Merits of PRETREAT™ Technology
Applications for the
Refinery/Petrochemical Industries
Joseph M. Gondolfe and Sabah A. Kurukchi, PhD

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Shaw Stone & Webster
Joseph M. Gondolfe and Sabah A. Kurukchi