Pluses and Minuses of Caustic Treating

Reprinted from Hydrocarbon Processing October 1996 Proper use and spent solution management ensure the safest and most cost-effective operations F. J. Suarez, Merichem Co., Houston, Texas In recent years, refineries and petrochemical plants worldwide have faced stricter controls on liquid and gas effluent discharge streams that could cause air or water pollution. Spent caustic (NaOH) solutions are liquid effluents that must be properly managed to maintain the plant discharge's quality. Since there are different types of spent caustic steams, refiners must correctly categorize them to use the most effective disposal or treating method. The hydrocarbon processing industry (HPI) has historically used caustic solutions to extract or treat acidic impurities such as hydrogen sulfide (H 2S), mercaptans and organic acids in hydrocarbon streams. Today, caustic solutions continue to be the primary reagents used in these treating operations because they have been proven safe, economical, effective and, above all, environmentally acceptable. When properly recycled or treated, used caustic streams do not constitute damaging, hazardous waste. Over 50 US refineries and 10 outside the US ship caustic solutions to US chemical plants. Yet these streams are not classified as RCRA waste by EPA because they are processed for beneficial reuse. Much of the concern expressed today about caustic use in HPI operations can he attributed to the following: Many plant operators are unaware of options for in-plant processing or recycling of spent caustic. Poorly designed caustic treaters can cause operating problems. Spent caustic can be turned into hazardous waste by outside disposal companies. Unfounded concerns about caustic use, such as these recent inaccurate statements: "Spent caustic will be regulated as hazardous waste by EPA" and Spent caustic disposal costs are as high as US$3.00/gal."

Based on the economic benefits, caustic is still the best treating reagent available to the HPI. In refineries, caustic is primarily used to remove sulfur compounds from light streams and oxidize mercaptans in heavier streams. The pluses and minuses of caustic treating are presented to help refiners and other petrochemical plant operators make careful, intelligent economic choices. Although the focus is on refinery treating operations, the information presented applies equally well to many other petrochemical operations. Table 1. Comparison of Capital and Operating Costs for 10,000-bpsd Jet Fuel Caustic Treater and a Comparable Hydrotreater Caustic Treating Capital costs, US $/bbl Operating costs U. S. $/bbl Catalyst and chemicals Utilities Labor Total 0.0172 0.0005 0.0060 0.0237 0.380 0.025 0.012 0.417 150 to 200 Hydrotreating 1,500 to 2,500

Removing Sulfur Compounds From Light Refinery Streams

The sulfur content of many refinery streams 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 H 2S 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 reliable 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 site while maintaining the attractive 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 extractable. 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 requirements, most gasoline, jet fuel, kerosene and diesel fractions can be satisfactorily sweetened with caustic. Hydrotreating, the most widely used alternative to caustic sweetening, is very effective. However, hydrotreating cannot compete with caustic treating in capital and operating costs. Table 1 compares capital and operating 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 shallots, a portion of which are incidentally extracted by the caustic treating solution. For jet fuel, kerosene 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 properly 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 compared to caustic, extra product cleanup steps and expensive catalytic additives must be used, substantially increasing treating costs. In addition, the aqueous ammonia byproduct solution and the ammonia-laden wash water can be even more difficult to manage than caustic treating byproducts. Ammonia 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, aluminum and edible oil. Economics Fig. 1 shows caustic prices on the US Gulf Coast over the last 10 years. Caustic prices fluctuate 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. Fig. 1. Average caustic prices (US Gulf Coast).

Safety Caustic is also safer than many other chemicals 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, H2S, 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 hydrocarbon 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, resulting 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 economics, 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 operation, 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 caustic in the same storage vessel, rendering the entire mixture unsalable Designing caustic storage systems that are too small to allow for the lowest possible transportation costs Processing a mixture of all types of caustics in a single treating plant designed for only one type Controlling the pH inadequately in the neutralizers, which reduces the effectiveness of contaminant removal. Table 2. Characteristics of a Typical Refinery Sulfidic Caustic Stream Free NaOH, wt% Na2S, NaHS as S-, wt% Mercaptides as S, wt% Carbonate as CO3, wt% pH Total Na+, wt% Ammonia 2 to 10 0.5 to 4 0.1 to 4 0 to 4 13 to 14 4 to 10 Traces

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 typical 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 treating 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, knowhow is extremely important to ensure that the treated caustic will not become an environmental 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 significantly reduce contaminants in these streams and has been improperly applied by many refiners without much environmental benefit. Partial oxidation of sodium sulfide to sodium thiosulfate. This allows oxidation to be completed in the wastewater treating plant to avoid the risk of releasing unsafe, odorous H2S and mercaptans. Since caustic is partially regenerated in the oxidation process, 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 wastewater 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 caustic 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, extracting these acids from gasoline is sometimes more profitable 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 valuable 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 drastically increases transportation and processing costs. For these reasons, this type of byproduct may be more economical 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 treating plant may remove remaining phenolics, provided the biological mass receives a steady diet of these compounds 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.

Table 3. Characteristics of typical refinery cresylic caustic streams Strong Caustic Operation NaOH (at pH 7), wt% Sulfide as S-, wt% Mercaptide as S=, wt% Cresylic acids, wt% Carbonates as C03, wt% pH 10 to 15 0 to 1 0 to 4 10 to 25 0 to 0.5 12 to 14 Dilute Caustic Operation 1 to 4 0 to 0.2 0 to 0.5 2 to 5 0 to 0.1 12 to 14

Table 4. Characteristics of Typical Refinery Naphthenic Caustic Streams Jet Fuel/Kerosene NaOH, wt% Sulfide as S , wt% Mercaptide as S+, wt% Naphthenic acids, wt% Phenolics, wt% pH
-

Diesel 1 to 4 Trace 0 to 0.5 2 to 15 0 to 1 12 to 14

1 to 4 0 to 0.1 0 to 0.5 2 to 10 1 to 3 12 to 14

Naphthenic Caustic These solutions typically contain 5 wt% to 15 wt% naphthenic acids, depending on the caustic concentration, caustic spending target and acidity of the jet fuel, kerosene or diesel stock being processed. Table 4 shows typical characteristics of naphthenate streams derived from kerosene 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/kerosene 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-plant processing may be the most economical option. Naphthenic solutions cannot be mixed and oxidized with sulfidic caustic since sodium naphthenate creates vigorous 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 problems with caustic treating operations is lack of know how by both engineering companies and plant operating 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 outside 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 disposal companies, spent caustic solutions can easily be transformed into hazardous wastes.