Environmental aspects of Petroleum refining

Briefly, petroleum production and petroleum refining produce chemical waste. If this chemical waste is not processed in a timely manner, it can become a pollutant. A pollutant is a substance present in a particular location (ecosystem) when it is not indigenous to the location or is present in a greater-thannatural concentration. The substance is often the product of human activity. The pollutant, by virtue of its name, has a detrimental effect on the environment, in part or in toto. Pollutants can also be subdivided into two classes: primary and secondary. Source Primary pollutant Secondary pollutant A primary pollutant is a pollutant that is emitted directly from the source. In terms of atmospheric pollutants, examples are carbon oxides, sulfur dioxide, and nitrogen oxides from fuel combustion operations: 2(C) Petroleum + O2 2CO2 (C) Petroleum + O2 CO2 2(N) Petroleum + O2 2NO (N) (S)
Petroleum

+ O2 NO2 + O2 SO2

Petroleum

2SO2 + O2 2SO3 Hydrogen sulfide and ammonia are produced from processing sulfurcontaining and nitrogen-containing feedstocks: (S)Petroleum + H2 H2S + Hydrocarbons (N)Petroleum + 3H2 2 NH3 + Hydrocarbons A secondary pollutant is a pollutant that is produced by interaction of a primary pollutant with another chemical. A secondary pollutant may also be produced by dissociation of a

primary pollutant, or other effects within a particular ecosystem. Again, using atmosphere as an example, the formation of the constituents of acid rain is an example of the formation of secondary pollutants: SO2 + H2O H2 SO3 (Sulphurous Acid) SO3 + H2O H2 SO4 (Sulphuric Acid) NO + H2O HNO2 (Nitrous Acid) 2NO2+2H2O 2HNO3 (Nitric Acid) In addition, hazardous waste is any gaseous, liquid, or solid waste material that, if improperly managed or disposed of, may pose substantial hazards to human health and the environment. In many cases, the term chemical waste is often used interchangeably with the term hazardous waste.

Gaseous Emissions:
Gaseous emissions from petroleum refining create a number of environmental problems. During combustion, the combination of hydrocarbons, nitrogen oxide, and sunlight results in localized low-levels of ozone, or smog. This is particularly evident in large urban areas and especially when air does not circulate well. Petroleum use in automobiles also contributes to the problem in many areas. The primary effects are on the health of those exposed to the ozone, but plant life has been observed to suffer as well. Acid gases corrode refining equipment, harm catalysts, pollute the atmosphere, and prevent the use of hydrocarbon components in petrochemical manufacture. When the amount of hydrogen sulfide is large, it may be removed from a gas stream and converted to sulfur or sulfuric acid. Some natural gases contain sufficient carbon dioxide to warrant recovery as dry ice, that is, solid carbon dioxide. Petroleum refining produces gas streams that often contain substantial amounts of acid gases such as hydrogen sulfide and carbon dioxide. More particularly hydrogen sulfide arises from the hydrodesulfurization of feedstocks that contain organic sulfur: (S)
Feedstock

+ H2 H2S + Hydrocarbons

In summary, refinery process gas, in addition to hydrocarbons, may contain other contaminants, such as carbon oxides (COx, where x=1 and 2), sulfur oxides (SOx, where x=2 and 3), as well as ammonia (NH3), mercaptans (RSH), and carbonyl sulfide (COS).

From an environmental viewpoint, it is not the means by which these gases can be utilized that is of concern, but it is the effects of these gases on the environment when they are introduced into the atmosphere. In addition to the corrosion of equipment of acid gases, the escape into the atmosphere of sulfur-containing gases can eventually lead to the formation of the constituents of acid rain, that is, the oxides of sulfur (SO2 and SO3). Similarly, the nitrogen-containing gases can also lead to nitrous and nitric acids (through the formation of the oxides NOx, where x=1 or 2) which are the other major contributors to acid rain. The release of carbon dioxide and hydrocarbons as constituents of refinery effluents can also influence the behavior and integrity of the ozone layer. Hydrogen chloride, if produced during refining, quickly picks up moisture in the atmosphere to form droplets of hydrochloric acid and, like sulfur dioxide, is a contributor to acid rain. However, hydrogen chloride may exert severe local effects because, unlike sulfur dioxide, it does not need to participate in any further chemical reaction to become an acid and under atmospheric conditions that favor a buildup of stack emissions in the area of a large industrial complex or power plant, the amount of hydrochloric acid in rainwater could be quite high. Natural gas is also capable of producing emissions that are detrimental to the environment. While the major constituent of natural gas is methane, there are components such as carbon dioxide (CO), hydrogen sulfide (H2S), and mercaptans (thiols; RSH), as well as trace amounts of sundry other emissions. The fact that methane has a foreseen and valuable end-use makes it a desirable product, but in several other situations it is considered a pollutant, having been identified a greenhouse gas. Acid rain has a pH less than 5.0 and predominantly consists of sulfuric acid (H2SO4) and Nitric acid (HNO3). As a point of reference, in the absence of anthropogenic pollution sources the average pH of rain is _6.0 (slightly acidic; neutral pH 7.0). In summary, the sulfur dioxide that is produced during a variety of processes will react with oxygen and water in the atmosphere to yield environmentally detrimental sulfuric acid. Similarly, nitrogen oxides will also react to produce nitric acid. Another acid gas, hydrogen chloride (HCl), although not usually considered to be a major emission, is produced from mineral matter and the brines that often accompany petroleum during production and is gaining increasing recognition as a contributor to acid rain. However, hydrogen chloride may exert severe local effects because it does not need to participate in

any further chemical reaction to become an acid. Under atmospheric conditions that favor a buildup of stack emissions in the areas where hydrogen chloride is produced, the amount of hydrochloric acid in rainwater could be quite high. In summary, and from an environmental view point, petroleum and natural gas processing petroleum but the constituent s are, in the majority of cases can result in similar, if not the same, gaseous emissions as coal. It is a question of degree insofar as the composition of the gaseous emissions may vary from coal to, the same. There are a variety of processes that are designed for sulfur dioxide removal from gas streams: but scrubbing processes utilizing limestone (CaCO3) or lime [Ca(OH)2] slurries have received more attention than other gas scrubbing processes. The majority of the gas scrubbing processes is designed to remove sulfur dioxide from the gas streams; some processes show the potential for removal of nitrogen oxide(s) too.

LIQUID EFFLUENTS:
Crude oil, as a mixture of hydrocarbons, is (theoretically) a biodegradable material. However, in very general term s (and as observed from elemental analyses), petroleum is a mixture of: (a) Hydrocarbons, (b) Nitrogen compounds, (c) Oxygen compounds, (d) Sulfur compounds, and (e) Metallic constituents. However, this general definition is not adequate to describe the composition of petroleum as it relates to the behavior of these feedstocks. Crude oil also contains appreciable amounts of organic nonhydrocarbon constituents, mainly sulfur-, nitrogen-, and oxygen-containing compounds and, in smaller amounts, organometallic compounds in solution and inorganic salts in colloidal suspension. These constituents appear throughout the entire boiling range of the crude oil but tend to concentrate mainly in the heavier fractions and in the nonvolatile residues. Although their concentration in certain fractions may be quite small, their influence is important. For example, the thermal decomposition of deposited inorganic chlorides with evolution of free hydrochloric acid can give rise to serious corrosion problems in the distillation equipment. The presence of organic acid

components, such as mercaptans (RSH) and acids (RCO2H), can also promote environmental damage. In catalytic operations, passivation and poisoning of the catalyst can be caused by deposition of traces of metals (vanadium and nickel) or by chemisorption of nitrogen-containing compound s on the catalyst, thus necessitating the frequent regeneration of the catalyst or its expensive replacement. This carries with it the issues related to catalyst disposal. In all cases careful separation of reaction products is important to the recovery of well refined materials. This may not be easy if the temperature has risen as a consequence of chemical reaction. This will result in a persistent dark color traceable to reaction products that are redistributed as colloids. Separation may also be difficult at low temperature because of high viscosity of the stock, but this problem can be overcome by dilution with light naphtha or with propane.

SOLID EFFLUENTS:
Catalyst disposal is therefore a major concern in all refineries. In many cases the catalysts are regenerated at the refinery for repeated use. Disposal of spent catalysts is usually part of an agreement with the catalysts manufacturer whereby the spent catalyst is returned for treatment and re-manufacture. The formation of consider able quantities of coke in the coking processes is a cause for concern as it not only reduces the yield of liquid products but also initiates the necessity for disposal of the coke. Stockpiling to coke may be a partial answer unless the coke contains leachable material s that will endanger the ecosystem as a result of rain or snowmelt. In addition, emission of sulfur oxides (particularly sulfur dioxide) is generated from combustion of sulfur-containing coke as plant fuel. Sulfur dioxide (SO2) ha s a wide range of effects on health and on the environment. These effects vary from bronchial irritation upon shortterm exposure to contributing to the acidification of lakes. Emissions of sulfur dioxide therefore, are regulated in many countries.