This paper provides a novel method for removal of hydrogen sulfide from waste water streams in oil refineries.

Sulfur is present in crude petroleum and during the process of refining is reduced to hydrogen sulfide. The hydrogen sulfide in waste water streams poses a serious health hazard and needs to be removed. The conventional method of removal of hydrogen sulfide is by neutralization with caustic soda, and the resultant spent caustic sludge is subsequently treated to remove the sulfides and the converted bicarbonate solution is used of neutralisation of refinery wastewater.

During the petroleum refining process, sulfur compounds in crude oil are converted to hydrogen sulfide. In the lighter fractions such as propane, butane, and gasoline, the hydrogen sulfide is chemically removed with caustic soda. During the process, the caustic soda is changed, producing a material difficult to manage due to its foul smell. Previously, this hazardous waste was shipped off-site and disposed of by deep-well injection. This management option was not only expensive, it was also not environmentally preferable. The Delaware City Refinery developed a process to remove from the spent caustic the compounds that tend to cause odors (sulfides, mercaptons and phenols). The processed spent caustic, now a bicarbonate solution, is then used for neutralization at the refinery wastewater treatment plant. http://www.chemalliance.org/Handbook/plant/case_study.asp?CSID=356
Heliodor Solutions provides a proven hydrogen sulfide removal system that has been used successfully in the petroleum and natural gas industries for more than ten years. The process removes H2S from both refinery process vapor streams and field production units and converts it to elemental sulfur suspended in a non-hazardous solution. Systems are custom designed to accommodate a wide range of flow rates, pressures and H2S concentrations.

http://www.heliodorsolutions.com/Hydrogen.htm
Hydrogen Sulfide Removal One of the most common and problematic toxic industrial chemicals is hydrogen sulfide (H 2S). Many industriesincluding petroleum, chemical processing, pulp and paper, and agriculturalspend considerable time and money dealing with this toxic acid gas.

NanoActive materials have proven effective in the adsorption of hydrogen sulfide, due to their high surface areas and enhanced chemical and physical properties. NanoActive Material H2S Removal

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(lb H2S/lb Formulation) NanoActive Calcium Oxide NanoActive Copper Oxide NanoActive Zinc Oxide 0.54 0.29 0.34

Performance of NanoActive materials in the removal of Hydrogen Sulfide.

NanoActive materials adsorption of Hydrogen Sulfide

http://www.nanoactive.com/content/nanoactive_materials/HydrogenSulfideRemoval.asp I. Adsorption

Adsorbers commonly used empty activated carbon or alumina pellets impregnated with permanganate. These materials are highly porous and consequently there is a large surface area upon which adsorption of odorous compounds may occur. Activated carbon is generally considered for organic gases and vapours, some inorganic gases and some metallic vapours. The mechanism which attracts and attaches the molesules to the surface of the pores known as Van der Waals forces. It is generally accepted that compounds with a molecular weight af at least 45 or with a boiling point over 0oC will be well absorbed on activated carbon. The odorous stream needs to be pretreated before it passes through activated carbon when its temperature is high, moisture content is high or it contains dusts. The odorous stream should be free of dust in order not to clog the surface of activated carbon. Activated carbon needs to be replaced before it is saturated. The used activated carbon can be regenerated, otherwise it should be disposed.

II.

Liquid scrubbing

Liquid scrubbing of gases for the removal of odours can involve either adsorption in a suitable solvent or chemical treatment with a suitable reagent. Liquid scrubbing becomes ecnomically attractive compared with incineration and adsortion on activated carbon when the volume of odorous gas to be treated is great than 5000 cubic metres per hour. Liquid scrubbeing of gases involves bringing the odorous gas stream into intiate contact with the scrubbing liquid. Liquid scrubber needs to be well designed to ensure adequate contact between the

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gas and liquid phases. The treatment ability should be sufficient enough to treat the odorous gases generated. The principal types of gas absorption equipments include packed towers, plate or tray towers, spray towers, venturi and fluidised-bed scrubbers. It is important that hot moist vapour streams be cooled before contacting scrubbing solutions. Direct or indirect condenser can be used to condense the moisture from the odorous stream (the indirect condenser is preferred). The most frequently used absorbing solutions are: Sodium hydroxide - ideal for absorb hydrogen sulfide and mercaptans Amine - used to trap hydrogen sulfide of hydrocarbon gases from petroleum refinery chlorine, sodium hypochlorite, potassium permanganate, ozone or hydrogen peroxide effective to absorb unsaturated organic compounds Diluted sulfuric acid - used to absorb ammonia

III.

Biofiltration

For biological odour control, the odour is removed by biological processes - bacterial action. The bacteria grow on inert supports, allowing intimate contact between the odorous gases and the bacteria. The process is self-sustaining. Biofiliters require careful attention to ensure continured operation. The bed may have to be replaced regularly because of mechanical failure.

IV.

Bioscrubbers

Bioscrubbers use teh combined principles of liquid scrubbing and the biofiltration in order to remove vapours pollutions from waste gases. Bioscrubbers can only be used successfully if the contaminants can be removed from teh waste gas by absorption in a water water/activated sludge mixture. Furthermore the contaminants must be biologically degradable.

http://www.odour.unsw.edu.au/odour-control.html

Petroleum refineries extract hydrogen from natural gas to produce plastics (e.g., polyethylene) and add the hydrogen to crude oil to make gasoline. To remove sulfur during gasoline production, hydrogen is added under pressure along with a catalyst to produce hydrogen sulfide, which is removed as a gas. To produce the maximum amount of gasoline from crude oil, the process of adding hydrogen must be run in a narrow temperature and pressure range. The catalyst used effectively removes most sulfur-containing compounds. "To get rid of the most difficult sulfur compounds, the refinery must operate at a lower temperature or higher hydrogen pressure, which will raise its fuel production costs," Schmidt says. "At a lower temperature, the reaction will go slower, so more refining capacity must be added and more crude oil must be used to produce the normal yield of gasoline. At a higher pressure, the wall thickness of the refinery

units must be doubled or tripled, which is a difficult and expensive engineering problem." A novel chemical-biological process for removing sulfur from gasoline and diesel fuel has been developed by Abhijeet Borole, Catherine Cheng, Eric Kaufman, and Brian H. Davison, all of ORNL's Chemical Technology Division, in collaboration with Petro Star, a small refinery in Anchorage, Alaska, and Travis/Peterson Consulting, Inc., also of Anchorage. Petro Star, which funded ORNL's biodesulfurization research, has developed a chemical process that adds oxygen to sulfur compounds in the diesel fuel to allow their selective removal using a solvent. As a result of this oxidation-extraction process, a desulfurized fuel and a high-sulfur extract are produced. The extract is about 10% of the original fuel and has recoverable hydrocarbons, the fuel's energy source. During the research project, this extract was sent to the ORNL group, whose job was to use bacteria to remove the sulfur from the extract and recover its fuel value. "Biological processes may not be fast enough alone to give commercially economic rates of desulfurization," Borole says. "So, Petro Star's chemical process is being studied as an initial step because it is believed that oxidized sulfur species are more soluble in water where the bacteria reside, making it easier for the microbes to act on the sulfur. Our studies have indicated that this is the case." For the research project, the ORNL group used genetically engineered Pseudomonas bacteria obtained from a Spanish molecular biology organization (Consejo Superior de Investigaciones Cientificas of Madrid). Each microbe carries an inserted gene from another bacterium that breaks the carbon-sulfur bond by adding two oxygen atoms, converting each sulfur species to a sulfate (SO 4-2). The Pseudomonas bacteria were selected to carry this gene for two reasons. They have a high tolerance of the oil in which the sulfur compounds and hydrocarbons are present. In addition, because they can potentially produce biosurfactants, they can increase the contact between the oil and the water in which they reside. This increased mixing reduces mass transfer limitations and speeds up the biological oxidation reaction by which dibenzothiophene sulfone (an organic sulfur compound in diesel fuel) is converted to sulfate and sulfur-free hydrocarbons. In addition, the newly formed sulfate is soluble in the water phase, which naturally separates from the oil. The hydrocarbon-rich oil that remains can be used as a fuel.

"We measured the amount of energy the bacteria require for biodesulfurization, and we studied how well and how fast they remove sulfur from the diesel extract," Borole says. "It was not as fast as we'd like. We need to do more research to determine the best way for the bacteria to get more energy for desulfurization through metabolism of carbon sources. We need to find ways to increase the reaction rate to speed up the biological process for sulfur separation."

Borole notes that biodesulfurization is a potentially economical process because it can be performed at room temperature. Conventional refinery techniques for sulfur removal, which add hydrogen to crude oil, gasoline, and diesel to produce hydrogen sulfide gas, require temperatures as high as 300C. "Biodesulfurization," Borole says, "may ultimately cost less because it will use much less energy."
http://www.ornl.gov/info/ornlreview/v33_3_00/emissions.htm
Subterranean rock formations, particularly those of dome shape, are often found to contain natural gas; the domes are tapped by drilling. Natural gas and oil (petroleum) are often found in the same or adjacent areas. Significant producing areas are in the Persian Gulf area, the Gulf Coast areas of the United States, southwestern Soviet Union, Rumania, Indonesia, the North Sea and western Canada. Natural gas is usually over 80% CH4, with decreasing quantities of ethane, propane, and butane, and may contain nitrogen in varying proportions. The higher hydrocarbons are more valuable as raw materials for industry than as a fuel and therefore are often stripped from the gas stream by plants built astride the pipelines. A significant impurity in some natural gas sources is H2S. Such "sour" gas must be purified by removal of the H2S before sale since SO2 would be formed on combustion. Sulfur removal is generally achieved by use of some variant of the Claus process in which the hydrogen sulfide is partially oxidized. The hydrogen sulfide is absorbed from the natural gas at ambient temperature in a scrubber, either in alkanolamine-glycol solution: H2S(g) + H2NROH(aq) <--> HS- - [+NH3ROH](aq) or in aqueous alkaline carbonate solution: Na2CO3(aq) + H2S(g) <--> NaHCO3(aq) + NaSH(aq) Both systems can extract some 90% of the hydrogen sulfide on one pass, but multiple extractions are necessary for quantitative removal. The reversible reactions then yield hydrogen sulfide again on heating in a separate column, and the regenerated carbonate or alkanolamine solutions are recycled. The Claus reactions proper follow the extraction steps. The hydrogen sulfide is partially oxidized to SO2 with considerable evolution of heat: 2H2S + 3O2 --> 2SO2 + 2H2O, DH0 = -1036.04 kJ/mole reaction The resulting sulfur dioxide is then reacted with hydrogen sulfide in the presence of Fe 2O3 as a catalyst to yield the more conveniently handled elemental sulfur: 2H2S + SO2 --> 2H2O + 3S, DH0 = -145.55 kJ/mole reaction The elemental sulfur in turn may be oxidized to sulfuric acid or stored as sulfur depending upon economic demands.

http://www.psigate.ac.uk/newsite/reference/plambeck/chem1/p01264b.htm
Soaking up a stink Hydrogen sulphide is a gaseous by-product of many industries including wastewater treatment, paper manufacturing and petroleum refining. This gas is responsible for the unpleasant rotten egg smell and can be detected by people at concentrations as low as one part per billion. Ensuring complete cleansing of this gas is extremely important as the smell can lower quality of life as well as being damaging to vegetation and highly corrosive. Researchers at the University of La Corua, Spain, have developed a method to remove hydrogen sulphide using a biotrickling filter. This combines both inorganic longevity with excellent biological removal of the gas. A filter of plastic rings with a very high surface area has hydrogen sulphide degrading bacteria trickled onto it from above, and as the gas rises it is

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degraded by the bacteria. Degradation rates of up to 100% were achieved, making this an excellent technology for treatment of waste gases. Autotrophic deodorisation of hydrogen sulfide in a biotrickling filter, Yaomin Jin, Mara C Veiga, Christian Kennes, Journal of Chemical Technology and Biotechnology, DOI: 10.1002/jctb.1275 (Available on EarlyView)

Cutting the cost of sulfur removal

Refiners are under immense pressure to find an economical way to remove sulfur from gasoline and diesel fuel, as governments worldwide mandate tough new air-quality standards requiring cleaner commercial fuels. In anticipation of these upcoming regulations, researchers are developing cost-effective new technologies for desulfurizing fuels that could keep refineries from going out of business. Stringent U.S. EPA regulations for highway diesel, which will be phased in beginning in 2006, require a reduction in sulfur content from the current average of 500 parts per million (ppm) to 15 ppm. The EPA standard for gasoline, which phases in from 2004 to 2006 for large refineries, requires an average sulfur level of 30 ppm. In the European Union, the regulations are even stricter, requiring gasoline and diesel to have <10 ppm sulfur by 2005 (Environ. Sci. Technol. 2003, 37, 85A86A). Similarly tough regulations are also being implemented in Japan. To meet EPA regulations for highway diesel, a typical refinery will have to spend $35100 million, according to industry experts. The cost depends on what technology a refinery already has in place and where it is now in taking out sulfur, says Geoff Dolbear, a consultant for the refining and chemical businesses, based in southern California. Refineries that only have to spend $35 million have already invested a lot in sulfur removal, he says. The most common approach for removing sulfur from fuels is a process called hydrodesulfurization, which uses a catalyst, such as Co-Mo/Al2O3 or Ni-Mo/Al2O3, to break down sulfur compounds under high pressures of hydrogen (20100 atmospheres) and elevated temperatures (300340 C), forming hydrogen sulfide gas. The technology has been around since the 1930s, and several companies have recently developed new catalysts to make the reaction more efficient. Even so, to meet the new regulations, many analysts predict that higher temperatures and pressures will be needed and the reactors will have to be considerably larger, resulting in higher costs for the industry. The expense is the investment

7 for the equipment, says Dolbear. If you have to put $50 million into your refinery and it does not change by one gallon the amount of product that comes out the back, it is very hard to figure out how you are going to pay for it. It is very difficult to pass the costs on to the consumer, he adds. One way to avoid the increased costs is to use a different approach, such as adsorption, which operates at ambient temperature and pressure. Researchers have been searching for many decades for adsorbent materials that are highly selective toward sulfur compounds, but until recently, none have proven to be effective for removing large amounts of sulfur from fuels (Environ. Sci. Technol. 2000, 34, 142A143A). Researchers at the University of Michigans Ann Arbor campus believe they have now discovered a promising new zeolite sorbent that could be just the material the petroleum refining industry needs (Science 2003, 301, 7981). The new sorbent, which costs about $4.4 per kilogram, is produced by a simple ion-exchange reaction in which Na+ ions in zeolite Y are replaced with Cu+ or Ag+ ions. The resulting product is capable of reducing the sulfur content in commercial diesel fuel from 430 to <0.2 ppm by weight, and each gram has the ability to clean 34 cm3 of diesel. Most importantly, the new sorbent is regenerable, says Ralph Yang, a chemical engineering professor who developed the new sorbent with the help of graduate student Arturo Hernndez-Maldonado and postdoc Frances Yang. Although it is not 100% regenerable, it is probably 9598% regenerable, which means that it can be used for at least 20 cycles, he says. The new sorbent is highly selective toward aromatic sulfur compounds, such as thiophene and its derivatives, which are not efficiently removed by hydrodesulfurization (Environ. Sci. Technol. 2000, 34, 161A). The Cu+ and Ag+ zeolites form a weak chemical bond with the thiophene compounds, so it is reversible, Yang says. The sulfur compounds can therefore be easily removed, allowing the sorbent to be reused multiple times. Yang is currently working with a large oil company to commercialize the new sorbent, but some experts are quick to point out the difficulties of bringing a refining technology to market. Whether or not you could devise some sort of a refinery process or unit that could use this technology is a matter of economics and practicality, says Lester Wyborny, a chemical engineer with EPAs Office of Transportation and Air Quality. Refiners love continuous technologies where you just run the thing for several years and shut it down once in a while, he says. The new sorbent developed by Yang and colleagues was able to reduce the sulfur content of commercial diesel fuel from 400 to <1 ppm, but after a matter of days, the sulfur began to break through, he adds. That is something that has to be considered with respect to how refineries normally operate. Dolbear sees a couple of niche areas in which the new sorbent could be used. If you have the ability to get down to 4050 ppm sulfur and just have to take out half of what is left, an adsorbent would make a marvelous technology, he says. Taking out 1015 ppm is not going to require an immense bed. Taking out 100 ppm, on the other hand, will require a lot of adsorbent material and an immensely large adsorbent bed. The problem is that refineries handle a tremendous amount of material. A typical refinery handles 100,000200,000 barrels a day, Dolbear estimates. If a particular stream has 500 ppm sulfur in it, you will need a lot of adsorbent material and a bed that could be half the size of the refinery, he adds. According to Yang, however, the bed size can be reduced significantly by shortening the adsorption/regeneration cycles. Adsorption processes are cyclic. The simplest operation

8 involves two beds; one undergoes adsorption, while the other undergoes regeneration. The amount of sorbent depends on the cycle frequency, he explains. The other place I can see it being used is in cleaning up samples that get accidentally tainted, Dolbear says. For example, if a gasoline sample that meets EPAs standard leaves a refinery and somehow gets contaminated before it reaches the pump, the material cannot legally be sold. It could be possible to have small units around, which contain sorbent beds, to clean out that little bit of sulfur. You could make them portable, truck-mounted units, Dolbear adds. Yang believes the new sorbent also has great potential for use with fuel cells, which need a source of hydrogen. When gasoline is used to produce the hydrogen, a fuel processor is needed to convert the liquid fuel into hydrogen. The fuel processor requires liquid fuel that has less than 0.1 or 0.2 ppm sulfur. Otherwise the sulfur will poison the catalyst, Yang says. The new sorbent could be just what is needed to remove any traces of sulfur from the gasoline. It is too early to calculate the economics of the new sorbent technology. EPAs most recent cost estimate for achieving a 15-ppm standard for highway diesel using conventional hydrodesulfurization technology is about 3.5 cents per gallon, Wyborny says. The new sorbent would have to do better than that to be considered. BRITT E. ERICKSON http://pubs.acs.org/subscribe/journals/esthag-w/2003/jul/tech/be_sulfur.html

SULFIRAN

Technology of Single Stage process for removing H2S from gas streams and converting it to innocuous elemental sulfur on liquid Redox (Reduction-Oxidation) reaction
H 2S is a toxic, corrosive & odorous compound

HYDROGEN SULFIDE
When dissolved in water, forms an acidic solution, which can be very corrosive to pipelines and equipment. When burned, forms sulfur dioxide (SO2) which is a precursor to acid rain. SO2 is itself the subject of regulatory concern. Is strong poison for most of industrial catalysis and deadly poison

Direct Removing H2S from Gas Streams

There are 3 main methods of removing H2S:

Liquid & Solid H2S Scavengers such as Triazines & Iron sponge Liquid Redox processes employ aqueous-based solutions containing metal ions, usually iron,which are capable of transferring electrons in reduction-dation (redox) reactions Cluse systems

SULFIRAN

Is a Liquid Redox Process

SULFIRAN process
Is a Special Technology Developed by RIPI(Research Institute of Petroleum Industry) Has a 99+% H2S Removal Efficiency Using Iron Chelate Catalyst Licensed by RIPI Is High Flexible and Can be Used on a Wide Variety of H2S Containing Gases Has a Catalyst which Continuously Regenerated in an Oxidizer

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SULFIRAN Process

Sweet Gas Acid Gas

Air

Absorption

Oxidizer

Filter

Sulfu r Cake

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Absorber Reactions
alkaline, aqueous RIPI Catalyst: H2S(g) + H2O(liq) H2S(liq) H2S(liq)

In the absorber, H2S is absorbed into the sl

HS- + H+

which finally bisulfide is oxidized to sulfur b

Then the H2S ionizes to bisulfide(HS HS- + 2 Fe+++ ):

reducing the iron ion from the ferric( Fe+++ ) the ferrous( Fe++ ) state S(soild)+2Fe+++H+

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Oxidizer Reactions
In the oxidizer, atmospheric oxygen is absorbed into the RIPI solution: O2 +H2O O2 (liq)

The ferrous iron is reoxidized to ferric iron, regenerating the catalyst: O2(liq.) + 2 Fe++ + H2O 2 Fe+++ +2 OH
_

The regenerated catalyst is ready for use in the absorber section

Overall Reactions

The overall reaction is an isothermal reaction:

Liquid Redox Claus To maintain the above reactions some chemical additions Scavengers Scavengers required: Gas Treated Caustic for maintaining the pH Acid gas Replacement Yes Yes iron lost in the Yessulfur removal Yes of chelated Natural Gas Turndown Cost Operating Equipment Limits $20 / kg of Sulfur Low <50 kg S/day economic
process

Liquid

Solid

Yes Sensitive

Yes Not Sensitive $6.64 / kg of Sulfur Moderately Low <150 kg S/day economic

Yes Not Sensitive $0.35 / kg of Sulfur Moderately High <20 TPDS economic

No Sensitive

Replacement of degraded chelating agents

Comparison Table ~ $0 High >15 TPD S >15% H2S

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SULFIRAN Semi Commercial Unit At FAJR-E-JAM Gas Refinery

Based on the results obtained in the laboratory & pilot plant, RIPI has been designed and constructing a semi commercial unit at Fajr-E-Jam gas refinery with following specifications: Capacity: 450,000 SCFD Feed : A portion of Amine tail gas containing Max 2% wt H2S Catalyst: Iron Chelate 2000 PPM Licenced by RIPI H2S in outlet gas: Nil

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Summary
The SULFIRAN technology is applicable to all types of gas streams including : Air, sour gas, CO2, amine acid gas, biogas, landfill gas, refinery, fuel gas, etc. In cases of sulfur recovery from .2 up to 20 TPD ,SULFIRAN is the Best Choice in economical &technical view of point The liquid catalyst adapts easily to variations in flow and concentration. Flexible operation allows 100% turndown in gas flow and H2S concentrations. So Units require minimal operator attention

http://www.ripi.ir/en/sulfiran.asp The Capstone Turbine Corporation, a Cali-fornia-based publicly held corporation produces low-emission micro turbines that burn air pollutants to generate clean electric power. As applied to reduce air pollution from the very sour (high in hydrogen sulfide) solution gasses otherwise flared into the atmosphere by oil refineries in Alberta, Canada, Capstones micro turbines have virtually eliminated the release of 250 potentially dangerous chemical compounds, including hydrogen sulfide, toluene and benzene, as well as greenhouse gasses, such as nitrous oxide (NOx) and carbon monoxide (CO). Using a single moving part, the micro turbines burn these toxic flare gasses to generate electric power that can be used either at the refinery or on the electric power grid. Capstones micro turbines are fitted with a Digital Power Controller that assures that generated electricity meets qualitative requirements of electric power utilities. In addition to the treatment of solution gas from petroleum refineries, Capstone micro turbineselegant technology contributes to low-emission and relatively quiet distributed generation of electric power in other settings, such as landfills where odoriferous methane is used to generate electric power. Capstone also applies its micro-turbine technology in powering hybrid electric vehicles, such as busses. A fascinating look at how Capstones micro turbines work is available at the companys Web site: http:// www.capstoneturbine.com.

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