World War II and the start of catalytic age of refinery

It has been a long history since petroleum refinery started in 1855 in U.S. During 1910 to 1940, thermal refinery was the major refinery process to produce light and middle distillate petroleum products. However, the new chemistry was introduced and catalytic refinery process was developed in 1930s. Compare to thermal refinery, catalytic refinery produces higher yield of petroleum products with higher octane number that reduce knocking. During the World War II, the U.S need higher yield of petroleum products and require higher octane number to run more powerful engines. The pressure from the war provides stimulus to urgently develop catalytic technologies. The World War II helped to start the catalytic age of refinery which between 1940 and 1970.

During the catalytic cracking, reforming, alkylation, polymerization was introduced and they changed the way of making high octane number gasoline. Hydrotreatment was also invented to protect platinum catalyst that used in reforming. During the World War II, intense activities of development of catalytic refinery happened. Visbreaking, alkylation, isomerization and fluid catalytic cracking were invented. All four technologies contribute to increase the yield of petroleum products which with higher octane number. These technologies are still important in the refinery process today. The catalytic age of refinery was end in 1970 not because the new chemistry was introduced. It is due to the 1973 and 1979 oil crises and environmental concerns. The World War II helped to start the catalytic age of refinery. Even the catalytic age of refinery ended, the lessons and experience we learned from catalytic age helped us go even further in the age of heavy end conversion refinery.

References

1. F SC 432 class website Lesson 11

https://www.e-education.psu.edu/fsc432/content/catalytic-refinery-1940-1970

2. Katrina C. Arabe, “How Oil Refining Transformed U.S. History & Way of Life”  January 17th, 2003.

http://news.thomasnet.com/IMT/2003/01/17/how_oil_refinin/

3.Congressional Research Service, “The U.S. Oil Refining Industry: Background in Changing Markets and Fuel Policies”

http://fas.org/sgp/crs/misc/R41478.pdf

The Influence of World War II on Petroleum Refining.

Petroleum refining has been around since the 1850s, when a single pot batch distillation was first done to produce kerosene as the major product, and since then it has evolved in many ways into an integrated, complex process that we use today to produce a vast amount of products and fuels. During its existence, petroleum refining has been influenced by many historical events that the world has seen. One of these historical events that greatly influenced petroleum refining, is the Second World War

In the late thirties, new catalytic technologies were being investigated by scientists in the US and around the world. When World War II came around in the forties, countries and scientists were put under intense pressure to make strides in the advancement of petroleum refining, thus providing the stimulus needed to urgently develop catalytic technologies. This catalytic age took place from 1940 to 1970 and was thoroughly fueled by World War II. The historical timeline of petroleum refining shows a clear influx of process development during the age of World War II.

The catalytic refinery of the 1940s largely resembles that of which we use today, in that the goal is to produce high yields of gasoline. This age saw the introduction of catalytic cracking, reforming, alkylation, and polymerization, all of which have contributed to revolutionizing the production of high octane number gasoline. These revolutions largely contributed to the war effort as well. The Catalytic refinery also saw the development of hydrotreatment, which was essential to protect the platinum catalysts used in reforming.

 

References:

1. https://cms.psu.edu/section/content/default.asp?WCI=pgDisplay&WCU=CRSCNT&ENTRY_ID=F20C6357261A4AE2A750C141B721E8C1

Water Treatment of Wastewater from Refining

In petroleum refining, a large amount of water is used in the refining process. This water is processed using wastewater treatment techniques. Since the amount of water used in refining is so vast, waste water treatment is an integral part of the refining process. There are four different types of waste water; cooling water, process water and steam, storm water and sanitary sewage water. These four types of water carry large amounts of pollutants as well. Pollutants like, liquid hydrocarbons, suspended and dissolved solids, mercaptans, phenols, amines, and cyanides. All of these pollutants are a direct result of the water’s use in the refinery.

There are two types of measurement systems that are used to measure the level of contamination in waste water. Those two types are the Biochemical Oxygen Demand and the Chemical oxygen demand. Biochemical Oxygen Demand measures the amount of oxygen consumed by microorganisms in decomposing organic matter, and the Chemical Oxygen Demand measures the total oxygen consumption by organic and inorganic chemicals present in water.

Refinery waste water however, can’t be treated in municipal waste water treatment plants. This is because the municipal water treatment plants are not capable of processing the contaminants that arise from water that is used in petroleum refining. It is also important to keep the different wastewater streams segregated as the different types of wastewater have different levels of different contaminants. This making the combining of the streams undesirable as the treatment of the water would be much more difficult, placing to high of a strain on the water treatment machinery.

References.

1. https://cms.psu.edu/section/content/default.asp?WCI=pgDisplay&WCU=CRSCNT&ENTRY_ID=F20C6357261A4AE2A750C141B721E8C1

Wastewater Characterization and Processing

In a golden age of corporate personhood, U.S. refineries may actually have more in common with humans than ever before. Water sustains both human and refinery life. As a community’s water consumption increases, so must its municipal wastewater treatment capacity increase. Likewise, as regulations necessitate more hydrotreatment processing, refineries must increase sour water treatment capacity. While this notion might harmoniously unify a refinery and its perpetually protesting community, in reality it causes downstream issues with contamination risks galore.

As a general rule in wastewater treatment, “do not mix different wastewater streams before treatment.” Although cooling water and sanitary sewage may require the least amount of treatment, an operator must be mindful of the refinery’s process and instrument drawing (P&ID) in the event of an oil spill, in which these flows could be contaminated. Storm water may be contaminated by air pollutants and should be dealt with accordingly. The most heavily polluted wastewater feeds stream from process water and steam units; these must be sweetened, and oils and solids must be separated from the wastewater.

In order to minimize the load on the treatment units, the operator must separate different wastewater streams based on their characteristics. A complete wastewater characterization includes biochemical oxygen demand (Standard Methods 5210), chemical oxygen demand (Standard Methods 5220), suspended solids, hydrocarbon content, nitrogen content, phenols [all in mg/L], and acidity [pH]. The EPA provides guidelines for industrial wastewater limitations and Standard Methods for the Examination of Water and Wastewater provides EPA-approved wastewater analytical procedures.

In July 2012, The Carlyle Group and Sunoco, Inc. formed a joint venture, Philadelphia Energy Solutions, to continue refinery operations at the oldest continuously operating refinery on the east coast. The Carlyle Group and the Commonwealth of Pennsylvania agreed to provide funding for the catalytic cracker unit, a train terminal for transporting Bakken crude oil, and a mild hydrocracker unit. All of these modifications will increase the water consumption as well as the required wastewater treatment capacity of the refinery. The EPA required Sunoco to continue to remove groundwater contaminants such as hydrocarbons and heavy metals. On the other hand, the new owners must increase their wastewater treatment capacity. While there are plenty of people who might disagree, I believe this has been the healthiest business agreement in past decade between industry and government in the PA energy sector.

Wastewater Treatment

There are a number of reasons why refineries treat their wastewater right on site instead of sending it off to a municipal treatment plant, but for the most part, it has to do with the contaminants present in the samples. Wastewater from processes such as desalting, distillation, thermal and catalytic cracking, and coking possibly contain benzene (toxic aromatic compound), H2S, NH3, heteroatoms, and acids. Requirements for wastewater in municipal treatment plants vary from state to state so refineries are just playing it safe by treating their water in-house. The refineries have the equipment and knowledge to detect the exact amount of contaminant species, therefore they should be the ones who treat it. On top of all this, you can’t combine the four different types of wastewater (cooling water, process water and steam, storm water, and sanitary sewage water) so transporting it to the municipal plant would require four different vehicles, a bunch of unneeded money spending, and communication of specifics. Even though industrial wastewater treatment plants are capable of removing chemicals and acids, it is not safe to use the facilities for water that has came in contact with petroleum fractions. The contaminants found in this water is basically human poison and is best left to the people who know where the all the water has came from.

 

Sources:

Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press NY, 2007, Chapter 13, Supporting Processes, pp. 290-293.

 

http://en.wikipedia.org/wiki/Industrial_wastewater_treatment#Oils_and_grease_removal

 

http://10statesstandards.com/wastewaterstandards.html#52

 

 

 

Water Treatment

Heavily polluted wastewater streams come in direct contact with petroleum fractions and require serious treatment processes for purification. Hydrocarbons such as aromatic compounds and heteroatoms can be found in wastewater streams from distillation and different forms of cracking. There is a set of quality parameters to measure the treatment required for the wastewater processes including amount of suspended solids, hydrocarbon content, nitrogen content, phenols content, and acidity. Municipal wastewater treatment cannot handle treating the pollutants because the different streams need to be kept separate to reduce the load on the treatment units. The wastewater treatment constitutes a very significant supporting process for safe operation. Most municipal wastewater treatment facilities can only handle cooling water and sanitary sewage water after it has had minor treatments. The amount of refinery equipment and treatment processes require expensive machinery as well as many units for the processes that municipals may not be able to afford. Primary treatments are physical whereas secondary treatments are biological processes. Primary treatment of sour water contaminated with oils and solid particles involve the stripped of dissolved H2S using steam, separators, and settling tanks. After primary treatments are conducted typically water can be sent to municipalities for further treatment processes because they are at a acceptable level for municipalities to handle. Secondary treatments utilize microorganisms to further remove organic contaminants.

Russell Hedrick . Refinery wastewater treatment

The wastewater from refineries can not be treated in regular municipal wastewater treatment plants for a variety of reasons. Municipal wastewater treatment plants are designed to treat wastewater from residential houses. There can also be some rainwater runoff going it to these plants as well. These plants are not equipped to clean the wastewater that would be coming from a refinery. The waste water coming from a refinery is divided into four different types. The types of wastewater are Storm water, sanitary sewer water, cooling water, and the most polluted process water and steam. The process water and steam contains many forms of pollutants that include liquid hydrocarbons, suspended solids, dissolved solids, mercaptans, phenols, amines, and cyanides. These chemicals would not be able to be processed by a municipal wastewater treatment because of the toxicity of some of these compounds. These compounds have to be stripped from the sour water using steam to remove H2S, float/sink density separators, as well as settling tanks to separate heavier oils. After these processes are completed the water can be directed to a wastewater treatment plant where the water can be completely processed. There is also a secondary treatment process that uses microorganism to remove organic compounds from the waste water. This process produces a substance called biocoke.

Effects of Wastewater Treatment Processes in a Municipal Plant

The reason refinery wastewater cannot not be treated in a municipal wastewater treatment plant is because of the levels of contaminates that exist in these stream. These contaminates include hydrocarbons, suspended solids, Mercaptans, Phenols, dissolved gases, and acids. In general the entire wastewater treatment process is a very delicate balance of processes. After taking a tour at Penn State’s Wastewater Treatment Plant I was amazing to learn how much attention was taken to ensure that the BOD levels and contaminate levels were suitable for proper digestion from their microorganisms, or as they referred to them as, “their bugs”. This balance was so delicate that the operators had to take samples, multiple times a day, from the wastewater stream to ensure a proper balance. Overall, if the refinery wastewater streams were sent to a municipal wastewater treatment plant it would need to be heavily treated before the actual treatment of the waste stream. According to Penn State’s wastewater treatment facility, the wastewater is treated to remove solids, BOD and other nutrients that cause excessive vegetative growth. [1] The increase of pretreatment may be too much for the plant to handle and would cause the system balance to be thrown off which may harm the microorganisms. All in all, a municipal wastewater treatment plant is an ecosystem of its own. By increasing the levels of nitrogen oxides, sulfur oxides and hydrocarbons, the wastewater ecosystem could be destroyed potentially throwing off the entire treatment process.

Sources:
1. Wastewater Services FAQ. (n.d.). — Office of Physical Plant. Retrieved July 25, 2014, from http://www.opp.psu.edu/about-opp/divisions/ee/util/documents/wastewater-services-faq

Refinery Wastewater: Contaminants and Processes

Wastewater treatment is considered an important supporting process in petroleum refining. The four types of refinery wastewater include cooling water, process water and steam, storm water, and sanitary sewage water. The refinery stages that produce the most wastewater are desalting, distillation, thermal and catalytic cracking, and coking. The most polluted wastewater is the process water that comes into direct contact with petroleum fractions; thus it cannot be simply treated in municipal wastewater treatment plants. Storm water is considered contaminated as a result of incidental exposure to pollutant sources and accidental spills during refinery reactions. The refinery’s cooling water and sanitary sewage water will probably not require much treatment before sending it to public water facilities where municipal wastewater is treated. Different wastewater streams are usually not mixed even if it reduces the load on treatment units. This is because different wastewater streams have different components and toxicities. The wastewater’s contamination level depends on its usage in the petroleum refinery. Generally, the pollutants in the streams include hydrocarbons, particularly toxic aromatic compounds such as benzene. Also, the wastewater streams include other heteroatom compounds mercaptans, amines, phenols, and cyanides, dissolved gases (H2S and NH3), and acids (H2SO4 and HF). Such components require much more treatment than municipal wastewater. In addition, environmental policies such as the Clean Water Act and Safe Drinking Water Act require refineries to effectively treat their wastewater.

Source:

Course Website

Refinery Wastewater Precautions

Blog Post 9

Post your response to the blog discussing why refinery wastewater cannot be treated in municipal wastewater treatment plants.


 

Water and steam are used for treatment in huge quantities in petroleum refining. Of course a refinery thus generates a lot of waste water. The waste water faces many different levels of contamination based upon its usage within the refinery. The steam or water that comes into direct contact with the hydrocarbons or crude oil is the most highly contaminated and should be treated separately on its own. In order to have the best and most efficient water treatment process the key is segregation of the waste streams. This is because of the different forms of contamination. For example, desalting you don’t really need to use fresh water, you can use waste water that is contaminated with hydrocarbons but doesn’t contain salt to remove salt from crude oil as the very first process before undergoing distillation. Process water contaminated with hydrocarbons can be used effectively for desalting instead of fresh water. Different wastewater streams have different levels and different kinds of contaminants.  Combining them would increase the load on wastewater treatment facilities.

The units within a refinery that generate the largest amount of wastewater are desalting, distillation, cracking processes, coking, heat exchangers, and storage tanks The four types of refinery wastewater include cooling water, process water and steam, storm water, and sanitary sewage water. Storm water may be contaminated because of incidental exposure to pollutant sources on refinery surfaces and other accidental spills such as oil from automobiles.  Pollutants found in the wastewater streams include hydrocarbons that have a particular concern for toxic aromatic compounds, heteroatom compounds, dissolved gases, acids, and suspended or dissolved solids.  Cooling water and sanitary sewage water are forms that may not require much treatment before they are sent to public water treatment facilities due to their contamination levels. The most important thing to keep in mind is to avoid mixing different types of wastewater streams to reduce the load on the treatment units.