Cracking (chemistry)

In petroleum geology and chemistry, cracking is the process whereby complex organic molecules such as kerogens or heavy hydrocarbons are broken down into simpler molecules such as light hydrocarbons, by the breaking of carbon-carbon bonds in the precursors. The rate of cracking and the end products are strongly dependent on the temperature and presence of catalysts. Cracking, also referred to as pyrolysis, is the breakdown of a large alkane into smaller, more useful alkanes and an alkene. Simply put, hydrocarbon cracking is the process of breaking long-chain hydrocarbons into short ones.

Factory of Shukhov cracking process, Baku, USSR, 1934.

Contents

History and patents

The thermal cracking method (also known as "Shukhov cracking process") was invented by Russian engineer Vladimir Shukhov and patented in 1891 in the Russian empire, patent no. 12926, November 27, 1891. This process was modified by the American engineer William Merriam Burton and patented as U.S. patent 1,049,667 on January 7, 1913.

In 1924, the delegation of the American "Sinckler Oil" paid a visit to Shukhov. The "Sinckler Oil" firm protested the personal right appropriated by the Rockefeller "Standard Oil" concern on the discovery of oil cracking. It indicated that Burton's patent used by the "Standard Oil" concern was the modified patent of Shukhov. Shukhov proved to the Americans that the Burton's method was just the slightly changed modification of his 1891 patents. However, an agreement between the American companies finally was made not to buy the patent from Soviet Russia.[1]

Applications

Oil refinery cracking processes allow the production of "light" products such as liquified petroleum gas (LPG) and gasoline from heavier crude oil distillation fractions such as gas oils and residues. Fluid catalytic cracking produces a high yield of gasoline and LPG, while hydrocracking is a major source of jet fuel, diesel, naphtha, and LPG.

Thermal cracking is currently used to "upgrade" very heavy fractions ("upgrading", "visbreaking"), or to produce light fractions or distillates, burner fuel and/or petroleum coke. Two extremes of the thermal cracking in terms of product range are represented by the high-temperature process called "steam cracking" or pyrolysis (ca. 750 °C to 900 °C or more) which produces valuable ethylene and other feedstocks for the petrochemical industry, and the milder-temperature delayed coking (ca. 500 °C) which can produce, under the right conditions, valuable needle coke, a highly crystalline petroleum coke used in the production of electrodes for the steel and aluminium industries.

Fluid catalytic cracking

Fluid catalytic cracking is a commonly used process, and a modern oil refinery will typically include a cat cracker, particularly at refineries in the U.S., due to the high demand for gasoline.[2][3][4] The process was first used in around 1942 and employs a powdered catalyst. During the Second World War, in contrast to the Axis Forces which suffered severe shortages of gasoline and artificial rubber, the Allied Forces were supplied with plentiful supplies of the materials. Initial process implementations were based on low activity alumina catalyst and a reactor where the catalyst particles were suspended in a rising flow of feed hydrocarbons in a fluidized bed.

Aluminum-catalyzed cracking systems are still in use in high school and university laboratories in experiments concerning alkanes and alkenes. The catalyst is usually obtained by crushing pumice stones, which contain mainly aluminium oxide and silica into small, porous pieces. In the laboratory, aluminium oxide (or porous pot) must be heated.

In newer designs, cracking takes place using a very active zeolite-based catalyst in a short-contact time vertical or upward sloped pipe called the "riser". Pre-heated feed is sprayed into the base of the riser via feed nozzles where it contacts extremely hot fluidized catalyst at 1230 °F to 1400 °F (665 °C to 760 °C). The hot catalyst vaporizes the feed and catalyzes the cracking reactions that break down the high molecular weight oil into lighter components including LPG, gasoline, and diesel. The catalyst-hydrocarbon mixture flows upward through the riser for just a few seconds and then the mixture is separated via cyclones. The catalyst-free hydrocarbons are routed to a main fractionator for separation into fuel gas, LPG, gasoline, naphtha, light cycle oils used in diesel and jet fuel, and heavy fuel oil.

During the trip up the riser, the cracking catalyst is "spent" by reactions which deposit coke on the catalyst and greatly reduce activity and selectivity. The "spent" catalyst is disengaged from the cracked hydrocarbon vapors and sent to a stripper where it is contacted with steam to remove hydrocarbons remaining in the catalyst pores. The "spent" catalyst then flows into a fluidized-bed regenerator where air (or in some cases air plus oxygen) is used to burn off the coke to restore catalyst activity and also provide the necessary heat for the next reaction cycle, cracking being an endothermic reaction. The "regenerated" catalyst then flows to the base of the riser, repeating the cycle.

The gasoline produced in the FCC unit has an elevated octane rating but is less chemically stable compared to other gasoline components due to its olefinic profile. Olefins in gasoline are responsible for the formation of polymeric deposits in storage tanks, fuel ducts and injectors. The FCC LPG is an important source of C3-C4 olefins and isobutane that are essential feeds for the alkylation process and the production of polymers such as polypropylene.

Hydrocracking

In 1920, a plant for the commercial hydrogenation of brown coal was commissioned at Leuna in Germany.[5]

Hydrocracking is a catalytic cracking process assisted by the presence of an elevated partial pressure of hydrogen gas. Similar to the hydrotreater, the function of hydrogen is the purification of the hydrocarbon stream from sulfur and nitrogen hetero-atoms.

The products of this process are saturated hydrocarbons; depending on the reaction conditions (temperature, pressure, catalyst activity) these products range from ethane, LPG to heavier hydrocarbons consisting mostly of isoparaffins. Hydrocracking is normally facilitated by a bifunctional catalyst that is capable of rearranging and breaking hydrocarbon chains as well as adding hydrogen to aromatics and olefins to produce naphthenes and alkanes.

Major products from hydrocracking are jet fuel and diesel, while also high octane rating gasoline fractions and LPG are produced. All these products have a very low content of sulfur and other contaminants.

It is very common in India, Europe and Asia because those regions have high demand for diesel and kerosene. In the US, Fluid Catalytic Cracking is more common because the demand for gasoline is higher.

Steam cracking

Steam cracking is a petrochemical process in which saturated hydrocarbons are broken down into smaller, often unsaturated, hydrocarbons. It is the principal industrial method for producing the lighter alkenes (or commonly olefins), including ethene (or ethylene) and propene (or propylene).

In steam cracking, a gaseous or liquid hydrocarbon feed like naphtha, LPG or ethane is diluted with steam and briefly heated in a furnace without the presence of oxygen. Typically, the reaction temperature is very high, at around 850°C, but the reaction is only allowed to take place very briefly. In modern cracking furnaces, the residence time is reduced to milliseconds to improve yield, resulting in gas velocities faster than the speed of sound. After the cracking temperature has been reached, the gas is quickly quenched to stop the reaction in a transfer line heat exchanger.

The products produced in the reaction depend on the composition of the feed, the hydrocarbon to steam ratio and on the cracking temperature and furnace residence time.

Light hydrocarbon feeds such as ethane, LPGs or light naphtha give product streams rich in the lighter alkenes, including ethylene, propylene, and butadiene. Heavier hydrocarbon (full range and heavy naphthas as well as other refinery products) feeds give some of these, but also give products rich in aromatic hydrocarbons and hydrocarbons suitable for inclusion in gasoline or fuel oil. The higher cracking temperature (also referred to as severity) favours the production of ethene and benzene, whereas lower severity produces higher amounts of propene, C4-hydrocarbons and liquid products. The process also results in the slow deposition of coke, a form of carbon, on the reactor walls. This degrades the efficiency of the reactor, so reaction conditions are designed to minimize this. Nonetheless, a steam cracking furnace can usually only run for a few months at a time between de-cokings. Decokes require the furnace to be isolated from the process and then a flow of steam or a steam/air mixture is passed through the furnace coils. This converts the hard solid carbon layer to carbon monoxide and carbon dioxide. Once this reaction is complete, the furnace can be returned to service.

Chemistry

"Cracking" breaks larger molecules into smaller ones, through thermic or catalytic method.

The thermal cracking process follows a homolytic mechanism, that is, bonds break symmetrically and thus pairs of free radicals are formed.

The catalytic cracking process involves the presence of acid catalysts (usually solid acids such as silica-alumina and zeolites) which promote a heterolytic (asymmetric) breakage of bonds yielding pairs of ions of opposite charges, usually a carbocation and the very unstable hydride anion. Carbon-localized free radicals and cations are both highly unstable and undergo processes of chain rearrangement, C-C scission in position beta as in cracking, and intra- and intermolecular hydrogen transfer or hydride transfer. In both types of processes, the corresponding reactive intermediates (radicals, ions) are permanently regenerated, and thus they proceed by a self-propagating chain mechanism. The chain of reactions is eventually terminated by radical or ion recombination.

Thermal cracking

The first thermal cracking method, the Shukhov cracking process, was invented by Russian engineer Vladimir Shukhov, in the Russian empire, Patent No. 12926, November 27, 1891.[6]

William Merriam Burton developed one of the earliest thermal cracking processes in 1912 which operated at 700 - 750 °F (370 - 400 °C) and an absolute pressure of 90 psi (620 kPa) and was known as the Burton process. Shortly thereafter, in 1921, C.P. Dubbs, an employee of the Universal Oil Products Company, developed a somewhat more advanced thermal cracking process which operated at 750°F -860 °F (400°C - 460 °C) and was known as the Dubbs process.[7] The Dubbs process was used extensively by many refineries until the early 1940s when catalytic cracking came into use.

Modern high-pressure thermal cracking operates at absolute pressures of about 7,000 kPa. An overall process of disproportionation can be observed, where "light", hydrogen-rich products are formed at the expense of heavier molecules which condense and are depleted of hydrogen. The actual reaction is known as homolytic fission and produces alkenes, which are the basis for the economically important production of polymers.

A large number of chemical reactions take place during steam cracking, most of them based on free radicals. Computer simulations aimed at modeling what takes place during steam cracking have included hundreds or even thousands of reactions in their models. The main reactions that take place include:

Initiation reactions, where a single molecule breaks apart into two free radicals. Only a small fraction of the feed molecules actually undergo initiation, but these reactions are necessary to produce the free radicals that drive the rest of the reactions. In steam cracking, initiation usually involves breaking a chemical bond between two carbon atoms, rather than the bond between a carbon and a hydrogen atom.

CH3CH3 → 2 CH3•

Hydrogen abstraction occurs where a free radical removes a hydrogen atom from another molecule, turning the second molecule into a free radical.

CH3• + CH3CH3 → CH4 + CH3CH2•

Radical decomposition occurs where a free radical breaks apart into two molecules, one an alkene, the other a free radical. This is the process that results in the alkene products of steam cracking.

CH3CH2• → CH2=CH2 + H•

Radical addition, the reverse of radical decomposition, occurs where a radical reacts with an alkene to form a single, larger free radical. These processes are involved in forming the aromatic products that result when heavier feedstocks are used.

CH3CH2• + CH2=CH2 → CH3CH2CH2CH2•

Termination reactions occur when two free radicals react with each other to produce products that are not free radicals. Two common forms of termination are recombination, where the two radicals combine to form one larger molecule, and disproportionation, where one radical transfers a hydrogen atom to the other, giving an alkene and an alkane.

CH3• + CH3CH2• → CH3CH2CH3
CH3CH2• + CH3CH2• → CH2=CH2 + CH3CH3

Thermal cracking is an example of a reaction whose energetics are dominated by entropy (∆S°) rather than by enthalpy (∆H°) in the Gibbs Free Energy equation ∆G°=∆H°-T∆S°. Although the bond dissociation energy D for a carbon-carbon single bond is relatively high (about 375 kJ/mol) and cracking is highly endothermic, the large positive entropy change resulting from the fragmentation of one large molecule into several smaller pieces, together with the extremely high temperature, makes T∆S° term larger than the ∆H° term, thereby favoring the cracking reaction.

Here is an example of cracking of butane CH3-CH2-CH2-CH3

CH3* / *CH2-CH2-CH3

After a certain number of steps, we will obtain an alkane and an alkene: CH4 + CH2=CH-CH3

CH3-CH2* / *CH2-CH3

After a certain number of steps, we will obtain an alkane and an alkene from different types: CH3-CH3 + CH2=CH2

After a certain number of steps, we will obtain an alkene and hydrogen gas: CH2=CH-CH2-CH3 + H2 this is very useful since the catalyst can be recycled.

References

  1. ↑ [1]
  2. ↑ James H. Gary and Glenn E. Handwerk (2001). Petroleum Refining: Technology and Economics (4th ed.). CRC Press. ISBN 0-8247-0482-7. 
  3. ↑ James. G. Speight (2006). The Chemistry and Technology of Petroleum (4th ed.). CRC Press. ISBN 0-8493-9067-2. 
  4. ↑ Reza Sadeghbeigi (2000). Fluid Catalytic Cracking Handbook (2nd ed.). Gulf Publishing. ISBN 0-88415-289-8. 
  5. ↑ 1920 - Hydrocracking
  6. ↑ Vladimir Grigorievich Shukhov (Biography)
  7. ↑ U.S. Supreme Court Cases & Opinions, Volume 322, UNIVERSAL OIL PRODUCTS CO. V. GLOBE OIL & REFINING CO., 322 U. S. 471 (1944)

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