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Faculty of Engineering

Chemical Department

Faculty of Engineering Chemical Department Soran University ( Production of Naphthalene) Supervisor:_ mr.Ali Husain

Soran University

( Production of Naphthalene)

Supervisor:_ mr.Ali Husain Prepared by:_ Kubra Edrıs rasul

introduction

Naphthalene: is an organic compound with formula C10H8. It is the simplest polycyclic aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08 ppm by mass. As an aromatic hydrocarbon, naphthalene's structure consists of a fused pair of benzene rings. It is best known as the main ingredient of traditional mothballs.

History: In the early 1820s, two separate reports described a white solid with a pungent odor derived from the distillation of coal tar. In 1821, John Kidd cited these two disclosures and then described many of this substance's properties and the means of its production. He proposed the name naphthaline, as it had been derived from a kind of naphtha (a broad term encompassing any volatile, flammable liquid hydrocarbon mixture, including coal tar). Naphthalene's chemical formula was determined by Michael Faraday in 1826. The structure of two fused benzene rings was proposed by Emil Erlenmeyer in 1866, and confirmed by Carl Gräbe three years later.

in 1866, and confirmed by Carl Gräbe three years later. ( Naphthalene ) Physical properties :A
in 1866, and confirmed by Carl Gräbe three years later. ( Naphthalene ) Physical properties :A
in 1866, and confirmed by Carl Gräbe three years later. ( Naphthalene ) Physical properties :A
in 1866, and confirmed by Carl Gräbe three years later. ( Naphthalene ) Physical properties :A

(

Naphthalene )

Physical properties:A naphthalene molecule can be viewed as the fusion of a pair of benzene rings. (In organic chemistry, rings are fused if they share two or more atoms.) As such, naphthalene is classified as a benzenoid polycyclic aromatic hydrocarbon (PAH).

The eight carbons that are not shared by the two rings carry one hydrogen atom each. For purpose of the standard IUPAC nomenclature of derived compounds, those eight atoms are

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numbered 1 through 8 in sequence around the perimeter of the molecule, starting with a carbon adjacent to a shared one. The shared carbons are labeled 4a (between 4 and 5) and 8a (between 8 and 1).

Molecular geometry:The molecule is planar, like benzene. Unlike benzene, the carbon– carbon bonds in naphthalene are not of the same length. The bonds C1−C2, C3−C4, C5−C6 and C7−C8 are about 1.37 Å (137 pm) in length, whereas the other carbon–carbon bonds are about 1.42 Å (142 pm) long. This difference, established by X-ray diffraction, is consistent with the valence bond model in naphthalene and in particular, with the theorem of cross-conjugation. This theorem would describe naphthalene as an aromatic benzene unit bonded to a diene but not extensively conjugated to it (at least in the ground state), which is consistent with two of its three resonance structures.

is consistent with two of its three resonance structures. Because of this resonance, the molecule has

Because of this resonance, the molecule has bilateral symmetry across the plane of the shared carbon pair, as well as across the plane that bisects bonds C2-C3 and C6-C7, and across the plane of the carbon atoms. Thus there are two sets of equivalent hydrogen atoms: the alpha positions, numbered 1, 4, 5, and 8, and the beta positions, 2, 3, 6, and 7. Two isomers are then possible for mono-substituted naphthalenes, corresponding to substitution at an alpha or beta position. Bicyclo[6.2.0]decapentaene is a structural isomer

with a fused 48 ring system.

is a structural isomer with a fused 4 – 8 ring system. (Bicyclo[6.2.0]decapentaene) Electrical conductivity :Pure

(Bicyclo[6.2.0]decapentaene)

Electrical conductivity:Pure crystalline naphthalene is a moderate insulator at room temperature, with resistivity of about 1012 Ω m. The resistivity drops more than a thousandfold on melting, to about 4 × 108 Ω m. Both in the liquid and in the solid, the resistitivity depends on temperature as ρ = ρ0 exp(E/(k T)), where ρ0 (Ω m) and E (eV) are constant parameters, k is Boltzmann's constant (8.617×10−5 eV/K), and T is absolute temperature (K). The parameter E is 0.73 in the solid. However, the solid shows semiconducting character below 100 K.

Chemical properties

Reactions with electrophiles:In electrophilic aromatic substitution reactions, naphthalene reacts more readily than benzene. For example, chlorination and bromination of

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naphthalene proceeds without a catalyst to give 1-chloronaphthalene and 1- bromonaphthalene, respectively. Likewise, whereas both benzene and naphthalene can be alkylated using FriedelCrafts reactions, naphthalene can also be easily alkylated by reaction with alkenes or alcohols, using sulfuric or phosphoric acid catalysts.

or alcohols, using sulfuric or phosphoric acid catalysts. In terms of regiochemistry, electrophiles attack at the

In terms of regiochemistry, electrophiles attack at the alpha position. The selectivity for alpha over beta substitution can be rationalized in terms of the resonance structures of the intermediate: for the alpha substitution intermediate, seven resonance structures can be drawn, of which four preserve an aromatic ring. For beta substitution, the intermediate has only six resonance structures, and only two of these are aromatic. Sulfonation gives the "alpha" product naphthalene-1-sulfonic acid as the kinetic product but naphthalene-2- sulfonic acid as the thermodynamic product. The 1-isomer forms predominantly at 25 °C, and the 2-isomer at 160 °C. Sulfonation to give the 1- and 2-sulfonic acid occurs readily:

Further sulfonation give di-, tri-, and tetrasulfonic acids

Lithiation:Analogous to the synthesis of phenyllithium is the conversion of 1- bromonaphthalene to 1-lithionaphthalene, a lithium-halogen exchange:

C10H7Br + BuLi → C10H7Li + BuBr

The resulting lithionaphthalene undergoes a second lithiation, in contrast to the behavior of phenyllithium. These 1,8-dilithio derivatives are precursors to a host of peri-naphthalene derivatives.

Reduction and oxidation:With alkali metals, naphthalene forms the dark blue-green radical anion salts such as sodium naphthalenide, Na+C10H−8. The naphthalenide salts are strong reducing agents.

Naphthalene can be hydrogenated under high pressure in the presence of metal catalysts to give 1,2,3,4-tetrahydronaphthalene(C10H12), also known as tetralin. Further hydrogenation yields decahydronaphthalene or decalin (C10H18).

Oxidation with O2 in the presence of vanadium pentoxide as catalyst gives phthalic anhydride:

C10H8 + 4.5 O2 → C6H4(CO)2O + 2 CO2 + 2 H2O

This reaction is the basis of the main use of naphthalene. Oxidation can also be effected using conventional stoichiometric chromate or permanganate reagents.

Production:Most naphthalene is derived from coal tar. From the 1960s until the 1990s, significant amounts of naphthalene were also produced from heavy petroleum fractions

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during petroleum refining, but today petroleum-derived naphthalene represents only a minor component of naphthalene production.

Naphthalene is the most abundant single component of coal tar. Although the composition of coal tar varies with the coal from which it is produced, typical coal tar is about 10% naphthalene by weight. In industrial practice, distillation of coal tar yields an oil containing about 50% naphthalene, along with twelve other aromatic compounds. This oil, after being washed with aqueous sodium hydroxide to remove acidic components (chiefly various phenols), and with sulfuric acid to remove basic components, undergoes fractional distillation to isolate naphthalene. The crude naphthalene resulting from this process is about 95% naphthalene by weight. The chief impurities are the sulfur-containing aromatic compound benzothiophene (< 2%), indane (0.2%), indene (< 2%), and methylnaphthalene (< 2%). Petroleum-derived naphthalene is usually purer than that derived from coal tar. Where required, crude naphthalene can be further purified by recrystallization from any of a variety of solvents, resulting in 99% naphthalene by weight, referred to as 80 °C (melting point). Approximately 1.3M tons are produced annually.

In North America, the coal tar producers are Koppers Inc., Ruetgers Canada Inc. and Recochem Inc., and the primary petroleum producer is Monument Chemical Inc. In Western Europe the well-known producers are Koppers, Ruetgers, and Deza. In Eastern Europe, naphthalene is produced by a variety of integrated metallurgy complexes (Severstal, Evraz, Mechel, MMK) in Russia, dedicated naphthalene and phenol makers INKOR, Yenakievsky Metallurgy plant in Ukraine and ArcelorMittal Temirtau in Kazakhstan.

Other sources and occurrences:Aside from coal tar, trace amounts of naphthalene are produced by magnolias and certain species of deer, as well as the Formosan subterranean termite, possibly produced by the termite as a repellant against "ants, poisonous fungi and nematode worms. Some strains of the endophytic fungus Muscodor albus produce naphthalene among a range of volatile organic compounds, while Muscodor vitigenus produces naphthalene almost exclusively.

Naphthalene in the interstellar medium:Naphthalene has been tentatively detected in the interstellar medium in the direction of the star Cernis 52 in the constellation Perseus. More than 20% of the carbon in the universe may be associated with polyaromatic hydrocarbons, including naphthalene.

Protonated cations of naphthalene (C10H+9) are the source of part of the spectrum of the Unidentified Infrared Emissions (UIRs). Protonated naphthalene differs from neutral naphthalene (e.g. that used in mothballs) in that it has an additional hydrogen atom. The UIRs from "naphthalene cation" (C10H+9) have been observed by astronomers. This research has been publicized as "mothballs in space.

Uses

Naphthalene is used mainly as a precursor to other chemicals. The single largest use of naphthalene is the industrial production of phthalic anhydride, although more phthalic anhydride is made from o-xylene. Many azo dyes are produced from naphthalene, and so is

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the insecticide 1-naphthyl-N-methylcarbamate (carbaryl). Other useful agrichemicals include naphthoxyacetic acids.

Other useful agrichemicals include naphthoxyacetic acids. ( Nadoxolol is a beta blocker) Naphthalenesulfonic acids and

(Nadoxolol is a beta blocker)

Naphthalenesulfonic acids and sulfonates

Many naphthalenesulfonic acids and sulfonates are useful. Alkyl naphthalene sulfonate are surfactants, The aminonaphthalenesulfonic acids, naphthalenes substituted with amines and sulfonic acids, are intermediates in the preparation of many synthetic dyes. The hydrogenated naphthalenes tetrahydronaphthalene (tetralin) and decahydronaphthalene (decalin) are used as low-volatility solvents. Naphthalene sulfonic acids are also used in the synthesis of 1-naphthol and 2-naphthol, precursors for various dyestuffs, pigments, rubber processing chemicals and other chemicals and pharmaceuticals.

Naphthalene sulfonic acids are used in the manufacture of naphthalene sulfonate polymer plasticizers (dispersants), which are used to produce concrete and plasterboard (wallboard or drywall). They are also used as dispersants in synthetic and natural rubbers, and as tanning agents (syntans) in leather industries, agricultural formulations (dispersants for pesticides), dyes and as a dispersant in leadacid battery plates.

Naphthalene sulfonate polymers are produced by treating naphthalenesulfonic acid with formaldehyde, followed by neutralization with sodium hydroxide or calcium hydroxide. These products are commercially sold as superplasticizers for the production of high strength concrete.

Laboratory uses:Molten naphthalene provides an excellent solubilizing medium for poorly soluble aromatic compounds. In many cases it is more efficient than other high-boiling solvents, such as dichlorobenzene, benzonitrile, nitrobenzene and durene. The reaction of C60 with anthracene is conveniently conducted in refluxing naphthalene to give the 1:1 DielsAlder adduct. The aromatization of hydroporphyrins has been achieved using a solution of DDQ in naphthalene.

Wetting agent and surfactant:Alkyl naphthalene sulfonates (ANS) are used in many industrial applications as nondetergent wetting agents that effectively disperse colloidal systems in aqueous media. The major commercial applications are in the agricultural chemical industry, which uses ANS for wettable powder and wettable granular (dry- flowable) formulations, and the textile and fabric industry, which utilizes the wetting and defoaming properties of ANS for bleaching and dyeing operations.

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As a fumigant:Naphthalene has been used as a household fumigant. It was once the primary ingredient in mothballs, although its use has largely been replaced in favor of alternatives such as 1,4-dichlorobenzene. In a sealed container containing naphthalene pellets, naphthalene vapors build up to levels toxic to both the adult and larval forms of many moths that attack textiles. Other fumigant uses of naphthalene include use in soil as a fumigant pesticide, in attic spaces to repel animals and insects, and in museum storage- drawers and cupboards to protect the contents from attack by insect pests.

Other uses

It is used in pyrotechnic special effects such as the generation of black smoke and simulated explosions.]It is used to create artificial pores in the manufacture of high-porosity grinding wheels. In the past, naphthalene was administered orally to kill parasitic worms in livestock. Naphthalene and its alkyl homologs are the major constituents of creosote. Naphthalene is used in engineering to study heat transfer using mass sublimation.

Naphthalene Toxicology:

High Risk Populations

There are genetic and developmental factors that can increase an individual’s susceptibility to the effects of naphthalene. Under normal circumstances, there are multiple mechanisms within the RBC to prevent toxicity from oxidative stress. The most important protective effect is via the generation of reduced nicotine adenine dinucleotide phosphate (NADPH) from the hexose monophosphate shunt. The NADPH is used to maintain adequate stores of reduced glutathione to prevent hemolysis from oxidative stress.

Individuals who have glucose-6-phosphate deficiency (G6PD) do not produce as much NADPH. Such individuals have lower levels of glutathione and are subsequently at much higher risk of hemolysis and methemoglobinemia after exposure to naphthalene . As the gene coding for G6PD is X-linked, males are more commonly affected than females. The prevalence of G6PD is highest among individuals of African, Asian, Mediterranean, and Middle Eastern descent .In a retrospective review of 24 African-American children with G6PD who were hospitalized with acute hemolytic anemia, 14 were reported to have had exposure to naphthalene-containing mothballs . It is of interest that this case series observed that naphthalene mothballs had frequently been used in these environments for the fresh scent, and not for repellent purposes in a manner consistent with their labeling instructions.

Neonates are more susceptible to the effects of oxidative stress from naphthalene, as they have thinner skin and decreased stores of reduced glutathione . There is also evidence that naphthalene and its metabolites are capable of crossing the placenta resulting in perinatal toxicity. A case report described an African American female with methemoglobinemia and hemolytic anemia of unknown origin who gave birth to an infant with fetal distress and cyanosis . Methemoglobinemia and hemolysis was observed in the newborn, who recovered after exchange transfusion. In this incident, an entire box of moth flakes containing naphthalene had been spilled into a heating vent at home during the week prior to delivery.

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In utero exposure to naphthalene is also of relevance given reports of maternal pica and chronic ingestion of mothballs during pregnancy

Health effects

Exposure to large amounts of naphthalene may damage or destroy red blood cells, most commonly in people with the inherited condition known as glucose-6-phosphate dehydrogenase (G6PD) deficiency, which over 400 million people suffer from. Humans, in particular children, have developed the condition known as hemolytic anemia, after ingesting mothballs or deodorant blocks containing naphthalene. Symptoms include fatigue, lack of appetite, restlessness, and pale skin. Exposure to large amounts of naphthalene may cause confusion, nausea, vomiting, diarrhea, blood in the urine, and jaundice (yellow coloration of the skin due to dysfunction of the liver).The US National Toxicology Program (NTP) held an experiment where male and female rats and mice were exposed to naphthalene vapors on weekdays for two years. Both male and female rats exhibited evidence of carcinogenesis with increased incidences of adenoma and neuroblastoma of the nose. Female mice exhibited some evidence of carcinogenesis based on increased incidences of alveolar and bronchiolar adenomas of the lung, while male mice exhibited no evidence of carcinogenesis.

The International Agency for Research on Cancer (IARC) classifies naphthalene as possibly carcinogenic to humans and animals (Group 2B). The IARC also points out that acute exposure causes cataracts in humans, rats, rabbits, and mice; and that hemolytic anemia (described above) can occur in children and infants after oral or inhalation exposure or after maternal exposure during pregnancy. Under California's Proposition 65, naphthalene is listed as "known to the State to cause cancer".A probable mechanism for the carcinogenic effects of mothballs and some types of air fresheners containing naphthalene has been identified.

Regulation:US government agencies have set occupational exposure limits to naphthalene exposure. The Occupational Safety and Health Administration has set a permissible exposure limit at 10 ppm (50 mg/m3) over an eight-hour time-weighted average. The National Institute for Occupational Safety and Health has set a recommended exposure limit at 10 ppm (50 mg/m3) over an eight-hour time-weighted average, as well as a short-term exposure limit at 15 ppm (75 mg/m3).

Mothballs and other products containing naphthalene have been banned within the EU since 2008.

In China, the use of naphthalene in mothballs is forbidden. Danger to human health and the common use of natural camphor are cited as reasons for the ban.

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Naphthalene derivatives

Naphthalene derivatives Heating or Cooling naphthalene Melting Point :Melting Point is the temperature at which the

Melting Point:Melting Point is the temperature at which the solid and liquid forms of a pure substance can exist in equilibrium.

Freezing Point :Freezing Point Freezing Point is the temperature at which a liquid becomes a solid.

Point is the temperature at which a liquid becomes a solid. Boiling Point : Boiling Point

Boiling Point :Boiling Point is the temperature at which the pressure exerted by the surroundings upon a liquid is equalled by the pressure exerted by the vapour of the liquid. Under this condition, addition of heat results in the transformation of the liquid into its vapour without raising the temperature.

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The Graph of the Heating Process

The Graph of the Heating Process (The graph above shows the heating curve of naphthalene) A

(The graph above shows the heating curve of naphthalene) A:Naphthalene is in solid state at any temperature below its melting point. The particles are very closely packed together in an orderly manner. The forces between the particles are very strong. The particles can only vibrate at a fixed position.

A-B:As the naphthalene is heated, heat energy is converted to kinetic energy. Kinetic energy increases and the molecules vibrate faster about their fixed positions and the temperature increases.

B:Naphthalene is in solid state at any temperature below its melting point. The particles are very closely packed together in an orderly manner. The forces between the particles are very strong. The particles can only vibrate at a fixed position.

B-C:Naphthalene exists in both solid and liquid states. The temperature remains constant because the heat that supplied to naphthalene is used to overcome the forces of attraction that hold the particles together. The constant temperature is called the melting point. The heat energy that absorbed to overcome the intermolecular forces is named as the latent heat of fusion.

C:All the naphthalene has completely melted. Solid naphthalene has turned into liquid.

C-D:Naphthalene is in liquid state. As the liquid naphthalene is heated, the molecules gain more heat energy and the temperature continues to increase. The particles move faster and faster because their kinetic energy is increasing.

D:Naphthalene still exists in liquid state. Naphthalene molecules have received enough energy to overcome the forces of attraction between the particles in the liquid.

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Some of the naphthalene molecules start to move freely and liquid naphthalene begin to change into gashave received enough energy to overcome the forces of attraction between the particles in the liquid. Some of the naphthalene molecules start to move freely and liquid naphthalene begin to change into gas

D-E:Naphthalene exists in both liquid and gaseous states. The temperature remains unchanged. The is because the heat energy absorbed is used to overcome the intermolecular forces between the particles of the liquid rather than increase the temperature of the liquid. This constant temperature is the boiling point.

E:All the naphthalene has turn into gas.

E-F:The gas particles continue to absorb more energy and move faster. The temperature increases as heating continues.

The Graph of the Cooling Process

as heating continues. The Graph of the Cooling Process P: The substance exists in gaseous state.

P:The substance exists in gaseous state. The particles have very high energy and are moving randomly. The intermolecular forces between the particles are very weak and can be ignored.

P-Q:The substance is in gaseous state. The particles lose kinetic energy during cooling, the particles getting closer to each other and the temperature drops.

Q:The substance still exists as a gas. As the molecules are close enough, stronger forces of attraction result in forming of intermolecular bonds. The gas begins to condense and become liquid.

Q-R:The process of condensation going on. Stronger bonds form as gas changes into liquid.

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The substance exists in both gaseous and liquid states. The temperature remains unchanged. This is because the energy produced during the formation of bonds is equal to the heat energy released to the surroundings during cooling. This constant temperature is the boiling point. The heat energy that releases during this condensation process is called the latent heat of vaporization.

R:The substance exists only in liquid state as all the gas particles have condensed into liquid.

R-S:The substance exists as a liquid. As the temperature falls, the naphthalene molecules lose heat energy. Their movement shows down and they move closer to each other.

S:The substance still in liquid state. The particles have very little energy and begin to move closer towards one another as it starts to freeze into solid.

S-T:The liquid is changing into solid form. Molecules rearrange to form the molecular arrangement of a solid. The substance exists as both liquid and solid. The temperature remains constant until all the liquid changes to solid. This is because the energy released is the same as the energy lost to the surroundings during cooling. This constant temperature is the freezing point. The heat energy that releases during this freezing process is called the latent heat of fusion.

T:All the liquid freezes into solid. The particles are now closely packed in an orderly manner.

T-U:Once all the liquid has become solid, the temperature falls once again until it reaches room temperature. The substance is in the solid state here.

U :The substance reaches room temperature and remain at this temperature as long as the room temperature remain the same

Supercooling

may b some of u still blu abt supercooling

the most easier to show u s/cooling is ice

u put some

water into the freezer, after 20min, it seems oredi freeze, but if press it with yo finger, the upper

layer of ice will break, inside still remain water

this is what we call supercooling.

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supercooling occur bcos the cooling temperature is not uniform. to avoid this , the boiling

supercooling occur bcos the cooling temperature is not uniform. to avoid this , the boiling tube which is placed in the conical flask must continuously stirredthroughout the cooling

process.

Production methods

Naphthalene is produced by the following processes:

1- Recovery from coal tar

2- From

petroleum

Naphthalene in petroleum

Naphthalene is present, in varying amounts, in all petroleum-derived pyrolysis

products which have been exposed to a temperature of over 500°C or to catalytic processes under relatively severe conditions.

It can thus be found in the appropriate distillation fractions of the liquid products of

- steam cracking for the production of ethylene,

- in by-products of crude oil cracking

- and in residues of catalytic gasoline reforming

- as well as catalytic cracking of gas oils.

- The extraction of kerosene fractions provides a further source of naphthalene, after the separation of aliphatics.

This project presents a detailed design of naphthalene distillation column with its overhead condenser. Process design requires thermo physical property data, most of which are generated using contribution methods.

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(block digram for Naphthalene in petroleum) PROCESS FOR PRODUCING NAPHTHALENE This invention relates to the

(block digram for Naphthalene in petroleum)

PROCESS FOR PRODUCING NAPHTHALENE

This invention relates to the preparation of naphthalene from hydrocarbon stocks and more particularly to the dealkylation of hydrocarbon stocks which comprise alkyl naphthalenes for the purpose of conversion to naphtha lene. Petroleum fractions which boil within the range of 400-550 F. generally contain substantial amounts of alkyl naphthalenes, such as mono-, di-, and trimethyl naphthalenes and in smaller quantity, the ethyl naphtha lenes. Recycle fractions, which are formed in the crack ing of petroleum stocks and which include this boiling range, often contain major proportions of aromatic hy drocarbons that are mainly alklyl naphthalenes. Such fractions typically may have aromatic contents varying within the

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range of 25-97% but usually contain between 50% and 95% aromatics depending upon the particular operation in which the petroleum fractions are produced. These hydrocarbon charge stocks are obtained in both catalytic and thermal cracking processes and in opera tions in which combinations of catalytic and thermal cracking steps are utilized. Stocks having high alkyl naphthalene contents can also be obtained by extracting straight run petroleum fractions of appropriate boiling ranges, such as kerosene, or catalytic fractions such as catalytic gas oil, with solvents, such as furfural or sulfur dioxide, or by selective adsorption with silica gel. These aromatic concentrates may contain up to 100% aromatic hydrocarbons. The present invention is directed to the preparation of naphthalene from aromatic hydrocarbon charge stocks which comprise a mixture of alkyl naphthalenes and which can be derived from such sources as referred to above. The charge stock generally boils within the range of 400 550 F. but more preferably in the range of 440-515 F. and preferably is composed mainly of alkyl naphtha lenes in which the alkyl groups appear at both the alpha and beta positions on the naphthalene nucleus. It has been proposed heretofore to prepare naphtha lene by subjecting aromatic hydrocarbon stocks contain ing alkyl naphthalenes to high temperature dealkylation in the presence of hydrogen. As a general rule, the de alkylation conditions employed can effect only a partial dealkylation in one pass of the alkyl naphthalenes through the reactor. In order to increase the yield of naphthalene, it is desirable to fractionate the reaction product to obtain the desired naphthalene product and also to recover another fraction comprising unconverted and only partially converted alkyl naphthalenes. The re covered alkyl naphthalenes can be recycled to the de alkylator to effect further conversion. It has now been found that when the alkyl naphtha lenes, which are separately recovered from the dealkyl ator reaction product, are recycled for further reaction along with additional charge stock, the overall rate of dealkylation is substantially reduced. This is for the reason that under the dealkylation conditions employed, which generally include a temperature in the range of 1100-1500 F. and more usually 1200-1400° F., the alkyi substituents which are in the alpha position are re moved from the naphthalene nucleus at a rate which is roughly about twice as fast as the rate of removal of beta substituents. Hence the alkyl naphthalenes that are recovered after the reaction are considerably enriched

with respect to components having beta substituents; and this material when recycled is substantially more refrac tory than the original charge stock. The present invention provides an improved process for producing naphthalene in which a substantially in creased overall rate of dealkylation of alkyl naphthalenes is attained. According to the invention, the alkyl naph thalenes recovered from the dealkylation product are sub jected to an isomerization operation in which the condi tions are effective to shift the position of alkyl groups on the naphthalene nucleus. The isomerization results in an alkyl naphthalene product having an increased ratio of alpha to beta substituents. This isomerization product is recycled to the dealkylation step, with the result that a higher conversion per pass of the alkyl naphthalenes to naphthalene is achieved. The invention is described more specifically with ref erence to the accompanying drawing which is a schematic flowsheet illustrating a preferred processing operation for producing naphthalene from a hydrocarbon stock con taining alkyl naphthalenes. The process as illustrated in the drawing involves a preliminary catalytic

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hydrocracking-desulfurization step adapted to condition the alkyl naphthalene charge mate rial prior to a thermal dealkylation step for producing the naphthalene. The charge, which enters the system through line 10, is a gas oil fraction boiling in the range of 400-550 F. and containing alkyl naphthalenes, and preferably is a catalytic gas oil aromatic extract boiling in the range of 440-515 F. and containing a major proportion of dicyclic aromatics together with a minor proportion of aromatics having only one aromatic ring and only a small amount or no saturated hydrocarbons. For example, a preferred charge may contain 60% di cyclic aromatics, 35% monocyclic aromatics and 5% Saturates. The heated charge together with hydrogen from line 11 passes through line 12 to a catalytic hydrocracker 13 which preferably contains a desulfurization catalyst such as cobalt molybdate on alumina or molybdenum desulfide on alumina. The conditions for conducting this catalytic conditioning step include a temperature within the range of 800-980 F., a pressure of 150-1000 p.s.i.g., with a range of 200-500 p.s.i.g. preferred, a hydrogen to hydro carbon mole ratio of 3:1 to 25:1 and preferably 5:1 to 15:1, and a liquid hourly space velocity of 0.5 to 10 (vol umes of charge per hour per bulk volume of catalyst). The hydrogen consumption under these conditions should be between 65-500 s.c.f. per barrel of liquid feed per per cent sulfur in the feed and preferably between 200 and 400 s.c.f. per barrel. This conditioning step effects cracking of most of the saturates and some of the monocyclic aro matics and also converts most of the sulfur in the hydro carbon stock to hydrogen sulfide. From hydrocracker 13 the reaction product preferably is sent through line 14 to fractionator 15 from which normally gaseous components are removed overhead through line 7 and a C-400 F. gasoline fraction is ob tained from line 18. The 400--° F. fraction which con tains the alkyl naphthalenes is removed via line 16 and sent to thermal dealkylator 21. Alternatively all of the reaction product from hydrocracker 13 can be sent to the dealkylator as indicated by dashed line 27. The 400-- F. fraction from line 16 is admixed with a recycle fraction from line 33, as hereinafter specified, and the mixture passes through line 20 together with hy drogen introduced via line 19 into dealkylator 21. In the preferred embodiment the dealkylation is effected ther mally without a catalyst. The conditions for this opera tion include a pressure of 150-1000 p.s.i.g., preferably 200-800 p.s.i.g., a hydrogen to hydrocarbon mole ratio within the range of 3:1 to 25:1 and preferably 5:1 to 3 15:1, a residence time of 2-300 seconds with a preferred residence time of 10-60 seconds, and a temperature above 1000 F., preferably within the range of 1200-1400 F., sufficient to effect dealkylation of alkyl naphthalenes. In this reaction, as previously stated, only a partial dealkyla tion occurs and the alkyl groups which are in the alpha position on the naphthalene nucleus are removed at about twice the rate as those in the beta position. Hence the reaction product which leaves the reactor through line 22 contains, in addition to the desired naphthalene, unreacted naphthalenes and partially dealkylated naphthalenes, and the alkyl naphthalene portion of the mixture is enriched with respect to beta alkyl groups as compared with the charge material fed to dealkylator 21. The reaction product from line 22 passes to fraction ator 23 from which gases and a C5-400° F. aromatic gaso line cut are removed, respectively, from lines 26 and 25. The desired naphthalene product is taken from line 24 as material boiling in the 400-450 F. range. Typically this fraction is composed predominantly of naphthalene and has a freezing point of 78.6 C. and a sulfur content of the order of 0.06%. The 450-- F. material withdrawn from fractionator 23 via line 28 is composed mainly of monomethyl and

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di methyl naphthalenes with the alkyl groups in the beta position predominating. This

stream also contains a small amount of material boiling above dimethylnaphtha lenes which desirably should be removed. Hence the stream is passed through line 28 to fractionator 29

from which the mono- and dialkyl naphthalenes are obtained overhead through line 30 and the higher boiling material is removed as bottoms via line 32. In order to increase the yield

of naphthalene from the process, the unconverted alkyl naphthalenes should be

continuously recycled to the dealkylation zone. How ever, direct recycling will result in a relatively low over all rate of conversion in the dealkylator due to the high beta alkyl content

of this material. Accordingly, the present invention provides a means of increasing the over

all rate of the dealkylation reaction by first subjecting the alkyl naphthalenes to catalyic isomerizaion in zone 31. This effects a shift of a substantial portion of the alkyl groups to the alpha position. For example, (3-methyl naphthalene is partly converted to o- methylnaphthalene. Likewise, 2,3-dimethylnaphtlalene is partly converted to 1,3- and 1,4-

dimethylnaphthalene, and 2,6-dimethyl and 2,7-dimethylnaphthalenes are partly converted

to alpha methyl naphthalenes such as the 1,5-, 1,6-, 1,7- and 1,8- isomers. It should be

noted, however, that the isomeriza tion does not effect any shift of an alkyl group from one

of the aryl rings to the other in the same molecule, al though some amount of

disproportionation between sepa rate molecules may occur. One manner of effecting the isomerization in zone 31 is to contact the alkyl naphthalenes with any solid acidic cracking catalyst Such as silica-alumina, silica-magnesia, silica-zirconia and acid activated clays. The reaction temperature should be in the range of 300-500 C. and more preferably 350-400° C. The liquid space velocity can vary between 0.1 and 20 volume hydrocarbon per volume catalyst per hour and more preferably is main tained in the range of 0.5-6.0. It is desirable to conduct the isomerization at a low hydrocarbon partial pressure and generally in the range

of 0.05-0.5 atmosphere, as otherwise coking tends to occur rapidly with resultant de

activation of the catalyst. The low partial pressure can be maintained either by holding a

vacuum in isomeriza tion zone 31 or by introducing an inert diluent along with hydrocarbons, for example, nitrogen, hydrogen, methane, propane, butanes, and the like. Whenever the activity of the catalyst has dropped enough to require regeneration, this can be done in conventional manner merely by blow ing air through the hot catalyst to burn off the coke de posits. Thereafter the catalyst can be re-used for further isomerization.

By way of example as to the effectiveness of the above described isomerization procedure

in producing alpha substituted naphthalenes, when 2,3-dimethylnaphthalene was reacted

over a silica-alumina cracking catalyst at a temperature of 375 C., a liquid hourly space velocity of about 0.3 and using heptane as diluent so that the partial pressure of the dimethylnaphthalene was 0.046 atmos phere, the isomerization product had the following com position: Mole percent 1,3-dimethylnaphthalene ------------ 43 1,4-dimethylnaphthalene ----- 34 2,3-dimethylnaphthalene----------- 20 1,2-dimethylnaphthalene -------- Negligible Methylnaphthalenes------------- 3 These data show that at least 77% of the 2,3-isomer was converted to products having an alpha substituent. The isomerization in Zone 31 can also be effected at low temperature using HF--BF3 as catalyst. In practicing the isomerization in this manner, the alkyl naphthalenes from line 30 are first dissolved in a suitable solvent, such as benzene or heptane, and the mixture is contacted with the catalyst at a temperature

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preferably in the range of 0-30 C. and generally for several hours. Only a small amount of BF need be used and the HF can be present in a large molar excess over the BF3 to provide sufficient catalyst volume for good contact. After the isomeriza tion the solvent can be removed by distillation (not shown) and the isomerized product can be recycled through line 33 to dealkylator 21. Generally, some amount of tarry material may be formed during this type of isomerizing operation and it also can be removed by distillation prior to recycling the isomerizate. By way of example, when a 10 weight percent solution of 2,3- dimethylnaphthalene in benzene was contacted at 27 C. for 4 hours with BF in HF solution, about 95% of the dimethylnaphthalene product was the 1,3-isomer. When 2,7- dimethylnaphthalene was contacted similarly for 20 hours, about 20% of the product was the 1,7- isomer. The above-described process can be modified by carry ing out the dealkylation reaction in Zone 21 catalytically employing a desulfurization catalyst such as is used in the hydrocracker 3. The presence of the catalyst in the latter step facilitates the dealkylation reaction and in Some cases permits. it to be carried out at a lower tem perature than that required for thermal dealkylation. The catalyst also effects the conversion of any remaining sul fur into hydrogen sulfide and hence permits the prepara tion of naphthalene having negligible sulfur content. The conditions for the catalytic dealkylation step include a pressure of 150-1000 p.s.i.g. with a range of 200-500 p.s.i.g. preferred, a hydrogen to hydrocarbon mole ratio of 5:1 to 25:1, a liquid hourly space velocity of 0.2-5.0, and a temperature above 1000 F., usually between 1100 F. and 1200° F., sufficient to dealkylate the alkyl naphthalenes and convert any remaining sulfur mainly in to hydrogen sulfide. In both the hydrocracker and dealkylator of each of the foregoing embodiments, coking occurs after a time to such extent that coke removal from the reaction zone is required. This can be done in conventional manner by passing an oxygen-containing gas through the reaction zone to burn out the coke. In the steps in which a desul furizing catalyst is used, burning of coke from the cata lyst restores its catalytic activity. We claim: 1. Process for producing naphthalene from an aroma tic hydrocarbon charge stock comprising a mixture of alkyl naphthalenes which comprises subjecting said charge stock in the presence of hydrogen to a temperature in the range of 1000-1500 F., whereby partial dealkylation of alkyl naphthalenes occurs and alkyl groups in the alpha position are removed at a rate faster than alkyl groups in the beta position; distilling the reaction product to obtain a naphthalene fraction and an alkyl naphthalene fraction; subjecting said alkyl naphthalene fraction to isomerizing conditions effective to shift the position of alkyl groups on the naphthalene nucleus, whereby an alkyl naphthalene product having an increased content of alpha alkyl naph thalenes is obtained; and recycling said alkyl naphthalene product to the partial dealkylation step. 2. Process according to claim 1 wherein said partial dealkylation is effected thermally without a catalyst at a temperature of 1200-1400 F., pressure of 200-800 p.s.i.g., hydrogen to hydrocarbon mole ratio of 3:1 to 25:1, and a residence time of 2-300 seconds. 3. Process according to claim 2 wherein said charge stock is an aromatic extract separated from catalytic gas oil. 4. Process according to claim 3 wherein said charge stock boils within the range of 400-550 F. 5. Process according to claim 1 wherein said isomeriz ing conditions include contacting said alkylnaphthalene fraction with a solid acidic catalyst in the presence of an inert diluent at a temperature of 300-500 C., hydro carbon partial pressure of 0.05-0.5 atmosphere, and a liquid hourly space velocity of 0.1-20. 6. Process

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according to claim 2 wherein said isomeriz ing conditions include contacting said alkylnaphthalene fraction with a solid acidic catalyst in the presence of an inert diluent at a temperature of 300-500 C., hydro carbon partial pressure of 0.05-0.5 atmosphere, and a liquid hourly space velocity of 0.1-20.

atmosphere, and a liquid hourly space velocity of 0.1-20. References 1. ^ Nomenclature of Organic Chemistry

References

1. ^ Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 13, 35, 204, 207, 221222, 302, 457, 461, 469, 601, 650. doi:10.1039/9781849733069-FP001. ISBN 978-0-

2. ^ a b c "Ambient Water Quality Criteria for Naphthalene" (PDF). United States Environmental Protection Agency. Retrieved 2014-06-21.

4. ^ a b c Anatolievich, Kiper Ruslan. "naphthalene". chemister.ru. Retrieved 2014-06-21.

5. ^ a b c d e f Seidell, Atherton; Linke, William F. (1919). Solubility of Inorganic and Organic Compounds (2nd ed.). New York: D. Van Nostrand Company. pp. 443446.

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