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NAPHTHA HYDROTREATING
Naphtha
Naphtha is a complex mixture of liquid hydrocarbons, with boiling ranges of about 38 to 205 C and with vapour pressures of about 0.69 bar. Crude distillation, catalytic cracking, delayed coking and visbreaking units produce naphtha with low octane number and contains deferent types of contaminants at the same time .
NAPHTHA HYDROTREATING
As more demand for high Gasoline Octane no. to match with modern motor. Chemical structure modification is achieved on an expensive Platinum catalyst at Catalytic reforming and Isomerization unit. Sulfur, Nitrogen, Oxygen and other impurities in Naphtha work as a poisonous for Pt catalyst activity. Hydrotreating is used to prepare a clean feedstock to protect catalyst used in naphtha reforming.
NAPHTHA HYDROTREATING
1897 : Paul Sabatier, French chemist discovered the fixation of hydrogen on hydrocarbon (ethylene, benzene) double bonds using nickel containing catalyst. 1903 : Wilhelm Normann, German chemist applied catalytic hydrogenation to Saturate Organic acids. 1950's : First catalytic reforming process was commercialized. At the same time, the catalytic hydrodesulfurization of the naphtha feed to such reformers was also commercialized. Currently : All petroleum refineries world-wide have one or more HDS units.
NAPHTHA HYDROTREATING
Straight Run Naphtha Catalytic cracking Naphtha. Delayed Coking Naphtha. Visbreaking Naphtha. FCC Naphtha
Naphtha Hydrotreating
NAPHTHA HYDROTREATING
Using expensive Platinium catalyst on chlorinated alumina. Dehydrogenation of Nahthenes , Dehydrocyclization & Isomerization of Paraffins.
NAPHTHA HYDROTREATING
NAPHTHA HYDROTREATING
Impurities Removal
Sulfur Removal Nitrogen Removal Oxygen Removal Metallic Compounds Unsaturated Products Halide Removal
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Sulfur Removal
NAPHTHA HYDROTREATING
Sulfur Removal
Thiophenes:
Benzothiophenes: Dibenzothiophenes
NAPHTHA HYDROTREATING
Sulfur Removal
Distribution of sulfur compounds in the cuts from distillation of a crude with 1.2%wt sulfur.
NAPHTHA HYDROTREATING
Nitrogen Removal
Pyridines:
Quinoline:
Isoquinolines:
Pyrroles:
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Nitrogen Removal
Indoles:
Carbazoles:
Methylamine:
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Oxygen Removal
Phenols:
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Oxygen Removal
Naphthenic acids:
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Metallic Compounds
Impurities Ni,V As Hg NaCl Fe Si Pb Source
Crude Crude Crude Crude
Main Cut
Distillates Residues All Naphtha Residues
Catalyst Poison
Strong, deposit inside catalyst and plugging Strong, deposit at top of reactor Slight, only slightly retained Strong, deposit at top of reactor, generates pressure loss Slight, deposit at top of reactor, generates pressure loss Very slight, deposit inside catalyst and plugging Strong, deposit at top of bed
All
Distillates Gasoline
0.1-0.5 5-10
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Unsaturated Products
Linear olefin:
Cyclic olefin:
Aromatics Saturation: the-main unsaturated compounds present in oil, The number of aromatic rings increases with the distillation temperature of the cut.
NAPHTHA HYDROTREATING
Halide Removal
Organic halides can be decomposed in the Naphtha Hydrotreating Unit to the corresponding hydrogen halide, which is either absorbed in the reactor effluent water wash or taken overhead in the stripper gas.
NAPHTHA HYDROTREATING
NAPHTHA HYDROTREATING
Hydrotreating Processes
The Naphtha Hydrotreating Process is : Catalytic refining process employing a selected catalyst and a hydrogen-rich gas stream Decompose organic sulfur, oxygen and nitrogen compounds contained in hydrocarbon fractions. In addition, hydrotreating removes Organometallic compounds and saturates olefinic compounds.
NAPHTHA HYDROTREATING
FCC Naphtha
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Hydrotreating Process
Product Condenser 02E-02 Feed Surge Drum 02V-01 Charge Heater 02H-01 T=301 oC Reactor 02-R-01 P=45.5 barg T=325 oC T=55 oC 02-K-01 T=50 oC P=10.4barg Separator 02V-02 HCK DCU CDU T=154 oC Stripper 02T-01 HP Steam Condensat e Recycle Gas Sour water to U15 T=120 oC R.C.Suction Drum 02-V-03 Stripper Condenser 02-E-05 Sour Gas To U-12 T=99 oC P=7.1 barg T=48 oC Stripper Receiver 02V-04
T=343 oC Tank-0809
T=201 oC
T=159 oC
T=148 oC Naphtha splitter feedBottom Exchange 03-E01 Hydrotreated Heavy Naphtha P=10.3 barg T=124 oC
51-TK-9
Penex Feed
NAPHTHA HYDROTREATING
Hydrotreating Process
1.
NAPHTHA HYDROTREATING
Hydrotreating Process
2.
Maintain catalyst in its active form. Limited Applications due to its complicated design.
NAPHTHA HYDROTREATING
Low operating cost and investment requirement. Ease of operation. Limited Mercaptan treating not less than 5ppm.
NAPHTHA HYDROTREATING
Meeting finished product specifications Kerosene hydrotreating: a) Reduces mercaptans, sulfur, aromatics, b) Improves smoke point. Gas oil hydrotreating: a) Reduces sulfur, nitrogen, aromatics, olefins, b) Improves cetane number, thermal stability. Lube oil hydrofinishing: a) Reduces sulfur, Conradson carbon (CCR), b) Improves colour, oxidation stability.
NAPHTHA HYDROTREATING
Preparing the feed for other refinery processes. Naphtha hydrotreating : is a pre-treatment for isomerization and catalytic reforming processes. The objective is to reduce sulfur, nitrogen (<0.5 ppm wt), and olefins (< 0.1% wt). Vacuum distillates: such as straight run, visbreaking, coking and deasphalted oil are hydrotreated as pre-treatment for FCC and hydrocrackers. Improves hydrogen content, crack ability, results increased conversion, reduced impurities in products, lower SOx and NOx emissions in gases exiting the regenerator.
NAPHTHA HYDROTREATING
Hydrotreating Process
NAPHTHA HYDROTREATING
Hydrotreating Process
Petroleum Cut Naphtha Kerosene Gas Oil Vacuum Gas Oil Atmospheric residue Vacuum residue
NAPHTHA HYDROTREATING
Hydrotreating Process
200 54 23
Naphtha
Residuals
VGO
Distillate
NAPHTHA HYDROTREATING
Hydrotreating Process
Egypt has eight petroleum refining companies distributed around the country. In Cairo, Alexandria, Suez, Asyut and Tanta. Six of eight companies have constructed a naphtha hydrotreating unit.
Barrel/Day 35000 30000 25000 20000 15000 10000 5000 0 Midor Alexandria Suez Ameria Cairo Asyut
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Process Variables
Temperature Reactor Pressure Hydrogen to Hydrocarbon Ratio Space Velocity
NAPHTHA HYDROTREATING
Temperature
The treating severity increases directly with temperature to decrease the content of sulfur, nitrogen, oxygen, and metallic compounds in the treated product. Factors affect selecting treating temperature: Feed Quality Changes. Changes in Feed Rate. Catalyst End-Of-Run. Maximum temperature catalyst can withstand , after this temprature , it will not give the required product quality .
a) b) c)
NAPHTHA HYDROTREATING
Temperature
When operating at too high temperature for maximum sulfur removal. Recombination of hydrogen sulfide with small amounts of olefins can result, producing mercaptans in the product
NAPHTHA HYDROTREATING
Reactor Pressure
1)
As the partial pressure of hydrogen increases: Rate of hydrogenation increases, the treating reactions are brought to a greater degree of completion. Catalyst is generally effective for a longer time owing to less formation of carbonaceous deposits which deactivate the catalyst activity.
2)
NAPHTHA HYDROTREATING
Increasing the hydrogen charge rate: Increases the rates of hydrogenation reactions. Reduce the tendency of coke formation on the catalyst. Calculation:
Recycle Gas to Reactor (Nm3 /h) x H 2 Purity (Mole Fraction) H 2 /HC Naphtha Feed (m3 /h)
NAPHTHA HYDROTREATING
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Space Velocity
The severity of the operation is determined by the relative volumes of fresh feed and catalyst. Operating with low S.V. means low capacity of the unit, which has bad effect on flow distribution of feed in the catalyst bed with the result of higher rate of cake formation High S.V. will require increased temperature for the same reaction severity with the result of high coke formation. Calculation: volume of charge per hour (m 3 /h) S.V. volume of catalyst (m 3 )
NAPHTHA HYDROTREATING
Reactions Kinetics
NAPHTHA HYDROTREATING
Reactions Kinetics
1)
2)
Substitution
NAPHTHA HYDROTREATING
Reactions Kinetics
1)
2)
Denitrogenation of Quinoline
NAPHTHA HYDROTREATING
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The primary causes of catalyst deactivation are: Rate of carbon deposition on the catalyst. The gradual accumulation of inorganic species picked up from the charge stock, ex: arsenic, lead, calcium, sodium, silicon and phosphorus
NAPHTHA HYDROTREATING
Reactions:
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