Hydroprocessing

Dr. George Georgiadis

Hydroprocessing: Hydrocracking and Hydrotreating

The terms hydrotreating, hydroprocessing, hydrocracking, and hydrodesulfurization are used rather loosely in the industry because, they all occur simultaneously and it is relative as to which predominates.

Sources of Hydrogen in Refineries Hydrogen became available with the advent of platinum catalyst reforming. In the modern refinery hydrogen is scarce and its use is expected to increase. Hydrogen is used to produce higher yields and upgrade the quality of fuels produced by the refinery in several ways.

Catalytic Reformer

This is most important source of hydrogen for the refiner. Typically (avg.) 90 vol% from a continuously regenerated reformer and (avg.) 80 vol% from semi regenerated reformer.

FCCU Off Gas

Typically 5 vol% hydrogen with methane, ethane and propane. Several methods for recovery; can be combined
(a) Cryogenic (b) Pressure swing adsorption or (c) Membrane separation

Steam methane Reforming

Most common method of manufacturing hydrogen Uses methane, ethane, or heavy components reformed to hydrogen, carbon dioxide, and water in a series of three reactions: Methane catalytically reacts to form hydrogen and carbon monoxide in an exothermic reaction Carbon monoxide shifted with steam to form additional hydrogen and carbon dioxide in an endothermic reaction Carbon dioxide removed using one of several absorption processes

Process Flowsheet-SMR Process

Operating Conditions for Reforming Section Equipment

Flowsheet Element Parameter Baseline Temperature Steam feed e 950 F Pressure 30 bar Desulfurized feed to Temperature 950 F pre-reformer Pressure 28.5 bar Temperature 950 F Pressure drop 25 psi Pre-reformer Effectiveness The reactor is assumed to achieve equilibrium concentrations. Pre-reformed feed to Temperature 1200 F primary reformer Pressure 27 bar Temperature 1500 F Pressure drop 25 psi Reformer Effectiveness The reactor is assumed to achieve equilibrium concentrations.

Capital & Energy Costs

$60 million (1991) including CO2 removal for a 100MMSCFD Fuel Consumption 315MBTU/MSCF Hydrogen

Synthesis Gas

Partial oxidation (gasification) of heavy resid feed using the Water gas shift technology from asphalts, resids, and other very heavy liquid or coal slurry. Synthesis gas will contain equal volumes of carbon monoxide and hydrogen with about 5 vol% carbon dioxide and smaller volumes of methane, nitrogen, water and sulfur. Hydrogen recovered normally by pressure swing adsorption or membrane separation. Its is however more expensive than steam reforming but can destroy a variety of polluted streams as well as low quality by product streams

Hydroprocessing - Hydrotreating

Removal of hetero atoms and saturation of carbon carbon bonds

Nitrogen, oxygen and metals removed Olefinic and aromatic bonds saturated

Reduce average molecular weight and produce higher yields of fuel products

Hydrodesulfurization

Remove sulfur compounds Minimum conversion of feed to lighter products 10% to 20% conversion

Hydrocracking

Severe type of hydrotreating

Cracking of carbon carbon bonds Drastic reduction of molecular weight

50%+ conversion

Hydrogen Consumption

Hydrogen Consumption

The Amount of hydrogen consumed is a function of bonds broken, hydrogen lost with products and chemical consumption due to hydrogenation reactions that are generally exothermic.

Hydrodesulphurization

Sulfur is converted to hydrogen sulfide (H2S) using hydrogen to break the carbon sulfur bonds and to saturate the remaining hydrocarbon chains. This process creates some light ends. Heavier distillates make more light ends from breaking more complex sulfur molecules. The form of the sulfur bonds in naphtha are generally mercaptans (thiols) and sulfides. In heavier feeds, more sulfur as disulphides and thiopenes.

Hydrodenitrozation

Pyridines and pyrroles are nitrogen containing compounds. This nitrogen is converted to ammonia (NH3) although nitrogen removal is minor in naphtha hydrotreating. As the feeds becomes heavier, denitrogenation becomes more significant, such as in heavy distillate and gas oil hydrotreating. Nitrogen removal requires about four times as much hydrogen as the equivalent sulfur removal.

Hydrodeoxygenation

Examples of oxygen containing compounds are phenols and peroxides and the oxygen converted to water (H2O). Like nitrogen removal, oxygen removal is minor in naphtha hydrotreating but significant in heavy distillate hydrotreating. Oxygen requires about two times as much hydrogen as the equivalent sulfur removal.

Other Contaminants

Organic chlorides are converted to hydrogen chlorides that are usually present in small amounts and the hydrogen usage per molecule is similar to desulfurization

Saturation of Hydrocarbons

Olefins are saturated to form light hydrocarbons and the consumption is stoichiometric with one hydrogen molecule added for each double bond. Olefins are prevalent in cracked streams such as naphtha streams from a coker or visbreaker, catalytic cracker cycle oil, and catalytic cracker gasoline.

Selective catalysts are available for use in hydrotreating and catalytic cracking gasoline for sulfur removal but not to saturate olefins, thus maintaining high octane ratings Aromatic rings are hydrogenated to cycloparaffins (naphthenes). This is a severe operation and the hydrogen consumption is a strong function of the complexity of the aromatics. Ring saturation arises in heavy distillate hydrotreating, gas oil hydrotreating, and hydrocracking.

Hydrogen Losses

Hydrogen is lost in equilibrium with light gases. The amount is significant and may double the amount required for sulfur removal. Hydrogen is also absorbed in liquid products however this is usually small compared to hydrogen used for sulfur removal. Hydrogen is also removed with purge gas used to maintain a high purity of hydrogen as the light ends formed dilute the hydrogen concentration

Hydrocracking

The Hydrocracker is similar to the FCC in that it is a catalytic process that cracks long chain gas oil molecules into smaller molecules that boil in the gasoline, jet fuel and diesel fuel range.

The fundamental difference is that cracking reactions take place in an extremely hydrogen rich atmosphere. First carbon bonds are broken followed by attachment of hydrogen. Hydrocracker products are sulfur free and saturated.

Another difference is operating conditions.

High temperature 650-800F (345-425C) and very high pressures of 1500-3000 psi (105-210 bar) & circulation of large quantities of hydrogen to prevent catalyst fouling and permits long runs.

Hydrocracker reactors contain multiple fixed beds of catalyst typically containing palladium, platinum, or nickel. These catalysts are poisoned by sulfur and organic nitrogen, so a high-severity HDS/HDN reactor pretreats feedstock prior to the hydrocracking reactors.

Hydrocracker units may be configured in single stage or two stage reactor systems that enable a higher conversion of gas oil into lower boiling point material.

Typical Hydrocracker Feedstocks

Feed Kerosine Straight run diesel Products Naphtha Naphtha and/or jet fuel

Atmospheric gas oil Naphtha, jet fuel, and/or diesel Vacuum gas oil FCC LCO FCC HCO Coker LCGO Coker HCGO Naphtha, jet fuel, diesel, lube oil Naphtha Naphtha and/or distillates Naphtha and/or distillates Naphtha and/or distillates

Hydrocracking Reactions

Although there are hundreds of simultaneous chemical reactions occurring in hydrocracking, it is the general opinion that the mechanism of hydrocracking is that of catalytic cracking with hydrogenation superimposed

An example of the scission of a carboncarbon single bond followed by hydrogenation

Careful preparation of the feed is also necessary in order to remove catalyst poisons and to give long catalyst life. Frequently the feedstock is hydrotreated to remove sulfur and nitrogen compounds as well as metals before it is sent to the first hydrocracking stage or, sometimes, the first reactor in the reactor train can be used for this purpose.

Typical Hydrocracker Products

Heavy naphtha from the Hydrocracker makes excellent Catalytic Reformer feedstock. Distillates from Hydrocracking make excellent jet fuel blend stocks.

Light ends are highly saturated and a good source of iso-butane for alkylation. The yield across a Hydrocracker may exhibit volumetric gains as high as 20-25% making it a substantial contributor to refinery profitability.

Hydrogen Required for Hydrocracking

Hydrocracking Yields

Gas Production

mol%

wt%

C1
C2

20
15

8.8
12.4

C3
Total

65
100

78.8
100.0

Catalytic hydrocracking unit investment cost: 1999 U.S. Gulf Coast.

Catalytic Hydrocracking Unit Cost Data

Hydrocracker Material Balance: 100,000 BPCD, Alaska North Slope Crude Oil Basis (10,621 BPCD Fresh Feed; Severity, 2,000 scf H2/bbl)

Hydrocracker Material Balance: 100,000 BPCD, Alaska North Slope Crude Oil Basis (10,621 BPCD Fresh Feed; Severity, 2,000 scf H2/bbl)

Hydrocracker Catalyst and Utility Requirements

Steam, Mlb/day
Power, MkWh/day

797
138

Cooling water, Mgpn

Fuel, MMBtu/day

3.3
138

Catalyst, $/day

2124

A hydrocracker feedstock has a boiling range of 650 to 920F, an API gravity of 23.7, and contains 1.7 wt% sulfur. If the hydrocracking hydrogen consumption is 1500 scf/bbl of feed and the feed rate is 7500 BPSD, determine
(a)
(b) (c)

total hydrogen consumption, barrels of gasoline, and barrels of jet fuel produced per day.

For the feed of problem 1, calculate the feed rate in barrels per day needed to produce sufficient isobutane for an alkylation unit producing 3500 BPD of alkylate. Assume the hydrocracking hydrogen consumption is 1750 scf/bbl of feed, and 0.65 bbl of isobutane is needed to produce 1 bbl of alkylate.

Hydrocracking refers to processes whose primary purpose is to reduce the boiling range and in which most of the feed is converted to products with boiling ranges lower than that of the feed. Hydrotreating and hydrocracking set the two ends of the spectrum and those processes with a substantial amount of sulfur and/or nitrogen removal and a significant change in boiling range of the products versus the feed are called hydroprocessing

Hydrotreating is a process to catalytically stabilize petroleum products and/ or remove objectionable elements from products or feedstocks by reacting them with hydrogen. Stabilization usually involves converting unsaturated hydrocarbons such as olefins and gum forming unstable diolefins to paraffins. Objectionable elements removed by hydrotreating include sulfur, nitrogen, oxygen, halides, and trace metals.

Hydrotreating is applied to a wide range of feedstocks, from naphtha to reduced crude. When the process is employed specifically for sulfur removal it is usually called hydrodesulfurization, or HDS. To meet environmental objectives it also may be necessary to hydrogenate aromatic rings to reduce aromatic content by converting aromatics to paraffins.

Hydrotreating Catalysts

Catalysts developed for hydrotreating include cobalt and molybdenum oxides on alumina, nickel oxide, nickel thiomolybdate, tungsten and nickel sulfides, and vanadium oxide. The cobalt and molybdenum oxides on alumina catalysts are in most general use today because they have proven to be highly selective, easy to regenerate, and resistant to poisons. They must be activated by converting the hydrogenation metals from the oxide to the sulfide form.

Cobaltmolybdenum catalysts are selective for sulfur removal and nickel molybdenum catalysts are selective for nitrogen removal, although both catalysts will remove both sulfur and nitrogen.

Reactions

The main hydrotreating reaction is that of desulfurization but many others take place to a degree proportional to the severity of the operation.

Process Variables

The principal operating variables are temperature, hydrogen partial pressure, and space velocity. Increasing temperature and hydrogen partial pressure increases sulfur and nitrogen removal and hydrogen consumption. Increasing pressure also increases hydrogen saturation and reduces coke formation. Increasing space velocity reduces conversion, hydrogen consumption, and coke formation. Although increasing temperature improves sulfur and nitrogen removal, excessive temperatures must be avoided because of the increased coke formation.

Naphtha Hydrotreating

Naphtha is hydrotreated primarily for sulfur removal. The sulfur present as mercaptans (RSH), sulfides (R2S), disulfides (RSSR), and thiophenes (ring structures). Straight run gasoline may be added to naphtha prior to hydrotreating. Combining offers advantages at the crude unit but calls for a larger hydrotreater and a splitter to separate Pentane/hexane overhead to isomerization as well as bottoms to reformer.

Naphtha Hydrotreating Process

Distillate Hydrotreating Process