# Patent

## Title
Process for increasing the mono-aromatic content of polynuclear-aromatic-containing feedstocks

## Abstract

Hydrocarbons containing polynuclear aromatics, such as cycle oil and pyrolysis fuel oil (PFO), are upgraded using an catalyst complex that selectively cracks the polynuclear aromatic compounds to form higher value mono-aromatic compounds, such as benzene toluene, xylenes and ethyl benzene (i.e., BTX). The catalyst complexes include a catalytic metal center and a plurality of organic ligands. During the hydrocracking procedure, the organic ligand preserves one of the aromatic rings of the polynuclear aromatic compounds while the catalytic metal breaks the other aromatic rings thereby yielding a monoaromatic compound.

## Background
BACKGROUND OF THE INVENTION
1. The Field of the Invention
The present invention relates generally to processes for upgrading low value by-products generated during petroleum refining. More particularly, the present invention relates to methods for increasing the mono-aromatic content of refining by-products that contain polynuclear aromatics, such as but not limited to cycle oils and pyrolysis fuel oil.
2. The Related Technology
Effective techniques for manufacturing the greatest amount of high quality products from low quality crudes are needed for the economic viability of the petroleum refining industry. Because crude oils are obtained from the ground, they can have widely varying types and amounts of hydrocarbons and impurities. Distillation of crude oils produces large fractions of hydrocarbons that are not very useful as fuels or other higher end uses. For decades, the refining industry has been intensively researching ways to economically convert these fractions into products that are more valuable. There are now many refining techniques that economically convert unusable fractions into higher value petroleum products.
Ideally all the hydrocarbons in a barrel of oil would be upgraded to high-value, useable products. However, despite the industry's extensive research there are certain by-products of the various refining processes that are difficult to upgrade. Difficult-to-upgrade hydrocarbons include pyrolysis fuel oil, which is a by-product of steam cracking to make olefins, and cycle oil, which is a by-product of fluidized catalytic crackers that are used extensively to produce gasoline stocks.
These hydrocarbons can be difficult to upgrade because they often contain impurities such as sulfur and heavy metals and/or significant quantities of very high molecular weight hydrocarbons, polynuclear aromatics, and asphaltenes. Hydrocarbons containing these types of hydrocarbons tend to form coke under hydrocracking conditions, which can foul reactors and reduce the yield of the hydrocracking process. Consequently, these products are often used “as is” in their low-value form.
Because pyrolysis fuel oil and cycle oil are a byproduct of important refining processes, these products are necessarily produced in most refineries and must be dealt with. The traditional approach has been to sell PFO and cycle oil as a fuel to be burned in power generation. PFO and cycle oils have a foul smell, are toxic, and produce pollution when burned. Environmental agencies have for years regulated the disposal and burning of PFO and cycle oils. These oils typically must be blended with other higher grade fuel oils to pass regulatory restrictions when burned. The restrictions make it even more difficult to use these materials as fuels and have suppressed the price that industry is willing to pay for them. Despite the continuing pressures to catalytically upgrade hydrocarbons such as PFO and cycle oil, thereby creating a long-felt but unsatisfied need, an economical process has thus far eluded the industry.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to a process for hydrocracking hard-to-upgrade refining by-products such as, but not limited to, cycle oil and pyrolysis fuel oil (PFO). The refining by-products used in the process of the present invention are hydrocarbons produced in a refining process, downstream of distillation, and that include significant quantities of polynuclear aromatic compounds. The process of the present invention improves the economic viability of hydrocracking refining by-products that contain polynuclear aromatic compounds by using a catalyst that selectively cracks the polynuclear aromatics to higher value mono-aromatic compounds (e.g., benzene, toluene, and xylene).
The process includes hydrocracking the hydrocarbon feedstock using a catalyst complex that selectively cracks polynuclear aromatic compounds to mono-aromatic compounds. The catalyst complex includes a catalytic metal center that is bonded to a plurality of organic ligands that make the catalyst complex oil-soluble.
The active metals included in the catalysts of the invention are metals that are useful for cracking polyaromatic compounds found in pyrolysis fuel oil, cycle oils, and similar hydrocarbons. In one embodiment the catalytic metal atom can be a group VIB metal, a group VIIIB metal or a combination of these. Examples of suitable catalytic metals include tungsten, molybdenum, chromium, nickel, cobalt, iron, vanadium, titanium, manganese, and combinations of these.
The ligand bonded to the metal atom includes an aromatic group that can form pi-pi (π-π) stacking interactions with polynuclear aromatic compounds in the hydrocarbon feedstocks. The aromatic group of the ligand is typically a substituted or unsubstituted five or six member aromatic ring (e.g., aryl group). The aromatic group can also be alkylated or functionalized in other ways to provide desired steric hindrances and/or bonding interactions with other ligands or molecules in the hydrocarbon feedstock, so long as the complexes including the ligands remain oil soluble. In a preferred embodiment, the aromatic group of the ligand is monocyclic. Alternatively the organic ligand can be non-aromatic and include a carbon ring structure that provides proper spacing based on steric hindrances. In one embodiment, the carbon ring structure is at least a six-membered carbon ring.
In one embodiment, the organic ligands include a carbon ring and a ligand spacer group. The ligand spacer group provides spacing of 2-6 atoms between the metal center and the carbon ring. The spacing between the carbon ring and the catalytic metal center can advantageously provide spacing that selectively cracks polynuclear aromatic rings while preserving one of the aromatic rings, thereby increasing the content of mono-aromatic compounds in the hydrocarbon material.
In this embodiment, the ligand spacer group can be any group that can be bonded to the aromatic ring and to the catalytic metal and can provide spacing of 2-6 atoms between the metal atom and the aromatic ring of the ligand. In one embodiment, the catalyst can have the following structure:




In the foregoing structure, M can be a group VIIIB metal, a group VIB metal, a base transition metal, or a combination thereof; L1 and L2 are ligand spacer groups with a first atom bonded to the aromatic group and a second atom bonded to the metal and providing a spacing of 2-6 atoms between the aromatic group and the metal; R1-R10 are independently a hydrogen, an alkyl group, or a bond to a ligand of another metal-ligand complex; X1-X4 are optional ligands to the catalytic metal.
The aromatic ring and the metal atom provide a molecular template that acts to control the catalytic hydrocracking process so as to selectively crack polynuclear aromatic compounds into higher value mono-aromatic compounds. Mono-aromatic compounds are produced from the catalyst template because one aromatic ring of the polynuclear aromatic compound interacts with the aromatic ring of the catalysts and the other ring(s) of the polynuclear aromatic compounds is/are positioned near the catalytic metal. The catalyst selectively cracks one or more of the aromatic rings of the polynuclear aromatic compounds while preserving one of the rings, thereby forming a mono-aromatic compound.
Because of the longstanding need to dispose of hard-to-upgrade hydrocarbons, there have been many attempts in the prior art to crack these products. Many of these methods have used catalysts that crack the polynuclear aromatics in a non-specific manner to form alkanes such as diesel and gasoline. However, these processes have yet to be shown to be economically viable. In contrast, the process of the present invention solves the long-felt need to dispose of these refining by-products by unexpectedly cracking the polynuclear aromatics in a controlled and selective manner to produce a significant fraction of higher value aromatics (e.g., BTX products), thereby increasing the economic viability of the process. Importantly, the catalyst can produce the mono-aromatic compounds directly from the polynuclear aromatic compounds during the cracking process, rather than producing straight-chained hydrocarbons that would have to be converted to an aromatic product using a separate process. Mono-aromatic compounds such as BTX have higher commercial value compared to diesel and gasoline, which are composed largely of non-aromatic alkanes.


DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS
I. Introduction and Definitions
The present invention is directed to a process for hydrocracking hydrocarbon materials that contain polynuclear aromatic compounds to increase the monoaromatic content (e.g., BTX content) of the hydrocarbon material. The hydrocracking process uses a catalyst complex that selectively cracks the polynuclear aromatics to form higher value monoaromatic compounds (e.g., BTX).
For purposes of this invention, the term “acid residue” is the portion of an acid molecule that persists after the acid has been reacted with another molecule. The acid residue therefore differs from its acid molecule by the loss of an atom (e.g., a hydrogen) resulting from the reaction of the acid with another molecule. For example, an ester group and a metal carboxylate are examples of acid residues of a compound containing a carboxylic acid.
For purposes of this invention, the term “substantially free of Ramsbottom carbon residue” means a Ramsbottom carbon content of less than 1.0% as determined according to ASTM D524.
The term “BTX” refers to benzene, toluene, xylene and ethyl benzene.
For purposes of this invention, the term “refining by-product” is a hydrocarbon product obtained from refining a petroleum distillate where the “refining by-product” is lower in value and produced in lower quantities than at least one other hydrocarbon product produced during the same refining process.
II. Components Used to Make Oil Soluble Catalyst
The catalysts of the invention include a plurality of catalyst complexes, which include a catalytic metal center and a plurality of organic ligands. Optionally, the catalyst complexes can be dispersed in a solvent or carrier. The following components can be used to manufacture the catalysts of the invention.
A. Catalytic Metals
The catalytic metal is a transition metal selected for its ability to form a bond with the organic ligand and to catalytically crack aromatic rings of polynuclear aromatic compounds under hydrocracking conditions. In one embodiment, the catalytic metals are selected from groups VIB and VIIIB of the Periodic Table. Examples of suitable metals include, but are not limited to, tungsten (W), molybdenum (Mo), chromium (Cr), nickel (Ni), cobalt (Co), iron (Fe), vanadium (V), titanium (Ti), and manganese (Mn).
The catalyst atoms may be provided in the form of metal hydroxide, metal chloride, metal sulfate, metal nitrate, metal oxide, or other metal salts. For example, where molybdenum is used, examples of suitable molybdenum compounds include molybdenum halides such as molybdenum hexafluoride and molybdenum pentachloride, the various oxides of molybdenum such as molybdenum dioxide, trioxide and sesquioxide, and the like; alkali and alkali earth molybdates such as cesium molybdate, sodium molybdate, potassium molybdate, calcium molybdate and the like; and ammonium molybdate or molybdic acid. Examples of other suitable metal compounds include cobalt (II) hydroxide, nickel (II) hydroxide, hydrated iron (III) oxide (FeO(OH)), manganese (II) oxide, FeCl3, Fe(NO)3, and Fe2(SO4)3.
The catalytic metals can be used alone or in combination. In one embodiment, at least Mo is used as a primary metal component and optionally in combination with at least one other base transition metal. The use of Mo in combination with at least one other base transition metal has been shown to provide superior results compared to Mo alone or the base transition alone.
B. Organic Ligands
The organic ligands are organic compounds that can form a complex with the catalytic metals. The organic ligands include a carbon ring group and a ligand spacer group. The ligand spacer group is attached to the carbon ring and provides the bonding interaction with the catalytic metal. The carbon ring can be any ring structure and can have any substituents bonded thereto so long as the organic ligand is capable of being bonded to the catalytic metal through the ligand spacer group and the complex that includes the ligand can be oil soluble. The carbon ring can be bicyclic or monocyclic. In a preferred embodiment the carbon ring is aromatic. Monocyclic aromatic rings are preferred for their ability to pi-stack with one aromatic ring in the polynuclear aromatic compounds to be hydrocracked. In one embodiment, the aromatic group is a five or six member aromatic ring. The ring structure can be all carbons or can include heteroatoms (e.g., nitrogen or oxygen). The carbon ring can also include substituents. In one embodiment, the carbon ring includes alkyl substituents, which can provide added solubility in oil. These alkyl groups can be straight-chain or branched and typically have between 1 and 18 carbon atoms, more preferably between 2 and 12 carbon atoms, and most preferably between 3 and 8 carbons.
The organic ligands include at least one functional group that can bond the catalytic metals to form a complex (e.g., a hydroxyl). In one embodiment, the organic ligands may include one or more ligand spacing groups that include the at least one functional group. The ligand spacing group can include a chain of atoms that are bonded or can be bonded at the ends to the carbon ring and the catalytic metal to provide spacing of 2-6 atoms between the aromatic group and the catalytic metal. More preferably the ligand spacing group includes a chain of atoms that provide spacing of 2-4 atoms.
The ligand spacing group of the organic ligand includes at least one functional group that can form a bond with the catalytic metal. In one embodiment, the available functional group on the organic ligand is an acid group. Examples of suitable acid groups include carboxylic acids, phosphonic acids, sulfonic acids, boric acids, nitric acid, and derivatives thereof.
Examples of suitable acids that can be used as an organic ligand include compounds that contain one ring or two fused rings and contain from 6 to 14 atoms. Examples of suitable compounds include benzene carboxylic acid, naphthalene carboxylic acid, methylbenzoic acid, ethyl phenyl acetic acid, and the like. Single rings are preferred for their selective production of mono-aromatics in the hydrocracking process. In the case where the ligand is non-aromatic, examples of suitable organic ligands include 2-methyl-2,5-cyclohexadiene-1-carboxylic acid.
Optionally, the ligand spacing group includes one or more side groups that extend from the main chain of 2-6 atoms linking the catalytic metal to the aromatic ring. The side groups can provide oil solubility and/or electric or steric hindrances between the catalytic metal and the polynuclear aromatics that are bonded to the aromatic ligand through pi-pi stacking interactions.
In one embodiment, the organic ligand is provided as a single molecule that includes both the carbon ring (e.g., benzene ring) and the ligand spacing group in a single molecule. Alternatively, the organic ligand can be provided by reacting a ring compound (e.g., an aromatic compound) with a ligand spacer molecule which, once attached to the ring compound and the metal atom, serves as the ligand spacer group. The ligand spacer molecule includes a first functional group capable of reacting with the catalytic metal as described above. The ligand spacer molecule also includes a second functional group capable of reacting with an aromatic compound.
The linkage between the ligand spacer molecule and the ring compound will depend on the functional groups available on the ring compound. Any suitable linkage known in the art can be used. Examples of suitable functional groups include hydroxyl, carboxyl, carbonyl, amine, amide, nitrile, thiol, a sulfonic acid, and the like. For example, in one embodiment, the ring compound can include a hydroxyl group that can react with an acid group of a ligand spacing molecule to form an ester linkage.
One type of molecule that can be used as a ligand spacer molecule is a diacid or a diprotic acid. Examples of suitable acid groups include carboxylic acids, phosphonic acids, sulfonic acids, boric acids, nitric acid, and derivatives thereof. Examples of specific compounds include oxalic acid, oxamic acid, malonic acid, succinic acid, glutaric acid, propylphosphonic acid, tert-Butylphosphonic acid, 3-(Methylphosphinico)propionic acid, dibutyl phosphate, bis(2-ethylhexyl) phosphate, sulfoacetic acid, methylboronic acid, isopropylboronic acid, butylboronic acid, isobutylboronic acid and their derivatives
In some cases, the organic ligand can function as a solvent for the reaction to make the catalyst complexes. This is typically the case where the organic ligand is a liquid under the reaction conditions. However, if needed, other solvents can be used. The additional solvent should dissolve the organic ligands and the catalytic metal compounds and not interfere with the reaction between them. Suitable solvents include benzene, toluene, xylene, naphtha, mineral oil, mineral spirits, combinations thereof, and the like.
C. Reducing Agents
Optionally, a reducing agent can be added to the reaction mixture during the formation of the catalyst complexes to cause the metal atoms and ligands to more readily form a complex and/or to obtain metal complexes with a desired number of ligands. The use of a reducing agent has been found to be particularly useful for the formation of complexes with molybdenum atoms in combination with an acid bearing ligand. In one embodiment, the reducing agent can also be used to maintain at least a portion of the molybdenum atoms in an oxidation state below 4+.
Any reducing agent that can reduce the catalytic metal atoms can be used. In a preferred embodiment, the reducing agent is a strong reducing agent under the reaction conditions described herein. Suitable reducing agents include methane, ethane, olefins such as ethylene and propylene, aldehydes such as formaldehyde, and hydrogen. Hydrogen gas is a particularly preferred reducing agent for its strong reducing potential.
The suitability of the reducing agent often depends on the temperature at which the reaction is performed. At higher temperatures (e.g., 150° C.), organic reducing agents such as methane and formaldehyde have suitable reducing potential. However, at low temperatures (e.g., below 50° C.) or room temperature it can be advantageous to use a stronger reducing agent such as hydrogen gas.
III. Methods of Making Hydrocracking Catalyst
The process for making the hydrocracking catalysts according to the present invention can be carried out by reacting a plurality of organic ligand molecules with a plurality of catalytic metal atoms. An organic ligand capable of bonding with the catalytic metal atoms is mixed together with the catalytic metal and optionally one or more solvents to form a mixture. The catalytic atoms are allowed to react with the functional group available on the ligand to form a metal ligand complex. The optimal reaction temperature for carrying out this reaction will depend on the particular catalytic metal and organic ligand. In one embodiment, the temperature for reacting the catalytic metal (e.g., with benzene carboxylic acid) is typically in a range from about 100 to about 300 degree C., more preferably about 150 to about 250 degree C.
Optionally, the catalyst complex can include a ligand spacer group that provides spacing of 2-6 atoms between the ligand and the catalytic metal, thereby enhancing selective cracking of the polynuclear aromatics. The ligand spacer group can be provided as a functional group of the aromatic compound (i.e., the ligand spacer group and aromatic ring are provided as a single molecule) or alternatively a ligand spacer molecule and an aromatic ring compound can be provided separately and reacted together to form the organic ligand. The ligand spacer molecule can be reacted with an aromatic compound before, after, or simultaneously with the reaction with the catalytic metal.
The use of a ligand spacer molecule can be advantageous for obtaining good yields of certain metals (e.g., base transition metals such as nickel) which can be more difficult to react directly with some organic ligand compounds. In addition, the use of a ligand spacer molecule is advantageous where it is desired to provide side chains that extend from the ligand spacer group. By providing the ligand spacer group separately from the aromatic compound, the side chain groups can be selected independently from the aromatic compound. This feature allows greater flexibility in providing the desired solubility and steric effects of the side chains.
In one embodiment, the catalyst of the invention includes at least two different catalytic metals. The bimetallic or multimetallic catalysts can be manufactured by making separate catalyst complexes using a single metal and then combining the complexes to form the bimetallic or multimetallic catalysts. Any combination of metals can be used; however, the combination of molybdenum and another base transition metal has been found to be particularly useful for hydrocracking pyrolysis fuel oil and/or cycle oils. In one embodiment, the ratio of the first metal (e.g., molybdenum) to the second metal (e.g., nickel) is in a range from about 50/1 to about 1/20, more preferably about 10/1 to about 1/5, and most preferably in a range from about 6/1 to about 1/2. The first and second catalytic metals can be complexed using the same or different organic ligands.
In one embodiment of the invention, the reaction of the catalytic metal with the organic ligand is carried out in the presence of a reducing agent. The use of a reducing agent can produce a catalyst with the catalytic metal in a lower oxidation state and thereby reduce the amount of organic ligands per catalytic metal. In addition, the use of a reducing agent can improve the solubility of the catalyst in PFO and cycle oil. In a preferred embodiment, the reducing agent used is hydrogen.
IV. Oil Soluble Catalyst
The methods of the present invention can be used to manufacture an oil soluble catalyst that is useful for upgrading polynuclear aromatics to mono-aromatic compounds. The oil soluble catalyst includes a plurality of organic ligands bonded to a catalytic metal center. The oxidation state of the metals and the number and type of organic ligands is selected to ensure that the catalyst complex is soluble in the hydrocarbon feedstock to be cracked.
In one embodiment, the catalyst complexes have the following structure:




In the foregoing structure, M can be a group VIB metal, a group VIIIB metal, a base transition metal, or a combination of these, more preferably M is W, Mo, Cr, Ni, Co, Fe, V, Ti, Mn, or a combination of these; L1 and L2 are ligand spacer groups with a first atom bonded to the aromatic group and a second atom bonded to the metal and providing a spacing of 2-6 atoms between the aromatic group and the metal; R1-R10 are independently a hydrogen, an alkyl group, or a bond to a ligand spacing group that is bonded to another metal atom; (e.g., which can form an extended network of intercomplexed ligands and metal atoms, e.g., structure 3 below). X1-X4 are optional ligands bonded to the catalytic metal.
In an alternative embodiment, the catalyst can have the following structure:




In structure 2, M, R1-R10, and X1-X4 are the same as in Structure 1. A1 and A2 comprise a single atom or a chain of atoms, at least one of the atoms is selected from the group consisting of B, N, P, S, or C; and R11-R14 are independently a single bonded oxygen, a double bonded oxygen, or an alkoxide.
An exemplary extended network of intercomplexed ligands and metal atoms is shown below in the following structure:




In structure 3, M is a metal such as W, Mo, Ni, Co, Fe, Group VIB metal, or Group VIIIB metal, L can be C, B, N, P, or S.
In one embodiment, the oil soluble catalyst is a mixture of two or more complexes with different metals. Mixtures of Mo or tungsten complexes with Ni, Co, and/or Fe have been found to work surprisingly well for cracking polynuclear aromatic compounds. In one embodiment, the oil soluble catalyst includes a Mo complex and a complex that includes Ni, Co, and/or Fe in a ratio of 50:1 to 1:20, more preferably 10:1 to 1:5. Preferred organic ligands for the molybdenum complexes include aromatic carboxylic acids where the carboxylic acid serves as the ligand spacer group. Preferred ligand spacer groups for the Ni, Co, and/or Fe include carboxylic acids, phosphonic acids, sulfonic acids, boric acids and derivatives thereof.
In an alternative embodiment of the invention, the catalyst complexes of the oil soluble catalyst can have an organic ligand that is not aromatic. In this embodiment, a carbon ring (e.g., a six-membered cyclic ring) is bonded to the catalytic metal. In one embodiment, the carbon ring is at least a six-membered carbon ring and can be monocyclic or bicyclic. This non-aromatic ligand provides steric hindrances that space the catalytic metal in the feedstock. The spacing is at least the molecular distance of a monoaromatic ring. By spacing apart the catalyst atoms at distances of at least the width of a monoaromatic compound, the organic ligands reduce the likelihood that two neighboring catalytic atoms will crack the same polynuclear aromatic atom during the cracking process, thereby preserving one aromatic ring of a polynuclear aromatic compound. In a preferred embodiment, the catalyst complexes include at least two ligands, more preferably at least three ligands that are as large or larger than a six membered cyclic ring. The catalyst in this embodiment is able to preferentially crack the polynuclear aromatics by virtue of its proper spacing rather than a selective attraction to the polynuclear aromatics. The embodiment can be particularly beneficial where the cracking process uses a particularly high temperature that may cause the catalyst complex to decompose. In this case, the proper spacing of the catalytic metal prior to reaching the decomposition temperature can result in preferential cracking of the PNA.
V. Methods for Upgrading Polyaromatic Hydrocarbons
The catalysts of the present invention can be used to increase the monoaromatic content of hydrocarbon materials by converting polynuclear aromatic hydrocarbons to mono-aromatic hydrocarbons. The method includes providing a hydrocarbon material, blending the catalyst complexes of the invention into the hydrocarbon material, and processing the hydrocarbon material under hydrocracking conditions to increase the percentage of monoaromatic compounds while decreasing the percentage of polynuclear aromatics.
A. Providing Hydrocarbon Material
The hydrocarbon feedstock used in the process of the invention includes a by-product of a petroleum refining process (i.e., a by-product from refining a distilled fraction of a crude oil). The refining by-products suitable for use with the present invention have significant quantities of polynuclear aromatic hydrocarbons. Examples of the types of polynuclear aromatics that can be found in the refining by-products include, anthracene, benzopyrene, chrysene, coronene, corannulene, naphthacene, naphthalene, pentacene, phenanthrene, pyrene, triphenylene, and ovalene. The refining by-products can include polynuclear aromatics in a range from about 0.1% to about 99%, more preferably, in a range from about 10% to about 75%, and most preferably in a range from about 20% to about 60%.
Examples of suitable refining by-products that can be used in the process of the present invention include heavy cycle oils, FCC slurry oil, and pyrolysis fuel oils. Cycle oils are a byproduct of fluid catalytic cracking. Cycle oils are oily hydrocarbons that have very low Ramsbottom carbon residue (in one embodiment the cycle oils are substantially free of Ramsbottom carbon residue) and have little to no heavies boiling over 1000° F. In one embodiment, the carbon residue is less than 1.0 wt %, more preferably less than about 0.9 wt % and most preferably less than about 0.8 wt % and the amount of heavies boiling above 1000° F. are less than about 10 wt %, more preferably less than about 5 wt %, and most preferably less than about 2 wt %. Yet, cycle oils are difficult to upgrade because they contain significant quantities of polynuclear aromatic compounds. The relatively high polynuclear aromatic content and relatively low to non-existent content of Ramsbottom carbon residue and heavies has been found to be uniquely suited for the process of the invention, which produces mono-aromatic compounds from polynuclear aromatics.
Another type of refining by-product particularly suited for use with the catalyst of the invention is pyrolysis fuel oil, and particularly the heavy fraction of pyrolysis fuel oil. Pyrolysis fuel oil is a byproduct of steam cracking of naphtha and ethane to form olefins. Because of the complicated nature of the hydrocarbons in pyrolysis fuel oil, pyrolysis fuel oil is typically characterized by its source rather than the exact components that comprise this material. While the exact contents of pyrolysis oil can vary, pyrolysis fuel oil usually has significant quantities of polynuclear aromatic compounds. Pyrolysis fuel oil has been found to be a surprisingly good hydrocarbon source to derive a benefit from the catalyst of the present invention.
In one embodiment, the hydrocarbon feedstock used in the invention has between about 10 wt % and 90 wt % polynuclear aromatics, more preferably between 20% and 80%. Another way of determining the suitability of the hydrocarbon feedstock for use in the present invention is evaluating the percent of hydrocarbons boiling above 1000° F. In one embodiment, the feedstock includes less than 50 wt % of hydrocarbons boiling above 1000° F., more preferably less than 25 wt % and most preferably less than 10%. Alternatively, the hydrocarbon feedstock can be selected according to the wt % of hydrocarbons boiling in a range from about 350° F. to about 1000° F. In one embodiment, the hydrocarbon feedstock contains at least 50 wt % hydrocarbons boiling between about 350° F. and about 1000° F., more preferably at least about 70 wt % and most preferably at least about 90 wt %. While these materials have been found to be particularly suited for the process of the present invention, the invention is not limited to these hydrocarbon materials.
The hydrocarbon feedstock can also be a blend of different hydrocarbons from different sources. In a preferred embodiment, the hydrocarbon feedstock contains at least about 20 wt % of a refining by-product, more preferably at least about 50 wt %, even more preferably at least about 75 wt %, even more preferably yet at least 90 wt %, and most preferably substantially all of the hydrocarbon feedstock used in the process is a by-product of a refining process obtained downstream from distillation.
B. Blending the Catalyst Complex with the Hydrocarbon Material
The catalyst complex comprising the organic ligand and catalytic metal is blended into the polyaromatic-containing hydrocarbon feedstock. The catalyst can be blended directly into the feedstock or the catalyst can be diluted in one or more subsequent steps. The step-wise dilution can facilitate intimate mixing of the catalyst and the hydrocarbon. The hydrocarbon used to carry out dilution can be the same material to be hydrocracked, or alternatively, a different hydrocarbon can be used as the diluent. Examples of suitable diluents include vacuum gas oil, decant oil, or light gas oil. Suitable solvents include benzene, toluene, xylene, ethyl benzene, naphtha, mineral oil, mineral spirits, combinations thereof, and the like.
It has been found that pre-blending the precursor composition with a hydrocarbon diluent prior to blending the diluted precursor mixture with the feedstock greatly aids in thoroughly and intimately blending the catalyst complex within the feedstock, particularly in the relatively short period of time required for large-scale industrial operations to be economically viable. In one embodiment the catalyst is blended with the diluent for a period of time in a range of about 1⁄2 minute to about 20 minutes, more preferably in a range from about 1 minute to about 10 minutes, and most preferably in a range of about 2 minutes to about 5 minutes. Increasing the vigorousness and/or shearing energy of the mixing process generally reduce the time required to effect thorough mixing.
The catalyst or the diluted catalyst is blended with the hydrocarbon feedstock to achieve a desired metal concentration. In one embodiment, the concentration of the catalyst in the feedstock is in a range from about 1 ppm to about 1,000 ppm, more preferably 10 ppm to about 750 ppm, and most preferably 50 ppm to about 500 ppm.
C. Hydrocracking Polynuclear Aromatics to Mono-Aromatics
The hydrocarbon feedstock is reacted with hydrogen in the presence of the catalyst complex of the invention under hydrocracking conditions so as to increase the mono-aromatic content while reducing the polynuclear aromatic content in the feedstock.
The hydrocracking process can be carried out in any reactor so long as intimate contact can be maintained between the catalyst complexes, the hydrocarbon feedstock, and the free hydrogen gas stream during the hydrocracking process. The reactor can be a continuous reactor, semi-continuous reactor, or a batch reactor. The feedstock and catalyst can be pre-mixed before entering the reactor or mixed within the reactor. The reactor can be equipped with a mechanical stirrer or a static mixer or a recirculating pump. In a preferred embodiment, the reactor is a continuous stream reaction vessel with a recirculating pump. Continuous reaction vessels have been found to work well due to the homogeneous nature of the catalyst.
The reaction temperature is selected to promote the conversion of polynuclear aromatics to mono-aromatics. The particular temperature for a given reaction can depend on the hydrocarbon feedstock being used and the decomposition temperature of the catalyst. In general, the hydrocracking temperature can be in a range from about 450° F. to about 1000° F. or higher. Lower temperatures within the range are typically preferred to hinder decomposition of the catalyst. In a preferred embodiment, the hydrocracking temperature is less than about 950° F., more preferably less than 850° F.
Any suitable pressure can be used in the hydrocracking process of the invention. The reaction pressure can range from about atmospheric pressure to about 10,000 psig. Preferably the pressure is in a range from about 1,000 psi to about 3,000 psi.
Any suitable amount of hydrogen can be used in the hydrocracking process of the invention. In general the hydrogen flow can be in a range from about 100 to about 20,000 cubic feet of hydrogen per barrel (SCFB). In a preferred embodiment, hydrogen flow is in a range from about 200 scfb to about 2,000 scfb.
The reaction time is selected to ensure at least partial conversion of the polynuclear aromatics to mono-aromatics. In one embodiment, the reaction time is in a range from about 0.1 to about 10 hour, more preferably in a range from 1 to about 6 hour. For purposes of this invention, when using a continuous flow reactor, the reaction time is the residence time.
During the hydrocracking process of the invention at least a portion of the polynuclear aromatics are converted to mono-aromatic compounds. The catalyst, hydrocarbon feedstock, and hydrocracking conditions are selected to increase the mono-aromatic content in the feedstock and optionally increase the diesel/gasoline fraction while decreasing the amount of VGO and/or resid and minimize the production of light ends (C1-C7). In one embodiment, the increase in wt % of monoaromatic compounds in the product is in a range from about 10 wt % to about 80 wt %, more preferably about 20 wt % to about 60 wt %.
The mono-aromatic compounds produced from hydrocracking the polynuclear aromatics according to the process of the invention typically produces mono-aromatic compounds that are substituted with straight chain and/or branched alkyl groups. In one embodiment, this fuel product can be used as is and/or blended with other fuels (e.g., diesel or gasoline). In one embodiment, the product of the hydrocracking process of the invention can be blended with a #2 fuel oil and combusted. Alternatively the cracked product can be blended with a #2 fuel oil and then further refined using traditional refining techniques.
In yet another alternative embodiment, the cracked product is further refined to convert the substituted mono-aromatics to a BTX product or to remove double bonds (i.e., partially or fully saturated hydrocarbon). The BTX or other cyclic hydrocarbon can then be separated from the diesel and/or gasoline fraction. The conversion of substituted mono-aromatics to BTX or cyclic compounds can be carried out using known hydroprocessing techniques. The BTX or cyclic hydrocarbons can be separated from other hydrocarbons in the mixture using liquid-liquid extraction or another suitable separation technique.
In one embodiment, the method of the present invention includes determining the mono-aromatic content of the upgraded product and/or determining the amount by which the aromatic content in the feedstock has increased during the upgrading process. The determination can be made by measuring the actual mono-aromatic content of the upgraded product. Alternatively the determination can be made by selecting a feedstock mixture and hydrocracking conditions that, through prior runs, is known to increase the monoaromatic content within a desired range. This determination can be beneficial as it can provide a basis for determining the added value of the upgrading process and/or can be used to determine the efficiency of the overall upgrading process of the invention. Moreover, by knowing the amount by which the process increases mono-aromatic content, the process can be optimized at least in part on the production of mono-aromatics.
VI. Examples
The following examples provide formulas for making catalyst complexes according to the present invention and for using the catalyst complexes to upgrade hydrocarbon feedstocks that contain polynuclear aromatics.
Example 1
Preparation of Ni Catalyst
Example 1 describes the preparation of an oil soluble nickel complex according to one embodiment of the invention. 108.49 g of dibutyl phosphate (Aldrich, Cat#34810) was placed into a 500 ml round flask and 16 g of Nickel (II) hydroxide (Ni(OH)2, STREM, Cat#93-2847) was added to the dibutyl phosphate. 83.97 g of melted benzene carboxylic acid (ACROS Cat#130375000) was mixed with the nickel and dibutyl phosphate.
This mixture was heated in an oil bath at 130° C. with continuous stirring. The mixture was then heated to a temperature of 180-200° C. and held at this temperature until no water was observed in the distillate. The temperature of the water bath was then quickly decreased to 160° C. and held at this temperature for 1-2 hours until the inside mixture become transparent. The green color solution was then weighed and its metal concentration calculated. The content of nickel in this solution was 4.82 wt %. The following compounds are examples of products that can be produced in the foregoing process:




Example 2
Preparation of Mo Catalyst
Example 2 describes the preparation of an oil soluble molybdenum complex. 71.58 g of molybdic acid (Aldrich, MoO3≧85.0%) was added to 260.16 g of benzene carboxylic acid (98%) in a 500 ml flask. The flask was connected to a receiver and condenser, to allow water vapor to escape. The flask was purged with N2 at 220 ml per minute for about 10 minutes and then switched to H2 at 220 ml per minute. The flask was then placed in a silicone oil and the temperature of the mixture was raised to 210-220° C. and held for 15 hours. After cooling to room temperature the Mo content was calculated to be 14.0 wt % Mo.
Example 3
Preparation of Bimetallic Catalyst
Example 3 describes the preparation of a bimetallic catalyst. 275.41 g of the Mo catalyst prepared in Example 2 was placed into a metal vessel and the vessel was purged with nitrogen. Then, 200.15 g of the oil soluble nickel catalyst of Example 1 was added to the Mo catalyst with continuous stirring and with a nitrogen purpose. The mixture included 10 wt % metals.
Example 4
Light Cycle Oil to Monoaromatics
Example 4 describes the use of the catalyst of Example 3 to upgrade light cycle oil (LCO) by increasing the wt % of monoaromatic compounds. The LCO feedstock was 16.3% monoaromatics and 81.3 diesel, with negligible BTX or gasoline. A diluted catalyst was prepared by diluting 476 g of the catalyst of Example 1 in 1928 g of LCO to make 2404 g slurry with 2 wt % metal concentration. The sample was then mixed with LCO to produce a fresh feed with 400 wppm metal.
The reaction was run under reaction temperature 779° F., reaction pressure 1400 psig, the feed rate of fresh feed was 350 gms/hr, and with 50% O-6 recycle. Samples were taken and held separately every 24 hours. The reaction results were following: BTX yield 20.4%, Gasoline/Diesel yield 70.8%, 3.7% of C1-C7 (LPG) and 5.7% of VGO (The foregoing BTX yield includes straight chain and branched alkyl groups attached to aromatic rings).
Example 5
PFO to Monoaromatics
Example 5 describes the use of the catalyst precursor of Example 3 to upgrade pyrolysis fuel oil (PFO) by increasing the wt % of monoaromatics compounds. The PFO feedstock included 11.4% monoaromatics, 53.0% diesel, and negligible BTX or gasoline. A diluted catalyst was prepared by diluting 476 g of the catalyst of Example 3 in 1928 g of VGO oil to make 2404 g slurry with 2 wt % metal concentration at 120° F. The sample was then mixed with PFO to produce a fresh feed with 400 wppm metal at 120° F.
The reaction was run under reaction temperature 779° F., reaction pressure 1400 psig, the feed rate of fresh feed was 350 g/hr, and with 50% O-6 recycle. Samples were taken and held separately every 24 hours. The reaction results were the following: BTX yield 17.0%, Gasoline/Diesel yield 72.3%, 3.6% of C1-C7 (LPG), 5.0% of VGO, and 3.2% of resid (The foregoing BTX yield includes straight chain and branched alkyl groups attached to aromatic rings). As demonstrated in the examples, the catalyst and process of the present invention can increase the monoaromatic content of hydrocarbon feedstocks that include polynuclear aromatics. Surprisingly the increase in monoaromatics can be achieved with an increase in gasoline/diesel yields and while reducing unwanted compounds. Because the upgrading process of the invention yields high value mono-aromatics, while maintaining and/or increasing the content of other valuable products, the present invention provides a feasible route for upgrading hard-to-upgrade hydrocarbons that include significant quantities of polynuclear aromatics.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

## Claims

1. A process for hydrocracking a refining by-product containing polynuclear aromatic compounds and increasing monoaromatic content, comprising:
providing a refining by-product that includes polynuclear aromatic compounds;
providing a plurality of oil-soluble catalyst complexes, each catalyst complex comprising,
a catalytic metal; and
a plurality of organic ligands bonded to the catalytic metal, each organic ligand comprising a carbon ring spaced apart from the catalytic metal by at least 1 atom;

blending the plurality of catalyst complexes with the refining by-product to form a feedstock mixture; and
hydrocracking the feedstock mixture in a reactor containing a catalyst and operating under hydrocracking conditions and in a manner so as to form a product having an increased monoaromatic content compared to the refining by-product, the catalyst in the reactor consisting essentially of the catalytic metal provided by the oil-soluble catalyst complexes.

2. A process as in claim 1, wherein the refining by-product is comprised of a by-product of a catalytic upgrading process.

3. A process as in claim 1, wherein the refining by-product is comprised of cycle oil and/or pyrolysis fuel oil (PFO).

4. A process as in claim 1, wherein the concentration of catalyst complexes in the feedstock mixture is in a range from about 1 ppm to about 1000 ppm.

5. A process as in claim 1, wherein the catalytic metal is selected from the group consisting of group VIB metals, group VIIIB metals, and combinations thereof.

6. A process as in claim 1, wherein the catalytic metal is selected from the group consisting of tungsten (W), molybdenum (Mo), chromium (Cr), nickel (Ni), cobalt (Co), iron (Fe), vanadium (V), titanium (Ti), manganese (Mn), and combinations thereof.

7. A process as in claim 1, wherein the content of monoaromatics in the feedstock mixture is increased by at least about 10 wt % during the hydrocracking reaction.

8. A process as in claim 1, wherein the feedstock mixture includes at least about 20 wt % polynuclear aromatics.

9. A process as in claim 1, wherein the Ramsbottom residue in the feedstock mixture is less than about 1 wt %.

10. A process as in claim 1, wherein the Ramsbottom residue is less than about 0.8 wt %.

11. A process as in claim 1, further comprising determining the monoaromatic content of the product of the hydrocracking reaction.

12. A process as in claim 1, wherein the organic ligand is selected from the group consisting of benzene carboxylic acid, naphthalene carboxylic acid, methylbenzoic acid, ethyl phenyl acetic acid, and combinations thereof.

13. A process as in claim 1, wherein the plurality of organic ligands are non-aromatic and include a carbon ring of at least six members.

14. A process as in claim 1, wherein at least a portion of the catalyst complexes have the following structure:



wherein,
M is a group VIB metal, a group VIIIB metal, or a base transition metal;
L1 and L2 are ligand spacer groups with a first atom bonded to the aromatic group and a second atom bonded to the metal and providing a spacing of 2-6 atoms between the aromatic group and the metal;
R1-R10 are independently a hydrogen, an alkyl group, or a bond to a ligand spacer group bonded to another metal atom; and
X1-X4 are optional ligands bonded to the catalytic metal.

15. A process for upgrading cycle oil and increasing monoaromatic content, comprising:
providing a hydrocarbon feedstock that is predominantly cycle oil obtained from a fluidized catalytic cracker, wherein the cycle oil comprises polynuclear aromatic compounds;
providing a plurality of oil-soluble catalyst complexes, each catalyst complex comprising,
a catalytic metal including catalyst metal ions, each catalyst metal ion having valence electrons; and
a plurality of organic ligands bonded to the catalytic metal so that the valence electrons of at least a portion of the metal ions are all bonded to an organic ligand, each organic ligand comprising a carbon ring spaced apart from the catalytic metal by at least 1 atom;

blending the plurality of catalyst complexes with the hydrocarbon feedstock to form a feedstock mixture; and
hydrocracking the feedstock mixture in a reactor containing a catalyst and operating under hydrocracking conditions and in a manner so as to form a product having an increased monoaromatic content compared to the cycle oil, the catalyst in the reactor consisting essentially of the catalytic metal provided by the oil-soluble catalyst complexes.

16. A process as in claim 15, wherein the concentration of catalyst complexes in the feedstock mixture is in a range from about 1 ppm to about 1,000 ppm.

17. A process as in claim 15, wherein the catalytic metal is selected from the group consisting of group VIB metals, group VIIIB metals, and combinations thereof.

18. A process as in claim 15, wherein the content of monoaromatics in the feedstock mixture is increased by at least about 10 wt % during the hydrocracking reaction.

19. A process as in claim 15, further comprising determining the monoaromatic content of the product of the hydrocracking reaction.

20. A process for upgrading pyrolysis fuel oil and increasing monoaromatic content, comprising:
providing a hydrocarbon feedstock that is predominantly pyrolysis fuel oil obtained from a steam cracking process used to make olefins, wherein the pyrolysis fuel oil includes polynuclear aromatic compounds;
providing a plurality of oil-soluble catalyst complexes, each catalyst complex comprising,
a catalytic metal; and
a plurality of aromatic ligands bonded to the catalytic metal, each organic ligand comprising an aromatic ring spaced apart from the catalytic metal by at least 1 atom;

blending the plurality of catalyst complexes with the hydrocarbon feedstock to form a feedstock mixture; and
hydrocracking the feedstock mixture in a reactor containing a catalyst and operating under hydrocracking conditions and in a manner so as to form a product having increased monoaromatic content compared to the pyrolysis fuel oil, the catalyst in the reactor consisting essentially of the catalytic metal provided by the oil-soluble catalyst complexes.

21. A process as in claim 20, wherein the concentration of catalyst complexes in the feedstock mixture is in a range from about 1 ppm to about 1,000 ppm.

22. A process as in claim 20, wherein the catalytic metal is selected from the group consisting of group VIB metals, group VIIIB metals, base transition metals, and combinations thereof.

23. A process as in claim 20, wherein the content of monoaromatics in the feedstock mixture is increased by at least about 10 wt % during the hydrocracking reaction.

24. A process as in claim 20, further comprising determining the monoaromatic content of the product of the hydrocracking reaction.