WO2009011479A1

WO2009011479A1 - Process for manufacturing naphthenic base oils from effluences of fluidized catalytic cracking unit

Info

Publication number: WO2009011479A1
Application number: PCT/KR2007/005863
Authority: WO
Inventors: Chang Kuk Kim; Jee Sun Shin; Ju Hyun Lee; Sam Ryong Park; Gyung Rok Kim; Yoon Mang Hwang
Original assignee: SK Energy Co Ltd
Current assignee: SK Energy Co Ltd
Priority date: 2007-07-13
Filing date: 2007-11-21
Publication date: 2009-01-22
Anticipated expiration: 2010-01-13
Also published as: GB2463602A; GB201000082D0; JP2010533224A; CN101688131B; TWI457427B; TW200904961A; CN101688131A; US8691076B2; KR100841804B1; US20110005972A1; JP5439370B2; GB2463602B

Abstract

Disclosed is a method of manufacturing high-quality naphthenic base oil by subjecting, as a feedstock, light cycle oil (LCO) and slurry oil (SLO) obtained through fluidized catalytic cracking (FCC) to hydrotreating and dewaxing.

Description

[DESCRIPTION] [invention Title]

PROCESS FOR MANUFACTURING NAPHTHENIC BASE OILS FROM EFFLUENCES OF FLUIDIZED CATALYTIC CRACKING UNIT [Technical Field]

The present invention relates to a method of manufacturing naphthenic base oil from hydrocarbon oil fractions having high aromatic content and large amounts of impurities, and more particularly, to a method of manufacturing high-quality naphthenic base oil by subjecting, as a feedstock, light cycle oil (LCO) or slurry oil (SLO) obtained through fluidized catalytic cracking (FCC) to hydrotreating and dewaxing. [Background Art]

Naphthenic base oil is base oil that has a viscosity index of 85 or less and in which at least 30% of the carbon bonds of the base oil are of a naphthenic type, according to ASTM D- 2140. Recently, naphthenic base oil is widely used in various industrial fields, including transformer oil, insulation oil, refrigerator oil, oil for processing rubber and plastic, fundamental material of print ink or grease, and base oil of metal processing oil.

Most conventional methods of manufacturing naphthenic base oil are conducted in such a manner that naphthenic crude oil having a high naphthene content (naphthene content: 30-40%), serving as a feedstock, is passed through a vacuum distillation unit to thus separate a paraffinic component and then through extraction and/or hydrogenation units to thus separate an aromatic component and/or convert it into naphthene, after which impurities are removed.

However, these methods are problematic in that the essential use of the naphthenic crude oil, having a high naphthene content, as the feedstock encounters a limitation in the supply thereof, and furthermore, the extraction procedure for extracting the aromatic component must be conducted, undesirably decreasing the total product yield and deteriorating the quality of the product.

International Patent No. WO 2004/094565 discloses a method of manufacturing naphthenic base oil by subjecting mixed effluents of various processes, serving as a feedstock, to hydrofindng to thus obtain an oil fraction, which is then stripped to separate only an oil fraction having a boiling point within a predetermined range, and then dewaxing the separated oil fraction. However, the above method is disadvantageous because, among the effluents of the hydrofining process, only a middle oil fraction, excluding a light oil fraction and a heavy bottom oil fraction, is used to produce the naphthenic base oil, undesirably decreasing the total product yield. Further, because the effect of the hydrofining process for removing impurities is not high, sulfur is contained in a large amount in the middle oil fraction, separated through stripping, undesirably remarkably reducing the activity and selectivity of a catalyst used for a subsequent dewaxing process.

[Disclosure] [Technical Problem]

Accordingly, the present invention provides a method of manufacturing naphthenic base oil, which includes hydrotreating and dewaxing an inexpensive hydrocarbon feedstock having a high aromatic content and large amounts of impurities, in particular, an effluent of an FCC process, for example, LCO or SLO, under extreme conditions, thereby producing expensive naphthenic base oil at high yield while minimizing the loss and removal of the oil fraction. [Technical Solution]

According to the present invention, a method of manufacturing a naphthenic base oil from an oil fraction of fluidized catalytic cracking may include (a) separating a light cycle oil and a slurry oil from an oil fraction obtained through fluidized catalytic cracking of petroleum hydrocarbon; (b) hydrotreating the light cycle oil, the slurry oil, or a mixture thereof, separated in the (a), under conditions of temperature of 280~430°C, pressure of 30-200 kg/cm², liquid hourly space velocity (LHSV) of 0.2-3 hr^"1 and a volume ratio of hydrogen to the fed oil fraction of 800-2500 NmVm³ in the presence of a hydrotreating catalyst; (c) dewaxing the hydrotreated oil fraction obtained in the (b), under conditions of temperature of 280~430°C, pressure of 30-200 kg/cm², liquid hourly space velocity (LHSV) of 0.2-3 hr^"1 and a volume ratio of hydrogen to the fed oil fraction of 300-1500 Nm³An³ in the presence of a dewaxing catalyst; and (d) separating the dewaxed oil fraction obtained in the (c) according to a range of viscosity, all of which are conducted sequentially.

[Advantageous Effects] In the present invention, LCO and/or SLO, obtained through an FCC process, which are inexpensive products having high aromatic content and large amounts of impurities, are used to produce high-quality naphthenic base oil, thereby considerably mitigating the limitation of a feedstock to thus improve economic efficiency and facilitating the manufacture of products having excellent performance at high yield. According to the present invention, hydrotreating is conducted under extreme conditions, thus remarkably diminishing the level of impurities, by which isomerization actively occurs in a subsequent dewaxing process, thereby enabling the production of high-quality products at high yield.

[Description of Drawings] FIG. 1 is a schematic view illustrating the process of manufacturing naphthenic base oil, according to the present invention.

<Description of the Reference Numerals in the Drawing> FCC: fluidized catalytic cracking Rl : hydrotreating R2: dewaxing Vl, V2: vacuum distillation [Best Mode]

Hereinafter, a detailed description will be given of the present invention. According to the present invention, as illustrated in FIG. 1, the manufacturing process 5 includes subjecting light cycle oil (LCO) and slurry oil (SLO), obtained through fluidized catalytic cracking (FCC) of petroleum hydrocarbons, to hydrotreating Rl, subjecting the hydrotreated oil fraction to dewaxing R2, and separating the dewaxed oil fraction according to the range of viscosity using a separation unit V2.

The method of manufacturing the naphthenic base oil according to the present 0 invention is characterized in that the naphthenic base oil is produced from the LCO or SLO having a high aromatic content and large amounts of impurities, which is separated from an effluent of FCC of petroleum hydrocarbons.

The LCO or SLO used in the present invention is obtained through the FCC process.

The FCC (Fluidized Catalytic Cracking) process is a technique for producing a light petroleum5 product by subjecting an atmospheric residue feedstock to FCC under temperature/pressure conditions of 500~700°C and 1-3 atm. Such an FCC process enables the production of a volatile oil fraction, as a main product, and propylene, heavy cracked naphtha (HCN), LCO, and SLO, as by-products. Among the products thus obtained, the LCO or SLO, but not the light oil fraction, is separated using a separation tower. Because this oil has a high O concentration of impurities and large amounts of heteroatom species and aromatic material, it is difficult to use as a light oil fraction, which is a highly valued product, and is mainly used for high-sulfur light oil products or inexpensive heavy fuel oils.

In the method according to the present invention, as illustrated in FIG. 1, atmospheric residue (AR) is introduced to the FCC process, to thus obtain the LCO or SLO, which is then 5 used as a feedstock to manufacture high-quality naphthenic lube base oil. As the feedstock of the method according to the present invention, the LCO and the SLO may be used alone, or may also be used mixed at a predetermined ratio.

As shown in FIG. 1, the SLO used in the present invention may be subjected to vacuum distillation Vl before being subjected to hydrotreating Rl. Then, light slurry oil (Lt- SLO) having a boiling point of 36O-480°C, separated through vacuum distillation Vl, may be subjected alone to hydrotreating Rl, or alternatively, may be supplied in the form of a mixture with LCO.

Useful as the feedstock in the present invention, the LCO, the SLO, the Lt-SLO separated through vacuum distillation, and mixture oil of LCO and part or all of SLO or Lt- SLO, mixed at equivalent volume ratios, are summarized in terms of their properties in Table 1 below.

TABLE l

Note: MAH: mono-aromatic hydrocarbon DAH: di-aromatic hydrocarbon PAH: poly-aromatic hydrocarbon TAH: total aromatic hydrocarbon As is apparent from Table 1, the LCO and the SLO used for the production of naphthenic base oil according to the present invention, having a sulfur content of 5000 ppm or more, a nitrogen content of 1000 ppm or more, and a total aromatic content of 60 wt% or more, can be seen to have impurity content and aromatic content much higher than general naphthenic crude oil, which contains about 0.1-0.15 wt% sulfur, about 500-1000 ppm nitrogen, and 10-20 wt% aromatics.

Because the LCO or SLO, serving as the feedstock, contains large amounts of aromatics and impurities, sulfur, nitrogen, oxygen, and metal components contained in the feedstock are removed through hydrotreating Rl, and the contained aromatic component is converted into a naphthenic component through hydrogen saturation.

In the method of manufacturing the naphthenic base oil according to the present invention, the hydrotreating Rl is conducted under conditions of temperature of 280~430°C, pressure of 30-200 kg/cm², LHSV (Liquid Hourly Space Velocity) of 0.2-3 hr^"1 and a volume ratio of hydrogen to feedstock of 800-2500 Nm³/m³. By supplying a large amount of hydrogen and applying extreme conditions of temperature and pressure, the amounts of aromatics and impurities contained in the feedstock may be drastically decreased. In the present invention, in particular, the volume ratio of hydrogen to feedstock plays an important role. In the hydrotreating process according to the present invention, the partial pressure of hydrogen is maintained very high, which is essential for maintaining the performance of the hydrotreating catalyst in terms of the following two points. First, the concentration of hydrogen is increased, thereby increasing the activity of the catalyst to thus raise the hydrotreating rate. Second, the production of a derivative forming coke on the surface of the activated catalyst is inhibited, thereby decreasing the formation of the coke. This helps decrease the rate of fouling of the catalyst. In the present process, in order to prevent the decrease of the activity of the catalyst and maximize the reactivity and the yield, the preferable volume ratio of hydrogen (H₂/oil) is set to 1000-2000 Nm³An³.

The hydrotreating catalyst used in the hydrotreating process is preferably composed of metals of Groups 6 and 8 to 10 in the periodic table, and more preferably contains one or more selected from among CoMo, NiMo, and a combination of CoMo and NiMo. However, the hydrotreating catalyst used in the present invention is not limited thereto, and any hydrotreating catalyst may be used so long as it is effective for hydrogen saturation and the removal of impurities.

The hydrotreated oil fraction has impurities and aromatics in drastically decreased amounts. In the method according to the present invention, the hydrotreated oil fraction has a sulfur content of less than 300 ppm, a nitrogen content of less than 50 ppm, and an aromatic content of less than 80 wt%. In particular, the amount of poly-aromatic hydrocarbon is decreased so that it is not more than 10%.

In the method according to the present invention, the oil fraction, subjected to hydrotreating Rl, has impurities at very low levels and low poly-aromatic hydrocarbon content, thereby maximally preventing a precious metal-based dewaxing catalyst for a subsequent dewaxing process from being inactivated by impurity poisoning.

In the case where the hydrotreating process is performed under optimal conditions mentioned above, the hydrotreated oil fraction, from which only the gaseous component is removed, is wholly subjected to dewaxing R2, without the need to additionally separate or remove a light oil fraction or a bottom oil fraction therefrom.

The catalytic dewaxing process R2 according to the present invention is largely divided into dewaxing, including selective cracking or isomerization of a paraffinic oil fraction, and hydrofinishing. In the course of dewaxing using isomerization, isomerization occurs more actively because the amount of impurities, such as sulfur and nitrogen, is drastically decreased through upstream deep hydrotreating. Thereby, high-quality naphthenic base oil, in which a naphthenic component is enriched and from which considerable amounts of impurities are removed, is produced at high yield.

More specifically, the dewaxing process R2 is conducted under conditions of temperature of 280-430°C, pressure of 30-200 kg/cm², LHSV of 0.2-3 hr^"1, and a volume ratio of hydrogen to feedstock of 300-1500 NmV.

The dewaxing catalyst used for the dewaxing process R2 preferably contains one or more selected from among precious metals of Group 9 or 10 in the periodic table, and more preferably one or more selected from among Pt, Pd and a combination of Pt and Pd. However, the dewaxing catalyst used in the present invention is not limited thereto, and any dewaxing catalyst may be used without limitation as long as it is effective for dewaxing through selective cracking or isomerization.

In the method of manufacturing the naphthenic base oil according to the present invention, the oil fraction, subjected to dewaxing R2, contains sulfur in an amount of 100 ppm or less and naphthene in an amount of 35 wt% or more. Although the oil fraction subjected to dewaxing R2 may be used as naphthenic base oil without change, in the present invention, in consideration of various end uses of the naphthenic base oil, it may be separated into a plurality of base oils having viscosity ranges suitable for respective end uses. To this end, separation V2 of the dewaxed oil fraction is conducted. For example, the separation V2 enables the dewaxed oil fraction to be separated into naphthenic base oils having kinetic viscosities at 40°C of 3-5 cSt, 8-10 cSt, 43-57 cSt, 90-120 cSt, and at least 200 cSt.

The process for separating the dewaxed oil fraction may be performed using a known separation unit that is suitable for the above separation conditions. Examples of such a separation unit include an atmospheric distillation tower or a vacuum distillation tower. Particularly useful is the vacuum distillation tower. [Mode for Invention]

A better understanding of the present invention may be obtained through the following examples, which are set forth to illustrate, but are not to be construed as the limit of the present invention. Example 1

Production of Naphthenic Base Oil from Light Cycle Oil

A light cycle oil (LCO) fraction having a boiling point of 310-380⁰C was separated through FCC and was then supplied to a hydrotreating reactor.

The hydrotreating was conducted using a combination catalyst of cobalt-molybdenum and nickel-molybdenum as a hydrotreating catalyst, under conditions of LHSV of 0.5~2.0 hr^" , a volume ratio of hydrogen to feedstock of 1000-2000 Nm /m , pressure of 120-160 kg/cm , and temperature of 300~400°C.

After the hydrotreating process, the resultant middle oil fraction had a sulfur content of less than 100 ppm, a nitrogen content of less than 20 ppm, and an aromatic content of less than 70 wt%, and preferably a sulfur content of less than 40 ppm, a nitrogen content of less than 10 ppm, and an aromatic content of less than 66 wt%.

For a subsequent dewaxing process, an isomerization dewaxing catalyst and a hydrofinishing catalyst, composed of (Pt/Pd)/zeolite/alumina, which is commercially available, were used, and the dewaxing was conducted under conditions of LHSV of 0.5-2.0 hr^"1, a volume ratio of hydrogen to feedstock of 400-1000 NmV, and pressure of 120-160 kg/cm². For this, the reaction temperature was set to 300~350°C for isomerization dewaxing and 210-300⁰C for hydrofinishing.

Table 2 below shows the properties of the feedstock (LCO) of the present example and of the naphthenic base oil (product) obtained therefrom using hydrotreating and dewaxing. As is apparent from Table 2, through the method according to the present invention, high- quality naphthenic base oil, having a naphthene content of about 63.5%, kinetic viscosity of about 8.89 cSt at 4O⁰C, and sulfur and nitrogen content and aromatic content much lower than those of the feedstock, and in which a naphthene component was enriched, was produced.

TABLE 2

Example 2

Production of Naphthenic Base Oil from Light Slurry Oil

Slurry oil (SLO) having a boiling point of 345⁰C or higher, obtained through FCC, was separated into a light oil fraction, a middle oil fraction, and a bottom oil fraction using a vacuum distillation unit (VDU). The light oil fraction or the middle oil fraction, but not the bottom oil fraction, was supplied to a hydrotreating reactor. In the present example, naphthenic base oil was manufactured using, as a feedstock, the light oil fraction having a boiling point of 360~480°C.

The hydrotreating was conducted using a combination catalyst of nickel-molybdenum, available from Nippon Ketjen, under conditions of LHSV of 0.5-2.0 hr^"1, a volume ratio of hydrogen to feedstock of 1500-2000 NmV³, pressure of 140-200 kg/cm², and temperature of 330~400°C.

After the hydrotreating process, the resultant middle oil fraction had a sulfur content of less than 110 ppm and poly-aromatic hydrocarbon in an amount of 10 wt% or less. Subsequently, dewaxing was conducted using an isomerization dewaxing catalyst and a hydrofinishing catalyst, composed of (Pt/Pd)/zeolite/alumina, which is commercially available, under conditions of LHSV of 0.5-2.0 hf ', a volume ratio of hydrogen to feedstock of 400-1000 Nm³W, and reaction pressure of 140-160 kg/cm². For this, the reaction temperature was set to 300~370°C for isomerization dewaxing and 210~300°C for hydrofinishing.

Table 3 below shows the properties of the light slurry oil (Lt-SLO) used as the feedstock and the product (after CDW). The sulfur content and the nitrogen content in the product were drastically decreased compared to those in the feedstock, and, in the product, the naphthene content was about 56%, and kinetic viscosity at 40⁰C was about 45.5 cSt.

TABLE 3

Example 3

Production of Naphthenic Base Oil from Mixture of Light Cycle Oil and Light Slurry Oil

The LCO, separated through the FCC in Example 1, and the Lt-SLO, separated using the VDU in Example 2, were mixed at the same volume ratio and used as a feedstock in that state.

Hydrotreating was conducted using a combination catalyst of nickel-molybdenum, available from Nippon Ketjen, under conditions of LHSV of 0.5-2.0 hr^~l, a volume ratio of hydrogen to feedstock of 1300-2000 NmV, pressure of 130-190 kg/cm², and temperature of 340~400°C.

After the hydrotreating process, the resultant middle oil fraction had a sulfur content of less than 40 ppm.

Subsequently, dewaxing was conducted using an isomerization dewaxing catalyst and a hydrofinishing catalyst, composed of (Pt/Pd)/zeolite/alumina, which is commercially available, under conditions of LHSV of 0.5— 2.0 hr^" , a volume ratio of hydrogen to feedstock of 400-1000 NmVm³, and reaction pressure of 130-160 kg/cm². For this, the reaction temperature was set to 300~370°C for isomerization dewaxing and 210~300°C for hydrofinishing.

Table 4 below shows the properties of the feedstock and the product (after CDW). In the present example, the final oil fraction could be used as naphthenic base oil without change, but was separated into four naphthenic base oils having kinetic viscosities at 40°C of 3-5 cSt, 8-10 cSt, 43-57 cSt, and at least 200 cSt, in order to be adapted to various end uses of the naphthenic base oil. The sulfur content and the nitrogen content in the product were drastically decreased compared to those in the feedstock, and high-quality naphthenic base oil products having naphthene in an amount of about 55% or higher were manufactured.

TABLE 4

Example 4

Production of Naphthenic Base Oil from Slurry Oil

Naphthenic base oil was manufactured using SLO having a boiling point of 345°C or higher, obtained through FCC, as a feedstock. Hydrotreating was conducted using a combination catalyst of nickel-molybdenum, available from Nippon Ketjen, under conditions of LHSV of 0.5-2.0 hr^"1, a volume ratio of

1 ¹X 0 hydrogen to feedstock of 1500-2000 Nm /m , pressure of 150-200 kg/cm , and temperature of 350~400°C.

After the hydrotreating process, the resultant middle oil fraction had a sulfur content of less than 110 ppm and poly-aromatic hydrocarbon in an amount of 10 wt% or less.

Subsequently, dewaxing was conducted using an isomerization dewaxing catalyst and a hydrofmishing catalyst, composed of (Pt/Pd)/zeolite/alumina, which is commercially available, under conditions of LHSV of 0.5-2.0 hr^"1, a volume ratio of hydrogen to feedstock of 400-1000 Nm /m , and reaction pressure of 140-160 kg/cm . For this, the reaction temperature was set to 320~370°C for isomerization dewaxing and 210~300°C for hydrofinishing.

Table 5 below shows the properties of the slurry oil (SLO) as the feedstock and the naphthenic base oil as the product (after CDW). In the present example, the sulfur content and the nitrogen content in the product were drastically decreased compared to those in the feedstock, and, in the product, the naphthene content was about 52% and the kinetic viscosity at

40°C was about 110 cSt.

TABLE 5

Claims

[CLAIMS] [Claim 1 ]

A method of manufacturing naphthenic base oil from an oil fraction of fluidized catalytic cracking, comprising: (a) separating a light cycle oil and a slurry oil from an oil fraction obtained through fluidized catalytic cracking of petroleum hydrocarbon;

(b) hydrotreating the light cycle oil, the slurry oil, or a mixture thereof, separated in the (a), under conditions of temperature of 280~430°C, pressure of 30-200 kg/cm , liquid hourly space velocity (LHSV) of 0.2-3 hr^"1 and a volume ratio of hydrogen to the fed oil fraction of 800-2500 NmV in presence of a hydrotreating catalyst;

(c) dewaxing a hydrotreated oil fraction, obtained in the (b), under conditions of temperature of 280~430°C, pressure of 30-200 kg/cm², liquid hourly space velocity (LHSV) of 0.

2-3 hr^"1 and a volume ratio of hydrogen to the fed oil fraction of 300-1500 NmV in presence of a dewaxing catalyst; and (d) separating a dewaxed oil fraction, obtained in the (c), according to a range of viscosity, all of which are conducted sequentially. [Claim 2]

The method according to claim 1, wherein the slurry oil used for the hydrotreating of the (b) is light slurry oil having a boiling point of 360~480°C, obtained by subjecting the slurry oil, obtained through the fluidized catalytic cracking, to vacuum distillation.

[Claim 3]

The method according to claim 1, wherein the hydrotreating catalyst contains one or more selected from among metals of Groups 6 and 8 to 10 in a periodic table.

[Claim 4] The method according to claim 1 , wherein the dewaxing catalyst contains one or more selected from among precious metals of Group 9 or 10 in a periodic table.

[Claim 5]

The method according to claim 1, wherein each of the light cycle oil and the slurry oil has a sulfur content equal to or greater than 5000 ppm, a nitrogen content equal to or greater than 1000 ppm, and an aromatic content equal to or greater than 60 wt%.

[Claim 6]

The method according to claim 1, wherein the (d) is conducted using a vacuum distillation tower.

[Claim 7] The method according to claim 1, wherein the (d) enables the oil fraction to be separated into naphthenic base oils having kinetic viscosities at 4O⁰C of 3-5 cSt, 8-10 cSt, 43-57 cSt, 90-120 cSt, and at least 200 cSt. [Claim 8]

The method according to any one of claims 1 to 7, wherein the naphthenic base oil has a sulfur content less than or equal to 100 ppm and a naphthene content equal to or greater than 35 wt%.