JP2002503754A - Improvement method of low temperature performance of base oil using combination catalyst system - Google Patents

Abstract

  (57) [Summary] A metal hydrogenation component is provided on a carrier containing a first dewaxing component selected from 10- and 12-membered molecular sieves and a mixture thereof and a second isomerization component that is an amorphous inorganic oxide. The waxy feed is converted to a base oil using an integrated mixed powder pellet catalyst. The first and second components are present in a ratio sufficient to promote wax isomerization and naphthene decomposition without causing a substantial reduction in VI.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to a crude wax, a crude wax isomer, a Fischer-Tropsch wax, a Fischer-Tropsch hydroisomer, a waxy raffinate, a waxy wax to produce a lubricating base oil or a lubricating oil blending stock. The present invention relates to hydrodewaxing a waxy raw material such as a distillate. More particularly, the present invention relates to a mixed catalyst capable of promoting wax isomerization and naphthene cracking to form a lubricating base oil with minimal VI reduction and good low temperature properties. For the conversion of waxy feedstocks.

BACKGROUND OF THE INVENTION Performance criteria for lubricants such as those used in automatic transmission oils and passenger car engine oils have become increasingly stringent, and consequently users have better anti-wear, improved volatility. A need has arisen for a base oil with good properties and low temperature properties.

[0003] Waxy feedstocks can be converted to liquid products using well-known catalytic dewaxing catalysts. However, in this case, the selective degradation of paraffins typically results in an undesirable decrease in viscosity index (VI).

[0004] In contrast, isomerization of waxy feeds using a molecular sieve based catalyst having a linear 1D pore structure provides a lubricating base oil without a reduction in VI. . This isomerization process offers greater benefits than catalytic dewaxing, but nevertheless, to obtain a lubricating base oil having good low temperature properties without significant reduction in VI, There is a need for other improved methods for effecting feedstock conversion.

SUMMARY OF THE INVENTION The present invention is directed to a process for hydrodewaxing a feedstock to produce a lubricating base oil having improved low temperature properties. The method comprises contacting the feedstock under hydrodewaxing conditions with an integrated mixed powder pellet catalyst, the catalyst comprising:
A metal hydrogenation component on a carrier containing a first dewaxing component selected from 10- and 12-membered molecular sieves and a mixture thereof and a second isomerization component that is an amorphous inorganic oxide, Wherein the first and second components of 1,1-dimethylcyclopentane, 1,2-dimethylcyclopentane,
When evaluating the conversion of methylcyclohexane to 3-dimethylcyclopentane and ethylcyclopentane, the catalyst was found to have a trans-1,2-dimethylcyclopentane / trans-1,3-dimethylcyclopentane ratio of at least 1, and At least about 5 selectivity to ethylcyclopentane at 10% conversion
It is present in a ratio that gives 0%.

[0006] This and other embodiments of the invention are described below.

DESCRIPTION OF THE INVENTION [0007] Feedstocks suitable for carrying out the present invention include crude wax, crude wax isomers, Fischer-Tropsch wax, Fischer-Tropsch hydroisomer, waxy raffinates, waxy distillates and the like. Wax-containing hydrocarbon oils. Typically, such a feedstock will have a wax content of 15% or more. Preferred feedstocks will each have a nitrogen and oxygen content of less than about 20 wppm by weight. In practice, if the feedstock contains higher amounts of sulfur and nitrogen, first hydrotreat the feedstock under typical hydroprocessing conditions to reduce the sulfur and nitrogen content. be able to. Conventional hydrogenation catalysts such as alumina supported on Ni / Mo, alumina supported on Ni / W, and alumina supported on Co / Mo can be used. In other words, groups VIB to VIII
Any of the metal oxide refractory supports loaded with a group of metals and their mixtures [the metal groups referred to here and hereinafter refer to these metals in the Periodic Table of the Elements (Sargent-Welch Scientific Co.)] May be. Examples of commercially available products of such a catalyst include HDN-30 and KF-840.

[0008] The hydrotreating is carried out by using 20 ppm or less of nitrogen or 20 ppm or less of sulfur, particularly 1 ppm or less.
It is done to reduce the sulfur and nitrogen content to a level of less than 0 ppm nitrogen and less than 10 ppm sulfur, most preferably less than 5 ppm nitrogen and less than 5 ppm sulfur.

[0009] Wax-containing feedstocks obtained from natural petroleum resources contain various amounts of sulfur and nitrogen compounds, which are known to deactivate the wax hydroisomerization catalyst. . To prevent this deactivation, the feedstock should contain no more than 10 ppm of sulfur, preferably less than 2 ppm, and no more than 2 ppm of nitrogen, preferably 1 ppm.
It preferably contains less than nitrogen.

Preferably, the feedstock is hydrotreated to reduce the sulfur and nitrogen content so that it falls within these limits.

[0011] The hydrogenation treatment is performed on Ni / Mo supported alumina, Co / Mo supported alumina, Co / N
Any typical hydroprocessing catalyst such as i / Mo supported alumina, for example, KF-
840, KF-843, HDN-30, HDN-60, Criteria (Crit
eria) It can be carried out using C-411 or the like. Similarly, bulk catalysts containing sulfides of Ni / Mn / Mo or Cr / Ni / Mo as described in U.S. Patent No. 5,122,258 can be used.

The hydrotreating is performed at a temperature of 280 ° C. to 400 ° C., preferably 340 ° C. to 380 ° C., a pressure of 500 to 3000 psig (3.55 to 20.8 mPa),
Hydrogen feed gas amount ^{500~5000SCF / bbl (89~890m 3 / m} 3)
And the flow rate is in the range of 0.1-5 LHSV, preferably 1-2 LHSV.

The hydrotreated waxy oil is stripped to remove ammonia and H ₂ S and then subjected to the hydrodewaxing process of the present invention.

The catalyst used in the hydrodewaxing of the waxy feed according to the present invention is an integrated mixed powder pellet catalyst. As used herein and in the claims, the term "integral" means that each pellet was made as follows. That is, the powdered first catalyst component and the powdered second catalyst component are mixed together, and the mixture is further pelletized such that each pellet contains all of the aforementioned powder components. .

[0015] The preparation of the monolithic catalyst is based on the individually finished catalysts as starting materials, grinding these individually finished catalysts into powders, mixing the powdered materials together to homogeneity, By compressing / extruding and pelletizing to produce a monolithic pellet catalyst comprising a mixture of individual and distinct catalyst components. Grinding and pulverization are performed until a achievable uniformity is obtained using conventional pulverizing means such as a mortar and pestle.

[0016] The catalyst used in the process of the present invention includes a metal hydrogenation component supported on a two-component carrier. The metal hydrogenation component is at least one of a Group VIB or Group VIII metal, preferably a Group VIII metal, more preferably Pt or Pd. The metal is dispersed on one of the first and second components of the support, preferably on both components. Typically, the metal will be present in an amount of about 0.1 to about 30% by weight, preferably about 0.1 to about 10% by weight. If the metal is a Group VIII noble metal, the preferred amount is from 0.1 to 5% by weight. The catalyst may also include a substantially inert binder or matrix material.

[0017] The first component is a catalytic dewaxing component that includes crystalline 10- and 12-membered molecular sieves. Crystalline molecular sieves include metallosilicates and metallophosphates, such as aluminosilicates, aluminophosphates, and silicoaluminophosphates. Examples of the crystalline aluminosilicate include ZSM-5 and ZSM-1.
1, ZSM-12, Theta-1 (ZSM-22), ZSM-23, ZSM-35
, ZSM-48, natural and synthetic ferrierite, ZSM-57, beta mordenite, offretite and other zeolites. Examples of the crystalline aluminophosphate and the crystalline silicoaluminophosphate include SAPO-11 and SAP.
O-41, SAPO-31, MAPO-11, and MAPO-31. Preferred are ZSM-5, ZSM-22, ZSM-23, ferrierite, and SAPO-11.

The second isomerization component may be any of the typical isomerization catalysts. Such isomerization catalysts comprise Group VIB, VIIB, VIII metals and mixtures thereof, preferably a Group VIII metal, more preferably a Group VIII noble metal, most preferably Pt or Pd. Includes a refractory metal oxide carrier substrate (eg, alumina, silica-alumina, zirconia, titanium, etc.) supporting a catalytically active metal selected from the group, and optionally halogen, phosphorus, boria, yttria, rare earth oxide (Eg, oxides derived from La, Ce, etc.), magnesia and the like, preferably halogen, yttria, or magnesia, most preferably a catalyst containing fluorine as a promoter or dopant. The amount of the catalytically active metal is 0.1 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0 to 5% by weight.
. It is in the range of 1-2% by weight, most preferably 0.1-1% by weight. Co-catalysts and dopants are used to control the acidity of the isomerization catalyst. Thus, in the case of isomerization catalysts utilizing a substrate such as alumina, the addition of halogen, preferably fluorine, imparts acidity to the resulting catalyst. When a halogen, preferably fluorine, is used, its abundance is 0.1 to 10% by weight, preferably 0.1 to 3% by weight, more preferably 0.1 to 2% by weight, most preferably 0.5 to 2% by weight. １．５1.5% by weight. Similarly, if silica-alumina is used as the substrate, either by adjusting the silica to alumina ratio, or in U.S. Pat. No. 5,254,518 (Sol
ed, McVicker, Gates, Miseo), yttria, rare earth oxides that reduce the acidity of silica-alumina substrates (e.g.,
Acidity can be controlled by adding dopants such as oxides derived from La, Ce, etc.), boria, or magnesia.

[0019] The first and second components are combined in a ratio sufficient to promote wax isomerization and naphthene decomposition without substantially reducing VI. The ratio of zeolite to amorphous inorganic oxide of the catalyst according to the invention is between about 1: 1 and 1:20 on a weight basis.
Which is determined by the MCH test described below.

One method for determining the appropriate ratio of the first component to the second component in the catalyst is about 0.5 weight for the conversion of methylcyclohexane (MCH) to various cyclopentane compounds. % Based on the evaluation of a combination component containing Pt. Trans-1,2-dimethylcyclopentane versus t at 320 ° C.
The ratio of trans-1,3-dimethylcyclopentane (trans-1,2-DMC
(P / trans-1,3-DMCP) is at least 1 in the range of VI
Has been found to promote isomerization of the wax in the feedstock and decomposition of the naphthenes without substantial reduction of

The second factor is the use of a catalyst impregnated with about 0.5% by weight of Pt to convert methylcyclohexane (MCH) to various cyclopentane compounds at a conversion of 10%.
), The result is that the selectivity to ethylcyclopentane (ECP) formation is at least greater than 50%.

This technique is further described below. The reaction of MCH to various cyclopentane products when using a catalyst is shown in FIG. As shown in FIG.
Decomposition products include ethylcyclopentane, cis- and trans-1,2-
Includes dimethylcyclopentane, cis- and trans-1,3-dimethylcyclopentane, and 1,1-dimethylcyclopentane. This technique, also known as the MCH test, is used to define the acid point concentration, strength, and active site constraint relative to the catalyst of the present invention.

The important factors are summarized as follows. (1) The total conversion of MCH for a given catalyst weight at 320 ° C. is an indicator of the relative number of acid sites. (2) Conversion 10
% Selectivity for ECP is a measure of relative acid strength and is a measure of EC
A large value of the P selectivity means that the acid strength is small, and a small value of the ECP selectivity means that the acid strength is large. (3) trans-1,2-
The ratio of DMCP to trans-1,3-DMCP is associated with the degree of constraint at the active site of the catalyst, with a large ratio (> 1) meaning little or no physical constraint at the active site, Is small (<1) means that a physical constraint exists in the active site.

In the process of the present invention, to produce a catalyst exhibiting improved low temperature properties, trans- is mainly controlled by controlling the acid strength of the amorphous isomerization component.
Adjust the ratio of 1,2-DMCP to trans-1,3-DMCP from 1: 1 to 2: 1. It is preferable to use an amorphous component having a higher acid strength such as silica-alumina.

Conversely, catalysts that exhibit high yields are made by reducing the acid strength of the amorphous phase. In this case, it is preferable to use an amorphous component having a lower acid strength such as alumina. Another way to make such catalysts is to use the integrated catalyst trans-1,2-DMCP versus trans-1,3-DMC.
This is a method of changing the ratio of the microporous component to the amorphous component so that the ratio of CP is less than 1.

[0026] The hydrodewaxing process utilizing the catalyst of the present invention is carried out at a temperature of about 200 ° C to 400 ° C, preferably 250 ° C to 380 ° C, most preferably 300 ° C to 350 ° C,
0-5,000 psig (3.55-34.6 mPa), preferably 1,000
~ 2,000 psig (7.0-13.9 mPa) pressure, 500-10,000
^{_{0SCF H 2 / B (89~1,780m 3}} / m 3), preferably 2,000 to
^{_{5,000SCF H 2 / B (356~890m 3}} / m 3) hydrogen gas feed ratio,
And an LHSV of 0.5-5 v / v / hr, preferably 1-2 v / v / hr.

In another embodiment of the present invention, the feedstock is first subjected to a solvent dewaxing process such that the pour point is below about + 10 ° C.

Examples of the dewaxing solvent used include C ₃ -C ₆ ketones (eg, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), a mixture of MEK and MIBK), aromatic hydrocarbons (eg, toluene), Mixtures of ketones and aromatics (eg, MEK / toluene), ethers (eg, methyl t-butyl ether), and mixtures of ethers with ketones or aromatics are included. Similarly, liquefied versions of normally gaseous hydrocarbons such as propane, propylene, butane, butylene, and combinations thereof can be used as solvents. The solvent used will preferably be an equal volume mixture of methyl ethyl ketone and methyl isobutyl ketone. Typically, the ratio of isomerate to solvent will range from 1 to 10, and will preferably be about 1: 3. The dewaxed feedstock is then subjected to the hydrodewaxing process described above.

The present invention will be described with reference to the following examples, but the present invention is not limited to these examples.

Examples Comparative Example 1 Using a catalyst (B) containing 0.5% by weight of Pt ZSM-5 (silica / alumina ratio 220: 1) + alumina at a weight ratio of 25:75, the following properties were obtained: The dewaxing experiment of the hydrocracking distillate having the following was performed twice. KV at 100 ° C, cSt 3.808 KV at 135 ° C, cSt 2.28 Pour point, ° C 39 Boiling range (GCD) 325-503 ° C The dewaxing conditions used are listed in the accompanying table. The results are shown in column B of the table described after Example 2.

Screening for activity and selectivity using methylcyclohexane showed that the catalyst had an ECP selectivity of 40, as shown in the table,
The ratio of trans-1,2-dimethylcyclopentane / trans-1,3-dimethylcyclopentane was 0.02. The low temperature properties of the product, expressed as Brookfield viscosity at -40 ° C (with the addition of a standard Ford type ATF additive pack), are also shown in the table. By performing catalytic dewaxing, the Brookfield viscosity is lower than for solvent dewaxed products. However, the Brookfield viscosity of both the solvent dewaxed product and the catalytic dewaxed product is very poor.

Comparative Example 2 0.5 wt% Pt ZSM-5 (silica / alumina ratio 220: 1) + silica−
The hydrocracking distillate having the properties described in Comparative Example 1 was dewaxed using the catalyst (C) containing alumina in a weight ratio of 50:50. This catalyst is a powder ZSM-
5 (Si / Al ratio 110) was mixed with the powder amorphous component at a weight ratio of 50:50, and platinum was supported by an initial wet method using platinum dichloride tetraamine.

Screening for activity and selectivity using methylcyclohexane revealed the ECP of this catalyst as shown in the table following Example 2.
The selectivity is 47, trans-1,2-dimethylcyclopentane / tran
The s-1,3-dimethylcyclopentane ratio was 0.82. As can be seen from a comparison of columns A and C in the table, the VI of the resulting liquid product (350 ° C. +) was smaller than the VI obtained by solvent dewaxing. The low temperature properties of the product, expressed as Brookfield viscosity at -40 ° C (with the addition of a standard Ford type ATF additive pack), are also shown in the table. By performing the catalytic dewaxing, the Brookfield viscosity is lower than that of the solvent dewaxed product, but the value is not much different from the value obtained using the alumina-supported catalyst of Example 1. Is also big.

Example 1 0.5 wt% Pt ZSM-5 (silica / alumina ratio 220: 1) + silica-
The hydrocracking distillate having the properties described in Comparative Example 1 was dewaxed using the catalyst (D) containing alumina at a weight ratio of 10:90. This catalyst is a powder ZSM-
5 (Si / Al ratio 110) was mixed with the powdered amorphous component at a weight ratio of 10:90, respectively, and platinum was supported by an incipient wetness method using platinum dichloride tetraamine.

Screening for activity and selectivity using methylcyclohexane revealed the ECP of this catalyst as shown in the table following Example 2.
The selectivity is 50 and trans-1,2-dimethylcyclopentane / tran
The s-1,3-dimethylcyclopentane ratio was 1.80. All of these values satisfy the requirements for the catalyst of the present invention. As can be seen from a comparison of columns A and D of Table 1, the VI of the resulting liquid product (350 ° C +) was greater than the VI obtained by solvent dewaxing. The low temperature properties of the product expressed as Brookfield viscosity at -40 ° C (with the addition of the standard ECA / ATF additive pack) are also shown in the table. By performing catalytic dewaxing with this catalyst, the Brookfield viscosity is lower than for the solvent dewaxed products described in Table 1.

Example 2 Pt-loaded theta-1 (TON) / silica core with a weight ratio of 25:75 by weight 0.5%
Lumina (Catalyst E) and Theta-1 (TON) / Al carrying 0.5% by weight of Pt₂0 ₃ (Catalyst F-Comparative Example) was used and treated according to the procedure of Example 1. Theta-1
Is a 10-membered zeolite, which is described in EP 057049.
It is listed. This catalyst uses powdered TON zeolite (Si / Al ratio 30) as powder
After mixing with the amorphous component in various ratios, the mixture is first treated with platinum dichloride tetraamine.
It was produced by supporting platinum by a wet method. Table 1 shows the conditions and results.
In columns E and F.

[0037]

[Table 1]

The results shown in the table are further illustrated in FIG. This figure is a graph showing Brookfield viscosity versus yield for various catalyst combinations.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating the conversion of methylcyclohexane to various cyclopentane compounds at 320 ° C.

FIG. 2 is a graph showing Brookfield viscosity vs. yield when using various catalyst mixtures.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C10G 35/06 C10G 35/06 35/085 35/085 35/095 35/095 (72) Inventor Cody, Ian, Alfred United States, 70809, Louisiana, Louisiana 70809, Baton Rouge, Renwood Boulevard 7942C (72) Inventor Wittenblink, Robert, Jay United States, Louisiana 70816, Baton Rouge, Shady Glen Drive 836 (72) Inventor, Sored, Stuart, Leon United States, New Jersey 08867, Pittstown, Cooks Cross Road 21 (72) Inventor McVicker, Garry, Bryce 07830, New Jersey, United States Fon, Main Street 65 (72) Inventor Hunter, Sylvain United States, 70769, Louisiana, USA Prairie Villa, Seven Oaks A Avenue 37620 (72) Inventor, Lineck, Sandra, Jean United States, Louisiana 70806, Baton Rouge, Claycut Road 5202 F term (reference) 4H006 AA02 AC11 AC26 BC10 BC11 BC19 BE20 DA12 DA15 4H029 CA00 DA00

Claims (14)

[Claims] 1. A method for hydrodewaxing a feedstock to produce a lubricating base oil having improved low temperature properties, the method comprising the step of: feeding the feedstock under hydrodewaxing conditions. With a monolithic mixed powder pellet catalyst, wherein the catalyst is a first dewaxing component selected from 10- and 12-membered molecular sieves and mixtures thereof and a second isomer, which is an amorphous inorganic oxide. A metal hydrogenation component on a support containing a hydrogenation component, wherein the first and second components are 1,1-dimethylcyclopentane,
When the conversion of methylcyclohexane to 1,2-dimethylcyclopentane, 1,3-dimethylcyclopentane, and ethylcyclopentane was evaluated, the catalyst was found to be trans-1,2-dimethylcyclopentane / trans-1,3- A hydrodewaxing process, characterized in that it is present in a ratio such that it gives a dimethylcyclopentane ratio of at least 1 and a selectivity to ethylcyclopentane at a conversion of 10% of at least about 50%. 2. The hydrodewaxing process according to claim 1, wherein the metal hydrogenation component is at least one of Group VI or VIII metals. 3. The hydrodewaxing process according to claim 2, wherein the metal hydrogenation component is a Group VIII metal. 4. The hydrodewaxing method according to claim 2, wherein said metal hydrogenation component is dispersed on at least one of said first and second components. 5. The hydrodewaxing method according to claim 4, wherein the hydrogenation component is dispersed on both the first and second components. 6. The hydrodewaxing process according to claim 4, wherein the hydrogenation component is dispersed in an amount of about 0.1% to about 30% by weight. 7. The hydrodehydration of claim 2, wherein the selectivity for ECP formation in the second component is at least about 50% or greater when the conversion of methylcyclohexane at 320 ° C. is evaluated. Wax method. 8. The hydrodewaxing method according to claim 1, wherein the feed material is a solvent which is solvent dewaxed to have a pour point up to + 10 ° C. 9. The method according to claim 1, wherein the feed material has a temperature of 280 to 400 ° C.,
3000 psig (3.55-20.8 mPa) pressure, 500-5000 SC
F / bbl (89 to 890 m ³ / m ³ ) hydroprocessing feed gas amount, and 0.1 to
The hydrodewaxing method according to claim 1, wherein the hydrotreating is performed at a flow rate of 5 LHSV. 10. The hydrodewaxing process according to claim 1, wherein the 10- and 12-membered molecular sieves are selected from aluminosilicates and aluminophosphates. 11. The method according to claim 11, wherein the aluminosilicate is ZSM-5, ZSM-11, ZS.
The hydrodewaxing according to claim 10, characterized in that it is selected from M-12, ZSM-22, ZSM-23, ZSM-35, natural and synthetic ferrierite, ZSM-57, beta mordenite, and offretite. Law. 12. The said aluminophosphate is SAPO-11, SAPO-41.
11. The hydrodewaxing method according to claim 10, wherein the method is selected from SAPO-31, SAPO-31, MAPO-11 and MAPO-31. 13. The method of claim 1, wherein the molecular sieve is ZSM-5, ZSM-22, ZSM-5.
11. The hydrodewaxing method according to claim 10, wherein the method is selected from SM-23, ferrierite, and SAPO-11. 14. The hydrodewaxing method according to claim 1, wherein the amorphous inorganic oxide is promoted or doped with yttria, rare earth oxides, boria, and magnesia.