JPS60212487A - Catalytic dewaxing process using zsm-11 zeolite - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field] The present invention relates to a catalytic brazing process for wax-containing hydrocarbon charges.

[Conventional technology]

Modern petroleum refining relies in large part on catalytic operations that chemically transform the naturally occurring components of petroleum.

The porous inorganic solids originally found to be useful in catalytic operations include hydrocracking, catalytic cranking, reforming, and hydrotreating, including certain clays, aluminas, silica-aluminas, etc. or other silicas co-precipitated with, for example, magnesia, and these solids are still used extensively in industry. In general, not all of the above-mentioned solids have pores of uniform size; most of the pore volume is within pores with a diameter of about 3θA or more, and some pores have pore sizes of about /θθA or larger. have.

Zeolite molecular sheets have been observed to be very effective as hydrocarbon conversion catalysts. The conversion of gas oil to gasoline and hydrogen distillate by catalytic cracking, the alkylation of benzene to ethylbenzene, the isomerization of xylenes, and the disproportionation of toluene all have critical dimensions of /, 3.
It encompasses molecules of diameter smaller than S-triethylbenzene, which are absorbed and acted upon by the zeolite molecular sheep with an effective pore diameter of about /θ. Catalytic conversions featuring molecular sheep catalysts of particular interest are in lowering the pour point of waxy distillate and residual hydrocarbon fractions. Effective pour point reduction depends on the selective conversion of high melting point paraffinic molecules with an effective critical diameter of about X to lower molecular weight materials that are easily separated from the lower pour point product. An effective catalytic membrane wax depends at least in part on the ordered pore size of the crystalline zeolite to selectively convert undesired components.

Dewaxing of oils by shape selective cracking and hydrocracking on ZSM-3 zeolite was carried out by Cheno (ch.
The invention is described in U.S. Reissued Patent No. 2, No. 3-8 by et al. U.S. Patent No. 3. q3&/02 discloses the dewaxing of petroleum fractions using ZSM-, S'. Catalytic membrane waxing of petroleum stocks in mordenite The Oil End-Gas Journal [tbec
lil and 0asJournal (/97
! It is described on pages 69 to 73 of [Published on June 6, 2009]]. Also, U.S. Patent No. 17.6A &, / / 3
Please refer to the specification.

crystalline zeolite) ZSM-// is U.S. Pat. No. 3,709
．． 9? 'Disclosed in Specification Z. Example D of this patent teaches fluid catalytic cranking at qbg'c (gq!i°F) of gas oil having a pour point of 37° goC (/QO°F). Olefins were obtained in high yield and the pour point of the product was reduced.

Current percentage of improvement in contact arm row method
teaches that it is preferable to use shape-selective zeolites for contact membrane waxes. These documents indicate that any shape-selective zeolite with a control index l~/, 2 as described later can be used, but ZSM-3 and ZS
M-// is taught to be particularly preferred. The reported experiments were performed using ZSM-3 only.

Representative examples of these patents include solvent purification, catalytic membrane waxing on medium pore size zeolites, e.g. ZSM-s, and subsequent hydrotreating of lower pour point lubricating base oils from waxy crude oil fractions. U.S. Patent No. t teaching a method of manufacturing
<Itxsqg issue.

U.S. Patent No. 'I, 332. No. 7O teaches a catalytic membrane waxing process for middle distillates by using medium pore size zeolites to produce low pour point fuel oils. There are no examples showing the use of ZSM-ii.

[Problem that the invention seeks to solve]

It would also be desirable to have a catalyst that could achieve effective dewaxing and minimize the loss of beneficial liquid that typically occurs when using typical shape-selective dewaxing catalysts. The only way to remove wax using the seven zeolites mentioned above is to crack the wax into small molecules.

[Means to solve the problem]

We have found that ZSM-//, which has hitherto not been given any experimental attention by all researchers, is better than ZSM-5 for contact membrane waxes in the lubricating oil and fuel oil range.

Accordingly, the present invention provides a contact waxing process of a wax-containing hydrocarbon charge to dewaxed oil, in which said charge is heated in a reaction zone at a temperature of 23θ to ttso'c and a pressure of atmospheric pressure to /IA
ZSM-i at a pressure of 000 kPa and in the presence of hydrogen
An object of the present invention is to provide a contact membrane waxing method characterized by contacting with an i-containing catalyst.

In another embodiment, the present invention provides a process for making a lubricating base oil having a high viscosity index, comprising a waxy component-containing lubricating base oil charge, a ZSM-//catalyst 1 o-qs weight ratio, and a refractory inorganic oxide binder. A catalyst containing qo-s wt% was heated to a temperature of 2.3
O-1IOθ℃, pressure atmospheric pressure ~ / θθ0kPa, liquid hourly space velocity o, i ~ coθ, and liquid oil with a standard ratio of hydrogen to hydrocarbon in the presence of hydrogen/H2 per volume in a standard state To provide a method for producing a lubricating base oil having a high viscosity index, comprising contacting in a contact membrane wax zone operated under conditions of 30-1000 vol. to produce a lubricating base oil with reduced waxy content. be.

In a more limited embodiment, the present invention provides a catalytic membrane waxing process for wax-containing oils, in which the oil is heated in the presence of hydrogen for 2 hours.
．． 30~txso. At temperature c, hydrogen partial pressure atmospheric pressure ~/
To provide a catalytic membrane waxing method for wax-containing oil, which comprises contacting ZSM-// with a fixed bed of a platinum group metal component-containing catalyst at AOθo kPa to catalytically produce dewaxed oil. be.

Details of the method for preparing ZSM-// ZSM-ii are provided in U.S. Patent No. 3, ?
It is described in OZ 979 specification. ZSM-//
Various properties of zeolite will be described later.

Silica/Alumina Ratio +□□-□-□□-□-□ The silica/alumina molar ratio of ZSM-// and other zeolites can be determined by conventional analysis.

This ratio is meant to represent as accurately as possible the silica/alumina molar ratio in the rigid anionic framework structure of the zeolite crystals, and the aluminum in the binder or the aluminum cations in the zeolite grooves or other forms of aluminum. It means to exclude.

Although zeolites with a silica/alumina molar ratio of at least 10 are useful, it is preferred to use zeolites with a silica/alumina molar ratio of about 12 or more, with a molar ratio of about /! ;-2000
Those having a molar ratio are preferred. Additionally, zeolites as characterized herein except that aluminum is substantially absent, i.e. zeolites with silica/alumina molar ratios up to infinity, have been found to be useful, and in some cases preferred. Even. 1 Such "high silica" or "high silica" zeolites tend to be hydrophobic and are intended to be included within the scope of this invention. Also included within the scope of this limitation are substantially pure analogs of the useful zeolites described herein, i.e., those with an unmeasurable amount of aluminum (infinite silica/alumina molar ratio), but Others are zeolites that include the disclosed characteristics.

Generally, the higher the alumina content in the zeolite framework, the higher the acid activity imparted to the catalyst. Acid activity is crystallization of ZSM-// that contains almost no aluminum, crystallization of ZSM-// that contains a large amount of aluminum,
Adjustment can be made by steaming the ZSM-//, acid extraction, or other means conventionally used to control acid activity.

A method/method for measuring alpha active acid activity is to measure the cracking activity of the catalyst to obtain the alpha value or alpha activity. The method for measuring alpha activity is described in U.S. Patent No. ttoit, rig.
It is stated in the specification of the No.

The alpha test is an excellent measure of cracking activity, but not hydroisomerization activity. ZSM of the present invention-//
The dewaxing operation appears to proceed by cracking and hydroisomerization, and therefore alpha activity provides only some information on approximately 7 of the several reactions that are likely to occur during dewaxing. Activated macroporous zeolites, such as RENaX, can have alpha activities in excess of /0.000 and are excellent FCC catalysts, but do little or no dewaxing. Excellent dewaxing catalysts, e.g. Ni partially deactivated by coking
-ZSM-3 may have low alpha activity, but still provides excellent dewaxing performance as long as the reactor temperature is raised slightly to adjust for low alpha activity.

Control Index The control index can be determined by passing an equal weight mixture of n-hexane and 3-methylpentane continuously over the zeolite under test at atmospheric pressure according to the procedure described below.

The zeolite under test in the form of pellets or extrudates is ground to approximately coarse particle size and loaded into a glass tube. The zeolite is heated for at least 3 J g 'C before testing.
Treat with air flow. Next, wash the zeolite with helium and increase the temperature to obtain a total conversion rate of lθ~bo%!
;-! ; Adjust to between 10°C. A mixture of hydrocarbons with a helium/(total) hydrocarbon molar ratio made using a helium diluent/liquid time continuous rate (i.e. amount of liquid hydrocarbons/volume/volume of zeolite per 7 hours) )
Pass it over zeolite. After 20 minutes of operation, a sample of the effluent stream was analyzed, most conveniently by gas chromatography, to determine the unreacted residual fraction of each of the two hydrocarbons.

For samples with very low activity, such as samples with very high silica/alumina molar ratios, it may be necessary to use more severe conditions.

The control index is calculated as follows: The control index approximates the ratio of cracking rate constants for two hydrocarbons. Control index for ZSM-3 (
C.I. ) value is approximately 8.3, while the control index of ZSM-7l is 8.7. These values may vary depending on test conditions.

Catalytic Dewaxing of Lubricating Oils The refining of suitable crude oils to obtain a variety of lubricating oils that perform effectively in a variety of environments has become a highly developed and complex technology. Although the broad principles involved in purification are qualitatively understood, the principles of purification remain poorly understood due to quantitative uncertainties that require considerable experience when performing purification. do not have. The basis of these quantitative uncertainties lies in the complexity of the lubricant's molecular composition. Since most lubricating oils are based on petroleum fractions boiling above 22 g'C, the molecular weight of the hydrocarbon components is high and these components exhibit almost every imaginable structure or structure type.

For lubricant refining, crude oils containing appropriate lubricant stock fractions are usually selected for processing as determined by experience or analysis. Purification processes for isolating lubricating oils consist of a set of unit operations that remove undesirable components. The most important above-mentioned unit operations include distillation, solvent refining, and dewaxing, which are essentially physical separation methods in which all separated fractions are recombined to form crude oil.

Refined lubricant stocks can be used as lubricants and can be mixed with other refined lubricant stocks with somewhat different properties. In addition, the refined lubricating oil stock is blended with seven or more additives that act as oxidation inhibitors, extreme pressure additives, and viscosity index (V) improvers before being used as lubricants. be able to. The term “stack” used herein
j further limits the term, whether or not it relates only to hydrocarbon oils without additives. As used herein, "raw 5t06k)j" is a viscous distillate fraction isolated by vacuum distillation of atmospheric residue from the atmospheric distillation of crude oil and subjected to further processing. The term "raffinate" refers to oils refined with a solvent, such as furfural. The term ``dewaxed stock'' or ``dewaxed raffinate'' refers to a process in which the wax content in the oil is removed or otherwise converted, thereby reducing the pour point of the oil. It is related to.

As used herein, the term "waxy" refers to oils with sufficient wax content to have a pour point above 0°C.

The term "Stock (StOCk)" as used herein, unless otherwise specified, generally refers to a viscous fraction at any stage of purification and in all cases contains no additives.

What is currently being done is to perform vacuum distillation of the atmospheric distillation column residual oil from a suitable crude oil as the first step. This provides seven or more roasts with a boiling range of 230-sbsC. Next, the roasted twig is added to e.g. furfural, phenol or Clolex (2t2-
One product name of dichloroethyl ether, Union Kerr/(
Aromatic hydrocarbons are selectively solvent extracted with a solvent such as Ido Corporation) to remove undesired components. The raffinate from the solvent purification is then dewaxed by mixing with a solvent such as a mixture of methyl ethyl ketone and toluene. The mixture is cooled to crystallize the rough wax fraction, and then sufficient paraffinic wax crystals are separated from the dewaxed raffinate to obtain a final recovered raffinate. The catalytic dewaxing method of the present invention, which will be explained in detail later, is used in place of solvent dewaxing. Hydrotreating or hydrofinishing methods can be used in conjunction with catalytic dewaxing. Hydrofinishing or clay percolation processes can be used to reduce the nitrogen and sulfur content, if necessary, and also to improve the color and oxidation resistance of the lubricant crude oil.

Hydrotreating methods can be used in place of or in conjunction with solvent purification to prepare the feedstock of the present invention.

The advantage of hydrotreating prior to catalytic dewaxing is that many catalyst poisons are catalytically converted in the hydrotreater or deposited on the hydrotreating catalyst. This results in superior operation and longer operating life of the catalytic dewaxing equipment.

Conventional hydroprocessing methods include catalysts containing the hydrogenation component on a support, preferably a non-acidic support, such as Co on alumina.
-Use a catalyst supporting MO or Ni-Mo.

Hydrotreaters are usually operated at relatively low temperatures, typically 200
It is operated at a temperature of ~5oTL, preferably 300-qsC.

Although the hydroprocessing catalyst can be installed as a fixed bed, fluidized bed or moving bed of catalyst, downflow fixed bed operation is preferred for its simplicity. When the hydroprocessing catalyst is arranged as a fixed bed catalyst, the liquid hourly space velocity, i.e. the volume of liquid charge per hour measured at the standard state volume of the catalyst, is usually θ. /~lθ, preferably about /~S. Typical hydrogen partial pressures are /~100 atmospheres (absolute pressure). Hydrogen can be added to the charge in a disposable manner or can be cycled by conventional means.

A suitable hydrotreating/hydrogenating component is the 11th element of the periodic table of elements.
Group, Group 1II, Group ■, Group ■, Group VIB, Group ■B
7 or more metals or compounds thereof selected from the group consisting of Group 11, Group 11, and mixtures thereof. Suitable metals include molybdenum, tungsten, vanadium, chromium, cobalt, titanium, iron, nickel and mixtures thereof.

Usually, the hydrogenation metal component is 0.0% of the support based on the element. /
Good results are obtained if the metal hydride is present in an amount of ~20 parts by weight and is operated with a metal hydride of 0°/~10 parts by weight.

The hydrogenation component is usually disposed on a support, preferably an amorphous support such as silica, alumina, silica-alumina, and the like. Also, any other conventional supports can be used. Acid-active components such as acid ion exchange clays or zeolites can also be included on the support.

It is the intention of the present invention that the support is preferably not very acidic and that the hydrogenation takes place primarily in the hydrotreating zone and that cranking or other reactions in the zone are minimized. . The support should have either no change in the pour point of the lubricating oil passing through the hydroprocessing zone or a sufficiently low acidic activity to cause the hydroprocessing to change the pour point by no more than 3-6°C. preferable.

The viscosity index (■.■) is a rather important parameter of quality for lubricating oil classes for use in automobile and aircraft engines. This index is a series of numerical values ranging from 0 to /θ0 or more, and indicates the rate of change in viscosity due to temperature change. A viscosity index of 700 indicates an oil that does not tend to become viscous at low temperatures or flowable at high temperatures. ag℃ and 99℃ (/θ0'F and 2
Measurement of the Saybold Universal viscosity of an oil at 10° F. and a description correlating to the viscosity are as follows: It provides a measure of

V, 1. A published by ASTM, Race Street, Philadelphia, Pennsylvania, USA.
It is specified in the viscosity index table of STM (D, 5-67).

To prepare high viscosity index automotive and aircraft lubricants, refiners typically select crude oils that are relatively rich in paraffinic hydrocarbons. This means that low paraffinic crude oils, commonly referred to as naphthene-base J crude oils, have little or no V, I content above about qo.

This is because it has been empirically shown that refined oil with [See Nelson's Crude Oil Grades, page 8.about.8/8] Suitable stocks for industrial high viscosity index oils contain a significant amount of wax content which results in a high pour point, solvent refined lubricating oil.

Distillate lubricating oil rawstock typically does not have a particularly high viscosity. However, solvent refining, such as using furfural, not only removes unstable, sludge-forming components from the crude distillate, but also removes components that adversely affect the viscosity index. Therefore, stocks that are solvent purified prior to dewaxing usually have a viscosity index that exceeds specifications.

In general, the catalytic hydrogenation membrane waxing process of the present invention has approximately 2. ?
o ~q o o 'C,, atmospheric pressure ~/l<000'k
Pressure of Pa, liquid hourly space velocity θ. l~20. Preferably, it is operated at a hydrogen/hydrocarbon ratio of 0 to 100 θ volumes of hydrogen at standard conditions per volume of liquid oil at standard conditions. Any of the conventional contact membrane wax conditions can be used.

Catalytic membrane waxing can be carried out by passing the feed over a fixed bed, fluidized bed or moving bed of ZSM-ii containing catalyst.

ZSM-//Although the catalyst itself can be used, ZSM-/
It is preferred to use / in combination in a binder such as alumina or silica/alumina.

Surprisingly good results are obtained by simply using ZSM-ii instead of the ZSM-50 previously used in the contact membrane wax.

The addition of hydrogenation/dehydrogenation components, ie, base metal or platinum group metal components, to the dewaxing catalyst is within the scope of this invention.

The hydrogenation/dehydrogenation component appears to promote hydroisomerization activity in addition to the shape-selective cranking activity that occurs with ZSM-//. The combination of these activities is ZSM
The activity selectivity obtained when using the -3 catalyst yields a product with even higher activity and better selectivity and lower pour point than the low pour point product.

The hydrogenation/dehydrogenation component can be added to the support by ion exchange or impregnation, or by any other method known in the art for admixing the hydrogenation/dehydrogenation component to the support; The support is ZSM-// alone or a mixture of ZSM-ii and a refractory inorganic oxide binder. Suitable hydrogenation/dehydrogenation components are listed in Item ■ of the Periodic Table of Elements.
Group, Group ■, Group ■, Group V, Group VIB, Group ■B,
It can be selected from one or more metals or compounds thereof selected from the group consisting of Group Ⅰ or mixtures thereof.

Suitable base metals include molybdenum, tungsten, vanadium, chromium, cobalt, titanium, gold, nickel or mixtures thereof such as cobalt-molybdenum or nickel-molybdenum.

Suitable platinum group metals are platinum, iridium or palladium, with platinum giving particularly good results.

Platinum group components can usually be added as soluble and decomposable compounds. ZSM-//After mixing the metals described above onto the catalyst, binder, or both, the resulting composite can typically be calcined to firmly fix the metal components to the catalyst.

The metal component is brought into contact with a solution of the metal compound in a predetermined amount necessary to bring the catalyst or its components to the desired concentration within the scope of the present invention.

It can be incorporated into the catalyst by impregnation, ion exchange or other means. The metal components can be mixed at any stage during catalyst preparation or after the final catalyst has been prepared. A preferred method of mixing consists of ion-exchanging the crystalline aluminosilicate and then compositing the ion-exchange product with the porous matrix. Ion exchange or impregnation of siliceous solids or clays is also useful. Suitable metal compounds are metal halides, preferably chlorides, nitrates, ammine halides,
Includes oxides, sulfates, phosphates and other water-soluble inorganic salts and metal carboxylates, alcoholates having 7 to 5 carbon atoms. Particularly suitable examples are palladium chloride,
Second chloroplatinic acid, ruthenium pentaamine chloride,
Includes osmium chloride, perrhenic acid, dioxybis(ethylenediamine)rhenium (V) chloride, rhodium chloride, and the like. Alternatively, a metal oil-dispersing compound or an oil-dispersing compound can be mixed into the catalyst by adding a predetermined amount of a metal oil-dispersing compound or an oil-dispersing compound to the feedstock, for example gas oil, when cracking the feedstock. Such compounds include metal diketonates, metal carbonyls, metal metallocenes, olefin complexes of metals with 2 to 20 carbon atoms, acetylene complexes, alkylphosphine complexes, arylphosphine complexes, and carboxylates with 2 to 29 carbon atoms. Examples of these are platinum acetylacetonate, tris(acetylacetonate)rhodium(2), triiodoiridium Ql
l)) dicarbonyl, -cyclopentadienyl rhenium (■) tricarbonyl, ruthenocene, -cyclopentadienyl osmium (1) dicarbonyl dimer, dichloro(ethylene) palladium (II) dimer (-cyclopentadienyl) ( ethylene) rhodium(I), diphenylacetylenebis(triphenyl-phosphino)platinum(0), bromomethylbis(triethylphosphino)
Platinum (■), tetrakis(triphenylphosphino)palladium (0), chlorocarbonylbis() IJ −
yenylphosphino)iridium (■), palladium acetate and palladium naphthenate.

The hydrogenation/dehydrogenation component can also act to some extent as a hydrogenation/dehydrogenation promoter, but this is not the primary purpose of adding this component.

For example, the presence of platinum group components may result in a small amount of hydrotreating reactions, i.e., removal of sulfur and nitrogen compounds present, but this advantage is not intended by the present invention.

The hydrogenation/dehydrogenation component is believed to promote hydroisomerization of long chain n-paraffins or slightly branched long chain paraffins to more branched paraffins. This hydroisomerization converts waxy long chain paraffins to materials that are miscible with the fuel oil product, thereby increasing fuel oil yield when using the process of the present invention. From a liquid yield standpoint, it is more beneficial to hydroisomerize long chain paraffins to other liquid products than simply hydrocracking.

The amount of hydrogenation/dehydrogenation component added to the catalytic membrane wax catalyst is not narrowly limited (approximately θ, calculated as elemental metal based on the total catalyst weight) It can be within the range of

Calculated as Pt group components as elemental metals: 0°O5~5
Weight-based operations yielded good results, and pt.
The preferred amount of the group metal component is 0°/~. θ is in charge of weight.

Dewaxing of distillate oils to improve the pour pointCatalytic membrane waxing of oils to reduce the pour point Another application of the striped contact membrane waxing process. To reduce the pour point, the charge material is usually not obtained by solvent refining a specific lubricating oil stock.

The contact membrane waxing conditions used to reduce the pour point of fuel oils are typically somewhat more severe than those used for dewaxing lubricating oils, typically at temperatures of 260-q3o0C, and LH8V O
6/~lO.

Catalytic membrane waxing of fuel oils can be performed using the same equipment used for dewaxing lubricating oils, such as vfzu-// single catalyst or preferably ZSM-// with alumina or silica/
This can be carried out by passing the charge over a fixed bed, fluidized bed or moving bed of composite catalyst mixed in a binder such as alumina.

Suitable fuel oils or distillate oils include waxy hydrocarbon oils with boiling points ranging from /75°C to SSO°C.

Gas oil, kerosene, vacuum gas oil and whole crude oil, as well as oils derived from tar sands, shale and coal are contemplated for use in this invention.

〔Example〕

The present invention will be further explained with reference to Examples (hereinafter simply referred to as "one example" unless otherwise specified).

This example is based on US Patent No. '1. /gl! Example 3, described in No. 9g, describes the production of heavy automotive neutral oil by solvent extraction, catalytic membrane waxing on non-steam treated ZSM-5, and hydrotreating.

Nominal at 3g'c (toooF) industrially prepared from Arabian Light crude oil //, S'08US classification qqoG (70°F)
Furfural extraction was carried out using furfural in an amount of % by volume. Furfural raffinate having a pour point of q/°C (1010 s'F) is catalytically membrane waxed/hydrogenated in a two reactor system consisting of a first and second reactor;
The effluent from the first reactor was passed directly to the second reactor. ZSM-3 has a ratio of 5io2/kJ-20 and 70/l, and the α activity of the ZSM-5 extrudate is 200
Met. The first reactor contains a NiZSM-3 (Ni/wt% by ion exchange) catalyst for dewaxing, and the first reactor contains a commercially available hydrotreating catalyst (2°8 wt% Coo/wt) catalyst.
q, q% by weight MOO, /Ap2o,). Both reactors were heated to 8o LH8V 1.2. qookPa(l
ll100psi, H2'I at standard conditions per volume of liquid oil at standard conditions! ;0 volume stage temperature is 2gg°C (sso'
F), and the initial temperature of the hydrotreating reactor is 26°C.
(p7y0F).

The properties of the dewaxed/hydrotreated oil are shown below: pour point 'C
(°F) -7 (+2o) Viscosity index (■. Engineering) 92 Bromine number o, q 3Q, 1°C+ (6Sθ'F+) (Liquid volume %) g
/,9 The bromine number is the unsaturation index and must be low to obtain good stability. Dewaxed/hydrogenated oils are standard 50 hour Caterpillar oils.
) /-H engine test, indicating acceptable quality for high-end automotive applications.

This example uses a conventional catalyst, i.e. steam treated 0°9mmN1
-bs%ZSM-s/3s%AJ! 20. 1 illustrates a dewaxing step in an industrial operation using (Ni by ion exchange). ZSM-3 is sio2/A
v 2o and a ratio of about 70/l.

The industrially produced and extruded catalyst was heated to 82°C (900°C).
(Bottom) was subjected to laboratory steam treatment for 6 hours.

,/ll in a pressure-resistant reactor with a patch stirrer, 300k
Pa (5θo psig) was used to wax the hydrogenated membrane at an oil/catalyst weight ratio S/, t for 30 min in N2;
The experiment was carried out at 7110C, 28g℃ and 3ib℃ (!;
2! ; below, SSθ°F and 6θO), respectively, with fresh catalyst, and the product was heated to 311.3°C (45θ'
F) was distilled. The residual oil had the following properties: Temperature °C ('F) 271 I (, t, z, t) 2 gg (s
so) 3ib (boo) Pour point °C (lower) 10 (+s
o) -7(+ko-, 77(-35) viscosity index (v,
1. ) q? q3gt bromine number 8,! ; /, l12
゜3 This example illustrates the use of a non-steam treated catalyst in a dewaxing process.

The same commercially available catalyst that was steamed in Example 1 was used for dewaxing in the same manner as in Example 1, without steaming. The results are listed below: Residual Temperature °C (0F) 27g (5J5) 2g&(55(7)
Pour point 'C (°F) Da (+ Dao), -/& (viscosity index (v, I.) q7gq Bromine number /, / /, g The above results indicate a pour point of -7°C (+20 below) The results show that non-steam treated catalysts are more active than steam treated catalysts for dewaxing targeting.

27 Non-steam treated Z with z'c (s s yoF )
The pour point achieved using SM-3 is steam treated Z
6°C (10°) below the pour point achievable using SM-3.
H) Low.

Presentation-Jun-Saeike Fariji 2μsha-// This example is a non-steam treated ZSM in the dewaxing process-//
This explains the use of catalysts.

ZSM-// (still crystallized) 65 weight clerk and AJ
, □033S wt% mixture was extruded and! ;、?
Preliminary firing with g'c (ioo ooF), NH4N0
．． to reduce sodium by ion exchange with Ni(NO3
The catalyst was prepared by ion exchange with )2 and calcination at 538°G (/θθ0°F). N1 content is θ
. There was a 6th weight class. Z used in this example and the following experiments
SM-// is 5102/A engineering, 0. The ratio is 78/l.

The obtained extrudate (catalyst) had an alpha activity of //3.

This catalyst was used for dewaxing as in Example 2 and the following results were obtained: Resid temperature 'C (0F) 2bo (soo), 1qq (sx
s) cogg (sso) pour point'C('F) ai(7o
) −<z(2,t) −J7(−J5) viscosity index (v
,■,) ioo 9J g.

The above results indicate that the non-steamed ZSM-// catalyst is more active than the steamed 23M-3 catalyst of Examples 1 and 3 or the non-steamed ZSM-3 catalyst. Pour point reduction was achieved with the non-steamed ZSM-ii catalyst regardless of reactor temperature.

Example 5 Dewaxing of lubricating oil ZSM-//Example ZSM-//7 parts of the catalyst were added to 1I02 in the same manner as in Example
Steam treatment was performed at 9°C (9θO'F) for 6 hours.

A steam treated catalyst was used for dewaxing as in Example 2 and the following results were obtained: Resid temperature 'C (thousands) 2 gg (sso) Pour point °C ('F)' -2/(=, t) Viscosity index (
■. ■. ) gg Steam processing ZSM-// is an example of steam processing ZSM
-5 is much more active.

Dewaxing of World B Lubricating Oils - ZSM-// The catalysts of Examples λ to Example S contain about /, θ overlapping parts or slightly less N1 by ion exchange.

Example B's catalyst does not contain ion-exchanged nickel, /
Consisting of s%HzSM-/ / /3 s%A4,05.

When a non-steam treated catalyst was used for dewaxing as in Example 1, the following results were obtained: Residue Oil Temperature 'C ('F) 27z (r2.t) Pour Point °C ('F
) −/2(+/ viscosity index (V, 1.) ?/ The above results show that the difference in activity between nickel ion exchange catalysts and non-nickel ion exchange catalysts is significant.

Example 7 Dewaxing of lubricating oil - ZSM - // This example uses NiMo impregnation in the dewaxing process, no steam treatment
．． 6wt%N1-(63%ZSM-//33%Af
203) Explains the use of catalysts.

For example, the catalyst of G was mixed with J, 5% by weight Mob, and/or. 2wt%N
iO and calcined at 33 g C (1000 C 1→. Oil reactor temperature 'C ('F) 2Ao (!io's 2!4Δ
24277 (Pour point 'C('F) -z(, +5
) -ig (O) -zO(-g viscosity index (■.■
,) qs qo gttExample g A NiMo catalyst was prepared similarly to the catalyst of Example 7, without pre-ion exchange of the nickel onto the support.

The obtained catalyst was heated to a reactor temperature of 263°C (, to, t'F
) was used for dewaxing in the same manner as in Example 1, except that only 10% of the wax was used. The resid product has the following properties: resid reactor temperature 'CCF) 2g3(,to5) pour point 'C
(°F) −9(+15) Viscosity Index (v, ■, ) qlI The above results are similar to those of Example 7. Therefore, nickel ion exchange (Example 7) is not necessary to realize the benefits of nickel and molybdenum impregnation.

Discussion of Lubricating Oil Film Waxes Using Base Metal ZSM-// The inventive catalyst of Example 7 produces a much lower pour point product than the commercial dewaxing catalyst of Example.

At a target pour point of -7°C (20'F), the activity advantage is 2
6°C (+!x°F).

! ll] The catalyst of No. 17 has a higher V and I than the commercially available dewaxing catalyst in Example-〇. of residual oil product. ■ Advantage in target pour point. ■. l. Exceeds 0.

The ZSM-5 catalyst was steam treated. Non-steam processing Z
SM-3 has the advantage of initial activity over steam-treated ZSM-5, but non-steam-treated ZSM-3
is rapidly deactivated in the dewaxing of gas oil, and therefore industrially steam-treated ZSM-3 was used in this experiment.

Yields are reported for stirrer pressure tests rather than calculated values. This batch test is useful for screening, but does not accurately correspond to industrial operations, which are usually continuous, with fixed beds of catalyst. This batch testing method does not allow for accurate yield calculations. We found that the yield of oil dewaxed by ZSM-// was ZSM-! ; is believed to be as good or better than the yield that can be obtained by dewaxing to the same pour point.

Another section of the example ZSM-// catalyst was impregnated with dichloroplatinic acid. Ni-ZSM-//catalyst was used as the raw material. This is because the Ni-ZSM-//catalyst happened to be readily available at the time the tests were conducted.

Pt J. /S weight ratio containing H2PtCf6 solution. 69
was weighed and diluted to 79 ml, and this solution was added to the nickel ZSM-//A of Example 1 in a rotary impregnator.
420, added to catalyst s09. Co, is added to the rotary impregnator, then the vessel is evacuated and more CO2 is added to remove the vacuum, and this operation is repeated several times to ensure a CO2 atmosphere. Rotary impregnation continued for 60 minutes, then 127°
Dry at 230°F, 'Ig2°C (qoooF)
Calcined in a stream of air for 3 hours.

The temperature increased at a rate of 2-3°C (3-5'F) per 7 minutes. pt-N1-ZSM-it/A12o3 catalyst is 0
,! ; It had a packing density of Q 2 g/cc. Final catalyst. qsg was collected.

This material was tested on a lubricating oil film wax similar to Example 2. Although platinum was present on the catalyst, the catalyst was not presulfided before use. The experimental results are described below.

Residual oil temperature °C (lower) agg (sso) pour point 'C ('F) -λ9 (-2 viscosity index (V, I.) The results were not convincing.The above results should be compared with the example, i.e., non-steam treated Ni-ZSM, since when using Pt, the elemental metal is used before Pt is used. .

Example/t (pt-ZSM-, t) (Comparative Example) Catalysts with platinum supported on substrates containing ZSM-// and ZSM-S were prepared by the procedure used in Example F; It does not contain nickel. pt-ZSM-
Let ii be an example io and pt-ZSM-3 be an example //.

Examples 2-9 were stirrer pressure tests useful in screening catalysts. Fixed bed pilot plant tests are preferred, although they require more time. This is because the test is suitable for industrial implementation and rqoθkPa (llOθpsi
g), reduced with hydrogen at 1182°C (9000F) for 1 hour and tested using a light neutral feedstock under the following conditions: Pressure 2.9θθkPa (#OOpsig) Space Velocity / LH8V Results are listed in Table 1 .

The results in Table 1 show that after 3 days of operation -9'C (t soP) the required temperature 'C ('F); aga/s da o 2q/
/354 -9/-//.

Viscosity index 95.2 7q, g +o, g Lubricating oil yield 2
Weight% 889 8θ. S +/, the above result is Pt
-Z3M-//-9'C catalyst is light neutral raw material
Active with respect to dewaxing to a pour point of (/!; °F), V
This shows that it has advantages over Pt-ZSM-j in terms of I and yield.

Example/J (Testing on Prite Stock) The catalysts of Example 1θ and Example/I were also tested in a fixed bed apparatus using prite stock at the conditions described below: Pressure 2900 kPa (410 psig) Space Velocity θ. 7 S LH8V Hydrogen circulation amount 4t50VI■ (J5θO standard cubic feet/◇ (rel) The results are listed in Table 2.

From the above results, the catalyst of Example 10 (P t-Z SM-/
/ ) is clearly more active at about 22°C (O'F+) than the catalyst of Example // (pt, ZSM-s) (comparative example). In addition, at a pour point of -2/''C (-!;00F), an increase of 2.7% by weight of the lubricating oil raw material with 03g higher V and I was obtained.

This example uses a conventional catalyst, namely steam treated 0.9%Ni.
1 illustrates the dewaxing of distillate using -6S%zslv-s/3s%A1°o, (Ni by ion exchange). ZSM-3 has a 5in2/A420° ratio of about 70.

The industrially produced extruded catalyst was heated to 'Ig2℃ (900'
F) was subjected to steam treatment for 6 hours. The steam treated catalyst was used to hydrogenate membrane wax a feedstock having the properties shown in Table 3.

Table 3 Density 9 /cc O,,gg5O09θ3 0. gg!
Specific gravity, 'API 3! ;, 9 2g. g 2g, 0 pour point 'C ('F) 2'1 (73) 1g (65) 29
(gs) Cloud point 'C ('F) Jg (1oo) 3t (
gg) KV '100G, cs 7.07 28b'
l 2.3.77KV 100°G, cs 2.7gA
11. /69 f, 4L23 sulfur 2% by weight 0°09
2゜2S θ. 8g nitrogen 1pl) m /8θ ti6
o st,.

Hydrogen 2% by weight/3°65/2°60/3°/g Bromine number 0°g. 32° / 9% carbon residue by MCRT - 0,020° 0 / θ60 / Vacuum distillation -
D//6θ °F °C Lower 'C'F 'C Initial boiling point (Ig, 2 230 bAOJ'l!
ri36ri336710 33/ 2gg 7/'l 3
7? ? 26. 3gA, 2Q! g! , 3θ7 Kukoshi Jgri 5S Gu0ko3 (7AAt J, lg 2J6 3ri/ 77/ , %//lI0 Otsugu/
3311 7'lta J98 7g, 2 Q/73Q
AA8 333 7 Otsu J 'IOA 7q<' ke23
60 69J Ji 776 gu/3 80 yu gu 28
70 72/, 3g3 789g27g//'
1.3380 74"i' 39b go, 7'12
8 g23 Ta3q90 7q/ Gu22 82 Tag qθ g, 36 ”I'1795 gJ/ 'I Gug
83rig 4'7 g'17 '733 end point g7! ;
'Ibg g37 417 g70 V66 catalyst was placed as a fixed bed in the reactor.

The reaction conditions and product properties are listed in Table 9 of the following example.

Non-steam treated t(ZSM-s Ca s wt %ZSM
-/l (silica/alumina molar ratio approximately 70) and 35% by weight
Particle size made of alumina of about 0.60 to 2 mm
(i q ~, 2s mesh)] was washed with C02 for several minutes, and then impregnated with cochloroplatinic acid to bring the platinum content to the O,S overlapped part to prepare the catalyst used in this example. Prepared. Platinum ZSM-//catalyst was loaded into the same fixed bed reactor as used in Example/q, where hydrogen, :b,
qookPa (qoopsig)? -82°C (9
00'F) for 1 hour. After reducing the reactor temperature to the desired set point, the light neutral feed as well as hydrogen were pumped into the reactor. After S days of operation with light neutral feedstock, the charge is replaced with prite stock. The above experiment was carried out with rj,,g 2-J 07°C (s
q o ~s g s'1: ), 2900 kPa
(1100 psig) of N2, N2 circulation amount qs.

VIV (2300 standard cubic feet/barrel) and 0.
It was carried out at 75-80 LH8V. After 5 days, the charging material was changed to light oil A.

Test conditions and properties of dewaxed distillate products treated with Pt-ZSM-//catalyst (invention) were determined by N1-ZSM-s
A comparison with (prior art, comparative example) is listed in Table 9.

Comparison of properties of dewaxed distillate catalyst Steam treated Non-steam treated Ni-ZSM-
3Pt-ZSM-// (Example/1I) (Comparative example) (Example 15) Reactor temperature 'C ('F), yqi < to, yq
i (396 (71III) pressure of qθ, kPa (p
sig) x, qoo(l/, oo) xytoo(l
Ioo)s, qoo(lloo)LH3V//
/ Number of operation days /3 /3 /'1 Above pour point) -7 (,2 LT-51I (-65
) LT-! ;1I(-45) product selectivity 1 overlap part C,~C20,,l O,/ ,0. /c, s, 3/
, 2.7 /I, /.

C49°, 77°/6. q C5/44°C(,7Jo')'), 2? ,,2 2
0.2 22.3/Otsu 6°C+ (330°F+) sb
, o sg , q sg , t.

At 37/C (700'F) 17) reactor temperature, Pt-Z
The product from SM-// is -s lI'C(-t, 5
6F) has a lower pour point than Ni-ZSM-
! The product from r has a pour point of -7°C (,2 (7'F)), which indicates that pt-, ZSM-// is more active than Ni-ZSM→S for dewaxing distillate oils. This shows that.

Almost the same distillate yield was obtained with both catalysts as shown in Table 9. In the dewaxing of distillate oils, removal of waxy components that reduce the pour point usually results in product removal, resulting in lower yields. As a result, Pt-ZS
The yield of distillate using M-// is determined by increasing the reactor temperature to -2°C (
-0°F) to obtain a pour point of 60
The weight will increase and the price will increase. Pt-ZSM-/
l is much more selective than ZSM-3.

The catalyst of Example/S was used for the dewaxing of gas oil B. The results are listed in Table 5. The reactor pressure, LH8V and hydrogen circulation rate are the same as listed in Table 1.

Catalyst Steam treated Non-steam treated Ni-ZSM-
3Pt-ZSM-// Reactor temperature °C (0F) 37/(7θ 32v (gx,
t) Pour point °C ('F) -15 (S') -/-1) Product selectivity 2M dosing section, -tt, ty Ke. O C57gg℃ (3300F) 9.0g, 7/Chang0c
+-(330°F+) g7. Og7. ．． 3 Regarding diesel oil B, Pt-ZSM-//catalyst is steam-treated old-ZS
It is more active at 730F than M-3, but the product selectivity is comparable.

Example/7 Dewaxing of fuel oil - ZSM-ii The catalyst of Example 15 is used for the dewaxing of light oil C. did. Rice polishing is shown in No. 6: Table 6 Catalyst Steam treatment Non-steam treatment Ni-ZSM-
3Pt-ZSM-// Reactor temperature 'C ('F), 777 (311x of 7/
(6, ty) Pour point 'C ('F) -7g (of -/
g(0) Product selectivity 9% by weight C4-Otsu, Otsu s, q C5166°C (J3piF)//. llq, gl Otsu 6°
G+(,y3d:'lnee1-)g2. o gq, s For gas oil C, P t-Z SM-/ / catalyst exceeds steam-treated Ni-ZSM-3 3 /'C(5, t'
P t-Z ).
SM-/ improves the selectivity of /64°C+ (J30°F+) by 2°5%.

If we are currently building a contact membrane waxing equipment to produce lubricating base oil feedstock, we will use ZSM-//A! a catalyst consisting of 33 parts by weight of Al2O, to which about 1 part by weight of nickel and about 3 parts by weight of molybdenum have been added by ion exchange or impregnation, will be used.

Some experiments added platinum to the ZSM-// catalyst.

By adding platinum, a profit commensurate with the cost of adding the platinum component can be obtained.

Regarding dewaxing of lubricating oil, 240-340℃, 7300℃
~j, hydrogen pressure of 50θkPa, 100~3θ0VIV
17) It is preferred to arrange the catalyst as a fixed bed in a reactor operated with a hydrogen circulation rate of 0.5 N'2.0 LH3V. The catalytic membrane wax effluent is passed to a hydrotreater containing the hydrogenation component on a non-acidic support such as cobalt Φ molybdenum or nickel molybdenum on alumina as a catalyst. .

If necessary, the catalyst can be steamed before use. For some feedstocks, steaming reduces the activity of the catalyst at the beginning of the operation, but the activity of the catalyst lasts longer.

For fuel oil film waxes, we can use similar base catalysts, but containing about 0.5% by weight of Pt added by impregnation as the hydrogenation component.

The ZSM-// used is 5102/A, L20. figurative 7
0 and has not been subjected to steam treatment. To fix the Pt on the support, the Pt can be calcined and then reduced to the elemental state with hydrogen.

The catalyst temperature is 260~gSθ℃, l! ;00~3.300k
It can be arranged as a fixed bed in a reactor operated at a hydrogen pressure of Pa, a hydrogen circulation rate of ioo to SOO IV, and a hydrogen circulation rate of 0.5-2.0 LH3V.

In general, the use of ZSM-//zeolites as dewaxing catalysts results in at least twice as much hydroisomerization of waxy components as can be achieved using conventional shape-selective zeolites. can be done. For example, ZS
5 to 70 times more ZSM-// compared to dewaxing with M-3
It is possible to achieve hydroisomerization at

It is preferred to convert the majority of the waxy components, such as n-paraffins and slightly branched paraffins, to less waxy components. It is preferred to obtain as much isomerization as possible, and an attempt was made to produce at least 5 to 70 moles of hydroisomerized product, an expensive liquid product, for every mole of waxy component/θO converted.

Continued from Page 1 0 Inventor Jeffrey Singa 218 R.D. Φ Box, Swedesboxon Mill Road, New Jersey, United States of America

Claims (1)

[Scope of Claims] l A waxy hydrocarbon charge is contacted in a reaction zone with a shape-selective waxy cranking catalyst having a control index l~/2 under contact membrane wax conditions to increase the waxy content. In a process for catalytically dewaxing said feedstock to produce a dewaxed oil by cracking into light boiling range components, a crystalline catalyst having a crystal structure of ZSM-// is used to perform the cracking and A method for producing dewaxed oil, characterized by removing wax content by both isomerization. Contact membrane brazing conditions are atmospheric pressure~/'1.000 kP
2. The method of claim 1, comprising a hydrogen pressure of a, a hydrogen/hydrocarbon ratio of H290-900 volume per charge/volume, and a liquid hourly space velocity of 0° s -s. 3. The method of claim 1 or 2, wherein the catalyst contains ZSM-// and a refractory inorganic oxide binder. q The method according to claim 3, wherein the binder is alumina, silica, or silica-alumina. A method according to any one of claims 1 to 3, wherein the S catalyst contains 10N9s (7) ZSM-// and alumina ranging from 90 to S by weight. 6. A method according to any one of claims 1 to 5, wherein the ZSM-ii has a silica/alumina ratio of /2// or more. 7ZSM-// is the silica/alumina ratio/s/l~koOO
The method according to claim 1, having //. g. A method according to any one of claims 1 to 7, wherein the catalyst contains a hydrogenation/dehydrogenation component. 9 A hydrogenation component in which the catalyst is selected from the group consisting of Groups ■, Groups ■, Groups ■, Groups V, Groups ■, Groups ■, Groups ■, or mixtures thereof of the periodic table on an element-by-element basis. as0007
9. The method according to claim 8, containing ~30% by weight. 10. The method of claim 8, wherein the catalyst contains a platinum group metal at a ratio of 0° θ/~/wt based on elemental metal. //. The method according to any one of claims 1 to 70, wherein the charged raw material is a lubricating base oil. /2 The method according to any one of claims 1 to 1θ, wherein the charged raw material is fuel oil. /3 The method according to any one of claims 1 to 72, wherein most of the wax content in the charged raw material is converted. llI Claim 1 in which at least mol of S per 700 mol of wax converted is converted by hydroisomerization.
The method according to any one of Items 1 to 13. 11I, wherein at least 70 moles of /S are converted by hydroisomerization.