JP2003522250A - Quenching of dewaxing reactor by recycling heavy dewaxed material - Google Patents

Abstract

(57) Abstract: During catalytic dewaxing of paraffinic hydrocarbons, heavy dewaxed material having an initial boiling point of 800 ° F + or higher is separated and cooled, and recycled as a quench liquid to a dewaxing zone. Mild the catalytic dewaxing reaction, which is exothermic. Heavy dewaxed products react very little, if any, with hydrogen in the dewaxing zone. This has been found to be particularly useful for dewaxing hydroisomerized paraffinic Fischer-Tropsch synthetic hydrocarbons.

Description

Detailed Description of the Invention

[0001]Field of the invention   The present invention is a method of quenching a dewaxing reactor with recycled heavy dewaxed material.
Regarding More specifically, the present invention recycles heavy dewaxed material into the reactor as a quench liquid.
It is characterized by controlling the temperature of the dewaxing reaction which is exothermic by cycling.
Catalytic desorption of highly paraffinic Fischer-Tropsch synthesized waxy hydrocarbon fraction.
Regarding waxing method.

[0002]BACKGROUND OF THE INVENTION   Recently, Fischer-Tropsch wax and hydrotreated slackwa
Clearly Can Produce Premium Quality Fuels, Solvents and Lubricants
I was killed. "Fischer-Tropsch wax" means H_TwoAnd a mixture of CO
The syngas feedstock containing the Fischer-Tart is treated under conditions effective to produce hydrocarbons.
Fischer-Tropsch hydrocarbon synthesis method in which reaction is performed in the presence of a Ropsch catalyst
Is a term used to describe the wax-containing hydrocarbons produced by. Wack
Typical methods for producing these high-quality products from wastewater are fractionation, hydroisomerization and
And dewaxing (particularly catalytic dewaxing). Especially oil-derived slurry
In the case of cook wax, hydrotreating may be necessary before hydroisomerization. For example
U.S. Pat. No. 4,963,672, hydrotreating, hydroisomerization and solvent desorption.
The wax-containing Fischer-Tropsch hydrocarbons can be added to a high V
A method for converting to a lubricant base oil having I and a low pour point is disclosed. Europe
Patent application publication EP 0 668 342 A1 discloses wax-containing Fischer-Tropsi.
Lubricate by hydrolyzing, followed by hydroisomerization and then dewaxing
Methods have been proposed for producing base oils. Decrease hydroisomerization temperature to extend catalyst life
To prolong, the hydrogenation is carried out without cracking. This known to those skilled in the art
Both of these processes are adversely affected by the presence of oxygenates and heteroatoms in the wax-containing feedstock.
to be influenced.

[0003]Summary of the invention   The present invention recycles the heavy dewaxed product as a quench liquid to the reactor.
A wax-containing hydrocarbon feedstock (characterized by controlling the temperature of an exothermic dewaxing reaction (
Hereinafter referred to as "wax-containing raw material"). Presence of dewaxing catalyst for wax-containing raw materials
Catalytic dewaxing is carried out by reacting with hydrogen under high temperature and high pressure. Wax-containing means 75 ° F
And a hydrocarbon which solidifies at room temperature and room pressure standard conditions of 1 atm.
means. Heavy dewaxed material is in the range of about 800 to 950 ° F, preferably 850 °.
It is a fraction of a dewaxed wax-containing raw material having an initial boiling point of F or higher (850 ° F +). This
To separate at least a portion of the heavy dewaxed product from the total dewaxed product and increase the temperature of the catalytic dewaxing zone.
Cool to a temperature sufficient to control and not below its cloud point. Re
The cycled heavy dewaxed material has very little if any reaction in the dewaxing zone
Reacts only with hydrogen and thus gives a significant amount of heat to the dewaxing reaction which is exothermic
Turned out to be no. The waxy material is about 800-950 ° F, preferably 8
Hydrocarbons having an initial boiling point of 50 ° F. or higher, at least 15% by weight, preferably
It contains at least 25% by weight, more preferably at least 35% by weight. Dewaxing anti
At least 50% by weight, preferably at least 90% by weight of the wax-containing raw material fed to the reactor
Weight percent has an initial boiling point in the range of 650-750 ° F (650-750 ° F +
Fractions) with end points above 1050 ° F, preferably above 1050 ° F.
A preferred wax-containing raw material is a hydroisomerized highly paraffinic Fischer-Tropsy
Includes synthetic hydrocarbons. Other less preferred waxy hydrocarbons, such as slurries
Wax-containing hydrocarbons derived from wax and hydrocrackers are extracted and / or contacted with water.
Non-paraffins, such as aromatics and other unsaturated components, that have been processed by digestion refining
The system hydrocarbon is removed together with the heteroatom compound to produce a wax-containing raw material. These places
The wax-containing feedstock obtained by the process typically does not involve a hydroisomerization step.
Supplied to the dewaxer. Dewaxed material is separated and re-cycled as quench liquid
To separate and cool at least a portion of the heavy dewaxed product for
A lubricating oil and fuel product fraction is obtained.

Accordingly, the present invention provides for the reaction of hydrogen with a wax-containing paraffinic hydrocarbon feedstock in a catalytic dewaxing zone to produce a dewaxed product having a reduced pour point and a heavy fraction. Contacting a wax-containing paraffinic hydrocarbon feedstock with hydrogen in the presence of a dewaxing catalyst under conditions of high temperature and high pressure effective for; separating and cooling at least a part of the heavy fraction;
And a catalytic dewaxing method including returning it to the dewaxing zone as a quench liquid for temperature control. More specifically, the present invention provides a wax-containing feedstock comprising a hydrocarbon having an initial boiling point in the range of 650 to 750 ° F and a fraction of 800 ° F + in the dewaxing zone to the presence of a dewaxing catalyst. Reacting with hydrogen at elevated temperature and pressure under pressure to produce a dewaxed product with a reduced pour point containing a fraction of 800 ° F +; subsequently 800 ° F from the dewaxed product.
At least a portion of the + fraction is separated and cooled to a temperature above its cloud point and below the dewaxing temperature; the cooled dewaxed material is recycled as a quench fluid to the dewaxing zone for dewaxing. Includes a catalytic dewaxing process characterized by reducing the temperature of the zone. In a preferred embodiment, the present invention comprises hydroisomerizing a Fischer-Tropsch synthesized waxy hydrocarbon to produce a hydroisomerized product containing a waxy feed containing a 800 ° F + fraction; To produce a dewaxed product having a reduced pour point; separating at least a portion of the 800 ° F + heavy fraction from the dewaxed product; cooling at least a portion of the heavy fraction. And a method of dewaxing Fischer-Tropsch synthesized waxy hydrocarbons by returning it to the dewaxing zone as a quench fluid. In a more detailed embodiment, the present invention synthesizes a waxy paraffinic hydrocarbon fraction from a syngas containing a mixture of H ₂ and CO; the waxy fraction is hydroisomerized to produce a hydroisomer. Catalytically dewaxing the hydroisomerate in a dewaxing zone to produce a dewaxed product having a reduced pour point and containing a heavy dewaxed fraction;
An integrated hydrocarbon synthesis process that includes cooling a portion of the heavy dewaxed fraction for use as a quench liquid in the dewaxing zone. This method comprises the steps of: (a) reacting H ₂ and CO in the presence of a Fischer-Tropsch hydrocarbon synthesis catalyst containing a catalytic cobalt component under reaction conditions effective to produce highly pure paraffinic wax-containing hydrocarbons. Reacting the mixture, wherein at least a portion of the wax-containing hydrocarbon is liquid under the reaction conditions; (b) sending the wax-containing hydrocarbon to a hydroisomerization reaction zone; (c) In the hydroisomerization reaction zone, the wax-containing hydrocarbon is reacted with hydrogen in the presence of a bifunctional hydroisomerization catalyst to produce an initial boiling point in the range of 650 to 750 ° F and an end point of 1050 ° F or higher. (D) reacting the hydroisomer with hydrogen in the presence of a catalyst containing a Group VIII catalytic metal component and a crystalline aluminosilicate component at high temperature and high pressure. More, to reduce its pour point by catalytic dewaxing a hydrogen isomerate in catalytic dewaxing zone, 65
A process for producing a dewaxed product containing hydrocarbons having an initial boiling point higher or lower than the range of 0 to 750 ° F, wherein the dewaxed product has an initial boiling point in the range of 800 to 950 ° F. (E) separating at least a portion of the heavy hydrocarbon dewaxed from the rest of the dewaxed; and (f) the separated heavy hydrocarbon. Cooling at least a portion of the dewaxed product to a temperature below the temperature of the catalytic dewaxing zone; and (g) returning the cooled dewaxed product as quench liquid to the dewaxing reaction zone.

In a preferred embodiment, in the Fischer-Tropsch method, H ₂ and CO are reacted in a slurry containing a hydrocarbon slurry liquid, bubbles and a particulate hydrocarbon synthesis catalyst, and the slurry liquid is reacted under the above reaction conditions. It is a method for synthesizing a slurry hydrocarbon containing a liquid synthetic hydrocarbon. The slurry liquid is taken out of the Fischer-Tropsch hydrocarbon synthesis reactor and sent to the hydroisomerization reaction zone of step (b).

[0006]Detailed Description of the Invention   Hydroisomerization and other hydroconversion processes include hydrocarbons at 650-750 ° F +
Some of them have boiling points below the range of 650-750 ° F (650-75 ° C).
Converted to hydrocarbons with 0 ° F-). This low boiling point material is a hydrogenated product (eg
(For example, hydrogen isomerate), the size of the dewaxing reactor and
To minimize the amount of dewaxing catalyst required, it is preferable to remove it before dewaxing.
Good Removal of low boiling components can be accomplished by, for example, roughly flushing and / or dewaxing.
Alternatively, it can be achieved by performing separation. The choice is determined by the practitioner.
Lower boiling components can be used as fuel. As mentioned above
, The dewaxed product is separated into various desired fractions, typically 850 ° F + fractions.
In addition, it contains two or more lubricant base oils (fractions). Lubricant base oil refers to the
Means all or part of the 650-750 ° F + dewaxed product produced by the process
It As is known to those skilled in the art, lubricant base oils have a general lubricant range.
It is a lubricating-quality oil that has a boiling point in, and can be used with various lubricants such as lubricating oil and grease.
Useful for preparation.

Dewaxing is 40 wt% or less, preferably 30 wt% or less, 650-750 ° F +
Of the hydrogen isomerate of 650 to 750 ° F-. The degree of conversion depends not only on the dewaxing catalyst but also on the feed fed to the dewaxer. In contrast to the method disclosed in U.S. Pat. No. 4,963,672 referred to above, the wax-containing hydrocarbons produced by the Fischer-Tropsch process have very low concentrations of nitrogen and sulfur compounds or It has zero and very low levels of oxygenates so it can be hydrotreated or hydrotreated to remove heteroatoms, aromatics and other unsaturations prior to hydroisomerization to produce a waxy feed. Doing is usually not required. Also, regardless of amount, the only heteroatom compounds present in Fischer-Tropsch synthesized hydrocarbons consist of oxygenates, but most of these oxygenates are:
It is present in the 400 ° F-hydrocarbons which are easily separated from heavier hydrocarbons. 650-750 ° F + waxy Fischer-Tropsch hydrocarbons, for example 5
When containing less than 400 wt .-% hydrocarbons by weight, it is typically not necessary to carry out hydrotreating prior to hydroisomerization to produce a waxy feed. This is especially true for petroleum-derived slack waxes, which may contain significant amounts of heteroatom compounds, especially those containing sulfur and nitrogen, as well as aromatics and other unsaturations. Not applicable. Typical hydrotreating catalysts include:
Known hydrotreating catalysts such as Co / Mo or Ni / Mo supported on alumina are included. Other hydrotreating catalysts include combinations of Co and / or Ni and Mo and / or W supported on a silica / alumina base. Typically, such catalysts are sulfurized. Hydrotreated hydrocarbons, H 2 _S, water, to remove nitrogen and other catalyst deactivation species, it is subjected to stripping before dewaxing. Typical conditions for hydrotreating slack wax and hydrocracked hydrocarbons to produce a waxy feed for dewaxing are about 45
Temperatures in the range of 0-800 ° F, hydrogen pressures of about 400-2500 psia, about 0.
A space velocity of 5 to 3 V / V / Hr (volume of raw material / volume of catalyst per hour) and a hydrogen gas ratio of about 500 to 5000 scf / b can be mentioned.

The wax-containing raw material is (i) a hydrotreated slack wax or hydrocracked product in which heteroatom compounds, aromatic components and other unsaturated components are removed, and preferably hydroisomerized before dewaxing. And (ii) a hydroisomerized wax-containing hydrocarbon produced by a hydrocarbon synthesis method, wherein an initial cut point of 650 to 750 ° F determined by a practitioner, a raw material, a catalyst, and It is preferred to include all 650-750 ° F + cuts, any of the waxy hydrocarbons having an exact end point, preferably greater than 1050 ° F, as determined by process variables. For the wax-containing raw material,
Lower boiling materials (650-750 ° F-) may be included if desired. This low boiling material is not useful as a lubricant base oil, but is useful as a fuel when processed by the method of the present invention. Wax-containing materials are also over 90%, typically 95%
It includes superparaffinic hydrocarbons, which is what is meant by "paraffinic" as used in connection with the present invention. Most hydrocarbons in Fischer-Tropsch wax are normal paraffins. Wax-containing feedstocks derived from hydroisomerization of Fischer-Tropsch wax-containing fractions have negligible amounts of sulfur and nitrogen compounds (eg less than 1 wppm). The Fischer-Tropsch wax-containing raw material having these properties and useful in the method of the present invention is a raw material derived from a wax-containing fraction produced by a slurry Fischer-Tropsch method using a catalyst having a catalytic cobalt component. In practicing the present invention, it is preferred to use a slurry Fischer-Tropsch hydrocarbon synthesis method to synthesize the waxy feed, and in particular to provide a high cobalt to produce a more desirable high molecular weight paraffin, the catalyst cobalt. A method using a Fischer-Tropsch catalyst containing the components is preferred.

In practicing the present invention, it is not limited to the use of any particular dewaxing catalyst, but any dewaxing catalyst that lowers the pour point of the waxy feed, preferably the desired dewaxed distillate fraction. It is possible to carry out with a catalyst which produces the fraction in a suitable yield. Such catalysts include at least one metal catalyst component and an acidic refractory metal oxide component. The catalytic metal component is one or more compounds or metals of Group VIII of the Periodic Table of the Elements,
It may preferably contain at least one noble metal component, for example platinum, but is not limited thereto. The families described herein are Sargent Wel
ch Scientific Company acquired copyright in 1968 Sargent Welch Periodic Table of the
Refers to the tribe found in Elements. The refractory metal oxide component preferably comprises at least one crystalline aluminosilicate, preferably at least one zeolite. These materials include shape-selective molecular sieves, such as mordenite, ZSM, which have been shown to be useful in dewaxing Fischer-Tropsch wax and slack wax when combined with at least one catalytic metal component. -5, ferrierite, ZSM-11, ZSM-23,
ZSM-22 and S, also known as ZSM-35, Theta-1 or TON
Examples include silicoaluminophosphate known as APO (No. 5,135).
, 638). Dewaxing can be carried out with the catalyst in a fixed bed, fluidized bed or slurry bed. Typical dewaxing conditions include temperatures in the range of about 400-600 ° F, pressures of 500-2500 psig, 1000-5 to the flow-through reactor.
H ₂ supply of 000 SCF / B and 0.1-10, preferably 0.2-2.0
LHSV of. Dewaxing is typically up to 40% by weight, preferably 30
It is carried out to convert less than wt.% 650-750 ° F + hydroisomers to lower boiling materials.

Dewaxing catalysts (Pt / H-mordenite) containing a catalytic platinum component and a hydrogen-containing mordenite-containing component are particularly preferred for dewaxing wax-containing feedstocks derived by the Fischer-Tropsch process. It has been found that when used to dewax these very pure highly paraffinic hydroisomers, the dewaxing catalyst and conditions are not necessarily equivalent because of the cracking reaction that occurs during dewaxing. by. When such a decomposition reaction occurs, a substance having a lower boiling point is produced. For example, U.S. Pat. No. 3,539,49
No. 8 uses 0.5 wt% platinum supported on H-mordenite to dewax a light lube oil distillate feedstock (600-700 ° F) until the pour point reaches 10 ° F. It is disclosed that the product yield was only 68% by volume. In U.S. Pat. No. 4,057,488, platinum on H-mordenite was used to dewax denitrogenated raffinate having a boiling point of 740-950 ° F., yield 65.5 vol. % Was disclosed. Surprisingly, Pt
/ H-mordenite was used to dewax hydroisomerized Fischer-Tropsch wax-containing feedstocks having boiling points in the lubricating oil range (eg, 650 to 750 ° F +) to lower hydrocarbons to lower boiling points. It was surprisingly found that high conversion levels were not observed. When a noble metal is used, the noble metal loading is about 0.1-1.0 wt%, preferably 0.3-0, based on the total weight of mordenite and noble metal.
． It is in the range of 7% by weight, and at this time, it is preferable that the noble metal contains Pt. Other noble metal Pd may be used in combination with Pt. When a hydroisomerized wax-containing raw material derived by a slurry Fischer-Tropsch method using a catalyst containing a cobalt catalyst component and a Pt / H-mordenite dewaxing catalyst are combined, a wax-containing raffinate derived from petroleum oil is obtained. It was found that the pour point was lower at a given conversion level than when combined with the same catalyst. This is surprising.

When hydroisomerizing a wax-containing hydrocarbon to obtain a wax-containing raw material, 650 to 750 ° F +
To about 650 to 750 ° F-hydrocarbons, based on a single pass of feed to the reaction zone, of about 20-80% by weight, preferably 30-70%.
More preferably, it is in the range of about 30-60%. Prior to hydroconversion, the waxy feed may contain small amounts of 650-750 ° F-substances, at least a portion of this lower boiling material being converted to lower boiling components. Typical hydroisomerization reaction conditions include temperatures and pressures in the range of 300 to 900 ° F and 0 to 2500 psig, with preferred ranges of 550 to 750 ° F and 300, respectively.
~ 1200 psig. The hydrogen treatment ratio is 500 to 5000 SCF / B,
The preferred range is 2000-4000 SCF / B. Hydroisomerization catalysts include one or more Group VIII catalytic metal components, preferably Co, Ni, to impart to the catalyst both hydrogenation and acidic hydrocracking functions for hydroisomerizing hydrocarbons.
And one or more non-noble metal, such as Fe, typically further a Group VIB metal (eg, Mo or W) oxide promoter is included supported on an acidic metal oxide support. The catalyst may also contain a Group IB metal such as copper as a hydrocracking inhibitor. The cracking activity and hydrogenation activity of a catalyst are, as is known, determined by its particular composition. In a preferred embodiment, the catalytically active metals include cobalt and molybdenum. Acidic oxide carriers or carriers include silica, alumina, silica-alumina, silica-alumina-phosphate, titania, zirconia, vanadia and other Group II, IV, V or VI element oxides, and ultrastable Y. Y-sheave like sheave is mentioned. Preferred carriers include silica, alumina and silica-alumina, more preferably a silica concentration in the bulk carrier (as compared to surface silica) of less than about 50% by weight, preferably less than 35% by weight, more preferably Silica-alumina, which is 15-30% by weight. When the carrier is alumina, small amounts of fluorine or chlorine may be incorporated therein, as is known, to enhance the acidic function. The surface area of the carrier is
In the range of about 180 to 400 m ² / g, preferably 230 to 350 m ² / g,
The pore volume, bulk density and side crush strength are 0.3 to 1.0 mL / g, preferably 0.35 to 0.75 mL / g; 0.5 to 1.0 g / mL, and 0.8, respectively.
Is in the range of up to 3.5 kg / mm. A particularly preferred hydroisomerization catalyst comprises cobalt, molybdenum, and optionally copper, supported on an amorphous silica-alumina support containing about 20-30% by weight silica. The preparation of these catalysts is well known and reported. Specific examples of such catalysts, information on their preparation and use, can be found, for example, in US Pat. Nos. 5,370,788 and 5,378.
, 348, but is not limited thereto.

Particularly preferred hydroisomerization catalysts for practicing the present invention include both cobalt and molybdenum catalyst components supported on a low silica amorphous alumina-silica support, most preferably: Before adding the molybdenum component, the cobalt component was deposited on the carrier and fired. This catalyst has a silica content of 20 to 3 as a carrier.
It contains 10-20 wt% MoO ₃ and 2-5 wt% CoO supported on an amorphous alumina-silica support in the range of 0 wt%. This catalyst has been found to have good selectivity retention and resistance to oxygenate deactivation found in the Fischer-Tropsch produced waxy feed. Addition of a copper component suppresses hydrocracking. The preparation of this catalyst is described, for example, in US Pat.
, 757,920 and 5,750,819. The disclosures of which are incorporated herein by reference.

Referring to FIG. 1, there is shown a simplified schematic flow diagram of a dewaxing apparatus 10 and method useful in practicing the present invention. Thus, hydroconversion reactor 12, catalytic dewaxing reactor 14 and vacuum distillation column 16 are shown. Associated with these are three flash drums 18, 20 and 22 and two heat exchangers 24 and 26. The wax-containing paraffin hydrocarbon fraction is supplied to the hydroconversion reactor 12 via a line 28. The waxy fraction has an initial boiling point in the range of 650 to 750 ° F and boils continuously to endpoints above 1050 ° F. Reactor 12 may be any of a hydrogenator, a hydrotreater and a hydroisomerizer. In the hydroconversion reactor, a waxy feed flowing downstream is fed into the reactor via line 30 in the presence of a suitable catalyst in a fixed catalyst bed 32, toward the downstream. Reacts with flowing hydrogen. For illustration purposes, the waxy fraction is assumed to have been produced by a slurry Fischer-Tropsch hydrocarbon synthesis process and reactor 12 is a hydroisomerization unit. The hydroisomerization catalyst in the reactor 12 has a silica content of 10 to 30% by weight.
Supported on the amorphous alumina-silica carrier component in the range of
Of MoO ₃ and 2-5 wt% CoO. Reaction conditions include temperatures of 713 ° F and 725 psig and hydrogen pressure. About 4 of raw materials during hydroisomerization
0% by weight is converted into a light hydrocarbon fraction having a boiling point lower than the initial boiling point of the wax-containing fraction, and the remaining 60% by weight of the heavier hydroisomerized raw material is subjected to the dewaxing operation. To be done. The hydroisomerized hydrocarbons are withdrawn from the bottom of the reactor via line 34 and sent to a simple separation drum 18 where light hydrocarbons are withdrawn as vapor overhead via line 36. This separation also includes a rectification column (not shown) for treating the separated liquid before it is sent to the downstream dewaxer.
May be included. The heavy wax-containing raw material is taken out of the drum 18 as a liquid,
It is sent to catalytic dewaxing reactor 14 via line 38. Reactor 14 includes a fixed bed 40 of dewaxing catalyst containing 0.5 wt% Pt supported on H-mordenite. Hydrogen or hydrogen-containing feed gas is sent to the reactor via line 42. Dewaxing conditions in the reactor include a temperature of about 550 ° F and a hydrogen pressure of about 725 psig. The waxy feed reacts with hydrogen in the presence of a dewaxing catalyst which lowers its pour point and converts some of the feed to lower boiling materials. During dewaxing, about 20 wax-containing raw materials
Volume% is converted to lower boiling materials. Dewaxed hydrocarbons are in line 44
Is discharged from the dewaxing reactor via the and is fed to the flash evaporator 20 operated at a pressure lower than that of the dewaxing reactor. The flash evaporator is also a simple drum separator. The lighter material is withdrawn as vapor overhead via line 46. The remaining 650-750 ° F + dewaxed product is withdrawn via line 48 and sent to distillation column 16 where it is fractionated into the desired number of lubricant and fuel fractions as shown. It The vapor overhead is sent via line 55 to the heat exchanger 24 where a portion of the hydrocarbon vapor is condensed and the resulting liquid-vapor mixture is sent via line 25 to the separation drum 22. The vapor and liquid are separated, the vapor is withdrawn from the top of the column via line 27 and the condensate is returned to the top of the column as reflux via line 23. A portion of the overhead liquid (23A) is withdrawn as a light product stream. It can be used as a light lubricant base oil or fuel. Less than 10% by volume of the feedstock sent to the distillation column via line 48 is converted to a light vacuum gas oil fraction suitable for use in diesel fuel. It is removed from the column via line 50.
About 25% by volume is withdrawn as automatic transmission fluid base oil via line 52.
About 50% by volume of the dewaxed distillate is withdrawn via line 54 as a lubricant fraction useful as a base oil for passenger car motor oil (crankcase motor oil). The remaining 25% by volume is the heavy lubricant base oil fraction, which is withdrawn from the bottom of the column via line 56. It has an initial boiling point in the range of 800-850 ° F and approximately 1142.
It has an end point of ° F. About 75% by volume of this heavy dewaxed product is sent via line 58 for further processing and converted into a heavy lubricant for industrial and / or heavy engine oil applications. The remaining 25% by volume is sent via line 60 to heat exchanger 26 where it is cooled to a temperature below 550 ° F. and then quenched via lines 62, 64 and 66. Is sent to the reactor 14. As shown in the examples below, this quench fluid is unlikely to react to any significant extent with hydrogen in the presence of a dewaxing catalyst, for reasons that are not fully understood. This chilled recycled dewaxed product allows the dewaxing reactor to operate at the desired temperature without the need to use chilled feedstock, chilled gas, dewaxed products and other chilled hydrocarbon liquids or indirect heat exchange systems to dilute the feedstock. Hold at 550 ° F.

FIG. 2 is a flow chart outlining an integrated hydrocarbon synthesis process useful in practicing the present invention, including hydroisomerization and dewaxing of Fischer-Tropsch synthesized waxy fractions. The same numbers as in FIG. 1 shown in FIG. 2 refer to the same reactors, heat exchangers, separators, lines and distillation columns. Referring to FIG. 2, the integrated device 1
00 comprises a slurry hydrocarbon synthesis reactor 110 containing a three-phase slurry 112. The reactor has a gas distribution plate 114 at the bottom of the slurry for injecting syngas from the lower plenum region, and further has a liquid filtering means, indicated by box 116, immersed in the slurry. ing. A mixture of H ₂ and CO (
A synthesis gas having a molar ratio of 2.1: 1) is sent to a reactor via a line 118 together with a slurry liquid containing a synthetic hydrocarbon that is liquid under the reaction conditions, and the slurry liquid as a filtrate via a line 120. Continuously withdrawn, the gaseous reactor effluent is withdrawn from the top of the column as tail gas via line 122. A filtrate containing a synthetic hydrocarbon that is liquid under the reaction conditions and containing a fraction having a boiling point of 650 to 750 ° F.
It is the same as in FIG. 1 and is sent to the hydroisomerization reactor 12 containing the same catalyst.
In the hydrocarbon synthesis reactor 110, H ₂ and CO in the synthesis gas react in the presence of a particulate catalyst to produce a desired hydrocarbon (most of which constitutes a slurry liquid) and a gas reaction product (mostly). Produce water vapor and CO ₂ ). The circles at 112 represent the bubbles of synthesis gas or gas product, while the solid circles represent the particulate Fischer-Tropsch hydrocarbon synthesis catalyst. The gaseous overhead vapor, CO _2, gaseous hydrocarbon products, include unreacted synthesis gas and minor amounts of oxygenates. The overhead is sent to hot and cold heat exchangers 124 and 126 where it is cooled to condense some of the water and hydrocarbons. Then, further, the condensed hydrocarbon liquid is sent to the high temperature and low temperature separators 128 and 130, and the condensed hydrocarbon liquid is recovered.
At this time, the gas overhead is sent to a high temperature heat exchanger 124 via a line 122 to condense some of the steam and heavy hydrocarbons as a liquid, and then a mixture of gas and liquid via a line 132. It is sent to a separator 128 where water and liquid hydrocarbons are separated from the rest of the gas as separate liquid layers. The aqueous layer is withdrawn via line 134, while the hydrocarbon liquid is withdrawn via line 136 and sent to hydroisomerization unit 12 with the filtrate from filter 116. The hydrocarbon liquid taken out from the high temperature separator 128 contains hydrocarbons that solidify under standard conditions of room temperature and room pressure, and is useful as a part of the wax-containing raw material for the hydroisomerization device 12. The non-condensed gas is withdrawn from separator 128 and sent to low temperature heat exchanger 126 via line 140 to condense more water and light hydrocarbons as a liquid. The gas and liquid mixture is then sent via line 142 to the cryogenic separator 130 where the liquid is separated from the non-condensing gas as two separate layers. Water is withdrawn via line 144 and hydrocarbon liquid is drawn through line 14
Via line 6 to line 34. Non-condensed vapor is withdrawn overhead from line 150. Hydrogen or hydrogen-containing feed gas is sent to the top of the hydroisomerization unit via line 30. The hydrocarbons are hydroisomerized and the hydroisomerized hydrocarbon and gas mixture is withdrawn from the reactor via line 34,
The light hydrocarbons from 6 are sent to a fractionator 156 operating at atmospheric pressure or higher. There, the light components are separated as fuel fractions such as naphtha fraction taken out via line 158 and jet / diesel fuel fraction taken out via line 160 and unreacted hydrogen (taken out via 138). And the light hydrocarbon gas is withdrawn as tail gas via line 162. Heavy hydroisomerates containing the desired hydrocarbons with boiling points in the lubricating oil range and initial boiling points in the range of 650 to 750 ° F are withdrawn from the bottom of the fractionator via line 164. Thus, in this embodiment, the light ends in the hydroisomerate are separated from the lubricating oil material prior to dewaxing. This greatly reduces both the load on the dewaxer and the subsequent vacuum pipe stills. A lubricating oil fraction having an initial boiling point of about 700 ° F. and an end point greater than 1050 ° F. is fed via line 164 to a catalytic dewaxer 14 comprising a fixed bed 40 of dewaxing catalyst with Pt / H-mordenite. Sent to. Hydrogen or hydrogen-containing process gas is sent via line 42 to the top of dewaxing reactor 14 where it reacts with the hydrogen isomerate to lower its pour point and produce a dewaxed product containing lubricant base oil. . This dewaxed product, along with unreacted hydrogen and the gas product of the dewaxing reaction, is sent to simple flash fractionator 20 via line 44 to remove steam and gas as overhead and then via line 48. It is sent to the vacuum distillation column 16. Similar to the case of hydroisomerization, when catalytic dewaxing is performed, a part of the base oil substance is decomposed into a substance having a lower boiling point and a light fraction is produced. In the vacuum pipe still, the light ends are separated from the dewaxed base oil and removed from the system via line 158, and the dewaxed lubricant base oil is removed from the system via line 56. Although only one base oil stream is shown for convenience, more typically, multiple base oils having different viscosities are produced by vacuum fractional distillation. Light hydrocarbon gas and residual unreacted hydrogen are stored in line 8
It is taken from the top of the tower via 0. Most of the heavy base oils (eg over 50%)
It is removed via line 58 for further processing and converted to various lubricants. The remainder is sent via line 60 to heat exchanger 26, where it passes, where it is cooled to a temperature well below that in the dewaxing reactor and used as a quench fluid. This chilled quench fluid is returned to the dewaxing reactor via lines 62, 64 and 66, where the chilled quench fluid reacts with hydrogen in the reactor to such an extent that it becomes less effective as a quench fluid. There is no such thing.

Suitable Fischer-Tropsch reaction type catalysts are, for example, Fe, Ni, Co
Although containing one or more Group VIII catalytic metals such as Ru, Ru and Re, it is preferred in the process of the invention that the catalyst comprises a cobalt catalytic component. In one embodiment, the catalyst is a catalytically effective amount of Co and Re, Ru, Fe, Ni, T supported on a suitable inorganic support material, preferably a support material comprising a refractory metal oxide.
It contains at least one of h, Zr, Hf, U, Mg and La. A preferred support for Co-containing catalysts especially contains titania. Useful catalysts and their preparation are known, and specific examples thereof are, for example, US Pat. Nos. 4,568,663; 4,663,305; 4,542,122; 621,072 and 5,545,674, but is not limited thereto. In a preferred Fischer-Tropsch hydrocarbon synthesis method for carrying out the present invention, in a slurry hydrocarbon synthesis method, the synthesis gas containing a mixture of H ₂ and CO is a liquid hydrocarbon product of the synthesis reaction under reaction conditions. Is bubbled as a third phase into the slurry in the reactor containing the particulate Fischer-Tropsch type hydrocarbon synthesis catalyst dispersed and suspended in the slurry liquid containing. The molar ratio of hydrogen to carbon monoxide can range widely, from about 0.5 to 4, but more typically about 0.7 to 2.75.
, Preferably about 0.7 to 2.5. The stoichiometric molar ratio of the Fischer-Tropsch hydrocarbon synthesis reaction is generally about 2.0, but in the slurry hydrocarbon synthesis method, it is typically about 2.1 / 1. It is also possible to increase the desired amount of hydrogen from the syngas for this purpose. The slurry process conditions vary slightly depending on the catalyst and the desired product. In practicing the present invention, it is preferred to carry out the hydrocarbon synthesis reaction under conditions in which there is little or no water gas shift reaction during hydrocarbon synthesis, more preferably no water gas shift reaction. It is also possible to carry out the reaction under conditions which achieve an α of at least 0.85, preferably at least 0.9, more preferably at least 0.92 in order to synthesize more of the more desirable higher molecular weight hydrocarbons. preferable. This was accomplished in a slurry process with a catalyst containing a catalytic cobalt component.
It is known to the person skilled in the art that α means Schultz-Flory kinetic α. In a slurry hydrocarbon synthesis method utilizing a catalyst containing a supported cobalt component,
Typical conditions effective to form hydrocarbons consisting mostly of C ₅₊ paraffins (eg C _{5+ to} C ₂₀₀ ), preferably C ₁₀₊ paraffins (more preferably C ₂₀₊ ) include, for example, about 320 to about 600 ° F temperature, 80 ~
600 psi pressure and 100-40,000 V / hr / V hourly gas hourly space velocity (as a volume of CO and H ₂ gas mixture per unit time and unit volume of catalyst at standard conditions (0 ° C., 1 atmosphere)) (Represented). Hydrocarbons that are liquid under the reaction conditions are removed from the reactor using filtration means.

[0016]   The invention will be further understood with reference to the following examples.

[0017]Example Fischer-Tropsch synthesis   In the slurry reactor, H_TwoH with a molar ratio of CO to 2.11 to 2.16_TwoWhen
Fischer-Tropsch synthesized waxy carbonized water from synthesis gas feed containing a mixture of CO
Generated a prime. The slurry contains cobalt and rhenium supported on titania.
Fischer-Tropsch hydrocarbons consisting of and dispersed in a hydrocarbon slurry liquid
Particles of synthesis catalyst were included in the slurry along with bubbling synthesis gas
. The slurry liquid contains the hydrocarbon products of the synthetic reaction that are liquid under the reaction conditions.
I was there. The reaction conditions include a temperature of 425 ° F, a pressure of 290 psig and a pressure of 12
A gas feedstock linear velocity of -18 cm / sec was included. Α of synthesis process is more than 0.9
It was great. It is a liquid under the reaction conditions, and the wax-containing hydrocarbon that constitutes the slurry is filtered.
More removed from the reactor. The boiling point distribution of this wax-containing hydrocarbon liquid is shown in Table 1.

[0018]

[Table 1]

Hydroisomerization The wax-containing liquid was subjected to fractionation without fractionation (hence 700% as shown in Table 1).
Hydroisomerization (contains 29% by weight of substances having a boiling point below ° F). Amorphous silica-alumina cogel Cobalt (CoO, 3.2 wt%) and molybdenum (MoO ₃ , 15.O3) supported on acidic components (of which 15.5 wt% was silica).
2 wt%) in the presence of a bifunctional hydroisomerization catalyst to hydroisomerize the wax-containing liquid with hydrogen. The catalyst has a surface area of 266 m ² / g and 0.6
Pore volume of 4 mL / g and had a _{(P.V. H2O).} This catalyst was prepared by precipitating a cobalt component on a carrier and calcining it before depositing and calcining the molybdenum component. The conditions for hydroisomerization are shown in Table 2. This condition is 700 ° F +
It was selected with the goal of achieving a conversion of 50% by weight of the distillate. The conversion rate is defined as follows. Conversion of 700 ° F + = [1- (weight% of 700 ° F + in the product) / (weight% of 700 ° F + in the raw material)] × 100

[0020]

[Table 2]

As shown in the table, 50% by weight of the 700 ° F + waxy feed is 700 ° F.
It was converted to a product with a boiling point of F-. Fractional distillation of hydrogen isomers at 700 ° F
The + fraction and the 700 ° F-fraction were separated and the separated 700 ° F-hydroisomer was further fractionated to recover a fuel product having a reduced cloud point and freezing point.

Table 3 lists 700 ° F + hydroisomers containing 86.8% by weight of hydrocarbons with boiling points in the range 700-950 ° F and 11.6% by weight of hydrocarbons with boiling points of 950 ° F +. Shows the nature.

[0023]

[Table 3]

Catalytic Dewaxing 700 ° F + hydroisomers shown in Table 3 were mixed with 0.5 wt% Pt / H.
Catalytic dewaxing with a mordenite catalyst to lower the pour point and produce a high VI lubricating base oil. In this experiment, a small upflow pilot plant device was used. Dewaxing conditions include 750 psig at 1 LHSV and 550 ° F temperature
H ₂ pressure and 2500 SCF / B nominal feed gas volume. The dewaxed product withdrawn from the reactor is fractionated using standard 15/5 distillation to remove the low boiling fuel components produced in the dewaxing reactor and produce 700 ° F + product. Hiv
Ac narrow distillation to obtain narrow cuts, then 730-950 ° F and 95
The low temperature characteristics were measured for the 0 ° F + part. The results are summarized in Table 4.

[0025]

[Table 4]

The data in Table 3 show the respective yields of 86.8 wt% hydroisomerate and 11.6 wt% 950 ° F + hydroisomerate having boiling points in the range of 700-950 ° F. ing. Therefore, of the 700 ° F + hydrogen isomers, 700 ° F +
Is 88.2% by weight and 950 ° F + is 11.8% by weight.
Table 4 shows that after dewaxing, only about 59.9% by weight of the dewaxed product at about 700 ° F + was 700.
° F +, while indicating that 23.5% by weight consists of 950 ° F + dewaxed product. This indicates that in the dewaxer, the 700-950 ° F hydroisomerate feedstock was significantly converted to lower boiling hydrocarbons, while the 950 ° F + dewaxed material was essentially lower boiling. It is suggested that it is not converted to hydrocarbons.

From this, 950 ° F + which is recycled and used as quench fluid
It is demonstrated that the heavy dewaxed products of ## STR3 ## are essentially non-reactive with the dewaxing catalyst.

Various other embodiments and modifications of the invention will be apparent to those skilled in the art, and are believed to be readily implementable without departing from the scope and spirit of the invention described above. Therefore, the claims appended hereto are not to be limited to the above detailed description, and the claims are equivalent to those skilled in the art to which the present invention pertains. All patentable novel features belonging to this invention are considered to be encompassed, including all features and embodiments treated as.

[Brief description of drawings]

[Figure 1]   1 is a flow chart outlining a dewaxing process useful in practicing the present invention.

FIG. 2 is a flowchart showing an outline of a slurry Fischer-Tropsch hydrocarbon synthesis method including a dewaxing method according to an embodiment of the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10G 45/64 C10G 45/64 65/04 65/04 65/12 65/12 67/02 67/02 ( 72) Inventor Dean, Christopher, M. 70809, Louisiana, United States, Baton Rouge, Jefferson Plais Boulevard 7955 (72) Inventor Wittenbrink, Robert, Jay United States, Texas 77345, Kingswood, Riverchase Trail 6018 (72) Inventor Ryan, Daniel, Francis United States , Louisiana 70820, Baton Rouge, Gabriel Oaks Drive 6211 F-term (reference) 4H029 CA00 DA00 DA01 DA11 DA12 DA13 DA14

Claims (22)

[Claims] 1. In a catalytic dewaxing zone, hydrogen reacts with a waxy paraffinic hydrocarbon feedstock to produce a dewaxed product having a reduced pour point and a heavy fraction. Contacting a wax-containing paraffinic hydrocarbon feed with hydrogen in the presence of a dewaxing catalyst under conditions of high temperature and high pressure; separating and cooling at least a part of the heavy fraction: and quenching it for temperature control A catalytic dewaxing method comprising the step of returning the liquid as a liquid to the dewaxing zone. 2. The method of catalytic dewaxing according to claim 1, wherein the heavy dewaxed fraction has an initial boiling point in the range of 800 to 950 ° F. 3. The method of catalytic dewaxing according to claim 2, wherein the wax-containing feedstock comprises a hydrocarbon having an initial boiling point in the range of 650 to 750 ° F. 4. The method of catalytic dewaxing according to claim 3, wherein the wax-containing raw material has an end point of 1050 ° F. or higher. 5. The catalytic dewaxing method according to claim 4, wherein the wax-containing raw material contains a hydrogen isomerate. 6. The dewaxing catalyst comprises at least one catalytic metal component and at least one acidic microcrystalline aluminosilicate component.
The catalytic dewaxing method described in. 7. The catalytic dewaxing process according to claim 6, wherein the catalytic metal component comprises at least one metal belonging to Group VIII. 8. The metal component comprises a noble metal component.
The catalytic dewaxing method described in. 9. The catalytic dewaxing method according to claim 8, wherein the wax-containing raw material is derived from Fischer-Tropsch synthesized hydrocarbon. 10. The catalytic desorption according to claim 8, wherein the wax-containing raw material is derived from slack wax or hydrocracked product treated to remove non-paraffinic hydrocarbons and heteroatom compounds. Wax method. 11. The catalytic dewaxing method according to claim 10, wherein the wax-containing raw material is hydroisomerized. 12. The method of catalytic dewaxing according to claim 8, wherein the catalyst contains Pt and H-mordenite. 13. A wax-containing paraffinic hydrocarbon fraction is synthesized from a synthesis gas containing a mixture of H ₂ and CO, and the wax-containing fraction is hydroisomerized to produce a hydrogen isomer. Catalytically dewaxing in the dewaxing zone, having a reduced pour point,
An integrated hydrocarbon synthesis process comprising producing a dewaxed product containing a heavy cut and cooling a portion of the heavy dewaxed cut for use as a quench liquid in the dewaxing zone. And (a) reacting H ₂ and CO in the presence of a Fischer-Tropsch hydrocarbon synthesis catalyst containing a catalytic cobalt component under reaction conditions effective to produce a high-purity paraffin wax-containing hydrocarbon. Reacting a mixture, wherein at least a portion of the wax-containing hydrocarbon is liquid under the reaction conditions; (b) sending the wax-containing hydrocarbon to a hydroisomerization reaction zone; (c) the The waxy hydrocarbon is reacted with hydrogen in the presence of a bifunctional hydroisomerization catalyst in a hydroisomerization reaction zone to have an initial boiling point in the range of 650 to 750 ° F and an end point of 1050 ° F or higher. Hydroisomers containing hydrocarbons (D) reacting the hydrogen isomerate with hydrogen at high temperature and high pressure in the presence of a catalyst containing a Group VIII catalyst metal component and a crystalline aluminosilicate component to produce the hydrogen in the catalytic dewaxing zone. Catalytic dewaxing of the isomer to lower its pour point, 65
A process for producing a dewaxed product containing hydrocarbons having an initial boiling point higher or lower than the range of 0 to 750 ° F, wherein the dewaxed product has an initial boiling point in the range of 800 to 950 ° F. (E) separating at least a portion of the heavy hydrocarbon dewaxed from the rest of the dewaxed; and (f) the separated heavy hydrocarbon. Carbonizing, comprising cooling at least a portion of the dewaxed material to a temperature below the temperature of the catalytic dewaxing zone; and (g) returning the cooled dewaxed material as a quench liquid to the dewaxing reaction zone. Hydrogen synthesis method. 14. The H ₂ and the CO react in a slurry containing a hydrocarbon slurry liquid, bubbles and a particulate hydrocarbon synthesis catalyst, and the slurry liquid contains a synthetic hydrocarbon that is liquid under the reaction conditions. The hydrocarbon synthesis method according to claim 13, wherein the slurry liquid is taken out from the slurry and sent to the hydroisomerization reaction zone of step (b). 15. The process for synthesizing hydrocarbons according to claim 14, wherein the quench liquid lowers the temperature of the dewaxing zone. 16. The wax-containing synthetic hydrocarbon fraction as set forth in claim 15, wherein the wax-containing synthetic hydrocarbon fraction comprises a hydrocarbon having an initial boiling point in the range of 650 to 750 ° F. and an end point of 1050 ° F. or higher. Hydrocarbon synthesis method. 17. The hydrocarbon synthesis method according to claim 16, wherein the hydroisomerization catalyst contains a Group VIII non-noble metal catalyst component and an acidic carrier. 18. The hydrocarbon synthesis method according to claim 17, wherein the dewaxing catalyst contains a zeolite component and a noble metal component. 19. The hydrocarbon synthesis method according to claim 18, wherein the dewaxing catalyst contains Pt and H-mordenite. 20. The hydrocarbon synthesis according to claim 18, wherein the hydroisomerization catalyst comprises cobalt and molybdenum catalyst metal components and the support comprises alumina-silica having up to 30 wt% silica. Method. 21. The slurry liquid comprises hydrocarbons at 650 to 750 ° F-, and at least a portion of the hydrocarbons are withdrawn before the slurry liquid is hydroisomerized. 15. The hydrocarbon synthesis method according to 14. 22. The hydrocarbon synthesis process of claim 13, wherein the heavy dewaxed fraction has an end point greater than 1050 ° F.