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Title:
PROCESS FOR PREPARING A HYDROWAX
Document Type and Number:
WIPO Patent Application WO/2014/095813
Kind Code:
A1
Abstract:
The invention provides a process for preparing a hydrowax comprising the steps of: (a) providing a hydrocarbonaceous feedstock which contains more than 4% by weight of hydrocarbons boiling in the range of from 550 to 800 °C; (b) hydrotreating the hydrocarbonaceous feedstock with a hydrotreating catalyst in the presence of a hydrogen- containing gas under hydrotreating conditions to obtain a hydrotreated product; (c) hydrocracking at least part of the hydrotreated product as obtained in step (b) with a hydrocracking catalyst in the presence of a hydrogen-containing gas under hydrocracking conditions to obtain a hydrocracked product, which hydrocracking catalyst contains a zeolitic component which is present in an amount of at least 14 wt%, based on the total weight of the hydrocracking catalyst, and wherein the volume ratio of the hydrotreating catalyst as used in step (b) and the hydrocracking catalyst is more than 1; and (d) recovering from the hydrocracked product as obtained in step (c) the hydrowax.

Inventors:
BARIC, John Joseph (Grasweg 31, HW Amsterdam, NL-1031, NL)
VAN DIJK, Nicolaas (Grasweg 31, HW Amsterdam, NL-1031, NL)
HUVE, Laurent Georges (Grasweg 31, HW Amsterdam, NL-1031, NL)
Application Number:
EP2013/076837
Publication Date:
June 26, 2014
Filing Date:
December 17, 2013
Export Citation:
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Assignee:
SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. (Carel van Bylandtlaan 30, HR The Hague, NL-2596, NL)
SHELL OIL COMPANY (PO Box 2463, One Shell PlazaHouston, Texas, 77252-2463, US)
International Classes:
C10G65/12; B01J21/12; B01J23/888; B01J29/08; B01J37/20; C10G73/44
Domestic Patent References:
WO1992001657A1
WO1992001769A1
Foreign References:
EP0697455A2
US6171474B1
EP0310165A1
EP0214717A1
US5122257A
EP0697455A2
US6576120B1
US5139647A
Other References:
MINDERHOUD J K ET AL: "First-stage hydrocracking: process and catalytic aspects", FUEL PROCESSING TECHNOLOGY, ELSEVIER BV, NL, vol. 35, no. 1-2, 1 September 1993 (1993-09-01), pages 87-110, XP025696593, ISSN: 0378-3820, DOI: 10.1016/0378-3820(93)90086-J [retrieved on 1993-09-01]
Attorney, Agent or Firm:
MATTHEZING, Robert Maarten (PO Box 384, CJ The Hague, NL-2501, NL)
Download PDF:
Claims:
C L A I M S

1. Process for preparing a hydrowax comprising the steps of:

(a) providing a hydrocarbonaceous feedstock which contains more than 4% by weight of hydrocarbons boiling in the range of from 550 to 800 °C;

(b) hydrotreating the hydrocarbonaceous feedstock with a hydrotreating catalyst in the presence of a hydrogen- containing gas under hydrotreating conditions to obtain a hydrotreated product;

(c) hydrocracking at least part of the hydrotreated product as obtained in step (b) with a hydrocracking catalyst in the presence of a hydrogen-containing gas under hydrocracking conditions to obtain a hydrocracked product, which hydrocracking catalyst contains a zeolitic component which is present in an amount of at least 14 wt%, based on the total weight of the hydrocracking catalyst, and wherein the volume ratio of the hydrotreating catalyst as used in step (b) and the hydrocracking catalyst is more than 1; and (d) recovering from the hydrocracked product as obtained in step (c) the hydrowax.

2. Process according to claim 1, wherein the

hydrocarbonaceous feedstock as provided in step (a) contains more than 8% by weight of hydrocarbons boiling in the range of from 550 to 800 °C.

3. Process according to claim 1 or 2, wherein the

hydrocarbonaceous feedstock as provided in step (a) contains between 8-30% by weight of hydrocarbons boiling in the range of from 560 to 800 °C.

4. Process according to any one of claims 1-3, wherein in the hydrocarbonaceous feedstock as provided in step (a) the ratio of the fraction of hydrocarbons boiling in the range of from 370-543 °C and the fraction of hydrocarbons boiling in the range of from 550-800 °C is less than 25.

5. Process according to any one of claims 1-4, wherein the zeolitic component in the hydrocracking catalyst is present in an amount in the range of from 18-30 wt%, based on the total weight of the hydrocracking catalyst.

6. Process according to any one of claims 1-5, wherein the zeolitic component comprises a zeolite Y.

7. Process according to claim 6, wherein the zeolite has a Si/Al ratio in the range of from 8-50.

8. Process according to any one of claims 1-8, wherein the hydrocracking catalyst also comprises an amorphous silica- alumina in an amount of less than 50 wt%, based on the total weight of the hydrocracking.

9. Process according to 1-8, in which the hydrotreating conditions in steps (b) comprise a temperature in the range of from 250-480 °C, a pressure in the range of from 30-250 bar, and a weight hourly space velocity in the range of from 0.2-10 hr-1.

10. Process according to any one of claims 1-9, in which the hydrocracking conditions in steps (c) comprise a temperature in the range of from 350-460 °C, a pressure in the range of from 80-240 bar, and a weight hourly space velocity in the range of from 0.4-7 hr-1.

11. Process according to any one of claims 1-10, wherein the entire hydrotreated product as obtained in step (b) is subjected to the hydrocracking in step (c) .

12. Process according to any one of claims 1-11, wherein at least part of the hydrocracked product as obtained in step (c) is recycled to step (b) .

13. Process according to any one of claims 1-12, wherein the hydrotreating catalyst as used in step (b) comprises one or more metals from Groups VB, VIB and/or VIII of the Periodic Table of the Elements, on a solid carrier.

14. Process according to any one of claims 1-13, wherein the hydrocracking catalyst as used in step (c) comprises comprises one or more metals from Groups VIB and/or VIII of the Periodic Table of the Elements.

15. Process according to any one of claims 1-14, wherein the hydrowax recovered in step (d) is subjected to a catalytic dewaxing step and hydrofinishing step.

Description:
PROCESS FOR PREPARING A HYDROWAX

Field of the Invention

The present invention relates to a process for

preparing a hydrowax.

Background of the Invention

Hydrowax is paraffinic fraction with a boiling point typicaly in the range of 340 to 560 °C which is obtainable from a hydrocracker . Hydrowax can for instance be used for the production of lubricating base oils and as a feedstock for producing lower olefins. Typically, a hydrowax is obtained by subjecting a refinery distillation fraction to a hydrotreating step and subsequently a hydrocracking step.

In EP 0 697 455 A2 , a process is described for

producing a hydrowax in which process a blend of a flashed distillate and a hydrodemetallised deasphalted oil is subjected to hydrocracking over a stacked bed of a

conventional first stage hydrocracking catalyst (NiMoP on alumina) on top of a dedicated second hydrocracking

catalyst (NiW on amorphous silica-alumina) . The hydrowax thus obtained can be used as the feedstock for a steam cracker to produce ethylene and propylene or as a feedstock for a dewaxing unit or hydroprocessing unit for producing lubricating base oils.

Generally, a higher conversion in the hydrocracker improves the quality of hydrowax as feedstock for a steam cracker or as feed for a base oil plant. However, a higher conversion also means that the hydrowax yield of the hydrocracker becomes smaller.

A drawback of the known processes to produce

hydrowaxes is that a higher conversion reduces substantially the ratio of heavy hydrowax over light hydrowax, which in turn reduces substantially the ratio of heavy lubricating base oils over light lubricating base oils .

At a constant level of conversion, a heavier feed to the hydrocracker will result in a heavier hydrowax.

However, in order to maintain the hydrowax quality for a heavier hydrocracker feed its conversion level has to be raised which in turn reduces the the ratio of heavy hydrowax over light hydrowax.

Object of the present invention is to provide a process which at a given feed heaviness and conversion level results in a higher ratio of heavy hydrowax to light hydrowax .

Summary of the invention

Accordingly, the present invention provides a process for preparing a hydrowax comprising the steps of:

(a) providing a hydrocarbonaceous feedstock which contains more than 4% by weight of hydrocarbons boiling in the range of from 550 to 800 °C;

(b) hydrotreating the hydrocarbonaceous feedstock with a hydrotreating catalyst in the presence of a hydrogen- containing gas under hydrotreating conditions to obtain a hydrotreated product;

(c) hydrocracking at least part of the hydrotreated product as obtained in step (b) with a hydrocracking catalyst in the presence of a hydrogen-containing gas under

hydrocracking conditions to obtain a hydrocracked product, which hydrocracking catalyst contains a zeolitic component which is present in an amount of at least 14 wt%, based on the total weight of the hydrocracking catalyst, and wherein the volume ratio of the hydrotreating catalyst as used in step (b) and the hydrocracking catalyst is more than 1; and (d) recovering from the hydrocracked product as obtained in step (c) the hydrowax.

In accordance with the present invention a higher ratio of heavy hydrowax to light hydrowax can attractively be obtained when compared with conventional processes.

Detailed description of the invention

The hydrocarbonaceous feedstock as provided in step (a) contains preferably more than 8% by weight of hydrocarbons boiling in the range of from 550 to 800 °C. More

preferably, the hydrocarbonaceous feedstock contains between 8-30% by weight of hydrocarbons boiling in the range of from 550 to 800 °C. In the hydrocarbonaceous feedstock as provided in step (a) the ratio of the fraction of hydrocarbons boiling in the range of from 370-543 °C and the fraction of hydrocarbons boiling in the range of from 550 to 800 °C is preferably less than 25. The

hydrocarbonaceous feedstock useful in the process of the present invention may be either heavy gas oil fractions obtained from the atmospheric distillation of a crude oil or flashed distillate fractions obtained from the vacuum flash distillation or vacuum distillation of an atmospheric hydrocarbon oil residue. For the purpose of the present invention it is not strictly required to use sharply defined distillate fractions (such as obtained in vacuum distillation) and therefore it is preferred that the distillate fractions are produced by the less expensive vacuum flash distillation of an atmospheric hydrocarbon oil residue.

At least part of the hydrocarbonaceous feedstock as provided in step (a) can suitably be a blend obtained by blending at least one distillate fraction, preferably a vacuum distillate fraction, and a deasphalted oil (DAO) . The DAO that can be used is suitably obtained by

deasphalting a residual hydrocarbon oil, preferably a vacuum residue. The deasphalting may be carried out in any conventional manner. A well known and suitable deasphalting method is solvent deasphalting, which involves the

countercurrent treatment of the residual hydrocarbon oil feed with an extracting solvent. This extracting solvent usually is a light hydrocarbon solvent containing

paraffinic compounds having 3 to 8 carbon atoms, such as propane, butane, isobutane, pentane, isopentane, hexane and mixtures of two or more of these. Preferred paraffinic hydrocarbons are those having 3 to 5 carbon atoms with butane, pentane and mixtures thereof being most preferred. The solvent deasphalting treatment is conveniently carried out in a rotating disc contactor or a plate column with the residual hydrocarbon oil feed entering at the top and the extracting solvent entering at the bottom. The lighter hydrocarbons present in the residual hydrocarbon oil dissolve in the extracting solvent and are withdrawn at the top of the apparatus. From this top-fraction, the DAO is obtained after recovery of the extracting solvent. The asphaltenes, which are insoluble in the extracting solvent, are withdrawn at the bottom of the apparatus . The

conditions under which deasphalting takes place are known in the art. Suitably, deasphalting is carried out at a total extracting solvent to residual hydrocarbon oil ratio of 1.5-8 wt/wt, a pressure of 1-50 bar and a temperature of

160-230 °C. The deasphalted oil may be obtained by deasphalting a distillate fraction, preferably a vacuum distillate

fraction, containing hydrocarbons that have a boiling point in the range of from having a 550-800 °C. At least part of the deasphalted oil may be derived from a coking unit in which a feed containing hydrocarbons boiling in the range of 370-543 °C are processed.

In step (b) , the hydrocarbonaceous feedstock is hydrotreated with a hydrotreating catalyst in the presence of a hydrogen-containing gas under hydrotreating conditions to obtain a hydrotreated product.

In step (c) , at least part of the hydrotreated product as obtained in step (b) is hydrocracked with a

hydrocracking catalyst in the presence of a hydrogen- containing gas under hydrocracking conditions to obtain a hydrocracked product, which hydrocracking catalyst contains a zeolitic component which is present in an amount of at least 14 wt%, preferably in the range of from 18-30 wt%, based on the total weight of the hydrocracking catalyst, and wherein the volume ratio of the hydrotreating catalyst as used in step (b) and the hydrocracking catalyst is more than 1.

Preferably, the volume ratio of the hydrotreating catalyst as used in step (b) and the hydrocracking catalyst is more than 1.5, more preferably in the range of from 2-4.

The zeolitic component preferably comprises a zeolite Y. Preferably, the zeolite has a Si/Al ratio in the range of from 8-50.

Suitably, the hydrocracking catalyst also comprises an amorphous silica-alumina in an amount of less than 50 wt%, preferably less than 45 wt%, and more preferably in the range of from 20-40 wt%, based on the total weight of the hydrocracking catalyst.

In the context of the present invention the amounts of the zeolitic component and the amorphous silica-alumina are determined on the basis of the total weight of the

hydrocracking catalyst in the fresh oxidic state.

Typical examples of the hydrocracking catalyst are NiW/zeolite and NiW/ zeolite/silica-alumina .

The hydrocracking catalyst may also contain a promoter in the form of phosphorus (P) .

Suitable hydrocracking conditions in steps (c) include a temperature in the range of from 350-460 °C, preferably in the range of from 370-420 °C; a pressure in the range of from 80-240 bar, preferably in the range of from 150-210 bar; and a weight hourly space velocity in the range of from 0.4-7 hr -1 , preferably in the range of from 2-5 hr -1 .

For the purpose of the present invention the

hydrocracking process can be a single- or a multiple-staged process. In the case of a single-staged process, a stacked bed of a hydrodenitrification/first-stage hydrocracking catalyst on top of the conversion catalyst can suitably be used. Particularly suitable hydrodenitrification/first- stage hydrocracking catalysts are NiMo/alumina and

CoMo/alumina , optionally promoted with phosphorus and/or fluorine.

The conversion hydrocracking catalyst is the

hydrocracking catalyst which contains the zeolitic

component which is present in an amount of at least 14wt%, as described hereinabove.

Preferably, the entire hydrotreated product as obtained in step (b) is subjected to the hydrocracking in step (c) . Suitably, at least part of the hydrocracked product as obtained in step (c) is recycled to step (b) .

The hydrowax in accordance with the present invention is very useful as a feedstock for a thermal steam cracker to produce lower olefins.

Thermal steam cracking is a known method for producing lower olefins, particularly ethene and to a somewhat lesser extent propene. It is a strongly endothermic process and basically involves heating a hydrocarbon oil feed to a sufficiently high temperature for cracking reactions to occur followed by rapid cooling of the reactor effluent and fractionation of this effluent into the different products. A steam cracker, also commonly referred to as an ethene cracker, usually consists of a hot section and a cold section. The hot section consists of cracking furnaces, a cooling section and a primary fractionator for separating the effluent in a cracked residue, pan oil, cracked gas oil and cracked gas. Steam is introduced into the cracking furnace to dilute the feed. This is favourable for the final olefin yield, while the added steam also suppresses the deposition of coke in said furnace. In the cold section the cracked gas is further separated into the various end products among which are pure ethene and propene. In general, this separation is achieved by first compressing the cracked gas from the primary fractionator to a pressure of about 30-40 bar followed by cooling the compressed gas to temperatures below -100 °C to enable separation into the various pure end products. The removal of gases such as carbon dioxide and hydrogen sulphide also takes place in the cold section of the steam cracker. Because of the strong endothermic nature of the steam cracking process adequate and efficient heat recovery is very important in order to make the process economically viable.

The hydrowax in accordance with the present invention is very useful as a feedstock for producing lubricating base oils.

The hydrowax recovered in step (d) is therefore suitably subjected to a dewaxing step. Preferably, the hydrowax recovered in step (d) is subjected to a dewaxing step and the dewaxed product thus obtained is subjected to a hydrofinishing step. The dewaxing step may be a solvent dewaxing step or a catalytic dewaxing step. Preferably, the dewaxing step is a catalytic dewaxing step. Hence, in a particular attractive embodiment of the present invention the hydrowax recovered in step (d) is subjected to a catalytic dewaxing step and the dewaxed product thus obtained is subjected to a hydrofinishing step.

The hydrowax recovered in step (d) has a high viscosity index (VI) which enables the production of high VI

lubricating base oils.

By catalytic dewaxing is here meant a process for decreasing the pour point of lubricating base oil products by selectively converting the components of the oil feed which impart a high pour point to products which do not impart a high pour point. Products which impart a high pour point are compounds having a high melting point. These compounds are referred to as waxes. Wax compounds include for example high temperature melting normal paraffins, iso- paraffins and mono-ringed compounds. The pour point is preferably reduced by at least 10 °C and more preferably by at least 20 °C. The hydrocarbon oils to be used as feed in the process according to the present invention will thus contain waxy molecules which impart an undesirable high pour point. Small amounts of these compounds can strongly influence the pour point. The feed will suitably contain between about 1% and up to 100% of these waxy compounds.

In the catalytic dewaxing step in accordance with the invention the hydrowax is contacted under catalytic dewaxing conditions with a catalyst composition comprising metallosilicate crystallites, a binder and a hydrogenation component .

Catalytic dewaxing conditions are known in the art and typically involve operating temperatures in the range of from 200-500 °C, suitably from 250-400 °C, hydrogen pressures in the range of from 10-200 bar, suitably from 15-100 bar, more suitably from 15-65 bar, weight hourly space velocities in the range of from 0.1-10 hr "1 , suitably from 0.2-5 hr -1 , more suitably from 0.5-3 hr -1 and hydrogen to oil ratios in the range of from 100-2,000 litres of hydrogen per litre of oil. In the dewaxing catalyst to be used the weight ratio of the metallosilicate crystallites and the binder is preferably between 5:95 and 35:65.

Preferred dewaxing catalysts to be used in accordance with the present invention have been described in US 6,576,120 which is hereby incorporated by reference.

The dewaxed product obtained in the catalytic dewaxing step according to the invention can be subjected to a hydrofinishing step. Hydrofinishing is known in the art and examples of suitable hydrofinishing steps are disclosed in, for instance, US-A-5139647 , WO-A-9201657 and WO-A- 9201769. Generally, hydrofinishing comprises contacting a

hydrocarbon feed, in this case a feed comprising the dewaxed lubricating base oil, with a hydrogenation catalyst under relatively mild conditions in order to saturate at least part of the aromatics still present in the dewaxed base oil. Suitable catalysts are those normally applied for this purpose with noble metal-based catalysts, such as those comprising Pt and/or Pd supported on an amorphous silica-alumina carrier or comprising Pt on an alumina support, being preferred options. Hydrofinishing conditions normally involve operating temperatures up to 350 °C and preferably in the range of from 150-300 °C, operating pressures in the range of from 10-200 bar and weight hourly space velocities in the range of from 0.5-7.5 hr -1 .

The effluent from the catalytic dewaxing process or optionally the effluent of a hydrofinishing treatment applied subsequently is separated into a gaseous fraction and a liquid fraction. Such separation or fractionation can be attained by conventional methods, such as by

distillation under atmospheric or reduced pressure. Of these, distillation under reduced pressure, including vacuum flashing and vacuum distillation, is most suitably applied. The outpoint (s) of the distillate fraction (s) is/are selected such that each product distillate recovered has the desired properties for its envisaged application.