Hydrocracking Catalyst (Shell)

Hydrocracking Catalyst (Shell)
United States Patent Application 20160074846
DOMOKOS; Laszlo ;   et al.   March 17, 2016
Applicant: Shell Oil
Abstract
Process for preparing a hydrocracking catalyst carrier which process comprises subjecting a carrier comprising an amorphous binder and zeolite Y having a silica to alumina molar ratio of at least 10 to calcination at a temperature of from 700 to 900.degree. C., hydrocracking catalyst carrier comprising amorphous binder and zeolite Y having a silica to alumina molar ratio of at least 10, the infrared spectrum of which catalyst has a peak at 3690 cm.sup.-1, substantially reduced peaks at 3630 cm.sup.-1 and 3565 cm.sup.-1 and no peak at 3600 cm.sup.-1, hydrocracking catalyst carrier comprising an amorphous binder and zeolite Y having a silica to alumina molar ratio of at least 10, which catalyst has an acidity as measured by exchange with perdeuterated benzene of at most 20 micromole/gram, hydrocracking catalyst derived from such carrier and hydrocracking process with the help of such catalyst.
BACKGROUND OF THE INVENTION
[0003] Processes that comprise treating crude oil and other petroleum feedstocks with hydrogen in the presence of a catalyst are well known. One such process is hydrocracking, in which heavy distillate hydrocarbons are converted under hydrogen pressure into products of lower molecular weight in the presence of a catalyst. Hydrocracking is used in the oil industry to prepare a wide range of materials, ranging from C3/C4 production to luboil manufacture.
[0004] Hydrocracking may be operated as either a single or two-stage process. Two-stage hydrocracking involves a first stage, which is predominantly a hydrotreatment stage wherein impurities and unsaturated compounds are hydrogenated in the presence of a first catalyst having a high hydrogenation function, and a second-stage where most of the cracking occurs in the presence of a second catalyst having a strong cracking function. In single-stage hydrocracking, the treatment and cracking steps occur in one reactor and may be performed using a single catalyst. The catalysts employed in hydrocracking are generally made from a carrier material on which there are deposited catalytically active metals such as nickel, molybdenum, tungsten and palladium.
[0005] It is advantageous to have a catalyst which enables the refinery to produce the most attractive product slade for the refinery in question. A product slade which can be advantageous is one having an increased gas oil yield. Gas oils are hydrocarbons boiling in the range of from 250 to 370.degree. C. at atmospheric pressure, and are suitable for use as diesel. Especially in Europe and Asia, there tends to be an increased demand for diesel and reduced demand for gasoline. Further, an improved denitrogenation was observed.
SUMMARY OF THE INVENTION
[0006] It has now surprisingly been found that a catalyst having a higher selectivity for gas oil can be obtained in a simple and efficient way by calcining a carrier comprising amorphous binder and zeolite Y at a relatively high temperature. The catalyst was further found to have improved denitrogenation properties.
[0007] Accordingly, the present invention provides a process for preparing a hydrocracking catalyst carrier which process comprises subjecting a carrier comprising an amorphous binder and zeolite Y having a silica to alumina molar ratio of at least 10 to calcination at a temperature of from 700 to 900.degree. C. Furthermore, the present invention relates to hydrocracking catalyst carrier obtainable by such process.
[0008] Prior art documents such as WO2004047988 and WO2005084799 mention a broad temperature range for calcining a catalyst carrier. However, someone skilled in the art would not seriously consider use of the full range especially as a high temperature is suspected of breaking down the zeolitic structure. Someone skilled in the art would only consider a relatively narrow range of the full temperature range of 300 to 800.degree. C. mentioned in WO2004047988 or 300 to 850.degree. C. mentioned in WO2005084799 namely a range close to the calcination temperature actually applied, i.e. 535.degree. C.
[0009] Further, it was found that the hydrocracking catalyst carriers obtained by the process of the present invention, differ from known hydrocracking catalysts in their infrared spectrum. Therefore, the present invention further relates to hydrocracking catalyst carriers comprising an amorphous binder and zeolite Y having a silica to alumina molar ratio of at least 10, the infrared spectrum of which carrier has a peak at 3690 cm.sup.-1, substantially reduced peaks at 3630 cm.sup.-1 and 3565 cm.sup.-1 and no peak at 3600 cm.sup.-1 and to hydrocracking catalyst comprising a Group VIII metal, a Group VIB metal and such carrier.
[0010] Furthermore, it was found that a specific kind of acidity of the catalysts obtained by the process of the present invention is less than the acidity of known catalysts. Therefore, the present invention also relates to hydrocracking catalyst carrier which comprises an amorphous binder and zeolite Y having a silica to alumina molar ratio of at least 10, which carrier has an acidity as measured by exchange with perdeuterated benzene of at most 20 micromole/gram, and to hydrocracking catalyst comprising a Group VIII metal, a Group VIB metal and such carrier. It is especially surprising that carrier comprising zeolite Y having a reduced acidity gives increased gas oil selectivity at the same activity. Reduced acidity conventionally results in reduced hydrocracking activity.
Free Full Text Source:  http://appft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&p=1&u=%2Fnetahtml%2FPTO%2Fsearch-bool.html&r=8&f=G&l=50&co1=AND&d=PG01&s1=catalyst.TTL.&s2=shell.AANM.&OS=TTL/catalyst+AND+AANM/shell&RS=TTL/catalyst+AND+AANM/shell