阅读说明：本技术 挤出的残油脱金属催化剂 (Extruded resid demetallization catalysts ) 是由 V.杜马 M.伍兹 于 2013-02-14 设计创作，主要内容包括：本发明涉及挤出的残油脱金属催化剂。公开了催化剂载体、担载的催化剂,以及制备和使用用于使含金属重油原料的脱金属的催化剂的方法。催化剂载体包含氧化铝和5%或更少的氧化钛。由载体制备的催化剂,其孔体积的至少30-80体积%为直径200-500埃的孔。本发明的催化剂对于在氢转化过程期间从重原料中去除金属显示改进的催化活性和稳定性。催化剂也显示提高的硫和MCR转化率。(The present invention relates to extruded resid demetallization catalysts. Catalyst supports, supported catalysts, and methods of making and using catalysts for demetallizing metal-containing heavy oil feedstocks are disclosed. The catalyst support comprises alumina and 5% or less titania. A catalyst prepared from a support having at least 30-80% by volume of its pore volume in pores having a diameter of 200 and 500 angstroms. The catalysts of the invention exhibit improved catalytic activity and stability for the removal of metals from heavy feedstocks during hydrogen conversion processes. The catalyst also exhibits improved sulfur and MCR conversion.)

1. A process for preparing a porous support material for supporting a catalytically active metal suitable for the hydrodemetallation of heavy hydrocarbon fractions containing metal under hydrotreating conditions, which process comprises

a) Preparing an extrudable titania alumina having a titania content selected from 0.3 wt% to less than 5 wt%, 0.3 wt% to 4 wt%, or 0.3 wt% to 2.5 wt% titania, based on the total weight of the titania alumina;

b) optionally peptizing the titania alumina;

c) extruding the titania alumina to form a titania alumina extrudate; and

d) calcining the extrudate at a temperature of 960 ℃ to 1050 ℃ to obtain a calcined support,

wherein:

(i) the support has a total pore volume of 0.7 to 1.2cc/g,

(ii) greater than 40% of the total pore volume has pores with a diameter greater than 200 Å,

(iii) 30% or more of the total pore volume has pores of 200 Å -500 Å, and

(iv) greater than 10% of the total pore volume has pores with a diameter greater than 1000 Å, and

wherein the support comprises titania alumina having a titania content selected from 0.3 wt.% to less than 5 wt.%, 0.3 wt.% to 4 wt.%, or 0.3 wt.% to 2.5 wt.% titania, based on the total weight of the titania alumina.

2. The process of claim 1 wherein the titania alumina of the support comprises at least 90 wt% alumina having an R value of from 0.4 to 1.7.

3. The process of claim 1 wherein the alumina-titania of step (a) is formed by: aluminum sulfate and titanium sulfate are co-precipitated with sodium aluminate, the amount of titanium sulfate used being sufficient to provide a porous support comprising titania alumina having a selected titania content.

4. The process of claim 1 wherein the titania alumina of step (a) is formed by: mixing alumina and titania in an amount sufficient to provide a support comprising titania alumina having a selected titania content, based on the total weight of the titania alumina.

5. The process of claim 1 wherein the titania alumina of step (a) is formed by: impregnating an alumina powder with a titanium compound in an amount sufficient to provide a support comprising titania alumina having a selected titania content, based on the total weight of the titania alumina.

6. The process of claim 1, wherein the support is calcined at a temperature of 980 ℃ to 1040 ℃.

7. A catalyst support prepared by the method of any preceding claim.

8. A catalyst support comprising titania alumina having a titania content selected from 0.3 wt% to less than 5 wt%, 0.3 wt% to 4 wt%, or 0.3 wt% to 2.5 wt% titania, based on total titania alumina, the support having a total pore volume of 0.7 to 1.2cc/g, and a pore volume distribution such that greater than 40% of the total pore volume has pores with a diameter of greater than 200 Å, 30% or more of the total pore volume has pores with a diameter of 200 Å to 500 Å, and greater than 10% of the total pore volume has pores with a diameter of greater than 1000 Å.

9. The support of claim 8 wherein the titania is present in the titania alumina in an amount of 0.3 wt% to 4 wt%, based on the total weight of the titania alumina.

10. The support of claim 9 wherein the titania is present in the titania alumina in an amount of from 2.5 to less than 5 wt% titania, based on the total weight of the titania alumina.

11. The support of claim 8 or 10 wherein the support comprises at least 90 wt% titania alumina having an alumina R-value of 0.4 to 1.7.

12. The carrier of claim 8 wherein 50% to 90% of the total pore volume is pores having a diameter greater than 200 Å.

13. The carrier according to claim 8, wherein 30% to 80% of the total pore volume is pores having a diameter of 200- "500 Å".

14. The carrier of claim 8 wherein greater than 15% of the total pore volume of the carrier has pores with a diameter greater than 1000 Å.

15. The support material according to claim 8, wherein the pore volume and pore size distribution properties are determined by mercury porosimetry using a mercury porosimeter under conditions of pressure ranging from atmospheric pressure to 4000 bar, contact angle θ =140 °, and mercury surface tension of 0.47N/m, 25 ℃.

16. A process for the preparation of a catalyst having high activity and stability for the hydrodemetallation of heavy hydrocarbon fractions containing metals during hydrotreating, which process comprises impregnating a porous extruded support with an aqueous solution comprising at least one catalyst or catalyst precursor comprising:

(I) at least one metal selected from group 6 of the periodic Table of the elements; and

(II) at least one metal selected from the group consisting of: metals of group 9 of the periodic table and metals of group 10 of the periodic table, and combinations thereof; and

(III) optionally phosphorus;

the catalyst or catalyst precursor may be thermally converted to a metal oxide and the resulting impregnated support thereafter dried and calcined to provide a supported catalyst, the support being prepared by the process of any one of claims 1 to 6.

17. A catalyst prepared by the process of claim 16.

18. A catalyst having improved activity and stability for hydrodemetallation of heavy hydrocarbons comprising

a) An extruded alumina support comprising titania alumina having a titania content selected from 0.3 wt% to less than 5 wt%, 0.3 wt% to 4 wt%, or 0.3 wt% to 2.5 wt% titania, based on the total weight of the titania alumina; and

b) a catalyst or catalyst precursor comprising:

(i) at least one metal selected from group 6 of the periodic Table of the elements; and

(ii) at least one metal selected from the group consisting of: metals of group 9 of the periodic table and metals of group 10 of the periodic table, and combinations thereof; and

(iii) optionally phosphorus;

c) wherein the carrier has a size of 50-150m²A surface area per gram and a total pore volume of 0.7 to 1.2 cubic centimeters per gram, greater than 40% of the total pore volume having pores with a diameter greater than 200 Å, 30% or more of the total pore volume having pores with a diameter of 200 Å to 500 Å, and greater than 10% of the total pore volume having pores with a diameter greater than 1000 Å.

19. The catalyst of claim 18, wherein the support has been calcined at a temperature of 960 ℃ to 1050 ℃.

20. The catalyst of claim 19, wherein the calcined support comprises titania alumina comprising at least 90 wt.% alumina having an R value of 0.4 to 17.

21. The catalyst of claim 18, wherein the pore volume and pore size distribution properties of the support are determined by mercury porosimetry using a mercury porosimeter at a pressure range from atmospheric pressure to 4000 bar, with a contact angle θ =140 ° and a mercury surface tension of 0.47N/m, at 25 ℃.

22. The catalyst of claim 18 comprising a co-precipitated titania alumina.

23. The catalyst of claim 18, wherein the at least one catalyst or catalyst precursor comprises a metal selected from the group consisting of cobalt, nickel, molybdenum, phosphorus, and combinations thereof.

24. The catalyst as recited in claim 18, wherein 30% to 80% of the total pore volume of said support is pores having a diameter of 200- "500 Å.

25. The catalyst of claim 18 wherein 50% to 90% of the total pore volume of the support is pores having a diameter greater than 200 Å.

26. A process for hydrotreating a metal-containing heavy hydrocarbon feed to remove metals, which process comprises contacting said heavy hydrocarbon feed with the catalyst of claim 1 or 18 under hydrotreating process conditions and reducing the metal content in said heavy hydrocarbon fraction.

27. The process of claim 26 wherein the heavy hydrocarbon feed is contacted with the catalyst under the following conditions: reaction temperature of 300 ℃ to 450 ℃, hydrogen pressure of 25 to 200 bar, H₂Oil ratio of 150-^-1。

28. The process of claim 26 wherein the heavy hydrocarbon feed comprises a metal selected from the group consisting of nickel, vanadium, and combinations thereof.

29. The process of claim 26 wherein the heavy hydrocarbon feed further comprises sulfur and the amount of sulfur is reduced simultaneously with the reduction in metals.

30. The process of claim 29 wherein the heavy hydrocarbon feed has a microcarbon residue (MCR) content and the MCR content is reduced concurrently with the reduction of metals.

31. A process for reducing the microcarbon residue (MCR) content in a heavy hydrocarbon feed comprising contacting a heavy hydrocarbon feed having an MCR content with the catalyst of claim 17 or 18 under hydrotreating process conditions and providing a hydrotreated hydrocarbon fraction having a reduced MCR content as compared to the MCR content of the heavy hydrocarbon feed.

32. The process of claim 31 wherein the heavy hydrocarbon feed is contacted with the catalyst under the following conditions: reaction temperature of 300 ℃ to 450 ℃, hydrogen pressure of 25 to 200 bar, H₂Oil ratio of 150-^-1。

33. The process of claim 32 wherein the heavy hydrocarbon feed further comprises a metal selected from the group consisting of nickel, vanadium, and combinations thereof, and wherein the hydrotreated hydrocarbon fraction has a reduced metal content as compared to the heavy hydrocarbon feed.

34. The process of claim 33 wherein the heavy hydrocarbon feed further comprises sulfur, and wherein the hydrotreated hydrocarbon fraction has a reduced sulfur content as compared to the heavy hydrocarbon feed.

Technical Field

The present invention relates to the catalytic hydrotreating of liquid hydrocarbons comprising a feed stream. In particular, the present invention relates to catalyst supports, catalyst compositions prepared using the supports, methods of preparing the catalyst compositions, and methods of reducing the metal content of hydrocarbon heavy feedstocks using the above catalyst compositions.

Background

In the petroleum refining industry, it is often useful to upgrade certain oils and fractions, such as heavy oils and residual oils, by hydrotreating. Examples of such hydrotreating processes are hydrodemetallization, hydrodesulfurization and hydrodenitrogenation. In these processes, the feedstock is contacted with a hydrogen conversion catalyst in the presence of hydrogen at elevated pressure and temperature. Due to the strict requirements imposed by ecological regulations, the refining industry is becoming more and more focused on producing cleaner fuels with high quality and minimal content of pollutants (such as sulphur, nitrogen and heavy metals).

Catalysts used in hydrotreating processes typically comprise catalytically active metals from groups 6, 9 and 10 of the periodic table of the elements and are typically supported on alumina, which may be combined with other inorganic refractory materials such as silica, magnesia, titania, zirconia, and the like. Secondary promoters or additives, such as halogens, phosphorus and boron, are also used to enhance the catalytic properties. To achieve maximum effectiveness of the hydrotreating process, it is necessary to optimize the catalyst activity and selectivity to the desired hydrotreating reaction. Catalyst activity and selectivity are determined and influenced by these factors: the nature and properties of the catalyst support, the activity and selectivity of the catalyst, cocatalyst and the preparation and activation method used.

Where the heavy feedstock contains organometallic compounds, the effectiveness of the hydrotreating and downstream catalysts tends to decay relatively rapidly, particularly when the impurities exceed about 10-20ppm metals, such as dissolved nickel and vanadium. These metal impurities are said to deposit on the surface and within the pores of these catalysts, reducing their effectiveness. One approach to the problem of metal impurities is to modify the pore structure of the hydrotreating catalyst. However, determining which pore structure to use is unpredictable and not readily available. There is a conflict in the art in considering the optimal pore structure. Several patents have discussed this conflict, including U.S. Pat. nos. 4,066,574; us patent No. 4,113,661 and us patent No. 4,341,625.

Hydrotreated hydrocarbon feedstocks with low Conradson Carbon Residue (CCR) are also highly desirable in the refining industry. Char residue is a measure of the tendency of hydrocarbons to form coke. Expressed in weight%, char residue may be measured as Micro Char Residue (MCR). The MCR content in the hydrotreated residual feedstock is an important parameter, as the hydrotreated residue is typically passed as a feed to a coker or to a Fluid Catalytic Cracking (FCC) unit. Reducing the MCR content in the hydrotreated residue reduces the amount of low value coke produced in the coker and increases the amount of gasoline produced in the FCC unit.

For this purpose, there remains a need to develop catalyst compositions that are less expensive and/or more effective in removing metal and/or sulfur contaminants, particularly heavy hydrocarbon feed streams, from hydrocarbon feed streams during hydrotreating processes. There is also a need for improved hydrodemetallization and/or hydrodesulfurization catalysts that provide good MCR conversion during the hydrotreating process.

Summary of The Invention

The present invention is based on the following findings: high temperature calcination of titania alumina comprising 5 wt.% or less titania, based on the total weight of titania alumina, unexpectedly provides an extruded catalyst support having a unique pore structure from which supported catalysts having improved catalytic activity and stability for metal removal during hydrotreating processes can be prepared. Advantageously, the supports of the present invention provide lower cost economics because the catalyst compositions prepared therefrom use lower catalytically active metal content while maintaining high catalytic performance.

In one aspect of the invention, an extruded titania alumina support having a unique pore structure is provided. The pore size distribution of the carrier of the invention is determined by mercury intrusion porosimetry, and satisfies the following: a total pore volume of about 0.7 to about 1.2cc/g, greater than 40% of the total pore volume having a diameter greater than

About 30% or more of the total pore volume of

-about

And greater than 10% of the total pore volume is diameter

The above holes.

The present invention also provides an extruded titania alumina support comprising at least 90 wt% titania alumina having an alumina R value of from about 0.4 to about 1.7, the R value being defined as the ratio between the integrated intensity of the X-ray diffraction peak at 2 θ ═ 32 ° and the integrated intensity of the X-ray diffraction peak at 2 θ ═ 46 °.

In another aspect of the present invention, an improved hydrotreating catalyst is provided for reducing the metal content in a heavy hydrocarbon feedstock containing metals during a hydrotreating process. The catalyst of the invention is prepared by: the extruded support of the invention is impregnated with a catalytically active group 6, 9 and 10 metal or precursor metal compound, and optionally a phosphorus compound.

In yet another aspect of the present invention, an improved hydrotreating catalyst is provided that is capable of reducing the metal content in a hydrotreated heavy hydrocarbon fraction while reducing the sulfur and microcarbon residue (MCR) content.

The present invention also provides a method of making an extruded titania alumina support having a unique pore size distribution.

Another aspect of the invention provides a method of making a catalyst composition comprising an extruded titania alumina support comprising at least 90 wt% titania alumina having an alumina R value of from about 0.4 to about 1.7 and comprising 5 wt% or less titania, based on the total weight of the titania alumina.

In yet another aspect of the invention, an improved hydrotreating process is provided using the supported catalyst compositions and methods of the invention.

These and other aspects of the invention are described in more detail below.

Detailed Description

The present invention provides a catalyst composition consisting of: a catalytically active metal of groups 6, 9 and 10 of the periodic table of the elements or a precursor metal compound of the metal and optionally a phosphorus compound, said catalyst composition being supported on an extruded titania alumina support. In one embodiment of the invention, the support material used to prepare the catalyst of the invention comprises titania alumina containing 5 wt.% or less titania, based on the total weight of the titania alumina composition. In another embodiment of the invention, the support material comprises less than 5 wt.% titania, based on the total weight of the titania alumina composition. In yet another embodiment of the invention, the support material comprises from about 2.5 to about 4 weight percent titania, based on the total weight of the titania alumina composition. In yet another embodiment of the invention, the support material comprises from about 0.3 to about 1 weight percent titania, based on the total weight of the titania alumina composition.

In a preferred embodiment of the invention, the titania alumina used to prepare the support of the invention comprises at least 90 wt.% alumina having a mixture of gamma alumina and delta-and/or theta alumina such that the titania alumina composition exhibits an alumina R value in the range of from about 0.40 to about 1.7, preferably from about 0.6 to about 1.4. The term "R-value" as used herein is used to indicate the ratio between the integrated intensity of an X-ray diffraction peak at 2 θ ═ 32 ° and the integrated intensity of an X-ray diffraction peak at 2 θ ═ 46 °. The R value is determined by the method disclosed and described in U.S. patent 5,888,380, the entire contents of which are incorporated herein by reference.

The R value can be represented by the following formula:

in which [ I (2 θ) ═ 32 ° ] and [ I (2 θ) ═ 46 ° ] denote the integrated intensities of the peaks at 32 ° and 46 ° of the 2 θ angle of the X-ray diffraction spectrum, respectively, in the present specification, PANalytical X' Pert X-ray diffractometer was used, using the following measurement conditions and equipment CuK α radiation container, container voltage 50kV, container current 30mA, biaxial vertical goniometer, scan rate 0.867 °/min, emission slit width 1 °, scattering slit width 1 °, reception slit width 0.3mm, 2 θ angle 4 ° ≦ 2 θ ≦ 82 °, the peak appearing at 2 θ ≦ 46 ° is attributed to γ -alumina, while the peak appearing at 2 θ ≦ 32 ° is attributed to δ -and/or θ -alumina.

In this respect, it is noted that the R value should be determined on a support in the absence of catalytically active metals.

The titania alumina support of the invention typically comprises at least 90 wt% titania alumina as described herein. Preferably, the support material comprises at least 95 wt% titania alumina, most preferably greater than 99 wt%, the wt% being based on the total weight of the support. The support material may thus "consist essentially of" titania alumina as described herein. The phrase "consisting essentially of … …" as used herein with respect to the composition of the support material is used herein to indicate that the support material may comprise titania alumina and other components, so long as these other components have no substantial effect or effect on the catalytic properties of the final hydrogen conversion catalyst composition.

Advantageously, the titania alumina support of the present invention has specific properties of surface area, pore volume, and pore volume distribution. Unless otherwise specified herein, the pore volume and pore size distribution properties of the titania alumina support as defined herein are determined by mercury intrusion porosimetry. Mercury measurements of pore volume and pore size distribution of the alumina support material were made using any suitable mercury porosimeter, and met a pressure range from atmospheric pressure to about 4000 bar, a contact angle 2 θ of 140 °, mercury surface tension of 0.47N/m, room temperature.

The surface area as defined herein is determined by BET surface area analysis. The BET method for measuring surface area is detailed by Brunauer, Emmett and Teller in J.Am.chem.Soc.60(1938) 309-.

The titania alumina support of the present invention has a surface area of about 50m²A/g of about 150m²(ii) in terms of/g. In a preferred embodiment of the invention, the titania alumina support has a surface area of about 90m²A/g of about 140m²/g。

The titania alumina support of the present invention has a total pore volume of from about 0.7cc/g to about 1.2 cc/g. In one embodiment of the invention, the total pore volume of the support is from about 0.8cc/g to about 1.0 cc/g.

The supports of the present invention have a unique pore volume distribution such that typically greater than 40% of the total pore volume is greater than 40% of the total pore volumeAbout 30% or more of the total pore volume is about diameter

-about

And greater than 10% of the total pore volume is diameter

The above holes.

In one embodiment of the inventionIn embodiments, about 50% to about 90% of the total pore volume of the support is greater than the diameter

The hole of (2).

In one embodiment of the invention, about 30% to about 80% of the total pore volume of the support is about diameter

-aboutThe hole of (2).

In another embodiment of the invention, about 15% to about 60% of the total pore volume of the support is in excess of the diameter

The hole of (2).

In yet another embodiment of the invention, greater than about 15 weight percent of the total pore volume of the support is the diameterThe above holes.

However, the titania alumina support of the present invention can be prepared by any conventional method of forming titania alumina supports, so long as the final support material comprises titania alumina having 5 wt% or less titania and having the desired pore structure. Typically, the vectors of the invention are prepared by: forming an extrudable titania alumina powder comprising 5 wt% or less titania; optionally peptizing the titania alumina powder; extruding a titania alumina powder to form an extruded material; the extruded material is thereafter calcined at a temperature of from about 960 c to about 1050 c, preferably from 980 c to about 1040 c, for from about 1 hour to about 3 hours to form a support having a pore size distribution as described herein above.

In one embodiment of the invention, the titania alumina support of the invention is prepared by: aqueous alumina sulfate and titanyl sulfate are co-precipitated in an amount sufficient to provide 5 wt.% or less titania in the co-precipitated titania alumina powder. According to this embodiment, alumina sulfate and titanyl sulfate are mixed with an aqueous stream comprising sodium aluminate and maintained at a pH of from about 7.5 to about 10.0 and a temperature of from about 50 ℃ to about 80 ℃ to precipitate titania alumina powder. The precipitated powder was filtered, washed with water and dried at a temperature of about 100 ℃ to about 150 ℃ until a powder having a moisture content of 20% to 40% by weight was obtained, as analyzed by a moisture analyzer at 955 ℃.

The dried titania alumina powder is thereafter treated with a peptizing agent to peptize the alumina powder. Suitable peptizing agents include, but are not limited to, strong monobasic acids such as nitric acid or hydrochloric acid, organic acids such as formic acid, acetic acid, or propionic acid, and aqueous bases such as ammonium hydroxide. The peptized powder is extruded and dried at a temperature of about 100 ℃ to about 150 ℃ for about 10 minutes to about 2 hours.

The dried extrudate is thereafter calcined at an elevated temperature of about 960 c to 1050 c for about 1 hour to about 3 hours to obtain a final support having the desired pore structure. Preferably, the dried extrudate is calcined at a temperature of from about 980 ℃ to about 1040 ℃ to obtain the final support.

In another embodiment of the invention, the titania alumina support of the invention is prepared by: the precipitated alumina powder having the desired R value is co-milled or co-mixed with a titania source to form a titania alumina powder comprising 5 wt% or less titania. Suitable sources of titania that can be used to prepare the titania alumina powder include, but are not limited to, fumed titania, precipitated titania, and the like. The titania alumina powder is thereafter optionally peptized with a peptizing agent such as nitric acid or the like. The resulting powder is then extruded to form titania alumina extrudates. The titania alumina extrudates are calcined at an elevated temperature of from about 960 c to about 1050 c, preferably from about 980 c to about 1040 c, for from about 1 hour to about 3 hours to provide the final catalyst support.

In yet another embodiment of the invention, the titania alumina support is prepared by impregnating an alumina powder having the desired R value, preferably a precipitated alumina, with an aqueous solution of a titanium-containing compound in an amount sufficient to provide 5 wt.% or less titania in the alumina. Suitable titanium-containing compounds include, but are not limited to, titanium sulfate, titanium chloride, titanium phosphate, titanium alkoxides, and the like. The resulting titania alumina is extruded and dried at a temperature of from about 100 ℃ to about 150 ℃ for from about 10 minutes to about 2 hours. The dried titania alumina extrudate is thereafter calcined at an elevated temperature of from about 960 c to about 1050 c, preferably from about 980 c to about 1040 c, for from about 1 hour to about 3 hours to provide the final catalyst support.

The extruded support of the present invention may have different geometric forms such as cylinders, rings and symmetrical and/or asymmetrical multilobal shapes, e.g., tri-or quadrulobal shapes. The nominal dimensions of the extrudate can vary. Typically about 1 to about 10mm in diameter and about 1 to about 30mm in length. In one embodiment of the invention, the diameter is from about 1 to about 2mm and the length is from about 2 to about 6 mm. As will be appreciated by those skilled in the catalyst art, the catalyst particles produced by the support are of similar size and shape to the support.

The catalyst of the invention is prepared as follows: the titania alumina support is contacted with an aqueous solution of at least one catalytically active metal or precursor metal compound to uniformly distribute the desired metal on the support. Preferably, the metal is uniformly distributed throughout the pores of the support. In a preferred embodiment of the invention, the catalyst is prepared by impregnating the catalyst support with an aqueous solution of the desired catalytically active metal or precursor compound to incipient wetness.

Catalytically active metal and/or precursor metal compounds useful for preparing the catalyst compositions of the present invention include, but are not limited to, metals or metal compounds selected from group 6 of the periodic table, group 9 of the periodic table, group 10 of the periodic table, and combinations thereof. Preferred group 6 metals include, but are not limited to, molybdenum and tungsten. Preferred group 9 and 10 metals include, but are not limited to, cobalt and nickel.

In a preferred embodiment of the invention, a combination of nickel and molybdenum catalysts is preferred. In a more preferred embodiment of the invention, the resulting catalyst comprises a Mo concentration in the range of from about 4 to about 6 weight percent, and a Ni concentration in the range of from about 0.1 to about 1 weight percent, the weight percents being based on the total catalyst composition.

Suitable precursor metal compounds of group 9 and 10 metals include, but are not limited to, metal salts such as nitrates, acetates, and the like. Suitable precursor metal compounds for the group 6 compounds include, but are not limited to, ammonium molybdate, molybdic acid, molybdenum trioxide, and the like.

The catalytically active metals contemplated for use in the support of the present invention are preferably used in the form of oxides and/or sulfides of the metals. Preferably, the catalytically active metal is used in the form of an oxide.

The catalyst composition of the present invention may also comprise a phosphorus component. In this case, the impregnation solution may contain, in addition to the desired catalytically active metal or precursor metal compound, a phosphorus compound, such as phosphoric acid, phosphate salts, etc. Phosphorus concentrations of from about 0.1 to about 1 wt.%, based on the total catalyst composition, are suitable for use in the catalyst of the present invention.

The support is then treated with an aqueous solution of a catalytically active metal or precursor compound, and the catalyst is optionally dried at a temperature of from about 100 ℃ to about 200 ℃ for a period of from about 10 minutes to about 2 hours. The dried catalyst is thereafter calcined at a temperature sufficient to convert at least a portion, and preferably all, of the metal components or precursors to the oxide form for a time in the range of from about 300 c to about 600 c for a period of from about 1 hour to about 3 hours.

As is clear to the person skilled in the art, there is a wide range of variations in the impregnation process used to support the catalytically active metal on the catalyst support. It is possible to apply multiple impregnation steps or impregnation solutions which may contain one or more components or precursors to be deposited, or a part thereof. Instead of the dipping technique, a dipping method, a spraying method, or the like may be used. In the case of multiple impregnations, immersions, etc., drying and/or calcination may be performed between steps.

The catalyst of the invention shows improved catalytic activity and stability for hydrodemetallation of heavy hydrocarbon feeds comprising metals during a hydrotreating process. The heavy hydrocarbon feedstock useful in the present invention can be obtained from any suitable source of hydrocarbons including, for example, petroleum crude oil and tar sands hydrocarbons, such as heavy oil extracted from tar sands. The heavy hydrocarbon feedstock may be a vacuum residue or an atmospheric residue component of petroleum crude or tar sands hydrocarbons. Heavy hydrocarbon feedstocks may also include light and heavy diesel fuels, as well as petroleum crude oils, atmospheric and vacuum residues blended with diesel fuels, particularly vacuum diesel oils, crude oils, shale oils, and tar sands oils.

Heavy hydrocarbon feedstocks typically include hydrocarbon mixtures derived from crude oil or tar sands hydrocarbon materials or other heavy hydrocarbon sources. A portion, preferably a major portion, of the heavy hydrocarbons of the mixture have boiling points in excess of about 343 ℃ (650 ° F). A heavy hydrocarbon feedstock is thus defined as having a boiling range (as determined by ASTM test procedure D-1160) such that at least about 20 weight percent of the heavy hydrocarbon feedstock boils at a temperature in excess of 524 ℃ (975 ° F). The preferred heavy hydrocarbon feedstock has a boiling range such that at least 30 weight percent boils at a temperature in excess of 524 ℃ (975 ° F), and most preferably at least 40 weight percent of the heavy hydrocarbon feedstock boils at a temperature in excess of 524 ℃ (975 ° F).

The heavy hydrocarbon feedstock may have an API weight of from about 3 to about 20, but more specifically the API weight is from 4 to 15, more specifically from 4 to 11.

The heavy hydrocarbon feedstock may have a Conradson char residual content in excess of 5 wt%, more specifically, a Conradson char residual content of 8 wt% to 30 wt%, as determined by ASTM test method D-189.

As previously noted, the metals contained in the heavy hydrocarbon feedstock may include nickel or vanadium or both. The concentration of nickel in the heavy hydrocarbon feedstock may exceed 10 parts per million by weight (ppmw) or may exceed 30 ppmw. More specifically, the nickel concentration in the heavy hydrocarbon feedstock may be in the range of from 40ppmw to 500 ppmw. The vanadium concentration in the heavy hydrocarbon feedstock may exceed 50ppmw or may exceed 100 ppmw. More specifically, the vanadium concentration in the heavy hydrocarbon feedstock may be in the range of from 150ppmw to 1500 ppmw.

The catalyst of the invention may also be used to enhance sulfur removal when demetallizing during a hydrotreating process in which the hydrocarbon feedstock to be treated contains both sulfur and metals. The sulfur content of the feed is typically above 0.1 wt% and typically more than 1 wt%. The nitrogen content is generally above 500ppm and generally between 500ppm and 4000 ppm.

Furthermore, the catalyst of the present invention provides improved conversion of microcarbon residue (MCR) during the hydrotreating process as compared to previous demetallization and/or desulfurization catalysts prepared from an alumina or alumina titania support, wherein the support is calcined at low temperatures (i.e., below 960 ℃). Thus, the resulting hydrotreated hydrocarbon fraction exhibits a reduced MCR content as compared to the MCR content of the starting heavy hydrocarbon feedstock.

The hydrotreating process using the catalyst composition of the invention may be carried out under hydrotreating process conditions in an apparatus whereby the catalyst composition is obtained in intimate contact with a feedstock comprising the metal and a gas comprising free hydrogen to produce a hydrocarbon-containing product having a reduced content of metals (e.g., nickel and vanadium) and optionally sulfur. According to the invention, the hydrotreating process can be carried out using a fixed catalyst bed. The hydrotreating process may be carried out as a batch process or a continuous process comprising one or more fixed catalyst beds or a plurality of fixed bed reactors in parallel or in series.

Typical hydrotreating process conditions that may be used in the present invention include, but are not limited to, temperatures of 300 ℃ to 450 ℃, hydrogen pressures of 25 to 200 bar, 150-₂Oil ratio, and space velocity (hr) of 0.1-5^-1). In one embodiment of the invention, the operating conditions of the process for the desulfurization of a hydrocarbon feedstock containing metals include: a reaction zone temperature of 350 ℃ to 400 ℃, a pressure of 100-.

To further illustrate the present invention and their advantages, the following specific examples are given. The examples are given as specific illustrations of the claimed invention. It should be understood, however, that the invention is not intended to be limited to the specific details set forth in the examples.

All parts and percentages in the examples, as well as in the remainder of the specification, refer to solid compositions or concentrations by weight, unless otherwise specified. However, all parts and percentages referred to in the examples and the remainder of this specification for the gas composition are by mole or by volume unless otherwise indicated.

Moreover, any range of values, for example, that represents a particular set of properties, units of measure, conditions, physical states or percentages, recited in the specification or claims is intended to be literally expressly incorporated herein by reference or to incorporate any number falling within the range, including any subset of values within any range so recited.

Examples

Five catalysts (catalysts A, B, C, D and E) were prepared and their performance was evaluated. The R values for the catalysts in the examples were calculated as described above.