FI60575B - FOERBAETTRAT FOERFARANDE FOER AVMETALLISERING AV EN KOLVAETERESTOLJA VID ETT TVAOSTEGSFOERFARANDE I VILKET OLJAN FOERST AVMETALLISERAS OCH DAEREFTER UNDERKASTAS EN KATALYTISK KONVERSION - Google Patents

Description

1 ΓβΊ / «^ ANNOUNCEMENT PUBLICATION, nrnc lBJ (11) utläggnincs $ krift6 ° 5 75 C Patent rayonneLly 10 02 1932 (patent meddelat” (51) K ».ik.3 / Int.ci.3 c 10 G 4-9 / 02 SUOMI-FINLAND (21) Pkt.nulh «k.mui - Paten taiuöknlng 3 ^ 7/7 ^. (22) Hakemltpllvl - AntOknlngadag 28.11.7 ^ + '' (23) Alkupllvl — Glltl (h« nyt | 28.11. 71 * (41) Tulkit lulkltekii - Bllvlt offentllg 31.05-75

Patent · and Registry Board, _____ '. . ', (44) Nlhtlvlkalpenon | date | u1kabun date. -

Patent-OCn registrarstyrelsen Antökan utlagd och utl.skriften publkerad 3O.10.8l (32) (33) (31) Requested privilege— Begird prloritet 30.11.73 29.07.7 ^ Holland-Holland (NL) 7316396, 7 ^ 10162 (71) Shell Internationale Research Maatschappij BV, Carel van Bylandt-laan 30, The Hague, Hollaxiti-Holland (NL) (72) Karel Maarten Adrianus Pronk, Amsterdam, Swan Tiong Sie, Amsterdam,

Jakob van Klinken, Amsterdam, Holland-Holland (NL) (7M Oy Kolster Ab (5 ^ +) Improved method for removing metals from residual hydrocarbon oil in a two-step process in which the metals are first removed from the oil and the oil is then subjected to catalytic conversion - that, for the purposes of this Regulation, the catalytic conversion and catalytic conversion

F1 Patent Application No. 2157/73 relates to a process for the catalytic conversion of residual hydrocarbon oil, in which process the metals are removed from the oil and the oil is then subjected to catalytic conversion. According to said patent application, the metals are removed by contacting the oil at elevated temperature and pressure and in the presence of hydrogen with a catalyst having one or more metals having a hydrogenating effect on the support, this catalyst meeting several requirements for particle size and porosity.

Further research on the removal of metals from residual hydrocarbon oils by catalysts which meet the requirements for particle size and porosity set out in that patent application has shown that the activity of such catalysts containing 0.1 to 15 parts by weight of one or more metals having hydrogenation activity as a support per 100 parts by weight of silica depends largely on their annealing loss, which is determined under standard conditions. For the purposes of this application, the loss on ignition of the catalyst, defined in standard 2 60575 conditions, is the percentage loss in weight when 5 to 10 g of catalyst applied in a 1 cm layer to a well-ventilated drying oven are heated within 1 hour from room temperature to 500 ° C. maintained at 500 ° C for 2 hours. For simplicity, the term "annealing loss" is used instead of "annealing loss determined under standard conditions".

It has been found that these catalysts have optimum activity in the case of an annealing loss of less than 1% by weight, whereas, in the case of catalysts containing vanadium or a combination of vanadium and one or more other metals with hydrogenation activity, optimum activity is obtained only if the annealing loss is less than 0.5 weight- $.

The present invention relates to an improved process for the catalytic conversion of a residual hydrocarbon oil by first removing metals from the oil and then subjecting the oil to catalytic conversion and removing the metals by contacting the oil at elevated temperature and pressure and in the presence of hydrogen with a catalyst containing one or more hydrogenation which meets the following requirements: 1) p / d> 3,5-0,02 v, where p is the specific average pore diameter in nm, d is the specific average diameter of the particles in mm and v is a percentage of the total volume consisting of pores, with a diameter greater than 100 nm.

2) the total pore volume is greater than 0.1 U ml / g, 3) v is less than 50 and d is 0.1 * ~ 5.0, and the 2 M surface area is greater than 100 m / g; and in the case of a catalyst with p and d such that the ratio p / d is more than 3,5 to 0,02 v but not more than 10 to 0,15 v, the catalyst must meet the following additional requirements: (a) the nitrogen pore volume is more than 0; 60 ml / kg, b) an area greater than 150 m / g, and c) p greater than 5 nm.

The invention is characterized in that the metals are removed in the presence of a catalyst containing 0.1 to 15 parts by weight of one or more metals having hydrogenation activity, with the exception of nickel-vanadium, per 100 parts by weight of silica used as support and having an annealing loss of less than 1 % by weight, and that in the case where the catalyst contains vanadium or a combination of vanadium and one or more other metals having hydrogenation activity, the annealing loss is less than 0.5% by weight.

3,60575

The process according to the invention preferably uses a catalyst having an annealing loss of less than 0.75% by weight and, if the catalyst contains vanadium, less than 0.2% by weight.

In the process according to the invention, it is important that at the stage when the catalyst is fed to the dewatering reactor, its annealing loss is less than 1.0% by weight and, if the catalyst contains vanadium, less than 0.5% by weight. This can be accomplished by both careful combustion and careful treatment of the catalyst. In this context, "careful combustion" of a catalyst means performing combustion to obtain a catalyst having an annealing loss of less than 1.0% by weight and a catalyst containing less than 0.5% by weight of vanadium. Careful combustion can be accomplished by applying a combustion treatment to a catalyst that is applied in a relatively thin layer and ensuring proper ventilation of the combustion chamber during combustion. The phrase "careful handling of the catalyst" as used above means that after the catalyst has been carefully burned, e.g. during both storage and transport of this carefully burned catalyst and feed to the dewatering reactor, concern that the annealing loss of the catalyst is kept to a minimum and in any case remains below 1% by weight and, in the case of vanadium, below 0.5% by weight. Careful handling of the catalyst means e.g. that the absorption of moisture into the catalyst is prevented as carefully as possible, e.g. when it comes into contact with moist air. If the catalyst has not been burned with sufficient care, or if the combustion has been carried out carefully but the treatment has not been carried out with due care, it is still possible to prepare a suitable catalyst by reducing the moisture content of the catalyst, e.g. by drying the catalyst in dry gas again before it is brought into contact with the material from which the metals are to be removed. Such a reduction in the moisture content of the catalyst can be carried out, for example, in the case where the catalyst is already present in the dewatering reactor.

The finding that the demetallization activity of the catalysts according to FI patent application No. 2157/73, which catalysts contain 0.1-15% by weight of one or more metals with hydrogenation activity per 100 parts by weight of silica, depends quite to a large extent on the annealing loss of these catalysts, and that these catalysts have optimum activity in the case where the annealing losses are less than 1.0% by weight and the catalysts contain less than 0.5% by weight of vanadium, it is quite surprising, given the fact that the activity of very close catalysts, which, however, contain alumina instead of silica as support, is independent of the annealing loss.

The process according to the invention suitably uses catalysts which contain, as metals having hydrogenation activity, one or more metals selected from nickel, cobalt, molybdenum and vanadium. It is further recommended that the catalysts contain at least one metal selected from a pair of nickel and cobalt and at least one metal selected from a pair of molybdenum and vanadium, and that in addition the atomic ratio of nickel and / or cobalt on the one hand and molybdenum and / or vanadium on the other hand is in the range of 005-3 , 0. Suitable metal combinations include nickel-vanadium, cobalt-molybdenum and nickel-molybdenum. The amount of metals having hydrogenation activity present in the catalysts is suitably 0.5 to 10 parts by weight, and in particular 2.0 to 7.5 parts by weight, per 100 parts by weight of the silica used as support. Particularly preferred according to the invention are catalysts containing about 1/2 part by weight of nickel and about 2 parts by weight of vanadium per 100 parts by weight of silica, as well as catalysts containing about 1 part by weight of nickel or cobalt and about 2 parts by weight of vanadium. 4 parts by weight of molybdenum per 100 parts by weight of silica. The metals may be present in the support as metals or their oxides or sulfides. In particular, catalysts are used in which the metals are present in the support as sulphides.

The catalysts of the invention can be sulfided by applying any of the methods known in the art for sulfidating catalysts. In addition to metals having hydrogenation activity, the catalysts may contain other substances which promote their action, such as phosphorus, boron or halogen.

Catalysts for metal removal can be prepared by depositing the corresponding metals on a silica support having a porosity such that upon deposition of the metals, a catalyst meeting the requirements of the invention is obtained, either as such or after a certain average particle diameter has been obtained. As explained in Finnish patent application so-called No. 2157/75, the porosity of a carrier depends mainly on the method of preparation of this substance. This application 2157/75 refers to methods by which the porosity of carriers can be influenced.

Catalysts can be prepared by any of the methods known in the art for preparing supported catalysts. It is not necessary to deposit the corresponding metals in the finished silica. The metals may also be incorporated into the carrier pressure silica during this preparation, e.g., prior to its formulation.

The silica used as a support is usually prepared by precipitating a silica hydrogel, after which it is shaped and burned. The hydrogel in silica is usually allowed to mature, i.e. age, before shaping. The highly effective deacidification catalysts of the invention can be prepared by incorporating the corresponding metals into a silica hydrogel prior to its formulation. The metals are suitably incorporated into the silica hydrogel after this has been matured. A rather effective demetallizing catalyst according to the invention can be prepared, for example, by incorporating a compound of nickel and vanadium in the silica hydrogel in amounts corresponding to about 1/2 part by weight of nickel and about 2 parts by weight of vanadium per 100 parts by weight of the finished support, after this hydrogel has been precipitated and matured but before its shaping and combustion.

Another interesting way to prepare the metal removal catalysts of the invention is to impregnate the support in one or more steps with an aqueous solution containing one or more metal compounds having hydrogenation activity, after which the catalyst is dried and incinerated.

Examples of water-soluble metal compounds which can be prepared for the preparation of the catalysts according to the invention are nitrates, chlorides, formates and acetates of nickel and cobalt, ammonium molybdate, vanadyloxalate, sulphate and acetylacetonate and ammonium vanadate.

Highly suitable supports for the catalysts according to the invention are silica particles prepared by spray-drying silica gel, after which the spray-dried microparticles are formed into larger particles, e.g.

Catalyst particles with a d of 0.4-5.0 mm are generally used to remove metals from the residue of hydrocarbon oils in a catalytic manner according to the invention. Catalyst particles with a d of 1.0-4.0 mm, especially 1.5 "> 5 mm, are particularly preferred for this purpose.

If a catalyst with a p / d ratio such that the ratio p / d is greater than 10.0-15 v is used in the process according to the invention, a catalyst with a total pore volume of at least 0.50 ml / g and a specific surface area of area greater than 150 m / g.

The invention is further illustrated by the following example, which relates to the metal removal step of the method.

Example

The hydrocarbon oil residue, which had a total vanadium and nickel content of 62 ppm by weight, had a C4 asphalt content of 6.4% by weight and a sulfur content of 3 * 9% by weight, which oil was obtained as a residue from Middle Eastern crude oil (Finnish in the climatic distillation of oil B) of patent application No. 2157/73, hydrogenative metal removal was carried out at different room rates and using 13 different catalysts. To this end, the oil, together with the hydrogen, was made to flow downwards through a cylindrical, vertical solid catalyst bed with a temperature of 420 ° C, a total pressure of 150 bar and a gas velocity (measured at the reactor outlet) of 250 N 1 hydrogen per kg of fresh feed. Catalysts were used as their sulfides.

The following explains the preparation of the 13 catalysts used in metal removal. The table summarizes the results of the metal removal tests as well as the space velocities used and the properties of the catalysts.

Catalyst preparation

Catalysts A and B

These catalysts containing 0.1 part by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of silica used as support were prepared by impregnating the silica with an aqueous solution containing vanadyl oxalate and nickel nitrate. The saturated material was dried at 120 ° C, after which it was fired as a 6 cm thick layer in an unventilated drying oven for one hour at 500 ° C. The burned material was divided into two parts. The second part was carefully burned as a 1 cm thinner layer in a well-ventilated drying oven for one hour at 500 ° C, and this part was used as a moisture-protected catalyst A in a dewatering reactor. The second portion was fed to the descaling reactor as catalyst B.

Catalysts C and D

These catalysts containing 1.0 part by weight of cobalt and 4 * 0 parts by weight of molybdenum per 100 parts by weight of silica were prepared using the same silica as the support used in the preparation of catalysts A and B, the silica being saturated with cobalt nitrate and ammonium. with an aqueous solution containing molybdate. The saturated material was dried at 120 ° C, after which it was burned in a 10 cm thick layer in an unventilated oven for one hour at 500 ° C. The burned material was divided into two parts. The second portion was carefully re-fired as a 1 cm thinner layer in a well-ventilated drying oven for one hour at 500 ° C, and fed as a moisture-protected catalyst G to a dewatering reactor. The second part was fed to the demetallization reactor as catalyst D.

Catalysts E and P

These catalysts containing 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of silica were prepared in the same manner as catalysts A and B by impregnating the silica used as support with an aqueous solution containing 7,60575 vanadium oxalate and nickel nitrate. The saturated material was dried at 120 ° C and then thoroughly fired in a 1 μm thinner layer in a well-ventilated drying oven for one hour at 600 ° C. The burned material was divided into two parts. The second part was fed to the dewatering reactor as moisture-protected catalyst E. The second oea was kept in contact with moist air for a week, after which it was fed to the dewatering reactor as catalyst P.

Catalysts G, H and I

These catalysts containing 1.0 part by weight of nickel and 4.0 parts by weight of molybdenum per 100 parts by weight of silica used as support were prepared using the same silica as in the preparation of catalysts E and P and impregnating this silica with an aqueous solution of nickel nitrate and ammonium molybdate. . The saturated material was dried at 120 ° C, after which it was carefully fired as a 1 cm thinner layer in a well-ventilated drying oven for one hour at 600 ° C. The burned material was divided into three parts. The first part was fed to the dewatering reactor as moisture-protected catalyst G, the second part was allowed to come into contact with the test air for 24 hours, after which it was fed to the dehydration reactor as catalyst H. The third part was allowed to come into contact with moist air for two weeks, then

Catalysts J and K

These catalysts containing 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of alumina used as support were prepared by impregnating the alumina with an aqueous solution containing vanadyl oxalate and nickel nitrate. The saturated material was dried at 120 ° C, after which it was carefully burned in a 1 cm thinner layer in a well-ventilated drying oven for one hour at 500 ° C. The burned material was divided into two parts. The second part was fed to the dewatering reactor as a moisture-protected catalyst J, the second part was allowed to come into contact with moist air for two months, and was then fed to the dewatering reactor as a catalyst K.

Catalysts L and M

These catalysts containing 1.0 part by weight of nickel and 4.0 parts by weight of molybdenum per 100 parts by weight of alumina used as support were prepared using the same alumina as in the preparation of catalysts J and K and impregnating this alumina with an aqueous solution containing nickel nitrate and ammonium molybdate. . After the saturated material dried at 120 ° C, it was carefully burned in a 1 cm thinner layer in a well-ventilated drying oven for one hour at 500 ° C. The burned material was divided into two 8,60575 tea sections. The second part was fed to the dewatering reactor as catalyst L. The second part was allowed to be in contact with moist air for a month, after which it was fed to the dewatering reactor as catalyst M.

The results obtained are shown in the following table.

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According to Finnish Patent Application No. 2157/73, the metal removal tests of the catalyst used under these conditions should satisfy the condition that the catalyst is still able to remove more than 40% by weight of the total vanadium and nickel present in oil B after treating 5 tons of oil with the catalyst at room speed. which is at least 2.9 x 1 xh

All the tests mentioned in the table (in which the catalyst met the above-mentioned requirement concerning the percentage of nickel + vanadium removed) are metal removal tests within the framework of Finnish Patent Application No. 2157/73.

In experiments 1-9, which used catalysts with 10.0-0.15 v = p / d = 3.5-0.02 v, these catalysts also met the additional requirements of the said Finnish patent application 2157/73: v (<$ 50) , p (≤ 5 nm), nitrogen pore volume 2 (> 0.60 ml / g) and specific surface area (> 150 m / g).

In experiments 10-13 using catalysts with p / d> 10.0-0.15 v, these catalysts also met the additional requirements of Finnish patent application 2157/73: v (<50 io) total pore volume (> 0.40 ml / g) and specific surface area (> ICC m 2 / g).

Catalysts with amounts of metal according to the present invention (0.1-15 parts by weight of metal per 100 parts by weight of support material) were used in all the experiments mentioned in this table.

Of the experiments listed in the table, Experiments 1 and 5 (using Ni / V / Si 2 - catalysts with an annealing loss of less than 0.5% by weight), Experiment 3 (using a Co / Mo / SiO 2 - catalyst) with an annealing loss of less than 1.0 wt.%, And Experiments 7 and δ (using Ni / Mo / SiO 2 catalysts with an annealing loss of less than 1.0 wt.%) Were metal removal experiments according to the invention.

Experiments 2, 4, 6 and 9-13 fall within the scope of this invention, but are included for comparison. Experiments 2 and 6 used Ni / w / SiO 2 catalysts with an annealing loss greater than 0.5 wt%. Experiments 4 and 9 used Co / Mo / SiO 2 or N 1 / Mo / SiO 2 catalysts with an annealing loss greater than 1.0 wt%. Experiments 10-13 were performed on catalysts containing alumina as support.

The effect of moisture on the metal removal capacity of the catalysts is clearly seen when comparing the results of experiments 1, 3 * 7 * 8 with the results of experiments 2, 4, 6, and 9. It is seen that the Ni / v / SiOg catalysts A and E of the present invention having an annealing loss of less than 0.5% by weight used in Experiments 1 and 5, and the Co / Mo / SiO 2 and Ni / SiOg catalysts Catalysts C, G and H, of this invention (having an annealing loss of less than 1.0 wt%) and used in Experiments 3, 7 and 8 show approximately equal percent V + Ni removal. after treatment of 5 tonnes of residue per kg of catalyst, than Ni / V / SiOg catalysts B and F (having an annealing loss greater than 0.5% by weight) not covered by this invention, and used in Experiments 2 and 6, and Co / Mo / SiOg and Ni / Mo / SiOg catalysts D and I (which have an annealing loss of more than 1.0% by weight) used in experiments 4 and 9, which are not within the scope of the invention. , which was considerably higher when five catalysts according to the invention were used than the other four catalysts.

The different sensitivity of the vanadium-containing catalysts according to the invention and the non-vanadium-containing catalysts according to the invention to moisture is clearly seen from the results of Experiments 1 and 7, compared with the results of Experiments 2 and Θ. Ni / v / SiOg catalyst B, which had an annealing loss of 0.5-1.0% by weight and was used in Experiment 2, showed a significantly lower metal removal capacity than Ni / v / SiOg catalyst A, which had a lower annealing loss. than 0.5 wt%, and used in Experiment 1, while the Ni / v / SiO 2 catalyst H, which had an annealing loss of 0.5-1 # 0 wt.%, and used in Experiment 8, showed approximately the same metal removal capacity as Ni / Mo / SiOg catalyst G, which had an annealing loss of less than 0.5 wt%, and was used in Experiment 7.

Comparing the results of Experiments 10 and 12 with the results of Experiments 11 and 13, it is found that the metal removal properties of the alumina-based catalysts of the invention are not sensitive to the moisture content of the catalyst. Although the annealing losses K and M of the catalysts used in Experiments 11 and 13 were 5.9 and 6.3% by weight, respectively, and the annealing losses of the catalysts J and L used in Experiments 10 and 12 were 0.0 and 0.1% by weight, respectively, considering the same metal removal ability in these experiments performed in pairs at the same space rate.

Claims (2)

12 60575 An improved process for removing metals from a residual hydrocarbon oil in a two-step process, wherein the oil is first metal depleted and the oil is then subjected to catalytic conversion, the metals being removed by contacting the oil at elevated temperature and pressure and in the presence of hydrogen with a catalyst containing one or more hydrogenation metals and meeting the following requirements: 1. p / d> 3,5 to 0,02 v, where p is the specific average pore diameter in nm, d is the specific average diameter of the particles in mm and v is the percentage of the total volume consisting of pores with a diameter greater than 100 nm, 2. a total pore volume greater than 0,1 + 0 ml / g, 3. v less than 50 and d less than 0,1 + -5,0, and 2 1+) specific surface area more than 100 m / g; and in the case of a catalyst with p and d such that the ratio p / d is more than 3,5 '0,02 v but not more than 10 to 0,15 v, the catalyst must meet the following additional requirements: (a) the nitrogen pore volume is more than 0; 60 ml / g, 2 h) a surface area greater than 150 m / g, and c) p greater than 5 nm; characterized in that the metals are removed in the presence of a catalyst containing from 0.1 to 15 parts by weight of metal having one or more hydrogenation activities, with the exception of nickel-vanadium, per 100 parts by weight of silica used as support and having an annealing loss of less than 1% by weight - and that in the case where the catalyst contains vanadium or a combination of vanadium and one or more other metals having hydrogenation activity, the annealing loss is less than 0.5% by weight. Process according to Claim 1, characterized in that the metal removal is carried out in the presence of a catalyst having an annealing loss of less than 0.75% by weight and, if the catalyst contains vanadium, less than 0.2% by weight.