FI64634C - PROCEDURE FOR THE EXHAUST OF METALS AND PISTON OILS - Google Patents

Description

ANNOUNCEMENT s * r 7 λ

Bj 1 uTLÄGcN, NGssKRiFT ^ 4634 c (45) '' '-! : r * 12 1933 (51) KY.Ik. ^ nt.Ct.3 c 10 G 45/04 FINLAND - FINLAND (21) P »t # nttlhakemu * - Patenting lining 7 72120 (22) H» Kemi * p * lvl - · AiwOknlngidag 06.07-77 ^ ^ (23) Alku cloud - Glltlghetjdig θβ. 07.77 (41) Became public — Bllvlt offentllg 09.01.78

National Board of Patents and Registration NlhtlvMulpanon |. heard.Publish.your date- ^ ”

Patent · och registrstyrelsen Ansökan utlagd ech utl.skrlften publlcerad j ± .UO.0j (32) (33) (31) Pyydetty etuoikeus — Begird prlorltet 08.07.76

Ho11anti-Holland (NL) 7607951 (71) Shell Internationale Research Maatschappij B.V., Carel van Bylandtlaan 30,

The Hague, The Netherlands (NL) (72) Dirk Bode, Amsterdam, Robert Hendrik Van Dongen, Amsterdam, Jakob Van Klinken. Amsterdam, Holland-Holland (NL) (7 ^) Oy Kolster Ab (5U) Method for removing metals from hydrocarbon oils - Förfarande för avlägsning av metaller ur kolväteoljor

The present invention relates to a process for removing metals from hydrocarbon oils by contacting the oils with a catalyst at elevated temperature and pressure and in the presence of hydrogen.

High-boiling hydrocarbon oils, such as residual oils obtained by distillation of crude oils at normal atmospheric pressure or under reduced pressure, and certain heavy crude oils, in particular crude oils from South America, contain significant amounts of high molecular weight , especially vanadium and nickel compounds. When these high boiling hydrocarbon oils are used as feedstock for catalytic processes such as cracking, hydro-cracking and dehydrogenation, metals such as vanadium and nickel are deposited on the catalyst particles. As a result of the increased concentration of vanadium and nickel in the active sites of the catalyst, 64634 results in a rapid loss of activity of the catalyst.

In order to increase the life of the catalyst, it has been proposed to remove metals from the feeder before the latter comes into contact with the metal-sensitive catalyst. This can be accomplished by contacting the fuel with a suitable me or Iin removal catalyst at elevated temperature and pressure and in the presence of hydrogen. Various catalysts have already been proposed for this purpose, which are a porous substance which may contain one or more metals having nitration activity.

Studies of the hydrometallic removal of hydrocarbon oils with a total vanadium and nickel content of more than 250 ppm using catalysts with a surface area 2 of up to 100 m / g have shown that good catalysts for this purpose must meet a number of requirements for porosity and particle size. These requirements depend in part on the partial pressure of hydrogen at which the hydro-metal removal is carried out. A good catalyst for the hydrometallic removal of hydrocarbons having a total vanadium and nickel content of more than 250 ppmw is, within the scope of this patent application, a catalyst with a sufficiently high degree of metal removal activity after half the catalyst life and sufficient metal uptake.

It has been found that for the catalytic hydro-metal removal of hydrocarbon oils with a total vanadium and nickel content of more than 250 ppmw by a catalyst having a surface area of not more than 100 m / g, the requirements for porosity and particle size that a good catalyst must meet are as follows. The total pore volume (V 2) of the catalysts must be greater than 0.2 ml / g and their characteristic average particle diameter (d) must be at least 0.4 and at most 5 mm. In addition, the catalysts shall have an average pore diameter (ps), VT and d such that the following requirement is met:

In o * 1.4 PH. 0 -1_> - x (- ^ - r, '/ d VT 15 0 3 64634

where P represents the partial pressure of hydrogen (p * nm, d mm, Vm ml / g, P

^ H2 bar). The above values of d and p * are defined as follows based on their method of determination.

The manner in which d is determined depends on the shape of the catalyst particles. If the shape is such that the diameter distribution of the catalyst particles can be determined by sieve analysis, d is determined as follows. After complete sieve analysis of a representative sample of the catalyst using ASTM standard sieves E 11-6, as described in the 1969 Book of ASTM Standards, part. 30, p. 97, d is read from a graph in which each successive screen fraction is plotted as a percentage by weight of the total weight of the catalyst sample cumulatively as a function of the linear particle diameter of the relevant screen fraction; d is the particle diameter corresponding to a total weight of 50¾. This method can be used to determine the value of d for spherical or granular substances or for substances with a similar shape to particles, such as extrudates and pellets with a particle length / diameter ratio between 0.9 and 1.1. The determination of the d-value for extrudates and pellets with a particle length / diameter ratio of less than 0,9 or more and for similar cylindrical particles for which the particle distribution cannot be determined by sieve analysis is carried out as follows. After a complete length distribution analysis (if the length / diameter ratio is less than 0,9) or after a complete diameter distribution analysis (if the length / diameter ratio is greater than 1,1) is performed on a representative catalyst sample, d is read a graph plotting each successive length and diameter fraction as a function of the linear average size of the cumulatively relevant fraction as a percentage by weight of the total catalyst sample; d is a value corresponding to 50% of the total weight.

After determining the total pore diameter distribution of the catalyst sample, p * is read from the graph cumulatively plotted for each increase in pore volume present in pores with a diameter range less than or equal to 2 nm and which volume increase is less than or equal to than 10% of the pore volume, the pore volume quota and the corresponding pore diameter range, as a function of the linear average pore diameter over the relevant pore diameter range; p is the pore diameter corresponding to 50% of the total quota.

6 4 6 3 4

The determination of the total pore diameter distribution of the catalyst can quite conveniently be carried out by the nitrogen adsorption / desorption method (described in EV Ballou and 0.K. Boolen, Analytical Chemistry 32, 532 (1960)) together with the mercury penetration method (described in HL Ritter and LC Drake, Industrial and Engineering Chemistry, Analytical Edition 17, 787 (19U5)) using mercury pressures at 1-200C bar. In this case, the pore diameter distribution of the catalyst in the diameter range below and equal to 7.5 nm is calculated from the nitrogen desorption isotherm (assuming cylindrical pores) according to the method described by J.C.P. Broekhoff and J.H. de Boer in Journal of Catalysis 10, 377 (1968) and the pore diameter distribution of the catalyst over a diameter range above 7.5 nm is calculated using the following formula: 15000

Pore diameter (nm) = -------- absolute mercury pressure (bar) The nitrogen pore volume and total pore volume mentioned in this patent application are determined as follows. The nitrogen pore volume of the catalyst is the pore volume determined by the above-mentioned nitrogen adsorption / desorption method. The total pore volume of the catalyst is the nitrogen pore volume in pores with a diameter of less than or equal to 7.5 nm (determined by the above-mentioned nitrogen adsorption / desorption method) plus the mercury pore volume in pores with a diameter of more than 7.5 nm (determined by the above-mentioned mercury . The areas mentioned in this patent application have been determined by the B.E.T. method.

The present invention thus relates to a process for demetallizing hydrocarbon oils by contacting the oils with a catalyst at elevated temperature and pressure in the presence of hydrogen, wherein the total vanadium and nickel content of the hydrocarbon oil to be treated is greater than 250 ppm while using a catalyst meeting the above requirements.

Very suitable substances for use as catalysts or catalyst supports in the process according to the invention are the oxides of the elements of groups II, III and IV of the Periodic Table of the Elements 5 64634 or mixtures of these oxides, such as silica (quartz), alumina, magnesium oxide, zirconia, silica, boride, silica, magnesium oxide and alumina magnesium oxide.

Another type of material that is well suited to act as a catalyst or catalyst support in the process of the invention is carbon black, especially soot obtained as a by-product in the partial oxidation of hydrocarbons with air, oxygen or mixtures of air and oxygen, either in the presence or absence of steam.

As catalysts or catalyst supports for the process according to the invention, aluminas, silicas and silica-aluminas are preferred. Very suitable catalysts or catalyst supports are alumina or silica particles prepared by spray-drying an alumina or silica gel, followed by shaping of the spray-dried microparticles into larger particles, e.g. by extrusion, and spherical alumina or silica. The latter method involves forming an alumina or silica hydrosol, combining the hydrosol with a gelling agent, and dispersing the mixture as droplets in an oil that can be maintained at an elevated temperature; the droplets remain in the oil until they have solidified into spherical hydrogel particles, which are then separated, washed, dried and calcined. Highly suitable silica-alumina catalysts or catalyst supports are cohesive of aluminum hydroxide gel and silica hydrogel.

The catalysts or catalyst supports of the present invention can be e.g. shaped by extrusion or pelletizing. In addition to these shaping methods, the well-known modulation method in particular is a rather convenient shaping method for the present catalysts or catalyst supports. According to this method, catalyst particles with a diameter of at most 0.1 mm are agglomerated with a granulation liquid to form particles with a diameter of at least 1.0 mm.

The catalysts used in the process of this invention may be accelerated by one or more metals having hydrogenation activity. When using accelerated catalysts, preference is given to catalysts containing 0.1-15% by weight of said 64634 mentioned metals per 100% by weight of support. Metals having hydrogenation activity are preferably selected from the group consisting of nickel, cobalt, molybdenum, vanadium and tungsten. It is also preferred that the catalyst contains at least one metal selected from the group consisting of nickel and cobalt and at least one metal selected from the group consisting of molybdenum, vanadium and tungsten, and in addition to that the atomic ratio of nickel and / or cobalt on one side and molybdenum, vanadium and / or tungsten-min from the other side is in the range 0.05 to 3.0. Suitable metal combinations include nickel-vanadium, cobalt-molybdenum, nickel-molybdenum and nickel-tungsten.

The amount of metal of the catalyst applied to the present invention is preferably 0.5 to 10% by weight and in particular 2.0 to 7.5% by weight per 100% by weight of support. Particularly preferred catalysts according to the invention are catalysts containing about 1/2% by weight of nickel and about 2% by weight of vanadium per 100% by weight of support and catalysts containing about 1% by weight of nickel or cobalt and about 4% by weight of molybdenum per 100% by weight of the carrier. The metal may be in the support in metallic form or as metal oxides or sulfides. Preference is given to catalysts in which the metals are supported in the form of metal sulphides.

When the process of the present invention is used for the removal of hydrometal from hydrocarbon oils having a total vanadium and nickel content of more than 1000 ppm, the hydrocarbon oils selected from the group consisting of crude oils and distilled crude oils (petroleum oils), priority is given to the catalyst: 1) VT is greater than 0.6 ml / g, 2) d is not less than 1.5 and not more than 3 mm, 3) then d, and is placed in the formula

P

B

ln P * l · 1 * * (2) 2 / • d '^ VT 150 it is observed that p must be greater than a certain value expressed in Q nm; in the present case, p must have a value greater than Q + 10 nm.

7 64634

The above-mentioned advantageous properties for catalysts for the removal of hydrometallics from hydrocarbon oils with a total vanadium and nickel content of more than 1000 ppm are suitable for both suspended catalysts and non-accelerated catalysts.

The demetallization activity of the present catalysts can be increased by the addition of hydrogen sulfide. Therefore, the process according to the invention is preferably carried out by adding hydrogen sulphide. Further studies on the effect of hydrogen sulfide addition when using the present catalysts to remove metal from heavy hydrocarbon oils have shown that the effect of hydrogen sulfide is highly dependent on the partial pressure of hydrogen and the total pressure used. Given that the use of hydrogen sulphide for metal removal is economically attractive, especially when a certain total pressure results in an increase in metal removal activity of more than 50%, it is found that this requirement can be met if the amount of hydrogen sulphide is chosen so that the quotient Ρτ. „/ Ρτ, is at least ____________________ 4 + 200. . 2Pt-60 —p— 7ΓT2 and up to - rT vrT; PT + 60

Within the limits set by the formula, the dewatering activity of the catalyst reaches an optimum value with a certain value Pu o) · rl 2 «->

The value of P g is different for different catalysts and can be determined from preliminary experiments. When P is c above or below p H 5 but within the given limits, an increase in metal removal activity of more than 50% results, but this increase is less than the maximum achievable.

It will be appreciated that during the metal removal process, P 2 g or some other P 1 g may be continuously controlled by supplying a sufficient amount of hydrogen sulfide from an external source to the oil from which the metal is to be removed. From an economic point of view, however, it is more attractive to utilize as much as possible the hydrogen sulfide released in the demetallization process and / or in the desulfurization process carried out after the demetallization process. This review led to the following three embodiments of the metal removal process of the invention in the presence of additional hydrogen sulfide.

1) Gas recirculation in the metal removal process, as much hydrogen sulfide as possible is left in the recirculating gas until the desired g. A certain amount of hydrogen sulfide is then continuously removed from the recirculating gas to maintain the desired hydrogen sulfide concentration.

2) Especially when a high Pu Q is desired, a considerable amount of time may be required before the hydrocarbon concentration in the recirculating gas has reached the desired value. This difficulty can be overcome by supplying hydrogen sulfide from an external source during the early stages of the process and gradually reducing the hydrogen sulfide supply as the process progresses. This additional amount of hydrogen sulfide can come from the hydro-desulfurization process, for example.

3) Instead of recirculating the gas to the metal removal reactor or together with this recycling, the exhaust gas from the desulfurization reactor installed downstream of the metal removal reactor is used as the feed gas to the metal removal reactor. A process diagram for a combined metal removal / desulfurization process in the presence of hydrogen, which formula is based on the above principle, is described in the accompanying drawing and will be explained in more detail below.

The plant sequentially includes a hydro-dewatering unit 1, a first gas-liquid separation unit 2, a hydro-desulfurization unit 3, a second gas-liquid separation unit 4, and a desulfurization unit 5. The residual carbon-hydrogen oil 6 containing metal and sulfur is subjected to a metal removal operation. under the action of two gas streams 7 and 8 containing hydrogen and hydrogen sulphide and, if desired, together with the hydrogen sulphide stream 9 from an external source. The product 10 thus obtained is separated into a low-metal liquid stream 11 and a gas stream 7 containing hydrogen and hydrogen sulfide, the latter being recycled to a dewatering unit. The liquid stream 11 is subjected to a desulfurization operation together with a hydrogen-containing gas stream 12 and a hydrogen stream 13 fed from an external source. The product 14 thus obtained is divided into a low-metal and low-sulfur liquid stream 15 and a gas stream 16, 64634 9 containing hydrogen and hydrogen sulphide, the latter being divided into two parts 8 and 17 having the same composition. Part 8 is recirculated to the dewatering unit and part 17 is recirculated to the desulfurization unit as a gas stream 12 after hydrogen sulfide removal.

The process according to the invention is preferably carried out by passing one or more vertically arranged reactors (reaction vessels) at elevated temperature and pressure in the presence of hydrogen in the presence of hydrogen, containing the catalyst particles in question as a solid or moving bed (mattress). For example, the process can be accomplished by passing hydrocarbon oils, together with hydrogen, upwardly through a vertically positioned catalyst bed, with liquid and gas velocities adjusted to cause the catalyst bed to expand (using effervescent bed operation). A very attractive embodiment of the process is one in which the hydrocarbon oil is passed through a vertically arranged catalyst bed, during which fresh catalyst is periodically introduced onto the bed and the spent catalyst is removed from the bottom of the bed (bunker flow operation). Another very attractive embodiment of the invention is one having a plurality of reactors, each containing a solid catalyst bed, which reactors are used alternately for the process in question; when the process is carried out in one or more of these reactors, the catalyst is regenerated in the other layers (solid bed inversion). If desired, the process can also be carried out by suspending the catalyst in the hydrocarbon oil to be treated (slurry phase operation).

The process according to the present invention is preferably carried out at a temperature of 350-450 ° C, a hydrogen partial pressure of 25-200 bar and a catalyst throughput rate of 0.1-10 kg · kg · · · h-1. Preference is given in particular to the following conditions: temperature 375-425 ° C, -1 -1 hydrogen partial pressure 50-150 bar and speed 3.5-5 kg.kg .h. Hydro-metal removal of a metal-containing hydrocarbon oil is particularly important if the oil is subsequently subjected to cracking, hydrocracking or hydro-desulfurization. The result is a significant reduction in the hydro-metal removal-deactivation of the catalyst used in this process. Hydrocracking and hydro-desulphurisation of hydrocarbon oils can be accomplished by contacting the oils at elevated temperature and pressure and in the presence of hydrogen with a suitable catalyst, which may be present as a solid bed, mobile bed, or as a suspension of catalyst particles. An attractive combination of metal removal and hydrocracking or hydrodesulfurization according to the invention is one in which the metal removal is carried out as a solid bed reversing operation or a bunker flow operation while the hydrocracking or hydrodesulfurization is carried out as a conventional, fixed bed operation.

Examples of hydrocarbon oils with a total vanadium and nickel content of more than 250 ppm which are suitable for the metal removal according to the invention are crude oils and residues obtained from the distillation of crude oils, such as distilled crude oils, long residues and short residues. residues).

The invention is illustrated below by means of examples.

Example I

Residual hydrocarbon oil with a total vanadium and nickel content of 1250 ppm, obtained by initial distillation and dehydration of crude oil from South America, was stripped of catalytic metal using nine different non-accelerated catalysts. For this purpose, the oil together with hydrogen was passed downwards through a cylindrical, vertically arranged catalyst bed at a temperature of U10 ° C, a hydrogen partial pressure (measured at the reactor inlet) of 150 bar, a feed rate of 2.1 kg per kg of catalyst per hour and a gas flow rate of 1000 N1 H2 / kg fresh feed. The liquid reaction product was divided into two portions of the same composition in a volume ratio of 22: 1. A smaller portion was removed from the system and a larger portion was recirculated to the reactor inlet.

The results of the metal removal test together with the properties of the catalysts are summarized in Table A. To determine the large p and total pore volume, the nitrogen adsorption / desorption method and the mercury penetration method were used as previously described above.

6 4 6 3 4

II

11

I II

v 1 l II

I I II

m χ. I I n γη v I χ I -s LO lt \ -T o o o m vo u

JX I I rH \ -l H vH i-l τ-i χ- \ ν 'O II

tO I ...........

O F; I O O O O O O O O O 'II

• P, l II

Ui a I n

II

II

* o'3 I II

X I · I II

aj I — I I m rvi m cm is \ ό oi o o m F -hi rn ro ^ 3 · o- u \ m t i cm 11> 'F I n 11

I II

.1 II

r l "B hO 1 OOKNVOCMCMinOUMn H · '1 LPit ^ -vovoKN σν ov n 13 cm 1 η • H 1 — I n 1 n

Oops m ^ j \\

II

I «" II

ω m. u

• HID J

C o ω 1 o o Ln o o o m up in n <C o X id n 1 υ co r-- eri σ> σ \ oj o · r-ι n -¾ 2 ^ ή> · · · · · · · · n

^ i2 jc + J E- 1 a CD <PCP <P C <GCXCD II

I-I 11

D £ | II

^ £ i ^ rLTi ^ r ^ T ^ r ^ rLTi ^ rmn -I 1 CMXVCMCMCMCMLnCMr-fll

Ό I II

II

II

1 il ε i Μ C rorac ^ -ooooooraii I ^ TI ^ iLn-g-CMLn ^ rCMLOll

Λ 1 ΚΛ VO II

* I C II

£ n I "

II

II

1 ί * Λ II

1 o n

• H I CU II

ij I ι-l "%: f

I — I I ai (M OJ (\ J o CM o CM o II

_g I O O O O CM O CM O CM II

f * i I · ri · r ~ i * rH * ri r ~ 1 Ή * ri 1 — I H

^ I c / j O) U} C /) «a. C / j <C / J <u li u s * 11

• H · 1 IJ

C / 5 o I T-Ι C \ J K '* ~ T LO U') l · · CO Cf \ I »ω; ; i il 12 64634

The performance of the catalysts is evaluated on the basis of V and k. - JTLciX _L 5 o. V is the maximum amount of vanadium, expressed as a percentage by mass of the amount of fresh catalyst which the catalyst particles are able to absorb in their pores, and k, ς is the activity of the catalyst • · -1 -1 - ± '5 expressed in kg.kg .h (ppm V) after half the service life of the catalyst (calculated from the amount of vanadium absorbed) has elapsed, k, c is calculated from the formula l, b ppm V in the feed - ppm V in the product (ppm V in the product) 1 1/2

The performance of the catalyst is considered good under the conditions used in this metal removal if the following criteria are met: V is greater than 30% by weight and k, _ is max -1/7 ö greater than 0.08 kg.kg .h (ppm V).

The performance of the catalyst is considered excellent under the conditions used in this demetallization if the following criteria are met: V is greater than * + 0 weight percent and k, r is -1-1 ~ 1/2 greater than 0.08 kg.kg .h. (Ppm V)

Experiments 1-6, in which the above-mentioned conditions for Vmax and k? 5 were satisfactory, are metal removal experiments according to the present invention. In these experiments, where catalysts were used of the formula:

* PH

In p * 1M · „(2) 2 - 7 - x - V * d VT 150, these catalysts also fulfilled the additional requirements of this invention with a surface area of 100 m 2 / g), V 2, (> 0.2 ml / g) and d (0.4-5 mm). In Experiments 3-6, catalysts were used which additionally met the additional requirements for the following quantities px (> Q + 10 nm), ^ ^ ^ (> 0.6 ml / g) and d (1.5-3 mm), and accordingly according to the invention are considered to be excellent catalysts. Experiments 7-9, in which the above-mentioned conditions are not satisfied with respect to the quantities V i and k, c, are deprotected outside the scope of the present invention. In the experiments Ί- ° - '"' • y-catalysts that did not meet the condition were found

In p * 1.4 (* H2) 2 -> - x - 'f d Vrj, 150

In addition, in Experiment 7 the catalyst had a d> 5 m and in Experiment 3 a catalyst with V, p <0.2 ml / g was used.

Example II

Experiment 4 of Example I was repeated several times each time using a different partial pressure of hydrogen sulfide. In these experiments, hydrogen sulfide was added from an external source. A constant total pressure of 150 bar (at the reactor inlet) was used in all experiments. The results of these experiments are summarized in Table B.

Table 3

Experience PH0 pHoS 'o Gain in magnitude

Well. 1 -1, -i bar bar ‘kgv n'h / o kI, 5 (Dpm V) -i / 2 l

Q

4,150 0 0.14 10 147 3 0.17 21 11 140 10 0.24 71 12 125 25 0.32 1; 13 35 56 0.22 57 14 64634

In experiments 11-13, the ratio P „/ P„ was used, which satisfied the formula * 2 H2 * + 200 PH S / PH 2Pt-60 _t _ <2 2 5. _? T (PT) 2 PT + 60 and reached more than 50% improvement in metal removal activity.

In Experiment 10, a P „/ Pr, ratio was used, which does not satisfy the formula given above Πλ Π9, and less than a 50% improvement in demetallization activity was achieved.

Claims (5)

15 6 4 6 3 4 Claims 1. VT is more than 0,6 ml / g, 2. d is not less than 1,5 mm and not more than 3 mm and 3. after the equation PH In P *> Irl x <2) 2 T d VT 150 is placed d , Vm and P state that p * must be greater than a certain value of Q in nm; in the present case, the value of p * must be greater than Q + 10 nm. 1. In P *> Iti x (H2) 2 Ύ d VT 150 where p * is the mean pore diameter in nm, d is the mean particle diameter in mm, VT is the total pore volume in ml / g and P is the partial pressure of hydrogen bar, H2 2 2. surface area not more than 100 m / g, A process for the removal of metals from hydrocarbon oils, characterized in that hydrocarbon oils with a total vanadium and nickel content of more than 250 ppm (by weight) are contacted at elevated temperature and pressure and in the presence of hydrogen with a catalyst which meets the following requirements: Process according to Claim 1, characterized in that the metals are removed from a hydrocarbon oil having a total vanadium and nickel content of more than 1000 ppm (by weight) which is crude oil or pre-distilled crude oil, using a catalyst which meets the following requirements: Process according to Claim 1 or 2, characterized in that it is carried out by adding hydrogen sulphide. 3. V is more than 0,2 ml / g and 4. d is not less than 0.4 mm and not more than 5 mm. Process according to Claim 3, characterized in that it is carried out in the presence of an amount of hydrogen sulfide such that the ratio P „0 / Ρ__ satisfies the equation H2: H2 64634 4 200 2P -60 - + -7 <PH S / PH 1 —- PT (PT) H2S H2 Pt + 60 where P „f P and Pm denote the partial pressure of hydrogen, respectively ** 21 i the partial pressure of hydrogen sulphide corresponding to the total pressure barrna. Process according to one of Claims 1 to 4, characterized in that it is carried out at a temperature of 350 to 450 ° C, a partial pressure of hydrogen of 25 to 200 bar and a feed rate of 0.1 to 10 kg. kg \ h 1. 64634 17