DE1770630C - Method and device for reducing the sulfur content of heavy petroleum fractions in a fluidized bed system - Google Patents

Description

200 '5

consists.

5. Device according to claims 2 to 4, characterized in that between the height (/ I from the opening of the feed inlet (2) to the beginning of the conical tapering of the reactor (!) and / to Absland (c) of the lower end of the inner tube i3) from this opening the relationship

f gc, 40
consists.

6. Device according to claims 2 to 5, characterized in that the angle of inclination {(->) of the conical section of the reactor (!) Of the relationship

10 <(-) < 70 "
follows.

7. Device according to claims 2 to 6, characterized in that the relationship between the inner diameter Ui) and the length (/) of the inner tube (3)

Hd < 50

consists.

The invention relates to a method for reducing the sulfur content of heavy Petroleum fractions in a fluidized bed system and on a device for carrying out the process.

The reduction of the sulfur content of heavy

Petroleum fractions (hereinafter referred to as hydrodesulphurisation by bringing a hydrodesulfurization catalyst into contact with a heavy one Petroleum feedstock and a gas containing a substantial amount of hydrogen (hereinafter referred to as hydrogen-containing gas) at increased Temperatures and pressures are known.

For the catalytic hydrodesulphurisation process of Lrdcjl; nan developed and practically carried out various refining processes using a fixed bed or a Wiibel bed, using distilled oils as the starting material. However, in the treatment of heavy petroleum fractions containing asphaltenes, particularly heavy oils, fractions containing the distillation residue oils and crude petroleum, the catalytic activity reduction due to the asphaltenes and metals in the feed is excessive, resulting in a shortening of the life of the catalyst and therefore difficult to work continuously over long periods of time . For example, distillation residues oils, crude petroleum oils and the like contain about 1 to 15 percent by weight asphaltenes, and the asphaltenes tend to excrete char products during the hydrogenation reaction, these char products depositing on the catalyst surface, covering the active sites, which reduces the catalytic ones Activity. It is also known that the metals (mainly vanadium and nickel) present in asphaltenes are also present in the

Catalyst surface are deposited, turning of particularly expensive specialties; vu.

an important cause of the degradation of the Kalalv alloys.

iic activity. The charring product The solution to this problem in a process / ar are easily removed by burning, and if reduction in the amount of peat is severe, therefore, the catalyst, whose potassium activity is 5 petroleum fractions in one cycle. which is reduced in this way is regenerated, so the heavy petroleum fraction and hydrogen halide can be used repeatedly. However, if there is a risk of being introduced to the bottom of a reactor with a fixed bed, repeated mixing of the oil and a H> dr <>cniseiiwelel'.ii; i-breehung the work process is necessary. Since on the catalyst in the fluidized state, on the other hand, the catalyst on which metals have passed and the l-ehaiideltc i >> deposited is difficult to regenerate. must be deducted from the upper part of a separation zone.;, ^! According to the invention, after a certain amount of separated me-off, it means that the petroleum fraction with the volatile gas containing gas is exchanged for a fresh catalyst . env become. located at the bottom of the reactor. Kaiahvu. r he. · .-

In order to promote hydrodesulphurisation effectively, 15 introducing a holding vortex start zone, the Gemi>c; i. It is essential that the catalyst, the oil and after it has been in contact with one another in the reactor through (ho vortex reaction.> ne gestro'nii hydrogen) are brought into a separation zone above the vortex reaction is achieved by fluidizing the catalyst in the fluidized reaction zone connected to the reactor and a uniform temperature distribution 20 of the larger cross-section '-r separation zone reduced in the reactor, whereby the hydrodesulphurisation is carried out at flow rate litet and the conditions advantageous in the separation zone separated catalyst in a below the fluidization of the catalyst, the reaction separation zone is carried out, with the peripheral area of this separation zone generally in a fluidized bed or moving bed separation zone in direct connection

In the hydrodesulphurisation of heavy oil under a catalyst, the bottom part of this settling zone enters the

If a fluidized bed is used, the catalyst fluidised starting zone is recycled.

particles preferably small. However, if a catalyst The process according to the invention can under \ er

Sator too small in the vortex state uses twist of the device described below

is, the separation of the resulting oil 30 will be carried out conveniently and easily. It acts

difficult from the catalyst particles. it is a reactor with a fluidized bed zone and

To overcome this disadvantage, one can use inlet and exhaust pipes. He is marked,

a catalyst comparatively coarse particles through a conically tapered part of the lower part of the

use size. In this case, however, the downstream "reactor" enters the vortex start zone with a

part on that the linear velocity of gas and 35 centrally located at the lower end inlet for the

of oil must be increased to a great extent to produce oil and the hydrogen-containing gas. also by a

to swirl up the catalyst sufficiently, whereby Vv. ii-V-el-

wiedrrum the efficiency of the catalyst verrcaktions / .one in the form of an open top and bottom

will wrestle. vertically and coaxially arranged inner ron '-

Even if the hydrodesulphurisation is carried out using a .; 40 also by a ring around the vortex reaction

Catalyst is carried out in the fluidized state, zone running catalyst settling zone, which on

some or all of the catalytic converter must either lower part over an annularly narrowed

replaced by fresh or regenerated catalyst passage between the inner reaction wall and the

vverden. wall of the inner tube with the vortex start zone

Furthermore, the constant replacement of the catalyst is in direct contact, as well as by sators by filling and removing the catalyst a separation zone arranged above the vortex reaction zone and the catalysts the steady state inside the reactor satorabsetzzonc, which in up to a certain Extent interrupted when the central section is used directly with the vortex reaction, a conventional device with a fluidized zone and directly with the catalyst in the peripheral area. 51 catalyst settling zone is in communication, w.mei

It is also a fluidized bed process for catalytic further on the outer wall of the reactor pipes / around

Cracking known, with the gas and catalyst in the gas vent, to the oil vent, to the catalyst loading: · \ ·

a fluidized bed with different catalyst and catalyst extraction are provided,

density are brought into contact and a connection for a better understanding of the invention is aul

accumulation of the catalytic converter in the lower part of an inner 55 reference is made to the drawing, which shows a

Tube takes place, with constantly regenerated catalytic sectional view of an embodiment of a

must be introduced from the outside and is connected to the reactor used in the invention.

separate separators are required to separate the feedstock and the hydrogen-containing gas

cracked vapors from solids mixed therewith pass through feed inlet 2 and overflow

to free particles. 60 the vortex start zone 14 into the vortex reaction zone 3

The object of the invention is to create a club which is surrounded by the inner wall of a pipe 3.

drive to reduce the sulfur content is given at 8, the catalyst is in the fluidized state

Heavy oils with economic utilization of the held. With the catalyst in the fluidized state, hu ^

catalyst used in this case can be referred to without a significant state in which the

constructive effort as well as the creation of a 65 lumen of the catalyst particles by at least

Apparatus for performing this method 2 ° / ₀ , preferably 10 to 100%, compared to that

while avoiding erosion and corrosion of the catalyst particle volume at standstill, expands,

Device walls without the need for when the reactor is performing its function. The linear

Speed of the oil and the hydrogen-containing z. B. a residual oil of distillation under normal

Gas when passing through zone 8 must be under and reduced pressure, which is over 1 weight

Be sufficient to contain the catalyst particles in the vortex percentage sulfur and in general as

to keep state. It is generally referred to in the area of heavy fuel oil.

from 0.2 to 20 cm per second. If the catalyst 5 The used in the process according to the invention

Nichl through the entered raw material alone in the delen catalysts can be made of Aluininiumoxide or

A part of silica-alumina will be made up on that

of the product returned to the linear speed of one or more metals of groups VI or VIII

to increase the efficiency of the oil within the reactor. of the periodic table have been plotted,

This returned oil is also used to increase 10 z. B. nickel and molybdenum, nickel, and cobalt

of descrambling percentage. Molybdenum, cobalt and molybdenum as well as nickel and

The catalyst particles rise in the eddy tungsten.

rcaktionszonc 8 while they maintain their fluidized state spherical catalysts with a diameter im. However, since the flow rate range from 0.1 to 10 mm and by extrusion of the oil and gas in the separation zone 10 formed with 15 catalysts can be used. If the cross-section is reduced, the spherical catalysts are particularly effective, the catalyst whose specific weight is greater and the catalysts formed by extrusion are separated from the bottom with that of the oil. Those with a diameter of 0.1 to 2 mm. Furthermore, Kalalysalorpartikel, which are used in the separation zone 10 catalysts, whose real settled, enter a catalyst settling ao specific gravity in the range of 1.50 to 5.00 and / one 9, which from an annular passage their apparent Specific weight, calculated as the ratio of the mass per volume unit of the catalyst and the outer wall of the inner tube 3 formed by the inner wall 1 of the reactor to the ratio of the satorticle particles (including the inner pores). In the catalyst density of water at 4 ° C., in the range from 0.30 to absctz / .one, the catalyst particles are more densely packed than in the vortex reaction 25 is 1.50. The eddy state can be controlled by feeding into a 8. The catalyst in zone 9 moves a part of the at least one part of the fluid downward and enters the eddy zone 14 in the circulation through an annularly narrowed passage 11. be promoted. If, however, a catalyst with The catalyst is here again by means of the oils «; If small particles are used, this can cause the on "-" * * initial whirl and the whirling reaction effect of the whirling up of the caialysis naturalpeak zone 8, so that the circuit recovers the required amount of oil flow with less. Since the packing density of the reaction zone 8 is reached expenditure and the volume of the reactor is smaller than that of the settling zone 9 and the pressure can be kept lower than if catalyst with large losses during the oil and gas passage due to particle sizes is used,
zone 9 is greater than the pressure loss during 35. Furthermore, in the hydrodesulphurisation process of passage through zone 8, the ascent treatment is generally more conveniently carried out by oil and cias flowing from inlet 2 when the ones introduced into the reactor have been introduced , essentially through zone 8, with hydrogen being present in sufficient excess, the desulfurizing hydrogenation is essentially carried out. It is therefore advantageous to pass the unreacted water. 40 material to be returned. In this case needs

The reactor with the separation zone 10 is above the only a small amount of fresh, hydrogen-vortex zone 8 as well as with a gas dwell zone containing gas can be introduced into the reactor in order to half of the former. The oil is left upright via the vortex state of the catalyst particles 5 from the separation zone 10 to obtain the hydrogen-containing gas and to achieve the desired hydrodynamic level withdrawn from the gas retention zone 13 via outlet 4. 45 lungsbehar.dlung to be carried out.

The catalyst is introduced into the catalyst settling zone 9. In the process according to the invention, the place where the reaction takes place via a catalyst charging opening 6 is the fluidized reaction zone 8, point above the catalyst settling zone, while the catalyst settling zone 9 and the or are filled, whereas the catalyst is drawn off. Separation zone IQ essentially no reaction takes place by means of a catalyst discharge opening 7, see s °. Therefore, the amount of catalyst which is preferably seen at the lower part of zone 9 in front of the hydrogen and that of the hydrodesulphurisation. The charging and replenishing of the oil which is inferior to the catalyst treatment comes into contact with the catalyst and the removal of the exhausted catalyst only part of the total amount of catalyst. Ver can be provided both continuously and intermittently with those cases where the catalyst follows in line, including several inlet and outlet openings in contact with the oil to be treated. which contaminates the catalyst is here the

Since in the process according to the invention, the rate of contamination of the catalyst is lower. The addition and removal of the catalyst and the decrease in the effectiveness of the catalyst in the reactor takes place outside the vortex reaction zone, which is therefore slower. As a result, the frequency of the vortex reaction zone is reduced by charging, replenishing 60 catalyst changes, and withdrawing the catalyst not at all. This leads to a very cylindrical shape, and the cross-section simplifies the work process. The reactor according to the invention is also preferably Kre ^; t-shaped. The process is therefore an improvement over the conventional process. a cylinder with an even larger diameter, and

Each fraction can be used as a heavy petroleum fraction. The catalyst settling zone 9 is annular, whereby it

«Ends, which contains asphaltenes and sulfur, coaxially surrounds the vortex reaction zone. To the

To keep catalyst particles in the fluidized state in zone 8 and to cause their immediate settling in separation zone 10, it is preferred that the following relationship between the outer diameter d of the inner tube 3 and the inner diameter D of the outer casing, ie the reactor circumferential wall 1, be maintained will.

(1) D - d £ 3 cm

DId <> 2.5

If this relationship is observed, the catalyst particles are separated from the oil and hydrogen-containing gas and enter the settling zone 9. The catalyst particles accumulated in zone 9 pass through the passage 11 between the inner tube and the outer housing by gravity and move into the vortex reaction zone 8. To ensure that this movement is carried out effectively, it is preferred that the distance b of the passage 11 has a value V200 to Vs of the inner diameter D of the outer housing.

^D 200

In addition, the lower part 15 of the outer housing must be tapered. This lower part can be both straight and curved: however, if it is curved, then its radius of curvature R should preferably be greater than _four .

is subject to corrosion conditions, do not pay attention to its compressive strength needs to be directed and also the exchange of the pipe is also feasible is.

S The reaction conditions used depend on the properties of the feed material and the desired properties of the product different. In general, the aforementioned heavy fuel oil and the hydrogen-containing gas with the hydrological

schwefclungskatalysator, placed within the reactor at a temperature of 200 to 500 ⁰ C, preferably to 450 C, and under a pressure of 10 to atmospheres, preferably 100 to 300 atm in contact. The hourly liquid space velocity

digkcit of the heavy oil is 0.2 to 5.0 V / V / h, preferably 0.5 to 3.0 V / V / h, and the ratio of the flow rates of the hydrogen? to the input material at 50 to 1000 liters (normal pressure and temperature, ie 1 atmosphere and 0 ⁰ C)

ao per liter of input material.

The hydrodesulphurized oil that the reactor has left, either steam stripping, steam stripping at reduced pressure, distillation at normal or

»5 reduced! Pressure or a combination of these

Subjected treatments to the dissolved gas

and remove the low boiling components.

like cracked light oils.

The advantages achieved in practicing the invention

ίο sinrt rfip f! d

R >

Regardless of whether the inclined surface 15 is straight or curved, on the other hand, there is the preferred relationship between the height /, the height from the opening of the supply inlet c to the extreme end of the inclined floor, and the height e, the distance of the inner tube from this opening;

(4)

^ «740

In addition, it is preferable that when the inclined surface 15 is straight, the inclination θ, or when the inclined surface 15 is curved, the inclination θ of a tangent drawn at the lowest point satisfies the following relationship:

(5)

10 ° - θ < 70 °

For the design of the vortex reaction zone, it is preferred that the relationship between its diameter d and its length be:

(6)

1.2

50

Since the pressure to which the inner and outer surfaces of the inner tube 3 are subjected, the same is, the thickness of the tube can be made thinner than the thickness of the outer casing. In the device according to the invention, the outer housing is therefore which must withstand the reaction pressure, not easily eroded brw. corroded, whereas the inner Ruhr, which Frmions- and FroMonvKor-

1. A fluidized state of the catalyst particles can be maintained in the fluidized reaction zone using a wide range Catalyst particles, including spherical catalysts with particle diameters from 0.1 to 10 mm and extrusion molded catalysts, as well as other catalysts whose true specific gravity ranges between 1.50 and 5.00 is, and the separation of the catalyst particles from the oil and gas can take place in the separation zone easily accomplished.

2. Fine catalyst particles can be used, which makes it possible to

swirl the catalyst particles in the circuit to reduce the amount of oil and gas. This can reduce the cost of construction and labor of the device.

3. In the reactor used according to the invention, the amount of catalyst which comes into contact with the starting material is only a part of the Amount of catalyst present in the reactor. As a result, compared to the reactor type, at which is all of the catalyst in the reactor

is in contact with the feed, the rate at which the activity of the Katysators less, whereby the frequency of the catalyst exchange is lower.

4. In the reactor used according to the invention, the part that must be pressure-resistant is erosive or

not exposed to corrosive action, while on the other hand the part which erosion and F. is subject to corrosion-corrosion conditions, does not have to be pressure-resistant, only the last part alone has to be thus be replaced.

To further illustrate the invention, the following examples are given:

309634/213

Examples

A reactor of the type shown in the drawing was used and a hydrodesulfurization reaction was used accomplished. The properties of the feed, the catalysts, the reaction conditions, the dimensions of the reactor as well the properties of the product are given in the table.

10

The separation of oil, hydrogen-containing gas and Catalyst particles took place very satisfactorily. Furthermore, the replacement of the catalyst in Carried out at intervals of about 15 hours without interrupting the steady state and without changing the properties of the product. Furthermore, there was little, if any, erosion and erosion corrosion of the inner wall of the outer casing of the reactor was determined.

Example 1 Insert Mutcrinl I Product Example 2
Insert material product

Example 3 Application / material I product

Properties of the oil
Class of input material

Total sulfur (percent by weight)

Degree of desulphurisation (%)

Coke residue (weight percent)

yield

Viscosity (cSt at 50 ⁰ Q ..

catalyst
Class of the catalyst

Khafji oil, normal pressure distillation residue

4.25

13.1 1075

10.31 95.2 775.3

Particle shape and diameter

Co-Mo *) on silica-alumina support

0.3 mm, spherical 3.00

400 ⁰ C 270 kg / cm *

1.0

93 hours

5.0 m '/ m ^{3 of} supplied oil

830 m ^a / m ^{3 of} fed oil

10 cm 7 cm 100 cm

70 cm scm 1 cm

*) From oxide, 10 weight percent metal calculated from metal oxide.

Real specific weight.

Reaction conditions

temperature

pressure

Space velocity

length of time

oil quantity guided in the cycle ...

Amount of hydrogen carried out in the cycle

Reactor dimensions

D.

d

L.

Khurusanya oil, normal pressure distillation residue

3.97

9.8

351.2

0.80
80

7.2
93.2
245

Ni-Co-Mo *) on silicon dioxide-aluminum oxide carrier

0.55mm, extrusion molded
3.3

410 ⁰ C
kg / cm ²

1.0
Hours.

8.8 m ³ / m ^{3 of} supplied oil

m ³ / m ^{3 of} supplied oil

cm

cm
cm
cm

cm cm

Khafji oil,

Normal pressure distillation residue

4.25

13.1
1075

10.3 90.9 79.1

Ni-Mo *) on aluminum oxide

0.15 mm, spherical 3.2

39O ° C
170 kg / cm ²

0.8
200 hours

7.0 m ³ / m ³ supplied oil

250 m ³ / m ^{3 of} fed oil

10 centimeters

Scm

200 cm

150 cm

10 centimeters

0.7 cm

1 sheet of drawings

Claims (4)

Patent claims: 1. Method of reducing Is sulfur gchalies ν 11 for heavy petroleum fractions in one \ Virhelhett -> \ 3iem. in the case of the heavy hearing fraction and hydrogen-containing ^ gas on the ground a reactor are introduced, the mixture of the oil and an Lhdrodesulfurization caialysaior passed upwards through a vortex reaction zone in the whirlwind state and the treated Oil on the upper part of a door: i;: one peeled off will. thereby gek e η η ζ -_ ■ i c h η <: i. that the heavy petroleum fraction with the wjss <vsti'ffhalii ^ ci'i Ga.-. in a? on the testicle of the ReakU: i .-> communal. Ka'alysator revealing vertebral beginnings introduces the mixture, after it has flowed through the Wii + elreaktioiibi-une, into an over tier Vortex reaction zone, the separation zone, the center of which is directly linked to the vortex reaction, one is connected, with reduced as a result of the larger cross section of the separation zone Flow rate directs and the catalyst separated off in the separation zone in a below the separation zone, with the peripheral area of this separation ore in surrounding connection the standing sensor settling zone and return the catalyst from the bottom part of this sedimentation zone to the vortex start-up zone. 2. Apparatus for performing the method according to claim 1, consisting of a reactor with fluidized bed zor.j and with inlet and outlet pipes, characterized by one arranged in the lower conically tapered part of the reactor (1) Vortex start zone (14) with an inlet (2) for the Oil and the hydrogenous gas. furthermore one arranged above the vortex start zone Vortex reaction zone (S) in the form of a vertically and coaxially arranged one that is open at the top and bottom inner tube (3), furthermore through a catalyst settling zone running annularly around the vortex reaction / one (9, soft on the lower part over an annular narrowed passage (1.1) / wipe Reactor ;; nenvvand and the outer wall of the inner tube with the vortex start zone in the immediate vicinity Connection is, as well as further by one above the vortex reaction zone and the Separation zone (10) arranged in the catalyst settling zone. which in the central section directly with the vortex reaction zone and in the peripheral area directly in connection with the catalyst settling zone stands, furthermore on the outer wall de? Reactor pipes for gas extraction (4), for oil extraction (5), for catalyst charging (6) and for catalyst exhaust (7) are provided. 3. Apparatus according to claim 2, characterized in that the relationships between the inner diameter (D) of the peripheral wall of the reactor (1) and the outer diameter (c!) Of the Innenrohrcs (3) D - el 2; 3 cm and D / d ^ 2.5 exist. 4. Apparatus according to claim 2 or 3, characterized in that the relationship between the gap (b) of the annular \ narrowed passage (11) and the diameter ( D)