DE2160704C3 - Process for the catalytic hydrogenation of petroleum hydrocarbons containing distillation residues and a catalyst therefor - Google Patents

Description

a) the support by passing a hydrosol of basic aluminum sulfate with a molar ratio of SOJAl ₂ O ₃ in the range from 0.8 to 1.6 or a mixture of this hydrosol with a hydrosol of silicon dioxide through a heated to 40 to 100 ° C, with Water-immiscible liquid heating medium, washing the hydrogel obtained in this way with water until the molar ratio of SO ₃ / A1 ₂ O ₃ ^{a5 is} in the range from 0.4 to 0.7, further washing the hydrogel with an aqueous alkaline solution and with water as well Drying and calcining of the washed hydrogel has been obtained,

b) said support has a surface area of 250 to 450 m ² / g, a pore volume of 0.5 to 1.5 cm ³ / g and an average pore radius of 40 to 100 Å, and

c) a width of 10 Å within this average pore radius range Maximum value, which accounts for more than 15% of the specified pore volume.

2. The method according to claim 1, characterized in that the catalytic hydrogenation at a Temperature of 300 to 500 ° C and a pressure of 50 to 300 atü is carried out.

3. Catalyst for use in the process according to claims 1 and 2, which consists of a metal catalyst effective in the hydrogenation, which is applied to a support consisting of alumina or alumina-silica, said gel having a surface area of not less than 200 m ² / g, determined by the BET method, has a pore volume of not less than 0.5 cm ³ / g and an average pore radius of not greater than 100 Å, characterized in that

a) the support by passing a hydrosol of basic aluminum sulfate with a molar ratio of SO ₃ / Al ₂ O ₃ of 0.8 to 1.6 or a mixture of this hydrosol with a hydrosol of silicon dioxide through a heated to 40 to 100 ° C, with Water-immiscible liquid heating medium, washing the hydrogel obtained in this way with water until the molar ratio SO ₃ / A1 ₂ O _{3 is} in the range from 0.4 to 0.7, further washing the hydrogel with an aqueous alkaline solution and with water and drying Calcining the washed hydrogel has been obtained,

b) the support has a surface area of 250 to 450 m ⁸ / g, a pore volume of 0.5 to 1.5 cm ³ / g and an average pore radius of 40 to 100 Å, and

c) at a width of 10 Å within said average pore radius range a maximum value is to which more than 15% of said pore volume accounts for.

The invention relates to a process by means of which continuous catalytic hydrogenation of petroleum hydrocarbons or gasoline hydrocarbons containing distillation residues effective and durable over a prolonged period of time with improved catalytic activity and Life of the catalyst can be carried out, as well as a catalyst for use in this procedure.

The invention relates to a process for the catalytic hydrogenation of petroleum hydrocarbons containing distillation residues, the hydrocarbons being applied in the presence of a metal catalyst active in the hydrogenation, applied to a support consisting of aluminum oxide or aluminum oxide-silicon dioxide gels, these gels having a surface area of not less than 200 m ² / g, determined by the BET method, have a pore volume of not less than 0.5 cm ³ / g and an average pore radius of not greater than 100 Å, are brought into contact with hydrogen, which is characterized in that

a) the support by passing a hydrosol of basic aluminum sulfate with a molar ratio of SO ₃ / A1 ₂ O ₃ in the range from 0.8 to 1.6 or a mixture of this hydrosol with a hydrosol of silicon dioxide through a to 40 to 100 ^° C. heated, water-immiscible liquid heating medium, washing of the hydrogel obtained in this way with water until the molar ratio of SO ₃ / A1 ₂ O _{3 is} in the range from 0.4 to 0.7, further washing of the hydrogel with an aqueous alkaline solution and with Water and drying and calcining of the washed hydrogel has been obtained,

b) said support has a surface area of 250 to 450 m ² / g, a pore volume of 0.5 to 1.5 cm ³ / g and an average pore radius of 40 to 100 Å, and

c) a maximum value within this average pore radius range within a width of 10 Å which accounts for more than 15% of the specified pore volume.

The invention also relates to a catalyst for use in the above process which consists of a metal catalyst which is effective in hydrogenation and which is applied to a support consisting of alumina or alumina-silica gels, this gel having a surface area of not less than 200 m ² / g, determined by the BET method, has a pore volume of not less than 0.5 cm ³ / g and an average pore radius of not more than 100 Å, which is characterized in that

3 O ₄

a) the carrier by passing a hydrosol from One of these proposals is the British Patentbaaschem Aluminum sulphate with a molecular code of 9 33 663. It states that the subject matter of SOa / AljOa from 0.8 to 1.6 or a position method of the catalyst its properties Mixture of this hydrosol with a hydrosol determined and shown that two catalysts of the of silicon dioxide with a nominal composition equal to 40 to 100 ° C 5, but produced

"Heated liquid that is immiscible with water is very different according to different methods

Heating medium, washing the resulting hydro properties can have. The proposed is the

gels with water until the molar ratio SO ₃ ZAl ₂ O ₃ using gamma aluminum oxide, which

in the range from 0.4 to 0.7, further washing by calcining alpha-aluminum oxide mono-

of the hydrogel is produced with an aqueous alkaline io hydrate and has a surface area of 200

Solution and with water as well as drying and up to 240m ^a / g as well as an average pore size

Calcimers of the washed hydrogel obtained in diameter from 70 to 100 Å (average

has been, pore radius of 35 to 50 Å) and preferably of

b) the support has a surface area of 250 to 450 m '/ g, 70 to 90 Å (average pore radius of 35 to a pore volume of 0.5 to 1.5 cm ³ / g and 15 45 Å). For this purpose, it is stated that the pore has an average pore radius of 40 to volume, generally 0.3 to 0.6 cm ³ / g and before _{-100 Å} , and is preferably from 4 to 0.5 cm ³ / g.

c) within a width of 10 Å within said I _n this proposal, the above average pore radius ranges will be the highest problems associated with the catalytic value, accounted for by the pore volume containing more than 15% of said ao hydrogenation of still bottoms. Petroleum hydrocarbons occur, not particularly

What mentions the catalytic hydrogenation of petroleum, but it is stated that gamma-aluminum

met, numerous purification processes have used deminoxide to treat a wide area

winds and used in connection with the cases of gas oils can be used. Regarding the

where distillate oil, such as light oil, is used as a load, the surface will be a lower value than the lower one

is turned. Called limit according to the invention. During the

Recently, the catalytic hydrogenation of average pore diameters and the appropriate

Petroleum coal containing distillation residues give pore volumes near the lower limit

Hydrogen has found great interest, and it was in accordance with the invention, is the specified

a number of suggestions, such as the following 30 area much deeper,

described, made, It is also stated that only gamma aluminum

It was known, however, that in the case of the Behändminium oxide obtained by calcination, alpha the fraction which contains the distillation residue aluminum oxide monohydrate and not other aluminum, a continium oxides obtained by other methods over longer periods of time The precise procedure was very difficult to carry out, 35 could be used. Most of all it was because of the short life of the catalyst, which is the importance of the distribution of the pore radius the considerable drop in the activity of the catalyst is not recognized.

sators is attributable to what is different from those in the loading As a suggestion in which the above problem

Asphaltenes and metals contained in the cargo when carrying out the catalytic hydrogenation

originates from. A process was therefore sought to remove 40 petroleum alcohols containing distillation residues.

which would enable catalytic hy- drogen hydrocarbons to be recognized is the USA.

Dried treatment resistant and with good writing 33 83 301 to be mentioned for this purpose

Proposes activity over a prolonged period of time by a carrier. It is stated therein that

to lead. in the alumina carrier a larger part of the

It has also been known that the distillation back pore volume 45 for pores with a radius of stood, and especially the asphaltenes contained therein, less than 300 angstrom units and far more tended to deposit a large part of the total pore volume in carbon in the containing material during the hydrogenation process relatively small pores with a radius of 0 to in the conventional method of causing it to be 120 angstrom units. It goes on from there wherein the deposited carbonaceous material 50 protrudes that specifically to achieve a larger covered the surface of the catalyst and thus effective in the desulphurisation of residues caused its catalytic activity to decrease. not a catalyst with a large pore concentration it is also known that the metals (mainly necessary for any particle size, otherwise Vanadium and nickel), which in the distil- dem tends to be a catalyst with a fairly equation residue and especially in the widespread distribution of pores over those held therein Asphaltenes are pre-banded, likewise on the entire radius range from 0 to 120 A. This is done Surface of the catalyst are deposited and a composite catalyst proposed so the further decrease in the efficiency of the catalyst in the case of the within a 10 Angstrom increase of the cause. Pore radius in the range of pores with a

Thus, as indicated above, problems the 60 radius from 0 to 120 Angstrom units are no longer

in the catalytic hydrogenation of distillates, which account for 15% of the total volume of the pores from a

Essentially no distillation residue - total radius range from 0 to 300 angstroms

hold, did not exist, recently with which catalyzes should be, as well as at least 10% of the mentioned

table hydrogenation of distillation residues ent- pore volume in pores with a radius of holding petroleum hydrocarbons emerged. It 65 less than 30 angstrom units, at least 15%

are various proposals to try, one or the mentioned pore volume in pores with a

To solve several of these technical problems, radius greater than 30 angstrom units and smaller

knows. than 70 angstrom units and at least 30% of the

f.

named pore volume in pores with a radius aqueous-colloidal solution of basic aluminum greater than 70 Angstrom units and less than sulfate and silicon dioxide sol have the properties 120 angstrom units should be included. to gel when heated, resulting in the production of a

This publication teaches that hydrogel distribution is exploited. To be uniform To promote hydrogel formation of the pores over the entire radius range of 5, water is preferred 0 to 120 A should be uniform and wide. in an amount of 10 to 30% by weight of the

Additionally, this publication recommends that starting solution be heated immediately before this the surface of this composite catalyst is to be added, should be at least 100 m * / g. The formation of the hydrogel can easily be achieved by

Also in US Pat. No. 33 93148, io driving can be achieved in which the combined hydrosol is an indication of the treatment of residues. Solution by a water-immiscible heating-In this publication it is proposed that the medium, such as a petroleum hydrocarbon, in particular aluminum oxide with a surface in which spindle oil and light oil is carried out, is in the range from about 150 to about 50OmVg, especially one Temperature of 40 to 100 ⁰ C is heated. ^{According to this method, in the range from about 300 to about 350 m 2} / g, a spherical hydrogel can be obtained, preferably in the range from about 320 to 340 m 2 / g. The size of the hydrogel and therefore an average pore diameter in the size of the catalyst support can range from about 100 to 200 A (average nozzle through which the starting solution in the heat pore area in the range of about 50 to 100 A) to medium is injected by the difference of the related. It is also recommended that the pore specific gravity of the starting solution and the volume of this carrier be 0.54 to 2.36 cm ³ / g. Heat medium as well as viscosity and

Investigations have now been carried out to determine how the surface tension of the starting solution is set these technical difficulties that are catalyzed in the process. Is it desirable a completely spherical one To obtain hydrogenation of distillation residues from the shape of a catalyst, the duration of the holding petroleum hydrocarbons occur, as warming can be precisely controlled. Furthermore could be avoided. It has been found that this should help avoid cracking during the gelled product that becomes the starting solution by heat treatment of a hydrosolation process from basic aluminum sulfate or preferably freed from any gas dissolved in it Mix this hydrosol with a hydroso! before it is used. Silica, has been obtained as a carrier 30 Around the time for washing with water and for material shows particularly superior effects. A neutralization process that affects education Method of making this support is to be followed in the hydrogels, shorten, and speed-DT-OS 17 70 383. the speed with which these processes are carried out.

It has further been found that when the increase is used, the hydrogels become small in size by heat treatment of the aforementioned 35 are preferred.

The hydrogel formed in this way is very unstable and

Being a peak in the distribution of the has a tendency to revert to the sol-solution-is critically important pore radius and that form if left to stand. The action of a catalyst must therefore be hydrolyzed by pouring hot water over it, this type of carrier is regulated by combining, in order to meet some of the sulfuric acid residues of requirements that affect the surface, the removed and the molar SO ₃ / Al ₂ O ₃ ratio to i I pore volume and the mean pore radius, such as 0.4 to 0.7. The hydrogel is made by I.

above under b), concern, as well as this process not only stabilized, but it r

In addition, due to the need to distribute the, impure salts that are in the starting solution are also present

Pore radius are contained within a certain middle 45 away. I.

Width of the pore radius, as indicated under c). It is then the hydrogel with an aqueous s

it has been found that even when the Er- alkaline solution is brought into contact with it, its e

requirements a) and b) to raise the pH achieved by the invention and thereby the sulfuric acid Improvement can only be achieved if the residues are removed as sulfates. If exactly spherical /

Requirement c) in connection with a) and b) fulfilled 5 ° shaped hydrogels are desired, then the

will. pH value can be raised gradually. Becomes the- P

The hydrosol solution of basic aluminum- at this point the pH value suddenly raised. Works b

sulfate, which for the production of the gelled product after this has an unfavorable effect on the hydrogels, so that a) is used, will cracks or fractures occur through slow addition or they tend to * v

of finely divided Caicäumcarbonat in a concentrated 55 break during drying, whereby the st

trated aqueous aluminum sulfate solution with violent breaking due to the drop in its pressure resistance fa

Stir to express the sulphate groups as calcium sulphate or to produce their abrasion resistance T

to fall, received. Preferred is a molar ratio. As an alkali to the pH (Ii

in the range from 0.8 to 1.6 for the value-setting ratio, a substance is preferred

SO ₃ / A1 ₂ O ₃ in this aqueous solution. The hydrosol 60 that does not remain in the hydrogel applies to- A

Solution of basic aluminum sulfate and silicon, for example ammonia water. After finishing the al

Dioxydsol can be de-sulfuric acid by simply mixing together alkali treatment

can be obtained. Ions such as Na ^+, K ^+, Mg ⁺ +, Ca ⁺ + as completely as possible by washing with water ve

Zn ⁺⁺ , Fe ⁺⁺ and NH ,, + can be removed as impurities. In this way you either get aluminum

in the starting solution of aluminum oxide hydrogels or aluminum oxide-silicon-Ti used here

may contain minium sulfate. Dioxyd hydrogels with a water content of 60 to 99 pieces

The aqueous colloidal solution of basic weight percent is. gr

miniumsulfat and the combined solution from the order from the above hesrhrirhpnpn aluminum

oxide hydrogels or aluminum oxide silicon dioxide surface to become larger when the hydrogel To obtain a catalyst support, a solution of a hydrosol of basic alumina is used the hydrogels dried and calcined. minium sulfate and a silica sol in place

The drying of the spherical hydrogels of the hydrosol of basic aluminum sulfate is preferably used slowly in the presence of the starting solution.
Saturated steam is carried out because the hydrogel should be subjected to an extrusion deformation of the hydrogel

If drying is carried out too quickly, if the drying is carried out too quickly, there is a tendency that the gel cracks is carried out. in the ratio in which the water content at the

The aluminum oxide extrusion deformation step of the hydrogel used according to the invention, after or aluminum oxide-silicon dioxide carrier must also io to which this has been kneaded and then through In addition, the above conditions b) and c) heating was dried, the lower the fulfill. The pore radius is larger and the surface area is smaller.

If the carrier used has a surface, it will continue to undergo extrusion deformation

below 250 m ² / g, the desired powder gel is used, so the activity tends not to be reached. On the other hand, in the case of 15, the pore radius must decrease as the amount of a support which has a surface area of 450 m ² / g set water amount is increased,
exceeds that the pore volume is extremely large. The obtained in the manner described above

to a mean pore radius in the aluminum oxide or aluminum oxide-silicon di-area from 40 to 100 A. This is oxidized with an aqueous solution of a however, for reasons of strength of the carrier 20, it is impregnated and hydrogenation-sensitive metal compound not wanted. then dried in the usual way and calci-

If the pore volume is less than 0.5 cm ³ / g to obtain the catalyst,
the surface must be made extremely small. Hydrogenation-active components are made of metals

otherwise a mean pore radius of 40 to groups VI and VIII of the periodic table. Be-100 A cannot be sustained. Since, like 25, cobalt, nickel, molybdenum and stated above, the activity is reduced tungsten.

if the surface area is small this is undesirable. The catalyst metal is usually in one

worth. On the other hand, if the carrier has a pore volume amount on the order of 5 to 20 weight greater than 1.5 cm ³ / g, its percentage production is plotted.

with regard to the strength of such a carrier, differs from the deposition of those described above rig. Catalyst metal components on the carrier too

If the mean pore radius of the used effect, the impregnation, the drying carrier is less than 40 Å, the desired and the calcination can be carried out in the usual way. Lifetime of the catalyst cannot be achieved, however, since an effective activity does not come about whereas in the case where the mean pore radius 35 comes when the calcination temperature is too low greater than 100 A, the pore volume is greater than, the calcination should preferably be at an I. , 5cm ³ / f? must be made to a surface temperature above 350 ⁰ C must be carried out. Maintain ge above 250 m ^s / g. For the above-mentioned reasons, this is not desirable. Order from 350 to 600 ° C applied.

If, on the other hand, in the carrier 40 used, the method according to the invention can either no width of 10 A within the pore radius - continuously or in layers, range between 40 and 100 A, on the In addition, with continuous reduction 15% of the total pore volume is accounted for by various well-known methods, such as Festso are used for the activity and lifespan of the bed, fluidized bed or fluidized bed. The desired values of the catalytic converter are not developed, 45 The catalytic converter can also be pre-sulphurised, even if the foregoing conditions a) and b) The presulfurization of the catalyst can be carried out in a conventional manner meets wind. Way to be made.

In order to achieve the above-mentioned properties of the The reaction conditions when carrying out

Aluminum oxide or aluminum oxide-silicon dioxide hydrating desulphurization of distillation oxide carrier Safe to obtain, the following 50 levels should be petroleum hydrocarbons Points in the preparation of the carrier carefully usually the following: temperature 300 to 500 ° C, get noticed. Pressure 50 to 300 atmospheres, hourly in the liquid state

The pore volume and pore radius of the carrier and the flow rate of the feed oil are greatly influenced by the way in which the 0.2 to 5 vol / vol / hour. and ratio of hydrosulfuric acids Residues after the heat gelation 55 to charge oil 300 to 30001 at Norfahren were removed and how the subsequent painting temperature and pressure / 1.

Drying process has been carried out. This desulphurised oil, which is the reaction column

indicates that the pore volume and the pore radius leaves, is after separation from the gas with steam Stripped by treating the hydrogels with dilute, under reduced pressure with steam Stripped ammonia water before performing the main 6 °, distilling in vacuo or under alkali treatment or by gradually increasing atmospheric pressure, or a combination of these the pH during the course of the main alkali treatment is subjected to treatments to give the final product can be enlarged. Regarding the drying received.

The following procedure must be carried out: The slower the B e i s ρ i e 1 1

Drying in an atmosphere of high humidity 65

speed and temperature is carried out so that calcium carbonate was slowly

the resulting pore radius becomes larger. temperature to a saturated aqueous aluminum sulfate

In addition, the pore radius and the solution tend to be joined, with vigorous stirring, in order to

To obtain a standing aqueous colloidal solution of basic aluminum sulfate, which contains 121.3 g Al ₂ O ₃ per liter and 116.5 g SO ₃ per liter molar ratio of SO ₃ / A1 ₂ O ₃ = 1.22).

After removing the gas dissolved in this sol by degassing for 5 hours under reduced pressure, water was added in an amount of 200 cm ³ / l of the sol for each. Immediately thereafter, the liquid was dropped from above into a container which was filled to a height of 8 m with spindle oil and was kept at a temperature of 70 ^° C., spherical hydrogels 1 to 2 mm in diameter being formed. The hydrogels were then transferred to a container filled with water and washed with a continuous stream of fresh hot water for 24 hours in order to remove some of the sulfuric acid residues which were present in the hydrogels. After the end of the washing with water, the molar ratio of SO ₃ / A1 ₂ O _{3 in} the hydrogel had dropped to 0.65.

A tank into which the aluminum oxide hydrogels had been placed was then filled with highly dilute ammonia water (pH 7.6) with a concentration of 0.3%, which was then ^{heated to a temperature of 45 °} C. and then removed. This process was repeated twice. After heating to a temperature of 55 ° C, the liquid was removed. After this was repeated eight times, the pH had gradually risen to 8.5, and the remaining sulfuric acid groups were converted into ammonium sulfate. Then the hydrogels were heated with water until no sulfuric acid groups were reached could be determined, with spherical aluminum oxide hydrogels were obtained.

The aluminum oxide hydrogels obtained in this way were dried by heating to about 100.degree. C. and

ίο kneaded smoothly in a kneading machine. Whom the water content had dropped to 42 percent by weight, the mass was shaped by extrusion, The extrusion molded product was then at 110 "C dried over the course of about 5 hours

and then calcined at 550 "C for 3 hours to give the carrier (Example 1).

For comparison purposes, 4N ammonia water was slowly converted to a 10% strength at room temperature aqueous aluminum nitrate solution added until one

pH value of 9.5 was reached. After standing for 24 hours, this mixture was separated by filtration and washed, an aluminum oxide hydrogel being obtained which was extrusion molded, ^{dried at 110 °} C. for 5 hours and then

Calcined at 550 ° C. for 3 hours to give a carrier (Comparison 1).

The properties of the supports of Example 1 and Comparison 1 are shown in Table 1.

Table 1 example 1 276 Comparison 1 volume
(%) 274 0.495 2.0
4.0
8 1 Surface (m ² / g) 0.630 78.8
7.1
0 Pore volume (cm ³ / g) 46 volume
(7o) Average Pore radius
(A) 4.8
2.4
4.8 Pore radius (A) 300 to 70
70 to 60
60 to 50 62.7
15.9
9.4
η Pore radius
(A) 50 to 40
40 to 30
30 to 20
20 to 10 300 to 60
60 to 50
50 to 40 40 to 30
30 to 20
20 to 10 Pore distribution

As can be seen from Table 1, the surfaces of the two supports of Example 1 and Comparison 1 are approximately the same, but in the case of Example 1 the pore volume is more than 0.5 cm ³ / g and the average pore radius is over 40 Å, whereas in the case of Example 1 Comparison 1 the pore volume is below 0.5 cm ³ / g and the average pore radius is below 40 Å.

290 cm ^{3 of} water and then 550 cm ^{3 of} ammonia water at a concentration of 28% were added to 271.4 g of ammonium paramolybdate with stirring in order to achieve complete dissolution of the salt. Separately, an aqueous solution of cobalt nitrate was prepared by dissolving 214.3 g of cobalt nitrate in 220 cm ^{3 of} water produced. Then "the cobalt nitrate solution was slowly added dropwise to the ammonium molybdate solution with stirring.

600 cm ^{3 of} the combined solution thus obtained were then used to impregnate the carrier of Example 1 (extrusion-molded products of 3 mm diameter) and the carrier of Comparison 1 (extrusion-molded products of 1.3 mm diameter in the same way). The impregnation of each of these carriers with 300 cm ³ of the above solution was ^ra 8 achieved through 3-hour immersion u * ^{ers in the} solution, followed by drying at 110 C for 5 hours and finally calcined 3 hours at 500 ⁰ C. The metal content of the catalysts obtained in this way was 8.9 to 9.1 Ge

weight percent molybdenum and 2.5 to 2.7 weight percent Cobalt.

The hydrogenative refining of heavy residual Iranian oil from distillation at atmospheric pressure was carried out by means of a fixed bed reaction column using the above Catalysts carried out.

The properties of the feed oil are shown in Table 2.

Table 2

Specific weight (i / V) 0.960

Viscosity (cSt at 50 ⁰ C) 328.7

Coke residue (weight percent) 9.29

Ash (weight percent) 0.033

Asphaltenes (percent by weight) ... 4.58

Sulfur (weight percent) 2.43

Pour point ( ⁰ C) +17.5

V (ppm) 126

Ni (ppm) 38

N (weight percent) 0.37

The catalyst was packed in the reaction column and kept at a temperature of 370 ° C and at Presulfurized at atmospheric pressure using hydrogen with 3 mole percent hydrogen sulfide.

Reaction conditions: temperature 380 ° C., pressure

150 atm, liquid hourly space velocity of the feed oil 0.8 v / v-hr.

and a ratio of hydrogen to feed oil of 1000 1 at normal temperature and pressure / 1.

The refined oil that left the reaction column was stripped off under reduced pressure to remove the hydrogen sulfide and other gases as well to distill off and remove the decomposable light oils. That way became the final product receive.

The changes in the sulfur content of the product up to 1000 hours after the start of the test are compiled in Table 3. For this purpose, Table 4 shows the properties of the product for one 500 hours after the start of the examination.

Table 3

attempt Total sulfur total
sulfur (Weight percent) 0.55 100 hours after 500 hours Ni after 1000 hours Feed oil Weight
percent) after 50 hours 0.63 0.59 (ppm) 0.72 example 1 2.43 0.50 0.97 1.24 Comparison 1 2.43 0.49 Koksrück
was standing Table 4 (Weight
percent) Asphaltenes V N viscosity (Weight
percent) (ppm) (Weight
percent) (cSt at
50 ° C)

Feed oil 2.43 328.7 9.29 4.58 126 38 0.37 example 1 0.59 120.6 5.32 2.60 38 13th 0.27 Comparison 1 0.97 188.1 6.81 3.40 59 17th 0.30

As the comparison with comparative sample 1 shows, the catalyst used according to the invention retains contributes to its activity over a significantly longer period of time.

Example 2

Calcium carbonate was slowly added at room temperature to a saturated aqueous aluminum sulfate solution with vigorous stirring to prepare a supernatant aqueous colloidal solution of basic aluminum sulfate containing 118.7 g of Al ₂ O ₃ per liter and 105.7 g of SO ₃ per liter (molar ratio of SO ₃ ZAl ₂ O ₃ = 1.13).

After the gas dissolved in this sol was removed by degassing under reduced pressure for 4 hours, water was added in an amount of 250 cm ³ per liter of the sol. Immediately thereafter, the liquid was dripped from above into a container filled with light oil to a height of 10 m and kept at a temperature of 80 ° C. In this way, spherical hydrogels 3 to 5 mm in diameter were formed. The hydrogels were transferred to a container filled with water and washed for 24 hours with a continuous stream of hot water in order to remove some of the sulfuric acid residues contained in the hydrogels. After the end of the washing with water, the S0 ₃ / Al ₂ 0 ₃ molar ratio in the hydrogel had dropped to 0.61.

Subsequently, a container in which the AIuminiumoxydhydrogele were filled, filled with highly dilute ammonia water at a concentration of 0.3% (pH 7.5), then heated to a temperature of 5O ⁰ C, was removed and then the ammonia water. This was repeated twice. After heating to a temperature of 55 ° C., the liquid was removed. After this process had been repeated ten times, the de! The pH value gradually increased to 8.5 and the remaining sulfuric acid groups were converted into ammonium sulfa. The hydrogels were then washed with water for a long time until no more sulfuric acid residues could be found.

The hydrogels thus obtained lasted 25 hours

dried in a sealed container at a constant temperature of 120 ⁰ C. Then the hydrogels were calcined for 3 hours at 55O C ^1, yielding the spherical Aluminiunioxydträger of 1.5 to 2.5 mm in diameter (Example 2) received. For comparison purposes, 1000 g of commercially available finely divided aluminum hydroxide, 800 g of water and 16 g of 60% strength nitric acid were mixed and the mixture was triturated for about 10 minutes. Subsequently, the mixture was extrusion-molded with a press to a desired shape, dried and then the molded material for 20 hours at 120 ⁰ C and then for 2 hours at 600 ⁰ C calcined to a exlrusionsverformten carrier of 1.2 to 1.5 mm diameter ( Comparison 2). The properties of the supports of Example 2 and Comparison 2 are summarized in Table 5.

Table 5 Example 2 volume Comparison 2 volume 323 (7.) 225 (7o) Surface (m ² / g) 0.935 7.5 1.325 13.5 Pore volume (cm ^a / g) 58 2.7 118 5.2 Average 4.3 7.8 Pore radius (A) Pore radius 7.5 Pore radius 10.1 (A) 14.4 (A) 14.3 300 to 100 33.1 300 to 190 10.6 Pore distribution 100 to 90 20.9 190 to 180 6.8 90 to 80 9.6 180 to 170 4.5 80 to 70 0 170 to 160 3.8 70 to 60 160 to 150 15.1 60 to 50 150 to 140 3.0 50 to 40 140 to 130 2.5 40 to 30 130 to 120 1.9 30 to 10 120 to 110 0.8 110 to 60 0 60 to 50 50 to 40 40 to 30 30 to 20 20 to 10

As can be seen from Table 5, the surface of the carrier of Example 2 is large and its pore radius averages 58 Å, whereas the average pore radius of the carrier of Comparison 2 is over 100 Å and its surface area is below 250 m ² / g.

Subsequently, as described in Example 1, using supports according to Example 2 (spherical bodies of 2 mm diameter) and test 2 (spherical bodies of 1.3 mm diameter the catalysts). The metal content of the catalysts made in this way was 9.9 to 10.1 percent by weight molybdenum and 2.8 to 3.1 percent by weight cobalt.

The hydrogenative refining of residual Arabian oil from distillation at atmospheric pressure was carried out in a fixed bed reaction column using the above catalysts.

The properties of the feed oil used are summarized in Table 6.

Specific weight (</ '/) 0.965

Viscosity (cSt at 50 ⁰ C) 234.0

Coke residue (weight percent) 9.54

Ash (percent by weight) 0.002

Asphaltenes (weight percent) .... 48.2

Sulfur (weight percent) 3.70

Pour point ( ⁰ C) +7.5

V (ppm) 31

Ni (ppm) 12

N (weight percent) 0.27

In conducting the refining, the Vorschwefelungsmethode and the reaction conditions applied in Example 1, wherein the reaction temperature was 37o C ^0.

The changes in the total sulfur content up to 1000 hours after the start of the investigation are compiled in table 7. The properties of the product at a time of 500 hours after the start are shown in Table 8.

Table 7 Total sulfur
Feed oil (Weight percent)
after 50 hours after 100 hours after 500 hours after 1000 hours attempt 3.70
3.70 0.68
1.31 0.80
1.45 0.87
1.53 0.93
1.60 Example 2
Comparison 2

15 16

Table 8

total
sulfur viscosity Koksrück
was standing Asphaltenes V Ni N (Weight
percent) (cSt at
50 ° Q (Weight
percent) (Weight
percent) (ppm) (ppm) (Weight
percent) Feed oil 3.70 234.0 9.54 4.82 31 12th 0.27 Example 2 0.87 92.35 5.75 2.32 10 6th 0.08 Comparison 2 1.53 134.3 6.83 2.95 15th 7th 0.11

It can be seen that the surveyor according to the invention can be obtained. The hydrogels thus obtained

The catalyst used in comparison with the catalyst was transferred to a tank filled with water.

sator of comparative sample 2 has an exceptional lead and 24 hours with a continuous

has great activity. Stream of hot water washed to such a thing

_R. . . , »Ο part of the sulfur contained in the hydrogels

uei play j _{acidic residues from Hydro} | remove _{yse m.} To

Calcium carbonate was slowly released at room temperature. The temperature to a saturated aqueous solution of aluminum was the molar ratio of SO ₃ ZAl ₂ O _{3 of} the hydrogel 0.65.
Miniumsulfat added with vigorous stirring, in order to obtain a Subsequently ammonia water of a Konüberstand aqueous-colloidal solution of basic concentration of 5% the container, which the aluminum-aluminum sulfate, which contained 108.5 g Al ₂ O ₃ per oxide-silicon dioxide hydrogels and in the liter and contained 86.8 g of SO ₃ per liter (molar ratio of ^{circulating hot water of 55 °} C., added. So of SO ₃ / A1 ₂ O ₃ = 1.02). One liter of this solution was kept at the pH in a period of 20 hours. 100 cm ^{3 of} a silica sol that increased the from 3.8 to 9.2. Then the 1.6 g SiO ₂ per liter contained, intimately mixed, washed after 30 hydrogels with water until none of these could be determined separately by degassing for 3 hours under further sulfuric acid residues under reduced pressure of the gases dissolved therein. Subsequently, the hydrogels were 50 stun exempt. in a closed, on a constant

This combined solution was then held at temperature of 120 ⁰ C dried tank

Light oil was dropped, which was heated at 9O ⁰ C with 35 and it calcinhrt 3 hours at 550 ⁰ C to lugel-

a pre-shaped aluminum oxide-silicon dioxide carrier 101 1.5 identical to that used in Example 2

direction was used to give spherical hydrogels up to 2.5 mm in diameter (Yergleichspn b: 3).

from 3 to 5 mm in diameter. The properties of the carriers of Example 3 and

The hydrogels formed were drawn off through a tube. Comparison 3 is summarized in Table 9,

and into another container 40 filled with water. As can be seen from Table 9, the carrier has

convicted. In the container, the hydrogels from Example 3 not only had a large surface, but

mixed with fresh hot water, which again also has a pore distribution, after which on the

was withdrawn; this process was repeated 8 times - widths of 90 to 80 and 80 to 70 A each more than

get. As a result, some of the 15% of the total pore volume on the hydrogels was omitted. On the other hand

bonded sulfuric acid residues by hydrolysis 4b, the surface of the support of comparison 3 is not

washed out and the molar ratio of SO ₃ / A1 ₂ O ₃ only small, but no width of 10 Å from the

of the hydrogel decreased to 0.53. After subtracting the pore distribution range from 40 to 100 A.

Water was drawn again in an amount - more than 15% of the total pore volume,

adds to cover the hydrogels, and the pH was 263.4 g of ammonium paramolybdate using

^{50 178.2 cm 3 of} water were added by a particularly slow, dropwise addition, followed by stirring

from 28% ammonia water to 9.5 to 9.7 cm ³ 28% ammonia water was added

placed, whereupon the mixture was heated ^{to 50 ° C. for 10 hours.} to complete the ammonium paramolybdate

To dissolve the sulfuric acids remaining in the hydrogel. Separated therefrom was an aqueous solution

Remnants were converted into ammonium sulfate of 234.2 g of cobalt nitrate and 117 g of nickel nitrate in

and separated from the hydrogel. This produced 55 207.5 cm ^{3 of} water. This solution from

Washed with water until no sulfur, cobalt and nickel nitrates were slowly taking

more acidic residues could be found. Stirring added dropwise to the ammonium molybdate solution.

The hydrogels were then sealed for 30 hours using 700 cm ^{3 of} the thus obtained one sealed solution combined at a constant temperature were those according to the above

temperature of 120 ⁰ C kept container dried and 60 method obtained carrier of Example 3 (2 mm

subsequently calcined for 3 hours at 550 ^° C. to impregnate the spheres) and comparison 3 (2 mm spheres), spherical alumina-silica carriers, each carrier in 350 cm ^{3 of} the solution for 3 hours

from 1.5 to 2.5 mm in diameter (Example 3). was immersed, then 5 hours at 110 ° C

For comparison purposes, a combined solution was dried and then ^{calcined for 3 hours at 500 °} C. from an aqueous solution of aluminum sulfate 65. The content of active metal in the thus obtained and a silicon dioxide sol, obtained as in the retained catalyst, was 9.7 to 10.2 percent by weight 3, as described there, added dropwise to light oil, percent molybdenum, 2.8 to 3.1 percent by weight Koum spherical hydrogels with a diameter of 3 to 5 mm and 1.4 to 1.5 percent by weight nickel.

Table 9 Example 3 volume Comparison 3 volume 310 (7a) 200 (Vo) Surface (m ² / g) 1.175 8.5 0.845 37.9 Pore volume (cm ³ / g) 75.8 3.4 85 8.3 Average 4.7 12.4 Pore radius (Ä) Pore radius 6.0 Pore radius 12.4 (A) 11.1 (A) 8.9 300 to 130 16.6 300 to 100 7.1 Pore distribution 130 to 120 17.4 100 to 90 4.7 120 to 110 12.8 90 to 80 4.2 110 to 100 8.1 80 to 70 4.1 100 to 90 6.8 70 to 60 0 90 to 80 4.6 60 to 50 80 to 70 0 50 to 40 70 to 60 40 to 30 60 to 50 30 to 20 50 to 40 20 to 10 40 to 30 30 to 10

The hydrogenative refining of an Arabic low pressure distillation residue oil was carried out in a fixed bed apparatus in which the above catalyst was packed. The properties of the feed oil are shown in Table 10.

Table 10

Specific gravity (d'j) 0.945

Viscosity (cSt at 50 "C) 108.9

Coke residue (weight percent) 7.67

Ash (percent by weight) 0.004

Asphaltenes (percent by weight) .... 2.4 Total sulfur (percent by weight) 2.81

Pour point ( ⁰ C) +7.5

V (ppm) 25

Ni (ppm) 5

N (weight percent) 0.14

35

The catalyst was not presulfurized. The reaction was carried out under the following conditions accomplished:

Temperature 360 ^° C., pressure 120 atm., Liquid space flow rate of the feed oil 1 vol / vol / hour and ratio of hydrogen to feed oil 9001 (at normal temperature and pressure / 1). The refined oil exiting the reaction column was steam stripped to remove the hydrogen sulfide and other gases as well as decomposable light oils. The end product was obtained in this way.

The change in total sulfur content up to 1000 hours after the start of the test is shown in Table 11 shown. For this purpose, the properties of the product are at a point in time 500 hours after the start of the Experiment compiled in Table 12.

Table 11

attempt Total sulfur (percent by weight)
Feed oil after SO hours after total
sulfur
(Weight
percent) 0.61
0.75 0.72
0.88 100 hours after 500 hours 0.81
0.95 Ni
(ppm) 1000 hours Example 3
Comparison 3
Table 12 2.81
2.81 viscosity
(cSt at
5O ⁰ C) Koksrück
was standing
(Weight
percent) 0.76
0.93 Asphaltenes
(Weight
percent) V
(ppm) N
(Weight
percent)

Feed oil 2.81 ¹ 08.9 7.67 2.48 Example 3 0.76 65.34 4.01 0.93 Comparison 3 0.93 78.91 4.95 1.18

25th

11th

5 0.14 3 0.09 4th η 11

/ 11

As a comparison with the catalyst according to comparative sample 3 shows, the catalyst used according to the invention has Catalyst great activity.

Example 4

A combined solution of an aqueous colloidal solution of aluminum sulfate and a silica sol obtained as in Example 3 was injected into a constant temperature atmosphere maintained at 90 ° C. by circulation of heated air, whereupon hydrogels of small particle diameter were injected received. The hydrogels obtained in this way were then treated as in Example 3 and then ^{dried for 15 hours in a closed container at a constant temperature at 120 °} C., a gel being obtained.

1 kg of this gel was mixed with 1 kg of water and 15 g of 60% nitric acid, whereupon the mixture Was triturated for 10 minutes and then extrusion-molded with a former. To

20 hours of drying the extrusion-molded product at 120 ⁰ C was calcined for 2 hours at 600 ⁰ C. The aluminum oxide-silicon dioxide carrier was obtained in this way (Example 4).

For comparison purposes, small particle diameter hydrogels were prepared as above in Example 4, treated as in Experiment 3 and then in a sealed container for 25 hours Constant temperature container at

ίο 120 ° C dried, whereby a gel was obtained.

1 kg of this finely divided gel was mixed with 0.7 kg of water and 20 g of 60% strength nitric acid and, after the mixture had been triturated for 10 minutes, it was extrusion-molded with a former. After the extrusion-molded product had been dried for 20 hours at 120 ^° C., it was ^{calcined for 2 hours at 600 °} C. in order to obtain the aluminum oxide-silicon dioxide carrier (comparative sample 4).

The properties of the example 4 and in

Ao equal to 4 supports obtained are listed in Table 13.

Table 13 Example 4 volume Comparison 4 volume 266 (7 ") 238 CA.) Surface (m * / g) 1,250 11.2 1.125 26.7 Pore volume (cm ^s / g) 94 3.2 95 35.6 Average 4.8 3.6 Pore radius (A) Pore radius 15.6 Pore radius 4.0 (A) 24.4 (A) 4.0 300 to 130 9.6 300 to 200 4.4 Pore distribution 130 to 120 7.6 200 to 100 4.4 120 to 110 6.4 100 to 90 4.9 110 to 100 5.6 90 to 80 8.8 100 to 90 5.2 80 to 70 3.6 * 90 to 80 4.8 70 to 60 0 80 to 70 1.6 60 to 50 70 to 60 0 50 to 40 60 to 50 40 to 30 50 to 40 30 to 20 40 to 30 20 to 10 30 to 20 20 to 10

As can be seen from Table 13, the pore volumes and the average pore radius are Carrier according to Example 4 and Comparison 4 approximately the same, but for the carrier according to Example 4 the amount is the pores, which are distributed in the Angstrom range from 100 to 90, more than 15% of the total pore volume; while in the case of the carrier according to Comparison 4 to no width of 10 A within the Angstrom range from 40 to 100 more than 15% of the total pore volume is accounted for. There is also the Surface of the latter carrier is smaller.

As described in Example 3, the carriers from Example 4 (extrusion molded product with 1.3 mm diameter) and from comparison 4 (likewise extrusion-formed product of 1.3 mm diameter) catalysts. The metal content of the catalysts thus obtained was 10.3 to 10.7 percent by weight molybdenum, 3.0 to 3.3 percent by weight cobalt and 1.6 to 1.7 percent by weight Nickel.

Hydrogen refining Iranian distillation residue oil (distilled under reduced pressure) was made using the above catalysts carried out in a fixed bed reaction column.

The properties of the feed oil used are summarized in Table 14.

^TabeUe14 NiGewichtsp ^ ozenö ':: ^^>

Specific gravity (d'f) 0.944 Reaction was performed under the same condi-

Viscosity (cSt at 50; C) 133.9 J? L * $? £ Example 3 given, carried out.

Coke residue (weight percent) 6.63 5 W ™ total sulfur content up to

Ash (percent by weight). 0.021 The anaerobic tests are

Asphaltenes (percent by weight) ... M? 1000 Stua (ta ^nacn ; f _{in Tabdle 16 are the property}

Total sulfur (percent by weight) 2.36 ^ _{n of the} product at a time from

"λ '::::: eiL .ο ₅ S hours after the start of the examination together

or 65 set.

Table 15. . .

Test total sulfur (percent by weight), feed oil after 50 hours after 100 hours after 500 hours after 1000 hours

Example 4 2.36 0.45 0.51 0.62 0.68

Comparison 4 2.36 0.52 0.64 0.78 0.83

Table 16 —— "

Total viscosity coke back asphaltenes V Ni N

sulfur stood

(Weight- (cStat (weight- (weight- (ppm) (ppm) percent) 50 "C) percent) percent)

Feed oil 2.36 133.9 6.63 1.37 65 16 0.25

Example 4 0.62 73.06 3.50 0.25 15 5 0.16

Comparison 4 0.78 81.54 4.02 0.34 20 5 0.19

It can be seen that the activity of the catalyst used according to the invention in comparison with that of the catalyst of Comparative Sample 4, is large.

Claims (1)

21 704 claims: 1. A process for the catalytic hydrogenation of petroleum-based hydrocarbons containing distillation residues, the hydrocarbons being applied in the presence of a metal catalyst active in the hydrogenation, applied to a support consisting of aluminum oxide or aluminum oxide-silicon dioxide gels, these gels having a surface area of not less than 200m ² / g, determined by the BET method, have a pore volume of not less than 0.5 cm ³ / g and an average pore radius of not greater than 100 Å, are brought into contact with hydrogen, characterized in that