DE2200269C3 - Process for the preparation of a hydrodesulfurization catalyst and its application - Google Patents

Description

? ίΥ ° Τ ™ * " ^{WdSe manufactured} 8 aluminum oxide ^hydrates.

SSSS SiSS

calls for very special or very special 5 turns. Da ^ procedure isf
Way produced aluminum oxide hydrates, what the two-stage calcination after the
Aawendungsbrejte_ des Prozessbetulichem- thermally decomposable & Αϊ ^ ίϊΑ & 2 sends F ^e X ¹⁵ J ^d ^ V ^erf J « ⁿ Jfrhalhus Maß, g active metal components to carry out, particularly in the usual treatments of the carrier material with regard to the .nder practices required already Contribution de? Components, amounts of such hydrodesulfurization catalysts, such as, for example, the hydrothermal treatment according to which it is disadvantageous. discussed US-PS 33 40 180 are not required.

The one according to the above-mentioned and the one after anyway, if the according to the invention is adhered to

prescribed measures established by the procedure described last, a hydrodefulfur-

Hydrodesulfunerungskatalysatoren we.sen x ₅ approximation catalyst of improved activity received, such as

useful desulphurisation performance, but also through the later examples with comparative

There is naturally a strong interest in attempting the technology is evidenced

in terms of production and / or effective- As already mentioned, the inventive

ieii further improved catalysts. _gem ä _ß hydrodesulfurization catalyst prepared

The object of the invention is accordingly in particular for the hydrogenative desulfurization of

reasons, a process of the type mentioned at the beginning of residual oils. Under residual oils are those at

for the production of a hydrodesulfurization catalyzer- separation of lighter fractions from crude oils

tors to make the m easier to understand how residual materials persist

lead and thereby a catalyst they often improved as asphalt oils, liquid asphalt,

Performance, also and especially with the as black oils, so named after their usually deep

Hydrodesulfurization of heavy residual oils, dark to black color, petroleum residues,

results. topped crude oil residues or bunker fuel oils be

Surprisingly, it has been found that these are drawn. Usually, this return task has an initial boiling point of over 343 ° C in a process for the oils mentioned at the beginning.
nen type by a special two-stage calcination 3o Features and preferred treatment of the catalyst after introducing embodiments of the method are explained in more detail, training of the thermally decomposable compounds of the poorly fusible support materials from catalytically active metal components is dissolved. Inorganic oxides come in particular from aluminum. The object of the invention is accordingly a minium oxide, silicon dioxide, zirconium oxide, thorium process for the production of a hydrodesulfurization oxide, boron oxide and combinations thereof, additional catalyst made of at least one catalytically active, for example aluminum oxide-silicon dioxide or metal component groups VIa and aluminum oxide-zirconium oxide. The an-VIII of the Periodic Table of the Elements on an organic oxide support material contributes to a hard-to-melt inorganic support material, measures the overall activity, selectivity and the catalytically active metal components contribute to the stability of the catalyst. Aluminum oxide is preferred to the carrier material in the form of thermally decomposable carrier material.

Compounds are incorporated and a two- The carrier material is preferably used in the

a thorough calcination treatment is carried out, the size and shape of the final cat-

when used in the first stage in a water vapor holding lysatorteilchen. A powder can be used for this

gene and in the second stage in a substantially 45 of the carrier material mixed with a binder

dry atmosphere is worked, which in turn leads to pellets of uniform size and shape

is characterized by the fact that you are first pressed to the. Alternatively, a powdery

Carrier material the thermally decomposable compound mixture of all catalyst components

fertilize the catalytically active metal components of an extrudable mass processed and through

incorporated in a known manner and thereby extruded 50 openings and then to the desired

obtained mixture, optionally cut or broken according to the previous length. Suitable

drying, then first at least 0.5 hours Binder or lubricant are starch, polyvinyl alcohol,

at a temperature in the range of 260 to 371 ° C, methyl cellulose and graphite.

in an oxidizing, more than 20 percent by volume A particularly effective hydrodesulfurization

A steam-containing tmosphäre and thereafter 55 catalyst is obtained if the support material has a

about 1 to 4 hours at a temperature in the specific surface area of about 140 to 270 m ² / g

ranging from about 427 to 649 ° C in an essentially mean pore volume of about 0.3 to 0.7 m ³ / g

lent dry oxidizing atmosphere calcined. and an average pore diameter of

Preferably the first calcination treatment will be about 60 to 120 Angstrom units. the

development in an approximately 50 to 95 volume percent water- 60 physical properties of the finished catalyst

vapor-containing atmosphere carried out. tors are largely determined by the physical

The hydrodesulfu properties of the carrier material produced according to the invention are determined. The

ration catalyst is particularly suitable for the preferred carrier material with this physical

lyric hydrative desulfurization of reverse properties is alumina, especially in

standing oils. 65 shape of spherical particles.

The manufacturing method according to the invention is a method for manufacturing spherical aluminum

not known as the process of the previously discussed ternium oxide particles; usually becomes

th US-PS 33 40 180 on very special or in completely thereby an aluminum oxide sol and the sol

22 OO

dispersed in droplet form in hot oil, causing gel formation under the influence of a neutralizing agent ammonia is present. The spherical particles are then aged, dried and calcined.

When incorporating the catalytically active metal components by impregnation, this can be done in the usual way by impregnating the carrier material take place with an aqueous solution emer connection of the blown metal component. The impregnated carrier material is expediently dried afterwards.

As catalytically active metal components kornmen metals of Groups VIa and VIII of the Periodic Table, ie chromium, molybdenum i _S and / or tungsten in combination with one or more metals of Group VIII ie iron, nickel, cobalt, platinum, palladium, ruthenium, Rhodium , osmium and iridium. Suitable thermally replaceable compounds of metals from group VIa are e.g. B. ammonium molybdate, ammonium paramolybdate, molybdic acid, ammonium chromate, ammonium peroxychromate, chromium acetate, chromium (II) chloride, chromium nitrate, ammonium metatungstate and tungstic acid. When incorporating * 5 through the impregnation, a common solution of a compound of a metal from group VI a and a compound of a metal from group VIII is expediently used. Suitable soluble and thermally decomposable compounds of Group VIII metals are e.g. B. Nickel nitrate, nickel sulfate, nickel chloride, nickel bromide, nickel fluoride, nickel iodide, nickel acetate, nickel formate, cobalt (II) nitrate, cobalt (II) sulfate, cobalt (II) fluoride, iron (III) fluoride, iron (III) bromide, iron (III) nitrate, iron (III) sulfate, ksenic (ni) formate, iron (III) acetate, platinum chloride, chloroplatinic acid, chloropalladic acid and palladium chloride. Of the Group VIa metals, molybdenum is preferred. The Via Group metal is conveniently used in an amount equal to about 5 to 20 percent by weight of the final catalyst composition. The Group VIII metal, preferably cobalt, should constitute from about 0.1 to 10 weight percent of the final catalyst composition.

Conventional impregnation methods can be used be used, in which the carrier material is soaked, dipped, suspended or on is brought into contact with the impregnating solution in other ways under conditions in which the catalytic components are adsorbed thereon. The impregnation is preferably carried out during a relatively short period of time with a small volume of the impregnation solution with induction an even distribution of the catalytic Components on the carrier material. A drum dryer heated by steam jacket is preferred used. The carrier material is in the impregnation solution in the dryer circulated by the rotary motion of the dryer. By introducing water vapor into the dryer jacket and passing a drying gas through the dryer, suitably air or nitrogen the solution evaporated.

The support material and the thermal decomposable Compounds of the catalytically active metal components containing composition is then, if necessary after previous drying

dieendc the alzkiTerTn ^ oxo ^ in a more than 20 Volumprowährend a Zeitf ^ siun at a Tempebis 371 ⁰ C. It is a so ^ J ^ SS> S! ngdes produced catalyst begroijere veru β _{air portion} is _verminder t

watch out, the _{rigidness predominates}

'^ ^^ fSt Therefore, for water vapor ^ sten ^ _{stu {e} ^ ^ ^

fjwa 5ObS 95 percent by volume water vapor,. j calcination atmosphere used. ™ ^sc "** ^a _{the di} f _{uer calcination} in some expediently exceed ui. In

the ^ J ^^ ~ catalyst in an im the second '^ ™ »* ^J ™ _di atmosphere, like

Air or another « _42?

turn off the gas

649 C about ι dis <t aiui.u _e

at '«« y ™ ^ _essential ii _c hen dry «, like him

The ™ ^ Κ ^ m _e marking

^{'N de} ° ™ ^ ™ _atmo cp _h ary calcination in

the oxyo ^^ _f ^A ^ J, ⁿ _det , means that

the second stage we used

this atmosphere no longer than voiump.o water vapor is ^old ·

For hydrodesulence with £ em:

lenwasserstoffol and hydrogen at the e

temperature ™ * ^^ ££? ² ^ _n Z pressure of heats and with the catalysJ ^ J ^ " ¹ ^^ about 35 to 341 atm ^ g

i «^, ^ ^0. ^^ SuTdei S ^ water-

^^ ΐ ^ ⁵⁰ ^ * ^ ¹ ^ ^'3 _"ur ^ cleaning mt-rich gaseous phase .. Ve for" jg m

fresh coal waterBtomeschidcung ^^ leads will. From the remaining "

gungen fl ^uussl .gf, ^Αη1ει1 ^ ^Γ ^ " ζ J ^ ₀ H 3 the or stripping column SchwefeJw« * «™! and the

light hydrocarbons methane

pan away. The under ^K J ^^^ i £ ^ t mige phase from ^ m high pressure separator can be used

Removal of the A formed in the ^^ nitrogen compounds

towards the high pressure separator W g

and the water with then dissolved ammonia removed from the separator.

example 1

A spherical _η ^ 7 "^ ™™ ί £ ^ £ rial of about 1.6 mm diameter was determined by the above-öltropfmetiiode mfd express purpose, a Alumimumch was oridhydrosol, which had been obtained by digesting aluminum m dilute hydrochloric acid herges express, with Hexamethylentetranim The resulting spheres were aged in the oil bath overnight and then washed, dried and calcined in a two-zone oven for 1 mouth at 454 ° C. and 2 hours at 538 C. The spherical support material had a specific surface area of 220 mVg and a mean pore volume of 0.65 mVg.

The aluminum oxide carrier was_ then with 2 percent by weight cobalt and 12 percent by weight

7 8

cent molybdenum using an impregnation agent was found by analysis of the liquid product

Solution of ammonium molybdate and cobalt nitrate - a sulfur content of 1.35 percent by weight.

Hexahydrate, dissolved in 12 percent by weight aqueous. For further comparison, a spherical one was used

like ammonium hydroxide, impregnated. For this purpose, the catalyst was again produced in the same way.

which the alumina spheres in the impregnation 5, with the exception that the catalyst in the

solution in a drum heated by a steam jacket - first calcination zone of the oxidation furnace in

Dryer first 10 minutes at room temperature, stirring with 20 percent by volume of water vapor

circulated. Then steam was heated in the dryer-containing air stream. When testing

sheath introduced, making the solution to the action of this catalyst, again in the same

The analysis of the liquid product revealed dryness in contact with the carrier material

evaporated for about 2.5 hours. The impregnation has a sulfur content of 1.2 percent by weight,

th balls showed a loss on ignition at 500 ° C. Thus, the method of the invention gives one

about 30 percent by weight. better desulfurization catalyst, with a

The dried spheres were then achieved by means of the greater the improvement, the greater the improvement

a belt conveyor through a two-zone oxide 15 water vapor content in the first calcination stage

tiorssofen led. The bullets were in the first is.

Zone in contact with an approximately 50 volume percent ice ο ie 1 2
Air stream containing water vapor and in the

second zone in contact with a 10 volume To make an extruded catalyst

percent air stream containing water vapor is heated. 20 45 kg of linen powdered aluminum oxide

The spheres were carefully dry mixed through the first zone in a monohydrate weighing 9.5 kg

Amount / time that there is an average residence time in the finely powdered molybdic acid anhydride and 2 kg

first zone of 1 hour revealed, and through the finely powdered cobalt carbonate. The solid

second zone in an amount / time that a mixture was possible with 42.9 kg of a 5.0 weight percent

residence time of 2 hours resulted, promoted. The first 25 term nitric acid mixed for half an hour

The zone was kept at a temperature of 343 ° C to form an extrudable, plastic dough. the

th, the second zone at a temperature of 593 ° C. Mixture had a loss on ignition at 500 ° C of

The spherical catalyst obtained had a 53.5 weight percent. The mongrel was through

specific surface area of 177 m ² / g and a mean openings of 1.6 mm pressed into pieces of

Pore volume of 0.43 cm ³ / g. 30 broken 3.2 to 6.4 mm in length and at about 121 ° C

The catalyst produced in this way was dried for 2 hours, the volatile evaporation for the desulphurization of a residual raw constituents (loss on ignition at (500 ° C.) to about 30 oils) being tested. The residual crude oil contained 3.73 percent by weight sulfur and 8.84 weight percent of all official particles were then in the Zweizonenheptanunlösliche asphaltenes and had a specific oxydationsofen 35 in the same manner as in Beisches weight of 0,980 (15.6 ° C / 15.6 ⁰ C). Game 1 treated, ie They were placed in the first zone 100 cm ^{3 of} the catalyst were placed in one another in the oxidation furnace, again in contact with separate fixed beds of 25 cm ³ each oxidized extruded partial lyser beds in a single pass with a 40 surface had a specific surface area of 267 m ² / g hourly Space flow velocity and a mean pore volume of 0.5 cm ^s / g. At a liquid level of 1.0 and mixed with back testing, this extruded catalyst is passed into the guided hydrogen. In the manner described for hydrogen, the analysis of the liquid was: u the vertically arranged tubular product 1.10 weight percent sulfur, versus reactor in an amount of 891 m ³ (15 ° C, 1 atm) 45 3.73 weight percent sulfur in the feed, per m ^{3 of} the liquid hydrocarbon charge in the production of the extruded catalyst recycled to (15 ° C). The feed was previously heated in the same way except that the part was heated and entered the catalyst bed at 368 ° C in the first oxide calcination zone at a hydrogen pressure of 137 atm. The ionic furnace in contact with only a 20 volume maximum catalyst temperature was 397 ° C. The air stream containing 50 percent water vapor heated reactor effluent was passed into a high pressure separator, the sulfur content of the liquid product increased. Excess hydrogen was stripped off overhead to 1.26 percent by weight under the same, washed with water and added to the reac test conditions,
gate returned. The liquid part was from the

Separator passed into a stripping column. From the 55 comparative tests on the prior art

Stripping column, the liquid product was won- ,,,. ,,. . _o _, _,

nen. After 36 hours of operation, the liquid product had As a comparative catalyst according to the prior

product has a sulfur content of 0.98 percent by weight, the technique was a according to Example I of the introduction

compared to 3 73 percent by weight sulfur in the aforementioned US Pat. No. 33 40 180 prepared catalyst

Sending, as well as a specific weight of 0.9261 60 used This catalyst contained in accordance with

(15 6 ° C / 15 6 ° E mood with the information in Example I of the US

For comparison, a spherical catalyst was 0.5 weight percent nickel, 10 weight percent

tor made in the same way, with the cobalt and 8.0 weight percent molybdenum. Dk spe-

assumed that the catalyst in the first calcination-specific surface, measured according to the BET method

The oxidation zone of the oxidation furnace in contact with the 65 method by Söckstoffadsorpöon, was 165 mVg,

a flow of essentially dry air and the mean pore volume is 0.45 cmj / g.

was heated. When testing this catalyst in As a catalyst produced according to the invention

in the same manner as that described above, the was prepared according to the above Example 1

ίο

posed catalyst used. Its properties are listed in Example 1 above.

The two catalysts were under exactly matching test conditions after Test method described in Example 1 above, under the conditions and conditions specified there using the residual crude oil specified there as feedstock, on their desulphurisation performance checked. The results are shown in the table below.

catalyst Hourly space
flow rate
the liquid Operating time
hours Sulfur content
of the product
Weight percent comparison
comparison 1.0
1.0 11 to 20
21 to 28 1.20
1.38 invention
invention 1.0
1.0 11 to 20
21 to 28 0.95
1.03 invention
invention 0.75
0.75 11 to 20
21 to 28 0.74
0.82

From the above results, it is readily apparent that the prepared according to the present invention Catalyst is superior to the comparative catalyst according to the prior art. If they match hourly space velocity of the liquid of 1.0 and otherwise completely identical The test conditions are the desulphurization activity of that produced according to the invention Catalyst significantly higher. The increase in the residual sulfur content in the end product also contributes increasing operating time is significantly less for the catalyst prepared according to the invention than for the comparative catalyst according to the prior art, which improves the stability of the invention shows produced catalyst.

»5 The additionally attached results if adhered to an hourly space velocity of the liquid of 0.75, with otherwise changed Operating conditions show that as the throughput is decreased, i.e. H. the hourly Space flow velocity of the liquid, a further significant reduction in the residual sulfur content is achieved in the end product with approximately the same catalyst stability.

Claims (1)

22 OO 269 was burning oil of low sulfur content for η. ... »eoenwartiaen and" the expected future Patent claims: S is completely inadequate, has been a long-term on- material in the form of thermally decomposable compound firing, which is often also referred to as C einveSt Wen and a two-stage or this ™ * ™| ^ calcination treatment is carried out, never causes a decomposition in the first stage in one wasserdampfhal- cleavage of the sulfur-containing compounds to term and in the second stage in an essential formation ₁₅ ^ * g n.Schwefelwasserstoff undJKc ™™ * <- lichentrockenenAtmosphäregearbeitetwird.dastoffen, consequently, ^ r auxins Entferdurch in that voltage supply of stickstoffhaltigen.Verbindungen and a näcnst the carrier material, the thermally decomposable more or less B ™ * ^. *** "* ^ *" cash compounds of the catalytically active Me hydrocarbon feed Mate as, for example, of the ζ RucktaUkomponenten in manner known per se once * o Standbrennöls.D ^ hydrodesulfunerungw ^ dge ^ hnverlebt and the resulting mixture, possibly at a hydrogen pressure of ewι, 8 to if necessary after the previous one Drying, then carried out at 341 atm. Normally, the Kohzuerst is at least 0.5 hours at a temperature-lenwasserstofföl together nut What _s erstolIm a temperature in the range of 260 to 371 ° C in an amount of about 178-891 m * is hydrogen gemesoxydierenden, more than 20 percent by volume of a ₅ sen in 15 ° C and 1 atm, per m »of liquid carbon-water vapor containing atmosphere and hydrogen charge, measured at 15 ° C (after about 1 to 4 hours at a temperature called VA for the sake of simplicity), in the range from about 427 to 649 ° C in one or more with the hydrodesulfurization essential dry oxidizing atmosphere catalyst charged reactors. The recalcined 30 actuator temperature can be about 93 to 510 C. 2. Use of the hydrodesulfurization catalyst produced according to claim 1, a preferred range is about 316 to 510 ° C. of the charge, ge-residual oils measure as a liquid at 15 ° C, the per hour and 35 per part by volume of catalyst are enforced, can range from about 0.2-20. at Under such conditions, the catalyst should have a high desulphurisation performance. The invention relates to a process for the preparation of conventional hydrodesulfurization catalysts Development of a hydrodesulfurization catalyst from min-40 usually comprise a Group VIa metal at least one catalytically active metal component and one metal from group VIII of the periodic table from groups VI a and VIII of the periodic table of the elements on a refractory that is difficult to melt Elements on a hard-to-melt solid carrier material made of one or more inorganic materials Support material, the catalytically organic oxides, mostly aluminum oxide or active metal components of the support material in 45 a composition of aluminum oxide and Si form thermally decomposable compounds including silicon oxide. Usually they are catalytic and a two-stage calcination-active metal component from groups VI a treatment is carried out in the first and VIII of the periodic table by impregnation Stage in a water vapor-containing and in the two of the carrier material with an aqueous solution of one th stage in a substantially dry atmosphere 50 compound of the respective metal component in the sphere is being worked on. Incorporated carrier material. The impregnated carrier The hydrodesulfurization of hydrocarbon material is then heated to produce the compounds of the Oiling is known to be a thermal decomposition for the petroleum processing metal components and the This important and widespread procedure deploys metal components on the carrier material. Strike a desulphurisation of the 55 as far as possible. Hydrocarbon feedstocks are for reasons. It is also a process of the initially specified of environmental protection and the avoidance of a waste species has been described (US-PS 33 40 180), in the case of harmful amounts of sulfur, there would be an ir great importance and is also dealt with in hydrate 6 ₀ reciprocating in two stages and calcined view being necessary in the first stage a hydrothermal Bchandgebung to the increasingly severe legislative expectant. On the other hand, there is a large and steadily increasing heating in the presence of water when there is a need for hydrocarbon oils for the energy supply of the dried aluminum oxide hydrate, so that inevitably evaporation of the water results under the increasing degree of its own pressure, even to heavy carbohydrates sufficient temperature, that is, in hydrogen oils such as residual oils, which normally have a very high sulfur content carried out in an atmosphere containing water vapor, and in the second stage the hydrothermal treatment has to be taken. Since the supply of re-delted aluminum oxide hydrate in an essentially