DE2212121C3 - Process for the production of fuel or heating oils with a sulfur content of less than 1.0 percent by weight - Google Patents

Description

3. The method according to claim 1 or 2, characterized in that in the second stage a catalyst, the 4 to 30 weight percent of a molybdenum or tungsten component and 1 to

10 percent by weight of the nickel or cobalt component on a porous alumina-silica support is used.

4. The method according to claim 3, characterized in that a catalyst in the second stage is used with an amorphous carrier made of aluminum oxide and silicon dioxide.

5. The method according to claim 3, characterized in that that in the second stage a catalyst with a crystalline aluminosilicate containing Carrier is used.

6. The method according to any one of claims 1 to 5, characterized in that in the first stage a maximum catalyst bed temperature in the range from 316 to 482 ° C. is maintained.

7. The method according to any one of claims 1 to 6, characterized in that in the second stage a maximum catalyst bed temperature in the range from 288 to 454 ° C is maintained, which is around is about 28 ° C lower than the maximum catalyst bed temperature in the first stage.

The invention relates to a method of manufacture of fuel or heating oils with a sulfur content of less than 1.0 percent by weight from the highest », Feed materials with a sulfur SaSt of more than 2.5 percent by weight through two-stage catalytic, hydrogenating desulphurisation, with a partial desulfurization in the first stage Presence of a metal component of Group VIa of the periodic table on an alumimumoxydhalimen Carrier-containing catalyst carried out and in the second stage at least a part of the feedstock partially desulphurized in the first stage with hydrogen in the presence of a Group VIII metal component in combination with a metal component of group VIa of the periodic table on a silicon dioxide-containing Supported catalyst to the desired Final sulfur content is desulphurized by hydrogenation.

Such a method is known from U.S. Patent 3,591,489. With this well-known \ experienced is in the first stage with a smoldering-resistant catalyst, in particular made of nickel sulfide or cobalt sulfide in combination with tungsten sulfide or molybdenum sulfide on an aluminum oxide-silicon dioxide carrier, in the absence of hydrogen and in the second stage with a similar one The catalyst worked in the presence of hydrogen. A rapid one occurs in the first stage Deactivation of the catalyst and accordingly the catalyst of the first stage must very often again be regenerated. The regeneration takes place with hydrogen or a mixture of hydrogen and hydrogen at intervals of 1 hour to 1 week, preferably every 6 to 24 hours, since after that Information the activity of the catalyst of the first stage drops to about half in 48 hours Avoid constant business interruptions are therefore in the known method for the first Stage several desulphurisation reactors connected in parallel are used, which alternately on feed material desulphurisation or regeneration can be switched. The frequent regeneration, the arrangement several desulphurisation reactors connected in parallel and the resulting increased Quay analyzer quantities require a considerable process engineering and economic up-

uie U.S. Patent 3,055,823 describes an in Hydrocracking process carried out in three stages. in the first stage by reaction with hydrogen Presence of a sulfur-resistant hydrogenation catalyst, cobalt oxide. Cobalt sulfide. Nickel oxide. Nickel sulfide. Molybdenum oxide. Molybdenum sulfide, tungsten oxide and / or tungsten sulfide, if appropriate on a carrier and optionally together with stabilizers and promoters, contains a removal caused by nitrogen compounds. The oxides and are used as stabilizers and promoters Carbonates from K. Ag. Be, Mg.Ca.Sr.Ba.Ce.Bi.Cr.Th. Called Si, Al and Zr. Along with many other compounds, bismuth is also mentioned, however these compounds are not an essential component of the catalyst and they do are only used as additional promoters, if at all or stabilizers are used. The same applies to the optionally usable carrier for which practically any carrier can be used and aluminum oxide is not mandatory

represents required carrier component. The feedstock freed from nitrogen compounds is then in the second stage through a fixed bed one Sfliciumdioxyd-containing cracking catalyst passed at temperatures at which no essential Cracking occurs. Finally, in the third stage, there is hydrocracking by reaction with hydrogen in the presence of a hydrocracking catalyst, which is a metal component selected from the group VI and / or group VIII of the periodic table. Copper, copper oxide, copper sulfide, cadmium, cadmium oxide or contains cadmium sulfide on an active acidic cracking carrier. For processing according to Distillate fractions in the range from 90 to 454.degree. C. come in particular from this known process and preferably I boil 63 to 343 ° C, i.e. in animal Usually so-called gas oil fractions with a relatively low sulfur content of, for example around 1 percent by weight. Any of the well known three stage hydrocracking process Similar operation is not provided according to the invention.

The invention is based on the object of creating a method of the type specified at the outset, which does not address the shortcomings of the frequent catalyst regeneration process discussed above has a thorough desulphurisation also and in particular of high-boiling feed materials With a high content of sulfur, asphaltenes and metal veneers, which are customary deep dark to black appearance often referred to as black oils, allowed to do so too leads to a substantial improvement in catalyst stability and life and is still simple and can be carried out economically. A conventional one should continue to be used in the second process stage highly active desulfurization catalyst with a metal component of group VIII in combination with a metal component of group VIa of the periodic table while ensuring good catalyst stability can be used.

To solve this problem, the invention provides a process for the production of Brennoder Heating oil with a sulfur content of less than 1.0 percent by weight from higher-boiling feedstocks with a sulfur content of more than 2.5 percent by weight through two-stage, catalytic, hydrogenating Desulfurization, with a partial desulfurization in the presence of a one in the first stage Metal component of group VIa of the periodic table on a carrier containing aluminum oxide Catalyst carried out and in the second stage at least part of the in the first stage partially desulfurized feedstock with hydrogen in Gegenwj · 'rines a metal component of the group VIII in combination with a metal component of Group VIa of the Periodic Table on a silicon dioxide-containing Support-containing catalyst is desulfurized by hydrogenation to the desired final sulfur content is, which according to the invention is characterized in that the feedstock in the first stage with hydrogen in the presence of one in combination with the metal component of the group VIa of the periodic table containing a bismuth component to form a hydrocarbon stream with a sulfur content of 1.0 to 2.0 percent by weight, of which at least a part in the second stage to the hydrocarbon

product with a sulfur content of less than 1.0 percent by weight is converted.

A bismuth in combination with molybdenum or tungsten is preferably used in the first stage Support catalyst, as will be explained below, and in the second stage a nickel or Cobalt in connection with molybdenum or tungsten-containing supported catalyst of conventional type used. The catalyst for the second stage preferably contains an amorphous support made of alumina and silica or a carrier containing a crystalline aluminosilicate. Continue to be preferably in the first stage a maximum catalyst bed temperature in the range from 316 to 482 ° C and a maximum catalyst bed temperature in the range from 288 to 454 ° C. is maintained in the second stage.

Surprisingly, it was found that the prescribed according to the invention for the first stage Catalyst comprising a bismuth component in combination with the Group VIa metal component of the periodic table, e.g. B. molybdenum, contains high in the desulfurization of hydrocarbon oils Sulfur content, especially black oils, on one Sulfur content in the range from 1.0 to 2.0 percent by weight for dnc very little decrease in activity and thus has a long service life. Accordingly, this catalyst is used in the first stage of the process rings set to partially desulfurize the high-sulfur feedstock. Preferably will in the first stage partial desulphurization down to a sulfur content of 1.30 to 1.70 percent by weight. e.g. 1.5 percent by weight. Compared to conventional desulfurization catalysts slightly lower initial activity of this catalyst is more than offset by the respect the catalyst stability achieved advantages. In addition, it has been shown that with the high sulfur contents of such feedstocks, the black oils, the maximum characteristic of the catalyst activity Catalyst operating temperature of a conventional nickel-molybdenum catalyst increases very quickly anyway the initial maximum catalyst bed temperature of the bismuth prescribed according to the invention Catalyst increases.

Furthermore, it has been shown that the stability and service life of the for the second stage of the process prescribed catalyst comprising a Group VIII metal component in combination with a Contains metal component of Group VIa of the Periodic Table, through which in the first stage takes place Partial desulphurisation down to a sulfur content in the range from 1.0 to 2.0 percent by weight is very important is improved. For example, there was virtually no deactivation of a conventional nickel-molybdenum catalyst with a feed sulfur content of 1.5 weight percent and desulfurization was observed to have a final sulfur content of 1.0 weight percent in the product. Accordingly such a conventional second stage catalyst can be used to achieve a final sulfur content less than 1.0 percent by weight can be used while ensuring good catalyst stability.

In contrast, conventional catalysts of this type are subject to their use for desulfurization Sulfur-rich hydrocarbon oils, such as black oils, without the partial desulfurization prescribed according to the invention on the bismuth-containing catalyst

! represents necessary carrier component. The feedstock freed from Idcfotoffverbindungen is ΣΖ the second stage by a fixed bed of a containing cracking catalyst

, in which no significant 5 rSg occurs. Finally takes place in the sSbÄ Hydrocracking through implementation S in the presence of a hydrocracking catalyst

e metal component of the group vT S / or group VIII of the periodic table,, o Copper KupferoSd Copper sulfide, Cadmium "Cad-Sd or cadmium sulfide on an active & S containing. For processing according to Processes come in particular in the range from 90 to 454 ° C

and boiling from 163 to 343 ° C, so in the so-called gas oil fractions with a

, 5 J 4

product with a sulfur content of less than 1.0 percent by weight is implemented. bismuth

Preferably ui of the first stage becomes bismuth in connection with molybdenum or Wolfnwieiithal tender supported catalyst, as described below is explained, and in the pveiten »em nickel or

Cobalt in connection with molybdenum or tungsten Containing supported catalyst comes from Art

used. The catalyst for the two «>?« * "" * £ preferably an amorphous support made of aluminum

oxide and silicon dioxide or euien J ^ * ra »

Contains crystalline aluminosilicate.

preferably in the first, level

Analyzer bed temperature in the »« «« * X ™ ^

uod in the riding level emema ^ nale yt

bed temperature in the range of 288 to 4M L an _e e

keep

Sl Irwine the known three stages, "hydro" catalyst SkverFahren thnHche Arbci swe, se ernndur is _gS -. ^ ™™ £

vT _a der

S measuring imperfections. the "oh, your habit-"> lent tier dark b, s kwarts appearance often as until

Weight

and lifespan and still just UtonihiDbdHi _?

.

Si? UükIk * du _n tonih _ra i _rt .D a highly active desulfurization catalyst with a metal component of group VIII.

To solve this problem, the subject matter of the invention is a process for the production of fuel or heating oil with a sulfur content ν of less than KO weight percent from higher-boiling feed materials with a sulfur content of more than 2.5 weight percent by two-stage, catalytic hydrogenating desulfurization , wöbe, in the first stage a partial desulphurization in the presence of a metal component of group VIa of the penode system on an aluminum oxide-containing carrier he carried out and in the second stage at least part of the feed material partially desulphurized in the first stage m: t hydrogen in the presence of a one Metal component of group VIII in combination with a metal component of group VIa of the periodic table on a catalyst containing s.hc.umdioxydhaltigen support to the desired final sulfur content is desulfurized, which is characterized according to the invention that the feed materiala) in de r first stage with hydrogen in the presence of a combination with the metal component of group VIa of the periodic table a W.smut component f ^ _1n advantages. About the high sulfur oil

ateriaiien.die black / oils. Significant maximum of a conventional rs already very quickly _removed to the catalyst bed temperature _{upstream of the} adjacent bismuth

50

Γ «^^ g that stability and has sicn per g ^ _process

Catalyst, which is a Metallkom-VIII in combination with a K 'group VIa of the Periodene.η of the first stage

_on a sulfur content in the _{qcent essential} .

For example, was practically _iS conventional nickel ₅ ^ _a sulfur content of _{{m Dozent and Ent.}

^ f ^ Final sulfur content of the product cteiu ⁿ J ^d _ht observed. Accordingly

of 10 ^^ gitokömal catalyst for can en ^ derarag ^ _0Endschwefe i.

^ we.te Stu ^{e to} j _'s j ^ _Gewä hrleistung

ibility to be deployed

When used, such conventional ^η Γ f are subject to desulfurization

wise sodium ions, and hydroxyl ions, silicate anions or contains aluminate anions, whereupon the solid-liquid mixture is left to react until the crystalline aluminosilicate is formed Has. The zeolitic material can also be dispersed in an amorphous matrix in the carrier, the latter usually consisting of aluminum oxide, silicon dioxide or silicon dioxide-aluminum oxide.

The catalyst composition is then generally at a temperature of 93-316 ° C Dried for 0.5 to 24 hours and then at a temperature of 371 to 648 ° C for 0.5 to 10 hours calcined. If the support material contains a crystalline aluminosilicate, the calcination temperature is expediently a maximum of 538 ° C.

Although the catalyst for the first stage of the process by any of the known methods can be prepared, it has been shown that the use of catalyst particles, which by common Extrusion of the components have been produced, is particularly beneficial. The particulate catalyst is produced for this purpose by mixing the carrier material, be it amorphous or zeolitic Character, in talc-like powdery form with salts of the metal components, e.g. bismuth nitrate and molybdenum trioxide. The extrudable mass is then formed, for example, by blending the solid mixture with nitric acid, by milling, and aging the milled material during one Period from 15 minutes to 2 hours.

Although this is not absolutely necessary for successful desulfurization, a halogen component can may be introduced into the catalyst, with fluorine and chlorine being preferred. the The amount of halogen is chosen so that the final catalyst 0.1 to 3.5 and preferably 0.5 to 1.5 Contains percent by weight halogen, calculated as the element.

Before being used for the desulfurization of the hydrocarbons, the catalyst can undergo a reduction treatment be subjected. The calcined catalyst is z. B. at a temperature of 427 to 648 ° C for 0.5 to 10 hours with the hydrogen treated. This reduction can be carried out on site in the reaction zone prior to feeding the feed be made.

Often a further improvement is achieved if the reduced catalyst is subjected to a presulfiding treatment subject to thereby 0.05 to 0.5 weight percent sulfur, calculated as the element, in introduce the catalyst. The presulfiding takes place with hydrogen and a sulfur-containing compound. e.g. hydrogen sulfide. Mercaptans ^ low molecular weight, organic sulfides or Carbon disulfide. The reduced catalyst is expediently with a sulphidation gas. e.g. a Mixture of 10 moles of hydrogen per mole of hydrogen sulfide, until the desired amount is introduced Treated amount of sulfur. The presulfiding is preferably carried out on site in the reactor Introduction of a relatively low-boiling hydrocarbon feed, contains the sulfur-containing compound.

In the two desulfurization stages of the process the catalyst can be in the form of a fixed bed, moving bed, or fluidized bed. With regard to at the risk of abrasion loss, the application a fixed bed is preferred. A hydrogen-rich vapor phase and the feed become heated to the initial reaction temperature and then the mixture is poured into the fixed bed of the Catalyst containing conversion zone passed. The hydrocarbon conversion zone can consist of one or more reactors exist, in the latter case, if necessary, with the interposition of Facilities to ensure the desired

ίο Conversion temperature at the inlet to the following Catalyst beds. The reactants can flow in upward, downward, or radial flow may be passed through the catalyst, with a combined downward radial flow being preferred.

The operating conditions in the first and second desulfurization stages depend on the properties of the feedstock and the desired end results. A maximum catalyst bed temperature in the range from 316 to 482 ° C. is preferably maintained in the first stage. For the second stage, the maximum catalyst bed temperature should preferably be in the range from 288 to 454 ° C. and expediently about 28 ° C. lower than the temperature of the catalyst in the first stage. More preferably, pressures from 28 to 341 atm space liquid flow rates of 0.1 to 10.0 and hydrogen concentrations from 178 to 8900 normal m ³ jem ³ hydrocarbon feed, hereinafter abbreviated as Nm ³ cm. ³ The desulfurization reactions are mostly exothermic and there is therefore a temperature increase when the

• Hydrogen and the feedstock through the catalyst bed. To make sure the Catalyst bed temperature does not exceed the maximum allowable, can in conventional manner Cooling streams in the form of liquid under normal conditions or gaseous components are introduced into the catalyst bed at one or more points. When heavy hydrocarbon feedstocks are desulphurized and at the same time partially in lower boiling Hydrocarbons to be converted will usually be part of the normal conditions liquid product effluent boiling above the desired boiling point of the product, to the pooling either with the fresh feed or with the already partially desulphurized feed for the second stage or a part of each with both of these charges. Preferably be the heavier fractions returned to the fresh feed for the first stage in an amount that the Charge ratio is in the range from 1.1 to 6.Q.

The method is described below using an exemplary embodiment white ter illustrated with comparative studies.

Example with comparative studies

A conventional desulfurization catalyst has been made by impregnating caiciniites

te aluminum oxide-silicon dioxide balls. the 88, ( Containing weight percent aluminum oxide, with nickel nitrate hexahydrate and molybdic acid (85.0 ", Molybdenum trioxide) in such amounts that a «final catalyst composition with a

Content of 1.8 weight percent nickel and 16.Q weight percent molybdenum, calculated as elements revealed.

This catalyst was / ur processing a

topped crude oil with a specific gravity of 0.979, an initial boiling point of 343 ° C, a 30 volume percent distillation temperature of 437 ° C, a 50 volume percent distillation temperature of 490 ⁰ C and a 70 volume percent distillation temperature of 559 ° C used. At a temperature of 572 ° C, 73.0 percent by volume could be distilled. The sulfur content was 3.80 percent by weight, the heptane-insoluble fraction made up 7.11 percent by weight and the toppedi; Crude oil contained 102 parts per million by weight of nickel and vanadium and 4200 parts per million by weight of nitrogen.

At a pressure of 205 atmospheres, a hydrogen concentration of 890 Nm ³ / m ³ and an hourly space flow rate of the liquid of 1.0, a deactivation of 38 ° C. per 1000 l / kg resulted over a 224 hour operating time. The entire operation was quite unsteady, the sulfur contents increased immediately when the maximum catalyst bed temperature was increased. Under the same conditions, with the exception of a lower pressure of 137 atmospheres, the deactivation was 51 ° C. per 1000 l / kg.

Preliminary investigations had shown a certain improvement in the stability of the nickel-molybdenum catalyst when the space flow velocity was reduced. At a fluid volume flow rate of 0.5. a pressure of 205 atmospheres and an amount of hydrogen of 890 Nm ³ / m ^{3 again} resulted in a deactivation of 38 ° C. per 1000 l / kg. At 137 atmospheres, an amount of hydrogen of 890 Nm ³ / m ³ and a low volume flow rate of the liquid of 0.5, the deactivation rate was 29 ° C. per 1000 1 kg.

A bismuth-molybdenum catalyst according to the invention was produced by double impregnation of 110 g of spherical silicon dioxide-aluminum oxide particles, the aluminum oxide content of which was 88.0 percent by weight. The carrier material was first placed in a rotary dryer with 23.32 g of molybdic acid (85.0 ° _o molybdenum trioxide). dissolved in 175 ml of 3.3 weight percent ammonia, impregnated. After impregnation and drying at 107 C ^c, the material was calcined for 1 hour at 593 ° C. The calcined catalyst was reintroduced into the rotary dryer, along with 13.49 grams of bismuth nitrate pentahydrate. dissolved in 60 ml of water with the addition of 8 drops of concentrated nitric acid. After drying, the material was calcined again at 593 ° C. for 1 hour. Analyzes showed an apparent poke weight of 0.85 g / cm ³ raid a content of 4.6 percent by weight bismuth and 10.5 percent by weight molybdenum.

The above-described topped crude oil was partially desulfurized in the presence of the bismuth-molybdenum catalyst at a pressure of 137 atmospheres, an hourly space flow rate of the liquid of 1.0 and a hydrogen concentration of 1780 Nm ³ / m ³ . The objective was to determine (1) the temperature at which the product effluent contains around 1.5 weight percent sulfur, (2) the catalyst stability at sulfur levels of around 1.5%, and (3) the ability to achieve a sulfur content in the product of 1.0 percent by weight. The results are shown in Table I below.

Table I.

Stability of the bismuth-molybdenum catalyst (first desulfurization stage)

Operating period. Catalyst- sulfur Hours since temperature (Weight percent) Start of operation (C) 3.54 10 to 14 290 3.47 23 to 34 318 3.09 46 to 54 347 2.46 to 1.85 70 to 302 375 1.48 310 to 446 393 1.59 454 to 494 392.5 1.57 to 1.48 502 to 542 392.5 1.63 614 to 654 392.5 1.39 670 to 686 402 1.30 to 1.21 702 to 758 410 1.23 766 to 782 418

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drawn. Again, a very stable operation at a pressure of 137 atm. An hourly flow rate of the liquid of LU, a hydrogen concentration of 890 Nm ³ Zm ^3, maximum catalyst ^temperature of in λ u T " ^{51, the} five product mixtures are listed in Table II below
Table II
Product analyzes, first desulphurisation stage

Specific Cicwichl

Sulfur. Weight percent
Nitrogen. Parts per million
Boiling analysis. C.

Start of boiling

1 (1 "

30 "

50 "

70 "

mixture

0.952

1.57
3220

330
375
427
492
579

0.947
1.43
3380

294
366
416
484
566

0.949
1.49
3440

296
370
429
481

558

0.949 1.44 3630

298

371

431

490 *

561

F.

0.944 1.57 3430

296 362 418 483

572

These mixtures were then further desulfurized in the presence of a catalyst composed of 1.8% nickel and 16.0% molybdenum on a carrier composed of 88.0% aluminum oxide and 12.0% silicon dioxide. Processing took place at a pressure of 137 atmospheres, an hourly space velocity of the liquid of 1.0 and a hydrogen concentration of 890 Nm ³ / m ³ . The results are shown in Table III below.

With these further desulphurizations in the second stage, no or only an extremely low one occurred Catalyst deactivation, which results in excellent catalyst stability when using the inventive, previous.!) Partial desulphurization in the first stage proven.

Table III
Desulfurization in the second stage

Operating hours Catalysis Of- sulfur
(Weight specific product Boiling analysis, 10% 30% C. 50% 70% mixture satortemp. activation
"C each percent) 338 383 461 518 27 to 86 CC) 1000 IAg 0.80 0.9237 Start of boiling 343 388 466 522 A. 87 to 198 360 0 0.82 0.9391 207 352 398 473 531 B. 199 to 326 360 0 0.88 0.9352 227 360 420 478 532 C. 327 to 460 360 <1.6 0.92 0.9383 241 359 422 476 533 D. 461 to 562 360 <1.6 0.92 0.9390 261 E. 360 <1.6 260

Claims (2)

22 12 121 claims: 1. Process for the production of fuel or Heating oils with a sulfur content of less than 1.0 percent by weight from higher boiling fuel with a sulfur content of more than 2.5 percent by weight through two-stage, catalyushes, hydrogenating desulphurisation, with partial desulphurisation in the presence in the first stage one a metal component of Group VIa of the periodic table on an aluminiumoxydhal-. term carrier eftthaltenden catalyst carried out and in the second stage at least a portion of the feedstock partially desulphurized in the first stage with hydrogen in the presence of a Group VIII metal component in combination with a metal component of Group VIa of the periodic table on a silicon dioxide-containing Carrier-containing catalyst hydrogenating to / around the desired final sulfur content is desulfurized, characterized in that the feedstock in the first Stage with hydrogen in the presence of one in combination with the metal component of the group VIa of the periodic table containing a bismuth component to form a catalyst Hydrocarbon stream with a sulfur content of 1.0 to 2.0 percent by weight umsct / t, of the at least a portion in the second stage to the hydrocarbon product having a sulfur content less than 1.0 percent by weight is implemented. 2. The method according to claim 1, characterized in that that in the first stage a catalyst. of 4 to 30 percent by weight of a molybdenum or Tungsten component and 1 to 10 weight percent of the bismuth component on an amorphous one. Contains aluminum oxide containing carrier is used.