DE1443496A1 - Catalyst mixture and its use in hydrocatalytic processes - Google Patents

Description

Catalyst mixture and its use in hydrocatalytic processes The invention relates to catalysts and their use for hydrocatalytic Procedure.

Catalysts, the veine hydrogenation or dehydrogenation component on one Carriers included are well known. There are a number of different carriers. In some pollen, the carrier itself has considerable activity, e.g. in the case of of platinum-alumina catalysts for the production of gasoline fractions high octane number can be used, or in the case of catalysts on trays Silica-alumina used for hydrocatalytic cracking will. In other cases, however, a substantially inactive carrier is desired, which only serves to provide a large surface for the hydrogenation or dehydrogenation component to accomplish. A catalyst of this type is, for example, platinum on silica gel.

The invention relates to catalysts in which the hydrogenation / Dwhydrier activity is combined with limited isomerization activity. The invention Catalysts contain a hydrogenation / dehydrogenation component, an anhydrous neural Sulfate of a metal or anhydrous cobalt sulfate and an inactive carrier of the nearby described type.

The known hydrogenation / dehydrogenation components are preferred Metals of groups Via and VIII of the periodic table or their compounds, have the hydrogenation / dehydrogenation activity. Are particularly preferred the platinum group metals, in an amount of 0.01 to 5 wt .-% of the total catalyst can be present.

Furthermore, as components in T) oxides or sulfides of chromium, Molybdenum and tungsten, which are usually expressed in an amount of 2-30% ( as metal) of the total weight of the catalyst are present.

2) The oxides or sulfides of the iron group metals, the nora. Eost''oncs ? et. . t. d = v. nd0 3) Eombinations of those mentioned under 1) and 2) iysa.tos'aGHesondistc Unt@rinativenSlagcnaindSFges.Tomohi.die in AbsencevossetalsnSnifatoa.eervnKGltsulfa.t Tysators is present.

Under "inactive carriers" are sluggish? ': I'r: p -; =, i'v: r.;, S..a:'. 4'ia: J ': fL.LJ..l.w' .... 1'G9SYl. ~ ik.i: S7 ..; E.'e-9YF3.WnVLtL'TG: ici, 'Jvf.51g8.8: e:, PfY =. ~ DBCb'vi ~ f: .. ilJ dieinnEonsoladsorptioRserton? jGRis'sis3Ikroaol re -. s lu, j>. ', L- L ° c'd.'f'. , ufL. P ~ Y En 1i mol benzel / g catalyst, measured at @@@ C with a Partial vapor pressure ven about 0.1 mm Hg benzel in a purified nitrogen stream ven about 30 cm3 / minute.

A "neutral sulfate" is a sulfate that is a solution with a pH of 6 or more than 6.0 forms, if the ung according to one of the following Methods is made. A 0.1 molar solution of the sulfate is prepared, by adding the required amount of sulfate: Ln a corresponding amount of deionized Water that has recently been detilled under nitrogen is dissolved in the balla of sulfates, which are not in sufficient consentration to solve, in order to form a 0.1 molar solution, saturated solutions of the sulfate in Water prepared in the manner described above.

Sulphates of metals of groups II, III, Vu VI or VIII of the Periodic Table or used by tin, lead, titanium or Mengan, in particular sulfates of the empirical formula X2 (SO4) n, in which X is the metal atom and n mean its value.

The anhydrous sulfates are preferably obtained by dehydration the hydrated forms of sulfates. The dehydration occurs in the generally made by heating the hydrated salts, usually Temperatures are used at which there is practically no decomposition of the sulfate takes place. Sulfates of cobalt, calcium, magnesium and zinc are preferred, Carriers whose surface is greater than 100 m 2 / g are preferably used. Silica gel is preferred, but other carriers can optionally also be used will.

The silica gel is expediently obtained by precipitation from a solution of the silicate, for example sodium silicate, or by hydrolysis of organic Silioates, especially alk6yl silicates, e.g. B. o-ethyl silicate formed.

The catalyst advantageously contains at least 10%, in particular 20-30 % By weight of the neutral sulfate or cobalt sulfate.

The components of the catalyst can be in any convenient order can be added, but the hydrogenation / dehydrogenation component is preferably after the addition of the neutral sulfate or cobalt sulfate or at the same time as this added. For example, one can use the neural sulfate or the cobalt sulfate add inactive carrier by impregnation and add the impregnated carrier Dry and oil as needed. The hydrogenation / dehydrogenation component can then be used be suggested, and again expediently by impregnation, whereupon the Katlaysator is dried and calcined as required. During the second impregnation is thereon care must be taken to avoid a loss of neutral sulphate. To this end, will the solvent, for example, by evaporation and not by decanting or Filtration removed. It is also possible to use neutral sulfate or cobalt sulfate and the hydrogenation / dehydrogenation component simultaneously using a suspension or add solution of the components and then evaporate the liquid.

The invention includes processes for converting hydrocarbons by combining the hydrocarbons with catalysts of those described above Art.

For example, hydrogenation processes in which the degree of saturation can be considered is increased by hydrocarbons, e.g. B. the conversion of diolefins into olefins, from olefins to saturated compounds and from aromatics to naphthenes.

In particular, however, the catalysts for dehydrogenation processes can be used, especially those processes involving both dehydration every cyclization also takes place, for example by converting C6 and higher derivatives Paraffins in Aromates.

There is a special characteristic of the catalysts according to the invention in that they have low activity for cracking and polymerization reactions, however a certain activity for isomerization reactions show the one advantageous Supplement the dehydration and cyclization activity is. In the dehydration process can use the known conditions. be turned, but it was found that the inventive catalysts are particularly suitable for use at high Temperatures that favor dehydration and Cyolisierun are suitable, but that often not used because of the rapid formation of carbonaceous deposits can be. Temperatures in the range of 420-600 ° C. are therefore suitable, preferably from 450-550 ° C.

The dehydration is further reduced by a low total pressure and favored low hydrogen partial pressure. Come as the remaining procedural conditions In asks Druok 0 - 70 atmospheres, preferably 0 - 21 atmospheres, air velocity in space, V / 7 / Btd, 0.1 - 10 added or circulated hydrogen, m3 / m3 0 - 1800, preferably 0-360 all input materials for processes in which the inventive Catalysts used come from pure hydrocarbons or mixtures of Hydrocarbons, e.g. B. petroleum fractions in question. Beeondera is suitable as a starting material for dehydrogenation processes are saturated hydrocarbons or their mixtures with 4 - 24 carbon atoms e.g. B. petroleum fractions in gasoline, kerosene and The gas is boiling.

Example 1 A platinum-kisselic acid gel catalyst was made as follows manufactured: silica gel that was previously dried in air at 350 ° C for 2 hours was treated with an aqueous solution of chloroplatinic acid (H2PtCl6XH2O) impregnated, with such violent acid was used that # the end product 0.7 wt .-% Contained platinum. The idoung was allowed to breathe the slurry for 24 hours evaporated to dryness in the air at 110 ° C and finally caloinated at 440 ° C.

A platinum-magnesium sulfate-silica gel catalyst was prepared as follows manufactured silica gel, which was previously dried on the Lutt at 350 ° C for 2 hours was, with an aqueous solution of magnesium sulfate heptahydrate (analytical pure) merged, so much salt was used that the Final product contained 30% by weight anhydrous magnesium sulfate. The suspension obtained was left to stand for 24 hours, after which the above liquid was decanted became.

The impregnated gel was then dried in air at tlo ° a and finally dehydrated at 350gC.

This material was then prepared in the same manner as in the preceding Described in connection with the silica gel, impregnated with platinum.

The two catalysts were used together with a commercially available Platinum-alumina reforming catalyst containing 0.57 wt.% Platinum, on their dehydration and cyolization activity using n-hexane as Used material checked. The following process conditions were used: D @ Normal pressure room flow velocity 0.64 V / V / hour.

Amount of hydrogen used as carrier gas 10 cm3 / min.

Duration of experiment 4 hours. Catalyst volume 1 cm3 Temperatures applied. These temperatures are along with the results obtained listed in Table 1 below.

Table 1 Feedstock: n-hexane Temperature, ° C 440 500 550 Running time with this Temperature, minutes 60 60 120 Sales of products at the end of the specified term,% by weight Benzene isomers @ split Benzene isomers @ split Benzene isomers @ split product- product- product- te te te Pt / MgSO4 / SiO2 (30% by weight MgSO4, 0.67 wt% Pt) 0 13 2 9 20 3 54 10 5 Pt / SiO2 (0.44 wt% Pt) 0 0 0 0 0 0 0 6 0 More commercially available Pt / Al2O3 catalyst (0.57 wt% Pt) 7 39 15 33 14 45 38 5 40 @The isomers include methylcyclopentane, cyclopentane, and 2- and 3-methylpentane.

The values in the table above show that the commercial platinum alumina catalyst not only benzene but also great Amounts of cleavage products formed o by using silicon dioxide instead of Alumina coke was eliminated, but dehydrocyclization was also eliminated at the same time turned off and an inactive catalyst obtained. However, if magnesium oxide was added to the platinum-silica catalyst, the resulting catalyst had high dehydrocyclization activity with low cracking activity.

Example 2 In comparative experiments, toluene was made from n-heptane under Use of a catalyst which is 0.67 wt .-% platinum and 30 wt .-% magnesium sulfate Contained on silica gel, and a platinum-silica gel catalyst and a commercially available chromium oxide-aluminum oxide catalyst.

The conditions used and results obtained are below mentioned in table 2.

Table 2 feed material: n-heptane; Pressure: normal pressure; Room flow velocity: 0.53 V / V / hour

(related to the liquid state) Temperature, ° C 440 500 550 Running time in Minutes at this temperature 60 60 @ # catalyst wt .-% conversion in products that A. Pt (0.44% by weight) / toluene 0.45 was obtained at the end of the specified running line 75 silica gel benzene 0 0 5 fission 0 0 5 products B. Pt (0.67% by weight) / toluene 21 95 83 Mg sulfate (30% by weight) / benzene 2 0 5 silica gel cleavage products 5 5 6 Isomers ** 21 0 0 C. Chromium oxide-aluminum-toluene 0 60 74 oxide (commercially available) benzene 0 4 4 fission products 0 5 6 # space flow velocity for the catalysts B and C = 1.6 V / V / hr. (in liquid state) * The running time is 5 minutes for Catalyst A, 48 minutes for Catalyst B and 40 minutes for ** methylhexanes and Methylcyclohexane.

Although the sulfate-containing catalyst had a higher platinum content as the catalyst containing only silica gel as a carrier, it was at 550 ° C and a much higher space air velocity a higher activity.

Claims (10)

P a t e n t a n s p r ii c h e 1.) Catalyst mixture for the hydrocatalytic Treatment of hydrocarbon compounds containing a hydrogenation / dehydrogenation component, an anhydrous neutral metal sulfate or anhydrous cobalt sulfate and one inactive carrier. 2.) Catalyst mixture according to claim 1, characterized in that # as hydrogenation / dehydrogenation component metals or metal compounds with hydrogenation / dehydrogenation activity t from groups VIa and VIII of the Periodic Table are present, in particular a platinum group metal is present in an amount of 0.01 to 5% by weight. 3.)) Catalyst mixture according to claims 1 and 2, characterized in that that as anhydrous, neutral metal sulphate sulphates of the metals of group II, III, V, VI, VIII and / or sulfates of tin, lead, titanium or Ilangan are present. 4.) Catalyst mixture according to Claims 1 to 3, characterized in that that metal sulfates of the empirical formula X2 (SO4) n are present, in which X is the metal and n mean its value. 5. analyzer mixture according to claims 1 to 4, characterized in that because the sulfates in the catalyst mixture are those of cobalt, calcium, magnesium. or Zinc present. 6.) Catalyst mixture according to Claims 1 to 5, characterized in that since the inactive carrier has a surface area greater than 100 m2 / g, the is inactive carrier in particular silica gel. 7. catalyst mixture according to claims 1 to 6, characterized in that since the sulfate content is at least 10% by weight, preferably 20 to 30% by weight. 8.) Yerfahren for the hydrogenation of hydrocarbons, characterized in that that the starting material under hydrogenation conditions with the catalysts of the claims 1 to 7 is dealt with. 9.) Process for the dehydrogenation of hydrocarbons, characterized in that that the starting material under dehydrogenation conditions with the catalysts of the claims 1 to 7 is treated, preferably at temperatures of 420 to 600 ° C, in particular 450 to 550 ° C, printing from normal pressure to 71 kg / cm2, preferably normal pressure up to 22 kg / cm, a room flow rate of 0.1 to 10 V / V / hour. and one added or circulated hydrogen amount from 0 to 1800 m3 / m3, in particular 0 to 360 m3 / m3, is worked. 10. The method according to claim 9, characterized in that # as a hydrocarbon feed a petroleum fraction of the gasoline, kerosene or gas oil sector is used.