DE1470529B - Process for the hydrated desulphurisation of hydrocarbons - Google Patents

Description

1 2

Catalysts, the quantitative predominantly from soluble cobalt compound subjected to the

an alumina-containing carrier and to the small-. Sodium ions of the zeolite against cobalt ions

ren part of one or more metal oxides, how to exchange. This base exchange can be done with the

Molybdenum oxide, chromium oxide, cobalt oxide and the like, washed zeolite on the filter or with the

are already carried out for a wide variety of coal 5 dry and / or calcined zeolite

Hydrogen conversion processes, e.g. B. for the hy- be.

Dration, dehydration, reforming and aromati- Suitable cobalt solutions for this purpose are used. A special catalyst to- cobalt ammonium chloride and other soluble com-composition, the widest use in the plexe cobalt amines as well as solutions of cobalt conversion of hydrocarbons, especially io chloride, cobalt nitrate, cobalt acetate and cobalt sulfate, for the removal of sulfur and nitrogen compounds. As the anionic aluminum silicate crystal lattice, the fertilize and for the addition of hydrogen to which the actual molecular sieve body is, through strong If the more unsaturated components of the hydrochloric acids are decomposed, it is necessary to add them to the base material pleased, consists of molybdenum oxide exchange solution at a pH of and cobalt oxide, which hold in equimolecular amounts 15 not less than about 4. You also have to be in or in non-equimolecular amounts on anything essential given the alkaline nature of the sodium aluminum Carrier made of aluminum oxide and aluminum silicate slurries particularly carefully are distributed. With these catalysts, as practical, be careful that when using cobalt with all for the conversion of hydrocarbon salt solutions for the ion exchange no cobalt substances certain catalysts, it has been shown, 20 hydroxyd. precipitates. Preferably, but not. not-.that even small differences in the cohesive manner become for the base exchange to setting or in the process for producing the conversion of the molecular sieve into the cobalt form Catalysts' significant effects on the catalyzed complex cobalt amines used. The concentration have table properties. the cobalt solution is not critical. Concentrations

The invention now relates to a method for hydrating from about 1 to 20 percent by weight are effective in the same desulphurising manner of hydrocarbons. However, there must be sufficient usual conditions, which are characterized by the amount of cobalt added, in order to be at least net, that in the presence of a crystalline sodium half and preferably two thirds or more um aluminum silicate catalyst with a pore to exchange the sodium atoms. The exchange operates diameter 3-15 Å, in which more than 30, the sodium ions can barren at room temperature at temperatures up to 50% by cobalt ions replaced 100 ⁰ C are performed. It has been found that, and the molybdenum trioxide, cobalt molybdate, an exchange of only 50% of the sodium atoms molybdenum sulfide, cobalt sulfide or their mixtures, the adsorption capacity of the aluminum as further catalyst components in amounts of 5 silicate molecular sieves changes, the remaining up to 20 percent by weight contains. 35 sodium, however, has an adverse effect on everyone

It is known that certain naturally occurring processes in which the molecular sieve as Using zeolites such as chabazite and analcite and the like, the catalyst is used. Further it was found Have the property of selectively adsorbing η-paraffins that the exchange of two thirds or more of the beer and reject the branched-chain isomers. Sodium ions versus cobalt ions not just that These zeolites possess crystal structures with a 40 adsorptive properties, but also that large number of cavities, the remaining sodium as a catalyst poison impermeable to each other a number of even smaller cavities or makes it effective. In the context of the invention, therefore Pores are connected. These pores also contain about two thirds or more of the sodium by means of ines neatly uniform sizes and diameters. Base exchange process can be replaced by cobalt. Only molecules that are small enough to get into the pores 45 The resulting cobalt form of the zeolite is made enter can be adsorbed. The pores can then be filled with molybdenum oxide, cobalt molybdate, molybdenum with a diameter of less than 3 to more than sulfide, cobalt sulfide or mixtures of these substances vary than 15 Å; with each particular zeolite further catalyst components are combined. MoIy, however all pores are practically the same size. denoxide is used as a further catalyst component

Natural and synthetic zeolites contain particularly preferably. This stage of the process can

common silicon, aluminum, oxygen and an easily perform by adding the cobalt zeolite z. B.

Alkali and / or an alkaline earth metal, e.g. B. Sodium with a sufficient amount of ammonium molybdate

and / or calcium, magnesium, etc. Analcit has treated the solution to obtain the desired amount of molyb-

to introduce the empirical formula of denoxyd. For this impregnation of the cobalt

To show NaAlSiO-HO ■ ^{55, ammonium} molybdate solution is preferred,

²⁶² because it is alkaline and has no adverse effect

and in the treatment with calcium ions it is based on the anionic lattice of the aluminum silicate.

the dehydration in a molecular sieve that exercises. The amount of the cobalt form of the MoIe-

composition of kularsiebes to be combined further catalyst

CaNa ₂ Al ₂ Si ₄ O ₁₂ · 2 H ₂ O ^6o component can range from about 5 to 20 percent by weight, based on the total amount of the

over. It is also a synthetic zeolite with a molecular catalyst, vary,

larsie properties known to the empirical The following example serves for further explanation

Formula of the invention.

4 CaO-Al ₂ O ₃ -4 SiO ₂ 65 example

has. ^F.

According to the invention, a zeolite with a large A solution of 435 g of technical sodium meta-

Pore diameter of the base exchange with a silicate (29.1% Na ₂ O and 28.7% SiO ₂ ) in 1305 ecm

Water is poured into a 4-1 vessel. At room temperature, 265 g of sodium aluminate solution (20 percent by weight Al ₂ O ₃ ; molar ratio 3Na ₂ O · 2Al ₂ O ₃ ) are added with rapid and effective stirring. After stirring for 5 minutes, a further 1000 ecm of water is added and the whole is refluxed for 240 hours. The crystalline material is filtered off, washed well with water and dried in oven at 121 ⁰ C. This crystalline material is a molecular sieve with a uniform pore size of about 13 Å. After the molecular sieve has been calcined for 4 hours at 454 ° C., the material is examined for its adsorptive capacity. The adsorption capacity for n-heptane is 0.20 ecm of liquid per g of adsorbent, for toluene 0.23 ccm / g and for 2-methylpentane 0.19 ccm / g.

The cobalt form of this molecular sieve is produced as follows: 400 g of the molecular sieve are added to 1 liter of water. In another vessel, 454 g of cobalt chloride (CoCl ₂ -OH ₂ O) are dissolved in 3900 ecm of a solution containing 11% concentrated ammonium hydroxide (28% NH ₃ ). Air is bubbled through the cobalt-ammonium solution for 2 days. 1300 cc of the cobalt amine solution thus obtained is added to the wet molecular sieve slurry, whereupon the mixture is temporarily stirred at room temperature for 90 minutes. Then the supernatant liquid is decanted and the molecular sieve is washed with water and slurried again in fresh cobalt amine solution. This procedure is repeated again. The molecular sieve is then dried in an oven at 121 ° C. and calcined for 4 hours at 454 °. 200 g of the cobalt form of the molecular sieve are impregnated with 115 ecm of a solution containing 27.3 g of ammonium molybdate. The whole is dried in the oven at 121 ° C and then activated by heating at 454 ° C for 4 hours. This material contains 10% MoO ₃ on the cobalt form of a molecular sieve with a uniform pore size of 13 Å as a carrier. The catalyst is hereinafter referred to as Catalyst "A".

comparison

The sodium aluminum silicate of uniform pore size of 13 Å is prepared according to the above example. 400 g of the calcined product are mixed with 1 liter of water. In another vessel, 454 g of nickel chloride (NiCl ₂ · 6H ₂ O) are dissolved in 3 l of a solution containing 11% concentrated ammonium hydroxide (28% NH ₃ ), and air is passed through the resulting solution for 18 hours to allow it to dissolve forms the nickel-ammonium chloride complex compound. 11 of this nickelamine solution is then added to the wet molecular sieve and the whole is stirred for about 90 minutes. The supernatant liquid is decanted and the molecular sieve is washed twice with water, whereupon 11 fresh nickelamine solution is added. The treatment procedure is repeated and then repeated again with more fresh nickel amine solution. The final product is filtered, washed well with water, dried in an oven at 121 ° C and calcined for 4 hours at 454 ⁰ C.

. 187 g of the calcined nickel form of the molecular sieve are impregnated with a solution of 25.9 g of ammonium molybdate. The catalyst is then dried in the oven at 121 ° C and calcined for 4 hours at 454 ⁰ C. This catalyst contains 10% MoO ₃ on the nickel form of a molecular sieve with a uniform pore size of about 13 Å as a carrier and is referred to as catalyst "B".

A commercially available cobalt molybdate on alumina catalyst, which is known for its good activity in hydrogenating desulphurization, is used as catalyst "C". The catalyst contains 3% CoO and 10% MoO ₃ on an aluminum oxide carrier.

The catalysts "A", "B" and "C" are examined for their desulfurization activity by using them for the catalytic desulfurization of a heavy gasoline charge originating from a West Texas crude oil with a sulfur content of 0.31 percent by weight in quiescent bed at a pressure of 27 atm, are a hydrogen rate of 35.6 m ^3/1001 and temperatures in the range of 370 to 400 ° C used. The results are shown in the table below. In all cases the liquid product is practically completely recovered.

catalyst "A" "B" "C" Throughput speed,
Room parts / room part / hour
Sulfur in Liquid Pro
duct, weight percent ... 1.0
0.0015 1.8
0.034 1.0
0.0025

The values show "that the mixed according to the invention Catalyst "A" is extremely active in removing sulfur from sulfur-containing petroleum streams.

Claims (1)

Claim: Process for hydrated desulphurization of hydrocarbons under normal conditions, characterized in that one is in the presence of a crystalline sodium-aluminum-silicate catalyst works with a pore diameter of 3 to 15 Å, in which more than 50% of the sodium ions are replaced by cobalt ions, and the molybdenum trioxide, cobalt molybdate, molybdenum sulfide, cobalt sulfide or their mixtures as contains further catalyst components in amounts of 5 to 20 percent by weight.