DD206910A3 - METHOD OF LOW-LOWING THE LIVING AREA OF HIGH-LEVELING HYDROCARBON FRACTIONS - Google Patents

Abstract

THE INVENTION RELATES TO A METHOD OF HUMILIATION the boiling range of high-boiling hydrocarbon fractions BY hydrotreating IN A FORM SPECIFIC CATALYST TYPE NICKEL (II) OXIDE aluminosilicate having SILICON (4 OXIDE. OF-applying CATALYST INDICATES A NEW SECTION PROFILE ON THE MOSTLY BY FAR CURVED arches opposite curvature CONNECTED TO each other.

Description

Title of the invention

Process for lowering the boiling range of high-boiling hydrocarbon fractions

C 10 G 23/00

Field of application of the invention,

The invention relates to a process for lowering the boiling range of high-boiling hydrocarbon fractions by hydrogenating treatment on a form-specific catalyst for the production of fuel and heating oil components and raw materials for catalytic cracking plants.

Characteristic of the known technical solutions

It is known that high-boiling hydrocarbon fractions can be converted to lower-boiling hydrocarbon fractions by catalytic hydro-sparing.

The known processes for catalytic hydro-sparing, such as e.g. in Oil and Gas Journal 20.3.1967, p. 170, Oil and Gas Journal 31.5.1971, p. 70-73, Hydrocarbon Processing, VoI *. 51, lir. 9, Sept. 1972, pp. 139-146, ibid. Vol. 53, no. 9, Sept. 1974, pp. 126-132, ibid. Vol. 57, 1fr. 5, May 1978, pp. 117-121, ibid. Vol. 58, Ir. 5, May 1979 ,. S. described,.

especially when using high boiling hydrocarbon fractional in the reaction zone with very high pressures, generally between 15 to 20 MPa. On the one hand, this requires very high costs for the investment of such systems as well

_ .ρ _ A-. w w / w

On the other hand, very high operating costs due to jiioergie and hydrogen consumption. Furthermore, even with the use of highly selective catalysts in all previously known methods of hydro-cleavage, a considerable gas attack is observed, which adversely affects the economics of these processes in refineries. "In specific situations, the gasoline attack resulting from the hydrocracking is also disadvantageous if, for example, no There are no sales or processing capacities for these components and, on the other hand, there is a need for diesel fuel components. The latter problem can be solved according to US Pat. No. 3,668,112 by converting the gasoline fraction, which is undesired but inevitably produced during the hydroprocessing of hydrocarbon fractions, into C ₁ - to G 2 -hydrocarbons in a second process stage by means of hydrocatalytic cleavage. However, this solution is equipment-side and energetically very expensive and because of the thus still increasing? / Erserstoffbedarfs and the even higher gas yield material economically unfavorable. For these reasons, the further improvement of the selectivity of the hydroprocessing is sought. The effectiveness of processes for the hydroprocessing of hydrocarbon fractions with the aim of removing heteroatom compounds, in particular sulfur compounds and organometallic compounds and lowering the boiling range, is largely determined by the properties of the particular catalyst. Primarily used catalysts which are a combination of compounds of metals ¹ of VI. and VIII. Subgroup of the PSE and alumina or 'contain an aluraosilicate as the main component.'

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While for the hydrogenation of low boiling hydrocarbon fractions, e.g. of the gasoline and diesel oil range the combination of the above mentioned hydrogenation-active components with the surface-rich aluminum oxide or aluminosilicate is sufficient gain for the processing of higher-boiling fractions pore distribution, porin and grain size of the catalyst in importance. This is due to the fact that such fractions differ in molecular size, content of hetero compounds and structure of the compounds from the low-boiling fractions. For the hydrogenation of hydrocarbon fractions obtained, for example, by vacuum distillation and / or deasphalting from petroleum residues, catalysts are therefore proposed which have a special pore structure, as described, inter alia, in DE-OS 2330324 ".

Since the diffusion of the large molecules into the catalyst core is hindered, the catalyst grain size has been steadily reduced to improve pore utilization. However, grain size reduction is limited from the viewpoint of reactor loss, which is why special geometric shapes have been used (eg, US Pat. These molds also have the advantage of a favorable surface-to-volume ratio, which counteracts demetallization because of the low depth of penetration of the metal compounds into the molds, and despite the improvements achieved by these measures, some disadvantages of the process are not to be overlooked Although tubular bodies (so-called hollow strands) show hydrodynamic favorable properties, in catalysis they tend to increase from the inside out

coke. The shamrock profile (so-called triiobes) is attributed in EU-PS'8424 to the disadvantage of a so-called meniscus formation in the contact veins of the individual sheets, which likewise has catalytic disadvantages. However, the star profile given as an alternative solution in this patent has, with its mechanical instability, in particular the tips, yet another disadvantage. All known solutions for catalyst extrudates have in common that they have in cross-section scoring with acute or obtuse angles through which the oil film on the outer surface of the catalyst is unevenly distributed .und therefore find in the catalyst grain hydrocarbon molecules temporally and locally not uniform opportunity for implementation. This results in a poor utilization of the catalyst grain, which manifests itself in low activity, stability and in particular in reduced selectivity, vias especially at desired high degrees of hydrogenation leads to undesirable by-product accumulation.

With the previously known Kätalysatorformen and technically conventional solutions of the reactor design occur in particular when processing high-boiling fractions problems in the distribution of / gas FTüssigkeitsgemisches on the reactor cross-section, which currently limits the maximum possible catalyst bed heights, minimum possible gas velocities and maximum possible speeds of the liquid According to AICHE Journal VoI 21, Io 2, Mar. 1975, pp. 228, maximum catalyst bed heights are 6-8 m, minimum velocities of hydrogen-containing gases are greater than 357 cm / s liquid phase based on the empty

Reactor cross section less than 8.3 mm / s known. These limitations are contrary to the demands for the lowest possible Gasumlaufrat en and high liquid loads resulting from economic reasons.

Object of the invention

The aim of the invention is to find a powerful method for lowering the boiling range of high-boiling hydrocarbon fractions by hydrogenating treatment for the production of fuel and fuel oil components and raw materials for catalytic cracking.

Explanation of the essence of the invention

The object of the invention is to make a process for lowering the boiling range of high-boiling hydrocarbon fractions by hydrotreating on a form-specific catalyst for the purpose of generating fuel and fuel oil koraponenten and raw materials for catalytic cracking more effective and in particular to increase their selectivity to minimize undesirable by-product accumulation.

The object is achieved in that the method for lowering the boiling range of high-boiling hydrocarbon fractions by hydrogenating treatment of a form-specific catalyst consisting of a combination of 5-10 Ma. -% nickel (II3 oxide, 15-25 Ma % molybdenum (VI) oxide and a X-ray amorphous aluminosilicate with 3-30 Ma % silicon (IV) oxide at a hydrogen partial pressure of 1-8 MPa, a temperature from 550 - 700 K, a raw material load of

3 ^ 1-10 m ^ / m ^ h and a gas: product ratio of 80 - 1000: 1 nri.Itf./nr performed, according to the invention extruded catalyst particles are used with vortex-like cross-sectional shapes in which the boundaries of the cross-sectional area through wide-arched arches are given and the wide-swung arches are connected by tight arcs of opposite curvature. Thought straight connecting lines run between points on the wide arches outside the geometric body. , ·. ' It has proved to be expedient to use catalyst particles whose vortex-like cross-sectional shape is formed from three to four arms, which are bounded by substantially concave curved surfaces and a circumscribing diameter between 1.3 and. 3 mm. The catalyst particles have ratios between concave and convex curved surfaces in the range of 1: 1 to 100: 1, with the radii of curvature of the concave and convex surfaces having a ratio between 0.5: 1 to 20: 1. The catalyst has a macroporous fraction with pore diameters>. 20-60 nm from 1 to 10 % of the total pore volume. By using the form-specific catalyst particles taking into account the catalyst properties, it is possible to control the linear velocity of the liquid hydrocarbon phase in relation to the empty reactor cross section in the range of 3 mm / s to 20 mm / s and that of the gas phase under standard conditions of 100 cm / s to / 360 cm / s. Catalyst bed heights of 4 to 15 ei can be realized.

embodiment

He found a solution with the application of the Katal.ysatorforinlinge according to Pig. 1, 2 is illustrated by Table 1.

Table 1

Feedstock: K = Vakuumd 0 Stillat from Romaschkino Ancestry: = oil 0.91 g / cm " Density at 293 = 1.96 Ma. -% sulfur content Viscosity at = 19.2 mm ² / S 50 ⁰ C basic 273 mg I / l nitrogen 5 % K distillation 10 % K ASTM D2887 30 % 635 K 50 % 646 e 70% ι 665 K 90 % 683 K 95 % 699 K 719 733

attempt

Type of catalyst and size

catalyst composition

Catalyst volume üi r

Ingredient quantity in nr / h

Circulating gas quantity in nri.H./h

 Reactor inlet temperature in K Reactor inlet pressure in MPa Linear velocity of the liquid phase, mm / s Linear velocity of the gas phase, cm / s Catalyst bed height, m Sulfur content of the total liquid product in% Basic nitrogen of the total liquid product it in mg U / 1 Yields in% by wt. on use

Gases C; - C,

Irilobe 1, 6mm A ₂ Triiobe

2.77

389

0.1!

72

1.4 Vortex Triiobe WirbaL, - 6mm 1, 6mm 1, 6nmi

% nickel (II) oxide,% molybdenum (VI) oxide, % silicon (IV) oxide

10

20 28000 653

2.77

389 5 0,10 27

20.1 0.6

Mineral spirits C ₅ - ISO ^ C 4.1

Diesel fuel particle, component 180 - 36Ο ⁰ C 21.0 26.3

chemical H ^ consumption in Ma. -% bez. on use ao

20 80

18000

673

11:11 11,11

250

10

0.825 0.713

0.31 153

.1,6.

4.5

20.1 0.876

250 10

0.09 31

20.1

0.8

27.2

0.745

q 7 η

The high-boiling hydrocarbon fraction specific in Table 1 is subjected to a hydrogenating treatment in the experiments A., IL, Ap and Bp. In experiment A ₁ ', a known type of catalyst is used under conventional conditions. Compared to experiment B ₁ , in which a catalyst of the invention form under otherwise identical conditions as A _{1 is} applied, a significant difference in performance measured at the desulfurization, from degradation of basic nitrogen compounds, the gas and Spaltbenzinanfall and the hydrogen consumption is already recorded. In situations where the aim is to achieve the highest possible yield of diesel fuel component and the lowest possible gas and gasoline yield with a limited amount of hydrogen, the results of experiment B _{1 should be} given priority over A ₁ . However, it is particularly advantageous to use the solution according to the invention in accordance with experiment Bp, in which, apart from a new catalyst form, conditions not previously practiced that noticeably reduce the cost expenditures for these processes are used. Under these conditions, the power difference increases very significantly, as the comparison of the test results Ap and Bp shows. As a further very often significant advantage of Lösufig Bp is the not insignificant-higher degree of refining of the fraction 3 ^ 0 C +. '. ,

10

Claims (4)

- ίο - O O 0 7 ^ claim 1. A method for lowering the boiling range of high-boiling hydrocarbon fractions' by hydrogenating treatment on a form-specific catalyst consisting of a combination of 5-10 wt .-% nickel (II) oxide, 15 - 25 Ma. % Molybdenum (VI) oxide and an X-ray amorphous aluminosilicate with 3-30 Ma./SiIiCiUm (IV) -OSid at a hydrogen partial pressure of 1-8 MPa, a temperature of 550-700 K, a raw material loading of 1-10 2. The method according to item 1, characterized in that the vortex-like cross-sectional shape of the catalyst particles is formed from three to four arms, these catalyst particles are substantially limited by concave curved surfaces and a circumscribing diameter between 1.3 and 8 mm. Method according to items 1 and 2, characterized in that catalyst particles are used in which the ratio of the concave to the convexly curved surfaces is between 1: 1 and 100: 1 and the radii of curvature of the concave and convex surfaces is a ratio of 0.5: 1 to 20: 1. 3 3
nr / mh and a gas: product ratio of 80 to 1000: 1 ni.H./ni characterized in that extruded catalyst particles with vortex-like cross-sectional shapes are used, the boundaries of the cross-sectional area being given by wide-arched arcs and the lunettes being swung Arches are connected by tight arches. 4. The method according to item 1 to 3, characterized in that the macroporous fraction of the catalyst with pore diameters> 20 - 60 nm 1 - 10 % of the total pore volume. For this 1 sheet drawings