DD157200A1 - HYDROCATALYTIC METHOD FOR GENERATING CRACK INSERTS AND FUELS - Google Patents

Abstract

The invention relates to a process for the hydrocatalytic production of cracking feeds and fuels from higher boiling hydrocarbon fractions which are of primary, secondary or carbochemical origin. The process is characterized in that the hydrocarbon is passed over a two-layer catalyst combination which in the first layer is a predominantly refining hydrogenating catalyst consisting of nickel (II) oxide, tungsten (VI) oxide and weakly acidified roentgenamorphum aluminosilicate and in the second layer of a highly resilient consisting of a mixture of separate particles per one or more nickel and molybdenum or tungsten compounds and roentgenamorphischen and crystalline alumosilicate existing catalyst. The temperature profile is ascending adiabatic in both layers and can be lowered between the first and second layers or within the second by hydrogen or hydrocarbon addition. The advantages of the process of the present invention - the simultaneous production of low BMCI cracking feedstock raw materials and significantly improved fuel quality, high liquid product yield and low hydrogen consumption - are set forth in two examples.

Description

VEB Leuna-Werke leuna, 16 · Dec «1980

"Walter Ulbricht" DC.Ma/Stei

LP 80139 Title of the invention

Hydrocatalytic process for generating cracking feed. raw materials and fuels

Field of application of the invention

The invention relates to a process for the simultaneous production of above 623 K boiling aromatics and cycloalkane Krackeinsatzrohstoffen 'Diesel fuels'mit favorable cetane number, aromatics and cycloalkane rich Eeformerrohstoffen and isoparaffinreichen or «cycloalkanereichen Leichtbenzinen from higher boiling hydrocarbon fractions, the primary, secondary or carbokchemischeη origin can*

Characteristic of the known technical solutions

It is known to use in a process for producing highly hydrogenated hydrocarbon fractions, two catalysts of different types, wherein in a layer of a little azide essentially nickel and tungsten in the form of oxides and / or sulfides catalyst containing strong hygroscopic

a puncture and in a second layer of an element of the iron group and an element of group VI b of the PSE in the form of oxides and / or sulfides and an aluminosilicate-containing catalyst is incorporated with preferably isomerizing and cleaving puncture. The catalyst with preferably isomerizing and splitting puncture may also contain a synthetic, crystalline aluminosilicate (DD-PS 133901, Cl. B 01 Jj 23/84 and C 10 G, 23/02).

With such a catalyst arrangement and composition succeeds _? A disadvantage of the known solution is associated with the in-depth hydrogenation Zwangsanfall of gasolines and diesel fuels of insufficient quality, the high proportion of unselective gaseous fission products and related a high hydrogen consumption and a low liquid product yield _β

Object of the invention. -

The object of the invention is to develop a process for the hydro-catalytic production of cracking feeds and fuels by which arise in the process of deep hydrogenation of higher-boiling hydrocarbon fractions diesel and gasoline fuel components in a flexible amount and improved quality, which is above 623 K boiling residue fraction in, their chemical composition in the sense of the greatest possible production of lower alkenes used in hydrocarbon pyrolysis changed and the hydrogen consumption is lowered by reducing the formation of nonselective gaseous fission products.

Explanation of the essence of the invention

The invention has for its object to find a catalyst combination and the process conditions required to solve the objective.

According to the invention, this object is achieved by a process for the conversion of higher boiling hydrocarbon fractions of primary, secondary or oarbochemical origin to fuels and raw materials for thermal alkene production with values for the aroiaatically bonded carbon of less than 7 mass% and a BMCI value of less than 20 in the fraction boiling above 623 K, on a catalyst assembly in the presence of hydrogen or such containing gases, dissolved at elevated temperatures and elevated pressure, in which the higher boiling unrefined, partially refined or refined hydrocarbon feed via a catalyst combination comprising in a first layer a nitrogen and non-sulfur sensitive catalyst consisting of icing nickel = (II) oxide, tungsten (VI) oxide and lightly acidified X-ray amorphous aluminosilicate containing the aromatics and oils of the raw material at reactor inlet temperatures of 640 to 710 K and by the Re heat of reaction by 2o to 70 K • increased outlet temperatures of the first layer, Wasserstoffpartialdruoken from 12 to 35 MPa, catalyst loads of 1 to 6 v / vh reduced so far that the aromatically bonded carbon 10 mass- and the bromine number 2 g bromine / 100 g in the above 623 K boiling fraction is not exceeded and in a second layer, a highly resilient nitrogen and sulfur insensitive catalyst consisting of a mixture of separate particles of one or more nickel and molybdenum or tungsten compounds and a X-ray amorphous and crystalline aluminosilicate containing the polycyclic aromatic compounds are further hydrogenated, polycyclic ring structures of aromatic and naphthenic type and a part of the paraffins are reduced in molecular weight,

at inlet temperatures of the second layer of 655 to 710 K and by the heat of reaction by 10 to 40 K increased outlet temperatures of the second layer of the catalyst combination, but at most an outlet temperature of 740 K, hydrogen partial pressures of 12 to 35 MPa and catalyst loads of 4 to 30 v / vh is directed ·

The hydrocatalytic reaction takes place in the first layer of the catalyst combination on a catalyst consisting of -5 to 40% nickel (II) oxide,

- 30 to 70 mass% tungsten (VI) oxide

- And 20 to 50% by mass of a X-ray amorphous 5 to 50% by mass SiO.sub.x-containing aluminosilicate component, which may still contain compounds of metals of VI. VIII. Subgroup of the PSE contains, wherein the catalyst in the unreduced state o, 1 to 20% by mass may contain elemental sulfur ";

The proportion of SiOp causes the weak acidity of the catalyst. It has proven to be advantageous to use an aluminosilicate component which is used to form a surface

p.

of more than 200 m / g.

The addition of elemental sulfur to the metal-rich catalyst once leads to the improvement of the porosity and in particular in the macropores and simplifies, on the other hand, the sulfurization of the catalyst in hydrogen sulphide-containing hydrogen.

The hydrocatalytic reaction takes place in the second layer on a catalyst consisting of '

- 15 to 80% by weight of crystalline aluminosilicate, which is 2 to

Oj.

Contains 8 masses of nickel

and 20 to 85% by mass of amorphous aluminosilicate with 1 to 8% by mass of nickel and 8 to 30% by mass of molybdenum or tungsten.

The increased cracking activity of this catalyst is preferably achieved by using the H-Y-Porm of the crystalline aluminosilicate.

_. 5 -

The in situ successful activation is the same for both catalysts of the combination. Particularly favorable is the reducing sulfurization of the catalysts in hydrogen sulfide-containing hydrogen in the temperature range up to 673 K, preferably 473 to 573 Z ₉ " _:

The determination of the volume ratios of the first to the second layer of the catalyst combination primarily determines the degree of conversion of the residue fraction greater than 623 K boiling in the diesel and carburetor fuel range, where high fuel levels are achieved as the volume of the second layer is increased,

In addition to determining the volume ratios of the two layers of the catalyst combination according to the invention, the degree of conversion of the higher-boiling hydrocarbon fraction to diesel and carburetor fuel components and their qualities is determined by layer inlet temperatures, temperature profile and catalyst loading.

High conversion rates are advantageous if sufficient reformer capacity; is present, because the heavy spirits produced are particularly suitable for the production of aromatic-rich reformates due to their high cycloalkane and aromatic content. With increasing conversion of the residue fraction greater than 623 K boiling and associated increase in the SehY / erbbenzinanteiles decrease Zykloalkan · "and aromatics in heavy fuel with simultaneous preference of the Alkylzyklopentane over the Alkylzyklohexanen slightly, · .... increasing strokes. Heavy fuel quantities also result in significant volume increases in the light gasoline sector,

Surprisingly, it was found that conversion rates of the residue fraction and sharpness of the process conditions in the second catalyst layer of the process according to the invention only have a small influence on the octane number of the light gasoline.

22 6 846 2

However, the Bildimgsverhältnis of cycloalkanes, benzene and isoparaffins change greatly. Thus, at low conversions of the residue fraction, high concentrations of cycloalkanes and benzene and relatively low levels of isoparaffins are formed, with the cycloalkanes consisting in equal parts of alkylcyclohexanes and pentanes. As the process combination in the second layer of the catalyst combination increases, the formation of cycloalkanes and benzene decreases, with a concomitant increase in the isoparaffin content and lowering of the ratio of alkylcyclohexanes to alkylcyclopentanes.

The cycloalkane-rich light benzine fraction, which is formed at low to medium degrees of conversion, which is understood as a conversion of the above 623 K boiling residue fraction of 10 to 40 Wasse-fo , offers in addition to their suitability as Verggaserkraftstoffkomppnente also for benzene-forming reforming.

Pure in the range of 453 to 623 K boiling diesel fuel fraction applies that their amount also increases with increasing the degree of conversion to ca, 50% by mass. This is associated with a decrease in the aromatics and cycloalkane concentration. Medium conversion levels lead to particularly suitable diesel fuels.

The suitability of the higher boiling point fraction for the pyrolytic production of lower alkenes is that the lowest possible amounts of aromatically bound carbon (C. in mass- #) and low BM.CI values are to be aimed for, v / o for the BMCI Value from · ·.

87552 VABP = mean sieve

BMCI = vf # - + 473.7. <=> - 456,8 detempeiatur the

Fraction in ° Rankine

calculated. ,

  '288.6K

Q = specific ^J weight at

    7 7 R O / -C

CL DO η Ό Ζ

In particular, the formation of monocyclic Alky! Aromatics is considered to be favorable because they do not significantly increase the coking tendency of the raw material in pyrolysis and have a relatively low hydrogen demand for their formation This is by applying the method according to the invention in particular at average conversion degrees of 20 to 40 Mass% based on the above 623 K boiling residue reached.

It has further been shown that these intermediate conversions, at high liquid product yields and low hydrogen, give rise to C ^ values of less than 7 mass-4 and BMCI values of less than 20 in the residuum fraction suitable for use as pyrolysis raw material Surprisingly, it has proved to be particularly advantageous for the selectivity of the conversion and thus for the reduction of the formation of gaseous hydrocarbon and of the hydrogen compound to set an adiabatically increasing temperature profile in both layers of the catalyst combination.

In order to avoid exceeding the permissible maximum temperature of the catalyst combination according to the invention and to increase the selectivity of the hydrogenating-splitting reactions taking place on the catalyst of the second layer, it is necessary to prevent the addition of cold hydrogen-rich gas or cold hydrocarbon mixture between the first and the second second layer and optionally provided within the second layer of the catalyst combination. Good product qualities in all boiling ranges are thus obtained with average degrees of conversion of from 20 to 40% by weight, based on the above 623 K boiling fraction, and ascending adiabatic temperature in both layers of the catalyst combination, whereby favorable liquid product yields and the lowest hydrogen consumption are also achieved here ,

_ ₈ _ lib Ö46

Example 1 (according to the invention)

A vacuum distillate from the thermal cracking of residue fractions, boiling from 623 to 823 K and the characteristic values given in Table 1, was passed in a small-scale apparatus over a combination consisting of catalysts A and B in the volume ratio 4: 1, the catalyst A in the first layer and the catalyst B was housed in the second layer. The catalysts were composed as follows: Catalyst A:

27.4 Mass HiO

50.5 mass- $ W0 _O) . , '.'

22.1% by weight amorphous aluminosilicate, wherein the

.Aluminosilicate component

20% by mass

80 mass ~ $ ₂₃ related to the Glückückstand at 1073 K was.

Catalyst B:

Catalyst B consisted of three components.

1. A Ni-containing amorphous aluminosilicate of 12.0 mass% MIO 17.5 mass SiO ₂ 70.5 mass% Al ₂ Oo prepared by mixing filling and based on the ignition residue at 1073 K.

2. A MoOo-containing amorphous aluminosilicate of 20.0 mass # MoO ₃ 16.0 mass- $ SiO ₂

64.0 mass- ^ Al ₂ O ₃

prepared by impregnation and based on the ignition residue at 1073 K.

/..o o 4 b Z

3 .. A crystalline .Alumö ilikat type Y zeolite, exchanged for ITH. Ions and Ni. · Ions:

Ki-GeiAIt 3.9 Pale ^. ·

Balance Ha ₀ O 2.5 mass-4. ''

Components 1, 2 and 3 were mixed in the dry state at 1073 K in a ratio of 1: 4: 3.5, and then deformed, based on the incineration state *

The test conditions were: pressure 25

7

Katalysatorbe-

3

load 3 M raw material per nr catalyst and

hour

Gas-to-product ratio 1000: 1 m ³ . , _T gas / m ³ raw material

1 · JN o

1 layer (Catalyst A) inlet temp. 643 K outlet temp. 693 K

2nd layer (Catalyst B) inlet temperature 668 K exit temperature 683 K

Between the two layers, the temperature αμΓοη addition of cold hydrogen-containing gas was reduced. Analysis of the reaction products obtained gave the results shown in Table 2.

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Table 1

Analysis of the raw material

Boiling range K Total raw material Fraction Fraction

453-623 K larger 623 E

Share of total product. , ,

Density at 293/343 * K g / cm ³ 0.8710 *

Bromine number gBr / 100g 17.5

Bases mgiJHo / 1 415

Sulfur mass- $ 0.95

C: H ratio 6.80

Molgey / not D. 70 *

BMCI

C ^ mass ^

31.0 69.0 0.8877 - 0.8795 * 25 13 288. - 476 0.87 0.97 221. 326 1.4972 1.4913 * 48.1 45.6 24.7 21.1

226846

Table "2 '!

Catalyst 'A' B = 4:

Reaction temperature · ^ ₃ _ 593/553 _

Shares in mass ~ $>

greater 623 K 50.2

453 - 623 K 42.1

373- 453 E 5.2

smaller 373K. 2.5

Yield liquid product

in mass-4 ^98j6

Hydrogen yerbohoh l'h.

m. V / t raw material 215 Properties of the fraction greater than 623 K · · Sulfur in mass ^ 0,060 C. in mass ^ 5.4 BMCI-We'rt 17.5 453 - 623 K Cube in mass ^ 0.032 Ca in mass ~ $> 9.5 373 - 453 K _. Aromatics in bulk $ 23.1 Cycloalkanes in mass% 46.4 smaller 373K Benzene in mass- $ 3,1 ' Cyclohexane in Bulk $ 9.6 Methylcyclopentane in mass ^ 16.4 i / n C ₅ paraffins 1.1 i / n Cg paraffins 2.1 EOZ 75

Example 2 (according to the prior art)

226 846 2

The process was carried out using the raw material listed in Table 1 with the combination of catalysts C and D according to the prior art. «

Catalyst C: (low acid Hl / W hydrogenation catalyst): 28.5 wt% ITiO 71.5 wt% WO ^

Catalyst D (with preferably isomerizing and cleaving

Puncture):

The catalyst D consists of two components: 1 c hydrorefining catalyst · '

2.5 mass% $ 24.0 mass WOo

14.5 mass SiO ₂

59.0% by weight based on the Glühruckstand at 1073 K. The aluminosilicate is X-ray amorphous.

2, Hydrospaltkomponente ': ._. ;

A crystalline aluminosilicate type Y zeolite, exchanged

+ 2+

against KlL · ions and ITi ions consisting of 3.9 mass # Ui

2.5 mass% g

Components 1 and 2 were mixed together in the ratio 2: 3.

The catalyst C was used in the first layer and the catalyst D in the second layer of the combination, wherein the volume ratio of C: D was 1: 1. The temperatures were consistently 670 K in the first layer and 676 K in the second layer. The further test conditions corresponded to the example

A comparison of the results of the process according to the invention (Example 1) and of the prior art process (Example 2) shows the high liquid product yield and the reduced hydrogen consumption of the solution according to the invention. Surprisingly, the lower aromatics content of the above 623 K boiling point is surprising Eüekstandsfraktion and associated with a very low BMCI value · The diesel fuel and gasoline components also produced in the process are distinguished from known solutions by particularly high quality. In particular, the high content of aromatic and naphtheniseher ring structures in Schwerbenzin- and Leichtbenzinsiedebereich make these fractions appear as a particularly suitable raw materials for reforming heavy fuel or for benzene-forming reforming of light gasoline "In addition, the resulting in the process according to the invention light petrol is due to * its relatively high ROZ better as VK component as the light gasoline in the comparative example,

- 14 Table 3 Catalyst C: D =.

2268 46

Reaction temperature in E. 670/676 - 0,089 Shares in% by mass 8.6 greater 623 e 43.1 23.5 453 - 623 E 38.0 373 - 453 E 11.9 , 0,051 smaller 373 e 7.0 12.3 Yield pittssig product in mass $ 95.1. Hydrogen consumption in 234th 17.4 39.0 Properties of the fraction greater 623 e Sulfur in ETasse- $ Cf. in mass · » ¹ ^ BMCI value 453 - 623 E Sulfur in bulk # C. in mass 373 - 453 E Aromatics in mass % Cycloalkanes in bulk- $

smaller 373 e.

Benzene in mass-> 1.6

Cyclohexane in mass%. 6.2 Methylz'yklopentan in mass- $ '' 9.8

i / n Cc paraffins 1.1

i / n Cg paraffins · 2.0

ROZ. 70.5

Claims (5)

invention claim 1 _β Process for the conversion of higher boiling hydrocarbon fractions of primary, secondary or carbochemical origin to fuels and raw materials for thermal alkene production with values for the aromatically bound carbon of less than 7 mass ~ $ carbon and a BMCI value of less than 20 in the above 623 "boiling fraction on a catalyst assembly in the presence of hydrogen or gases containing such, at elevated temperatures and elevated pressure, characterized - That the higher-boiling unrefined, partially refined or refined Kohlenv / raw material via a combination of catalysts, in a first layer, a nitrogen and sulfur insensitive catalyst consisting of NiCiCeI- (II) -OXiCl, tungsten (VI) -Oxiä and weakly acidified X-ray amorphous aluminosilicate , which reduces the aromatics and olefins of the raw material at reactor inlet temperatures of 640 to 710 K and by the heat of reaction by 20 to 70 K increased outlet temperatures of the first layer, hydrogen partial pressures of 12 to 35 MPa, catalyst loads of 1 to 6 v / vh so far that the aromatically bound carbon 10 Eilasse- % and the bromine number 2 g bromine / 100 g in the above 623 K boiling fraction is not exceeded, and containing in a second layer a highly stable, nitrogen and sulfur-insensitive catalyst consisting of a mixture of separate particles, one or more εekel and molybdenum or tungsten compounds and an X-ray amorphous and crystalline aluminosilicate, which further hydrogenates the Pölyzyklischen Restaromäten, polysicyclic ring structures of aromatic and napthenic type and a portion of the paraffins are reduced in molecular weight, at inlet temperatures of the second layer from 655 to 710 K and by the heat of reaction by 10 to 40 K increased outlet temperatures of the second layer of the catalyst combination, but at most one outlet Tempe- 846 temperature of 740 K, hydrogen partial pressures of 12 to 35 and catalyst loadings of 4 to 30 v / vh. is directed. 2. The method according to item 1, characterized in that the hydrocatalytic reaction in the first layer of Kata- "lysatorkombination on a catalyst, consisting of 5 to 40% by weight nickel (II) oxide, - 30 to 70 Bulk $ Wolfram (Vl) Oxide, ^£ · " and 20 to 50% by weight of a roughness-amorphous 5 to 50% by mass of SiO 2 -containing aluminosilicate component, which is present. if still compounds of metals of Vl. and VIII. subgroup of the PSE may contain is carried out, wherein the catalyst in the unreduced state can contain 0.1 to 20% by mass of elemental sulfur, 3 "method, according to " point Ί, characterized in that the hydrocatalytic reaction in the catalyst of the second layer of the catalyst combination on a catalyst consisting of - 15 to 80 mass # crystalline aluminosilicate containing 2 to 8 mass ~ # nickel ²⁴ " - and 20 - 85 mass amorphous aluminosilicate with 1 to 8 mass <$> nickel and 8 to 30 mass molybdenum or tungsten takes place « 4. The method according to * Vunki 1 to ^ _9, characterized in that the reaction is carried out on a catalyst combination of an arrangement of 60 to 90 volume of catalyst of the first layer and 10 to 40 volume ^ catalyst of the second layer, which in a or multiple catalytic beds. 5 "Process according to 'Tunkt 1 to 5, characterized in that the pretreatment and activation of the catalyst combination takes place in situ during heating to temperatures of at most 673 K in hydrogen sulfide-containing hydrogen stream and optionally with Sehwefelverbindungshaltigem raw material at temperatures below 658 K is completed. δ « Ymikf method . 1 to 5 _? in _s daduroh that DIE Tarnperaturführung in the first layer is Katalysaterseh ascending adiabatically and between first and second, and within the second Katalysatorsehicht a temperature reduction tone 0 "may be carried out to 70 K duroh addition of cold hydrogen '' / rich gas, hydrogenate or commodity «So that the maximum permissible outlet temperature of 740 K is not exceeded and flexible product quantities and qualities of the gasoline, diesel fuel and residuals can be obtained,«