DE2010533A1 - Process for desulphurising kerosene containing sulfur - Google Patents

Description

SHELL INTERHAIIONALS IiESBARCH MAATSCHAPPIJ H.V., The Hague, Netherlands

"Process for the desulfurization of sulfur-containing kerosene ⁿ priority: 7 March 1969, Great Britain, No. 12 162/69

The invention relates to a method for desulfurizing sulfur-containing kerosene, which ^{boil in the temperature range from 150 to 3CO 0} C, in which the kerosene present at least partially in the liquid state at elevated temperatures and under elevated pressures in the presence of a free hydrogen-containing gas via a in the form of a Sulphurization catalysts arranged in a fixed bed are conducted

U.S. Patent 2,608,521 explains one method of this Art. Venn, however, a hydrogen partial pressure that is too low in this process is adjusted, based on the respective temperature, the refined keroein obtained is not colorless, Colorless kerosene, however, is required for many purposes.

Surprisingly, it was found that the aforementioned liachtell can be eliminated by getting a sufficiently high Hydrogen partial pressure, whereby the reaction temperature

001631/1811

tux- ^ leichaeivig ip_: v2vh & VD des 1) 30'.ί ^Γ ::! ^ ηΐ iiereicr.s lit ^ t; * ^ uh: wnü where, a certain leil the Kor - sin ;? in f "Uif ειί ^ ππ * Zui: Τϋ .-. · ^< ;. üet- del * i: dialysis tor ströiaen

GegeA! 3ta! .-. C oer Jirfincliing is son: It Bin ViM. * ■■. · ^Τ : θ.ί '-.um L'ntscnwe fein ac / .u ^ j.irlhaltif-ar *.? I; »In · * uJ. t a.: i oeb ^ rich at 'üem-perai.uren from lt> 0 bic? "> LC C o.ureh Uberlei te- de" -. · Aumii-üest tei.V white ixi iji.Ussigeni Zui> ta.nd present i "wr:.;■; ·, .inο at elevated temperatures and under ürhühten iirucicen .L. ^^^ ni-wart of a free hydrogen entuaXti; /. de.rx gas over h..j) .ci. Xr.? orm of an IPeet bed arranged A.ntfcCi ^ efelui-i.-s-KataiyKe ^ -.- r, clase thereby ^ t * icennseiejuiuit is _s that with i'tn-pta-atures ν ·. · VU 'up to 5bC ° O unc under V.'assKt'rstoffpartia.'larächen _C) earü € li; i. · ν .U'cU «ie BiQh geraäfi

he calculate, and cla & e at most SO * j öas liei: .. »λ & In the JOunipfphase present "

In the process of the invention, the Kerι aine, which are rai'finiürt Bollen, treated in üe ^ enwai ^ t scnv / efelbcatändi ^ er catalysts with the hydrogen-containing gas. Lurch this ha haiidlung v, ill dae Auegan ^ suiaterial not only sulfur but also contaminants such ftickefcoff-, oefreit Bauerstolf- and halogen compounds, while unsaturated compounds that can cause the formation of deposits can be made unacuädlieh by hydrogenation "

ate the aforementioned United States Patent 2 521 60Ü flows dna sulfur-containing Kerouin that ooll been refined, aumindeat partially in liquid Zuatand in tfoviu a thin üchieht

009839/1915

BATH ORIGINAL

via the ^ atalyäato.r, which is dried up as .BVvoiu-ett, and this mode of operation is also preferred within the scope of the invention. The temperature is ira. Process of the! -. Rfinuungp like 310 to 360 ° Cc at temperatures below 3'XO ⁰ C? takes place the

Cell-n ^ in zealous au low external conditions, while the procedure for Teiupsraturen is jüerhalD 560 "0 because of the too high required v.assex ⁱ 8toff" Pax ^v t: lEld.rt5fste imwirtsß ^ al'tXiöh-

The pressure in the method of the invention is at least 14 kg / cta, at the same time preferably such an amount of hydrogen containing gas Ixiiadurohrleitung, that the amount of gas after cooling the Reeictionsgewisches and the separation ues scxiv boot hydrogen from the exhaust gas 50 to 250 Hormalliter / kg of starting material is *

The aforementioned amount of gas relates to the exhaust gas, as the maintenance a certain excess of gas for the process the reaction is important. £ in characteristic ^ of the reaction the quantitative ratio of hydrogen used / hydrogen sulfide obtained in the reaction zone, this quantitative ratio can only be determined on the basis of the delivery product *

Of the invention as entnaltendes hydrogen gas is needed in the process not to use pure hydrogen _s but this gas may also contain inert impurities such as nitrogen or methane, containing. However, catalyst poisons such as carbon monoxide should not be present. Hydrogen-free waste gases originating from catalytic reforming devices are preferably used in the process according to the invention

0 0 98 39/1915

In the process of Krflndung can allow gas to be upward or downward through the reaction zone _o In the latter case may cool together wan the gas and the liquid. The process can be carried out under relatively low pressures, Zcβ. under pressures of not more than 60 atmospheres, preferably under a total pressure of 14 to 600 atmospheres (overpressure) O

The effectiveness of the catalyst remains under the aforementioned conditions received for a long time; without the need for regeneration, and a high Ilaf f inati on level can be achieved • Removal of the sulfur from which kerosene is obtained »

The fact that hydrogen quantities of up to 250 liters / kg of kerosene used; For example, 50 to 200 liters / kg of kerosene are deducted, brings with it a significant saving in operating costs.

There is a maximum of $ 80 in the method of the invention. The kerosene in the vapor phase before "If more than 80? 6 of kerosene is in vapor form during the hydrogenating desulphurisation, no colorless kerosene can be obtained as an induct"

A wide variety of sulfur-resistant compounds can be used in the process of the invention Use catalysts. Well-known such catalysts are the metals of groups II to VII of the periodic System in the form of their oxides or sulfides, while metals of groups I and VIII as metals, ale compounds, such as Gxide or Sulphides, or compounds can be used in the form of those metals or their oxides or

009839/1915

BAD'ORIGINAL

Supply sulphides. The catalysts can be applied to supports be like activated carbon, puller earth, kieselguhr, silicon dioxide, Aluminum oxide, flower stone, bauxite or baked clay · One for dafl Process of the invention contains very suitable catalyst Cobalt and molybdenum as well as all carriers aluminum oxide, with cobalt and molybdenum are all oxides and / or sulfides.

The height of the catalyst bed or the total height of several in A series of catalyst beds arranged in the process of the invention must be dimensioned so that there is sufficient contact is guaranteed. The contact time can also be requested Feed rate of the dehumidifying starting material can be adjusted, with the starting material in a Layer of variable thickness flows over the catalyst.

In general, we want to ensure that the liquid is uniformly distributed over the catalyst beds, ss.B · by means of distribution floors or suitable splitting Over several inlet pipes. For ■ maintenance All of the distribution can be carried out using the catalyst * .B. in Arrange several beds, where distribution floors are used

Hydrogen sulphide and / or Aa «oniak, which arise in the process of the invention, are completely or partially dissolved in the liquid and can be used for an after-treatment, such as by wiping with steam.

In addition to the starting material, the method of the invention can use relatively high rauagee diapers, see B. Rough"-

009839/1815

BATH

speeds vr? n over 1 kg Kt-rosin / Littr iJnta.Usator, h. Xiauir ^ sscMwinüi ^ i.eLteri are preferably used: 3 to 5 legs Ksroßin / liter of catalyst ₀ iu

The example! explains the discovery,

Example oil 1

Us is a kerosene "which has a" iedebegini · ν - .. · η 15C ^W C and a boiling point of 250 ⁰ C, under versoa ;;. animals Ke act ion s conditions Above a sulfidized catalyst, above 3 _? 5 wt, - ^ cobalt, 8 _r 5 wt, - ^ fiolvbaän unti. alö ir & ßer Alu ^ iniuriioxid contains,

The kerosene used as starting material contains O _s 25 Gev / , - '/. Sulfur ο pas descrambled icer; sin contains less than 0, Cl $> sulfur.

The table and the heating conditions and the results of four sulfur accusations can be seen.

Tabel

Try ~ lir, 1 2 3 4th Temperature, ⁰ o 310 330 340 360 Total pressure, kg / cm 33 33 33 33 Hydrogen partial pressure »
kg / cm 14.7 16.6 16.0 24.0 RaujQKeeohwindiKkeit . 3.0 3.0 3.0 3.0 kg / liter «h 38.5 55.5 6ö, 0 79.0 Present as steam
Kerosene, $> color
Come on color
Come on ge
colors color
Come on Quality of the sulphurized
Keroains

009839/1915

BATH ORIGINAL

The one after the Gleji cimng

P _H * 0/133 ο I - 26
^H 2

in the P ₁ , des. Hydrogen partial pressure in kg / one and T the Re-

^A ^ 2
reaction temperature in C _f is calculated Wasseretcff-Parti-aldruck is in the Versuoheij. 1 or 2 or, 3 or 4

2 2 2 2

13.2 kg / oia bzwc 16.0 kg / cm, or _e 17.2 kg / am _p or _e 20 kg / cm.

From the! Table shows sorait out that _p faxbloise desulfurized kerosene when using the Teniperaturbereiolie tos. 310 to 36O ⁰ C are then obtained, Viemi the hydrogen partial pressure (kg / cm) is at least 0.133 times the reaction temperature (° C) -28 and if at most 80 # of the kerosene is present as vapor.

However, when the partial pressure of hydrogen (kg / cm) is lower colored values are obtained as the value * calculated according to the above equation No, what is extremely inexpedient "

0 09839/1915

Claims (5)

- 8 -Patentanep r U ο h e 1. Process for the desulphurization of sulfur-containing kerosene with a boiling range at temperatures of 150 to 30.C ⁰ C by passing over kerosene, which is at least partially in the liquid state, at elevated temperatures and under increased drills in the presence of a gas containing free hydrogen. a desulfurization catalyst arranged in a Feetbett, thereby known without, that at temperatures of 310 to 36O ⁰ C and under Wasseratoff- Partial pressure is worked, the calibrated g — Mt 2. r "τ P _H (k ^ / cm) »| O, 133. Reaction β temperature I- 28 and that a maximum of 80 H of the kerosene is present in the vapor phase. 2. The method according to claim 1, characterized in that an amount of the hydrogen-containing gas is passed in such a way that the Gaameng · naoh cooling of the reaction mixture without the hydrogen sulfide being dissolved from the exhaust gas amounts to 50 to 250 normal liters / kg of starting material. 3. The method according to claim 1 or 2, characterized in that ¹ ** has a total pressure of 14 to 60 atmospheres (overpressure) are used. 4. Method according to claims 1 to 3 »because you know that a catalyst is used, contains cobalt, molybdenum and aluminum oxide as a carrier, cobalt and molybdenum being present as oxides and / or sulfides, 009839/1815 BATH 5. Procedure according to Anaprueh 1 to 4 _tons because of that, ge · ic. ennaeichuet, ' data at speeds of 3 to 5 kg kerosene / liter of catalyst 009839/1915 BADORfCälNAL .U-.IV-.