DE1770308A1 - Process for the production of fuel oil with low sulfur content - Google Patents

Description

Esso Research and Engineering Company Elizabeth, N.J. o72o7 (USA)

Process for the production of fuel oil with low

Sulfur content

The invention relates to a process for the production of fuel oil of the type burned in industrial furnaces especially in ovens that are in factories in or near metropolitan areas. The invention particularly relates to a process for processing crude petroleum or recovery fractions with a high content of sulfur and hetal len for use as an industrial fuel.

- 1 109841 / U33

BATH

Very large amounts of industrial fuel oils are used in Areas such as the eastern coast of the United States τοη America burned. Recently, regulations have come into force in metropolitan areas on the east coast that contain the Limit the sulfur content of the residual fuel. Sulfur contents below 3% by weight, preferably below 1% by weight required to reduce air pollution.

A number of Latin American crude oils are cheap for processing and transport to the major markets of the East Coast. However, these oils are excellent by one high sulfur content also characterized by a hphen content of metals such as iron, nickel and vanadium. These Iletalle have an unfavorable influence on the catalysts which are used in the hydrodeaulfurization of the residue. If the metals are present in the fuel, they also attack the refractory materials used to line the boiler pots and the combustion chambers, cause slag formation and the build-up of deposits on the boiler pots, combustion chamber walls and the blades of gas turbines and highly corrode high temperature metallic surfaces with which they come into contact come.

The feeds of the present invention are also stale due to high hydrocarbon content

.. 2 -109841 / U33

high molecular weight, the intricate ring structures and a high carbon to hydrogen ratio own, characterized. Asphaltenes and resins are representative of this type of hydrocarbon. These materials are the starting materials of the carbon deposits, which during the hydrodesulfurization reaction on the Precipitate catalyst surfaces.

The build-up of metals and coke on the catalyst accelerates deactivation. There have to be higher temperatures and higher hydrogen pressures can be used to to maintain hydrodesulfurization. Even with high Y / asaeratoffdrucken it is not possible to achieve a satisfactory Maintain catalyst activity with feeds containing high concentrations of metals and asphalt components, and consequently the running times are short and the costs are high the replacement of the catalytic converter. High pressures and temperatures also cause cracking and a reduction in the Amount of fuel oil product.

The invention is based on the object of an effective, economical process for the production of residual fuel oil fractions and fuel mixtures with a low sulfur content and low metal content due to hydrodesulfurization to accomplish.

- 3 109841 / U33

: Is Oiese object of the present invention, briefly summarized, achieved in that a high Brennölbeechiekung SohwsfGlgehalt v.mi high content of metals, a • aiXclen ICokung is subjected wherein daa entire fade overhead product of the coker, the above about 316 ⁰ C. (600 °?) &I:; c, yt or one of deia overhead product of the Eo-rcrs abje- ^ etmtG Fre & tion, which in dexc gas oil boiling range sisd-r ';, ίο ;? Hydrcäß'eiliurisrung be subjected.

In fei.Yiöu? The preferred form of management is Kolcs from the koituiv _: ,;: i: i1rafG aur Erscag-mg von Vfesserstoff and it vrii'il ε in Eo.kakoni '.; i "it:"? at with a high content of metals

The εeii ;; V5. Puncture effects of the organo-organic component of the Viöscliiolcung v ^r üi:. * At the end of the desulfurization stage siue. in ό.ΐ- · π i'iachfolßi. '/ jäai'i attempts to compare. Ambient A is a heavy oil Arabic atmospheric discharge. (Safaniya). J'ierjchickung B is a vene? jiiola raw material (Bacliaquoro) freed from the volatile constituents by distillation. Charge A contains 4: 0 Gevt-fs iSulphur and 84 ppn V, 32 ppm Ui and 11 ppm Pe, while charge B contains 2.65 Gew Sahvefολ and 316 ppm V _f 50 ppm Ii and 9 ppm Pe, also gevjientr .besogG: · !, contains. Pie processing conditions in don: .V: s ^ !!: ^ t; .vi.criiri £ _J 's - Ve; v; leiG} iavGrsrichen were 105 kg / cm

109841/1433 ORIGINAL BATHROOM

(1500 psig) pressure, 385 ⁰ C (725 ⁰ S ¹ ) initial temperature and 368 2 ton cubic meters / m ⁵ (1500 SCP / B) treatment gas (97 $ Hp, 5 ^c / 3 GH ^ ₁ ) and the experiments are over identical commercially available} CoMo / AlrjO., - catalyst carried out.

The table below compares the rate of loss of Catalan activity expressed as the percent loss of kinetic activity (rate constant) per day; furthermore, as a function of the time for ba: ". de coverings, the temperatures required to do a sulfur removal to reach 55 $ au o

Sage to oil activity veriiisi, $ / i ^l ag for 55 / ii-ge sulfur

required Temperature

⁰ G <° 3?)

Infeed Infeed Infeed ABAB

2.5 5.5 18.0 385 Γ725) 381 '719) 7.5 5.5 12.0 392 728) 397 (746) 12.5 4.5 8.9 598 (74B) 407 ^ 765) 17.5 5.6 6.5 402 '757? 417 (781) 22.5 2.8 5.5 406 (764 ^> 423 (793) 27.5 2.4 4.0 411 r / 71) 427 {800)

- 5 -
109841 / U33

Vie shows this comparison, the catalyst life in the -yerieEuelanischen feed with a high content of metals (feed B) is considerably short, since the Arbea / Jau above 416-427 ⁰ C (780 to SOO ⁰ P) to a considerable Crackling and significant product degradation leads. Your use of an injection stage prior to the desulfurization stage makes it possible to convert a charge with a high metal content into a charge with a moderate or low content; sn Hetal? .en u ^ Ki ^ VJ ^ næeln.

The invention is described in detail below with reference to the attached statement, which is a plus slip of an execution form of the Varfahrsne *

The sruiiuungsgsEiaSs gate is specially designed for the Ee: -: gi; slluiig τοπ pear oils from feeder with a holi3i2 Go £ jajifl; content of rock compounds, metal compounds and Eoksbilder-n, Su typical feeds include: -: ohwe ^ s C ? -osariitroliö?. € !, atmospheric residues, VakviurariicksüUnf.o. Yii / o: i £; .l: Gr-soil materials and bcholes, from which the flü :: iri; i.: - aii Sos ^ andio. '. lo by flash distillation or in α.ι "(2ε :: οΓ \, ^r eia-o euti'srn-j. In general, 30 JXS -10 Geu, - ^ aor Bsi ^ hung above 482 ° C (900 ° ϊ). The to ^ oiviugton? ;;: chio '>: ungen are atmospheric soil γϊ3ο!:; \; "^; : Λ <Ι; ~ ^ j: l ο:'. Ιι: λι Αι \ Γ» γλ. ^ esboiling point iia Bareich of 2'5C bic ^ n ⁰ O ν D'O b: .s COO ⁰ S '). The properties of the

109841/1433

BATH ORIGINAL

Feedings of the process are shown below in Table II

specified,

Table II Feed Properties

characteristic

Density, ⁰ API
Sulfur, wt. ^C / i
Conradson carbon, metals by weight, ppm

Vanadiuu

Together

Items 2 to 4 together, wt .- ^ Asphaltenes, wt .- ^ j

(modified naphtha-insoluble substances)

SSF Viscosity (122 ⁰ P) amount of feedstock boiling above 482OC (900OI ¹⁾ boils at 5O ⁰ C

broad Be
rich more preferred
area 5-25 5-20 1-8 2-5 5-25 8-20 100-700 200-650 10-120 20-100 5-75 5-50 115-870 225-800 7 ^ 33 1 * 0-25 5-25 8-20 25-10,000 75-500 30-90 40-75

Particularly suitable Brennol charges have properties like the Latin American ones shown below

¥ ral <: t ionen.

- 7 103841 / U33

Table III Charge Characteristics

Bachaquero Tia Juana Hedium Bachaquero raw atm. Residue VakuuiB-

Residue

]) ichtc, ⁰ API 16.5 16.4 6.7 Tail al "Grew" - /; 2.23 2.16 3.3 Carbon, G ο nrad son, G-eν. - ', j 9.8 10.9 18.4 Metals, ppm Vanadium 317 278 635 Hickel 55 34 90 iron 34 9 - Together 406 321 725

Items 2 to 4. zv. samr-jGn, Gev / > · - '/ -

12.03

13.06

21.7

CH ktiali-ε3. C ₅ Gev ;,

, Ct OW,

85.93 11.43

C / H AtH

0.63

10

17.1

Viscosity, SSI ¹ boi 50 ° (

Viscosity,
121 ⁰ G &quot; 2

at

77.5

226

349

the

! ■ 0

1098-1 / 1-33

150

BATH ORIGINAL

According to the drawing, a Bachaquero charge, consisting of the residue from the first crude oil distillation, which contains 601 ppm V, 93 ppm ITi and 22 GeV ₄ -S '' Conradson carbon , is passed through line 1 to flow coker 2. Through line 3 the coker vapor eye having a temperature from 482 to 566 ⁰ C (900 to 1050 ⁰ F). The coke is kept in a fluidized state. The coking is conducted at a temperature in the range 482-593 ⁰ C (900 to 110o ⁰ P) ₉ a pressure in the range of Atraosphären- pressure to 4.92 kg / cm absolute (70 psia) and in the presence of 5 to 100 wt .-γί steam, based on the charge, carried out. Small particles of petroleum coke, which are formed in the process itself, airculate in a fluidized state between the coker 2 u'id. your coke burner 4 and serve as '^ araicubertraguugsmoiliv-ue.' The Ko? is through line 5 nv äs »; ICokrbremier 4 slides, part of the coke, namely;> up to 50 % by weight, is continuously burned in the presence of air supplied by line 6. Hot coke wire! returned through line 7 arm Koker 2. If the subsequent hydrogen generation step is not used, a portion of the coke can be extracted from the burner 4 alf. a Koks-Me i, a ".U-Konaantrat can be obtained., The An? .ag (: and the ΐβοίικοΐα ;; j ο the J ^! 'lie3 ~ kokung is dent Fachmam? h ^ Lanrst and s'.tol? · !: j-joinon part of the present inventions »df-ij '«. Dor Kofairir ,,;. --Ileitt dor iSrfindun {; subordinated;;:> h vor-i Stand O.03. · Ί ¹ ; ür. l. "r dar.n etv / ao that the Kokuri, '/" li.uÄi - .. y4r -.,';; o "n nor · - ;. ·. ^ ---! - *; ·. ■ · ■; ■. ¹ ^ jIj \, -:} · /; »■

- D -109841 / U33

clev-j ma ij.ns Tcaxiriaie. Hsn ^ s ϋλ for the following HydrouesiL.i'uri .- ^ aiißBEiviiif: ., ργ, - · auaelr !, which have a low salary

! Oi ;; j-ic'iü ^ c vc'i CIr-. ■;?:. "■■ f.Λ:"..; * ·· - "^ mporauai ¹ and! üampfgeacbv / in- · Λί, ^!:. % /. τ /λ.· ^; " (-.:■ ?. '- ■» ■■ iCxv-.' ■■■ :. ;: - .. ·. Iv ■. (; ν.nc! clou Ke - ^ - llfiehalt den Brcniiö?.:.; '' .. '■ .. ■: ■ C ^ i-al: 5'Ί: .ΐΓ: ■ :::> ^! crmr οϋΛίβο norflinal 50 JJigoi:. ? 3aehaq ' ⁱ e; .c -. L..uc: h £ b: ^'! C '-. ß c: .1 ^ :? 3teä Rolvjlilestiilation Ψζϊ- ^ χ: -. {.Uli; ι: i. 'i) ° S (! ^' 5 ⁰ I-- ,!) oi-halton v / ircl, nsigen oils

^109841/1433 BADOR ₁ G ₁ NAL

Table IV

Ash release of flowable solids from 50 fSigen Bacbaqiiero Residue from the first crude oil distillation _———.

Temperature, ⁰ G ( ⁰ F) 503 538 538

(937) (1000) (1000)

Weight - \ 'y steam 60.1 55.3 23.4

546 ° C (1015 ⁰ F) conversion,

Vol. Ϊ 69.1 65.6 74.5

Auobonts,

on the charge of coke, wt .- ^

GZ-1 wt .-> i

C ₄ , vol. ^C />

C _r / U9 ° C (300 ⁰ F), vol. $ 149/316 ⁰ C (300/600 ⁰ F), vol. £ 316/552 ⁰ O (6OO / 1025 ° F), vol. J.

above 149 ⁰ C (300 ⁰ F +), vol. £ Conradson carbon, wt. -f nickel, ppm
Vanadium, ppm

11.7 1 15.0 17.8 6.1 6.9 5.9 0.8 1.2 1.1 9.3 11.1 8.3 8.9 11.8 9.8, 42.1 27.2 37.9 Loading
chicu - 79.2 73.6 72.9 22nd 4.6 12.2 8.9 93 16 20th 5 601 100 43 61

These results show that fluid coking is effective in reducing metal and Conradson carbon when residues are fed. The results are also
that the equivalent lowering of the intersection in

- 11 109841/1433

ö a Küicer by reducing the vapor dilution is just as effective v / ic dio tat β a creeping reduction in the coke temperature. The VMrkun. "C'es vapor consists in the" ivirJrcrunsn distillation point ¹¹ in the reactor to \ ti'D? Icl ^ r'.i. J) :: r v. ^R : Lrksa: the distillation start point is somt; λ1γ;.; k _; r considered a controlling factor in the removal of metals.

The coker protiulites are removed from the coker in the vapor phase through line 8 and passed to a suitable separating device, such as a Piaeh distillation tower 9 ». Gaes and lciohto substances and delicacies which contain up to zn 316 ⁰ G (60O ⁰ I ¹ ) are removed overhead from the tower through the junction 10. In the preferred embodiment, the converted 316 ⁰ C (600 ⁰ P) material is passed through line 11 to the H7drodesiiliurierurigsrep.ktor. The treatment of a high-boiling charge in the form of a high-boiling point is made possible by the reduction in metals and carbon dioxide achieved by the coking step. In another embodiment shown in the drawing, a tower for atr.o spherical ο distillation uses the lash tower and gin Üoitenschnitt, c.or sm range from 316 to 6TiI ⁰ C (600 bic I ¹ SO ⁰ P) forges , the HydrodeBulfurierungobeechickung ijGYoViü. yfi and the Bodenotuff c ims üübj ataoophärischon ab el ie Pm ^ t ^ on ubo-r C21 ° C (115O ⁰ F +), with deeul-

- 12 103Ö41 / 1433

BATH ORIGINAL

mixed oil. Alternatively, all ^{or part of the 3621 0} C (115O ⁰ P) fraction can be returned to the coker.

The coked hydrodesulfurization feed in line has at least 50 weight percent and more typically at least 75 weight percent reduced metal content. Ausaerdem is the Asphaltengebalt at least 50 parts by weight Js and more usually at least 75 wt. ~ ^C / o been reduced. Similarly, the Conradson carbon content of the oil is reduced by at least 70 #.

The fraction is fed into the hydrodesulfurization reactor 12 initiated. The reaction is carried out in a conventional reactor of the bed, moving bed, or triple bed type carried out. The oil is initially white in the liquid Phase contacted. Typical conditions are as follows:

- 13 109841 / U33

table V

Reaction conditions

wider loading bevorsugtar Be rich rich

260-482 343-427

Temperature, ⁰ C ( ⁰ F) (500-900) (650-800)

j, 35.2-211 793-155

J) JCUcV., Jig / car (psig) (5GO-3OOO) (1000-2200)

R; lu ni, ^r ; cs chv, ^r in di / vl: ο it,

V / V / h '0.2-4.0 0.5-2.0

Va &quot; (SCF / B) 4 ^r : -2'i5O '^ 68-AQO

(500-10 OOü) (i: ^r 00 - ii0ü0)

Horological hydrofining catalysts can also be used. Such catalysts include Group VI and VIII metals of the periodic table supported on a suitable porous support material such as aluminum oxide, silicon dioxide / aluminum oxide, bauxite, magnesium oxide and the like. Catalysts containing oxides or sulfides of cobalt, nickel, molybdenum and tungsten are preferred. Oxide catalysts are preferably verified before use or in t; itu. The most preferred catalyst contains 2 to 5 parts by weight cobalt oxide, 10 to 25% by weight molybdenum oxide and the remainder with aluminum oxide stabilized with aluminum oxide. Dq :? preferred silicon dioxide form of the ßs amounts to ⁵ ^ 1 »5 bic 5 Go \ i. ~ ^c / j.

1098Ai / Ü33

BATH ORIGINAL

Hydrogen is supplied to the reactor through lines 13 ~ ßd 14 suggests. The hydrodesulfurization effluent is from dea Reactor removed through line 15 and passed to separator 16. Return gas strörat overhead through line 17 of Soperator to gas cleaning system 18. Fuel oil with low Sulfur content is collected through line 19. If necessary the oil in line 19 can be fractionated into a plurality of fuel oil cuts by suitable means will.

In a SasroinigguildssysteE 18 hydrogen is separated from HpS, JIH ₅ , GO, CO ₂ and other gases and light compounds by known means, for example by cooling, washing with drums, amine washer, the hot carbonate process or a combination of these gas cleaning methods. V / oxygen is then returned to line 14 anyway. The gas contaminants are purged through line 20.

In a preferred embodiment, all or a portion of the hydrogen for the hydrodesulfurization is produced in the process. Coke is Laitung 21 at a Setiperatur of 704 860 ⁰ C (1300-1500 ⁰ F) by burning with air The Verbrannungsstufe leads to a concentration in the metallo Koka from the Kokabrenner. 4 The coke is passed from line 21 iu a water gas displacement converter 2 ", where it is with

- 15 109841/1433

1770300

Danpf is contacted from line 23. The hot coke and steam are subject to the well-known water gas verification reaction

C + H ₂ O - «- £. CO ₂ +

If desired, the CO and H ₂ product mixture can be processed further over a gap catalyst in order to generate additional etching:

Hi

CO + H ₅ O> 0O ₉ · »· H

^d 371 <> C (70O ⁰ P) *

The gas containing v.-aseeratbff from the converter 22 is passed through line 24 to the gas cleaning system 1Θ. to remove contamination from known smocks ssu

Alternative processes for the production of H ₂ eeau coca include the partial oxidation process (Hydrocarbon Processing, September 1966, Volume A3, to, 9) ·

A ^r IEIL of the coke is returned from the converter 22 to the burner 4 for V / iedererhitzen through line 25 and the coke is recovered Heat dec-metal Konaentr Koke & ts through line 26 in a .Form. The concentrate contains 10 to 90 gc y .- ^ Vanadiuia, Hiok & l and iron. Coking, coca burning and the waeF, erstoffhoretellungß3Chritte

109JB43 / -U33

BATH ORIGINAL

all serve to reduce the metal concentration in the through conduction 26 ^ evjonnenon concentrate increase. The metals can can be obtained from aerosol coke in a known manner. A typical one Process is described in U.S. Patent 3,226,316.

Write the preceding Bs in; g and the above results, a tendency that the succession of a mild coking, and a nrilden Eyui'odö'julfurierung an extremely effective way to © Hersteilung of Feuerungsölen z \\ manages ß starting materials, the iron very high Sehalt au sulfur, metals and Koksbildern own. If the steps of hydrogen production and the extraction of the concentrate of biscuit and metals are brought into the ancestors, the combination results in an effective, low-cost option for the production of petroleum oils from highly contaminated auegangia materials.

17 -

1098 ^ 1/14 33

Claims (9)

Patent claims: 1J Process for the production of a fuel oil with low a Sulfur content from a petroleum source material with ■ high content of sulfur and calcium carbonate, characterized? that he (1) DO. * Ölaucgangsmaterial a Pließverkokungsschritt at a temperature in the range 482-593 ⁰ C (900 to 1100 ⁰ P) and in the presence of at least 5 · SS ./.- subjecting ¹ / Daanpf, (2) a coked fraction with a reduced content of metals and asphaltene wins, and (5) the coked fraction is contacted with hydrogen and a Hydro deßii.lfurierungskatalysator under hydrodesulfurization conditions and the fuel oil with low sulfur content wins. 2. The method according to claim 1, characterized in that the amount of steam used in the flow coking step is proportionally reduced when the coking pera »door in the range of 402 to 593 ° C (900 to 1100 °?) Er-IVrjht v / ird, whereby the effective distillation intersection point becomes t. .. 18 - ORIGINAL BATHROOM 109341 / U33 4! 3. The method according to claim i or 2, characterized in that over YIiο bverkckuug3step in SegeHiw & rt of 5 bio 100 C-8W .- / S Darpf is carried out. 4. The method according to any one of the preceding claims, characterized in that the coked traction ^{boils above 316 0} C <600 ° f). 5. The method according to any one of the preceding claims, by the fact that the Hydroüeevlfurierurags ^ ato.-Ivf3ator a SaIs e "ie3 Hetalles of the üruppsn VX or VXXX dos periodic system iinü Kisshusgen äavcn a'af oiüeai suitable carrier material. 6. Method nv i?), a print ic Esraich vcu 3i3,2 to 211 kf / ciii ² (500 liis 3C00 p ^ itf) and 122 bib 24ϊΟ kcriüulkuMk-Bidder / m- ⁷ (500 bit? 10,000 SGF / B) oines waes eretoffhaltigon Gases luafc-eeen, 7. Proceed in accordance with one of the previous speeches. characterized in that the öiiius ^ ngsipaterial ninöesteus 1.0 G-evi-? S Schwai'el, n> i.?i (ieBton3 iOO pprMetals and uindeatena contains 5% by weight of asphaltxia. - 19 - BATH 109K1 / U33 3.6 8. The method according to claim 7 »characterized in that the coked fraction has a metal content and an aepbaltous content of less than $ 50 of the metal and asphaltene content άε · 3 C! Aue-gangsm? .Terial3. 9. The method according to claim 1, characterized in that that -Lan (1; uac ö: .a; sj; au, r; i; ^ aterial in einea fluid i3: .erten state coked, (?) a coked fraction that ^{boils in the range from 516 to 621 0} O (600 to 1150 ⁰ F) wins, (3) free-flowing petroleum coke extracts, (4) the coked fraction under hydrodesulphurisation conditions in the presence of a hydrodesulphurisation catalyst and hydrogen is subjected to hydrodesulphurisation, at least part of the hydrogen being generated by feeding the coke obtained in stage (5) to an eocat separator, burning coke with a temperature of at least 760 ⁰ O (HOO ⁰ F) a water gas shift converter üufühi-u UKd dan coke to generate a hydrogen-containing gas üit Daapf ', separates hydrogen from & en other product gases and the separated water content eu the Eydrodceulfurierungstuif; leads. t PS B K 1. '; ί. "· * BAD ORIGINAL