DE1545291A1 - Process for the production of a low-sulfur heating oil - Google Patents

Description

Alfred Hrepp ^ ner _ΛΛ _

Dr. Hans Jo.fiί.Γίν.ΌΙίί Zi Sep. 1966

Dr. Hans Chr. Beil

Frankfurt a. M.-Höchit Adtioutrafr 51 Tel 3124 49

Unaere no. 13 068

Ε330 Research and Engineering Company Elisauetn, r «". J., V.St.A.

Process for the production of a low-sulfur heating oil.

The invention relates to a multistage method of manufacture a sahwefelarintm fuel oil aua hochsch.vefelhaltigen Crude oil residue fractions that are used as heating oil in industrial furnaces, especially those that are located in factories in or in located near urban areas, is suitable and that includes HF treatment, coking and hydrodesulfurization.

Sulfur is found in petroleum in the form of mercaptans, sulfides, Disulfides and all part of substituted rings, of which thiophene, benaothiophene and biuenzothiophene die are typical representatives. Mercaptans are found in the lower-seeding factions, and so have been a number aaier process developed to remove them or put them in

BATH ORIGINAL

900848/1089

To convert mnulfides. DIl tin ζΐ <■■>. raun./, from ';-_> .. efol us the higher ..boiling Jc-.ix ". Ι.ιηοη iut JQ-iooh /.'si'unt ii. · ■ :: -.,. L ri ^ er. Here lio *. '. t aer Jchv / ei ^ l zum. "rebuked ^ jil in 7 / eril.; he responsive Forir ^ n before, ζ.'ά. : -Λ ;: sulfides, li-.v.Lfi in and al ;; Part of f3uo .-; tit.ii- ^r 'rten iiin ^ un .vie Ttiioihen-n, BenzothJ-Ophenen and Jicünzotriioi nenen. Lib ^ e jirL-ü. of Or ^ Mno; soii / bf ο! connections la; - .; en r> LcL anyvendüary 7 «rfahren nicnt,; j ;; tfernen. ! 'Jxti'akLiwnjvfH'i' are generally not toL'rieJenijtellönJ, in Uwe ;;. ;; Fractions .vie RohölrLuiK ^ tandafraktionen uinei. ;; our high percentage schvvefülhult; i. _: ; he remove molecules. As a result, the yields are united; "-Simple undesirably low.

Metalliöche Impurity-.arLjijn, v / ie zj liickol- am verbinaun ^ en, vveruen as nor ... aie Buatanu leilü in p all crude oils ^ efunaen with Je.a aaphaiti.chen and / oJer a3phaltenic part of rfuholj uii ^ houe: n Gor.:-; d.; on-carbon adsociated aind-, .Ver.u daj -iohöl zur i.nri'ernun «aer leicihtsn, below etv / a ά '/ 2., 2 bia 343, 5 G victorious fractions kopilestilli & rt .viri, Concentri'jrcjrx uich the metals in the Hliokstand. AuiierJeri; may contain the external links. 3o? / Ohl ais ^ .etalle, the Koköbilaner as well as oticKstoffverbindun ^ en beyii.fl all the catalysts naonteilig, 'Nenn üer.-Tucicrjtan-j treated wira. They also cause fjchlechto ileizöleigenschaf th in Ind us tr ie Ö £ s by Kok, - αη-Λ ocnlaLMubildung and aurch corrosion of the tie ta Hf laugh les oven.

The aim of the invention is a method for producing a Low-sulfur neizöls, the aujjerdeia have a low content of nitrogen and metals and that is a powerful and economical multi-stage process for production of a heating oil made from crude oil distilled overhead.

909848/1089 ^{BAD 0R1G! NAL}

May nrfii.jv ·. ». .. 'f ...,;! ... υ Vucfu ^ risU u:; ii'a..L> t.-tux * ;:.; i, S'i Λ (-ie an' -r lhanu <· .. ·.: '"OL-on.ten Vtr raiireiuiitafe .. .i'-r K / ir-iktion afs ito ^ i ton λο1ι ·" 1 ■ · ».it ueh ^ zu wa-i ^!: -) ßr "ivupi 'ifluorwaij.ei'. 'itoi'fipure, / üi'iüKun i" u extracts. ·, ji ,; ix'ofjht.actiwefelun ^ der verLoKt'iii j jU. · i jictiit una! mix jef; fly jroenti-ch.ve-f r?] th .Jt-üiTa 1: 1 jt J oil. .-. u L * * ■ 'Lii'i L der .iP-ii'mnri is anguK

Diu iri'iiiclUM «; We u. ciujv'i die i. "'3i. ^Y fji" *: ^r te /.eier now ₍ ;, di «a:''j ie» if3Oiiu! i: ii «ii. · r Auafiiiirun ^^ - fcrii aet: VerfaxirenH .iarüteilt _f ei '''eruj.i-ΐΰΐ ¹ iir.!; ¹ ;, rubbed.

The .'ier.j;'! :: i ^F ar T hesseieiiuet a Zufülirungsleitun .: ^T, by aie art ¹ liüouisuxi.vefuilialti '' KS HLicK53tand. .viru Joel directed to the ii-F-Dxtraktionuiionu ζ. ßer AUHciruek huciiijcnv.efelh. '. iti /; in acx · νjx'lie ^ ^ eiiaen Bescnreibun uiiii'a. liraclboHcliickunjLn st, the Mohr) as a 2 wt .. organic Ücii.vefelverbindun ^ en, column containing 2 to 10 (The '· ".-,.. Sulfur, before Ku ^. '^' - some contain 2 to 6% by weight of sulfur, can be processed with a heating oil with less than 2% by weight of sulfur, preferably less than 1% by weight of sulfur Oils containing 2 to 4 parts by weight of sulfur can be made into a heating oil that contains less than 0.5% by weight of sulfur, and such low-sulfur heating oils conform to most government regulations.

Suitable feed materials are e.g. heavy unprocessed crude oils, residues from atmospheric distillations, Vacuum residues, visbreaker residues, deasphalted oils and refinery cycle oils. If necessary leave highly viscous oils with a light dilution oil blend or dilute to a suitable viscosity or specific weight, so that they can be intimately mixed with the HF. The preferred Loads are residues from atmospheric

BAD ORiQiNAL

s 0 9 a 4 a / 1

Distillates that result in the formation of a bottom fraction, which • an Anfungüaiedebi
be distilled.

• has a starting point of 260.0 ° to 543 »3 ° C,

Almost water-free HF or hydrofluoric acid .vird is introduced into the extraction zone 2 through the line 5 and brought there together with the oil charge in the Geenotrom. The ratio of Hi? ¹ to Ül is up to 150 wt., 0, based on the Ül- The contact time varies between 2 and 180 minutes, preferably between

φ 20 and 60 minutes. The pressure in the contact vessel fluctuates between 1.4 atmospheres and 70.3 atmospheres, i.e. there is pressure which is sufficient to keep HF in a liquid state. The temperature in the Koritakt vessel is preferably in the range between 37.7 and 176.7 ° C. The contact can with a mechanical stirrer or the stirring can be carried out by means of an inert (Jase. If necessary can the contact vessel with inert packing such as Raschig rings or beryl saddles must be filled. The contact vessel can, however, also be equipped with trays, plates and inside Be provided with baffles. Any known means of Ensuring intimate contact between the oil and the HF can be used. Instead of a countercurrent

W contact can also be a Miech-settling system are applied.

The raffinate from the extraction stage is through the line 4 to HF stripper 5. Stripping can be done by releasing the pressure until the HF is out of solution boils, or in any other suitable manner. HF is in the HF contact zone through the Lines 6 and 3 returned. Line 7 is a Low-sulfur heating oil, which is made from about 60 to 80 wt.Tfc of the in the feeds introduced into zone 2 are deducted.

9098 /, 8/1009

BATH ORIGINAL

1 5Λ529Ί

The HJP-Ex tract, which consists of about 20 to 40 wt ./> of the in the. The feed introduced into zone 2 is withdrawn as a bottom fi'action through line θ and passed to stripper 9, in which the HF is discharged at the top through line 10 and returned through lines ό and 3 to the contact vessel 2. The Bxtx'akt in line θ evacuates the main part of the organochromes ο Iv bindings and iJetalle, which are present in the charge led to the HP contact vessel 2.

The data for a typical invention HJP extraction is shown in the table below. Dieae data obtained in the extraction Onea Huck "Tanda a atinoaphäriachen distillation Onea weat TexauJla with 100 ft Hf (be2sogen on feed) at 93.3 ⁰ C.

Table I. Feeding raffinate extract

Yield, fo

apezifischea weight, ⁰ API Conradson Kohlenatoff, ßew. ^ t sulfur, wt./ί

Vanadium, 'file / Million T.

Nickel, PartsAlillion Parts

The above extraction is carried out in one stage. Improved Results can be achieved through multi-stage contact process be achieved.

is can be seen that daa Haffinat now contains 1 fi sulfur and requires no further treatment for most uses of fuel oil. If necessary, it can

100 74 26th 19.5 23.7 1.2 5.5 1.8 20th '2.2 1.0 5.0 24 0 95 12th 1 46

BATH ORIGINAL

909848/1089

whole or part aea iiaffinata x.ydroentsoh. '. oi' ^ it be. The extract contains the greetings l'eii ier bilJner, aeu Jchv.ei'elfj, aer ..stalle to connect the btio. jJieuer 3toif is led through line 11 to iie Verkokun ^ ühiila ^ e 12. The appendix 12 ijt vo: iiu _t ; aweiae an iluiaverkoker, it kar.n however au: n ο ine delayed coking werutm applied. In the case of a "fluid coking the temperature i: .i liuuittor between about 482.2 ° and about Dy1.7 ° C, vorzugcTAoiae ζ.ιίιιαηαη oW _f 0 ° and i) 32.2 ° G, superheated ./a. 'jr: erda.! i [jf .in ir. ale coking plant through line 13 in an amount between about 5.71.4 to 17.3 kg / hl.

The coca particles are withdrawn from the plant 12 through the line 14 and mixed with air, fed through the line 15 and aie orhuity-ne Juapenaicn is introduced into the combustion _{and the} like; vessel 16, in which at least a portion the Kokoea win burned to raise the temperature of the coke particles to increase to a .7ert, uer 55.5 ° to 138.8 ⁰ C above the temperature of 7ericoKun-; is ureaktors. The temperature of the / arurennun ^ K ^ efäJes is about 565.6 dIm 67o, 7 C. The pressure in the coking ag ef.-ii 12 and deu Brennun ^ K ^ efäli 16 is about 0.7 to 4, 22 atu. Through the conduit 17 .verdeii new iCokateilcnen from the combustion ag ef AEII ac ^ ezcgen and Verkokunfiogeifäu in a Llenge returned sufficient in dieaem öefäü the desired tempera door orhalten. The particle size of the fluidized coke particles is between about 30 and 600 / rev, with the average particle size of 75 to 200 / rev. Verbrennungagase leave the burning vessel in the head through the line 18 and can £ for heat exchange uses v / ground. Excess coke is removed as product through line 19.

ORIGINAL BATH 909848/1089

The dan.rf J ";_ri.ii;; un I'roduutu j he V \ nv..cKun _t _ * γ" ground to the top of the / erKükaii ^; .. _o iif ^I: i; it auroh 1 2, Line 20 atj ^ u ^ ogen and to the üV: .iiitiünier _£ ; ef \ Ü 21. Ef. '. Iirt, in order to separate them from the "Vüi'itokuriiju.'Gf;! I-koiiiuenuen Dilaofo into the desired JTraktions au . A yes fraction is withdrawn from the JTraktiuniergiif IU at the head through line cZ . This gas can be passed through a hydrocarbon cracking plant and an erorming plant, in order to extract the gas from it. A Japntho fraction can be obtained through line 23 weruoji. The ^ ro..te toil of the product aas dem YerkokungL - .; cif-iß vvirj through the line 24 to the Hydroentüch .-- ofcluno ^ zone 2'j . iOie i3ei = chickun (j for the zone " d ^l j is urn: on cocoa-formers, that is, coliles <vase substances with a high Conraddonic carbon content, on metals and nitrogen compounds. As a result, the hydrogen-evaporation catalyst can be used for a long time without ionization A further advantage of the liF-flehanalanß and coking before the hydro-desulphurisation ... lies in the fact that the charge for the desulphurisation is smaller and less 7 / hydrogen is required.

Lie Hyaroentaohumung is carried out under mild conditions. Actuator temperatures between 316 and 427 ⁰ C and pressures between 35.2 and 141 atmospheres are used. Wa jseratoffgas is fed through line 26 at a rate of 173 to 86 a m '/ m ⁵ ul (1000 to 5000 hours cu.ft. per bbl). The hydrogen is through the pipes. 27 and 26 listed. The ul is fed to the reactor at a rate of 0. p to J _t 0 vol./vol./h, preferred catalysts are 5 to 1 x 5 wt.5 »molybdenum oil on porous clay and mixtures of cobalto; : yd {':> to G weight'; «) with Mo Iy bd an oxy d (6 to 12 Sew .-- ^)

BATHROOM ORIGlNAt.

909848 / Iüθ δ

on adsorbent clay. Just as well Ιβκηβη yourself ■ Catalysis authors use nickel, chrome earth, platinum and, Volfrain in j? ona of metals, oxydon and sulphides Contains clay, charcoal, Kieeelguhr and bauxite.

A _{gas containing H 2} and H 3 is withdrawn at the top through line 27, and the H ₂ S is removed by a customary process, for example by washing with amine. The washing device is not shown in the drawing.

The low-sulfur jeiz oil is removed through line 28 and mixed in line 7 with the raffinate from the IIF treatment plant. If necessary, the geoaml-e or part of the raffinate in line 7 can be conducted through lines 29 and 24 to the hydro ent fi ohwef ο lung stage. The letz ^J ere Auafiihrungßform provides a fuel oil product with a auiierordentlich low sulfur content,

In a specific embodiment Fortn be about 1635 m of a residue of atmospheric distillation, eggs above boiling from about 260 ⁰ C and has a specific gravity in accordance with API of about 19 "6 per working day, continuously introduced into the lowermost portion dea RF contact vessel. 2 The feed contains about 2.2 w / o sulfur, about 0.4 w / o nitrogen. Liquid HF is continuously fed to the uppermost section of the contact vessel at a rate of 1308 m / working day. The extraction is atd and using a contact time of about 4-0 minutes carried out at a temperature of about 93 "3 ⁰ C and a pressure of 10.5 etv.a. About 80 Vol.jS of the oil (1308 m ⁵ / day) "This raffinate withdrawn at the head boils at about 260 ⁰ C and contains less than about 1; ί sulfur. In the stripper 5, the HF is stripped from the raffinate by reducing the pressure to about 1.4 atmospheres and increasing the temperature to about 176.7 C. The HF extract fraction containing the

909848/1089 bmü original

. grb'jfcen leil of 3chvefela, major metals and Ütiokutoffverbindungen and h "hen Conradson Kohlenatoffe UNT holds, is from ¹ -contact ii i; ⁱ withdrawn ef ISS with a Geaehwinligkeit of about 521 m / day!.. The extract has an Aufangaiedepmkt of above about 260.0 ⁰ U. Ouch your extract v.'ird that rii? by lowering the Dra. * ka and Lrhitzeri a;) _t ; eatrippt, and the Hi? -i'reiö 3to £ f v. 'is fed to the coking ugefäi 12 with a carcass binding of 327 m / day. The, Yirbel.> Ciiichtverkoker works at 521.1 ⁰ G and a pressure of 1.05 atm. Water vapor is fed through line 13 at a speed of 138.7 kg per liter; for the coking process. The coking vessel contains about 4 kg of coca particles per coke .. ^ about 20 percent of the coke are burned in the Verbrennungagefäß 16 to the Verkokungsgefäß ./arme supply air is supplied through line 15 to maintain the combustion in the combustion vessel will be about 285 m material per Ta _t;.. from the head of the coking vessel to the fractionator 21. About 6 36 of this material are removed at the head al-Ί (Jao and petrol

■ 5
de-distilled. About 265 m! Of material per Ja ₀ * is fed through the line 24 to the Entachvveielunga installation 25. Dieaea Beschickungamaterial.enthält less ala about 10 parts / million parts LIetalla and has a Sch; .efel *; ehalt of about 5.5 G-ew ^ S "The Entachwefelunj is with one of GoO.MoO, Al ₀ O. existing catalyst at: 55G ° O, / pressure

^ 3/3

of 105.5 atmospheres and a / asaerstoiT quantity of 690 m / m

carried out. The entachy / efelte heating oil, which contains less than about 1.0 ge cer a la about 1.0 Gev. ^; .; o 5 -'-: ... a £ ol and very we-rii ^ «ietalle and äticKatoff revealed.

ü'aculeute on diejeiü (it'oiot can opti: .. pillars Beachickunc ^ ^ eaohZZindi Lyitoii uni deain _"to:: or;.. ':. r the Verfahrensanlacjen far the respective feed in dependence on the iiigur:. ;; enaf th der Deuchickun.-i

The skifenweiue dearueitun ^ j eined hoohachvvuf3i..aiLi ^ '. In Rückcitanda by ilP-Extrui: tion, VurKokunj um tlj λ ro ent achv / efelunt; to the one in uur doach-spelling. »ui.-je solves the scruples uei of the verbs! er.m. ·· of heating oil for mouern; Anfaruerun _r je :. on / irkHame una ..irt3 - .; n * .: 'tlicjh <i way.

BAD ORIGINAL 9 0 9 β / »8/1 0 8 9

Claims (1)

Pa t, t; ( 1 ./ Vorfanrun :: ur production- eiineii acli .-. Ofu! Poor heating oil by ku ta!, "Ti: -ehe IlyarOGntüem.ef elan ^ ·, thereby £; ekenn - /. Cich'iCit, lix.i ait; catalytic to n ,, iroent3c \ i. \ uf; l ι do: es chi clean, - before'jei.anuelt, by ruan a hcch-.j (!: i, '(3l'elhalti ;; · ;. "-, rjölriickatan ι in aufoinanJeriOl ^ enüHii stages with flii: j., I, eui iIP exti \ ihiort, HF from the extract auistrii t't, the extract coked, uio under ütwu 'iyi _% 2 G nieuendu frakti -ju separates from the top products of the coker un ■: α - ..;: r'icu.itäiiui ^ e Kopi'projukt des Vei-kukurr; üls iieri.'aiolcuiii 'fiii * the catalytic hydro desulphurisation ver. venaut. c. VGZ'fahron according to claim I ₁ dadurcf. This indicates that the raffinate is stripped from the HF and the tract and the Head per iukt deu coker with aem iiaff inat. Veruiiu the mixture as a feed for uie katalytinche Uy d x'o e η ι ϊ. ch ν: ef ü 1 ung ν e rvv end et. Method according to claim 1 or 2, characterized in that that the hocusulfur-containing residue is added liquid UP in a üegenatromkontaktzone in intimate Brings contact, separates a Haffinat phase on the head that Feeds extract residues to a coking zone, the residues coked under coking conditions, the top product of the coker supplies a distillation zone, which distills off the 23 ^, 2 ° ö-praction air head, the distillation residues a desulfurization zone feeds, ^ ie Deatillation residue in the presence of an Entechv.'efelungskatalyrja toru and 'V / asseratof f desulphurised, which de-LjGhwufelte Product wins and with the Rafüinatphaoe removed from the head under formation of its low-sulfur heating oil mix t. BAD ORlGiNAt 909848/1089 Process according to nii ^ pruch 1 to 3 »dadur-jn characterized, that one. üruö! backlog with a.Ti Seualt from 2 to 10 Grew.fi Scir.vefu .. and Or ^ cnombtaliverbinauri ^ en used, the contact between this residue and HF at a Temperature z "laugh '57, B and 177 C takes place, the coking The extract at a temperature between 462 and · ^ [? 1 ° 0 and a pressure zwiychan 0.7 and -, 22 ata and the decision of the back stanai./en head product of the coker at a temperature between 316 and 427 C, a pressure between 35.2 and 141 atmospheres and a fuel inlet speed between 173 and 866 m / m 01 by eh.j e leads weα. For Esso ran: tarch and iin ^ ineering Company ι
Lawyer 9 0 9 8 k 8/1 0 8 9 BAD ORSGlHAt