DE2015805A1 - Process for the production of lubricating oil - Google Patents

Description

ÜA-3483

the

Patent application

the

Oll OOMPAWX "
1608 Walttat'Street
Philadelphia, PA 19103, USA. .

concerned

Proceed?! z ur Her ste l development of Sohmi he ö l (priority 3 »April 1969 - No, 813,255 US).

The invention relates generally to the production of lubricating oils with high viscosity index and relates in particular to an improved procedure for the production of lubricating oils with high viscosity sin * des which are stable and high quality,

Various processes have been used over time to prepare lubricating oil feedstocks and other jar oil fractions, including lubricating oil stocks. These processes generally involved either solvent extraction or hydrogenation including hydro-oil ⁰ P) and above treated with a high hydrogen partial pressure on a catalyst * In recent times there has been a growing demand for

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Lubricating oils with high viscosity are «, lisuur ^ jättturloklan · * gen _s especially of the methods sum HydrooraoLan or for hydrotreating, as it is often called, AnIaS BU indicated an increased interest in the industrial application of this hydrogenation process as a method for preparing a lubricating oil feedstock To obtain lubricating oils with an increased viscosity index »Yes, there is at least a reason for this

P sum part of the decreasing accessibility is more natural

Sources from which lubricating oils with high viscosity «index can be obtained by conventional methods irie by solvent extraction * The difficulty of this Market au supply is driven by the growing demand for Lubricating oils with a high viscosity index with even higher Advertise the viscosity index reinforced,

In an industrial process, the solvent used for the extraction is also required

■ k to recover and reuse »because the only one

another alternative, discarding the solvent used represents a major economic loss, ale the Ko Bt β η of the recovery of the solvent. JSine Alternative eu the possibilities indicated (i.e. discarding the solvent after each use or the Purification and recovery of the solvent), which allows one or more process steps to be carried out and which show a noticeable improvement in profitability allowed in this industrial area, would therefore be very

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worth and a sweet treat

We have now found that in one process, a SohBierQlfxaiction ^ which was cracked over a hydrocracking catalyst for lubricating oil, under conditions: under which a shell fraction with increased viscosity index (VX) is obtained * an extraction with a »is subjected to solvent has the preferential solubility for aromatics and this extraction is carried out at a Te tape rat ur and a Lösungsmittelineatζ eindj _{c is} the chosen so that with high selectivity unstable polycyclic ^ aromatisehe structures have been removed and show the obtained hydrocracked lubricating oil products increased stability ? the solvent and the oil extract from the extraction can be used without any purification or separation for the solvent extraction of the crude gas oil or deasphalted residual oils used as feed for the hydrocarbon in order to reduce the polynuclear aromatics content of this material for the hydrocraken.

The figure represents an overall flow diagram in the diagram of the method according to the invention is a more detailed one Description will be given later

Each carried out in the inventive method Lösungemitte! Can ion extract in vullig same Assigns performed as rfehren in a V * nerd * n _t in which in each of the extractions, namely the extraction de «A-Mtzmateriäle for da · Î drocraoken and atabilizing extraction near the Hydroorackan, completely frieche · Löeunge-

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medium is used »You can Stufα des Hydroorackena also be carried out according to any of the Ee hire i oho η be Ice tint en suitable procedures «

To Vsranschaaliohufig * but not ssur .Siiisehrgü kung mentioned examples of solvents that can be used in both extractions process dos invention ,, furfural, acetophenone, phenol, Aceto * · nitrile Kit robe nao I ₅ are AnIUn ₁ 2.2-DiohXordiäthyläther, Di «methylsulfoxy oil or mixtures of these solvents. Sas "pesieHe, choice of solvent will often depend on vereohie ^ which Geeichtspunkten not auIetat from the Wirt8ο haltliohkeit" Allgetcein however, furfural and phenol as Löaongemittel most preferably _0, with the exception of Sohmierölen or lubricating oil fractions having a auereiohend small asphalt "and metal content sufweieen, dae .SiH-satBeaterial must FLIR hydrocracking prior to the first ßxtraktioa

de-asphalted «earth. For sowing materials with relative low »asphalt content, the well-known Duo-Sol extraction process, in which the asphalting and the extraction of the aromatics can be carried out at the same time «Known methods for improving the selectivity for aromatics can be used to advantage on this occasion. Examples of this are the following measures (1) Han ensures that there is a small amount of water while extracting ait furfural, (2) lean works in the lower part of the suitable temperature range for the

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Iiuaungsiaittel and (3) aan leads in & hraro üxtrak with low ratio of Lueungaiaittsl to oil

through or «combinations dxesar measures ends at ₀

'Ma JSstrektioaatöffiperaSttr and the iDiriaatztJtsa ^ ö dee Solvent stsh & n in guaanfinenhang and both the extraction As each, the solvent dosages depend in turn From the gathering of the extravagantKlan special Fraction from «The 'following .iBr3.äuterungön should be in the» |

his Susamaenhang understood «to earth _a

The temperature of all extractions carried out before the byarou ^ ascon must be lower, ala the temperature control temperature of the oil and the solvent so that an extractive separation is obtained. Usually, this temperature must be slightly below the mixture temperature, including a high working temperature with good results 'yields of oil as üineatzmaterial for hydrocracking sivl erzie. \ s ₀ the lower limit of the temperature is in part on the flow g

point (pour point) of the dewaxing insert material dependent. If the ßinaatzmaberial not dewaxed "lurddj, the minimum temperature of the attraction is set to the point ₉ at which solids occur" However, if the extraction temperature is also low, the selectivity of the extraction is also high and the use of collapse measures is necessary. never too high a proportion of the solvent and additional extraction stages required, as otherwise the advantages achieved are too limited. The temperature range that all suitably Vtr-

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Driving constant poratures for all "which includes solvents, is i" general "wisohon" taa "18 ° 0 bio 177 ° C ( ^{0 0} to 350 ° F) > A 52 to 163 ° 0 (125 to 325 ° F) applied * Seüst matt phenol solvent 9in _p , a temperature in the range of about 65.6 to 124 ° C (150 to 255 ° F) is usually preferred;

"Most of the in view of the Bemparatur g · * -

The above explanations also apply to the ratio of solvent to oil used. Since the temperature and the use ratio of the solution are dependent on each other and each of these parameters depends in turn on the raw material used and, above all, its boiling range or molecular weight range * In the case of high ratios of solvent to oil, never even at high temperatures there is a tendency to reduce the effectiveness

P of the process and it "ground lower yields of the than

iSineatematerial raffinates used for the Hydrooraoken achieved «These conditions are therefore to be avoided · Most of the time they have ratios of Solvent to oil ranging from about 6: 1 to about 0.25 Proven to be suitable for 1 · The most suitable, however, are ratios of solvent to oil in the order of magnitude of about 4 to 0 »8 t 1. In the following, these variables are sum better understanding with reference to an exemplary ▲ uefuhrungsfoxm explained how a Legotnedio raw fraction, the Ib range of about 454 to 510 ° C (8 $ 0 bia

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950 ° 3?) Boils, preferably at einar (Ss-inper-ature of about 93 to 121? O (200 to 250 ° P) and a solution dosage in the range of about 1 t 2 volume per unit of furfural Volume part of the η oil to be traded the solvent extract " tion, the fraction boiling over 510 ° C of the same crude oil, which was de-asphalted with propane, is pre-> sometimes with an iCemperatar vob about 107 to 135 ° C (225 up to 275 ° P) and a LöBunosmitte! dosage of about 2 t 1 |

Parts by volume of furfural per part by volume of the au treating oils extracted with solvent. The (850 ⁰ F) boiling fractions below about 454 ° C are generally not _s extracted as the benefits compared to the costs low are "fractions from different crude oils were of course certain changes of these features require ₀

The device to be used is not critical since any conventional device for solvent extraction can be used. ansohaulichung Extraktoreη with rotating disks, Podbielniak extractors and filled countercurrent extraction columns are called. As these explanations show, can the, extraction either ante Uwe ise or continuously be carried out, even if the latter procedure * leadership is generally more convenient and economical and therefore is preferred.

The residue and the deetillate fractions that have been extracted are then used as a conventional solitary animal (for eich or in G «ai« oh with

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other suitable JäinsatzstrBmon) supplied and gacraokt hydrogenating by conventional Bydrooraofcverfahren * In the erfißdungsgemiißen method Mnsatamaterialien can be used with so low viscosity such as 45 to 50 SUS at 99 ° C (210 ° F) "" JSs should be emphasized _f that the aas the Bores known in the art are suitable for the process of the invention, but are unnecessarily limited * The preferred hydrocracking process involves hydrocracking the solvent extracted material at about 343 to 440 ₉ 6 ° 0 (650 to 825 ° P), preferably between 317 and 427 ° C (700 and 800 ° P) for a pressure of about 105ο5 kg / cm (1500 pel), usually and preferably but over about 140 ", 6 kg / cm (2000 psi) and at an hourly space velocity of the Liquid between about 0.2 and 4.0, but usually about 0.4 and 1 * 5. The treatment of hydrogenative cracking is of course carried out in the presence of hydrogen over a hydrobrak catalyst, i.e. a catalyst which has both activity f ( For the aromatic saturation as well as for the ring cleavage, "in" is preferably used as sulfactive (sulfur-active) catalyst. SuIactive catalysts generally include sulfide, some inta-tails of the TI «K« b «ngroup of the periodic table or tin SnI- *

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fid © ines metal of the iron group uod contain se a sulphide of metals dor 71 «soil group of the period * syst ο bis in Chemisch with vain sulphide of an iäieangruppenms «· tallöo For example, one made from tfiükeleulfid is excellent and tungsten sulfide in a metal ratio of about 1 ι 1 up to 4: 1 existing catalyst on an aluminum oxide, Silicic acid or aluminum oxide-silicic acid rager Aue Hydrocraok catalystsa consisting of free metals, such as

• - · t

Palladium on a molecular sieve carrier uad dergleiohsn '

can also be used, but who! «=» ger preferred.

During the solvent extraction following the ^ jrdroorao ^ n it was found that not only the temperature the Järfc ra let ion is important, but also the number of Levels are critical for the desired result to be achieved will, both in terms of sludge formation and Color a possible poor quality to be obtained. The number of stages is, however, somewhat of the order of magnitude Munge of the solvent depends on that these two variables are inversely proportional to each other. If one of them is increased, the other has to be decreased «JSs was found that the mud *» education is essentially eliminated in certain cases when only two levels are used; that jadooh dl desired color properties cannot be achieved if not applied at least about 5 levels or if "LQtungenitteinengen are not used excessively"

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In general ernelean aioh 3 to 10 Stufon as completely suitable and are preferred and most preferred «Earth 5 to 10 levels, and if necessary call more applied as 10 levels η sr de α can «

The ratio of Solvent on oil is not particularly critical and ratios that vary over a wide range can be used.

^ never se be applied «With certain conditions, however, parts of the gate can be achieved» In general, will a ratio of solvent to oil of more than 2-1 does not applied! because the large volume of solvent to be handled makes the process economically viable Versohleohtart and the expansion of Sohmierölprodakt decreased. On the other hand, make ratios less than about 0.25 to 1 a compensating increase in the number of dor Levels required for the desired effect to be achieved will «Preferably a ratio of solvent

™ au oil in the order of 0.5 to 1 · 25: 1 applied

The temperature of course varies depending from the particular one used in a given pail

Solvent * in general, however, a temperature is applied for all solvents used which within the range of about -18 to + 149 ° C (0 ° to 300 ° F) is «To achieve high selectivity, a narrower temperature range within this range must of course be used with each of the suitable solvents« When using the preventive solvent test?

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A temperature in the range from about -18 to + 65 ° C. ( ⁰ ° to about 150 ° C.) can advantageously be used, but a low temperature is preferred. from about 27 to 54.4 ° C (BQ to 130 ° F) «The most preferred solvent eats phenol or ⁵¹ SeIeCtO * (phenol and a mixture of cresols) and the preferred temperature is above the Sohmelspanktee of phenol, that is, at about 41 to 60 ° C (106 to about 14o ° P), although this preferred temperature fluctuated occasionally \

Other examples fOr erfindungsgernöß usable töBungstnitbel Bind same solvent or Iiösungsmittelgetaisohe which are suitable for extracting the Eineatzmaterials for Hydrooracken _s is because the use of the same solvent for both extractions without Zffischenreinlgung an essential feature of JSrfindung "

The direction of the gate that is used to carry out the movement rens can be used does not have to be specially trained

det and any conventional one can be used for this purpose Devices used for solvent extraction are »examples given for ^ on which the process but not intended to be limited, extractors are using rotating disks, podbielniak extractors and countercurrent extraction columns and the like · It is ereloht « lioh that extractions carried out for both inventions were carried out the same «device type can be used ·

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201580S

- 12 -

Under dan örwähntaa devices extractor 'n with rotating discs or extract ions ko Io ans a aar implementation of it £ indungsgemä "KISSING muddled preferred Ea should be emphasized ₉ that the ßxtj? Atetion incrementally or continuously performed kana _s when AUOH the latter The procedure is more convenient and generally preferred is ο The device need not be set up for special pressure conditions, as atmospheric pressure is usually preferred.

When reusing the solvent-extract mixture according to the invention From the stage of product purification for the extraction of the feedstock, in all » mean a certain amount of extra fresh β furfural or another solvent is added, if larger amounts of solution are required for this extraction and in addition, in certain cases, those caused by the in the lungs Medium contained extract reduced Jüxtraktionskapasität Compensate for KU. The combined extracts from the two Extraction processes can gacraoct with the formation of gasoline "According to another embodiment, the combined extracts can be used as an oil additive for rubber * because of the" presence of unstable to UV light In certain cases, however, connections may be a StabilizationBtreatment desirable Legα

a raw material with the following properties was used *

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Density, API ⁰ 32.9 Sulfur, (Jew * $> , 01 ο 26 sns / ioo ° F (38 ° ο) 52o7 Flow point (pourpoint,
⁰ O (° F) -34.4 (-30 * 0) 0 «])« «a? Arbe 22270

The specified iSinsat »material is vacuum distilled the worst faction (which makes about $ 23 of the raw material) deasphalted with propane (oil yield about $ 50), whereby the following fractions can be achieved *

Boiling range

light Vakaaadistillat about 413 to 457? 0

(775 to 855 ° F)

A severe β vacuutade stops about 457 to 513 «0

(855 to 955 ° F)

deasphalted oil about 513 ° 0 and above

(955 ° F and above)

The heavy vacuum distillate and the deasphalted oil are then extracted separately with the contaminated oil from an extraction carried out after the hydro-racking. Since the initial extraction required before hydrocracking greatly exceeds that required for re-extraction, a supplementary proportion of a fresh or purified solvent with the solvent from the new extraction, which has been removed from the re-extraction, becomes unstable Contains materials, missed “This extraction is carried out in the following way!
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Solvent lamp «= - g ^c Baffinat telelnaats. r at or ( 1?) yield

Heavy vacuum distillet 150 ^ 104.4 (220 °) approx De-peeled oil 200 $ 104.4 (220 °) approximately

These factions have roughly the following JBigeno affiliations *

not extracted extracted frac-

gratet loo »η t learn η

Gew. '^ API-Diohte Rüokatand Gew., ^ API-Dicht · aromatics 15.6 0 naoh aromatics 15 _A 6 (60 ° y) Gonradaon (for V)

heavy β

Yakaaudeatil-

lat 50.4 21.9 33

Deasphalt machine-52.4 22.0 1.8-

tea oil 52 _e 8 22.3 1-98 43

The materials mentioned are mixed in the following manner in order to separate out insatiable materials for the hydrocraon

3 ^ 3lohtea Vaktuitodestlllat, <f> 29 _e 1

Extracted, heavy yakuum distillate, fi 24.3 Extracted, tntaaphaltiertea oil,% 46.6

The mixtures have approximately the following properties

API seal, 15.6 ° 0 (60 ° I) 27.7

Beginning of boiling, ⁰ O (° F) 706

5JC 762

10Ji 791

50 * 940

Boiling end 1030

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Template (receiver) j6 67 Conradson residue, Ge «· j6 1« O

Viscosity 71.1 ° C (160 ° F) 35 "47 Viscosity 99 ° C (210 ° F) 14o74 The mixed uses are as follows

subject to the Jydrocraeken *

Composition of the catalyst nickel sulfide "Wolf

ramsulf id in one |

Ratio of metals of about ti 1 on a silica-alumina support

Catalytic converter temperature (average) 399 ° C (750 ° F) space velocity (V / hr / V) I ₀ O

Hydrogen Drack 175 ₀ 8 kg / om

(2500 pei>

Hydrogen consumption (purity 100 $) 28 _e 32 m * per 0 «11924

a ⁵ (1000 SCF / BBL) J.

Pressed 01 from the above-mentioned dewaxing device " processing is then an ßxtrafctor with rotating disks citedj, which contains about 66 discs and has a diameter of 7 »6 cm. The extraction is carried out at a Temperature of approximately 49 ° C (120 ° F) using carried out about 100 percent by volume of furfural, a raffinate being obtained which made up about 97% of the ßinsatematerials added to the extract

The Haffinat then becomes three DaBtiHatfraktion «η

y ■■ 009849/16 67 BAD ORIGINAL

«16 ~

distilled "Hr _c 1 (100 ffeutralöl), Hr ₀ 2 (200 jfcatralöl) * Hr ₀ 4 (500 Heutralöl) in a Bright Stoeko The common" shells of these products, based on the dewaxed materials, have approximately the following values total lubricant ßlauBbe ute (be sheet on volume percent of the mineral material

for the Hydroeraoken) 58 _O 6 ji

VI ₀ - range 105-115

The color of the separated mixture components Sohmier ~ oil fractions _e consisting of a 100 Neutral Oil, a 200 Neutral oils a 500 neutral oil and bright stock consist _s Tariiert typically from about O <.25 to about 3 "0 entepreehend the color test according to ASTM D - 1500 _o

The flow diagram of the process according to the invention is shown in the accompanying drawing in the form of a diagram (the dewaxing has been omitted for the sake of simplicity) and will be explained below. Reference is made to the figure 1 in a first zone 2 ssur läxtraktion the Jäinsatssmaterials for the Hydrooraokon or ο for the extraction before the hydrocracking, in which the Riiokstandöl is extracted, to remove some of the more aromatic materials according to the inventive method »the raffinate with a small amount entrained Solvent is introduced through line 3 into a stage 4 for separating off the iüinsatssmeterials,

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IÖ & sr the solvent is removed, we & _9, for example, takes place as evidenced by distillation. The lubricating oil raffinate obtained from 4 is introduced into the Ifydrocracker 5 and there according to the basic procedure η hydrogenating cracked to The hydrogeeraektβ product is transferred through line 6 to the second extraction stage 7 and the solvent extraction with a fresh or purified solution in the middle.

aatκ subject, to achieve the degree of stability sia, the -

is beachi for such Sactrsktionen * iebenea Verfahrsn desired according to the "The raffinate from constitute second or Prodiikfceztraktionsstttfe 7 (for example a distillation column) introduced through line B in a product" -Trennstuf & 9 ₉ in which the -ferbiggasteUta Schmierölpro "· domestic product of the entrained solvent oil is separated off and obtained separately therefrom. The solvent containing the extract from the second extraction stage 7 is drawn off through line 10 and directly into the first extraction stage

tion stage introduced, This introduction takes place together with a supplementary amount of solvent, which is led through line 11, for example Solvent introduced where the solvent is purified and recovered »The solvent is reused ₉ by introducing it into line 14 and / or line 15» The iirfcraki; and other impurities are withdrawn through line 16 and gain ₀

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Claims (1)

Claims (1 J PROCEEDI η. "Or Herste slope το" high quality lubricating oil with good stability and high viscosity sindax wherein besitet a Sehmierölfraktion with a solvent which bevorzugtθ solubility for aromatics, a first solvent extraction to reduce the Ge "haltes to mehrkernigeη aromatics is subjected, the raffinate aas this fixtrektion under the conditions increasing the viscosity is hydrogeorect and the cooking oil product subjected to the hydroorak is subjected to a second η solvent extraction with a solvent, which has preferred solubility for aromatics, characterized in that one from LQ * eungsaittel obtained from the second solvent extraction with the extract from which nds η lubricating oil present as raffinate is separated and the solvent containing the extract is used to extract the insatamate for the Hydrooraokan In the first solvent extraction. 2 «The method according to spoke 1, characterized in that a Jülnsatsmatarial for the Hydroorackon is subjected to the first Lößungsmittöleitraktion, which aitdet ud einta ViekoBltätilndei τοπ at least« tw * 15 «ufweiet at very than 343 ° C (650 ° F). BATH ORIGINAL 009849/1667 3 * The method of claim 1 or 2 _g in in ,, that dae raffinate obtained by the first solvent extraction at a temperature in the range of about 343-441 ° C (650 to 825 ° F) at a Waseerstoffpartialdruck of at least about 105o5 kg / cm (1500 psi) in the presence of a Hydro era cir-Kat a Iy eater at a space velocity in the range of about 0 * 2 to 4 * 0 hydrogenating crackto 4 * Method according to claim 1 to 3, characterized in that that the first extraction ion in the range of -18 to + 177 ° C (0 to 350 ° F) is carried out * 5 «Method according to claims 1 to 4? characterized,, that furfural, phenol, acetophenone, acetonitrile, nitrobenzene, aniline, 2,2-diehlordiethylether or dimethylsulphoxide are used as junction solutions β ο method according to claim 1 to 5, characterized in that that the entire Schmiaröl-Fiineatmaterial for the Hydro- j orracks previously subjected to solvent extraction will. 7 "The method according to claim 1 to 6, thereby rewarded, that the Hydrocrackoa is carried out in the presence of a Hydrocrack-KatalYsatos, which is a metal of group VI B or VIII B, an oxide or sulfide of such a metal or a combination of such metals or metal compounds contains 8. The method according to claim 1 to I _9, known, «is worthwhile that mall the hydrogeoraoct product at least twice 0098V9 / 1667 at a Temperet or Im Berti oh vott -18 to + 65.6 ° C (0 to 190 ° 7) btl a · »Otauiiftfclttel« α oil content from ttwa Oo25 t 1 to 2 t 1 »radiated, 9 · Method according to spoke 1 to 8, characterized in _{that there is no t p} that mn the B ^ drooraoton under milder Oeeanrtbediog- $ en asle the corrrentionelle Bördrooraoken of the lubricating oil in question inaatraa te rial "Darohf UhTt ₀ 009849/1667