AU2491601A - Selective re-extraction of lube extracts to reduce mutagenicity index - Google Patents

Description

AUSTRALIA

Patents Act COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: Mobil Oil Corporation Actual Inventor(s): Anagha Avinash Gupte, David Owen Marler Address for Service: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: SELECTIVE RE-EXTRACTION OF LUBE EXTRACTS TO REDUCE MUTAGENICITY INDEX Our Ref: 638553 POF Code: 451357/278160 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): -1a- SELECTIVE RE-EXTRACTION OF LUBE EXTRACTS TO REDUCE MUTAGENICITY INDEX This is a divisional application of Australian Patent Application 61551/98 the entire content of which is herein incorporated by reference.

Mutagenicity of a lubricating oil extract, useful in ink oil and process oil for tire manufacture, obtained by solvent extraction of vacuum distillates or vacuum resids, is reduced by selectively re-extracting the lubricating oil extract to remove 3-7 ring polynuclear aromatics.

Solvent extraction of lube distillates and de-asphalted oils with furfural or Nmethyl pyrrolidone (NMP) is utilized to remove the 2+ ring aromatics and heteroatoms, resulting in improved thermal and oxidation stability of lubricant basestocks. The aromatic-rich lube extract "by products" from the solvent extraction process, such as furfural extracts, derived from vacuum distillates or vacuum resids 15 possess unique solvency properties that make them ideal as process oils for rubber and ink oil manufacture.

While bright stock or residual aromatic extracts derived from vacuum residuals are typically non-carcinogenic, solvent extracts derived from neutral distillates are among the more carcinogenic products produced in the refining of petroleum.

Recently, there has been growing concern over public and worker exposure to the polynuclear aromatics (PNA's) from distillate aromatic extracts (DAE's) used in the tire industry. Untreated lube extracts derived from vacuum distillates have been demonstrated to produce a number of tumors in mouse skin painting bioassays, and as such they are labeled "May Cause Cancer" in the European Union.

The mutagenicity of lube extracts is believed to be a function of the 3-7 ring polynuclear aromatic content in the extract. Due to concerns or worker exposure to these carcinogenic extracts, public exposure to road-side tire dust and used tires, the European tire industry is interested in converting from using the currently available toxic DAE's to non-toxic DAE's.

Since petroleum refiners that market these products must provide labels outlining potential risks associated with the use of these products, there is a significant incentive to upgrade DAE's to make them non-carcinogenic.

The EU utilizes the polycyclic aromatic (PCA) content of DAE's as an indication of their toxicity, as measured by a gravimetric test, IP346. For treated DAE's the EU W;\:\fion\NKIBSpccies\Div of 61551.doc WO 98/44075 PCT/US98/02562 -2requires the PCA content of the product as measured by IP346 to be below 3 weight% for non-toxic labe'ing.

The mutagenicity of petroleum distillates may also be measured on a Mutagenicity Index scale via an ASTM-approved procedure called the Modified Ames Assay, as described in "Predicting Carcinogenicity of Petroleum Distillation Fractions using a Modified Salmonella Mutagenicity Assay", by G. Blackburn, Cell Biology and Toxicology, 2, pp. 63-84, 1986 and U.S. Patent 4,499,187, the entire contents of which are hereby incorporated by reference. Current policy in the U.S. is that the measured M.I. must be less than 1 for non-toxic labeling.

10 As will be evident from the following examples, a PCA content of 3 wt%, :according to IP346, does not necessarily equate to a M.I. of 1. It should be noted that the EU requirement is a regulatory one, while the M.I. is based on an empirical evaluation of mutagenicity of samples.

Conventional vacuum stripping of DAE's has been demonstrated to be ineffective in reducing PCA content below 3 wt%, since the boiling points of many of the PCA's fall within the same range as that of the desireable components of the process oils to be produced. Likewise, oxidation of PCA's to reduce toxicity has been shown to be of limited effect. While some reduction in M.I. can be obtained by oxidation, the reduction is insufficient to bring the products within the non-toxic range.

One method of treating process oils to reduce the PCA content is described in EP 0 417 980 Al. wherein process oils with an aromatic content of more than 50 wt% and a PCA content of less than 3 wt% are prepared from a primary extract of a lubricating oil distillate by re-extracting with a polar solvent in a counter-current extraction column, such that the volume ratio of the primary extract to the polar solvent is in the range of from 1:1 to 1:1.8. Notably, the polar solvent used for the re-extraction is the same solvent utilized in the initial extraction step.

Disadvantageously, according to EP 0 417 980 Al, the temperature in the head region of the extraction column must be at least 10 0 C higher than the temperature at the bottom of the column, requiring careful monitoring and control of column temperature In differentials.

-3- Therefore, it would be desirable to develop a method of treating lubricating oil extracts to reduce the PCA content below 3 wt%, without expensive equipment for temperature monitoring and control of a counter-current extraction column.

The above discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed in Australia before the priority date of each claim of this application.

Throughout the description and claims of the specification the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives, components, integers or steps.

Summary of the Invention II..l: It would be desirable to reduce the mutagenicity of a lubricating oil extract, useful in ink oil and process oil for tire manufacture, obtained by solvent extraction o of vacuum distillates or vacuum resids, by selectively re-extracting the lubricating oil extract to remove 3-7 ring polynuclear aromatics.

It would also be desirable to reduce the mutagenicity of a lubricating oil extract by selectively re-extracting the extract to remove 3-7 ring polynuclear aromatics in a counter-current extraction column, without expensive temperature **monitoring and control equipment.

It would yet even further be desirable to reduce the mutagenicity of a lubricating oil extract from a solvent extractor by a low cost addition to an existing unit.

In one aspect the present invention provides a process for reducing the polycyclic aromatic content of a lubricating oil extract obtained by extracting vacuum distillates or vacuum resids with an extraction solvent to form a lubricant oil extract mix, comprising: mixing an anti-solvent with said lubricating oil extract mix to reduce the solvent capacity of said extraction solvent while increasing its selectivity for polycyclic aromatic compounds; and cooling the mixture to facilitate phase separation of non-toxic components from the toxic polycyclic aromatic components.

W:\Ion \NKI\Spcis\Di of6155 I.do WO 98/44075 PCT/US98/02562 -4.

Brief Description of the Drawings The above and other objects, features and advantages of the present invention will be better understood from the following detailed descriptions, taken in conjunction with the accompanying drawings, all of which are given by illustration only, and are not limitative of the present invention.

Figure 1 is a schematic illustration of an apparatus for practicing the first and 10 second embodiments of the present invention, wherein a counter-current extractor is provided with a secondary extraction solvent.

Figure 2 is a schematic illustration of an apparatus for practicing the third embodiment of the present invention, wherein an anti-solvent stream is introduced into a o.

stream of a primary solvent extract.

Figure 3 is a graph which illustrates the effectiveness of conventional vacuum stripping in removing PCA's from DAE.

Figure 4 is a graph which illustrates the effectiveness of selective re-extraction according to the present invention, in removing PCA's from DAE.

Figure 5 is a graph which illustrates the effect of multiple re-extractions on Mutagenicity Index of the extract phase.

Figure 6 is a graph demonstrating the correlation between measured M.I. and the relative PCA content of various DAE's.

Detailed Description of the Invention Further scopeof applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the an art from this detailed description.

WO 98/44075 PCT/US98/02562 According to the first and second embodiments of the present invention, a process is disclosed for reducing the Mutagenicity Index and/or the PCA content of a lubricating oil extract by re-extracting a lubricating oil extract with a second extraction solvent, different from the first extraction solvent, to form a secondary rafinate and a secondary extract mix; separating the secondajy raffinate from the secondary extract mix; and separating the secondary raffinate and the secondary extract from said second extraction solvent.

Fig. 1 illustrates an apparatus for practicing the invention of the first and second embodiments of the invention, wherein a counter-current extraction column 10 is fed with 1to a stream of a primary extract mix 15 recovered from a conventional solvent extractor, •said primary extract mix being composed of a first extraction solvent and a PCA-rich lubricating oil extract. A stream of a second extraction solvent 16, different from the first extraction solvent and having a higher dielectric constant than the first extraction solvent, enters the counter-current extraction column 10, and selective re-extraction takes place within the column. A secondary raffinate stream 20 is separated, which is composed of a PCA-depleted lubricating oil extract, which may be separated from the remaining extraction solvents by conventional techniques, such as distillation or flash-off, and utilized as the desired products discussed above, a non-toxic ink oil or a processing oil for rubber manufacture.

The PCA's which are removed by the selective re-extraction process exit the counter-current extraction column 10 in stream 19, along with a major amount of the secondary extraction solvent, which may be removed by conventional techniques, such as distillation or flash-off, and the secondary extractioT! solvent thus recovered may be recycled into the system.

Typically, the primary extraction solvent is one used in conventional solvent extraction techniques, such as phenol, N-methylpyrrolidone (NMP) or furfural.

The secondary extraction solvent is selected to be different from the first extraction solvent, and is selected to have a higher dielectric constant than that of the primary extraction solvent. Suitable examples of a secondary extraction solvent within the scope of the present invention include, but are not limited to dimethylsulfoxide (DMSO), sulfolane and propylene carbonate. The dielectric constant of the secondary WO 98/44075 PCT/US98/02562 -6extraction solvent may range from about 20 to 80, depending on the dielectric constant of the primary extraction solvent.

Additionally, the secondary extraction solvent may be a mixed solvent, so long as the dielectric constant of the mixture is greater than the dielectric constant of the first extraction solvent. Such mixed solvents include, but are not limited to NMP/water, furfural/water, NMP/ethylene glycol, furfural/ethylene glycol and DMSO/cyclohexane.

The dielectric constants of some representative solvents are as follows: TABLE 1 solvent tcmp °C furfural 46 I1C ,1 41 20 0

C

phenol 9.8 60 0

C

propylene carbonate 65.1 25 0

C

1. sulfolane 44 25 C ethylene glycol 41.2 water 77 25 0

C

triethylene glycol 23.7 23 0

C

S.DMSO 46.6 25 0

C.

The polarity of the solvent is related to the value of the dielectric constant; therefore, the higher the dielectric constant, the greater the polarity of the solvent.

Additionally, as is evident from the c values of furfural, the value of the dielectric constant is sensitive to changes in temperature. Generally, an inverse relationship exists between dielectric constant and temperature, such that as temperature decreases, the dielectric constant of a given solvent increases. Therefore, one manner of adjusting the dielectric constant of the secondary solvent according to the present invention is to cool the secondary solvent, thus raising its dielectric constant.

In a third embodiment of the present invention, illustrated in Fig. 2. an antisolvent stream 16a is added to the lubricating oil extract mix 15 exiting the solvent extractor (not shown), which is cooled by a heat exchanger 17 The thus mixed anti-solvent/lubricating oil extract streams enter the a settling vessel 12 wherein they are separated into a PCA-lean phase 20 and a PCA-rich phase 19, exiting the settling vessel.

WO 98/44075 I'CT/US98/02562 -7- According to the third embodiment, the anti-solvent is selected such that it decreases the solvent capacity of the primary extraction solvent, but increases its selectivity for PCA's. Suitable anti-solvents are necessarily limited by the nature of the primary solvent. For example, when furfural is used as the primary solvent, ethylene glycol is a good anti-solvent. Other suitable solvent/anti-solvent combinations are: NMP/water, furfural/propylene carbonate and furfural/sulfolane, for example.

As can be understood from Fig. 2, the materials necessary to effect the third embodiment may be easily added to existing solvent extraction systems, at relatively low cost.

10 According to the process of the present invention, the solvent treat, i.e. the volume ratio of secondary extraction solvent:lubricating oil extract, may range from 0.2 to 2, more preferably from 0.3 to 1. Advantageously, the solvent treat may be reduced substantially by lowering the temperature of the secondary extraction solvent, which provides not only a benefit in using less solvent, but also generally increases the yield of final product.

"The temperature range for the selective re-extraction of the present invention may range from about 0°C to 100°C, preferably from about 20 0 C to 65 0

C.

When utilizing a mixed solvent as the secondary extraction solvent, the ratio of the solvents may range between 99:1 and 1:99. with the relative concentrations being selected according to the dielectric constant of the mixed solvents.

According to the third embodiment of the present invention, the ratio of antisolvent to primary extraction solvent may range from 1:99 to 99:1, with the relative concentrations being selected according to the dielectric constant of the solveni/antisolvent mixture.

EXAMPLES

Batch extractions were conducted on two different DAE's: a 700 S.U.S. (700") furfural extract and a 450 S.U.S. (450") furfural extract. The extractions were conducted at differing solvent treats and temperatures and were performed in a 1L 3o jacketed glass extraction apparatus. Some samples were successively extracted with fresh solvent in order to simulate cross-current, multistage operation WO 98/44071 The relevanlt chcmical and phlysical paramneters of the IWO I)AE's were measured prior to re-cxtractiofl in ordcr to provide an appropriate baseline for evaluation of the inlventive process. Thc initial para nicters the DAE's arc presented in Tablc 11, below.

PCT/US98/02562 WO 98/44075 TABL JiE r r r r

API

Pour Pt, F Sulfur, wt% Nitrogen, ppm Basic N, ppm kv 40 C, cS kv 100 C, cS 1BP

EP

wt% Aromatics Mono-aromatics Di-aromatics Tri-aromatics Tetraaromatics Pentaromatics Aromatic Sulfur Compounds Unidentified Aromatics Mutagenicity Index PCA by IP346, wt% 700" lxtract 8.45 53.2 4.8 2300 1983 36.76 685.6 797.5 843 910 944 1016 1097 89.3 14.3 14.3 10.0 5.1 12.3 11.7 21.6 3.3 17.4% 450" Extract 10.6 4.2 1800 467 24.16 651.2 766.6 795 857.3 897.3 990.7 1094.6 81.9 13.0 7.9 8.9 5.6 11.0 6.7 28.7 2.9 17.3% Comparative Eample

A

In order to demonstrate the significance of the present inventive process over the conventional technique of vacuum stripping, the 450" extract was subjected to vacuum stripping, and various cuts of product were obtained by stripping ofTthe front end and PCA contents were measured by 1P346. Fig. 3 is a graph which illustrates that no statistically significant decrease in PCA content is obtained by vacuum stripping. Even at yields of only 39 vol% of stripped product, the PCA content is 17.1%. compared to 17.3% in the untreated DAE, which is within the statistical error of the test. This test WO 98/44075 PCT/US98/02562

-IO-

indicates that the toxic PCA's are distributed throughout the boiling point range of the 450" extract.

In some of the following examples, an alternative analytical predictor for M.I. was used in order to more rapidly evaluate the M.I. of the various secondary raffnates. The alternative analytical method measures the relative concentrations of PCA's. and is applicable to crude oil, distillates, extracts, raffinates and basestocks.

Fig. 6 is a graph demonstrating the correlation between measured M.I. and the relative PCA contents of various extracts. The correlation between measured M.I. and relative PCA content was 0.967. The predicted M.l.'s disclosed herein were obtained 10 using the regression equation in Fig. 6.

Example 1 200 mL ofthe 700" extract was mixed with 400 mL of DMSO solvent (200% treat ratio) in a IL glass extraction apparatus. The mixture was heated to 250 0 F (12 1C).

vigorously stirred at 1000 rpm for 25 minutes and allowed to separate into two phases.

The lighter raflnate was stripped with nitrogen under vacuum to remove the DMSO.

resulting in a PCA-lean secondary raffinate which was 81 vol% (,80 v1t%) of the original extract. The heavier PCA-rich secondary extract phase was also vacuum stripped of S*0. solvent, resulting in a PCA-rich extract which measured 20% of the oriuinal extract volume. The M.I. of the secondary raftlnate was determined by the Modified Ames Assay test to be Example 2 200 mL of the 700" extract was mixed with 400 mL of DMSO in a I.L lass extraction apparatus. The mixture was heated to 150 0 F (66 0 C) and vigorously stirred at 1000 rpm for 15 minutes and then allowed to separate into two phases The lighter secondary rafflnate was stripped with nitrogen under vacuum to remove the DMSO.

resulting in a PCA-lean secondary raffinate which was 88 vol% (87 wt% of the original extract volume. The Ml. of the secondary rafinate was measured as 1 5. which represents a 50% reduction in M.I. with only a 12%° yield loss by volume.

WO 98/44075 pCT/l1S98/02 562 AccordinglY. It is clear from Example)IS I and 2 that the re-extractioni temperature may he optimized to incr-case yileld, without detriment to the reduction in toxiCit.N of the secondary raffinate.

ExaMpl A sample was prepared and trcatcd as in Exampls I and 2, xcept that the temperature and treat ratio wvcrc varicd. in 'order to determine whether bettcr yields could be obtained, wvithout detriment to ihe NIT. In Examplc 3, the NIA was predicted by the relative PICA content.

1o Experimental parameters and results for Examples 1-3 are summarized in Table 111, below.

TA Q I111 Yield no Temp TreAt Pred INil. Ni.a 1l 12507 200% 81 80 1.4 2' 150OF 200%/' 88 87 1.6 3 1 000F 3000% 88 3 87 1 1 1 Prcdicied Mt 1. from rctauve PCA cow~cfli :Micasurcd Nt I from Niodificd MAncs est Examples 4-7, E xamples 4-7 were prepared similarly- to ExNamlplesI- 13. exept that thle 450, extract was uIsed as the untreated extract A mixture at 300Q 0 M )ISO 10'o cvclohexane (treat relative to the sample volume) was usedl as the secondary extraction solvent, and multiple extractions were performed The number Of extraction stages and the extraction temperatures were v--ried ats Indicated InI Table IV'. below WO) 98/440V75 PI,-1/L S98/02 562 .12- Ex. No 0tg' cr. 08l 6.3sN~l PC 54 4 75OF 83.5 80.1 0.7 086.

7 75OF 77 73 0.48 0. -3 305 6 5 120OF 6 6.2 63.5 0.3625 7 4 1 50OF 6 7.,2 65 0.46 )PCA iesurcd according to IP346 These data demonstrate that product vicid may be increased by utilizing more extractionl stagves at a lower temperature. without an increase in toxicity, as measured by 0.the PCA content. Fig. 5 is a plot of the predice la function of th nm1ro 15 stages for 3009%1 DMISOIIooo, cvclohexane extraction of tile 450" extract, as in Example 5. Each extraction stage employed fresh solvent, so as to simulate a multistagze crosscurrent extraction procedure. Thle plot in Fig 5 demonstrates that the dlegree of detoxification is sensitive to thle number of extraction stages. Moreover, in this case the a...measured PCA content of the product from thle 7-stage extraction met thle below 3 wvt limit for non-toxic treated extracts in Europe. as well ;is the NII (0 3) met thle less than I standard currently utilized in thle at a product yield of 77 vol 0 (73 vWI 0 o) Examples 8 and Treatment Of ExampleIIS S and using the 700"' extraci. is suiflflirized in) Table

V.

belowv !xtact o1l 700 xtract wit DNS) n NIS h exanC IS,~ Solve ni retC T'emp Yel 2Ls 1 Prd leasd vs(.\ Nil Nil 8 DMSO 30M% 7 5 "IT 7% 1 c o 0 o 1 5 -7 U DIlSOIC-l 1 10011 1000.0 75'1: 9s"' 0 7o 0 3 o) NX4 07V)(A/ISM~X0256 2 These dat a md liCa!e t ha11tile Ilse oI*evelohexafln III coml~iunet loll withl) NI SO improves the Sele ctivity\ of thle solvent I-or P)CA's and results in highcr product yields at approximaltelY thce same degreot.oxict~ Lmimnles 10 aid-l.

In Examples 10 and 11, an anti-SONTem. ethy lene givcol. Was mixed with Furfural at a ratio of 70/30 (vol/vol) Furfural/ethylcnCe glycol and uscd as the re-extraction solvent Example 10 utilized thle 450" extract, while Example 1 I utilized the 700" extract Results are suimmarized in Table VI, below 0* TAB L.E VIl Yield (vol%)O (wl% 42 39.6 75 73 5 I1I 100% Ig!fp 100 0

OF

I OO 0

F

0.7 These data indicate that addition of an ai -solvent to an existing lubricating oil extract. composed of a, DAE and a conventional extraction solvent, is, eff'ective to reduce either or both of the NIl. or the PC.\ content of the DAE Comparative Example's Thle following Comprative ExAamples are taken fromi the text ot ll -117 Al., Table 2. examiples 1-3. the entire content of w hich Is hereby incorporated Iw reference.

Comparative

C

D)

TA*BLE VI1 Primary Extract Nlesoralt-bnale Fuirfi Ir!L ratioQ )1i 1 yl 0 PC:A v0) WO 98/44075 PCT/US98/02562 -14- As can be seen from the comparative data, each of Comparative Examples B, C and D have drastically reduced secondary raffinate (rnesoraffinate) yields, as compared to the secondary raffinate yields of the present invention.

Importantly, it has been determined that the physical properties of the DAE's reextracted according to the presently disclosed process are not drastically altered, having viscosities and aniline points suitable for use in the intended products.

The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in to the art are intended to be included within the scope of the following claims.

0 *0 **4 0 o o 0

Claims (5)

1. A process for reducing the polycyclic aromatic content of a lubricating oil extract obtained by extracting vacuum distillates or vacuum resids with an extraction solvent to form a lubricant oil extract mix, comprising: mixing an anti-solvent with said lubricating oil extract mix to reduce the solvent capacity of said extraction solvent while increasing its selectivity for polycyclic aromatic compounds; and cooling the mixture to facilitate phase separation of non-toxic components from the toxic polycyclic aromatic components.

2. A process according to claim 1, wherein said extraction solvent is selected from the group consisting of phenol, N-methylpyrrolidone and furfural. o 15

3. The process according to claim 2, wherein said extraction solvent is furfural OS.. and said anti-solvent is selected from the group consisting of ethylene glycol, propylene carbonate, sulfolane and dimethyl sulfoxide.

4. A lubricating oil extract which has been treated by a process according to any one of the preceding claims. A process according to claim 1 substantially as hereinbefore described with reference to any of the examples. DATED:

5 March, 2001 PHILLIPS ORMONDE FITZPATRICK Attorneys for: MOBIL OIL CORPORATION W:\flona\NKI\Spccics\Div or61551.doc