(2) oy sy my o ey @y co) (60) Gn (2) United States Patent Stober et al METHOD AND EQUIPMENT FOR MAKING COMPLEX LITHIUM GREASE A sr Troy Stober, Woodbury, NI (US); Todd Timothy Nadasd, Mount Laurel, NJ (US): John Philips Doner, Sowell, NJ (US) John Kenneth Graham, Acdmore, PA (US): Norman Charles Yanlley, PA (US) 1 Richard Grives, Lumberton, 1X ), Barbara Anne Carfoit, Wallinaford, PA (US); James Fredrick ‘Van Auken, Beaumont, TX (US); James spagnoli, Mount Laurel, NI (US) Inventors ExxonMobil Research and Engineering Company, Annandale, NI ws) Assignee Notice: Subject to any disclaimer, the tem ofthis, pateat is extended or adjusted under 35 USC. 154(b) by 1233 days, Appl. Now 10987,375 Filed: Oet.1,2004 Prior Publication Data US 200510082014. A1 Apr. 21, 2005 Related US. Application Data Provisional application No, 60/512.S81, filed on Oct 17,2008. Incl. C10M 11706 (2006.01) €10M 15912 (2006.01) us.cl. ‘08/512; 508/496; S08!498;, 508/519, 508/539 'US007829512B2 (10) Patent No. 4s) Date of Patent: US 7,829,512 B2 Nov. 9, 2010 (58) Fleld of Classification Search 508/512, 508/539, 496, $19, See aplication file for complete search history 66) References Cited US. PATENT DOCUMENTS 2an91T A 8199 Hain aso 2ag20 A 91940 Houkos on 2OYe781 A 71860) Beetham el 3240 3300457 A 11967 Schmid et 300882 BATS335 A 10196) Green eta 229 AATS337 A 101969 Green Jee dey No3so01 A VI9T2 Urge ea 075M S920651 A * 121975 Muay eta 5085 (Cominved) FOREIGN PATENT DOCUMENTS ca, sssoes W970 (Comtinved) (OTHER PUBLICATIONS ‘Sami Beet tl “Coninwous Lithium Complex Grese Formation Using Mel Esters of 12-HyrorysteaicAeid and Azeaic Aci [NEG Spokesman, Feb 1999 ol. 62, No. opp. 17 (Continved) Primary Examiner—Bllen M MeAvoy on ABSTRACT A continuous process for preparing lithium complex greases ‘improved by using a complexing agent of dimers! gintarate, imethyl adipate, glutaric acid, adipic acid, or mixtures thereol and preferably also a specialized fash chamber t0 achieve a penetration split (60X-UW) of witha -20may/10%0 10 min/10, a roll stability (DI831) of <30 mm/I0, and a 240° C. Greases made by the improved process ‘of this invention with a hase oil witha viscosity of 90 110, ‘St @ 40 C. and a fatty matter wt % (FM %) within 13% t0 13.5%, preferably also have a 60X worked penetration (01403) of 280 mun/ 10, The greases of Examples 2-4, here inater described, ste within this range while those of eo a 6 parative Examples 1 and 5 are outside this range. FIG. $ Shows improved 6OX worked penetration (D1403) enabled by this invention. In the ASTM 2265 dropping point, simple lithium greases are generally <180° C. and lithium complexes are senerally >240° C. FIG. 3 shows that C {jection point for dropping pont ‘The thickener efficiency is a measure of how much thick ener is required to get a desired grease consistency or thick- ness. This ean be measured using the GOX-penctraion test (ASTM D217). The 160,000 stroke penetration is preferred ASTM D217 test. The har orthicker the grease a a given, thickener content (w% fatty mater in the grease, FM%), the snore elicient the thickener. "The sirctural stability can be evaluated by looking atthe illerence between the unworked and 6OX penetrations (ASTM D217), andthe penetration after shearing inthe Shell Roll Tester (ASTM DI831), The ASTM D183 is preferably rin fortwo bows. FIG, 6 shows improved penetration split (GOX-UW) enabled by this invention. Roll stability shows ‘whether a grease will become softer or harder during sheat- ing, Low roll stability numbers are preferable, FIG. 4 shows the improved roll stability enabled by this invention. "Table | shows the comparison ofthese parameters on test samples of lithium complex greases manufactured using either dimethyl azelate or combination of dimethyl adipate (60 wt %) and dimethyl guerate (10 wt %). The neaetio ‘were carried out using identical hase cis and thickener con: ‘ents with the complexing agent alternatively added in one of the four injection points (A-D). Table I shows the improved properties from using dimethyl glotaate (DMG), dimethy! adipate (DMA), and mixtures thereof instead of dimethyl alate (DMZ). TABLE cox Spe un Diaes Vara sa eas 0 is S26 Sp 0 bs Tho seftemessure pera Bois ‘ia a eas na ws 36 132 0s 0 o In the cases where dimethyl azelate (DMZ) were used, the roping points for injection points A, B, and C were very high 300°C.) however, forD,adropping point couldnot be measured because the grease did nat become heavy enotigh to even be considered grease. For the DMZ, injection points A,B, and, theelficieney ofthe grease was poor (grease was Iniely soft. For A and C there was also a lange difference between the unworked and 60X penetrations showing srve- ‘ural iasablity. Poor struct stability was also demon- strated in the Shell Roll shear stability test with injection points A,B. and C. An eflicient grease uses less thickener to fachieve the same penetration grade ‘When the shorter chain diaid esters dimethyl adipate and imethy! goterate (DMA/DMG) were used, acceptable drop: ping points were obtained for injection points. B, and C. in addition, theelliciencyof these greases were much better than ‘ith the DMZ samples (much heavier urease). In all threeUS 7,829,512 B2 7 ‘cases, the structural stability was better than for DMZ and the best conditions appear to be injection at point C. Injection point D gave a very inefficient grease. Unexpectedly, the Above data shows that a good structurally stable diacid Tithium complex grease with acceptable efficiency ean only beobtained onan ILGU when shorter chain diacids (or esters) are used and the points where they can be injected are restricted to before the second heat exchanger. Table 2 shows the improved properties of greases made with complexing agents dimethyl ylitarate, dimethyl aipate, lutaric aid, apie seid and mixtures thereof. Table 2 shows treases made from 26.336 wt 100 eSt (@ 40° C.) polyal- phaolefin, 54312 wt 8% 6 eSt (@ 40° C.) polyaiphaolefin, 3.008 wt % lithium hydroxide monohydrate, 13.248 wt % methyl. I2-hydroxystearate, and 2.897 wt % complexing ‘agent (listed in Table 2), The combined base oll viscosity Was 105 cSt @ 40° C. The fatty matter content in the grease was 132.wi% methyl 12-hydroxystearate. 8 The resulting mixture of base oils lithium hydroxide, water, and MHSA entered the reactor (7) which was held at 177° C. and 1,000 kPa(g) (determined by the setpoint of the Resetor Back Prossure Valve (8). The Reactor Reycle Pump (6) provided a sufficient reeyele rate to maintain turbulent low in the reactor coil (7). ‘A partly saponified material then exited the reactor and moved through the Reactor Back Pressure valve (8). ‘2.897 wie dimethyl azelate was metered ito the steam at Injection Point C (9). The steam then entered Heat Exchanger 2 (10), which was maintained at 183° C, and 380 KPa(g). The pressure was msinsined by the Heat Exchanger 12 Back Pressure Valve (12). The stream then entered the lash Chamber (13) which was maintained at 94 KPa(a) vacuum. The stream was then dehydrated while reeycling 10 20 times through the Flash Chamber Recycle valve (16), ‘whieh maintained back pressure of 800 kPa) on the Flash Chamber Reeyele Pump (18). The soup base was moved Complexing Ageor Point mmi10_mwvid__mmi0 m0 “c iSertecaiowrsses, ‘The following examples represent embodiments and com- parative examples andl are not meant 10 limit the seope ofthe EXAMPLE 1 Comparative A lithium complex grease ws manufaetured on the LGU depicted in FIG, 2 by the following method: Based on the weight ofall ingredients other than water, 3 mixture of 15.81% 10081 @ 100°C. polyalphaolefn base cil and 39.2 wt % 6 eSt @ 100° C. polyalphaolefin base oil, was introduced into the ILGU through low meters and meter- Jing pumps. into the stream labeled "#1 Oils” (1). The viscose lay of this base oil mixture was 105 eSt @ 40° C. Heat ‘exchanger #I"s (2) exit temperature setpoint was 164° C. 3.008 wt % lithium hydrowide monohydrate was dissolved Jn excess water and injected into the point labeled “Fat and Alli” (4) along with 13.248 wt % molten methyl 12-by- “droxysteararic seid (MISA). 0 o ‘through the Base Grease Pump (17) and alitional Base Oil (25.847 wt 6) was metered into the soap base to give a final MHSA content of 13.2 wt % (EM %). "The soup base was then passed through the Pinishing Valve (19), which was maintained ata pressure of 950 KPa(g), 10 prodace a homogenized grease Flow rates throughout the process were adjusted to meet the above formulation. The final grease had the following performance properties: ‘unworked penetration (UW, ASTM D1408 with 10,000 strokes) of 317 mimv/10;, (0X worked penetration (ASTM D1403) of 343 mm/10;, it (6OX-LIW) of 26 mm!10; ty (ASTM DI831) of 36 mm 10- anc dropping point (ASTM 2265) of >300"C. As indicated by the os results above, although the grease exhibited high dropping point, the penetration split and rl Stability indicatea poor degroe of strctural stability. Also, the high UW penetration indicatetan inelficient grease structureUS 7,829,512 B2 9 EXAMPLE2 Grease manvfactured by the above process had the same ormulation as Example 1, except using dimethy] adipate as the complexing agent. The grease had the following pefor- mance properties ‘UW (D1403) of 227 mav0; (OX worked penetration (D1403) of 223 maa/10: penetration split (6OX-UIW) of 4 mm: roll stability (DI831) of 18 mm/10; and dropping point (12268) of 280° C. EXAMPLES Grease manufactured by the above proces had the formu Jation had the same formulation as Exanople 1, except using «dimethyl glutarate 25 the complexing agent. The grease had the following peeformance properties: ‘UW (D1403) of 239 mav0; {6X worked penetration (D1403) of 233 mm/10; penciation spit (60X-UW) of -6 ma! 10; roll stability (D11831) of 16 mav/10; and dropping point (D2265) of 204°C EXAMPLES Grease manefactured by the above process had the same ‘formulation as Example 1, exeept using a mixture of 90% limethyladipate and 10 wt % dimethyl glutamate asthe com= plexing agent. The grease had the following performance Properties: UW (D1403) of 240 mm/10, (OX svorked penetration (D1403) of 257 mm 10; penetration spit (6OX-UW) of -3 mm/10; roll stability (DI831) of 4 mum/10; and dropping point (02265) of 262°C, EXAMPLE, Comparative Grease manufactured by the above process had the same ‘ormulationas Example 1, except using dimethyl suecinateas the complexing agent. The grease had the following perfor- mance properties ‘UW (D1403) of 225 mav/0; {6X worked penetration (D1403) of 217 mm/10; penetration spit (60X-UW) of -8 mm/10; roll stobity (D1831) of 32 mm/10; and dropping point (D2265) of 208° C. This dropping point of 208° C, shows that dimethyl sucei= nate cid no forma complex grease, What i claimed is 1. method comprising having 2 continuous grease manufacturing process ‘wherein a saponifiable material js reacted with a com- plexing agent and an aqueous solution ofa metal base in {reactor to produce a saponification reaction product, introducing the sspoificelion reaction product into a ash ‘chamber to remove water prevent in ssid saponification reaction product to form a dehydrated saponification reaction product, essing the dehydmted saponification reaction product ‘through a shear valve, and 0 o 10 ‘adding 8 lubricating oil wo the dehydrated saponitiat reaction product to produce a grease product, improvement which eomprises using a complexing agent that is at least one member selected from the group consisting of dialkyl glutarate, clalkyladipate, glutaric acid, adipic acid, and mixtures ‘thereof, whereinlky1 has Ito 8carbon atoms ala flash chamber comprising a ylindrical vessel with length o inner diameter ratio of 23.2, the vessel having a cov- ‘rod top end and a downwardly sloped conical shaped bottomend with an ineluded angle =90" terminating in ‘snout forremoval ofan atleast partially devolatilized reaction product fan inlet for intgodveing an at least partially seponified reaction prodvet into the vessel; ‘aconuit in communication witha vacuum source, extend ingintothetop endof the vessel, so that under conditions ‘of use the conduit wil terminate above the level of the at least partially ssponitiedresetion product, ‘an inlet for intoducing recycled atleast partially devola- lized reaction product dowensvardly into te vessel, said inlet located inthe tp or side and directed in a down- ‘ward dircetion into the flash chamber, so that under ‘conditions of use the conduit will terminate above the levelof the atleast partially saponified reaction product; and ‘an agitator positioned within the vessel above the conical slaped bottom end, the agitator provided witha plurality ‘of blades oriented at 15° to 75° from vertical to force saponified reaction product downwardly under con tions of use. 2. The method aceording to claim 1, wherein the improve- sent farther comprises adding the complexing agent betwen the reactor and the fash chamber '3. The method according to claim 1, wherein the Bash chanbee Further comprises steam jacket around at eas part of the exterior of the eylindrical vessel the included angle ofthe conical bottom is 95°to 105°; and the blades are angled at 30° to 55° from verical 4. A method of making a grease having a penetration spit (6OX-UW) of within -20 mm/10 10 +10 mav10, a rll sabil- ity (DI831) of <30 mm/10, and a dropping point (D2265) of 240° C., by an improvement according to claim 1 5. A metiod comprising, preparing a high dropping point lithium complex sep greane comprising continuously inteo- ‘ducing a reaction mixture comprising @ complexing agent, a hydroxy fart acid a lithium base anda lubricating ol into a reaction zone, to form a saponified material soap and volatile ‘components which are continuously introduced into a dehy ration zone comprising 2 lash chamber, the improvement ‘which comprises: ‘using asa complexing sgent a least one member selected from the group consisting of dialkyl glutarate, dialkyl ‘adipate, glutaric acid, adipic acid, and mixtures theroof, Wherein lky1 has 1 8 carbon atoms anda lash cham- bercomprsing acylindrical vessel witha lengthtoianer diameter ratio oF 23.2: the vessel having acovered top fend and a downwardly sloped conical shaped bottom fend with an included angle 290°, teminating in an ‘outlet for removal of an at least panally devolatilized ‘reaction product; fan inlet for introducing an at feast partially saponified reaetion prover into the vessel; ‘acon in communication witha vacuum source, extend ingintothetop end of the vessel, so that under conditions ‘of wie the conduit wil terminate above the level of the st least partially stponified eaetion product, theUS 7,829,512 B2 uw et for introducing recycled atleast partially devola- tilized reaction product dowavarily into the vessel, said {net located in the top or side and directed in a down- ‘ward diretion into the flash chamber, so that under ceonclitions of use the conduit will terminate above the levelof the at lest patially saponified reaction proc and ‘an agitator positioned within the vessel above the conical shaped bottom end, the agitator provided with plurality of Blades oriented at 15° to 75° from verical to foree ssponified reaction produet downwardly under eondi- tions of use 6, Tho method of claim 5, wherein the hydroxy fay acid, thu hase, and lubricating oil are first introduced int the reaction zone and the complexing agent is added 10 the ‘ponifiahle material before the introduction into the deby- ration zane. 7. The method of claim 8, wherein the hydroxy fay aid lithium base, and lubricating oil are first intodoced into the reaction zone and a least a portion ofthe saponifiable mate- rial is removed and recycled through the resetion zone and wherein the complexing agent is added to the seponiiable material being reeyeled. 8, The method of claim §, wherein the reaction zone is a about 121° C. 250° F) to about 208 the hydroxy fatty aid isat least one member selected fom the group consisting of melhyl-12-hydroxysteaat, T2-hydroxy stearic acid, and mixtures thereof as the Inydroxy fay aid 12 9. A method of making a grease having a penetration split (6OX-UW)of within 20 mu/10 o 410m 10, aol stabil (D1831) of <30 mm/0, and a deopping point (D2265) ‘of >240° C., by an improvement according to claim . 10, 8 method accoeding to claim 8, wherein the grease, whet made hy the improvement according to elas 8 with 2 base oil witha viscosity of 90 to 11D¢St @ 40° C. anda FM % within 19% to 13.5% has a GOX worked penetration (01403) of <280 mm/10. 11. A method according to clamn 5, wherein the complen- ‘ng agent i dimethyl glotarate; and The grease product bas a roll stability (DISS1) of <20 min. 12. A method aocording to claim 8, wherein the complex- ‘ng agent is dimethyl adipate. 13. A method according to claim 5, wherein the complex- ‘ng agent i glutaric sid 114. A method according to claim 5, whercin the complen- ng agent is ip aid 15, A method aovording to claim 5, whercin the complex- ‘ng agent sa mixture of about 90 wt % dimethyl adipate and about 10 wt % dimethyl gltarate; and the grease product has a roll stability (DISS1) of <20 min, 16. A method according to claim 5, wherein the complex- ing agent isa mixture of adipic acid and glutaric acid and the grease product as a roll stability (D1831) of <20 ‘mni10,