SA96170146B1 - Process for producing lube base oils - Google Patents

Abstract

Abstract: The present invention relates to a process for producing lubricating base oils, this process includes the steps: (a) contacting a watery wax produced as the bottom section of a hydrocracked flux with a catalyst that ignites platinum and/or palladium on a refractory oxide carrier in the presence of hydrogen under such conditions that at least 10% by weight, preferably at least 25% by weight, of the weight of the hydrocarbons having a boiling point of 370 C or higher, present in aqueous wax, is converted into hydrocarbons having lower boiling points, (b) separation of the resulting product In step (a) to at least one lighter distillate section and one heavy distillate section having a viscosity index of 125 or higher, preferably 135 or higher, and a kinematic viscosity at 100 °C of at least 3.5 cst, and (c) dewaxing the distillate section Heavy output in step (b). 0

Description

Y

Process for producing lubricant base oils Full description Background of the invention as lubricating base oils The present invention relates to a process for producing lubricant base oils more specifically The present invention relates to a process for producing lubricant base oils having a high viscosity index using wax Hydrocracking 0 or greater; 11 171 It is known that lubricant base oils with very large paraffins “sl” can be produced from feed stocks that contain relatively large amounts of waxy particles; long linear and branched alkyl-naphthenics s alkyl-aromatics to a small extent in addition to very large substances by themselves and accordingly; Positively affecting the VI series. These waxy particles; particulary; to the product in it. Controlled examples of such feed stocks having significant VI content contain 0 Fischer-Tropsch waxes are raw waxes Synthetic waxes produced by synthesis reactions of one or more by weight waxes; While the synthetic wax materials usually have 750 quenched wax materials by weight or more. The present invention is intended to provide a process in which 780 aad content La lube base oils are produced having such high levels of 1715 from a feed stock having a low wax content of less than 770 by weight. Particularly Lad of weight; 750 proportional ie; Wax content less than vo The present invention is intended to provide a process for the production of such lubricant base oils using a hydrocracking iS bottom section or a hydro-wax as a feed stock. The process of the present invention; Accordingly, it can be integrated to a very appropriate degree in a refinery with hydrocracking capacity. Known in art. In the ped, the processes for the production of lubricant base oils from hydrocarbon contain, for example; EP-A-0.272.729 Feed Stock Hydrocracking |» on a fast-flowing distillate resulting in a tailings conversion process; Then the wax is removed from the bottom section of the fracturing flux. The dewaxing treatment may be preceded or followed by a hydrotreatment step in order to hydrogenate any unsaturated components present. The preferred arrangement is to first dewax and then hydrotreat the dewaxed material. The final hydrogenation step increases the amount of isoparaffinic y paraffinic to the saturated olefins components present; By means of this, the hydrogenation of the final base oil obtained is 1 v. anyway; The aromatic constituents present in VI are preferred for the finished base oil and as a result they are not hydrogenated VI also have little or no effect on O 111 significantly. as a result; It is not possible to obtain base oils with a value of VI of 171 that contribute to the matching process 24-0.272.729-f5. lef General description of the invention The present invention aims to provide a process by which lubricant base oils of 171 111 can be produced or more effectively by starting from aqueous wax produced as the bottom section of a water-fractured flowing material. accordingly; The present invention relates to a process for producing lube base oils; This process includes the steps:

Jed with a Lola catalyst (a) contacting aqueous wax produced as the bottom section of a fractured flux 1 under hydrogen on a refractory oxide carrier in the presence of palladium and/or platinum at least by weight; Preferably at least 775 pounds of weight; of 701 such conditions so that it turns out to have a boiling point of 0+37°C and higher; (b) Separation of the resulting product in step (1) into at least one lighter distillate fraction and a heavy distillate fraction having 171 175 or (preferably lel 135 or higher; kinematic viscosity of at least 0°C Fe; and (c) dewaxing of the heavy distillate section produced in step (b). The feed used is In the process according to the present invention is the bottom fraction of a hydrofraction ov. This flux is correspondingly produced from a hydrofracturing process. The term “bottom fraction” refers to the extracted portion of the hydrofracturing flux at The bottom of the separator from which said flux separates. Accordingly, said bottom section—usually referred to as aqueous wax—is that section of the hydrofracted flux containing the heaviest constituents.Produced to an appropriate degree the aqueous wax used as feed in the vo process of the invention The current of the aqueous fractionated flux at an effective separation point in the range from Vee to 0°C; preferably 10 to 80°C. The degree of separation is the temperature at 1 o

¢

heat higher than that of at least 785 by weight and preferably at least 790 by weight;

The hydrocarbons present in the extracted aqueous wax have their boiling point. Hydrocracking is a conversion process that is well known in the art and primarily involves the catalytic conversion of hydrocarbon molecules into smaller hydrocarbon molecules in the presence of hydrogen. A variety of feed stocks can be used for hydrofracking operations; Included among others are distillate sections; Fast-flowing distillates by vacuum, resulting from hydrocarbon conversion processes and atmospheric residues. Hydrofracking conditions typically include temperatures in the range 0 to 000"C; partial hydrogen pressures in the range 1 to 00"QL vacuum velocities per hour for weight from 11 to 0 kg of feed / liter of catalyst / hour and gas / feed rates from 001 to 0000 liter of gas / kg of feed. Hydrocracking catalysts are also known in the art and include both amorphous and 2601116-based catalysts. As dale the hydrocracking catalyst includes at least one hydrogenation component of a group 1 metal and/or at least one hydrogenation component of a group 1 metal A and a carrier comprising an amorphous material; silica-alumina Jie is amorphous; silica or synthetic; and/or zeolite Zeolites that are particularly useful in this respect include zeolite 57 or a modification thereof; Like Zeolite 7 it's very stable. The latter type of zeolites is used in a more appropriate way. Consortia of amorphous materials and 26011185 may also be used. Suitable group 1 metals are Lay (Mo) molybdenum 5 (W) tungsten The suitable group A metals are the non-noble metals (Co) cobalt y (Ni) nickel in addition to the noble metals (Pt ) platinum palladium 000. Examples of suitable amorphous catalysts are those that include the Jie component »| Hydrogenation (components) Pd (Pt “COW (NiW” CoMo NiMo) or 0000. The hydrocracking process may be a single-stage process involving the use of a single bed catalyst; or a two-stage Aloe using two different catalyst beds. Obtaining the aqueous wax used as a feedstock

The process of the present invention is of any control hydrocracking process. Detailed description of the invention yo In step (a) of the process identical to the present invention the aqueous wax is contacted with a catalyst comprising palladium lf 5 platinum on an oxidant-oxide carrier in the presence of hydrogen under such conditions that a conversion of at least 007"*C occurs 701 of the weight; 775 of the weight is preferred over the less Vv o and also more preferable of at least 7705 of the weight. In an appropriate degree, a conversion must be derived from the weight; in a more appropriate degree less than 776 of the weight; because at AA Less than ARTY + 170 VI Too high conversion levels become the yield of a lubricant base oil product that has

A fT et or higher becomes less important from an economic point of view. It is a highly preferred conversion depending on use at RAT to 770 by weight. The expression 'convert Er m' in the range from hydrocarbons present in aqueous wax having a boiling point this side to weight 7 of those having a lower boiling point. assumes the occurrence of hydrocarbons or higher; which converts to 4 gory. Both the hydrogenation and hydrocracking reactions in step (a). Suitable reaction conditions include pressure AiR Fe preferably from geo to YO heat of reaction in the range from vacuum velocity in Ju Yor Ye to 060 bar preferably 01 mo of hydrogen in the range from 0 to © kg/l/1.7 kg/l/h; 10 to 1/1 hour is preferred for weighing in the range of 1NmL/kg; Preferably 90,000 to 100 hours; and a hydrogen-to-feed ratio in the range from 0001 to Ye, the catalyst used in step (a) is a noble metal based Sine including platinum and/or palladium ve supported on Refractory oxide carrier. The total amount of platinum and/or palladium contained in the catalyst shall be suitably in the range 1.1 to 75 by weight calculated: as a component on the basis of the total weight of the support; Most suitable in the range from 0.7 to 77 wt. when there are two; The weight ratio of platinum to palladium (calculated as an element) may vary within wide limits; But with a suitable degree it is in the range from 1.05 to 10; with a suitable degree more © 1.1 to 8.0 A preferred application of the present invention includes the catalyst platinum as the catalytic active metal cag while in an application Al is preferred for the invention The current catalyst includes a combination of platinum .sulphide element; oxide and/or Jia palladium platinum .palladium may be present along with the noble metal(s); The catalyst used in step (a) may also include a metal component such as a noble metal; At least one palladium may be from group (7b+). Specifically when using the presence of a group (1) metal component is useful. Suitable group (1) metal components include VO oxides, but also these metals in the form ctungsten or molybdenum “chromium” from sulfides s when present; Elemental chromium 5 tungsten metal constituent. Of these, preferably components

VV

+ group (7b+) usually present in an amount of 1 to 778 wt.; appropriately greater than * to 0 by weight; Jie is an element calculated and based on the total weight of the supporting material. Examples of very suitable noble metal-based catalysts lA Wha are those comprising palladium chromium s palladium sl tungsten s The carrier used includes a refractory oxide. Include suitable heat-resistant fluorinated oxides or mixtures of? or more amorphous alumina; silica-alumina alumina zeolites and mixtures thereof; Preferably amorphous zeolites; silica-alumina of these. Preferences suitable are the same as those described above for amorphous zeolites. The use of silica-alumina (modifier). Materials include 7 zeolite as being appropriately used in hydrocracking catalysts; i.e. alumina to 7176 of weight 01 amorphous suitable in the range of silica-alumina carrier 0

Jie zeolite is amorphous and/or silica-alumina and is available commercially. When the carrier includes a binder. The use of binders in Lad is an oxidation-resistant oxide; They may contain, in general; .alumina y silica catalysts well known in the art. Typical binders are The combined weight ratios of binder to refractory oxide may vary within wide ranges; However, to an appropriate extent it is in the range 0 (ie, no binder) to ©; With an appropriate degree of zero silica-alumina "lds" on palladium and platinum to ;. A particularly preferred catalyst includes an amorphous. The product from step (a) is then separated in step (b) into at least one lighter distillate fraction and a heavy distillate fraction having 115,171 or greater; 195 or oS preferred and kinematic viscosity © at 100*C (VK100) at least 3.5 cStoke; While it is preferable not to exceed 171100 over VY, two years. Very good results can be obtained when targeting a partition J whose VI is higher than VKI00, 08 in the range from ©,; to ©,7. Those skilled in the art will know that the Vk1005 VI combination will determine the effective degree of separation of the heavy section; any; The one at which at a higher temperature it has a TAC of at least by weight and preferably at least 790 by weight of the hydrocarbons ve in the said heavy fraction has its boiling point. In practice this effective separation score will be in the range from TOL to 000 **C; suitable 776 to 75?

for less. Also, these lighter fractions will have economically attractive properties that make them useful as a lubricant base oil - after dewaxing - in applications that do not require very large VI values. The waxing performed in step (c) can be performed by essentially any known waxing process. Examples of suitable dewaxing processes are conventional solvent dewaxing processes; Specifically as used toluene “methyl ethylketone le” or a mixture thereof Jie dewaxing solvent; catalytic waxing operations; Both types of waxing procedures are well known in the art. The most commonly used solvent dewaxing process is the Cus (MEK) methyl ethyl ketone dewaxing method. MEK is used as the dewaxing solvent; Possibly in a mixture with 1010©06. Catalytic dale dewaxing involves cracking and/or isomerization of 0 -_ linear and slightly branched hydrocarbon molecules - which negatively affect the cold flow properties of the base oil - in the presence of hydrogen and a dewaxing catalyst. Suitable dewaxing catalysts primarily favor cracking of paraffinic hydrocarbons comprising ferrierite < ZSM-5 and/or silicalite and optionally a hydrogenation component. Examples of essentially favorable catalysts include linear or slightly branched isomeric hydrocarbons; Catalysts include (SAPO) silicoaluminophosphate met SAPO-11 ZSM-23 (SAPO-41 5 SAPO-13 0 and 5852-32). A catalytic dewaxing step may be appropriately followed by a final hydrotreatment step for the hydrogenation of any species. Unsaturated colefins (aromatics) still remain. For the purpose of the present invention either solvent dewaxing or catalytic isomeric dewaxing is preferred; Any catalytic aqueous isomerism. The invention is further illustrated by the following examples. 0 eg:1 contacts aqueous wax having a boiling point distribution as specified in table ge) catalyst comprising 71 by weight Ys palladium , 70 by weight platinum (7 weight ratios depend on weight total of the carrier) on an amorphous silica-alumina carrier having an alumina content of 48 7 by weight. The operating conditions are such that a conversion of +70? is 749.5 percentile of the weight. This corresponds to ve operating temperature Asta hydrogen pressure JL 190 vacuum velocity per hour for weight 1 (WHSV) kg/l/h and gas rate Vor mol/g. The fractionated flux is separated at an effective separation temperature of 00?*C, and the section wax + afer is removed with a solvent through VV

A

Vk40 060 is a conventional VI. The toluene /MEK dewaxing product has a dewaxing process of 94, ; 2 cStoke at VKI00 yield 5 Motility at +?*Celsius (7.8 cStoke day) of weight when feeding. 2 Um"+1701 > Weight Lt FBP FBP? Developmental - AA Initial Boiling Point = [BP o Final Boiling Point = 7 Example ?: in contact with the same catalyst 1 in contact with wax Many has a boiling point distribution as specified in a table of 777.4 out of 45 YY 0 + the operating conditions are such that 1. is as described in the example la Ve speed hydrogen pressure ATA weight. This corresponds to an operating temperature of _0 kg/l/h and a gas rate of 150 mol/kg.1 (WHSV) vacuum per hour for weight and section he ¢©. - 6°" reticulum section YA 2 The fractional flux is separated into section- and section 408004 by the LACE 7/80 process dewaxed with a conventional Ailton + section solvent. The properties of the two dewaxed sections are shown in Table ?. toluene /MEK Waxing Table ? yo a Tee aE aw ak d | 4 avian [0 cents] (0 for throughput) at 705

VV q tv and with a good kinematic viscosity at 110 higher than VI. Table shows that the product with is produced; While the resulting other dewaxed product also has attractive properties (DAC) eg or higher. 1101 VI is very high ie; VI as lubricant base oil for those uses that do not require values

Vi

Claims (1)

Ye. protection elements 1-1 Process for producing base oils 11611021108 This process includes the steps: (a) Contact of aqueous wax produced as the bottom section of a hydrocracked flux with a catalyst 0 including platinum and/or palladium on a refractory oxide carrier in the presence of hydrogen: under these conditions so that at least 701 turns of weight; TY is preferred at least by weight; © by weight of hydrocarbons having a boiling point of 071°C and higher; present in aqueous wax; into hydrocarbons with boiling points “Jil v (b) Separate the product produced in step (a) into at least one lighter distillate fraction and one heavy distillate fraction 4 having viscosity index five dua bc lel Jao above; and for a kinematic viscosity at 4,001°C of at least 3.5 cst; and 0 (c) dewaxing of the heavy distillate section produced in step (b). 10 VI where the lighter distillate section of step (b) has 10 7”-process of claim 0 or higher. 7 01 “*-method identical to any one of claims 1 to oY wherein watery wax is produced from hydrocracked wile flux Y at an effective separation point in the range 00 to 1 0 percentage. ATA to ©01 of the security element?; In which the degree of separation is in the range from lik;-0 process idee —0 01 according to any one of claims 1 through 4; in which the refractory oxide carrier Y is amorphous silica-alumina; A carrier based on zeolite 7 or a mixture of . 1 it. platinum (a) staal +- process according to claim 0 where the catalyst used in includes an amorphous 1. silica-alumina on a palladium Y carrier 0 7 - process according to any one of claims 1 to ; where step (1) is carried out at temperature Y in the range from ToL to 05©**C; molecular pressure of hydrogen in the range from 10 to 1 500 cL vacuum velocity per hour for weighing in the range From 11 to 10 kg / liter / hour, and the ratio l hydrogen to feed in the range from 001 to 0000 liter / kg. ‎VV 1 365 wherein step (a) is carried out at a temperature in the range oF according to the element of protection Lee = A 1 bar; Vacuum velocity You to Ye Partial pressure of hydrogen in the range gions to >” h; hydrogen-to-feed ratio in [Al to 1.7 kg/hr wt in the range from ¥ NL/kg. 70000 To You Range From Step (c) Cum to “1” for any one of the lish 4-process 1 claims is removed by Solvent dewaxing. Y to 8; wherein the dewaxing is carried out in a step 1 process according to any one of claims catalytic 1-01; optionally followed by a hydroisomerisation step (c) with a hydroisomerization > aqueous final VV