MXPA00003794A - Isoparaffinic lube basestock compositions - Google Patents

Abstract

A liquid hydrocarbon composition, containing paraffinic hydrocarbon components in which the extent of branching, as measured by the percentage of methyl hydrogens (BI), and the proximity of branching, as measured by the percentage of recurring methylene carbons which are four or more carbons removed from an end group or branch (CH2>4), are such that:(a) BI - 0.5(CH2>4)>15;and (b) BI + 0.85(CH2>4)<45 as measured over said liquid hydrocarbon composition as a whole.

Description

ISOPARAFINIC COMPOSITIONS OF BASE MATERIAL BASE FOR LUBRICANT This application claims priority under title 35 of United States Code section 119 to United States Provisional Application No. 60 / 062,824. Base raw materials have been developed for high-performance lubricating oils that present characteristics unique in their composition and that demonstrate superior performance properties at low temperature.

The base raw materials for high performance, premium lubricants generally "present useful viscosities over a wide range of temperatures, have a better viscosity index and demonstrate lubricity, thermal and oxidative stability and equal or better pour point than traditional mineral oils. rheological and operating properties - advantageous improve their performance in lubricating formulations in relation to mineral oil-based formulations, including a wider operating temperature window, however, raw materials base for premium lubricants are more expensive to produce than Traditional mineral oil lubricants Many researchers have investigated ways to convert relatively low-value hydrocarbon feedstocks, such as natural gas, to higher-value products such as fuels and lubricants, and much research has been done on catalytic upgrading. of mate Waxy hydrocarbon raw materials, which have significant concentrations of linear chain paraffinic components, in more useful products by hydroisomerization and dewaxing, processes that isomerize and fractionate paraffin wax components of straight chain raw materials, respectively. Processes for the production of hydrocarbon fuels and lubricants from synthesis gas, a mixture of hydrogen and carbon monoxide, have been known for some time, and of these, the Fischer-Tropsch process (FT) is probably the best known. The development of the process and its most notable characteristics are given in Kirk-Oth er, Encyclopedia of Chemical Technology, 3rd edition, John iiey & Sons, New York, 1980, vol. 11, pp. 473-478. In the FT process, the synthesis gas, generally formed by partial oxidation of methane, passes over a catalyst at elevated temperature and pressure to produce a number of carbon monoxide reduction products including hydrocarbons, alcohols, fatty acids and other oxygenated compounds . Under favorable circumstances, the oxygenated materials may contain less than 1% of a total desired liquid product. The hydrocarbon product is highly paraffinic in nature and usually includes hydrocarbon gas, light olefins, gasoline, light and heavy fuel oils and waxy gas oils. Because the higher boiling fractions in the product are generally too waxy for general use as liquid fuels or lubricants, other processing or improvement is usually necessary before these can be used, either as such or being added to the overall combination of products. Advantageously, FT products contain little, if any, common oil contaminants, such as aromatics, cycloparaffin compounds (naphthenes), sulfur compounds and nitrogen compounds, due to the relatively pure nature of the compounds. the raw materials: hydrogen and carbon monoxide, and finally, methane and natural gas. U.S. Patent No. 4,500,417 describes the conversion of the high boiling fraction of the FT products by contact with a large pore zeolite, with high silica content and a hydrogenation component to produce a distilled fraction and a lubricating fraction characterized by a high IV (viscosity index) and low pour point. The catalysts include Y zeolite, beta zeolite, mordenite, ZSM-3, ZSM-4, ZSM-18 and ZSM-20.

U.S. Patent No. 4,906,350 discloses a process for the preparation of a lubricating base oil with a high IV and a low pour point by catalytic dewaxing at least part of the hydrodesintegration of a mineral oil fraction containing wax on a selected zeolitic catalyst. between ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-12, ZSM-38, ZSM-48, offerita, ferrierite, zeolite beta, zeolite teta, zeolite alpha and mixtures thereof. U.S. Patent No. 4,943,672 discloses a process for hydroisomerizing FT wax to produce lubricating oil having a high IV and a low pour point first by hydrotreating the wax under relatively severe conditions and then isomerizing the hydrotreated wax in the presence of hydrogen on a metal catalyst. of the particular fluorinated group VIII on alumina. U.S. Patent No. 5,059,299 discloses a method for isomerizing paraffin wax obtained from mineral oils and wax to form lubricating oil base raw materials with very low pour point, and with high IV isomerizing over a group VI-VIII catalyst on a carrier basis. halogenated refractory metal oxide, followed by dewaxing with solvent. U.S. Patent Nos. 5,135,638 and 5,246,566 disclose wax isomerization processes to produce lubricating oils having excellent viscosity, and pour point under isomerizing a waxy oil feed stream onto a molecular sieve having certain pore measurements and at least one metal group VIII. The catalysts include SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, and ZSM-35. U.S. Patent No. 5,282,958 discloses a process for dewaxing a hydrocarbon feed stream including straight chain and slightly branched chain paraffins having 10 or more carbon atoms to produce a dewaxed lubricating oil using catalysts of a specific pore geometry and containing at least one metal from group VIII. The feedstock is contacted with the catalyst in the presence of hydrogen; Exemplified catalysts include SSZ-32, ZSM-22 and ZSM-23. U.S. Patent No. 5,306,860 discloses a method of hydroisomerization of paraffins derived from FT over a series of catalysts including a zeolite Y catalyst to form low pour point, high IV lubricating oils. U.S. Patent No. 5,362,378 describes the conversion of the heavy end products of the TF with a platinum / boron-zeolite beta catalyst having a low alpha activity to produce an extra high IV lubricant, which can then be dewaxed by traditional dewaxing with conventional solvents. or increased the severity of the hydroisomerization step. European Patent No. 0 776 959 A2 describes a process for preparing base oils for lubricants having an IV of at least 150 from a feed stream of FT first hydroxide wax running over a suitable catalyst in the presence of hydrogen and then the solvent or the catalytic dewaxing of the intermediate fraction 390 ° C +. However, none of the references described above mentions or suggests the preparation of liquid hydrocarbons of a specific and limited range of compositions having any specific combination of branching properties, which gives rise to highly desirable lubricating properties including an unexpected combination high viscosity and low pour point. In fact, none of the mentioned references still describes or suggests the measurement of the branching index (IR) or proximity of the branching, as described below. U.S. Patent No. 4,827,064 discloses high IV synthetic lubricating compositions of polyalpha olefins, wherein a "branching ratio" CH3 / CH2 is measured.

The descriptions of the aforementioned US Patents are incorporated herein by reference in their entireties. A first object of the present invention is the production of a unique liquid hydrocarbon composition that can be useful as a base raw material for lubricating oil having useful low temperature viscometric properties. Another object of the present invention is to provide a market for low value natural gas, converting it into raw materials for high-quality value lubricants through a combination of Fischer-Tropsch synthesis steps, hydroisomerization and catalytic dewaxing. One embodiment of the present invention is directed to a composition of liquid hydrocarbons of paraffinic hydrocarbon components in which the degree of branching, as measured by the percentage of methyl hydrogens (IR), and the proximity of the branch (or "Branch Proximity"). ") measured by the percentage of recurring methylene carbons that are four or more carbons separated from an extreme group or branching (CH2 >4), are such that: (a) IR-0.5 (CH2 > 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; when measuring the composition of liquid hydrocarbons as a whole. Another embodiment of the present invention is directed to a lubricating oil feedstock composition having paraffinic hydrocarbon components in which the degree of branching, when measured by the percentage of methyl hydrogens (IR) and the proximity of the branching, when is measured by the percentage of recurring methylene carbons that are 4 or more carbons separated from an end group or branch (CH2> 4), are such that: (a) IR-0.5 (CH2> 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; when measured on the composition 'of raw materials for lubricating oil as a whole. In another embodiment, the present invention is directed to a lubricating oil composition of a liquid hydrocarbon composition having paraffinic hydrocarbon components in which the degree of branching, measured by the percentage of methyl hydrogen (IR) and the proximity of the branching , as measured by the percentage of recurring methylene carbons that are 4 or more carbons separated from an end group or branch (CH2> 4), are such that: (a) IR-0.5 (CH2 > 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; Measured on the - composition of liquid hydrocarbons as a whole, and optionally, effective amounts of lubricating oil additives such as, but not limited to, antioxidants, antiwear additives, extreme pressure additives, friction modifiers, index improvers viscosity, pour point depressants, detergents, dispersants, corrosion inhibitors, metal deactivators, additives for joint compatibility, demulsifiers, defoamer additives and mixtures thereof. The foregoing and other objects, features and advantages of the present invention will be well understood from the following detailed description, taken in conjunction with the accompanying drawings, all of which are given by way of illustration only and are not limiting of the present invention. Figure 1 is a graph comparing the low temperature viscosimetric properties of the liquid hydrocarbon compositions of the present invention with a raw material base for hydroprocessed lubricant Figure 2 is a graph illustrating mathematically the structural limitations of the IR and CH2 >4, as set forth in formulas (a) and (b), which define the limits of the compositions of the invention described herein Figure 3 is a comparison chart of dynamic viscosities (DV @ -40 ° C) , measured by the CCS method ASTM D5392, and the kinematic viscosities (KV @ 100 ° C) of different hydrocarbon fluids, including those of the pre This invention will also be apparent from the detailed description that is provided 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 some changes and modifications within the spirit and scope of the invention will be apparent to those skilled in the art. technique from the detailed description '. An embodiment of the present invention relates to a composition of liquid hydrocarbons of paraffinic hydrocarbon components in which the degree of branching, measured by the percentage of methyl hydrogens (IR) and the proximity of the branch, measured by the percentage of carbons Recurrent methylene which are 4 or more carbons separated from an extreme group or branch (CH2 > 4), are such that: (a) IR-0.5 (CH2> 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; measure on the composition of liquid hydrocarbons as a whole. The hydrocarbon fluids of the present invention preferably have IR greater than or equal to 25.4, and branching proximities (CH2 >4) less than or equal to 22.5, although any composition that complies with the limitations of formulas (a) and (b) is proposed to fall within the scope of the present invention. The measurement of the branching characteristics of the liquid hydrocarbons according to the present invention was performed by nuclear magnetic resonance (NMR) analysis and is described in more detail below. The liquid hydrocarbon composition of the present invention may have very low concentrations of common contaminants that are found in the raw materials of refined lubricating oils from natural mineral oils, depending on the nature of the feed stream used to produce the liquid hydrocarbons. . Ordinarily, the liquid hydrocarbon compositions of the present invention have less than 0.1% by weight of aromatic hydrocarbons, less than 20 ppm by weight of nitrogen containing compounds, less than 20 ppm by weight of sulfur-containing compounds and low levels. of naphthenic hydrocarbons, that is, cycloparaffins. It is expected that the levels of these contaminants will be much lower, or that these may be completely absent from the liquid hydrocarbons of the inventive. Accordingly, the concentration of the sulfur and nitrogen compounds in the inventive hydrocarbon compositions, when obtained from FT waxes, are preferably less than 10 ppm each, and more preferably less than 1 ppm each. Low concentrations of compounds containing sulfur and nitrogen are mainly due to the nature of the feed stream. The use of Fischer-Tropsch waxes, formed from gas mixtures of relatively pure synthesis that have few, if any, compounds containing nitrogen or sulfur in the gas phase gives rise to hydrocarbon fluids having very low concentrations of normal pollutants. On the contrary, natural mineral oils have substantial concentrations of organic sulfur and nitrogen compounds, which are difficult or impossible to eliminate by commercial physical separation techniques, such as distillation. The reasons for the low concentrations of aromatics and naphthenics in the liquid hydrocarbons of the present invention are twofold: First, the feed streams obtained from Fischer-Tropsch are inherently low in ring-containing molecules, as the conversion processes produce mainly, and almost exclusively, linear carbon chains, secondly, the careful selection of the catalysts for the conversion of hydrocarbons and the conditions that are used in the formation process of the materials of the present invention greatly reduce the formation of aromatics and naphthenics during hydroisomerization and catalytic dewaxing. Although it is preferable to produce the liquid hydrocarbons of the present invention from materials obtained from Fischer-Tropsch to obtain the very low concentration of contaminants in the product fluids, other waxy hydrocarbon materials, such as refined traditional waxy lubricants, paraffin waxes , depurated paraffin waxes, ox-leg oils and hydrodisintegrated lubricant distillates can be used to form the hydrocarbon compositions of the present invention. On average, the liquid hydrocarbon compositions of the present invention are paraffinic hydrocarbon components obtaining less than 10 hexyl or larger branches per 100 carbon atoms. In the same manner, the liquid hydrocarbon compositions of the present invention are paraffinic hydrocarbon components having on average more than 16 methyl branches per 100 carbon atoms. The hydrodewaxing step used to produce the liquid hydrocarbons of the present invention gives rise to significant isomerization concentrations of the long chain paraffins in the waxy feed streams, giving rise to paraffinic hydrocarbon components with a plurality of branches, as described in formulas (a) and (b) The hydrocarbon fluids of the present invention find use as raw materials for lubricating oils, or as components of formulated lubricating oils, that is, in combination with other raw materials for lubricating oils such as, for example, mineral oils, polyalphaolefins, esters, -polyalkylenes, alkylated aromatics, hydrodesintegrates and solvent refined raw materials. In another embodiment, the present invention is directed to a composition of raw material for lubricating oil having paraffinic hydrocarbon components in which the degree of branching, measured by the percentage of methyl hydrogens (IR), and the proximity of the branching, measured by the percentage of recurrent methylene carbons that are 4 or more carbons separated from a group or extreme branch (CH2 >4), are such that: (a) IR-0.5 (CH2 > 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; As measured on the composition of lubricating oil raw material as a whole. The base raw materials for lubricating oils of the present invention mainly contain isoparaffinic components with nominal boiling points of 370 ° C + and are not normal in that they unexpectedly exhibit a unique combination of extremely high viscosity indices and extremely low pour points. These two characteristics are generally known in the art to be related in direct proportion, ie, the pour point reduction of a hydrocarbon fluid gives rise to the decrease in the viscosity index and, therefore, it is very rare to obtain a point of extremely low fluidity and a relatively high viscosity index in the same fluid. For example, traditional mineral oil-based raw materials, such as comparative examples 3-15 herein, have relatively low IV when brought to low pour points (Table 1). However, the base raw materials of the present invention are characterized by extremely low pour points (PF) less than or equal to -18 ° C, preferably less than or equal to -30 ° C and more preferably less than or equal to at -40 ° C, with kinematic viscosities (VC) in the range from 2.0 cSt to greater than 13 cSt, preferably 4 cST to 8 cSt, to 100 ° C and viscosity indexes (IV) highs of 130-165, preferably of 140-165 and more preferably of 150-165, as well as IR and CH2 > 4 as established in formulas (a) and (b) above. In particular, the preferred products of the present invention are base raw materials for lubricating oil having a combination of IV and pour point of 130 IV / -66 ° C to 165 IV / -27 ° C, and most preferably from 144 IV / -40 ° C to 165IV / -27 ° C. Catalysts for the conversion of hydrocarbons useful in the conversion of the waxy raw materials described herein to form the hydrocarbon components of the present invention are zeolite catalysts, such as ZSM-5, ZSM-11, ZSM-23. , ZSM-35, ZSM-12, ZSM-38, ZSM-48, offerita, ferrierite, zeolite beta, zeolite teta, zeolite alpha, as described in U.S. Patent No. 4,906,350. These catalysts are used in combination with group VIII metals, in particular palladium or platinum. Group VIII metals can be incorporated into zeolite catalysts by conventional techniques, such as ion exchange. The manufacturing process of the base raw materials for lubricating oils of the present invention can be characterized as a hydrodewaxing process. The hydrodewaxing process can be carried out on a combination of catalysts or on a single catalyst. The conversion temperatures can be in the range from 200 ° C to 500 ° C at pressures in the range of 500 to 20,000 kPa. This process is operated in the presence of hydrogen and partial pressures of hydrogen will normally be from 600 to 6,000 kPa. The ratio of hydrogen to the hydrocarbon feed stream (hydrogen circulation rate) will normally be from 10 to 3500 n.l. I1 (56 to 19,660 SCF / bbl) and the space velocity of the feed stream will normally be from 0.1 to 20 LHSV, preferably 0.1 to 10 LHSV. For example, the conversion of the waxy feed stream can be performed on a combination of catalysts Pt / zeolite beta and Pt / ZSM-23 in the presence of hydrogen. Otherwise, the process for the production of the base raw materials for lubricating oils of the inventive may consist of hydroisomerization and dewaxing on a single catalyst, such as Pt / ZSM-35. In any case, it is possible to obtain the unique products of the present invention. In another embodiment, the present invention is directed to a lubricating oil composition of a liquid hydrocarbon composition having paraffinic hydrocarbon components in which the degree of branching, measured by the percentage of methyl hydrogen (IR) and the proximity of the branching , as measured by the percentage of recurring methylene carbons which are 4 or more • carbons separated from an extreme group or branch (CH2 > 4), are such that: (a) IR-0.5 (CH2 > 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; as measured on the composition of liquid hydrocarbons as a whole, and optionally, effective amounts of lubricating oil additives, such as for example antioxidants, antiwear additives, extreme pressure additives, friction modifiers, viscosity index improvers, pour point depressants, detergents, dispersants, corrosion inhibitors, metal deactivators, additives for joint compatibility, demulsifiers, antispintive additives and mixtures thereof. A study of conventional lubricant additives is provided in Lubricants and Related Products, by Dieter Klaman, in chapter 9, pages 177-217, Verlag Chemie ^ fc GmbH (1984), which indicates some suitable antioxidants such as phenolic or aromatic amines; as benzotriazoles anti-rust additives; metal deactivators like ethylene diamines and imidazoles; IV improvers such as polyisobutenes and polymethacrylates; Pour point reducers such as long chain alkyl phenols and dialkyl aryl esters of italic acid. As dispersants, for example, polyalkylene succinimides are described; as detergents Compounds such as sulfonates, phenates, sulfur phosphates, phosphates and the like. It also describes the use of anti-wear agents and extreme pressure additives, which may include organic sulfides, metal dithiocarbamates, chlorinated paraffins and organic phosphorous compounds, such as metal dithiophosphates; friction modifiers such as long chain fatty acids, fatty alcohols and fatty esters; as antifoaming additives, polydimethylsiloxanes and polyethylene glycol ethers are known; as additives for the compatibility of the board compounds as aromatics, -aldehydes, ketones and esters; dinonylnaphthalene sulfonates are known as demulsifiers; and "as tertiary amine corrosion inhibitors, fatty acid amides, phosphoric acid derivatives and sulfonic acids are examples, the skilled artisan will know that many other additive compounds are known in the art and may be useful with the base oils herein. The lubricating oil compositions of the present invention may contain other base raw materials for lubricating oils such as mineral oils, polyalphaolefins, esters, polyalkylenes, alkylated aromatics, hydrodesintegrates and base raw materials refined with solvents, in combination with the hydrocarbon components. paraffinic compounds described herein The paraffinic hydrocarbon compositions of the present invention can be used as the main base oil for a lubricating oil composition, with other base materials for more conventional lubricating oils added thereto, or they can be used s as an additive in combination with a significant amount of other base raw material for lubricating oil. However, it is preferred that the liquid hydrocarbon compositions of the present invention are present in concentrations of at least 5% by weight of the total composition of the lubricant base material.

EXAMPLES In the following examples, the conditions of hydroisomerization and catalytic dewaxing reaction were modified to obtain the desired products, with normal conditions in the range from, but not limited to, 200-370 ° C, 400-2000 psig, 0.20- 2.0 h "1 LHSV and 1900-5000 scf / B (standard cubic foot per barrel) H2 at the reactor inlet.

Physical properties of the lubricant base raw material Examples 1-4 A hydrogenated Fischer-Tropsch wax (Paraflint 80) was hydrodewaxed in the presence of hydrogen on a combination of pt / zeolite beta hydroisomerization catalyst and Pt / ZSM-23 selective dewaxing catalyst. 4 different hydrocarbon fluids were obtained under increasingly stringent processing conditions, having Values of VC, IV and PF as indicated in Table 1. Example 4 is an example of the present invention.

Examples 5 and 6 A refined waxy of the middle distillate synthesis (Shell MDS or "SMDS") hydrogenated and partially isomerized was hydrodewaxed in the presence of hydrogen on the catalyst combination used in Examples 1-4. Two different hydrocarbon fluids were obtained under increasingly stringent processing conditions, having values of VC, IV and PF as indicated in Table 1. Example 6 is an example of the present invention.

Examples 7-9 The Shell MDS feed stream of Examples 5 and 6 was hydrodewaxed on synthetic ferrierite in the presence of hydrogen, under varying stringency conditions to produce three different hydrocarbon fluids, having VC, IV and PF values as indicated in Table 1. Examples 7-9 are examples of the present invention.

Example 10 The waxy feed stream used in Examples 1-4 was hydrodewaxed on Pt-ZSM-48 in the presence of hydrogen to produce a hydrocarbon fluid having the values VC, IV, and PF indicated in Table 1. Example 10 is an example of the present invention.

Comparative examples 1, 2 and 6 The polyalphaolefinic base raw materials prepared Commercially of 3.87 cSt and 5.51 cSt of CV at 100 ° C are characterized by lower pour points than -65 ° C and IV of 130 (Comparative Example 1) and 135 (Comparative Example 2), respectively. Also included is a commercial polyalphaolefin of higher viscosity grade, 150 cSt CV at 100 ° C (Comparative Example 6).

^ WJ Comparative Examples 3-5 Some commercially prepared base raw materials obtained from hydrogenated crude oil fractions 20 were also evaluated. These included: pour point -18 ° C, 5.1 cSt VC @ 100 ° C, 147 IV base raw material Shell XHVI obtained from hydroisomerization of paraffin wax (Comparative Example 3), a base raw material of 4.0 cSt CV @ 100 ° C , Iv iv, Yukong 100N, characterized by a flow point of -15 ° C (Comparative Example 4); and a base raw material of 6.9 cSt CV @ 100 ° C, iv 102, Chevron RLOP 240N, and also characterized by a pour point of -15 ° C (Comparative Example 5). The common physical properties of the different commercial lubricating raw materials are compared with those of the FT UPL isomers (ultra low pour point) of the inventiveness in Table 1, below.

TABLE 1 PROPERTIES OF RAW MATERIAL DESCRIPTION Viscosity index Kinematic point viscosity fluidity ° C cSt @ 100 ° C Paraflint C80 Wax (feed) 9.42 - 83 Example 1 7.14 177 12 Example 2 6.52 171 -3 Example 3 5.72 161 -24 Example 4 * 5.54 145 -63 SMDS waxy Raffínate (feed) 5.07 - 39 Example 5 5.23 142 -24 Example 6 * 5.11 130 -66 Example 7 * 5.33 149 -18 Example 8 * 5.23 136 -59 Example 9 * 5.46 144 -40 Example 10 * 7.9 157 -42 Comparative examples CE 1 3.87 130 < -65 CE 2 5.51 135 < -65 CE 3 5.06 147 -18 CE 4 4.00 114 -15 CE 5 6.94 102 -15 EC 6 150 214 -42 The Examples of the present invention.

Figure 4 is a graphical comparison of the Cold Crank Simulation (CCS) operations of a common hydroprocessed hydrocarbon lubricant base stock (XHVI) and two base raw materials according to the present invention. The CCS test was performed according to the ASTM D5392 method, which is used to measure the apparent viscosity of engine oils. The CCS viscometer measures the dynamic viscosity of fluids at low temperature, low cutting speed and tension, simulating the flow of oil in a motor crankcase - Low temperature start (operation). The data of Figure 1 demonstrate that the base oils for the lubricants of the present invention have superior viscosimetric properties at low temperature.

Measurement of branching characteristics branching index (IR) For each base raw material indicated in Table 1, 1359.88 MHz were obtained in the NMR spectrum in solution H on a Bruker 360 MHz AMX spectrometer using 10% solutions in CDC13. The TMS was the reference for internal chemical displacement. The solvent CDCI3 gives a peak located at 7.28. All spectra were obtained under quantitative conditions using pulses of 90 ° C (10.9 μs), a pulse delay time of 30 s, which is at least 5 times the longest relaxation time of the hydrogen spin-reticle (Ti) , and 120 sweeps to guarantee good signal-to-noise ratios. The types of H atoms were defined according to the following regions: 9.2-6.2 ppm hydrogens in aromatic rings; 6.2-4.0 ppm hydrogens in olefinic carbon atoms; 4.0-2.1 ppm benzylic hydrogens at position a in aromatic rings; 2.1-1.4 ppm methino CH paraffinic hydrogens; 1.4-1.05 ppm hydroxymethylene CH2 paraffinic; 1.05-0.5 ppm hydroxygen methylene * CH3 paraffinic; The branching index (IR) was calculated as the ratio in percent and non-benzylic methyl hydrogens in the range of 0.5 to 1.05 ppm, for the total of non-benzylic aliphatic hydrogens in the range of 0.5 to 2.1 ppm. The results of these H NMR analyzes are summarized in Table 2 below.

TABLE 2% of different types of H from TJ IWR description% CH3% CH2% CH3 IR Paraflint C80 Wax (feed) Example 1 19.4 78.5 2.1 19.4 Example 2 22.3 76 1.7 22.3 Example 3 25.6 71.8 2.6 25.6 Example 4 * 27.6 68.1 4.3 27.6 SMDS waxy Raffinate 10.3 89.7 0 10.3 (feed) Example 5 22.6 70.1 6.3 23.6 Example 6 * 29.8 67.8 2.4 29.8 Example 7 * 26.2 71.2 2.6 26.2 Example 8 * 30 67 3 30 Example 9 * 27.9 69.9 2.2 27.9 Example 10 * 27 70.8 2.2 27 Comparative examples CE 1 22.7 74.8 2.5 22.7 CE 2 23.4 74.3 2.3 23.4 CE 3 26.9 69.4 3.7 26.9 CE 4 30.0 61.9 8.1 30.0 CE 5 31.5 55.3 13.2 31.5 EC 6 19.4 78.7 1.9 19.4 * The examples of the present invention.

Proximity of branching (CH2 > 4) For each base raw material indicated in Table 1, the C NMR spectra were obtained from a single pulse at 90.5 MHz and 135 Distortionles Enhancement by polarization Transfer (DEPT) NMR on a Brucker 360 MHz AMX spectrometer using 10% solutions in CDCI3. TMS was used as a reference for the internal chemical shift. Solvent CDCI3 gives a triplet located at 77.23 ppm in the 13C spectrum. All the single-pulse spectra were obtained under quantitative conditions using 45 ° pulses (6.3 μs), a pulse delay time of 60 s, which is at least 5 times the longest relaxation time of the carbon spin-lattice (Ti), to guarantee complete relaxation of the sample, 200 sweeps to ensure good signal-to-noise ratios, and decoupling of the ALTZ-16 proton. The types of atoms of C, CH3, CH2, and CH were identified from the experiment 135 DEPT 13C NMR. A principal resonance CH2 in all 13C NMR spectra at ~ 29.8 ppm is due to the equivalent recurrent methylene carbons that are four or more removed from a group or extreme branch (CH2> 4). The types of branches were determined based mainly on the chemical shifts of the 13 C for the methylene carbon at the end of the branch or the methylene carbon separated from the methyl at the branch. The proximity of the branches, indicated by CH2 > 4, and the type of carbons are summarized in Table 3.

TABLE 3 3% of different types of C from C 1 * 4R Description% CH3% CH2% CH% CH2 > Paraflint C80 Wax (feed) Example 1 13.6 81.3 5.1 38.2 Example 2 15.7 78.6 5.7 28.8 Example 3 17.3 76.3 6.3 22.5 Example 4 * 18 75.5 6.5 14.7 SMDS waxy Raffínate (feed) 6.2 93.8 0 58.8 Example 5 16.6 77.3 6 17.3 Example 6 * 24.9 67.4 7.7 7.7 Example 7 * 16.4 77.5 6.1 21.8 Example 8 * 19.3 75.1 5.6 12.8 Example 9 * 18.1 76.3 5.6 17.7 Example 10 * 15.9 76.3 7.7 20.5 Comparative examples CE 1 11.4 83.7 4.9 20.4 CE 2 13.2 -.81 5.8 20.6 EC 3 19 74.3 6.7 22.6 CE 4 16.7 72.3 11 20.4 EC 5 16.5 62 21.5 19.2 CE 6 12.3 83.9 3.8 17.3 * The examples of the present invention.

The characteristics of the branching and pour points of the isoparaffinic components of the exemplary base raw materials, as described in Tables 1-3, are compared in the following Table 4.

TABLE 4 Capping of Isoparaffinized Lubricating Opaquements Description IR% CH2 > 4 pour point ° C Paraflint C80 Wax (feed) 83 Example 1 19.4 38.2 12 Example 2 22.3 28.8 -3 Example 3 25.6 22.5 -24 Example 4 * 27.6 14.7 -63. SMDS waxy Raf fíte (feed) 10.3 58.8 39 Example 5 23. 6 17.3 -24 Example 6 * 29.8 7.7 -66 Example 7 * 26.2 21.8 -18 Example 8 * 30 12.8 -59 Example 9 * 27.9 17.7 -40 Example 10 * 27 20.5 -42 Comparative examples CE 1 22.7 20.4 < -65 CE 2 23.4 20.6 < -65 CE 3 26.9 22.6 -18 CE 4 30.0 20.4 -15 CE 5 31.5 19.2 -15 CE 6 19.4 17.3 -42 * The examples of the present invention.

The base raw materials of the present invention can be differentiated from other hydrocarbon based raw materials by the degree of branching as indicated by the IR and the proximity of the branch as indicated by CH2 > 4. These traces of the composition are graphed to help define the unique regions in this two-dimensional space of the composition as illustrated in Figure 2 (left quadrant). From Figure 2 it is clear that the branching characteristics of the isoparaffin base raw material compositions of the present invention are within a single region. Specifically, the composition can be described as consisting of mixtures of paraffinic hydrocarbon components in which the degree of branching, measured by the percentage of methyl hydrogens (IR), and the proximity of branching, as measured by the percentage of recurring methylene carbons that are four or more carbons separated from a branch or extreme group (CH2> 4), are such that: (a) IR-0.5 ( CH2 > 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; Figure 3 is a graphical comparison of the dynamic viscosities (VD @ -40 ° C), measured by the CCS method and the kinematic viscosities (VC @ 100 ° C) of different hydrocarbon fluids, including those of the present invention. The fluids of the present invention are indicated as FT I "Fischer-Tropsch Wax Isomerate", while the traditional hydrodegradable raw materials are indicated as "HDC." In particular, the points of the HDC data represent Comparative Examples 3-5 of the present invention It is clear from the data set forth in Figure 3 that the FT I fluids of the present invention have significantly improved low temperature viscosity characteristics compared to the traditional HDC fluids of the prior art. the liquid hydrocarbon fluids of the present invention fall below the dashed line of the graph and can therefore be described by the following equation: (c) DV @ -40 ° c <2900 (KV @ -100 ° c) -7000 The invention being thus described, it will be evident that it can be varied in different ways, such variations are not considered to be separate from the spirit and scope of the invention. invention, and all these modifications as will be obvious to the person skilled in the art are proposed to be included within the scope of the following clauses.

Claims (21)

1. A composition of liquid hydrocarbons, consisting of paraffinic hydrocarbon components in which the degree of branching, medium per percent of methyl hydrogens (IR), and the proximity of branching, measured by the percent of recurring methylene carbons that are four or more carbons separated from an extreme group or branch (CH2 > 4), are such that: (a) IR-0.5 (CH2 > 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; measured on the composition of liquid hydrocarbons as a whole.

2. The liquid hydrocarbon composition according to claim 1, which contains: less than 0.1% by weight of aromatic hydrocarbons; less than 20 ppm (by weight) of nitrogen-containing compounds; and less than 20 ppm (by weight) of sulfur-containing compounds;

3. The liquid hydrocarbon composition according to claim 1, wherein the pour point of the composition is less than -18 ° C.

4. The liquid hydrocarbon composition according to claim 3, wherein the pour point of the composition is less than -30 ° C. 5. The liquid hydrocarbon composition according to claim 1, wherein the paraffinic hydrocarbon components have IR > 25.4 and (CH2 > 4) < 22.

5.

6. The liquid hydrocarbon composition according to claim 1, wherein the paraffinic hydrocarbon components have nominal boiling points of 370 ° C +.

7. The liquid hydrocarbon composition according to claim 1, wherein the paraffinic hydrocarbon components comprise on average less than 10 hexyl branches or larger per 100 carbon atoms.

8. The composition of liquid hydrocarbons according to claim 1, wherein the paraffinic hydrocarbon components comprise on average more than 16 methyl branches per 100 carbon atoms

9. The liquid hydrocarbon composition according to claim 1, in where the combination of the dynamic viscosity, measured by the CCS at -40 ° C, and the kinetic viscosity measured at 100 ° C of the liquid hydrocarbon fluid is represented by the formula: (c) DV @ -40 ° c <2900 (KV®-100 ° c) - 7000.

10. A composition of base raw materials for lubricants, consisting of paraffinic hydrocarbon components in which the degree of branching, measured by the percent of methyl hydrogens (IR), and the Branch proximity, as measured by the percent of recurring methylene carbons that are four or more carbons separated from an extreme group or branch (CH2> 4), are such that: (a) IR-0.5 (CH2> 4) > 15; and (b ) IR + 0.85 (CH2 > 4) < Four. Five; measure on the composition of base raw materials for lubricants as a whole.

11. The composition of base raw materials for lubricant according to claim 10, which contains: less than 0.1% by weight of aromatic hydrocarbons; less than 20 ppm (by weight) of nitrogen-containing compounds; and less than 20 ppm (by weight) of sulfur-containing compounds;

12. The composition of base raw materials for lubricants according to claim 10, wherein the pour point of the composition is less than -18 ° C.

13. The composition of base raw materials for lubricants according to claim 12, wherein the pour point of the composition is less than -30 ° C.

14. The composition of base raw materials for lubricants according to claim 10, wherein the paraffinic hydrocarbon components have IR > 25.4 and (CH2 > 4) < 22.5.

15. The composition of base raw materials for lubricants according to claim 10, wherein the paraffinic hydrocarbon components have nominal boiling points of 370 ° C +.

16. The composition of base raw materials for lubricants according to claim 10, wherein the paraffinic hydrocarbon components comprise on average less than 10 hexyl branches or longer per 100 carbon atoms.

17. The composition of base raw materials for lubricants according to claim 10, wherein the paraffinic hydrocarbon components contain on average less than 16 methyl branches per 100 carbon atoms.

18. The composition of base raw materials for lubricants according to claim 10, wherein the combination of the dynamic viscosity, measured by CCS at -40 ° C, and the kinetic viscosity measured at 100 ° C of the liquid hydrocarbon fluid are represented by the formula: (c) DV @ -40 ° c <; 2900 (KV @ -1 0o ° c) - 7000.

19. A composition of lubricating oils, containing a composition of liquid hydrocarbons with a mixture of paraffinic hydrocarbon components in which the degree of branching, measured by the percent of hydrogens methyl (IR), and the proximity of branching, measured by the percent of recurring methylene carbons that are four or more carbons separated from a group or extreme branch (CH2> 4), are such that: (a) IR - 0.5 (CH2 > 4) > fifteen; and (b) IR + 0.85 (CH2 > 4) < Four. Five; when it is measured in the composition of liquid hydrocarbons as a whole; and optionally, effective amounts of additives for lubricating oils selected from the group consisting of antioxidants, antiwear additives, extreme pressure additives, friction modifiers, viscosity index improvers, pour point reducers, detergents, dispersants, corrosion inhibitors. , metal deactivators, additives for the compatibility with the gasket, demulsifiers, anti-foam additives and mixtures thereof. The lubricating oil composition of claim 19 further comprises a base raw material for lubricating oil selected from the group consisting of mineral oils, polyalphaolefins, esters, polyalkylenes, alkylated aromatics, hydrodesintegrates and solvent-refined base raw materials. The lubricating oil composition of claim 20, wherein the liquid hydrocarbon composition is present in a concentration of at least 5% by weight of the composition of base raw materials for total lubricant.