TW200521219A - Process to prepare a base oil - Google Patents

Abstract

Process to prepare a lubricating base oil having a saturate content of more than 90 wt%, a sulphur content of less than 0.03 wt% and a viscosity index of more than 80 starting from an intermediate lubricating base and a sulphur content of above 0.03wt%, which intermediate lubricating base oil product is obtained by first removing part of the aromatic compounds by means of solvent extraction of a petroleum fraction boiling in the lubricating base oil range resulting in a solvent extracted product and subsequently solvent dewaxing the solvent extracted product to obtain the intermediate lubricating base oil product wherein said intermediate product is contacted with a hydroprocessing catalyst in the presence of hydrogen, wherein said hydroprocessing catalyst comprises one or more metals of Group VIII and one or more metals of Group VIb in their oxide or sulfide form and a refractory oxide and the total content of the metals, calculated as if they are in their oxidic form, is greater than 60 wt%.

Description

200521219 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for preparing a saturated hydrocarbon content of more than 90% by weight, a sulfur content of less than 0.03% by weight, and a viscosity index (VI) of more than 80. Method of lubricating base oil. [Prior art] This type of base oil is sometimes referred to as API Group 11 base oil when its VI value is between 80-1 20 or Ap I No. III when its v I value is higher than 120. Base oil. It is defined in API Publication 1 509: Engine

Oil Licensing and Certification System, "Appendix E-API Base Oil Interchangeability Guidelines for

Passenger Car Motor Oil and Diesel Engine Oils ". Because Hyundai A car engines operate under more severe conditions and require lubricants formulated on the basis of base oils with the above specifications, there exists for these products Increasing demand. API U and U base oils are also used in Industrial Lubricants because of their improved oxidation stability. Lubricating base oils have traditionally been derived from vacuum distillates Or de-asphalted vacuum residue. These stray substances are obtained by first steaming the crude oil feed under atmospheric conditions to obtain the residue, and then obtaining the vacuum residue by depressing the residue under reduced pressure. The solvent extraction method was used to remove the aromatic compounds from the vacuum condensate and the vacuum residue 1 to obtain a solvent-extracted product of f aromatic compound. In a subsequent step, the product was removed from the solvent-extracted product 200521219 and removed by a solvent. ❹Remove. The product based on this material is called "careful, base oil." The founders of the AP η and m base oil products cannot be easily obtained from most crude oil sources in this way. A general review of typical approaches to the production of milk Group I 11 and 111 base oils is contained in, for example, Oli & GaS JUrnaI, Sept. "1997, pages 63-7.增加 In order to increase the n and saturated hydrocarbon content of the base oil product, an f treatment step can be used. Conventional hydrotreating catalysts are usually a form in which hydrotreating metals are deposited on a refractory oxide material carrier. The choice and amount of each component is determined by the end use. The two flammable oxide materials used in the art are a combination of amorphous or crystalline oxide oxides, silicon oxides, and petit temples. These oxide materials may have some inherent activity, but are often provided as a support for supporting active metal compounds thereon. Metals such as 唁 are usually a combination of non-precious metals from Groups VIII and m of the Periodic Table. Optionally, the oxides are vulcanized to enhance their activity before use. These methods and catalysts are described in, for example, US-A-3232863, US-A-3403092 and US-A-1178854. The production of US-A-3232863 describes a method for producing a naphthenic lubricating oil, in which the hydrogenation step is performed using a chain-molybdate catalyst supported by thorium oxide. The catalyst typically contains a total of about 10% by weight of metal supported on the oxide plate.

Us ~ A-3403092 describes a method for hydrotreating a lubricating oil, 20% by weight. NiMo catalyst used on alumina with a total metal oxide content of up to 200521219 GB-A-1 1 78854 describes a catalyst using N1W containing up to 50% reset on alumina and 2% fluorine Method for performing catalytic hydrogenation to strengthen lubricating oil. WO-A-0 0 73402 describes a method for preparing Αρι type π base oils starting from Solvex base oils, comprising first contacting the solvex base oil with a NiMo catalyst on the emulsified aluminum, and then separating the The sulfur gas fraction and then the liquid effluent is contacted with a pt / pd catalyst on silica-alumina. The disadvantage is the complexity of such a multi-step procedure. The object of the invention is to provide a simpler method. SUMMARY OF THE INVENTION This objective is achieved by the following method. An intermediate lubricating base oil product having a content of less than 90% by weight and a hydrocarbon content of more than 0.03% by weight is prepared with a saturated hydrocarbon content of more than 90% by weight, a sulfur content of :: 0.03% by weight, and Lubricity-based M Mm base oil products with a viscosity index exceeding 80% are obtained through the first benefit of the two: take the petroleum components in the range of lubricating base oils to remove ;; Γ: compounds to obtain solvent extraction ", And then subjecting the second product through the Γ mouth to the degreasing agent to obtain the intermediate lubricating base oil production mouth, wherein the intermediate product is brought into contact, wherein the nitrogen treatment catalyst includes: processing the catalyst Medium in the presence of chlorine—or more of Group VIII metals and sulphide forms' and Group VIb gold of refractory oxides, ^ Total metal content, calculated as hydrogenated form At that time, it is more than 60% by weight. 彳 Bi Xun's milk [Embodiment] 200521219 Fat Ji details 卞 Announces human hair, when using the method according to the present invention, you can use simpler Procedure to prepare API 帛 II base oil or APij m type base oil. An additional advantage is that it can be made into the desired product using a wide range of feed materials, that is, the base = oil obtained from the extraction of the solvent and the removal of the solvent. If the base oil is not fixed, it must be prepared at the same location where the method of January is performed. This is advantageous when the existing hydroprocessing facilities used to prepare the base oil are not at the same location as the solvent extraction and destructive facilities. 2. The content of sulfur and nitrogen represented by the weight percentage & Base oil products are obtained by solvent extraction and dewaxing of petroleum fractions boiling in the lubricating oil range. Suitable petroleum distillate fractions are vacuum distillate fractions derived from atmospheric distillation residues That is, the residue fractions obtained by distillation of crude oil from atmospheric pressure and then by vacuum distillation. The boiling range of these vacuum hall output fractions is usually between 300 and 62 ° C. Appropriate Between 350 and 58 (rc.) However, it is also possible to apply deasphalted residue oils including deaerated atmospheric residues and dewaxed vacuum residues. Solvent extraction is a technique widely used in the preparation of base oils and Contained in, for example, Lubricating base oil and wax processing ,,, by

Avilmo Sequeira, Jr., 1 994, Marcel Dekker Inc. New York, pages 81-118. Solvent extraction is suitably carried out using, for example, N-200521219 τ 丞 -z-pyrrolidone τ μ γ-milk rice 邛 for extracting the agent. The commonly used solvents are N-methyl-2 chicotosan and furanoic acid. In this solvent extraction, 'the aromatic compound is partially removed from the smoke mixture' thereby increasing the viscosity index of the product. Certain amounts of sulfur and nitrogen were also removed during this solvent extraction process. Solvent deworming is a technique widely used in the preparation of base oils. Available solvent sacrificial methods can be found in the aforementioned school LubriCatingbaseGllandwaxprGcessing ,,, byAvii ^

Rule% k, Marcel, such as Inc.-_eSl 53-1 92. The solvent material was quenched by quenching the feed with a rhenium solvent to crystallize the pseudomolecules. Subsequent recovery of the solvent by trituration. Examples of usable solvents are methyl ethyl ketone / toluene, methyl ethyl butyl ketone, methyl isobutyl rim / methyl ethyl hydrazone, dichloroethane / digas;

Shaoyuan, and propylene. T Intermediate lubricating base oil paid by solvent extraction and solvent de-tickling

ppmw…,… It has been discovered that the intermediate base oil product may contain a high amount of sulfur, such as exceeding 1 ppmw and up to 3% by weight. Such sulfur content will not adversely affect certain activity. ^ Using Solvex base oil as the better dry content of the present invention is less than 50 ρ _.... ': Intermediate product of human Chu oil. Nitrogen 70 ... _ Λ saturated ㉟ content is better than 70% Dong %. Except for saturated hydrocarbons, the base oil is broader than the sex compounds. Examples of polar compounds are: 10 200521219 A particularly suitable base oil in the present invention is the API Publication 1 509: Engine 〇i 1 Licensing and

Certification System, "Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oil and Diesel Engine Oils," as described in API Class I base oils. In the method according to the present invention, the sulfur and nitrogen content is determined by Increased content and improved viscosity index. Suitable catalysts used in the method according to the invention include at least one Group VIb metal component and at least one Group VIII metal component. The Group VIb metal component used is preferably molybdenum (Mo ), Tungsten (W) or chromium (Cr), more preferably M0 or w. For environmental reasons, it is better not to use chromium. The Group VIII metal used is preferably a non-precious metal Group III viii metal , More preferably nickel (Nι) & or cobalt (c). A suitable metal combination is one or more Group VI π metals and one or more Group m metals, and more preferably For a Group VIII metal and one or more Group VIb metals, the most preferred is a Group vm metal and a Group VIb metal. Examples of suitable catalysts include those containing the following Group vm metals and Group VI b Group metal combination anchor The mouth of the catalyst ·· NiW, NiMo, NiMnMo,

CrNiMo, CoMo and NiMoW.第 ντκ # Brother VIb private metals and Group VIII metals, in the form of oxides of the metal ★ The formula is very different%, their total relative to the total weight of the catalyst is greater than 60% by weight (percentage) % By weight), preferably more than 75% by weight. Although the metal may exist in other forms, i.e., elements and / or sulfides, for the calculation of ^ Μ e... In the four calculations, it is assumed that all the existing monarchs of the monarchy are now oxides of Peter ’s Temple. Shape 1 200521219 The flammable oxide can be any inorganic oxide ^ SI iyl · 'e ^ To be mixed with inert sticky materials. Appropriate refractory oxide compounds, such as silicon oxide, oxidized inscriptions ... mechanical, oxidized, ... human titanium, oxidized, oxygen '. And & into clay, two or more of these go 5 mixed. The preferred materials are silicon oxide, / ,,, e ../ emulsified aluminum and emulsified titanium, and mixtures thereof and / or a small amount and chiralized titanium. The content of the refractory oxide is both oxygen cutting or oxygen level.

10. The better is from 15% by weight to the amount%, and the better is from 30 to ^. 25 in particular to 20% by weight. The preferred composition contains a refractory oxide in an amount of from 10 to 30% by weight, and more preferably from L5 to 25% by weight. The catalysts containing these η 里 王 · and limited li inert refractory oxides are called "Medium" one by one. • No line of wheat, appeared in the CRC Handbook of Chemistry and

PhySlcs (The Rubber — μ., 66. Edition cover page and periodic table of elements using CAS version symbols (periodi (: TaMe 〇f Elements) 〇

The catalyst composition is preferably one having the following formula: ⑴b (M) c (Z) d (Y) e ⑴ The non-precious metal X is preferably one or two selected from iron, cobalt and nickel. Of those who are lucky, L is X, which is selected from nickel, Shi, and a combination of Ni and Shi. Whichever X means nickel. The non-noble metal M may be appropriately selected from chromium, molybdenum, and scale. M is preferably molybdenum. / Fan Su may be one or more elements selected from 0 or S. The oxygen component of the element that is represented by ζ as the element of γ together forms a refractory inorganic oxygen 12 200521219 compound. The element z may be-or an element in a multi-word. The better are the elements of z = n, wrong, na and ci. Best :; or a wide range of elements selected from Shao, Fa, and Wei. = Shi Xi as the main element, wait for the main element +. In the case of dead and one limb, the best z represents titanium as the rabbit, and inch is the only element. In this case, those who are the best, g, di ... prime z 'are those that use a small amount of outside (in the range from 1 to 3 weights) oxygen di =' rhyme to increase the surface area of the catalyst composition. "Benefits $ 子 & ^, c, d, and e represent the relative | M & dry 芩 芩 物 物 thing estimated by a component standard. In this paper, b and c Zhong Xi = are the reference and Determined as an integer. Then, the relative values of the metals X and M on the basis of the oxide. Establish a better 'c is the integer i, and the ratio b ·· c is from 0.75. The best is ": 1 To 2.5 small, especially in the range of 1: 1 3: Especially in the range of ": 1 to 5: 1; and the ratio e: c is from ./ .: f 5〇: 1 'and the best is 4: 1 to 2〇: Bu specifically within the range of 5: ~ 〇]. In a specific example, the catalyst composition of the present invention is _ bulk gold = chemical catalyst comprising at least one Group VI metal, at least one Group VIb metal and at least 50% by weight of titanium oxide. Refractory oxide material. The use of titanium oxide, or titanium dioxide as a catalyst carrier for conventional hydrotreating catalysts, is limited due to the lack of a useful pore structure. 13 200521219 A small number of oxidized catalysts present in the market have low pore volume and therefore are more commonly used in commercial commercial air-conditioning catalysts. Oxidized non-supported catalysts: 'or supported hydrogenated metal is less than thermally stable, low surface Λ can support the building or bearer. In general, titanium oxide-loaded hearts: Poor mechanical strength is the commercial use of catalyst systems that are considered to impede halberd. The Motoshin% found that by using the oxide catalyst system ... to prepare titanium, bulk metal catalysts. The mechanical strength and other issues, and has very good catalytic activity, the term "bulk metal oxide catalyst, but the thing is not a @, to understand the composition of this kind of pre-formed, shaped catalyst carrier The traditional form of conditional loading of metal is a kind of ", ... or a combination of = a mixture of metal and refractory oxide material, a load-type contact 31 crane, and this mixture is caused by sinking. The same as Cheng Liyi ’s material in this bulk metal oxide catalyst composition is no longer in the composition-individual is independent of the last, in most cases, the existence of titanium can be obtained from Then the two-two ': Λ is identified, and the composition and composition derived from the refractory oxide material containing titanium oxide can also be determined in the ratio by using the analysis techniques m㈣ and ⑽ (_Mahedianli analysis) commonly used in the art. Jen F column. The content of titanium oxide is preferably 50% by weight or more of the refractory oxide material, and the content is within a range from 7% to 5% by weight, or from 9% to 10.% by weight. Within. Its content is especially in the range of 14 * 200521219 and 95 to loo weight percent of the main refractory oxide materials. Particularly preferred, titanium oxide is resistant to the use of other refractory oxides, oxides, oxides, L "is also selected from the group consisting of oxygen, titanium, and oxygen, oxidized stone, and oxidant. The results of the discovery. ,,,,,,, and refractory oxide materials are good titanium oxide. In nature, redstone can be redstone (一 LE) , Ruiqin Mine: ,, :: heavy polymorphs: gold with thermal stability, the most oxygen-rich monsoon redstone, and can be converted into golden red at a very high age, sores, and any of the following: All anhydrides, more than 70% of this emulsified sharp form are used in the catalyst composition of the present invention. Use of those with the following formula: the best form is 80 to 100% by weight, And special results. Oxidation industry in the form of uranium oxide has been found to achieve good results.

The particle size of the catalyst can affect the aggravation of the activity of the most catalytic composition. Although all oxidized sharp powders are suitable for use in the invention, it is preferred to use a particle having a size of 5G microns or less: particle size, a particle size of 20 microns or less is preferred, and a particle size of 5 is particularly preferred. Micron's smaller particles of emulsified titanium powder. In general, the smallest average particle size of titanium oxide in the titanium oxide used is on the order of 0.05 micrometers. Herein, the average particle diameter is the diameter of 50% of the particles, also referred to as j) v50. Non-hanging 'suitable titanium oxide starting materials are available from Millenium

Chemicals, Degussa and Haishunde. For example, DT-51D and G5 products from Millenium, P25 products from Degussa and FCT 0 1 0925 products from Haishunde 15 200521219. Oxidin and other refractory oxides ㈣μ are commercially available, such as stone oxide-titanium oxide mixtures, such as the FTS 01 product available from Haishunde. The titanium oxide used has an appropriate surface area of β E. T. ranging from 10 to 3 m² / g (mVg), and more preferably from 20 to 4. 〇 m2 / g. The preferred vnu metal is one or two non-precious metals selected from the group consisting of hafnium and iron. Preferably, the metal of the Xianxian group is selected from the group consisting of Lu, Jie and Lu and Gu. Best to go ^ P ν τ τ τ ^ • Take the 5 Hele νιπ group metal as nickel. Group VIb metal is preferably one or two metals selected from the group of metals, and the other is the second: = non-precious metal of crane. Section VIb 1 mesh crane and a combination of both. The optimal VIb = depends on the temperature of the end use. For end-use applications in applications that are lower than 二, the preferred is 锢, and for end-use applications, the temperature is high. In the case of "or", the preferred one is the crane or eel "in the present invention = :: Γ contains residual ammonia, organic species and / or water species; use = ::: Can: It will contain different amounts and different types of Γ. Atmospheric conditions may also affect the two bases in the catalyst composition. In this article, the percentage content is preferred. The definition of two pounds is defined on the basis of oxides. Day,, and the amount of genus X is in the form of the halide of the metal and based on the total catalyst weight. 16% in the range of 200521219, but the better is in the range from 20 to 35 to 33% by weight. The most special is in the range of 25; the better Calculated in the form of two metal type oxides and the total catalyst weight is within the range of the weight of the metal, and more preferably within the range of 40 to 75 55 wt%. 0 and special 50 to

At the time, the system includes refractory oxide materials. The best C is from 10, the better is P, and the content is from 5, the more red is 15 to 40% by weight, the 25 is, and the special is 2 〇Weight 1 soil to 30, more preferably 30% by weight, more preferably rq "I and the product contains from 10 to t χ Λ 0 ^% and especially weight%." For the record and the better is 13 To π tongue said. / You are in the range of δ to 55% by weight, preferably and particularly in the range of 17 to 44% by weight; where M is a pin, preferably it contains 30 to 70 tongues. / Muyou ZU to 80% by weight, more preferably =: and especially a titanium ... in the range from 8 to 40% by weight, preferably 15 to 30% by weight, and the weight is "35" and ^ ^, Within, that is, Ni〇 / Mo〇3 / Ti〇2 Gong =% 'Good results have been served for the bulk metal oxide catalyst industry based on titanium oxide. According to the method used in the present invention- The vehicle composition may contain from 0 to 10% by weight on a total basis, and the most common is from 5 to 8% by weight: line retention: species such as organics, ammonia and / or water species. The existence of these ingredients The total amount can be determined through standard analysis techniques. The selection of the ingredients contained in the bulk metal oxide catalyst used in the present invention and other superior materials and their application in the present invention will be referred to in the following 17 200521219 It will be explained according to the general preparation technology. According to the bulk metal oxide of formula (I), the catalyst is decomposed by the precursor of formula (u) and the producer is prepared by passing (NH4) a (x) 5 (M) c (Z) d ((I) where a is an integer greater than 0, and χ, M, z, b, with Li Han a and e recognized above are all A: (b + G) Morse is from 0 1 : i., preferably from 0.1: 1 to 3: 1, b: C Moore 1 to 5: 1, preferably 盍 ... n Molar ratio is from 0.5: pregnant woman is k 〇 · 75 ·· i to 3 to 2.5: 1. The special one represented by d_ Γ is 0 · 8: 1 ^ The molar ratio represented by the appropriate is from 0 2 · (5 50.1, and the better is From 0.5: 丨 · to „ln, to 20 · 1, more preferably from 0 75 · 1 to 10 · • Bu, in particular, from 0.8: 1 to 5: 1. 6 疋 0 · 75.1 from 1 : 1 to 5〇: 1, the better is Mohr than the appropriate one ^ 1〇: 10, the better is 4.1 to 20: 1, especially 5: the decomposition of the precursor is from 10 〇i 60 (rC, the better is Jiang Gu in the range of 120 ° to 450 ° C, the degree from 120 to 360 °, and the better is to increase the temperature from 25 ° to 3 °. Μ & Tong +, C, Mo, 巳, 斤, and 要 are the amorphous materials, the w, and w degrees are better than no more than about 35, the special angle "~ ㈣ 300 C. The decomposition can be in the lazy flood enclosure, such as in nitrogen, any rare ~, into p 1 17 rare lice or their mixture, or in an oxidizing atmosphere, such as 4 or detective 々a Such as lice rolling, milk gas—nitrogen, air, one or more of them, such as 丄 & Liaoning, or 1 σ gas, hydrogen sulfide, or other The decomposition can be carried out within this compound. The decomposition can be carried out in the process of slurry treatment or in the privacy of the further processing of the composition to be used, such as in extrusion. 18 200521219 The preparation of the precursor of the general formula II can be carried out by the procedure described in, for example, EP-A-1 090 682, in which the metal compound is completely dissolved in the liquid used Informative I > The follower is a shellfish liquid, especially within water. The best is that the preparation uses a paddle fluid that includes. ^ _ Called a dagger to place one or more desired metals in a protonic liquid (such as water) (where the metal compound is present in both the solid phase and the dissolved phase) The contact with the refractory oxide in the presence of temperature and time conditions sufficient to produce the precursors of Muhai, Mushroom is carried out in this process. The metal herein does not refer to a metal in a metal phase, but refers to a metal compound having a desired metal ion in a relatively water-soluble form. All ingredients can be added to the proton-type liquid simultaneously or υ 4 1. In addition, you can also broadcast the + metal tablets and refractory metal oxides and the refractory oxides and the proton-type liquid virtual too / v will be V *, soil and month; in the slurry phase, the remaining Ingredients are added to it. The most suitable catalyst preparation procedure includes a polymer mixture of Group VIB and Group V⑴ metal compounds in water or other proton-based liquids at a high temperature, and an alkali and an inert oxygen compound I. A slurry of an emulsion (preferably silica and / or oxide) in water or other proton cracking liquid. The addition of individual compound-forming slurries is not critical, but a slight benefit can be seen when alkali-refractory oxide slurries are added to metal slurries / night. Blending or mixing can use, for example, U1 ΐτ ^ T.

Turrax machines. During the mixing or blending process. Various water-liquid components will co-sink under the action of an alkali precipitating agent to form a precursor to form your wind solid. This procedure is appropriate to maintain the right temperature for a period of time, and the appropriate buckets are controlled by the talents to achieve the desired 19 200521219. The first step is to determine the correct system of the desired end product-a routine thing. Where appropriate, the temperature is within the range of 25 to the order; and the sinking time is from 10 minutes to ", although the creatures from the material can be found, but the founder, / ^ & The final production of the mouth will cause the dissolution of these metal components, such as red, red, and red, and will not dissolve good end products ... and at too low temperatures, insufficient dissolution may occur. In the two examples, the goal is to have a solid content from the heart, which is 20 to ^^ means the amount of impurities added to the proton-type liquid = good = 2 such as wind) 1 is for each mole The metal is at least 0.5 Moore, based on Hita's Emulsified Emulsion) as the benchmark) is 50 Moore = M + X per mole of metal (in the final form of the oxide. In the zone, the amount of substance may be Alkaline substances (such as ammonia) that will affect the catalyst composition should be at least 0,075 ^ Morr_Metal_oxide_Morr. For testing, the better is at least G.8 , In particular, at least the substance as the benchmark) is a maximum of 5V ear: for each mole of gold (in the case of oxidized poly-mole. Mor, more preferably a maximum of 2 moles And especially the best younger Vib group metal is Gu Lu, nickel or a mixture of them. If, ";; Tian's younger group metal includes medium and therefore better, 荀, ~ is the water part Retained in solid phase, bromide, nickel phosphate, zinc formate / is a mixture of nickel lithium, nickel oxide, hydroxide and more :: and recorded, or their two or more than "molybdenum compounds (according to similar (Guideline) 20 200521219 is (one or two) molybdenum oxide, ammonium molybdate. These materials are all ^ μ claw 1 mesh, or their current commercially available laboratory operations I The waiter may use the general η: operation, such as Shen Xing, and the preparation. In addition to the 5 Italian metal, it also has the right material, usually because it has a lower environmental impact: the starting material that is the component is better, Because it is under heating :: The second one is better. Therefore, the content of the acid breaking acid _ v. T,?, The carbon contained in the starting material & Li, can be decomposed into oxygen ^ Precursor In the preparation, it is resistant to carbon dioxide and water. The inert material is suitable for use under the conditions of use. Flexion: The imperfections show relative health during use :: Low catalytic activity, or no surface area of amphiphilic materials. The appropriate ones are from ⑽ to 7 = better from 150 to 400 square halves / A Qianfangwei / g, the main examples of Qianfangwei / g in the range of oxidized stone oxime, oxidized oxide, oxidized # m This material search includes nucleation ... Emulsified titanium, hafnium oxide, boron oxide, Tunzhifeng emulsifier, natural And synthetic clay, or a combination of two or more of them. The preferred material is a mixture of silicon oxide, aluminum oxide, etc. and / or a small amount of A sheep titanium, and the oxygen cut used by them. The form and the best are oxidized stone eve. V dry Vi / < 又 / / 百 hundred restrictions and Doda recognition miscellaneous gifts, ^ ^ ugly hanging any catalyst silicon used in the catalyst carrier can be used in this Invented. One kind of non-suspended appropriate silicon oxide material is Wat 50, which can be obtained from Degussa, _ 子 的 白白 ㈣㈣_Slperrm is the trade name. The appropriate test used to prepare the mash with inert materials is one selected from the group consisting of gas oxides or emulsion hydrogen emulsions (QXQhydr0Xldes), such as hydroxides of Group ^ or IU metals, Group u or Group IIA; Acid salts, hydroxides of Group IA or Group IIA metals, equivalent compounds 21, 200521219, or any of them-Ί mixtures of one or more nights. Suitable &- i ^ Examples include ammonium hydroxide, hydrogen, hydrogen peroxide, hydrogen peroxide, sodium hydroxide, ammonium silicate, ammonium carbonate, and the best. 'The test compound is produced in solution compared with its use of water as a solvent. When produced in hydroxide form. In the specific example, the best combination of starting materials for preparing the bulk metal oxygen is nickel carbonate, and the preferred combination of zinc oxide and zinc oxide is zinc carbonate, _4, ..., his preferred fruit monoammonium molybdate and silicon oxide or Carbonic acid _ titanium oxide. Concatenate

Usually it is better to use the mixing and sinking parts, lower than the boiling point temperature of the solvent used, also; Medium :: Soluble: 丨 Keep in the neutral state of water, lower than the neutral pH in water 'Usually «the M value of the liquid is maintained after the precipitation process is completed, preferably the same day, h. The formation of all of them is maintained at the ambient temperature < (-Generally called the maturation heating time is usually from 30 minutes + ^

Within the range of 孰, θ, θ # γ If the best is known, within 4 hours, the heating temperature can be in the range from week to 95. 〇, preferably from 55 to: appropriate 80. C. The temperature during the hydration period is especially low, especially from 60 to low temperature. After looking back at October, and then cooling the resulting mixture to an unacceptable level of cooling, the resulting mixture can be re-obtained to obtain a solid content again. Straight air plugs include overruns, sprays that depend on many local ..., &. The system factors used include 'environmental regulations' and energy availability. Best 22 • 200521219 are filtration and spray drying. The former is a fast and non-energy-intensive person but requires two iterative steps and produces a larger volume of wastewater; the latter is a person that can = densely but produce a small amount of wastewater. In the% method, a better amorphous material can be obtained more uniformly under all refractory oxide contents using the slurry preparation method of the present invention. The solid product made in this way has a combustion loss of 5 to 95% l = the soil is composed of mainly amorphous materials, such as the use of powder χ-ray ①: Knife analysis of the measured out 'No Too specific examples suggest that it may contain crystalline materials, such as having a layered double hydroxide: oxygen test hydroxide. In this article, the combustion of a material is heated to 54nv%, and Feng Feng uses the following procedure to mix to prevent the relative mass of two minus f: the sample is fully and pre-calcined crucible # 二 二 将 无The sample is transferred to a weighed oven = 2 °; _ is placed in the 5 ^ preheated 15 knives 4 miles and 8 inches, but it is said that the " , At LOI%, Cu / Determine LOI according to the following formula:

Wcalc) / W ^ 100% where W is the initial weight of the sample ^ the weight of the sample burned, Tung is the weight of the forging after heating in the oven. Both weights have been corrected before being processed further. weight! . It is a filtration method. Ten to dry the prepared powder, especially eight to separate the solids. In any appropriate atmosphere, such drying or curing can be a mixture of them, or oxidized% lice milk, inert gas or gas, or Their current situation? 'For example, oxygen, oxygen-nitrogen, air or transport atmosphere, such as hydrogen, or reduction of 23 * 200521219 mixture of gas and inert gas ammonia and / or water gas, within. Biqin compound 'with or without 〇5 $ ± l 坫 The temperature is preferably from 20, usually 25 to 95 C, preferably 55 to 100 ° C. The powder prepared contains an oxidative condensate, and the special one is from 70 to 80 ° c. In the case of h, s ^ q, the better drying temperature is 隹 20, usually 25 to 200 V h n is from 7U13rc. From 55 to 150. (: And the special one 'calcined the obtained powder before molding. The appropriate calcination temperature is from 100 to 600. Tian's Ruyi is the most stable, which is 120 to 400. However, The taker should not burn the yoke at 35 (rc to prepare π 氺 / on the yoke, especially not more than 300. (:, Qi Wai / ^ He crystal type ㈣. _ Burning can also be in any suitable flood) Surrounding, such as ^ ^ ^ U U IU field ^ ^ ", " I gas, inert gas or their mixture, in a reactive atmosphere, such as oxygen one or # 客 I αα lice lice lice lice, air , Or their mixtures, or mixtures of inert gas and reactive gas, or liquids. The first two need to obtain the powder and additional materials in the solid phase T. Those in the solid phase include other uses For materials of 4 〃 / s, such as other catalytic materials used in the application of force cough treatment. You can add other supplementary materials in the study: = '. These include additional materials usually in materials. Appropriate examples In order to prevent the material containing ammonium fluoride or organic phosphorus compounds, the suspension of the 'eight: Urea compounds' Other transition metals, or their use:. Scale-containing compounds can be added in any preparation step. If necessary) can be emulsified. As a binder, the compound containing the dish (with or without stone) Shaw acid is used to increase pept ising. 24 • 200521219 Furthermore, additional materials can be included in technical agents "(* called g agent) or" forming aids ", which are called" forming includes Additives such as stearates, surfactants, Ishiguro,% 'can be used to maximize the strength of the resulting molding material: a mixture of special two, etc. In the case of molding, the amount is preferred-in the warp Any conventional extrusion in 4 can be used to help the resulting molding mixture. In addition, doubling ^ rb I can be added to the appropriate material in the liquid phase, including protic solvents: material solvents, such as b% Xifan Alcohol search, and two non-protonic substances can be added to a protic solvent such as water to make mixing. The L0I content of the substance is suitable for the content used for molding. In general: the materials in the solid and / or liquid phase will be Mixed together = / again in a special order It is important to ensure that the sample is thoroughly mixed to prevent unevenness. The other solids and liquids added during the molding process are preferred. The final weight is in the range of 0 to 95% by weight. It depends on the requirements of the intended catalytic application. Molding can be carried out in a variety of ways depending on the requirements of those applications. Methods include, for example, spray drying, extrusion, bead formation, and / Or granulation. The surface area of the final product measured by the B.E.T. method using nitrogen as the adsorbent is generally in the range from 10 to 35 square meters per gram, preferably more than 35. Squares per gram, more preferably 65 square meters per gram. The pore volume of the final product measured by the gas-gas adsorption method on the B.E.T. curve is as high as 95 nanometers (nm), preferably from 0.002 to 2.0 cubic centimeters / gram. Within the range from 〇 · 丨 to i. 〇cm3 / g. The flat bed crush strength (flat bed crush 25 * 200521219 strength) measured according to ASTM D6175 is preferably more than 50 Newtons / cm (N / cm), and more preferably more than 100 Newtons / cm, especially higher than 15 Newtons / cm. The Jiajia amorphous catalyst composition of the present invention has been found to have such high chipping strength. These catalysts show very high activity for the aeration treatment of intermediate lubricating base oil products ^. This activity is higher than that measured by traditionally supported Ni M0 and C0M0 catalysts prepared by pore volume impregnation. * Although it is not intended to be bound by any theory, it is currently believed that this kind of non-seeking activity is the ancient_eight ^ m of the metal in the overall oxide material achieved through careful control of the sinking process, The result of the dispersion factor of the degree of return. The goal of controlling the precipitation process is to prevent the formation of as little crystalline material as possible. High-level radioactivity should not be confused with dispersion uniformity. "The catalyst composition disk of the present invention The catalyst composition used in the present invention is dispersed under the metal in the entire oxide material," but not necessarily uniform The address% ^ J is also a knife-and-square; among them, it can have high activity. Although the better catalyst composition has a non-S-criminal ... and has a non-Japanese-Japanese nature, they still exhibit high fragmentation strength. The catalyst composition used in the method of the present invention is a substantially amorphous material, which does not have an XRD analysis under the short X-ray, X-ray, and X-ray of the powder. Detectable crystalline components. In the present invention, those within the dry area of the moon side also have δ in the catalyst. Some rabbits are detected according to XRD. 丄 丄, double-out, 纟 σ 曰 materials Ideally, it only exists in an amount that does not change the activity of the amorphous material. Since the base oil to be converted contains sulfur compounds, the catalyst used in the method of the present invention is better Go to the child + I wish to pass through at least part of the vulcanizer before the operation to increase its sulfur resistance. Touching, pre-carbonization can be achieved by known spoon methods in the art, such as in the following eight ρη ~ Λ newspaper Revealed methods: EP ~ A-181254, EP-A-329499, FPa " ㈣ EP-a-448435, EP-A-564317, 26 200521219 WO A-9302793, and WO-A-9425157. In general The pre-sulfidation is achieved by contacting the uncured catalyst with the appropriate & ί !! ί, such as hydrogen sulfide, element 2. Appropriate polysulfides, hydrocarbon oil containing sulfur compounds or two or more of these vulcanizing agents. Especially for in situ vulcanization, it is appropriate to make = = Quality: Hydrocarbon oil containing sulfur compounds is used as a vulcanizing agent. Then the temperature of this medium in the scriptures is gradually increased to between 150 and 250 ° C.

Between temperatures. The catalyst is kept at this temperature for a period of time between 10 and 20 hours. Then, gradually increase the temperature to the operating temperature. A particularly useful hydrocarbon oil vulcanizing agent can be used to feed base oils with sulphur-containing compounds that are significantly more expensive. In this case, the feed that has not been desulfurized can be contacted, for example, under operating conditions, thereby promoting the catalyst. Typically, the base oil feed should include at least 0.5 weight percent sulfur-containing compound, 1 weight percent refers to the amount of sulfur to be used relative to the total amount of feed. ] A few factors & The method according to the invention is operated under relatively mild conditions. And

The temperature is between 35 ° C and 30 ° C. The actual temperature is largely determined by the sulfur and / or nitrogen content in the feed and the degree of reduction to be achieved. Higher severity will cause S — and N_ The higher the level of reduction, the pressure can be in the range from ^ to 250 bar (bar), but the better is between 20 and 100 bar. Its weight space flow rate (Long 3 ^ can be Hours and liters of oil per kg from 0.1 to 10 kg (kg / ι.ιο and the appropriate range is from 02 to 5 kg / lh.) The present invention is based on the following non-limiting examples 27'200521219 Example 1 Catalyst having a nominal composition of Mo-O / S102 (26% -54% -20%) will be 109 g of NiC03 (industrial grade 39.5 wt%). ), 19/1 Tai, ,, Liri / G), 124 grams of ADM (4 molybdic acid 4A 'industrial grade 56.5% by weight Mo) and 45 grams of gas cut rQ. Fan Yang Si (Sipernat 5〇) Dispersed in 1485 grams of water with stirring at 81TC to form a slurry. M gas solution (m% by weight) was mixed with the slurry and aged for 1/2 hour. The radon mixture (8 (rc) was pumped to-without heating Inside the flask and use spray drying The solid was recovered, wherein the conditions used were maintained to a temperature such that the solid was not higher than 30 ° C. The resulting powder was compressed, pulverized, and selected to a different mesh size. The calcination was performed at 3GR / H, which was performed from the chamber The temperature starts at 200 C / hour. The element structure of the catalyst is as follows:

Nii.iMoi.oSii.oOe.! This composition appears to be amorphous by XRD analysis.

Comparison {Column A: Extraction of the vacuum chamber output using furan formic acid followed by solvent dehydration using methyl ethyl ^ toluene with the properties listed in Table 1 to obtain a base oil and hydrogen and commercially available NOM on the oxidized name. Catalyst C (Pany, Houston, c_424) of τχ). Its operating conditions are a hydrogen partial pressure of 100 bar, ws / g / l / hr, a circulating gas rate of 1,000 Nl / kg and a temperature of 32. 〇 and 36〇. 〇Temperature between 〇. The effluent was recovered and distilled to have a viscosity of more than 4 7 cSt under i 00 γ. The saturated hydrocarbon content (% by weight) and π of the base oil obtained at several reaction temperatures are shown in Figs. 1 and 2, respectively. Table 1 lists the properties of the end products recovered at a reaction temperature of 350 ° C. 28 • 200521219 Example 2 The comparative example is repeated. The difference is that 更 1 uses a catalyst with a nominal composition of N ^ Mo-O / SWs (26% -54% -20%). Prepared in 1. Table 1 lists the properties of the end products at the reaction temperature of 350 ° C. Figures 1 and 2 clearly show that the procedure using N · Nb M0 ~ 〇 / Si〇2 bulk metal catalysts can result in higher saturated hydrocarbons at the same and even lower temperatures. Higher VI. Table 1 Typical base oil feeds (*) Saturated hydrocarbon content (% by weight) HPLC (SNS 2660) 73. 3 Polars (aromatics) (% by weight) 1 —-— 26.7 Sulfur content (mg / 仟G) ----- 7060 nitrogen content (mg / kg) 27 viscosity index 104 viscosity (cSt) at 100 ° C 5. 23 viscosity (cst) at 40 ° C " ---- 30 09 pour point (° C) ~ one --------- -12 —10 112.

98. 3 1.

< 1 126 5. 049 25. 68 -9 Example 3 ', intentional ^ / ^ ⑴ ^ ⑽ ^ "" The catalyst with a nominal composition will be 157 grams of NiC03 (industrial grade 39% by weight), 281 grams of AMT (Tungsten rhenium, industrial grade 68 wt% W) and gram oxygen cut (Sipernat 50) were dispersed in 2 " 3 grams of water to form a slurry. 115 grams of ammonia solution (25 weight 29 200521219 1) was added to the lysate and cooked ... bell. The warm mixture was simmered. c): Go to an unheated flask and use a cargo mist to dry and recover the solid. The conditions used are maintained so that the solid will not be exposed to higher temperatures. The powder and tool were converted into a material form, and calcined at Gang C / 1 hour, where the temperature was 2 室温 from room temperature. The structure of the oxide precursor appears to be amorphous by ™ analysis. Example 4 A catalyst having a nominal composition of Nb Mo-0 / S102 (m_40%-40%) will be 165 g of NiC03 (industrial grade 39% by weight), 186 g of Gu di acid, industrial Grade 56.5% by weight of Mo) and 182 grams of oxygen cut (sip⑽750) were dispersed in 3G1G of water to form a slurry. A gram solution of ammonia (25% by weight) was mixed with the slurry and aged for 30 minutes. The warmed mixture (, c) was pumped into an unheated flask and the solids were recovered using spray drying, wherein the conditions used were maintained so that the solids were not exposed to higher temperatures. c's temperature. The obtained powder was pulverized and extruded according to a general operation, and was then subjected to 300. [The calcination was performed at eight hours, in which the temperature was raised from room temperature to 20 ° C / hour. The structure of the oxide precursor appeared to be amorphous by XRD analysis. FExample 5 The comparative example was repeated, except that the difference was that A catalyst with a nominal composition of Ni-w_〇 / Si〇2 (19% _61% -20%) was used, as prepared in Example 3. Table 2 lists the obtained at a reaction temperature of 350 ° C. The properties of the end product of Fenshi Example 6 30 200521219 The repeated comparative example of the end product obtained under the condition of d prepared in Example 4 using 〇 / Sl0: As prepared in Example 4, the difference is (20%-4 0%-40%) catalysts with a nominal composition. Table 2 lists the properties at a reaction temperature of 360 ° C.

Catalyst with Ni〇 / Mo〇3 / Ti〇2-27% by weight / 53 nominal weight% / 2% by weight

Table 2 Example 5 ----- Example 6 Saturated hydrocarbon content (% by weight) 98.2 ^ --- HPLC (SNS 2660) Sulfur content (mg / g) 11 ------ 4 Nitrogen content (mg / 仟 克) < 1 ~~ -— < 1 Viscosity index 118---114 Viscosity at 100 ° C (cSt) 4. 448 4. 738 Pour point (° C)--9 -10 Examples 7 In a 5 liter ball bottle, heat 2972 grams of water to 8 (rc. After reaching this temperature, add 84.2 grams of titanium dioxide (available from Dish v ^ a Millenium)

Chemicals' products DT_51D, βΕΤ surface is 00 ten squares per gram and the crystal form is 100% anatase titanium oxide based on oxides), 3 grams of nickel carbonate (39% by weight nickel), and 248.5 grams of Ammonium dimolybdate. Shortly thereafter, 111.6 g of an ammonia solution (25% by weight) was mixed / mixed with the slurry obtained above. The resulting mixture was kept at 80 ° C for 30 minutes. Its pH is 83. 31 • 200521219 After 30 minutes, turn off the heating source. 344 grams of solid material was recovered using spray drying. The osmium powder was extruded, and the resulting green extrudate was dried and thereafter at 300. Calcined under C. The β · E · T · surface area of the obtained product was 42 m2 / g. The total (nitrogen) pore volume measured on this & & τ adsorption curve up to 95 nm was ^ 23 m2 / g. Elemental analysis yielded Ni〇 / Mo〇3 / Tl02-27 · 5% by weight / 51 · 3% by weight / 20 · 8% by weight, which corresponds to b: cn 1, d: c = Q 7: 1, e : c = 5.5 ·· 1 0 [Schematic description] Figure 1 shows the base oil obtained in the experiment, which has a saturated smoke weight percentage content as a function of the reaction temperature (.0). Figure 2 depicts the results for the experiment. As a function of the catalyst used, its VI is a function of reaction temperature.

Claims (1)

200521219 10. Scope of patent application: 1. A kind of intermediate lubricating base oil product with a saturated hydrocarbon content of less than 90% by weight and a sulfur content of more than 0.03% by weight. A method of lubricating a base oil having a residual hydrocarbon content of less than 0.03 wt%, a sulfur content of less than 80% by weight, and a viscosity index exceeding 80, wherein the middle door / door π raw base oil product is obtained by first using Solvent extraction within the range of lubricating base oils. Forten ’s petroleum customers feed some aromatic compounds to the solvent-extracted product, and then apply the dazzling mouse to the solvent-extracted product: to the intermediate lubricating base. Oil products; where the intermediate product is 2 :: = Γ contacted in the presence of hydrogen 'wherein the hydrotreating contact is classified as an emulsion or a sulfur species and one or more of a host ^ or more of Group VIII Gold or more of the VIb group of metals, and other metals such as wash-resistant metals contain I, ιν # pound a person 丨 raw emulsion; and 60% by weight. ° Ten pounds a day, it is more than 2 · According to item 1 of the scope of the patent application, the total content is calculated in the form of their oxides :, of which: of these metals 3. It is greater than 75% by weight according to item 1-2 of the scope of patent application. The content of the refractory oxide is in the range of 0 to 25% by weight according to the method of // non-item. When calculating the emulsified form, • According to the scope of patent application, the refractory oxide is silicon oxide. 5, according to the scope of application for patents 1-3, the refractory oxide is titanium oxide. 6. The method according to any one of item 1 of the scope of patent application, the method of any one of them, wherein the catalyst composition in method I is 33 (I -200521219 (X) b (M) c (Z ) d ^ Y ^ where X represents the smallest _, ^ M. _ ^ — a group VIII metal that is a non-shell metal; eve — a group VIb metal that is a younger brother; z represents one or more elements selected from aluminum and; Γ of magnesium, titanium, hafnium, and zinc represents 0 and / or S; … Where one of them is an integer, and d, e and the other b and c mole ratios are in the range from 0.. 5M, so that b: c is in the range from, and d: Moore a ^ 1 〇5 c: within the range of c: and Moore ratio of e: c is within the range of 1.0 to 50, the ear ratio or range of the 6th method, the ... Within the range of two to two zr quasi from 25 to the benchmark from 5. To 55 wt .; tungsten and its content is in the form of an oxide ranging from 15 to 25 wt .: dry range, and oxidized stone or oxidized: 1 wt.%. 8. Please refer to any of the "7 patents for patent application"-the item in contact with the hydrogenation catalyst, /, whose t η, and the number of μ degrees are between 150 and 350. Guang Shi 9. According to the patent application Between C .: When the party of any one of the 18 items of Mole and the soil are in contact with the chlorinated catalyst, the dust force is between "10. According to the scope of the patent application" _9. Only < Wanfa, of which 34 200521219 has a viscosity index of more than 1 2 0. 11. The method according to any one of claims 1 to 10 in the scope of patent application, wherein the saturated hydrocarbon content of the lubricating base oil exceeds 96%. Eleven, schema: as the next page 35