CN106554819B - A method of lube base oil is prepared by high-content wax feedstock oil - Google Patents

Abstract

The invention relates to the field of oil refining, and discloses a method for preparing lubricating oil base oil from a high-waxy feedstock oil. The reaction is carried out in the hydroconversion reaction zone of the dewaxing catalyst to obtain the hydroconversion oil; (2) the hydroconversion oil is introduced into the isomerism depreciation reaction zone containing the isomerism dewaxing catalyst for reaction to obtain the wax conversion producing oil; (3) introducing the wax-converted resulting oil into a hydrofinishing reaction zone containing a hydrofinishing catalyst to obtain a hydrofinishing resulting oil; and (4) introducing the hydrofining resulting oil into a separation zone for separation . When the above method of the present invention is used to prepare lubricating oil base oil from high-waxy raw material oil, the difficulty of pour point depressing in the process of producing lubricating oil base oil can be significantly reduced, and lubricating oil base oil with low pour point can be obtained in high yield.

Description

A method for preparing lubricating oil base oil from high waxy raw material oil

technical field

The invention relates to the field of oil refining, in particular to a method for preparing lubricating oil base oil from high waxy raw material oil.

Background technique

The method of preparing lubricating oil base oil by adopting a full hydrogenation process is well known in the art, and its process mainly includes: hydrotreating-hydrodewaxing-hydrogenation supplementary refining; most of the hydrotreating process is based on hydrodesulfurization, The purpose of denitrification, deoxygenation and hydrogenation saturation of some aromatics; the purpose of hydrodewaxing is to reduce the pour point and convert the wax molecules in the raw oil, mainly including isomerization dewaxing process and catalytic dewaxing process; The hydrogenation supplementary refining process is to remove the residual sulfur, nitrogen, oxygen and other impurities in the dewaxed oil, and to saturate olefins to improve the stability and color of the oil.

CN1225662A discloses a method for preparing lubricating oil base stock, which comprises: a) in a hydrotreating reaction zone, at a hydrogen partial pressure lower than about 11MPa and a temperature between about 260°C and about 427°C, will have a normal boiling point A petroleum feedstock in the range of about 316°C to about 677°C is contacted with a hydrotreating catalyst to produce a hydrotreated oil having a viscosity index at least about 5 higher than that of the petroleum feedstock at 100°C its viscosity measured at the time is at least about 2 cSt; b) in a dewaxing reaction zone, under hydrodewaxing conditions, the hydrotreated oil is contacted with a mesoporous size molecular sieve catalyst to prepare a dewaxed oil having a pour point lower than the pour point of the hydrotreated oil; and c) in the hydrofinishing zone, the dewaxed oil is mixed under hydrogenation conditions with a platinum/palladium alloy containing The hydrogenation catalyst is contacted to produce a lube oil base stock in which the platinum/palladium alloy has a platinum/palladium molar ratio between about 2.5:1 and 1:2. However, when using this method to prepare lubricating oil base oil from raw material oil with high normal paraffin content, there are disadvantages such as difficulty in pour point depressing, high pour point of the produced base oil and even flocculation phenomenon.

CN102732300A discloses a method for producing high-viscosity-index lubricating base oil, comprising: a) in a hydrotreating reaction zone, hydrogen gas, lube oil distillate stock oil is contacted with a hydrotreating catalyst to obtain a hydrotreating reaction zone b) in a catalytic dewaxing reaction zone, the hydrogen gas, the hydrotreated oil is contacted with a catalytic dewaxing catalyst to obtain a dewaxed oil; c) in a hydrorefining reaction zone, contacting hydrogen, the dewaxed oil obtained in step b) with a hydrofining catalyst to obtain a hydrofined oil; d) separating the hydrofined oil in a separation zone to obtain a lubricating oil base oil; wherein, the hydroprocessing catalyst comprises sequentially layered catalyst I, catalyst II and catalyst III, by volume and based on the total amount of the hydroprocessing catalyst, the hydroprocessing catalyst The content of the catalyst I is 5-80%, the content of the catalyst II is 10-80%, and the content of the catalyst III is 5-60%. The catalyst I includes at least one or more of fluorine, boron and phosphorus. The hydrogenation catalyst Ia of the auxiliary agent component, the catalyst II is one or more selected from the hydrogenation catalysts containing fluorine and/or molecular sieves, and the catalyst III is selected from the hydrogenation catalysts without fluorine and/or molecular sieves One or more of them, the stratification makes the lubricating oil distillate feedstock sequentially contact with catalyst I, catalyst II and catalyst III in the hydrotreating reaction zone. However, when this method is used to prepare lubricating base oil, there are defects of low product yield and excessive loss of viscosity index.

CN102465024A discloses a hydrocracking method for producing lubricating oil base oil. The method comprises: the raw oil is first hydrocracked, the cracked oil enters the atmospheric tower for fractionation, and the resulting atmospheric tail oil enters the vacuum tower for fractionation. Light tail oil, intermediate tail oil and heavy tail oil are obtained, and the light tail oil and heavy tail oil are mixed to obtain lubricating oil base oil. The method adopts the method of direct hydrocracking to produce lubricating oil base oil, the cracking degree is high, the yield of the obtained lubricating oil base oil is relatively low, and the loss of viscosity index is relatively large.

Therefore, in order to produce lubricating oil base oil with low pour point from high waxy raw material oil under the premise of reducing the difficulty of pour point depressing in the process of producing lubricating oil base oil, and at the same time ensure the yield of lubricating oil base oil, research and development of new preparation The method of lubricating oil base oil is particularly necessary.

Contents of the invention

The purpose of the present invention is to produce lubricating base oil with low pour point from high-waxy raw material oil with high yield under the premise of reducing the difficulty of pour point depressing in the process of producing lubricating base oil.

In order to achieve the above object, the present invention provides a method for preparing lubricating oil base oil from high waxy stock oil, the method comprising:

(1) introducing the high-waxy feedstock oil and the hydrogen-containing stream into a hydroconversion reaction zone sequentially containing a hydrotreating catalyst and a catalytic dewaxing catalyst for reaction to obtain hydroconverted oil;

(2) introducing the hydroconversion oil into the isomerization depreciation reaction zone containing the isomerization depreciation catalyst for reaction to obtain the wax conversion oil;

(3) introducing the wax-converted oil into a hydrofinishing reaction zone containing a hydrofinishing catalyst to obtain hydrofined oil; and

(4) introducing the hydrorefined oil into a separation zone for separation.

When the above method of the present invention is used to prepare lubricating oil base oil from high waxy raw material oil, it can significantly reduce the difficulty of pour point depressing in the process of producing lubricating oil base oil, and obtain lubricating oil base oil with low pour point in high yield.

The above method provided by the present invention desulfurizes, denitrogenates, deoxygenates and hydrogenates part of the aromatic hydrocarbons in the heavy waxy feedstock oil in the hydroconversion reaction zone, and shortens and lightly isomerizes the long-chain normal paraffins in the feedstock , appropriately lowering the pour point. Then, the lightly isomerized alkane molecules undergo a deep isomerization reaction to produce multiple branched chains through the isomerization depreciation reaction zone to further reduce the pour point. Finally, after hydrofining and distillation separation, a lubricating oil base oil with a low pour point can be obtained.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. The circulating hydrogen compressor, heat exchanger, hydrogen recovery route, etc. are omitted in the drawings, which are well known to those skilled in the art. In the attached picture:

Fig. 1 is a schematic flow chart of the method provided by the present invention.

Explanation of reference signs

1. High waxy feed oil 2. Hydroconversion reaction zone I

3. Hydroconversion reaction zone II 4. Isomerization decondensation reaction zone

5. Hydrofining reaction zone 6. Separation zone

7. Lubricant base oil products

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The invention provides a method for preparing a lubricating oil base oil from a high waxy stock oil, the method comprising:

(1) introducing the high-waxy feedstock oil and the hydrogen-containing stream into a hydroconversion reaction zone sequentially containing a hydrotreating catalyst and a catalytic dewaxing catalyst for reaction to obtain hydroconverted oil;

(2) introducing the hydroconversion oil into the isomerization depreciation reaction zone containing the isomerization depreciation catalyst for reaction to obtain the wax conversion oil;

(3) introducing the wax-converted oil into a hydrofinishing reaction zone containing a hydrofinishing catalyst to obtain hydrofined oil; and

(4) introducing the hydrorefined oil into a separation zone for separation.

Compared with the prior art, the main purpose of the present invention is to solve the problems such as difficulty in pour point depressing and low yield of raw oil with high n-paraffin content in the process of hydrodewaxing, and proposes a pretreatment of isomerization pour point depressing In the method, in the hydroconversion reaction zone, through the gradation loading of the hydrotreating catalyst and the catalytic dewaxing catalyst, not only the sulfur, nitrogen and other impurities in the raw material oil are removed, but also the long-chain normal paraffins in the raw material are shortened and light The degree of isomerization reduces the difficulty of dewaxing in the subsequent isomerized pour point depressing process, avoids excessive cracking of heavy wax in the isomerized pour point depressing process, and is conducive to improving the yield of lubricating oil base oil.

In the present invention, the graded packing refers to packing the hydrotreating catalyst and the catalytic dewaxing catalyst in different catalyst beds in the hydroconversion reaction zone.

The high-waxy feedstock oil mentioned in the present invention refers to feedstock oil with relatively high normal paraffin content. Preferably, in the present invention, the n-paraffin content in the high waxy feedstock oil is 15-95% by weight; more preferably 40-90% by weight; especially preferably, the high waxy feedstock described in the present invention The oil is selected from at least one of vacuum distillate oil, wax paste, underwax oil, light deasphalted oil, hydrocracking tail oil and Fischer-Tropsch synthetic wax.

In the present invention, the hydrogen-containing stream refers to a stream that can provide hydrogen, including any one of new hydrogen, recycled hydrogen, hydrogen-rich gas, other gas-phase streams that can provide hydrogen, and other liquid-phase streams that can provide hydrogen or more. The hydrogen-containing streams described in the present invention can be the same or different, and those skilled in the art can clearly understand the hydrogen-containing streams described in the present invention after understanding the technical solution of the present invention.

In the present invention, in step (1), there is no particular limitation on the type of the hydrotreating catalyst and the catalytic dewaxing catalyst, and those skilled in the art can, after understanding the technical scheme of the present invention, The various hydroprocessing catalysts and catalytic dewaxing catalysts used are selected, as long as the selected hydroprocessing catalysts and catalytic dewaxing catalysts can remove impurities such as sulfur and nitrogen in the raw material oil, and remove long-chain impurities in the raw material. Normal paraffins are shortened and slightly isomerized. Preferably, in the present invention, the hydrotreating catalyst contains a carrier and an active metal element supported on the carrier, as well as optional auxiliary elements and optional organic additives, and the carrier is selected from silica , at least one of alumina, silica-alumina and molecular sieves; the active metal element is selected from at least one of nickel, cobalt, molybdenum and tungsten; the auxiliary element includes fluorine, boron and phosphorus at least one.

In the present invention, the "and optional auxiliary elements and optional organic additives" means that the hydroprocessing catalyst of the present invention may or may not contain auxiliary elements and may or may not contain organic additives .

According to the present invention, preferably, the active metal elements of the hydrotreating catalyst are nickel and/or cobalt and molybdenum and/or tungsten, based on the total weight of the hydrotreating catalyst, nickel and The hydrogenation is used when the total content of cobalt is 1-5% by weight, the total content of molybdenum and tungsten as oxides is 12-35% by weight, and the content of auxiliary elements as elements is 0-9% by weight The method of treating the catalyst can result in a lower pour point of the resulting lubricating oil base oil.

More preferably, in the present invention, in the hydrogenation catalyst, the molar ratio of the organic additive to the sum of active metal elements calculated as oxides is 0-2:1.

In a specific embodiment, the hydroprocessing catalyst is selected from at least one of the following catalysts, and these hydroprocessing catalysts include:

The catalyst disclosed in CN85104438A is composed of gamma-Al ₂ O ₃ loaded tungsten, nickel oxide and auxiliary agent fluorine, and its composition (weight): nickel oxide 1-5% by weight, tungsten oxide 12-35% by weight, Fluorine is 1-9% by weight.

CN1853780A discloses a fluorine-containing and phosphorus hydrogenation catalyst with silica-alumina as a carrier and its preparation. The composition of the catalyst after roasting is: nickel oxide 1-10% by weight, the sum of molybdenum oxide and tungsten oxide is 10 -50% by weight, 1-10% by weight of fluorine, 0.5-8% by weight of phosphorus oxide, and the balance is silicon oxide-alumina. The catalyst is prepared by a method including introducing fluorine, phosphorus, molybdenum, nickel and tungsten into a silica-alumina carrier, wherein the amount of each component makes the composition of the catalyst after calcination: nickel oxide 1-10% by weight, molybdenum oxide and The sum of tungsten oxide is 10-50% by weight, 1-10% by weight of fluorine, 0.5-8% by weight of phosphorus oxide, and the balance is silicon oxide-alumina.

CN1853779A discloses a fluorine-containing hydrogenation catalyst with silicon oxide-alumina as a carrier and its preparation. The composition of the catalyst after calcination is: nickel oxide 1-10% by weight, the sum of molybdenum oxide and tungsten oxide 10 to 50 % by weight, 1-10% by weight of fluorine, and the rest is carrier. The preparation method of the catalyst comprises introducing fluorine, molybdenum, nickel and tungsten into the silicon oxide-alumina carrier, wherein, the consumption of each component makes the composition after the catalyst is calcined: nickel oxide 1-10% by weight, molybdenum oxide and tungsten oxide The sum is 10 to 50% by weight, 1-10% by weight of fluorine, and the rest is carrier.

CN1853781A discloses a phosphorus-containing hydrogenation catalyst with silicon oxide-alumina as a carrier and its preparation. The composition of the catalyst after calcination is: 1-10% by weight of nickel oxide, and the sum of molybdenum oxide and tungsten oxide is 10 to 50 % by weight, 1-9% by weight of phosphorus oxide, and the rest is silicon oxide-alumina, wherein the molar ratio of tungsten oxide to molybdenum oxide is 2.6-30. The preparation method of the catalyst comprises introducing phosphorus, molybdenum, nickel and tungsten into the silicon oxide-alumina carrier, wherein, the consumption of each component makes the composition after the catalyst is calcined: nickel oxide 1-10% by weight, molybdenum oxide and tungsten oxide The sum is 10 to 50% by weight, phosphorus oxide is 1-9% by weight, and the rest is silicon oxide-alumina, and the molar ratio of tungsten oxide and molybdenum oxide is greater than 2.6 to 30.

CN1872959A discloses a fluorine-containing hydrogenation catalyst with alumina as a carrier and its preparation. The composition of the catalyst after calcination is: nickel oxide 1-10% by weight, molybdenum oxide and tungsten oxide the sum of 10-50% by weight, Fluorine is 1-10% by weight, and the rest is alumina. The preparation method of the catalyst comprises introducing fluorine, molybdenum, nickel and tungsten into the alumina carrier, wherein, the consumption of each component makes the composition of the catalyst after roasting: 1-10% by weight of nickel oxide, and the sum of molybdenum oxide and tungsten oxide is 10 to 50% by weight, 1-10% by weight of fluorine, and the balance is alumina.

CN1872960A discloses a phosphorus-containing hydrogenation catalyst with alumina as a carrier and its preparation. The composition of the catalyst after roasting is 1-10% by weight of nickel oxide, and the sum of molybdenum oxide and tungsten oxide is 10-50% by weight. Phosphorus is 1-9% by weight, and the balance is aluminum oxide, wherein, in terms of oxides, the molar ratio of tungsten and molybdenum is greater than 2.6 to 30. The catalyst consists of introducing phosphorus, molybdenum, nickel and tungsten into the alumina carrier, wherein the amount of each component makes the composition of the catalyst after roasting: 1-10% by weight of nickel oxide, and the sum of molybdenum oxide and tungsten oxide is 10% to 50% by weight, 1-9% by weight of phosphorus oxide, and the balance is aluminum oxide, wherein, in terms of oxides, the molar ratio of tungsten to molybdenum is greater than 2.6 to 30.

The catalysts disclosed in CN1853780A, CN1853779A, CN1853781A, CN1872959A and CN1872960A preferably also contain organic additives, wherein the molar ratio of the organic additives to the sum of hydrogenation active metal components calculated as oxides is 0.03-2:1 Preferably 0.08-1.5:1.

More detailed preparation methods of the above-mentioned catalysts are described in the above-mentioned prior art, and they are hereby cited as part of the content of the present invention.

In the present invention, preferably, the catalytic dewaxing catalyst contains a carrier and an active metal element loaded on the carrier, and the carrier includes a shape-selective cracking molecular sieve; the active metal element is Group VIB and/or For the Group VIII metal element, based on the total weight of the catalytic dewaxing catalyst, the content of the active metal element as an oxide is 0.1-10% by weight.

More preferably, in the present invention, in the catalytic dewaxing catalyst, when the shape-selective cracking molecule is selected from ZSM-5, ZSM-8, ZSM10, ZSM-11, ZSM-12, ZSM-22, When at least one of ZSM-23, ZSM-35, ZSM-38 and ZSM-48 is used, the method of using the catalytic dewaxing catalyst can make the yield of the obtained lubricating oil base oil higher.

In a specific embodiment, the catalytic dewaxing catalyst is selected from at least one of the following catalysts, these catalytic dewaxing catalysts include:

Catalytic dewaxing catalysts disclosed in CN1219571A, CN1210883A, CN102205250A, CN1966620A, CN101134170A, CN1362495A, CN1448484A and CN102205249A.

When the catalytic dewaxing catalyst disclosed in the above prior art is used in the method of the present invention, it can have very good shape-selective cracking reaction performance. In particular, the catalytic dewaxing catalyst disclosed in CN102205249A can obtain good catalytic dewaxing performance when used in the present invention, so it is particularly suitable for the present invention.

The method of the present invention has no special limitation on the loading volume of the hydrotreating catalyst and the catalytic dewaxing catalyst, and those skilled in the art can carry out the process according to conventionally used technical means in the field after understanding the technical scheme of the present invention. choose. Preferably, in the hydroconversion reaction zone, the loading volume ratio of the hydrotreating catalyst and the catalytic dewaxing catalyst is 1:0.1-10; more preferably 1:0.25-4.

In the present invention, the reaction conditions in the hydroconversion reaction zone are preferably controlled so that in the hydroconversion product oil, the weight ratio of the carbon content in isoparaffins to the carbon content in normal paraffins is 0.5-1: 1. The inventors of the present invention have found that by controlling the conditions so that the weight ratio of the carbon content in isoparaffins to the carbon content in normal paraffins in the hydroconversion oil is within the range of 0.5-1:1, it is possible to Obviously, the pour point of the lubricating base oil obtained is lower and the yield is higher.

Preferably, the reaction conditions in the hydroconversion reaction zone are controlled so that the freezing point of the hydroconversion-generated oil is 5-25°C lower than that of the high-waxy feedstock oil; more preferably, the reaction in the hydroconversion reaction zone is controlled The conditions are such that the freezing point of the hydroconversion oil is 8-25°C lower than that of the high-waxy feedstock oil.

According to the method provided by the present invention, the purpose of the isomerization depreciation reaction zone is to undergo a deep isomerization reaction of slightly isomerized paraffin molecules to generate multiple branched chains, so as to further reduce the pour point. The heterogeneous pour point depressant catalysts and reaction conditions involved in the present invention are well known to those skilled in the art, and may be catalysts and operating conditions commonly used in the art.

In the present invention, in the heterogeneous point-point depressing reaction zone, the heterogeneous point-point depressing catalyst contains a carrier and an active metal element loaded on the carrier, and the carrier is selected from the group consisting of silicon oxide, aluminum oxide, silicon oxide - At least one of alumina and molecular sieves, the active metal element being selected from at least one of cobalt, nickel, ruthenium, rhodium, platinum and palladium.

Preferably, in the present invention, in the heterogeneous pour point depressing catalyst, based on the total weight of the heterogeneous pour point depressing catalyst, the content of the active metal element in terms of metal is 0.1-10% by weight; more preferably It is 0.1-5% by weight.

According to the present invention, specific examples of preferred heterogeneous pour point depressant catalysts include the following heterogeneous pour point depressant catalysts disclosed in the prior art: CN1488733A, CN1448480A, CN1289643A, CN1228357A, CN1803998A and CN1382526A. Especially the heterogeneous pour point depressant catalyst disclosed in CN1382526A has better wax conversion activity and selectivity to lubricating oil base oil when used in the present invention, so it is particularly suitable for the present invention.

In the present invention, in the hydrofinishing reaction zone, the hydrofinishing catalyst contains a carrier, an active metal element supported on the carrier, and an optional auxiliary element. The optional auxiliary element mentioned in the present invention means that the auxiliary element may or may not exist, that is, the hydrotreating catalyst of the present invention may or may not contain the auxiliary element.

Preferably, in the hydrorefining catalyst, the carrier is selected from at least one of alumina, silica-alumina and molecular sieve; the auxiliary element includes at least one of fluorine, phosphorus and boron.

According to the method provided by the present invention, the hydrofining reaction zone mainly aims to remove impurities such as sulfur, nitrogen and oxygen remaining in the oil after dewaxing, and saturates olefins to improve the stability and color of the oil. The hydrofinishing catalyst and reaction conditions involved in the hydrofinishing reaction zone are well known to those skilled in the art, and may be catalysts and operating conditions commonly used in the art.

According to the present invention, specific examples of preferred hydrorefining catalysts include the following hydrorefining catalysts disclosed in the prior art: CN1245204A, CN1105053A, CN1136069A, CN1169336A and CN1803283A. Especially the hydrorefining catalyst disclosed in CN1245204A has higher hydrogenation activity and sulfur resistance when used in the present invention, so it is particularly suitable for the present invention.

The method of the present invention has no special limitation on the reaction conditions of the hydroconversion reaction zone, the isomerization depreciation reaction zone and the hydrofinishing reaction zone. Those skilled in the art, after understanding the technical scheme of the present invention It can be selected according to the conventional reaction conditions in this field. As long as the selected reaction conditions can realize the removal of impurities such as sulfur and nitrogen in the raw oil in the hydroconversion reaction zone, and shorten the long-chain n-paraffins in the raw material and lightly isomerize them, and avoid Excessive pyrolysis of heavy wax in the process of structural depreciation is sufficient.

According to the present invention, preferably, the reaction conditions of the hydroconversion reaction zone include: a pressure of 5-20MPa, preferably 8-18MPa; a temperature of 320-420°C, preferably 350-400°C; a volumetric space velocity of 0.3-5h ^-1 , preferably 0.5-2.5h ^-1 ; the volume ratio of hydrogen to oil is 100-2000, preferably 200-1500.

According to the present invention, preferably, the reaction conditions of the isomerization depreciation reaction zone include: the pressure is 5-20MPa, preferably 5-18MPa; the temperature is 280-390°C, preferably 300-370°C; the volume space velocity is 0.3- 5h ^-1 , preferably 0.5-2.5h ^-1 ; the volume ratio of hydrogen to oil is 100-2000, preferably 200-1500.

According to the present invention, preferably, the reaction conditions in the hydrofining reaction zone include: a pressure of 1-20MPa, preferably 3-18MPa; a temperature of 150-300°C, preferably 180-280°C; a volumetric space velocity of 0.3-5h ^-1 , preferably 0.5-3h ^-1 ; the volume ratio of hydrogen to oil is 100-2000, preferably 200-1000.

According to the method provided by the present invention, the separation zone is preferably a distillation zone, and the distillation method in the distillation zone is well known in the art, and can generally include one or more operations of flash evaporation, atmospheric distillation and vacuum distillation as required unit to accomplish the desired separation.

According to a preferred embodiment of the present invention, the method of the present invention adopts the technological process as shown in Figure 1 to carry out, specifically:

The high-waxy feedstock oil 1 and the hydrogen-containing stream are introduced into the hydroconversion reaction zone I2 containing the hydrotreating catalyst and the hydroconversion reaction zone II3 containing the catalytic dewaxing catalyst in sequence for reaction to obtain the hydroconversion product oil; The oil produced by the hydrogenation conversion is introduced into the isomerization decompression reaction zone 4 containing the isomerism depreciation catalyst for reaction to obtain the wax conversion product oil; the wax conversion product oil is introduced into the hydrofinishing reaction zone 5 containing the hydrofinishing catalyst , to obtain hydrorefined oil; introduce the hydrorefined oil into the separation zone 6 for separation, and obtain the lubricating oil base oil product 7.

In the above-mentioned preferred embodiment of the present invention, the hydroconversion reaction zone I2 and the hydroconversion reaction zone II3 are actually two catalyst beds in one hydroconversion reactor. That is to say, in the present invention, the hydrotreating catalyst and the catalytic dewaxing catalyst are sequentially packed in different catalyst beds of a hydroconversion reactor.

The present invention will be described in detail below by way of examples. In the following examples and comparative examples, unless otherwise specified, all raw materials used are commercially available.

Hydrotreating catalysts, catalytic dewaxing catalysts, heterogeneous pour point depressing catalysts and hydrorefining catalysts used in the following examples and their preparation methods are as follows:

1. Hydrotreating catalyst

The hydrotreating catalyst used in the embodiment of the present invention is prepared according to example 6 in CN1853780A with fluorine-containing silicon oxide-alumina carrier, fluorine, phosphorus, citric acid are auxiliary components, nickel, molybdenum, tungsten are active components. Wherein, based on the total amount of the catalyst, the mass fraction of nickel is 5% and the mass fraction of molybdenum is 4% in terms of oxides. The mass fraction of tungsten is 39.1%, the mass fraction of phosphorus is 2.4%, the mass fraction of fluorine is 3.5% in terms of elements, and the rest is silica-alumina carrier.

2. Catalytic dewaxing catalyst

The catalytic dewaxing catalyst used in the embodiment of the present invention is the catalyst prepared according to the embodiment 2 in CN102205249A with nickel as the active component loaded on the rare earth-containing ZSM-5 molecular sieve/alumina carrier, wherein the total amount of catalyst Based on the oxide, the mass fraction of nickel is 2%, and the rest is the carrier. Based on the carrier, the mass fraction of ZSM-5 molecular sieve containing rare earth is 58.8%, and the rest is alumina.

3. Heterogeneous pour point depressing catalyst

The heterogeneous pour point depressant catalyst used in the embodiment of the present invention is the catalyst prepared according to the embodiment 6 in CN1382526A with platinum as the active component loaded on the SAPO-11 molecular sieve/alumina carrier, wherein the total amount of catalyst is used as a benchmark , the mass fraction of platinum metal is 0.3%, and the rest is carrier. Taking the carrier as the benchmark, the mass fraction of SAPO-11 molecular sieve in the carrier is 75%, and the rest is alumina.

4. Hydrofining catalyst

The hydrorefining catalyst used in the examples of the present invention is prepared according to Example 3 in CN1245204A, wherein the mass fraction of platinum metal is 0.2%, the mass fraction of palladium metal is 0.6%, and the rest is alumina carrier.

Example 1

In this embodiment, a kind of high waxy raw material oil is used as raw material, and its properties are shown in Table 1.

Process the raw oil according to the technological process shown in Fig. 1. The catalysts are as follows: the upstream of the hydroconversion reaction zone is filled with the aforementioned hydrotreating catalyst, the downstream is filled with the aforementioned catalytic dewaxing catalyst, the isomerization decondensation reaction zone is filled with the isomerism depreciation catalyst, and the hydrofinishing reaction zone is filled with the hydrofinishing catalyst . Among them, the loading volume ratio of hydrotreating catalyst and catalytic dewaxing catalyst is 7:3, and the operating conditions are shown in Table 2. The properties of the hydroconversion oil obtained in the hydroconversion reaction zone are shown in Table 3, and the properties of the lubricating base oil product after distillation and separation in the separation zone are shown in Table 4.

Table 1

project High Waxy Raw Oil Density(20℃)/g·cm ^-3 0.8273 Freezing point/℃ 47 (melting point) Sulfur content/μg·g ^-1 1300 Nitrogen content/μg·g ^-1 1000 Distillation range/℃ initial boiling point 187 10% 321 30% 374 50% 400 70% 423 90% 451 95% 480 n-paraffin content/(weight)% 53

Table 2

Process conditions Hydroconversion reaction zone Heterogeneous depreciation reaction zone Hydrofining reaction zone Hydrogen partial pressure/MPa 16.0 10.0 10.0 Reaction temperature/℃ 370 330 210 Volumetric space velocity/h ^-1 0.5 1.0 2.0 Hydrogen oil ratio/(v/v) 800 500 500

table 3

Carbon percentage of n-paraffin/carbon percentage of isoparaffin (IP/NP) Freezing point/℃ Example 1 0.86 35 Comparative example 1 0.53 43

Table 4

Example 1 Comparative example 1 Yield/weight% 43.7 37.6 Kinematic viscosity/mm ² ·s ^-1 100°C 4.143 4.152 40℃ 18.63 18.78 viscosity index 126 125 Pour point/℃ -43 -42 Sulfur/μg·g ^-1 <5 <5 Nitrogen/μg·g ^-1 <1 <1 Aromatic content/wt% <1 <1

Comparative example 1

This comparative example uses the same raw material oil as in Example 1, the same type of catalyst hydrotreating catalyst, isomerism depreciation catalyst and hydrofining catalyst, the difference is that only the hydrotreating catalyst is filled in the hydroconversion reaction zone The catalyst is not loaded with a catalytic dewaxing catalyst, and the operating conditions are shown in Table 2. See Table 3 for the properties of the hydroconverted oil produced in the hydroconversion reaction zone, and see Table 4 for the properties of the lubricating base oil product after distillation and separation in the separation zone.

Example 2

In this example, a high-waxy feedstock oil is used as the raw material, and its properties are shown in Table 5.

Process the raw oil according to the technological process shown in Fig. 1. The catalysts are as follows: the upstream of the hydroconversion reaction zone is filled with the aforementioned hydrotreating catalyst, the downstream is filled with the aforementioned catalytic dewaxing catalyst, the isomerization decondensation reaction zone is filled with the isomerism depreciation catalyst, and the hydrofinishing reaction zone is filled with the hydrofinishing catalyst . Among them, the loading volume ratio of hydrotreating catalyst and catalytic dewaxing catalyst is 8:2, and the operating conditions are shown in Table 6. The properties of the hydroconversion oil obtained in the hydroconversion reaction zone are shown in Table 7, and the properties of the lubricating base oil product separated by distillation in the separation zone are shown in Table 8.

table 5

project High Waxy Raw Oil Density(20℃)/g·cm ^-3 0.8175 Freezing point/℃ 63 (melting point) Sulfur content/μg·g ^-1 958 Nitrogen content/μg·g ^-1 624 Distillation range/℃ initial boiling point 201 10% 334 30% 387 50% 424 70% 465 90% 514 95% 545 n-paraffin content/(weight)% 83

Table 6

Process conditions Hydroconversion reaction zone Heterogeneous depreciation reaction zone Hydrofining reaction zone Hydrogen partial pressure/MPa 16.0 8.0 8.0 Reaction temperature/℃ 380 340 210 Volumetric space velocity/h ^-1 0.5 1.0 2.0 Hydrogen oil ratio/(v/v) 800 500 500

Table 7

Carbon percentage of n-paraffin/carbon percentage of isoparaffin (IP/NP) Freezing point/℃ Example 2 0.78 44 Comparative example 2 0.47 56

Table 8

Example 2 Comparative example 2 Base oil yield/weight% 35.3 30.2 Kinematic viscosity/mm ² ·s ^-1 100°C 4.267 4.025 40℃ 19.72 18.03 viscosity index 124 123 Pour point/℃ -34 -31 Sulfur/μg·g ^-1 <5 <5 Nitrogen/μg·g ^-1 <1 <1 Aromatic content/wt% <1 <1

Comparative example 2

This comparative example uses the same raw material oil as in Example 2, the same type of catalyst hydrotreating catalyst, isomerism depreciation catalyst and hydrofining catalyst, the difference is that only the hydrotreating reactor is filled in the hydroconversion reaction zone The catalyst is not loaded with catalytic dewaxing catalyst, and the operating conditions are shown in Table 6. See Table 7 for the properties of the hydroconverted oil produced in the hydroconversion reaction zone, and see Table 8 for the properties of the lubricating base oil product after distillation and separation in the separation zone.

Example 3

In this example, a high-waxy feedstock oil is used as the raw material, and its properties are shown in Table 9.

Process the raw oil according to the technological process shown in Fig. 1. The catalysts are as follows: the upstream of the hydroconversion reaction zone is filled with the aforementioned hydrotreating catalyst, the downstream is filled with the aforementioned catalytic dewaxing catalyst, the isomerization decondensation reaction zone is filled with the isomerism depreciation catalyst, and the hydrofinishing reaction zone is filled with the hydrofinishing catalyst . Among them, the loading volume ratio of the hydrotreating catalyst and the catalytic dewaxing catalyst is 4:3, and the operating conditions are shown in Table 10. The properties of the hydroconversion oil obtained in the hydroconversion reaction zone are shown in Table 11, and the properties of the lubricating oil base oil product separated by distillation in the separation zone are shown in Table 12.

Table 9

project High Waxy Raw Oil Density(20℃)/g·cm ^-3 0.8161 Freezing point/℃ 85 (melting point) Sulfur content/μg·g ^-1 8 Nitrogen content/μg·g ^-1 7 Distillation range/℃ initial boiling point 228 10% 327 30% 365 50% 433 70% 482 90% 541 95% 575 n-paraffin content/(weight)% 90

Table 10

Process conditions Hydroconversion reaction zone Heterogeneous depreciation reaction zone Hydrofining reaction zone Hydrogen partial pressure/MPa 16 8 8 Reaction temperature/℃ 385 350 210 Volumetric space velocity/h ^-1 0.5 1 2 Hydrogen oil ratio/(v/v) 800 500 500

Table 11

Carbon percentage of n-paraffin/carbon percentage of isoparaffin (IP/NP) Freezing point/℃ Example 3 0.71 72 Comparative example 3 0.41 79

Table 12

Example 3 Comparative example 3 Base oil yield/weight% 29.5 24.8 Kinematic viscosity/mm ² ·s ^-1 100°C 3.900 3.894 40℃ 16.15 16.13 viscosity index 141 140 Pour point/℃ -31 -26 Sulfur/μg·g ^-1 <1 <1 Nitrogen/μg·g ^-1 <1 <1 Aromatic content/wt% <1 <1

Comparative example 3

This comparative example uses the same raw material oil as in Example 3, the same type of catalyst hydrotreating catalyst, isomerism depreciation catalyst and hydrofining catalyst, the difference is that only the hydrotreating catalyst is filled in the hydroconversion reaction zone The catalyst was not loaded with a catalytic dewaxing catalyst, and the operating conditions were shown in Table 10. See Table 11 for the properties of the hydroconverted oil produced in the hydroconversion reaction zone, and see Table 12 for the properties of the lubricating base oil product after distillation and separation in the separation zone.

As can be seen from the results of the above-mentioned examples and comparative examples, the method of the present invention can produce low pour point oil with high yield from high waxy feedstock oil under the premise of reducing the difficulty of pour point depressing in the process of producing lubricating base oil. Lubricant base oil.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (19)

1. A method for preparing lubricating oil base oil from high waxy stock oil, the method comprising: (1) introducing the high-waxy feedstock oil and the hydrogen-containing stream into a hydroconversion reaction zone sequentially containing a hydrotreating catalyst and a catalytic dewaxing catalyst for reaction to obtain hydroconverted oil; (2) introducing the hydroconversion oil into the isomerization depreciation reaction zone containing the isomerization depreciation catalyst for reaction to obtain the wax conversion oil; (3) introducing the wax-converted oil into a hydrofinishing reaction zone containing a hydrofinishing catalyst to obtain hydrofined oil; and (4) introducing the hydrorefined oil into a separation zone for separation. 2. The method according to claim 1, wherein the hydrotreating catalyst contains a carrier and an active metal element loaded on the carrier and optional auxiliary elements and optional organic additives, the carrier At least one selected from silica, alumina, silica-alumina and molecular sieves; the active metal element is selected from at least one of nickel, cobalt, molybdenum and tungsten; the auxiliary element includes fluorine, boron and at least one of phosphorus. 3. The method according to claim 2, wherein the active metal element of the hydrotreating catalyst is nickel and/or cobalt and molybdenum and/or tungsten, based on the total weight of the hydrotreating catalyst, expressed in terms of oxidation The total content of nickel and cobalt in terms of substances is 1-5% by weight, the total content of molybdenum and tungsten in terms of oxides is 12-35% by weight, and the content of additive elements in terms of elements is 0-9% by weight. 4. The method according to any one of claims 1-3, wherein the catalytic dewaxing catalyst contains a carrier and an active metal element loaded on the carrier, and the carrier includes a shape-selective cracking molecular sieve; The active metal element is a Group VIB and/or Group VIII metal element, based on the total weight of the catalytic dewaxing catalyst, the content of the active metal element as an oxide is 0.1-10% by weight. 5. The method of claim 4, wherein, in the catalytic dewaxing catalyst, the shape-selective cracking molecule is selected from ZSM-5, ZSM-8, ZSM10, ZSM-11, ZSM-12, ZSM- 22. At least one of ZSM-23, ZSM-35, ZSM-38 and ZSM-48. 6. according to the method described in any one in claim 1-3, wherein, described heterogeneous pour point depressing catalyst contains carrier and the active metal element that is loaded on the carrier, and described carrier is selected from silicon oxide, aluminum oxide At least one of silica-alumina and molecular sieves, the active metal element is selected from at least one of cobalt, nickel, ruthenium, rhodium, platinum and palladium. 7. The method according to claim 6, wherein, in the heterogeneous pour point depressing catalyst, based on the total weight of the heterogeneous pour point depressing catalyst, the content of the active metal element in terms of metal is 0.1-10 wt. %. 8. The method according to claim 6, wherein, in the heterogeneous pour point depressing catalyst, based on the total weight of the heterogeneous pour point depressing catalyst, the content of the active metal element in terms of metal is 0.1-5 wt. %. 9. The method according to any one of claims 1-3, wherein the hydrorefining catalyst contains a carrier and an active metal element loaded on the carrier and an optional auxiliary element; the carrier is selected from from at least one of alumina, silica-alumina and molecular sieve; the auxiliary element includes at least one of fluorine, phosphorus and boron. 10. The method according to claim 1, wherein, in the hydroconversion reaction zone, the loading volume ratio of the hydrotreating catalyst and the catalytic dewaxing catalyst is 1:0.1-10. 11. The method according to claim 1, wherein, in the hydroconversion reaction zone, the loading volume ratio of the hydrotreating catalyst and the catalytic dewaxing catalyst is 1:0.25-4. 12. The method according to any one of claims 1-3, wherein the content of normal paraffins in the high waxy feed oil is 15-95% by weight. 13. The method according to any one of claims 1-3, wherein the content of normal paraffins in the high waxy feed oil is 40-90% by weight. 14. The method according to any one of claims 1-3, wherein the reaction conditions in the hydroconversion reaction zone are controlled such that in the hydroconversion product oil, the carbon content in the isoparaffins is the same as that in the normal The weight ratio of carbon content in alkanes is 0.5-1:1. 15. The method according to any one of claims 1-3, wherein the reaction conditions in the hydroconversion reaction zone are controlled such that the freezing point of the hydroconversion-generated oil is 5-25% lower than the freezing point of the raw oil ℃. 16. The method according to any one of claims 1-3, wherein the reaction conditions in the hydroconversion reaction zone include: a pressure of 5-20 MPa, a temperature of 320-420°C, and a volume space velocity of 0.3- 5h ^-1 , the volume ratio of hydrogen to oil is 100-2000. 17. The method according to any one of claims 1-3, wherein the reaction conditions in the isomerization depreciation reaction zone include: a pressure of 5-20MPa, a temperature of 280-390°C, and a volumetric space velocity of 0.3 -5h ^-1 , the volume ratio of hydrogen to oil is 100-2000. 18. The method according to any one of claims 1-3, wherein the reaction conditions in the hydrofinishing reaction zone include: a pressure of 1-20MPa, a temperature of 150-300°C, and a volumetric space velocity of 0.3- 5h ^-1 , the volume ratio of hydrogen to oil is 100-2000. 19. The method according to claim 1, wherein the high waxy feed oil is selected from vacuum distillate oil, wax paste, underwax oil, light deasphalted oil, hydrocracking tail oil and Fischer-Tropsch synthetic wax at least one of .