CN113969186A

CN113969186A - Method for producing refrigerator oil

Info

Publication number: CN113969186A
Application number: CN202010714613.7A
Authority: CN
Inventors: 李洪辉; 高杰; 郭庆洲; 王鲁强; 李洪宝
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-07-23
Filing date: 2020-07-23
Publication date: 2022-01-25
Anticipated expiration: 2040-07-23
Also published as: CN113969186B

Abstract

The invention discloses a method for producing refrigerator oil. The method comprises the following steps: (1) taking base oil with the viscosity index of less than 80 as a raw material, and reacting the base oil through a hydro-conversion reaction zone filled with a hydro-isomerization treatment catalyst to obtain hydro-conversion generated oil, wherein a carrier of the hydro-isomerization treatment catalyst comprises at least one selected from silicon oxide, aluminum oxide and silicon oxide-aluminum oxide and at least one shape-selective cracking molecular sieve; (2) and separating the oil generated by the hydro-conversion in a distillation area according to the viscosity grade of the refrigerator oil to obtain the refrigerator oil. The method can produce the refrigerating machine oil product with high added value in high yield by carrying out one-step hydro-conversion reaction on the low-value I type base oil product, and improve the economic benefit of enterprises.

Description

Method for producing refrigerator oil

Technical Field

The invention relates to the field of oil refining, in particular to a method for producing refrigerator oil.

Background

Because some refineries need to produce special wax products, the production must be carried out by adopting the traditional 'old three sets' process production flow, so that the refineries produce a large amount of API I base oil products while producing the special wax products. However, in recent years, due to the reduction of high-quality paraffin-based crude oil resources, the increase of the proportion of imported crude oil, frequent oil type change and poor quality, the quality of base oil products of I-class lubricating oil produced by the 'old three sets' process is reduced, the viscosity index of the base oil is low, and some products cannot meet the standard of the base oil of I-class, so that economic benefits cannot be brought to refineries.

CN109852417A discloses a production method of naphthenic base special oil, which comprises the following steps: (1) mixing naphthenic base distillate oil and hydrogen, entering a hydrotreating reaction zone, and contacting with a hydrofining catalyst for reaction; (2) mixing the generated oil obtained in the step (1) with hydrogen, then feeding the mixture into a hydrogen mixing tank for hydrogen mixing, feeding the liquid phase effluent of the obtained saturated dissolved hydrogen into a complementary refining reaction zone, and contacting with a hydrogenation complementary refining catalyst for hydrogenation reaction; (3) and (3) carrying out gas-liquid separation on the supplementary refining reaction effluent obtained in the step (2), and fractionating the liquid to obtain corresponding special oil product fractions.

CN109852465A discloses a production process of naphthenic base lubricating oil, which comprises the following steps: (1) after being subjected to back flush filtration, the naphthenic base raw oil is mixed with hydrogen in a hydrogenation reactor, wherein the hydrogenation reactor consists of a first reactor, a second reactor and a third reactor; wherein, the first reactor is filled with a hydrogenation refining catalyst, and the raw oil undergoes hydrodemetallization, desulfurization, nitrogen reaction and aromatic saturation reaction; adding a hydrogenation pour point depression catalyst into the second reactor, and removing macromolecular normal paraffin with high pour point while further refining; a noble metal supplementary refining catalyst is additionally arranged in the third reactor, so that the low-temperature fluidity of the oil product is improved, and metal, sulfur and nitrogen impurities are removed; (2) the gas phase product obtained from the third reactor is subjected to hydrogen sulfide removal through an ammonia scrubber, then compressed through a recycle hydrogen compressor, and then returned to the hydrogenation reactor as recycle hydrogen; the obtained low-component gas is used as fuel to enter a fuel gas pipe network of the whole plant, and the acidic water is sent out of a boundary area for treatment; and the obtained low-fraction oil is sent to a fractionation system, byproducts fractionated by an atmospheric fractionating tower enter a naphtha oil tank area and a kerosene oil tank area respectively, and the main product is further fractionated by a reduced pressure fractionation tower to obtain transformer oil, refrigerator oil and a rubber plasticizer.

CN102311785B discloses a method for producing lube base oil by hydrogenating naphthenic distillate, which comprises the following steps: the naphthenic base distillate oil and hydrogen sequentially pass through a hydrotreating reaction zone, a hydrogenation pour point depression reaction zone and a hydrogenation refining reaction zone under the hydrogenation reaction condition, and the method is characterized in that: the hydrotreating reaction zone sequentially comprises a hydrotreating catalyst taking alumina as a carrier and a hydrotreating catalyst containing a modified beta molecular sieve according to the flowing direction of reaction materials; wherein the dosage of the hydrotreating catalyst containing the modified beta molecular sieve is 5 to 30 percent of the total volume of the two hydrotreating catalysts; the hydrofinishing catalyst takes gamma-Al 2O3 as a carrier, W and/or Mo of VIB group metals and Co and/or Ni of VIII group metals as active components, one or more elements of Si, P, F, B, Ti and Zr as auxiliaries, the VIB group elements account for 10 wt% -35 wt% of oxides, the VIII group elements account for 2.0 wt% -10.0 wt% of oxides, and the auxiliaries account for 0.1 wt% -10 wt% of the catalyst by elements.

The said process has long technological process and high production cost.

Disclosure of Invention

The invention aims to produce a refrigerating machine oil product with high yield from a low-value group I base oil product.

In order to achieve the above object, the present invention provides a method of producing a refrigerator oil, comprising:

(1) taking base oil with the viscosity index of less than 80 as a raw material, and reacting the base oil through a hydro-conversion reaction zone filled with a hydro-isomerization treatment catalyst to obtain hydro-conversion generated oil, wherein a carrier of the hydro-isomerization treatment catalyst comprises at least one selected from silicon oxide, aluminum oxide and silicon oxide-aluminum oxide and at least one shape-selective cracking molecular sieve;

(2) and separating the oil generated by the hydro-conversion in a distillation area according to the viscosity grade of the refrigerator oil to obtain the refrigerator oil.

In one embodiment, the support of the hydroisomerization treatment catalyst comprises a silica-alumina and a shape selective molecular sieve.

In one embodiment, the mass fraction of the silica-alumina is 60-90% and the mass fraction of the shape-selective cracking molecular sieve is 10-40% based on the total amount of the hydroisomerization catalyst carrier; preferably, the mass fraction of the silicon oxide-aluminum oxide is 70-85%, and the mass fraction of the shape-selective cracking molecular sieve is 15-30%.

In one embodiment, the hydrogenation-active metal component of the hydroisomerization treatment catalyst is one or more selected from the group consisting of nickel, cobalt, molybdenum, tungsten; the hydroisomerization treatment catalyst optionally contains a promoter component selected from one or more of fluorine, boron and phosphorus.

In one embodiment, the hydroisomerization catalyst comprises 5 to 20% by weight of nickel and/or cobalt in terms of oxide, 15 to 40% by weight of molybdenum and/or tungsten, and 0 to 9% by weight of one or more promoter components selected from fluorine, boron and phosphorus in terms of element, based on the total weight of the catalyst.

In one embodiment, the shape selective cracked molecular sieve is one or more of ZSM-5, ZSM-8, ZSM10, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, and ZSM-48.

In one embodiment, the base oil comprises a Low Viscosity Index (LVI) base oil having a viscosity index of less than 60 and/or a Medium Viscosity Index (MVI) base oil having a viscosity index of greater than or equal to 60 and less than 80.

In one embodiment, the Low Viscosity Index (LVI) or Medium Viscosity Index (MVI) base oil is a group I base oil produced by a conventional solvent refining process.

In one embodiment, the reaction conditions in the hydroconversion reaction zone are: the pressure is 5-20 MPa, preferably 8-18MPa; the temperature is 250-380 ℃, and preferably 280-360 ℃; the volume airspeed is 0.2-3 h^-1Preferably 0.5 to 2 hours^-1(ii) a The volume ratio of hydrogen to oil is 100 to 1500, preferably 200 to 1000.

In one embodiment, the distillation zone comprises one or more flash, atmospheric and vacuum distillation operating units.

The method provided by the invention is used for desulfurizing, denitrifying and saturating the LVI or MVI base oil in the hydro-conversion reaction zone, isomerizing normal paraffin in the raw material and reducing the pour point of the raw material so as to enable the pour point of the raw material to meet the standard requirement of the refrigerating machine oil. Finally, distilling and separating to obtain high-quality refrigerator oil with different grades. Compared with the multi-step hydrotreating process which adopts distillate oil as the raw material in the prior art, the method selects proper raw material and adopts specific catalyst to only adopt one-step hydroconversion reaction, so that the process is simple and convenient, and the cost is low; the method can produce the refrigerating machine oil product with high added value in high yield by carrying out one-step hydro-conversion reaction on the low-value I type base oil product, and improve the economic benefit of enterprises.

Drawings

FIG. 1 is a schematic flow diagram of a method of the present invention.

Detailed Description

The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.

As shown in FIG. 1, the present invention provides a method for producing a refrigerating machine oil, comprising

(1) Taking base oil with the viscosity index of less than 80 as raw oil, and reacting the base oil through a hydro-conversion reaction zone filled with a hydro-isomerization treatment catalyst to obtain hydro-conversion generated oil, wherein a carrier of the hydro-isomerization treatment catalyst comprises at least one selected from silicon oxide, aluminum oxide and silicon oxide-aluminum oxide and at least one shape-selective cracking molecular sieve;

In one embodiment, the base oil comprises a Low Viscosity Index (LVI) base oil having a viscosity index of less than 60 and/or a Medium Viscosity Index (MVI) base oil having a viscosity index of greater than or equal to 60 and less than 80. In one embodiment, the Low Viscosity Index (LVI) or Medium Viscosity Index (MVI) base oil is a group I base oil produced by a conventional solvent refining process.

In order to solve the problems of low value and difficult sale of low-end I base oil products for refineries, the characteristics of low paraffin content and high naphthene and aromatic hydrocarbon content in low-viscosity index (LVI) and medium-viscosity index (MVI) base oil are considered, and the low-pour-point low-paraffin-content medium-viscosity base oil just meets the requirements of low pour point, good compatibility with refrigerant, heat and oxidation stability and the like of refrigerating machine oil. The invention can produce the refrigerating machine oil product with high added value with high yield by carrying out one-step hydro-conversion reaction on the low-value I type base oil product, and improves the economic benefit of enterprises.

In the process of the present invention, the hydrotreating is carried out in the presence of a hydroisomerization catalyst. The application provides a hydroisomerization treatment catalyst, which comprises a carrier and a hydrogenation active metal component loaded on the carrier.

In one embodiment, the support of the hydroisomerization treatment catalyst comprises at least one member selected from the group consisting of silica, alumina, and silica-alumina, and at least one shape selective cracking molecular sieve. The hydroisomerization catalyst using the carrier can remove sulfur, nitrogen and aromatic hydrocarbon in the base stock oil, isomerize normal paraffin to reduce the pour point of the raw material and produce high-quality refrigerator oil with high yield. In one embodiment, the support of the hydroisomerization treatment catalyst comprises a silica-alumina and a shape selective molecular sieve. The carrier of the hydroisomerization catalyst is formed by mixing and kneading silica-alumina and a shape-selective cracking molecular sieve. On the basis of the total amount of the hydroisomerization catalyst carrier, the mass fraction of the silicon oxide-aluminum oxide is 60-90%, and the mass fraction of the shape-selective cracking molecular sieve is 10-40%. More preferably, the hydroisomerization catalyst comprises 70-85% by mass of silica-alumina and 15-30% by mass of a shape-selective cracking molecular sieve based on the total amount of the carrier.

In the hydroisomerization catalyst, the shape selective cracking molecular sieve is preferably at least one of ZSM-5, ZSM-8, ZSM10, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38 and ZSM-48, and most preferably the shape selective cracking molecular sieve is ZSM-48.

In one embodiment, the hydrogenation-active metal component of the hydroisomerization treatment catalyst is one or more selected from the group consisting of nickel, cobalt, molybdenum, tungsten; nickel, molybdenum, tungsten are preferred. In one embodiment, the content of nickel and/or cobalt in terms of oxide is 5-20% based on the total amount of the hydroisomerization catalyst; the content of molybdenum and/or tungsten is 15-40%.

In one embodiment, the hydroisomerization treatment catalyst also optionally contains a promoter component selected from one or more of fluorine, boron and phosphorus. In one embodiment, the content of the auxiliary component selected from one or more of fluorine, boron and phosphorus is 0 to 9% by element.

The preparation of the hydroisomerization catalyst may employ the following process: combining at least one selected from silica, alumina and silica-alumina and at least one shape-selective cracking molecular sieve in proportion to form a carrier; impregnating the carrier with a solution containing a compound of a hydrogenation active metal component and an optional compound of an auxiliary agent component, and roasting to obtain the hydroisomerization catalyst.

In one embodiment, during the preparation of the catalyst, it is also possible to optionally add organic additives in a molar ratio of 0 to 2: 1. in one embodiment, the organic additive is one or more selected from organic alcohol, organic acid and organic amine, and preferably the organic additive is organic acid.

According to the method provided by the invention, the raw oil is contacted with the hydroisomerization catalyst in the hydrogenation reaction zone under the hydrogenation condition to obtain the hydrogenated product oil with low sulfur, low nitrogen, low aromatic hydrocarbon and low pour point.

In the invention, the reaction conditions of the hydroconversion reaction zone can be controlled, so that after the hydroconversion generated oil is subjected to distillation separation, the pour point of the refrigerator oil product meets the pour point requirements of different grades of products in the refrigerator oil standard. In one embodiment, the reaction conditions in the hydroconversion reaction zone are: the pressure is 5-20 MPa, preferably 8-18 MPa; the temperature is 250-380 ℃, and preferably 280-360 ℃; the volume airspeed is 0.2-3 h^-1Preferably 0.5 to 2 hours^-1(ii) a The volume ratio of hydrogen to oil is 100 to 1500, preferably 200 to 1000.

After hydrotreating, the hydrotreated oil is subjected to distillation in a distillation zone. According to the viscosity, different grades of refrigerating machine oil can be obtained. In the present invention, the distillation process in the distillation zone is well known in the art and may generally include one or more of flash distillation, atmospheric distillation and vacuum distillation operating units as necessary to accomplish the desired separation.

The following examples further illustrate the invention.

The hydroisomerization treatment catalyst used in the examples of the invention is as follows:

(1) hydroisomerization process catalyst 1

The hydroisomerization catalyst 1 used in embodiments 1 and 2 of the present invention uses a carrier obtained by mixing and kneading silica-alumina and a ZSM-48 molecular sieve, fluorine and phosphorus as additive components, citric acid as an organic additive, and nickel, molybdenum, and tungsten as active components. Wherein the mass fraction of the silicon oxide-aluminum oxide is 80% and the mass fraction of the shape-selective cracking molecular sieve is 20% based on the total amount of the carrier. Based on the total amount of the catalyst and calculated by oxides, the mass fraction of nickel is 8%, the mass fraction of molybdenum is 5%, and the mass fraction of tungsten is 28%; calculated by elements, the mass fraction of phosphorus is 2.4%, the mass fraction of fluorine is 3.5%, and the balance is the carrier.

(2) Hydroisomerization treatment catalyst 2

The hydroisomerization catalyst 2 used in embodiment 3 of the present invention is a carrier obtained by mixing and kneading silica-alumina and a ZSM-48 molecular sieve, fluorine and phosphorus are auxiliary components, citric acid is an organic additive, and nickel, molybdenum, and tungsten are active components. Wherein the mass fraction of the silicon oxide-aluminum oxide is 70 percent and the mass fraction of the shape-selective cracking molecular sieve is 30 percent based on the total amount of the carrier. Based on the total amount of the catalyst and calculated by oxides, the mass fraction of nickel is 8%, the mass fraction of molybdenum is 5%, and the mass fraction of tungsten is 28%; calculated by elements, the mass fraction of phosphorus is 2.4%, the mass fraction of fluorine is 3.5%, and the balance is the carrier.

(3) Hydroisomerization treatment catalyst 3

The hydroisomerization catalyst 3 used in embodiment 4 of the present invention is a carrier obtained by mixing and kneading silica-alumina and a ZSM-48 molecular sieve, fluorine and phosphorus are auxiliary components, citric acid is an organic additive, and nickel, molybdenum, and tungsten are active components. Wherein the mass fraction of the silicon oxide-aluminum oxide is 80% and the mass fraction of the shape-selective cracking molecular sieve is 20% based on the total amount of the carrier. Based on the total amount of the catalyst and calculated by oxides, the mass fraction of nickel is 5%, the mass fraction of molybdenum is 2.1%, and the mass fraction of tungsten is 21%; calculated by elements, the mass fraction of phosphorus is 0.8%, the mass fraction of fluorine is 2.5%, and the balance is the carrier.

The preparation method comprises the following steps:

(1) mixing a silicon oxide-aluminum oxide carrier and a ZSM-48 shape-selective cracking molecular sieve according to a proportion, extruding and forming, drying at 120 ℃ for 5 hours, and roasting at 500 ℃ for 3 hours to obtain a catalyst carrier;

(2) preparing mixed solution of phosphoric acid, ammonium fluoride, citric acid, nickel nitrate, ammonium molybdate and ammonium metatungstate according to a proportion, impregnating a catalyst carrier for 2 hours, drying at 120 ℃ for 2 hours, and finally roasting at 500 ℃ for 4 hours to obtain the hydroisomerization catalyst.

Example 1

This example starts from an MVI 150 base oil, the properties of which are shown in Table 1.

The feedstock was processed according to the process flow of figure 1. Wherein the hydroconversion reaction zone was charged with hydroisomerization catalyst 1 under the operating conditions shown in Table 2. The properties of the refrigerator oil obtained by the hydroconversion reaction zone and separated by the distillation zone are shown in Table 3.

TABLE 1

Item	MVI 150
		Density (20 ℃ C.)/g. cm^－3	0.8682
Viscosity at 100 ℃/(mm)²/s)	5.075
		Viscosity at 40 ℃/(mm)²/s)	32.14
Viscosity index	76
		Pour point/. degree.C	-9
Sulfur content/. mu.g.g^-1	45.91
		Nitrogen content/microgram g^-1	7
Saybolt color comparison/number	27
		Paraffin content/%)	22.5
CycloalkanesContent/%	62.3
		Content of aromatic hydrocarbons/%)	15.2
Flash point/. degree.C	206

TABLE 2

Process conditions	Hydroconversion reaction zone
		Partial pressure of hydrogen/MPa	16.0
Reaction temperature/. degree.C	300
		Volume space velocity/h^-1	1.0
Hydrogen to oil ratio/(v/v)	500

TABLE 3

Product Properties	No. 32 refrigerator oil
		Yield/%	85.7
Viscosity at 40 ℃/(mm)²/s)	29.64
		Sulfur content/. mu.g.g^-1	<10
Nitrogen content/microgram g^-1	<1
		Pour point/. degree.C	-33
Saybolt color comparison/number	>+30
		Flash point/. degree.C	174
Total acid value/(mgKOH/g)	<0.01

Example 2

This example starts from an MVI 350 base oil, the properties of which are shown in Table 4.

The feedstock was processed according to the process flow of figure 1. Wherein the hydroconversion reaction zone was charged with hydroisomerization catalyst 1 and the operating conditions are shown in Table 5. The properties of the refrigerator oil obtained by the hydroconversion reaction zone and separated by the distillation zone are shown in Table 6.

TABLE 4

TABLE 5

Process conditions	Hydroconversion reaction zone
		Partial pressure of hydrogen/MPa	16.0
Reaction temperature/. degree.C	320
		Volume space velocity/h^-1	0.8
Hydrogen to oil ratio/(v/v)	500

TABLE 6

Product Properties	Number 68Refrigerating machine oil
		Yield/%	81.6
Viscosity at 40 ℃/(mm)²/s)	65.86
		Sulfur content/. mu.g.g^-1	<10
Nitrogen content/microgram g^-1	<1
		Pour point/. degree.C	-27
Saybolt color comparison/number	>+30
		Flash point/. degree.C	208
Total acid value/(mgKOH/g)	<0.01

Example 3

The example used the same starting material as in example 2, which was processed according to the process scheme of FIG. 1. Wherein the hydroconversion reaction zone was loaded with hydroisomerization catalyst 2 and the operating conditions are shown in Table 7. The properties of the refrigerator oil obtained by the hydroconversion reaction zone and separated by the distillation zone are shown in Table 8.

TABLE 7

Process conditions	Hydroconversion reaction zone
		Partial pressure of hydrogen/MPa	16.0
Reaction temperature/. degree.C	325
		Volume space velocity/h^-1	1.0
Hydrogen to oil ratio/(v/v)	500

TABLE 8

Product Properties	Number 68 refrigerator oil
		Yield/%	79.64
Viscosity at 40 ℃/(mm)²/s)	64.81
		Sulfur content/. mu.g.g^-1	<10
Nitrogen content/microgram g^-1	<1
		Pour point/. degree.C	-27
Saybolt color comparison/number	>+30
		Flash point/. degree.C	201
Total acid value/(mgKOH/g)	<0.01

Example 4

The example used the same starting material as in example 2, which was processed according to the process scheme of FIG. 1. Wherein the hydroconversion reaction zone was charged with hydroisomerization catalyst 3 and the operating conditions are shown in Table 9. The properties of the refrigerator oil obtained by the hydroconversion reaction zone and subjected to separation in the distillation zone are shown in Table 10.

TABLE 9

Watch 10

Product Properties	Number 68 refrigerator oil
		Yield/%	78.52
Viscosity at 40 ℃/(mm)²/s)	63.17
		Sulfur content/. mu.g.g^-1	<10
Nitrogen content/microgram g^-1	<1
		Pour point/. degree.C	-27
Saybolt color comparison/number	>+30
		Flash point/. degree.C	197
Total acid value/(mgKOH/g)	<0.01

Comparative example 1

This comparative example uses the same starting material as in example 1 and processes the starting material according to the process scheme of figure 1. Wherein the hydrogenation conversion reaction zone is filled with a hydrotreating catalyst RIPP industrial agent RL-2 without a shape selective cracking molecular sieve, and the operation conditions are shown in Table 11. The properties of the refrigerator oil obtained by the hydroconversion reaction zone and separated by the distillation zone are shown in Table 12.

TABLE 11

Process conditions	Hydroconversion reaction zone
		Partial pressure of hydrogen/MPa	16.0
Reaction temperature/. degree.C	330
		Volume space velocity/h^-1	1.0
Hydrogen to oil ratio/(v/v)	500

TABLE 12

Product Properties	No. 32 refrigerator oil
		Yield/%	76.4
Viscosity at 40 ℃/(mm)²/s)	28.93
		Sulfur content/. mu.g.g^-1	<10
Nitrogen content/microgram g^-1	<1
		Pour point/. degree.C	-33
Saybolt color comparison/number	>+30
		Flash point/. degree.C	168
Total acid value/(mgKOH/g)	<0.01

Comparative example 2

This comparative example uses the same starting material as in example 2 and processes the starting material according to the process scheme of figure 1. Wherein the hydroconversion reaction zone is filled with a hydroprocessing catalyst RIPP industrial agent RL-2 without shape selective cracking molecular sieve, and the operation conditions are shown in Table 13. The properties of the refrigerator oil obtained by the hydroconversion reaction zone and subjected to separation in the distillation zone are shown in Table 14.

Watch 13

Process conditions	Hydroconversion reaction zone
		Partial pressure of hydrogen/MPa	16.0
Reaction temperature/. degree.C	350
		Volume space velocity/h^-1	0.8
Hydrogen to oil ratio/(v/v)	500

TABLE 14

Comparing example 1 with comparative example 1, it can be found that the hydroisomerization catalyst of the present application can obtain the corresponding grade of refrigerator oil with higher yield, and meanwhile, the obtained refrigerator oil has higher viscosity, higher flash point and better thermal stability. Similar results were obtained comparing example 2 and comparative example 2. The result shows that the method for producing the refrigerator oil can convert the I-type base oil products such as Low Viscosity Index (LVI) and Medium Viscosity Index (MVI) base oil with low product value into the refrigerator oil product with high added value with high yield, and improves the economic benefit of enterprises.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims

1. A method of producing a refrigerator oil comprising:

2. The process of claim 1, wherein the support of the hydroisomerization treatment catalyst comprises silica-alumina and a shape selective molecular sieve.

3. The process of claim 2, wherein the mass fraction of silica-alumina is 60 to 90% and the mass fraction of shape selective cracking molecular sieve is 10 to 40% based on the total amount of the hydroisomerization treatment catalyst support.

4. The process of claim 2, wherein the mass fraction of silica-alumina is 70-85% and the mass fraction of shape selective cracking molecular sieve is 15-30% based on the total amount of the hydroisomerization treatment catalyst support.

5. The process of claim 1, wherein the hydrogenation-active metal component of the hydroisomerization treatment catalyst is one or more selected from the group consisting of nickel, cobalt, molybdenum, tungsten; the hydroisomerization treatment catalyst optionally contains a promoter component selected from one or more of fluorine, boron and phosphorus.

6. A process according to claim 5, wherein the hydroisomerization catalyst comprises from 5 to 20% by weight, calculated as oxide, of nickel and/or cobalt, from 15 to 40% by weight, of molybdenum and/or tungsten, and from 0 to 9% by weight, calculated as element, of one or more promoter components selected from fluorine, boron and phosphorus.

7. The process of any one of claims 1-6, wherein the shape selective cracking molecular sieve is one or more of ZSM-5, ZSM-8, ZSM10, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38 and ZSM-48.

8. The method of claim 1, wherein the base oil comprises a Low Viscosity Index (LVI) base oil having a viscosity index of less than 60 and/or a Medium Viscosity Index (MVI) base oil having a viscosity index of greater than or equal to 60 and less than 80.

9. The method of claim 8, wherein the Low Viscosity Index (LVI) or Medium Viscosity Index (MVI) base oil is a group I base oil produced by a conventional solvent refining process.

10. The process of any of claims 1-6, wherein the reaction conditions of the hydroconversion reaction zone are: the pressure is 5-20 MPa, preferably 8-18 MPa; the temperature is 250-380 ℃, and preferably 280-360 ℃; the volume airspeed is 0.2-3 h^-1Preferably 0.5 to 2 hours^-1(ii) a The volume ratio of hydrogen to oil is 100 to 1500, preferably 200 to 1000.