CN114736709A

CN114736709A - Wax oil processing method

Info

Publication number: CN114736709A
Application number: CN202110018654.7A
Authority: CN
Inventors: 秦波; 张信伟; 高杭; 柳伟; 王仲义; 王海洋; 吴子明; 杜艳泽; 侯栓弟
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2021-01-07
Filing date: 2021-01-07
Publication date: 2022-07-12
Anticipated expiration: 2041-01-07
Also published as: CN114736709B

Abstract

The invention discloses a wax oil processing method, which comprises the following steps: (1) separating the wax oil fraction to produce a wax oil fraction rich in saturated components and a wax oil fraction rich in unsaturated components; (2) the wax oil fraction rich in saturated components enters a hydrofining reaction zone A and a hydrocracking reaction zone B for reaction, and products are separated to obtain naphtha fraction, aviation kerosene fraction, diesel oil fraction and high-viscosity index tail oil fraction; (3) the wax oil fraction rich in unsaturated components enters a hydrofining reaction zone C and a hydrocracking reaction zone D for reaction, and the product is separated to obtain naphtha fraction, and optionally obtain aviation kerosene fraction and diesel oil fraction. The method can be used for producing high-value-added products such as high-viscosity index lubricating oil basic raw materials, high-grade special oil products and the like, and the utilization rate of wax oil fractions and the added value of the products are improved.

Description

Wax oil processing method

Technical Field

The invention relates to a wax oil processing method, in particular to a processing method for producing a high-viscosity index lubricating oil base oil raw material by using wax oil as a raw material.

Background

At present, the basic route of crude oil processing is to separate crude oil into different fractions including gas, naphtha fraction, aviation kerosene fraction, diesel fraction, wax oil fraction, residual oil fraction and other components through an atmospheric and vacuum distillation device. In general, naphtha fraction, aviation kerosene fraction and diesel oil fraction are directly used as fuel oil after being hydrorefined; hydrorefining the wax oil fraction to be used as a catalytic cracking raw material or producing naphtha fraction, aviation kerosene fraction, diesel oil fraction or tail oil fraction by a hydrocracking technology; and the residual oil fraction can be used for producing catalytic cracking raw material by residual oil hydrogenation or producing light component by residual oil hydrocracking.

The patent CN201811627078.0 discloses a wax oil hydrocracking method and system, in which the wax oil raw material oil is subjected to hydrocracking by a hydrocracking catalyst and hydroisomerization by an isomeric hydrocracking catalyst to be combined to flexibly produce naphtha products, high-quality aviation kerosene products and high-quality diesel oil products with various specifications, and high-quality steam cracking is performed to prepare ethylene raw materials, especially to produce high-quality lubricant base oil. Patent CN 201811113894.X provides a wax oil hydrocracking method, which takes vacuum wax oil as a raw material, and increases the yield of heavy naphtha with high aromatic hydrocarbon potential and improves the low-temperature fluidity and tail oil property of aviation kerosene and diesel oil products through reasonable combination of hydrocracking catalysts with different functions. Patent CN201920366310.3 provides a wax oil hydrocracking system, and the switching that the wax oil hydrocracking system that provides can produce diesel oil and produce light oil can be carried out, nimble adaptation market demand.

At present, wax oil components (with a distillation range of about 300-620 ℃) are mainly converted into naphtha fraction, aviation kerosene fraction, diesel oil fraction, tail oil fraction and other fractions through a hydrocracking technology, wherein the diesel oil fraction can be used as special oil, and the tail oil can be used as an ethylene raw material or lubricating oil base oil. Hydrocracking technology has an irreplaceable effect on the aspects of heavy oil lightening and cleaning, but due to technical limitations, the selectivity between different products and the quality of different products are difficult to be considered. For example, when the aromatic hydrocarbon content is lower than 5wt% in the prior art for producing white oil, the aromatic hydrocarbon content of the aviation kerosene product is reduced, the requirement of the aviation kerosene product on the aromatic hydrocarbon content cannot be met, meanwhile, the aromatic hydrocarbon potential of the heavy naphtha fraction is reduced, and the product quality is reduced. Therefore, the development of a new path for processing the wax oil fraction, the provision of raw materials for producing various special oils and raw materials for producing high-grade lubricant base oil has become an urgent need for the efficient use of wax oil hydrogenation.

Disclosure of Invention

Aiming at the defects in the prior art, the invention discloses a wax oil processing method which can be used for producing high-value-added products such as high-viscosity index lubricating oil basic raw materials, high-grade special oil products and the like, and improving the utilization rate of wax oil fractions and the added value of the products.

A wax oil processing method comprises the following steps:

(1) separating the wax oil fraction to produce a wax oil fraction rich in saturated components and a wax oil fraction rich in unsaturated components;

(2) the wax oil fraction rich in saturated components enters a hydrofining reaction zone A and a hydrocracking reaction zone B for reaction, and products are separated to obtain naphtha fraction, aviation kerosene fraction, diesel oil fraction and high-viscosity index tail oil fraction;

(3) the wax oil fraction rich in unsaturated components enters a hydrofining reaction zone C and a hydrocracking reaction zone D for reaction, and the product is separated to obtain naphtha fraction, and optionally obtain aviation kerosene fraction and diesel oil fraction.

In step (1) of the above process, the properties of the wax oil fraction are as follows: the distillation range is 260-650 ℃ (measured by adopting an ASTM D1160 petroleum product vacuum distillation method); the density at 20 ℃ is 0.81g/cm^-3~ 0.98g/cm^-3To (c) to (d); the sulfur content is between 0.05wt% and 4.0 wt%; the nitrogen content is 300-5000 mug/g.

In the step (1), the wax oil fraction raw material may be at least one of straight-run wax oil, coker wax oil, deasphalted oil, catalytic cycle oil, coal tar, direct coal liquefaction oil, indirect coal liquefaction oil, synthetic oil, shale oil, and the like.

In the step (1), the saturated component mass content in the wax oil fraction is 25% to 85%, preferably 35% to 65%, and more preferably 40% to 55%.

In the step (1), the saturated component content of the wax oil fraction rich in saturated components is more than 80% by mass, preferably 85-100% by mass, and more preferably 90-100% by mass.

In the step (1), the saturated component content of the wax oil fraction rich in the unsaturated component is less than 20% by mass, preferably between 0 and 20% by mass.

In the step (1), the wax oil fraction is separated by an adsorption separation technology. The adsorption separation technology comprises two operations of adsorption and desorption: under the conditions that the pressure is normal pressure-2 MPa, the temperature is 25-200 ℃ and the liquid phase volume space velocity is 0.1-5 h^-1Under the condition (1), contacting the wax oil fraction with an adsorbent to adsorb unsaturated components, wherein the obtained product is the wax oil fraction rich in saturated components; after adsorption, the desorption solvent is contacted with the adsorbent after saturated adsorption, and the obtained product is rectified to recover the solvent, so that the wax oil fraction rich in unsaturated components is obtained. The periodic operation is carried out according to two steps of adsorption and desorption, and the continuous separation of the wax oil fraction is realized. The device that the absorption adopted is the fixed bed device of multi-tower switching, and preferred is 2~6 towers. The desorption solvent is one or more of alkane, alcohol, ether and ester, and preferably one or more of n-dodecane, methanol, ethanol, ethylene glycol monomethyl ether and ethyl acetate. The adsorbent is one or more of activated carbon, alumina, silica gel, an A-type molecular sieve, a ZSM series molecular sieve, metal modified activated carbon, metal modified alumina, metal modified silica gel, a metal modified A-type molecular sieve and a metal modified ZSM series molecular sieve.

In the step (3), the operating conditions of the hydrorefining reaction zone a are as follows: the reaction pressure is 3 MPa-25 MPaPreferably 5MPa to 10 MPa; the reaction temperature is 220-450 ℃, preferably 300-380 ℃; the volume space velocity of the reaction process is 1.0-10.0 h^-1Preferably 2.0 to 8.0 hours^-1(ii) a The volume ratio of hydrogen to oil is 200-3000, preferably 500-1000.

In the step (2), the hydrocracking reaction zone B is operated under the following conditions: the reaction pressure is between 3MPa and 25MPa, and preferably between 5MPa and 10 MPa; the reaction temperature is 220-450 ℃, preferably 280-360 ℃; the volume space velocity of the reaction process is 1.0-10.0 h^-1Preferably for 2.0-8.0 h^-1(ii) a The volume ratio of hydrogen to oil is 200-3000, preferably 500-1000.

In the step (3), the operating conditions of the hydrorefining reaction zone C are as follows: the reaction pressure is 6-25 MPa, preferably 8-18 MPa; the reaction temperature is 280-450 ℃, preferably 320-410 ℃; the volume space velocity of the reaction process is 0.2-5.0 h^-1Preferably 0.8 to 2.0h^-1(ii) a The volume ratio of hydrogen to oil is 500-3000, preferably 800-1500.

In the step (3), the hydrocracking reaction zone D has the following operating conditions: the reaction pressure is 6-25 MPa, preferably 8-18 MPa; the reaction temperature is 280-450 ℃, preferably 320-410 ℃; the volume space velocity in the reaction process is 0.4-5.0 h^-1Preferably 1.0-2.0 h^-1(ii) a The volume ratio of hydrogen to oil is 500-3000, preferably 800-1500.

The hydrofining catalyst used in step (2) and/or step (3) of the above process has the following properties: the specific surface area is 100-300 m²The pore volume is between 0.25 and 0.45 ml/g; the active metal components are VIB group metals and VIII group metals, the VIB group metals are preferably tungsten (W) and molybdenum (Mo), and the VIII group metals are preferably cobalt (Co) and nickel (Ni); the weight percentage of the alumina is 60-85 percent; the VIB group metal (calculated by oxide) is 12% -30%; the VIII group metal (calculated by oxide) is 3% -10%.

The hydrocracking catalyst used in step (2) and/or step (3) of the above process has the following properties: the specific surface area is 150-500 m²The pore volume is between 0.20 and 0.60 ml/g; active goldThe metal components are VIB group metals and VIII group metals, the VIB group metals are preferably tungsten (W) and molybdenum (Mo), and the VIII group metals are preferably cobalt (Co) and nickel (Ni); according to the weight percentage of the catalyst, the alumina accounts for 30-75%; 5-50% of molecular sieve; 12 to 30 percent of VIB group metal (calculated by oxide); the VIII group metal (calculated by oxide) is 3% -10%.

The hydrofining catalysts loaded in the hydrofining reaction zones in step (2) and step (3) of the above-mentioned method may be the same or different, preferably different, except that: the mass content of the hydrogenation active metal of the catalyst in the step (3) is 3% -10% higher than that of the hydrogenation active metal of the catalyst in the step (2).

The hydrocracking catalysts filled in the hydrocracking reaction zone in step (2) and step (3) of the above method may be the same or different, preferably different, in that: the mass content of the molecular sieve of the catalyst in the third reactor in the step (3) is 5-30% higher than that of the silicon oxide in the catalyst in the step (2); the mass content of the hydrogenation metal of the catalyst in the step (2) is 5-40% higher than that of the hydrogenation metal of the catalyst in the third reactor in the step (3).

In the method, the wax oil fraction rich in the saturated component in the step (2) is pressurized by a high-pressure pump and then is sent into a reaction system together with high-pressure hydrogen for hydrogenation reaction, and the effluent after the reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange and then enters a fractionating tower for fraction separation.

In the method, in the step (3), the wax oil fraction rich in unsaturated components is pressurized by a high-pressure pump and then is fed into a reaction system together with high-pressure hydrogen for reaction, the effluent after the reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower for fraction separation to respectively obtain a naphtha fraction, a aviation kerosene fraction, a diesel oil fraction, a tail oil fraction and the like; or separating to obtain naphtha fraction and bottom effluent; the bottom stream or the tail oil fraction can be recycled to the reaction system of step (3).

In step (2) of the above process, the hydrofinishing reaction zone and the hydrocracking reaction zone may be arranged in one or more reactors connected in series. For example, 1-3 reactors are arranged in series, the reaction materials sequentially pass through each reactor, wherein the first reactor is independently filled with refined catalyst or the upper part and the lower part are respectively filled with refined catalyst and hydrocracking catalyst, and the rest reactors are filled with hydrocracking catalyst. When the first reactor is filled with a refining catalyst and a hydrocracking catalyst respectively, the volume ratio of the upper part of the hydrofining catalyst to the lower part of the hydrocracking catalyst is 4: 1-1. The hydrofining catalyst comprises hydrogenation active metal and an alumina carrier, and can be selected from various existing commercial catalysts, such as hydrofining catalysts such as FF-36, FF-46 and FF-66 developed by the Fushu petrochemical research institute (FRIPP); it can also be prepared according to the common knowledge in the field, if necessary. The hydrocracking catalyst comprises hydrogenation active metal, molecular sieve component, amorphous silica-alumina and alumina carrier, and can be selected from various existing commercial catalysts, such as hydrocracking catalysts developed by the Fushu petrochemical research institute (FRIPP), such as FC-52, FC-32, FC-50, FC-60, FC-76 and FC-80; it can also be prepared according to the common knowledge in the field, if necessary.

In the step (2) of the method, the diesel oil fraction can be used for producing special oil products such as industrial white oil, light white oil and transformer oil; the high viscosity index tail oil fraction can be used as a base oil raw material for producing high-grade lubricating oils with the viscosity indexes of more than 130, such as No. 4 and No. 6.

In step (3) of the above process, the hydrofinishing reaction zone and the hydrocracking reaction zone may be arranged in one or more reactors connected in series. For example, 1-3 reactors are arranged in series or in two-stage mode, wherein the first reactor is separately filled with refined catalyst, the second reactor is separately filled with refined catalyst or the upper part of the second reactor is filled with refined catalyst, the lower part of the hydrocracking catalyst, and the third reactor is filled with hydrocracking catalyst. When the second reactor is filled with the refined catalyst and the hydrocracking catalyst respectively, the volume ratio of the upper part to the lower part is 5: 1-1. The hydrofining catalyst comprises hydrogenation active metal and an alumina carrier, and can be selected from various existing commercial catalysts, such as hydrofining catalysts such as FF-36, FF-46 and FF-66 developed by the Fushu petrochemical research institute (FRIPP); it can also be prepared according to the common knowledge in the field, if necessary. The hydrocracking catalyst comprises hydrogenation active metal, molecular sieve component, amorphous silica-alumina and alumina carrier, and can be selected from various existing commercial catalysts, such as hydrocracking catalysts developed by the Fushu petrochemical research institute (FRIPP), such as FC-52, FC-32, FC-50, FC-60, FC-76 and FC-80; it can also be prepared according to the common knowledge in the field, if necessary. When the reactors are in a series connection, the reactant flow passes through each reactor at a time; when the two-stage type is adopted, the reaction effluent of the second reactor sequentially passes through a high-pressure separator, a low-pressure separator, a fractionating tower and the like, the effluent at the bottom of the fractionating tower enters a third reactor with high-pressure hydrogen through a pressure pump for hydrocracking reaction, and the reaction effluent sequentially passes through the high-pressure separator and the low-pressure separator and then enters the fractionating tower together with the effluent of the second reactor; the reaction system may share high pressure hydrogen and recycle hydrogen.

In the step (2) and the step (3), the nitrogen content of the refined oil after hydrofining is less than 50 mu g/g.

In step (2) and step (3) of the above process, the top of the optional hydrofinishing reaction zone is filled with one or more protecting agents. The protective agent comprises hydrogenation active metal and alumina carrier, and can be selected from various existing commercial catalysts, such as FZC and FBN series protective agents developed by Fushu petrochemical research institute (FRIPP); it can also be prepared according to the common knowledge in the field, if necessary.

In the above method, the reaction systems in step (2) and step (3) may share a high-pressure hydrogen and high-pressure hydrogen circulation system, etc.; the raw materials in the step (2) and the step (3) can be respectively or simultaneously subjected to heat exchange with the effluents in the step (2) and the step (3), so that the heat of the two reaction systems is fully utilized, and the energy consumption is reduced.

The method divides the wax oil fraction into the wax oil fraction rich in saturated components and the wax oil fraction rich in unsaturated components, and then respectively adopts the adaptive technology to process according to the characteristics of the wax oil fraction, thereby realizing the processing concept of aromatic hydrocarbon, olefinic hydrocarbon and oil. The paraffin content in the wax oil fraction rich in the saturated components is high, the saturation degree is good, the problem that the high-grade lubricating oil base oil raw materials of No. 4 and No. 6 with the viscosity index larger than 130 cannot be produced in a sufficient manner due to the lack of paraffin-based raw materials in China can be solved, and the added value of the product is greatly improved; the obtained wax oil fraction rich in unsaturated components has high aromatic hydrocarbon content, can be used for producing a maximum amount of reforming raw materials with high aromatic hydrocarbon potential, and solves the problem of shortage of PX raw materials. Through the deep fusion of the two processing technological processes and the sharing of part of public facilities, the energy consumption of the processing process can be effectively reduced, and the efficiency of the processing process is improved. The implementation of the scheme can effectively improve the utilization rate of raw materials and the added value of products, and simultaneously reduce the energy consumption in the processing process, and the economic benefit is remarkable.

Detailed Description

The hydrocracking process of the present invention will be described in detail below with reference to examples and comparative examples.

The properties of the wax oil fraction are shown in Table 1 and the technical comparison results are shown in Table 2.

Example 1

(1) At the pressure of 0.5MPa, the adsorption temperature of 50 ℃ and the liquid phase volume space velocity of 2h^-1Under the condition of (1), a switching fixed bed separation device is adopted to separate saturated components from unsaturated components, an iron-modified 4A type molecular sieve is adopted as an adsorbent, wherein the iron content is 5.0%, and dodecane is adopted as an analytic solvent. The wax oil fraction enters a fixed bed 1, unsaturated components are selectively adsorbed in the fixed bed 1, the effluent 1 is the wax oil fraction rich in saturated components, when the content of the unsaturated components in the effluent 1 is not less than 2 percent, the feed of the fixed bed 1 is changed from the wax oil fraction into a desorption solvent to be desorbed, meanwhile, the wax oil fraction is changed to enter the fixed bed 2 to be selectively adsorbed by the unsaturated components, the effluent 2 is the wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 2 is not less than 2 percent, the feed of the fixed bed 2 is changed from the wax oil fraction into the desorption solvent to be desorbed, simultaneously, the wax oil fraction is changed to enter a fixed bed 3 to be selectively adsorbed by the unsaturated components, the effluent 3 is the wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 3 is not less than 2 percentThe feeding of the fixed bed 3 is changed from wax oil fraction to desorption solvent for desorption, and simultaneously, the wax oil fraction is changed to enter the fixed bed 1 after the desorption for selective adsorption of unsaturated components. Wherein, when the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent for desorbing unsaturated components, when the content of the unsaturated components is not more than 20 percent, the desorption process is finished, and the obtained product is rectified to recover the desorption solvent, thereby obtaining the wax oil fraction rich in the unsaturated components. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, and the continuous separation of unsaturated components and saturated components of the wax oil fraction is realized.

(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, feeding the wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 8MPa and the hydrogen-oil volume ratio of 600, arranging the reaction system with 2 reactors to carry out hydrocracking reaction, sequentially passing the reaction materials through the 2 reactors in a series connection mode, filling FBN series protective agents and FF-36 refined catalysts into a first reactor, wherein the reaction temperature of a refining section is 330 ℃, and the volume space velocity is 4.0h^-1(ii) a The second reactor is filled with FC-80 hydrocracking catalyst, the reaction temperature of the cracking section is 350 ℃, and the volume space velocity is 3.0h^-1(ii) a The effluent after reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower for fraction separation to respectively obtain naphtha fraction, aviation kerosene fraction, diesel oil fraction, high-viscosity index tail oil fraction and the like; (ii) a

(3) Pressurizing the wax oil fraction rich in unsaturated components obtained in the step (1) by a high-pressure pump, then feeding the wax oil fraction and high-pressure hydrogen into a reaction system with a reaction system pressure of 15MPa and a hydrogen-oil volume ratio of 1000, wherein the reaction system is provided with 3 reactors for hydrocracking reaction, and adopts a series connection mode, wherein the first reactor is separately filled with an FBN series protective agent and an FF-66 hydrofining catalyst, the upper part and the lower part of the second reactor are respectively filled with an FF-66 refining catalyst and an FC-80 hydrocracking catalyst, the volume ratio of the FF-66 refining catalyst to the FC-80 hydrocracking catalyst is 3:1, and the third reactor is filled with an FC-52 hydrocracking catalyst; the reaction effluent passes through a high-pressure separator and a low-pressure separator in sequenceA separator, a fractionating tower and the like, and the bottom flow is conveyed to a raw material tank. The reaction temperature of the refining section is 360 ℃, and the volume space velocity is 1.0h^-1(ii) a The reaction temperature of the cracking section is 370 ℃, and the volume space velocity is 1.5h^-1。

FF-36 catalyst specific surface area 215m²The volume of the pores is 0.42ml/g, and the weight percentage of the catalyst is that the molybdenum oxide is 21.4 percent, the nickel oxide is 4.4 percent, and the rest is alumina; FF-66 catalyst specific surface area 201m²The catalyst comprises the following components in percentage by weight, wherein the volume of the catalyst is 0.39ml/g, the molybdenum oxide is 23.0 percent, the nickel oxide is 4.9 percent, and the balance is aluminum oxide; FC-80 catalyst specific surface area 215m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.35ml/g, the content of tungsten oxide is 23.0 percent, the content of nickel oxide is 6.5 percent, the content of silicon oxide is 21 percent, and the balance is aluminum oxide; FC-52 catalyst specific surface area 422m²The catalyst comprises 16.0 percent of molybdenum oxide, 5.5 percent of nickel oxide, 38 percent of silicon oxide and the balance of aluminum oxide in percentage by weight.

Example 2

(1) At normal pressure, adsorption temperature of 100 ℃ and liquid phase volume space velocity of 3h^-1Under the condition, a switching fixed bed separation device is adopted to separate saturated components from unsaturated components, manganese modified alumina is adopted as an adsorbent, wherein the manganese content is 3.5%, and an analysis solvent adopts ethylene glycol monomethyl ether. The wax oil fraction enters a fixed bed 1, unsaturated components are selectively adsorbed in the fixed bed 1, the effluent 1 is the wax oil fraction rich in saturated components, when the content of the unsaturated components in the effluent 1 is not less than 5 percent, the feed of the fixed bed 1 is changed from the wax oil fraction to a desorption solvent for desorption, simultaneously, the wax oil fraction is changed to enter a fixed bed 2 for selective adsorption of the unsaturated components, the effluent 2 is the wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 2 is not less than 5 percent, the feed of the fixed bed 2 is changed from the wax oil fraction to the desorption solvent for desorption, simultaneously, the wax oil fraction is changed to enter a fixed bed 3 for selective adsorption of the unsaturated components, the effluent 3 is the wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 3 is not less than 5 percent, the feed of the wax oil fraction is changed from the wax oil fraction to the desorption solvent, the desorption is carried out, and the desorption is carried out,meanwhile, the wax oil fraction is switched to enter the fixed bed 1 after the desorption is finished, and the selective adsorption of unsaturated components is generated. Wherein, when the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent for desorbing unsaturated components, the desorption process is finished when the content of the unsaturated components is not more than 15 percent, and the obtained product is rectified to recover the desorption solvent to obtain the wax oil fraction rich in the unsaturated components. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, and the continuous separation of unsaturated components and saturated components of the wax oil fraction is realized.

(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, then feeding the wax oil fraction and high-pressure hydrogen into a reaction system with a reaction system pressure of 10MPa and a hydrogen-oil volume ratio of 800, wherein the reaction system is provided with a reaction system with 1 reactor for hydrocracking reaction, the reactors are sequentially filled with an FBN series protective agent, an FF-36 refined catalyst and an FC-80 hydrocracking catalyst from top to bottom, the volume ratio of the FF-36 refined catalyst to the FC-80 hydrocracking catalyst is 3:1, the reaction temperature of a refining section is 340 ℃, and the volume space velocity is 1.0h^-1(ii) a The reaction temperature of the cracking section is 350 ℃, and the volume space velocity is 3.0h^-1. The effluent after reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower for fraction separation to respectively obtain naphtha fraction, aviation kerosene fraction, diesel oil fraction, high-viscosity index tail oil fraction and the like; the reaction temperature is 370 ℃; the volume space velocity is 1.8 h^-1In the middle of;

(3) pressurizing the wax oil fraction rich in unsaturated components obtained in the step (1) by a high-pressure pump, and then feeding the wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 20MPa and the hydrogen-oil volume ratio of 1200. The reaction system is provided with a reaction system with 3 reactors for carrying out hydrocracking reaction in a two-stage mode, wherein the first reactor is separately filled with an FBN series protective agent and an FF-66 hydrofining catalyst, the upper part and the lower part of the second reactor are respectively filled with an FF-66 refining catalyst and an FC-80 hydrocracking catalyst, and the volume ratio of the FF-66 refining catalyst to the FC-80 hydrocracking catalyst is 3: 1; the reaction temperature of the refining section is 390 ℃, and the volume space velocity is 0.8h^-1(ii) a Cracking stage reaction temperature was 390The temperature is higher, the volume space velocity is 1.5h^-1. The reaction effluent sequentially passes through a high-pressure separator, a low-pressure separator, a fractionating tower and the like, the effluent of the fractionating tower enters a third reactor with high-pressure hydrogen through a pressurizing pump to perform hydrocracking reaction, the pressure of a reaction system is 20MPa, the volume ratio of hydrogen to oil is 1000, the third reactor is filled with an FC-76 hydrocracking catalyst, and the reaction temperature is 340 ℃; the volume space velocity of the reaction process is 1.5h^-1(ii) a The reaction effluent sequentially passes through a high-pressure separator and a low-pressure separator and then enters a fractionating tower together with the reaction effluent; the reaction system may share high pressure hydrogen and recycle hydrogen.

FF-36 catalyst specific surface area 215m²The volume of the catalyst is 0.42ml/g, and the weight percentage of the catalyst is that the molybdenum oxide is 21.4 percent, the nickel oxide is 4.4 percent, and the rest is alumina; FF-66 catalyst specific surface area 201m²The catalyst comprises the following components in percentage by weight, wherein the volume of the catalyst is 0.39ml/g, the molybdenum oxide is 23.0 percent, the nickel oxide is 4.9 percent, and the balance is aluminum oxide; FC-80 catalyst specific surface area 215m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.35ml/g, the content of tungsten oxide is 23.0 percent, the content of nickel oxide is 6.5 percent, the content of silicon oxide is 21 percent, and the balance is aluminum oxide; FC-76 catalyst specific surface area 372m²The catalyst comprises the following components in percentage by weight, wherein the volume of the pores is 0.35ml/g, the molybdenum oxide is 15.2 percent, the nickel oxide is 5.3 percent, the silicon oxide content is 31 percent, and the balance is aluminum oxide.

Example 3

(1) At normal pressure, adsorption temperature of 100 ℃ and liquid phase volume space velocity of 3h^-1Under the condition of (1), a switching fixed bed separation device is adopted to separate saturated components from unsaturated components, nickel modified alumina is adopted as an adsorbent, wherein the content of nickel is 4%, and an analysis solvent adopts ethylene glycol monomethyl ether. The wax oil fraction enters a fixed bed 1, unsaturated components are selectively adsorbed in the fixed bed 1, the effluent 1 is the wax oil fraction rich in saturated components, when the content of the unsaturated components in the effluent 1 is not less than 10 percent, the fixed bed 1 is fed with a desorption solvent from the wax oil fraction for desorption, meanwhile, the wax oil fraction is switched to enter a fixed bed 2 for selective adsorption of the unsaturated components, the effluent 2 is the wax oil fraction rich in the saturated components, and when the effluent 2 is not rich in the saturated componentsWhen the content of the saturated component is not less than 10 percent, the fixed bed 2 feeds the wax oil fraction to be exchanged with the desorption solvent for desorption, meanwhile, the wax oil fraction is exchanged into the fixed bed 3 for selective adsorption of the unsaturated component, the effluent 3 is the wax oil fraction rich in the saturated component, when the content of the unsaturated component in the effluent 3 is not less than 10 percent, the fixed bed 3 feeds the wax oil fraction to be exchanged with the desorption solvent for desorption, and meanwhile, the wax oil fraction is exchanged into the fixed bed 1 after the desorption is finished for selective adsorption of the unsaturated component. Wherein, when the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent for desorbing unsaturated components, when the content of the unsaturated components is not more than 20 percent, the desorption process is finished, and the obtained product is rectified to recover the desorption solvent, thereby obtaining the wax oil fraction rich in the unsaturated components. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, and the continuous separation of unsaturated components and saturated components of the wax oil fraction is realized.

(2) And (2) pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, and then feeding the wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 9MPa and the volume ratio of hydrogen to oil of 900. The reaction system is provided with a reaction system with 1 reactor for carrying out hydrocracking reaction, the reactors are sequentially and respectively filled with FBN series protective agent, FF-36 refined catalyst and FC-60 hydrocracking catalyst from top to bottom, the volume ratio of the FF-36 refined catalyst to the FC-60 hydrocracking catalyst is 3:1, the reaction temperature of the refining section is 370 ℃, and the volume space velocity is 2.5h^-1(ii) a The reaction temperature of the cracking section is 350 ℃, and the volume space velocity is 2.0h^-1. The effluent after reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower for fraction separation to respectively obtain naphtha fraction, aviation kerosene fraction, diesel oil fraction, high-viscosity index tail oil fraction and the like;

(3) pressurizing the wax oil fraction rich in unsaturated components obtained in the step (1) by a high-pressure pump, and feeding the pressurized wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 14MPa and the hydrogen-oil volume ratio of 1500. The reaction system is provided with a reaction system with 3 reactors for carrying out hydrocracking reaction, and is of a two-stage form, wherein the first reactor is separately filled with FBN series protective agent and FFA-66 hydrofining catalyst, a second reactor is sequentially filled with an FF-66 refining catalyst and an FC-80 hydrocracking catalyst from top to bottom, the volume ratio of the FF-66 refining catalyst to the FC-80 hydrocracking catalyst is 2:1, the reaction temperature of a refining section is 390 ℃, and the volume space velocity is 1.0h^-1(ii) a The reaction temperature of the cracking section is 400 ℃, and the volume space velocity is 1.5h^-1. The reaction effluent sequentially passes through a high-pressure separator, a low-pressure separator, a fractionating tower and the like, the effluent of the fractionating tower and high-pressure hydrogen enter a third reactor through a pressurizing pump to carry out hydrocracking reaction, the pressure of the reaction system is 14MPa, the volume ratio of hydrogen to oil is 1000, and the third reactor is filled with an FC-52 hydrocracking catalyst; the reaction temperature is 350 ℃; the volume space velocity of the reaction process is 1.5h^-1(ii) a The reaction effluent sequentially passes through a high-pressure separator and a low-pressure separator and then enters a fractionating tower together with the reaction effluent; the reaction system may share high pressure hydrogen gas and recycle hydrogen.

FF-36 catalyst specific surface area 215m²The volume of the pores is 0.42ml/g, and the weight percentage of the catalyst is that the molybdenum oxide is 21.4 percent, the nickel oxide is 4.4 percent, and the rest is alumina; FF-66 catalyst specific surface area 201m²The volume of the pores is 0.39ml/g, and the weight percentage of the catalyst is 23.0 percent of molybdenum oxide, 4.9 percent of nickel oxide and the balance of aluminum oxide; FC-60 catalyst specific surface area 223m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.38ml/g, the content of tungsten oxide is 23.5 percent, the content of nickel oxide is 6.0 percent, the content of silicon oxide is 23 percent, and the balance is aluminum oxide; FC-80 catalyst specific surface area 215m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.35ml/g, the content of tungsten oxide is 23.0 percent, the content of nickel oxide is 6.5 percent, the content of silicon oxide is 21 percent, and the balance is aluminum oxide; FC-52 catalyst specific surface area 422m²The catalyst comprises 16.0 percent of molybdenum oxide, 5.5 percent of nickel oxide, 38 percent of silicon oxide and the balance of aluminum oxide in percentage by weight.

Example 4

(1) The pressure is 0.3MPa, the adsorption temperature is 40 ℃, and the liquid phase volume space velocity is 2h^-1Under the conditions of (1), a switching fixed bed separation device is adopted to separate saturated components from unsaturated components, and iron is adopted for modificationThe 5A type molecular sieve is used as an adsorbent, wherein the iron content is 4.0%, and dodecane is used as an analytic solvent. The wax oil fraction enters a fixed bed 1, unsaturated components are selectively adsorbed in the fixed bed 1, the effluent 1 is a wax oil fraction rich in saturated components, when the content of the unsaturated components in the effluent 1 is not less than 3 percent, the fixed bed 1 is fed with the wax oil fraction to be exchanged for a desorption solvent to carry out desorption, meanwhile, the wax oil fraction is switched to enter a fixed bed 2 to carry out selective adsorption of the unsaturated components, the effluent 2 is a wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 2 is not less than 3 percent, the fixed bed 2 is fed with the wax oil fraction to be exchanged for the desorption solvent to carry out desorption, meanwhile, the wax oil fraction is switched to enter a fixed bed 3 to carry out selective adsorption of the unsaturated components, the effluent 3 is a wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 3 is not less than 3 percent, the fixed bed 3 is fed with the wax oil fraction to be exchanged for the desorption solvent, the desorption is carried out, and simultaneously, the wax oil fraction is switched to enter the fixed bed 1 at the end of the desorption for the selective adsorption of unsaturated components. Wherein, when the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent for desorbing unsaturated components, when the content of the unsaturated components is not more than 20 percent, the desorption process is finished, and the obtained product is rectified to recover the desorption solvent, thereby obtaining the wax oil fraction rich in the unsaturated components. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, and the continuous separation of unsaturated components and saturated components of the wax oil fraction is realized.

(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, feeding the wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 8.5MPa and the hydrogen-oil volume ratio of 650, arranging the reaction system with 2 reactors to carry out hydrocracking reaction, sequentially passing the reaction materials through the 2 reactors in a series connection mode, filling FBN series protective agents and FF-46 refined catalysts into a first reactor, and controlling the reaction temperature of a refining section to be 335 ℃ and the volume space velocity to be 4.0h^-1(ii) a The second reactor is filled with FC-80 hydrocracking catalyst, the reaction temperature of the cracking section is 355 ℃, and the volume space velocity is 2.5h^-1(ii) a The effluent after reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower for distillationSeparating to obtain naphtha fraction, aviation kerosene fraction, diesel oil fraction, high-viscosity index tail oil fraction and the like; (ii) a

(3) Pressurizing the wax oil fraction rich in unsaturated components obtained in the step (1) by a high-pressure pump, feeding the wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 16MPa and the volume ratio of hydrogen to oil of 1100, wherein the reaction system is provided with 3 reactors for hydrocracking reaction and adopts a series connection mode, the first reactor is separately filled with FBN series protective agents and FF-66 hydrofining catalysts, the upper part and the lower part of the second reactor are respectively filled with FF-66 refining catalysts and FC-80 hydrocracking catalysts, the volume ratio of the FF-66 refining catalysts to the FC-80 hydrocracking catalysts is 3:1, and the third reactor is filled with FC-76 hydrocracking catalysts; the reaction effluent passes through a high-pressure separator, a low-pressure separator, a fractionating tower and the like in sequence, and the bottom effluent is conveyed to a raw material tank. The reaction temperature of the refining section is 360 ℃, and the volume space velocity is 1.0h^-1(ii) a The reaction temperature of the cracking section is 380 ℃, and the volume space velocity is 1.5h^-1。

FF-46 catalyst specific surface area 211m²The volume of the pores is 0.41ml/g, and the weight percentage of the catalyst is that the molybdenum oxide is 21.6 percent, the nickel oxide is 4.3 percent, and the rest is alumina; FF-66 catalyst specific surface area 201m²The volume of the pores is 0.39ml/g, and the weight percentage of the catalyst is 23.0 percent of molybdenum oxide, 4.9 percent of nickel oxide and the balance of aluminum oxide; FC-80 catalyst specific surface area 215m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.35ml/g, the content of tungsten oxide is 23.0 percent, the content of nickel oxide is 6.5 percent, the content of silicon oxide is 21 percent, and the balance is aluminum oxide; FC-76 catalyst specific surface area 372m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.35ml/g, the molybdenum oxide is 15.2 percent, the nickel oxide is 5.3 percent, the silicon oxide content is 31 percent, and the balance is aluminum oxide.

Example 5

(1) At normal pressure, adsorption temperature of 90 ℃ and liquid phase volume space velocity of 2.5h^-1Under the condition of (1), a switching fixed bed separation device is adopted to separate saturated components from unsaturated components, manganese modified alumina is adopted as an adsorbent, wherein the manganese content is 3.0%, and an analytic solvent is adoptedEthylene glycol monomethyl ether. The wax oil fraction enters a fixed bed 1, unsaturated components are selectively adsorbed in the fixed bed 1, the effluent 1 is the wax oil fraction rich in saturated components, when the content of the unsaturated components in the effluent 1 is not less than 5 percent, the feed of the fixed bed 1 is changed from the wax oil fraction to a desorption solvent for desorption, simultaneously, the wax oil fraction is changed to enter a fixed bed 2 for selective adsorption of the unsaturated components, the effluent 2 is the wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 2 is not less than 5 percent, the feed of the fixed bed 2 is changed from the wax oil fraction to the desorption solvent for desorption, simultaneously, the wax oil fraction is changed to enter a fixed bed 3 for selective adsorption of the unsaturated components, the effluent 3 is the wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 3 is not less than 5 percent, the feed of the wax oil fraction is changed from the wax oil fraction to the desorption solvent, the desorption is carried out, and simultaneously, the wax oil fraction is switched to enter the fixed bed 1 at the end of the desorption for the selective adsorption of unsaturated components. Wherein, when the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent for desorbing unsaturated components, when the content of the unsaturated components is not more than 10 percent, the desorption process is finished, and the obtained product is rectified to recover the desorption solvent, thereby obtaining the wax oil fraction rich in the unsaturated components. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, and the continuous separation of unsaturated components and saturated components of the wax oil fraction is realized.

(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, then feeding the wax oil fraction and high-pressure hydrogen into a reaction system with a reaction system pressure of 9MPa and a hydrogen-oil volume ratio of 850, wherein the reaction system is provided with a reaction system with 1 reactor for hydrocracking reaction, the reactors are sequentially filled with an FBN series protective agent, an FF-46 refined catalyst and an FC-60 hydrocracking catalyst from top to bottom, the volume ratio of the FF-46 refined catalyst to the FC-60 hydrocracking catalyst is 3:1, the reaction temperature of a refining section is 350 ℃, and the volume space velocity is 1.0h^-1(ii) a The reaction temperature of the cracking section is 360 ℃, and the volume space velocity is 3.0h^-1. The effluent after reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, enters a fractionating tower for fraction separation, and then naphtha fraction and aviation kerosene are respectively obtainedFractions, diesel fractions, high viscosity index tail oil fractions, and the like; the reaction temperature is 370 ℃; the volume space velocity is 1.8 h^-1To (c) to (d);

(3) pressurizing the wax oil fraction rich in unsaturated components obtained in the step (1) by a high-pressure pump, and feeding the pressurized wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 18MPa and the hydrogen-oil volume ratio of 1100. The reaction system is provided with a reaction system with 3 reactors for carrying out hydrocracking reaction in a two-stage mode, wherein the first reactor is separately filled with an FBN series protective agent and an FF-66 hydrofining catalyst, the upper part and the lower part of the second reactor are respectively filled with an FF-66 refining catalyst and an FC-80 hydrocracking catalyst, and the volume ratio of the FF-66 refining catalyst to the FC-80 hydrocracking catalyst is 3: 1; the reaction temperature of the refining section is 390 ℃, and the volume space velocity is 0.8h^-1(ii) a The reaction temperature of the cracking section is 390 ℃, and the volume space velocity is 1.5h^-1. The reaction effluent sequentially passes through a high-pressure separator, a low-pressure separator, a fractionating tower and the like, the effluent of the fractionating tower enters a third reactor with high-pressure hydrogen through a pressurizing pump to perform hydrocracking reaction, the pressure of a reaction system is 18MPa, the volume ratio of hydrogen to oil is 1000, the third reactor is filled with an FC-76 hydrocracking catalyst, and the reaction temperature is 350 ℃; the volume space velocity of the reaction process is 1.5h^-1(ii) a The reaction effluent sequentially passes through a high-pressure separator and a low-pressure separator and then enters a fractionating tower together with the reaction effluent; the reaction system may share high pressure hydrogen and recycle hydrogen.

FF-46 catalyst specific surface area 211m²The catalyst comprises the following components in percentage by weight, wherein the volume of the catalyst is 0.41ml/g, the molybdenum oxide accounts for 21.6 percent, the nickel oxide accounts for 4.3 percent, and the balance is aluminum oxide; FF-66 catalyst specific surface area 201m²The volume of the pores is 0.39ml/g, and the weight percentage of the catalyst is 23.0 percent of molybdenum oxide, 4.9 percent of nickel oxide and the balance of aluminum oxide; FC-60 catalyst specific surface area 223m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.38ml/g, the content of tungsten oxide is 23.5 percent, the content of nickel oxide is 6.0 percent, the content of silicon oxide is 23 percent, and the balance is aluminum oxide; FC-80 catalyst specific surface area 215m²The volume of the pores is 0.35ml/g, the weight percentage of the catalyst is that the tungsten oxide is 23.0 percent, the nickel oxide is 6.5 percent, the content of the silicon oxide is 21 percent,the balance of alumina; FC-76 catalyst specific surface area 372m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.35ml/g, the molybdenum oxide is 15.2 percent, the nickel oxide is 5.3 percent, the silicon oxide content is 31 percent, and the balance is aluminum oxide.

Example 6

(1) At normal pressure, adsorption temperature of 60 ℃ and liquid phase volume space velocity of 3h^-1Under the condition, a switching fixed bed separation device is adopted to separate saturated components from unsaturated components, nickel modified alumina is adopted as an adsorbent, wherein the nickel content is 3.5%, and an analysis solvent adopts ethylene glycol monomethyl ether. The wax oil fraction enters a fixed bed 1, unsaturated components are selectively adsorbed in the fixed bed 1, the effluent 1 is the wax oil fraction rich in saturated components, when the content of the unsaturated components in the effluent 1 is not less than 8 percent, the fixed bed 1 is fed with the wax oil fraction to be exchanged with a desorption solvent for desorption, meanwhile, the wax oil fraction is switched to enter a fixed bed 2 for selective adsorption of the unsaturated components, the effluent 2 is the wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 2 is not less than 8 percent, the fixed bed 2 is fed with the wax oil fraction to be exchanged with the desorption solvent for desorption, simultaneously, the wax oil fraction is switched to enter a fixed bed 3 for selective adsorption of the unsaturated components, the effluent 3 is the wax oil fraction rich in the saturated components, when the content of the unsaturated components in the effluent 3 is not less than 8 percent, the feed of the fixed bed 3 is exchanged with the wax oil fraction to be the desorption solvent, and (4) carrying out desorption, and simultaneously switching the wax oil fraction into the fixed bed 1 after the desorption to carry out selective adsorption of unsaturated components. Wherein, when the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent for desorbing unsaturated components, when the content of the unsaturated components is not more than 20 percent, the desorption process is finished, and the obtained product is rectified to recover the desorption solvent, thereby obtaining the wax oil fraction rich in the unsaturated components. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, and the continuous separation of unsaturated components and saturated components of the wax oil fraction is realized.

(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, and feeding the pressurized wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 10MPa and the volume ratio of hydrogen to oil of 950. The reaction system is provided with a reaction system with 1 reactor for carrying out hydrocracking reaction, the reactors are sequentially and respectively filled with FBN series protective agent, FF-46 refined catalyst and FC-80 hydrocracking catalyst from top to bottom, the volume ratio of the FF-46 refined catalyst to the FC-80 hydrocracking catalyst is 3:1, the reaction temperature of a refining section is 370 ℃, and the volume space velocity is 2.5h^-1(ii) a The reaction temperature of the cracking section is 360 ℃, and the volume space velocity is 2.0h^-1. The effluent after reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower for fraction separation to respectively obtain naphtha fraction, aviation kerosene fraction, diesel oil fraction, high-viscosity index tail oil fraction and the like;

(3) pressurizing the wax oil fraction rich in unsaturated components obtained in the step (1) by a high-pressure pump, and then feeding the wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 15MPa and the hydrogen-oil volume ratio of 1500. The reaction system is provided with a reaction system with 3 reactors for carrying out hydrocracking reaction in a two-stage mode, wherein the first reactor is independently filled with FBN series protective agents and FF-46 hydrofining catalysts, the second reactor is sequentially filled with FF-36 refined catalysts and FC-60 hydrocracking catalysts from top to bottom, the volume ratio of the FF-36 refined catalysts to the FC-60 hydrocracking catalysts is 2:1, the reaction temperature of the refining stage is 380 ℃, and the volume space velocity is 1.0h^-1(ii) a The reaction temperature of the cracking section is 395 ℃, and the volume space velocity is 1.5h^-1. The reaction effluent sequentially passes through a high-pressure separator, a low-pressure separator, a fractionating tower and the like, the effluent of the fractionating tower and high-pressure hydrogen enter a third reactor through a pressurizing pump to carry out hydrocracking reaction, the pressure of the reaction system is 14MPa, the volume ratio of hydrogen to oil is 1000, and the third reactor is filled with an FC-52 hydrocracking catalyst; the reaction temperature is 350 ℃; the volume space velocity of the reaction process is 1.5h^-1(ii) a The reaction effluent sequentially passes through a high-pressure separator and a low-pressure separator and then enters a fractionating tower together with the reaction effluent; the reaction system may share high pressure hydrogen and recycle hydrogen.

FF-46 catalyst specific surface area 211m²The volume of the pores is 0.41ml/g, and the weight percentage of the catalyst is that the molybdenum oxide is 21.6 percent, the nickel oxide is 4.3 percent, and the rest is alumina; FF-66 catalyst ratioSurface area 201m²The volume of the pores is 0.39ml/g, and the weight percentage of the catalyst is 23.0 percent of molybdenum oxide, 4.9 percent of nickel oxide and the balance of aluminum oxide; FC-80 catalyst specific surface area 215m²The catalyst comprises the following components in percentage by weight, wherein the volume of the catalyst is 0.35ml/g, the tungsten oxide is 23.0 percent, the nickel oxide is 6.5 percent, the silicon oxide content is 21 percent, and the balance is aluminum oxide; FC-60 catalyst specific surface area 223m²The catalyst comprises the following components in percentage by weight, wherein the pore volume is 0.38ml/g, the content of tungsten oxide is 23.5 percent, the content of nickel oxide is 6.0 percent, the content of silicon oxide is 23 percent, and the balance is aluminum oxide; FC-52 catalyst specific surface area 422m²The catalyst comprises 16.0 percent of molybdenum oxide, 5.5 percent of nickel oxide, 38 percent of silicon oxide and the balance of aluminum oxide in percentage by weight.

Comparative example 1

The wax oil fraction is pressurized by a high-pressure pump and then is sent into a reaction system together with high-pressure hydrogen with the pressure of 14MPa and the hydrogen-oil volume ratio of 1500, the reaction system is provided with 2 reactors for hydrocracking reaction, the reaction materials sequentially pass through the 2 reactors in a series connection mode, the first reactor is filled with FBN series protective agent and FF-66 refined catalyst, the second reactor is filled with FC-80 hydrocracking catalyst, the reaction temperature of the refined section is 360 ℃, and the volume space velocity is 1.0h^-1(ii) a The reaction temperature of the cracking section is 358 ℃, and the volume space velocity is 1.5h^-1. And (3) carrying out high-pressure separation heat exchange and low-pressure separation heat exchange on the reacted effluent, and then, introducing the effluent into a fractionating tower for fraction separation to respectively obtain naphtha fraction, aviation kerosene fraction, diesel oil fraction, high-viscosity index tail oil fraction and the like.

FF-66 catalyst specific surface area 201m²The volume of the pores is 0.39ml/g, and the weight percentage of the catalyst is 23.0 percent of molybdenum oxide, 4.9 percent of nickel oxide and the balance of aluminum oxide; FC-80 catalyst specific surface area 215m²The catalyst comprises, by weight, 23.0% of tungsten oxide, 6.5% of nickel oxide, 21% of silicon oxide and the balance of aluminum oxide, wherein the pore volume is 0.35 ml/g.

TABLE 1 wax oil fraction Properties

TABLE 2 Effect of application of the technique

TABLE 3 high viscosity index Lubricant base stock Properties

It can be seen from the implementation effects of the above examples and comparative examples that the yield of heavy naphtha, the yield of white oil and the yield of high viscosity index lube base oil raw material are greatly increased by adopting the technology of the present invention, especially the high value added products of white oil and lube base oil raw material, the utilization rate of wax oil fraction is greatly improved, the value added of the product is greatly increased, and good economic benefit is obtained.

Claims

1. A wax oil processing method is characterized in that: the method comprises the following steps:

2. The method of claim 1, wherein: in step (1), the properties of the wax oil fraction are as follows: the distillation range is 260-650 ℃; the density at 20 ℃ is 0.81g/cm^-3~ 0.98g/cm^-3To (c) to (d); sulfur content of 005wt% to 4.0 wt%; the nitrogen content is 300-5000 mug/g.

3. The method of claim 1, wherein: in the step (1), the wax oil fraction raw material is at least one of straight-run wax oil, coking wax oil, deasphalted oil, catalytic cycle oil, coal tar, direct coal liquefaction oil, indirect coal liquefaction oil, synthetic oil and shale oil.

4. The method of claim 1, wherein: in the step (1), the mass content of saturated components in the wax oil fraction is 25-85%, preferably 35-65%, and more preferably 40-55%.

5. The method of claim 1, wherein: in the step (1), the saturated component content of the wax oil fraction rich in the saturated component is more than 80% by mass, preferably 85-100% by mass, and more preferably 90-100% by mass.

6. The method of claim 1, wherein: in the step (1), the saturated component mass content in the wax oil fraction rich in the unsaturated component is less than 20%, preferably between 0 and 20%.

7. The method of claim 1, wherein: in the step (1), the wax oil fraction is separated by adsorption separation, and the adsorption separation comprises two operations of adsorption and desorption: under the conditions that the pressure is normal pressure-2 MPa, the temperature is 25-200 ℃ and the liquid phase volume space velocity is 0.1-5 h^-1Under the condition (1), contacting the wax oil fraction with an adsorbent to adsorb unsaturated components, wherein the obtained product is the wax oil fraction rich in saturated components; after adsorption, the desorption solvent is contacted with the adsorbent after saturated adsorption, and the obtained product is rectified to recover the solvent, so that the wax oil fraction rich in unsaturated components is obtained.

8. The method of claim 7, wherein: the desorption solvent is one or more of alkane, alcohol, ether and ester, and the adsorbent is one or more of activated carbon, alumina, silica gel, A-type molecular sieve, ZSM series molecular sieve, metal modified activated carbon, metal modified alumina, metal modified silica gel, metal modified A-type molecular sieve and metal modified ZSM series molecular sieve.

9. The method of claim 1, wherein: in the step (2), the operating conditions of the hydrofining reaction zone A are as follows: the reaction pressure is between 3MPa and 25MPa, and preferably between 5MPa and 10 MPa; the reaction temperature is 220-450 ℃, preferably 300-380 ℃; the volume space velocity of the reaction process is 1.0-10.0 h^-1Preferably 2.0 to 8.0 hours^-1(ii) a The volume ratio of hydrogen to oil is 200-3000, preferably 500-1000.

10. The method of claim 1, wherein: in the step (2), the operation conditions of the hydrocracking reaction zone B are as follows: the reaction pressure is between 3MPa and 25MPa, and preferably between 5MPa and 10 MPa; the reaction temperature is 220-450 ℃, preferably 280-360 ℃; the volume space velocity of the reaction process is 1.0-10.0 h^-1Preferably for 2.0-8.0 h^-1(ii) a The volume ratio of hydrogen to oil is 200-3000, preferably 500-1000.

11. The method of claim 1, wherein: in the step (3), the operating conditions of the hydrofining reaction zone C are as follows: the reaction pressure is 6-25 MPa, preferably 8-18 MPa; the reaction temperature is 280-450 ℃, preferably 320-410 ℃; the volume space velocity of the reaction process is 0.2-5.0 h^-1Preferably 0.8 to 2.0h^-1(ii) a The volume ratio of hydrogen to oil is 500-3000, preferably 800-1500.

12. The method of claim 1, wherein: in the step (3), the operating conditions of the hydrocracking reaction zone D are as follows: the reaction pressure is 6-25 MPa, preferably 8-18 MPa; the reaction temperature is 280-450 ℃, preferably 320-410 ℃; the volume space velocity of the reaction process is 0.4-5.0 h^-1BetweenPreferably 1.0 to 2.0 hours^-1(ii) a The volume ratio of hydrogen to oil is 500-3000, preferably 800-1500.

13. The method of claim 1, wherein: the mass content of the hydrogenation active metal of the hydrogenation refined catalyst in the step (3) is 3% -10% higher than that of the hydrogenation active metal of the hydrogenation refined catalyst in the step (2).

14. The method of claim 1, wherein: the mass content of silicon oxide in the hydrocracking catalyst in the step (3) is 5-30% higher than that of silicon oxide in the hydrocracking catalyst in the step (2); the mass content of the hydrogenation metal of the hydrocracking catalyst in the step (3) is 5-40% higher than that of the hydrogenation metal of the hydrocracking catalyst in the step (3).

15. The method of claim 1, wherein: in the step (2) and the step (3), the nitrogen content of the refined oil after hydrofining is less than 50 mu g/g.