CN114736709B - Wax oil processing method - Google Patents

Wax oil processing method Download PDF

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Publication number
CN114736709B
CN114736709B CN202110018654.7A CN202110018654A CN114736709B CN 114736709 B CN114736709 B CN 114736709B CN 202110018654 A CN202110018654 A CN 202110018654A CN 114736709 B CN114736709 B CN 114736709B
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wax oil
fraction
reaction
oil fraction
catalyst
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CN114736709A (en
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秦波
张信伟
高杭
柳伟
王仲义
王海洋
吴子明
杜艳泽
侯栓弟
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a wax oil processing method, which comprises the following steps: (1) Separating the wax oil fraction to generate 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 a product is separated to obtain a naphtha fraction, a aviation kerosene fraction, a diesel oil fraction and a 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 resultant is separated to obtain naphtha fraction, and optionally aviation kerosene fraction and diesel fraction. The method can produce high-value-added products such as high-viscosity index lubricating oil basic raw materials, high-grade special oil products and the like, and improves the utilization rate of wax oil fractions and the value added of the products.

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 taking wax oil as a raw material.
Background
At present, the basic route of crude oil processing is to divide crude oil into different distillate oil by an atmospheric and vacuum device, including gas, naphtha fraction, aviation kerosene fraction, diesel fraction, wax oil fraction, residual oil fraction and other components. In general, naphtha fraction, aviation kerosene fraction and diesel fraction are directly used as fuel oil after hydrofining; the wax oil fraction is hydrofined to be used as a catalytic cracking raw material or is subjected to a hydrocracking technology to produce naphtha fraction, aviation kerosene fraction, diesel fraction or tail oil fraction; while residuum fractions may be used to produce catalytically cracked feedstocks by residuum hydrogenation or to produce light components by residuum hydrocracking.
Patent CN201811627078.0 discloses a wax oil hydrocracking method and system, the method flexibly produces naphtha products, high-quality aviation kerosene products and high-quality diesel products with various specifications from the wax oil raw oil through a hydrocracking catalyst hydrocracking and isomerism type hydrocracking catalyst hydroisomerization cracking combined method, and prepares ethylene raw materials, in particular to produce high-quality lubricating oil base oil through high-quality steam cracking. Patent CN 201811113894.X provides a wax oil hydrocracking method, which uses decompressed wax oil as raw material, and increases the yield of heavy naphtha with high aromatic potential through reasonable combination of hydrocracking catalysts with different functions, and improves the low-temperature fluidity and tail oil properties of aviation kerosene and diesel oil products. Patent CN201920366310.3 provides a wax oil hydrocracking system, and the wax oil hydrocracking system that provides can carry out the switching of production diesel oil and production light oil, and the flexible market demand that adapts to.
At present, wax oil components (the distillation range is about 300-620 ℃) are mainly converted into fractions such as naphtha fractions, aviation kerosene fractions, diesel oil fractions, tail oil fractions and the like through a hydrocracking technology, wherein the diesel oil fractions can be used as special oil, and the tail oil can be used as ethylene raw materials or lubricating oil base oil. Hydrocracking technology has an irreplaceable role in 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 compatible. For example, when the aromatic hydrocarbon content is lower than 5wt% in the white oil production in the prior art, the aromatic hydrocarbon content of the aviation kerosene product becomes low, the requirement of the aviation kerosene product on the aromatic hydrocarbon content cannot be met, meanwhile, the aromatic potential of the heavy naphtha fraction is reduced, and the product quality is reduced. Therefore, developing a new way capable of processing wax oil fraction, providing raw materials for producing various special oil products and providing raw materials for producing high-grade lubricating oil base oil, has become an urgent need for efficient utilization of wax oil hydrogenation.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention discloses a wax oil processing method, which can produce high-value-added products such as high-viscosity index lubricating oil basic raw materials, high-grade special oil products and the like, and improves the utilization rate of wax oil fractions and the value added of the products.
A wax oil processing method comprises the following steps:
(1) Separating the wax oil fraction to generate 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 a product is separated to obtain a naphtha fraction, a aviation kerosene fraction, a diesel oil fraction and a 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 resultant is separated to obtain naphtha fraction, and optionally aviation kerosene fraction and diesel fraction.
In the step (1) of the method, the wax oil fraction has the following properties: the distillation range is 260-650 ℃ (measured by adopting an ASTM D1160 petroleum product reduced pressure distillation method); density at 20 ℃ is 0.81g/cm -3 ~ 0.98g/cm -3 Between them; the sulfur content is between 0.05wt% and 4.0 wt%; the nitrogen content is 300-5000 mug/g.
In the step (1) of the method, 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) of the method, the mass content of the saturated component in the wax oil fraction is 25% -85%, preferably 35% -65%, and more preferably 40% -55%.
In the step (1) of the method, the mass content of the saturated component in the wax oil fraction rich in the saturated component is more than 80%, preferably 85-100%, and more preferably 90-100%.
In the step (1) of the method, the mass content of the saturated component in the wax oil fraction rich in the unsaturated component is less than 20%, and preferably 0-20%.
In the step (1) of the method, the wax oil fraction is separated byAdsorption separation technology. The adsorption separation technology comprises two operations of adsorption and desorption: the pressure is normal pressure to 2MPa, the temperature is 25 ℃ to 200 ℃ and the liquid phase volume airspeed is 0.1 h to 5h -1 Contacting the wax oil fraction with an adsorbent to adsorb unsaturated components, wherein the obtained product is a wax oil fraction rich in saturated components; and after the adsorption is finished, the desorption solvent is contacted with the saturated adsorbent, and the obtained product is rectified to recover the solvent, so as to obtain the wax oil fraction rich in unsaturated components. And (3) performing periodic operation according to the two steps of adsorption and desorption to realize continuous separation of wax oil fractions. The device used for adsorption is a multi-tower switching fixed bed device, preferably 2-6 towers. The desorption solvent is one or more of alkane, alcohol, ether and ester, preferably one or more of n-dodecane, methanol, ethanol, ethylene glycol monomethyl ether and ethyl acetate. The adsorbent is one or more of active carbon, alumina, silica gel, A-type molecular sieve, ZSM series molecular sieve, metal modified active carbon, metal modified alumina, metal modified silica gel, metal modified A-type molecular sieve and metal modified ZSM series molecular sieve.
In the above method step (3), the operating conditions of the hydrofining reaction zone a are as follows: the reaction pressure is 3-25 MPa, preferably 5-10 MPa; the reaction temperature is 220-450 ℃, preferably 300-380 ℃; the volume space velocity in the reaction process is 1.0-10.0 h -1 Preferably 2.0 to 8.0 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of the hydrogen oil is 200-3000, preferably 500-1000.
In the above method step (2), the hydrocracking reaction zone B is operated under the following conditions: the reaction pressure is 3-25 MPa, preferably 5-10 MPa; the reaction temperature is 220-450 ℃, preferably 280-360 ℃; the volume space velocity in the reaction process is 1.0-10.0 h -1 Preferably 2.0 to 8.0 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of the hydrogen oil is 200-3000, preferably 500-1000.
In the above method step (3), the operation conditions of the hydrofining reaction zone C are as follows: the reaction pressure is between 6MPa and 25MPa, preferably 8MPa and 18MPa; the reaction temperature is 280-450 ℃, preferably 320-410 ℃; the volume space velocity in the reaction process is 0.2-5.0 h -1 Preferably 0.8 to 2.0 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of the hydrogen oil is 500-3000, preferably 800-1500.
In the above method step (3), the hydrocracking reaction zone D is operated under the following conditions: the reaction pressure is between 6MPa and 25MPa, preferably 8MPa and 18MPa; the reaction temperature is 280-450 ℃, preferably 320-410 ℃; the volume space velocity in the reaction process is 0.4-5.0 h -1 Preferably 1.0 to 2.0 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of the hydrogen oil is 500-3000, preferably 800-1500.
The hydrofining catalyst used in the above method step (2) and/or step (3) has the following properties: specific surface area is 100-300 m 2 The pore volume is between 0.25 and 0.45 ml/g; the active metal components are a VIB group metal and a VIII group metal, wherein the VIB group metal is preferably tungsten (W) and molybdenum (Mo), and the VIII group metal is preferably cobalt (Co) and nickel (Ni); the weight percentage of the alumina is 60% -85% of that of the catalyst; the VIB group metal (calculated by oxide) is 12% -30%; the metal of VIII group (calculated by oxide) is 3% -10%.
The hydrocracking catalyst used in the above process step (2) and/or step (3) has the following properties: specific surface area is 150-500 m 2 The pore volume is between 0.20 and 0.60 ml/g; the active metal components are a VIB group metal and a VIII group metal, wherein the VIB group metal is preferably tungsten (W) and molybdenum (Mo), and the VIII group metal is preferably cobalt (Co) and nickel (Ni); the alumina accounts for 30-75% of the weight of the catalyst; the molecular sieve is 5-50%; the VIB group metal (calculated by oxide) is 12% -30%; the metal of VIII group (calculated by oxide) is 3% -10%.
The hydrofining catalyst loaded in the hydrofining reaction zone in the above method step (2) and step (3) may be the same or different, preferably different, in that: the mass content of hydrogenation active metal of the catalyst in the step (3) is 3% -10% higher than that of the catalyst in the step (2).
The hydrocracking catalysts packed in the hydrocracking reaction zone in the above process steps (2) and (3) 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).
And (3) pressurizing the wax oil fraction rich in the saturated components in the step (2) by a high-pressure pump, sending the wax oil fraction and high-pressure hydrogen into a reaction system together for hydrogenation reaction, and allowing the reacted effluent to enter a fractionating tower for fraction separation by high-pressure separation heat exchange and low-pressure separation heat exchange.
The wax oil fraction rich in unsaturated components in the step (3) is pressurized by a high-pressure pump and then is sent into a reaction system together with high-pressure hydrogen to react, and the reacted effluent is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange and enters a fractionating tower to carry out fraction separation to respectively obtain naphtha fraction, aviation kerosene fraction, diesel fraction, tail oil fraction and the like; or separating to obtain naphtha fraction and bottom stream; the bottom stream or the tail oil fraction may be recycled back to the reaction system of step (3).
In the above method step (2), the hydrofinishing reaction zone and the hydrocracking reaction zone may be disposed in one or more reactors in series. For example, 1-3 reactors are arranged, the reaction materials sequentially pass through the reactors in a serial connection mode, wherein the first reactor is filled with refined catalyst alone or the upper part and the lower part are filled with refined catalyst and hydrocracking catalyst respectively, and the rest reactors are filled with hydrocracking catalyst. When the first reactor is filled with the refined catalyst and the 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 alumina carrier, and can select various existing commercial catalysts, such as FF-36, FF-46, FF-66 and other hydrofining catalysts developed by the pacifying petrochemical institute (FRIPP); can also be prepared as desired according to common general knowledge in the art. The hydrocracking catalyst comprises hydrogenation active metal, molecular sieve component, amorphous silica alumina and alumina carrier, and various existing commercial catalysts can be selected, such as FC-52, FC-32, FC-50, FC-60, FC-76, FC-80 and other hydrocracking catalysts developed by the petrochemical institute (FRIPP); can also be prepared as desired according to common general knowledge in the art.
In the step (2), the diesel oil fraction can be used as a special oil product for producing industrial white oil, light white oil, transformer oil and the like; the high viscosity index tail oil fraction may be used as a feedstock for producing high grade lubricant base oils having viscosity indexes greater than 130, no. 4 and No. 6.
In the above method step (3), the hydrofinishing reaction zone and the hydrocracking reaction zone may be disposed in one or more reactors in series. For example, 1 to 3 reactors are arranged, and a serial form or a two-stage form is adopted, wherein the first reactor is singly filled with the refined catalyst, the second reactor is singly filled with the refined catalyst or is partially filled with the refined catalyst, the lower part is filled with the hydrocracking catalyst, and the third reactor is filled with the 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 alumina carrier, and can select various existing commercial catalysts, such as FF-36, FF-46, FF-66 and other hydrofining catalysts developed by the pacifying petrochemical institute (FRIPP); can also be prepared as desired according to common general knowledge in the art. The hydrocracking catalyst comprises hydrogenation active metal, molecular sieve component, amorphous silica alumina and alumina carrier, and various existing commercial catalysts can be selected, such as FC-52, FC-32, FC-50, FC-60, FC-76, FC-80 and other hydrocracking catalysts developed by the petrochemical institute (FRIPP); can also be prepared as desired according to common general knowledge in the art. When the reactors are in series, the reactant stream passes through each reactor once; when the two-stage form 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 sequentially passes through a booster pump and high-pressure hydrogen to enter a third reactor 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 steps (2) and (3), the nitrogen content of the refined oil after hydrofining is less than 50 mug/g.
In the above method steps (2) and (3), the top of the optional hydrofinishing reaction zone is charged with one or more protecting agents. The protective agent comprises hydrogenation active metal and alumina carrier, and various existing commercial catalysts can be selected, such as FZC and FBN series protective agents developed by the Fushun petrochemical institute (FRIPP); can also be prepared as desired according to common general knowledge in the art.
In the above method, the reaction systems in step (2) and step (3) may share high-pressure hydrogen, a high-pressure hydrogen circulation system, and the like; the raw materials in the step (2) and the step (3) can exchange heat with the effluents in the step (2) and the step (3) respectively or simultaneously, so that the heat of the two reaction systems is fully utilized, and the energy consumption is reduced.
The method realizes the processing concept of aromatic hydrocarbon, alkene and oil by dividing 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 adopting the adaptive technology to process according to the characteristics of the wax oil fraction. The paraffin content in the wax oil fraction rich in saturated components is high, the saturation degree is good, the problem that the high-grade lubricating oil base oil raw materials with viscosity indexes larger than 130 No. 4 and No. 6 cannot be sufficiently produced 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 the maximum production of high aromatic potential reforming raw materials, and solves the problem of PX raw material shortage. Through the deep fusion of the two processing technological processes, partial public facilities are shared, so that the energy consumption in 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, so that the economic benefit is remarkable.
Detailed Description
The hydrocracking process according to the present invention will be described in detail with reference to examples and comparative examples.
The properties of the wax oil fraction are shown in Table 1, and the technical comparison effect is shown in Table 2.
Example 1
(1) At a pressure of 0.5MPa, an adsorption temperature of 50 ℃ and a liquid phase volume space velocity of 2h -1 Under the condition of adopting a switching fixed bed separation device to separate saturated components from unsaturated components, adopting an iron modified 4A type molecular sieve as an adsorbent, wherein the iron content is 5.0%, and adopting dodecane as an analytic solvent. The wax oil fraction is fed into a fixed bed 1, unsaturated components in the fixed bed 1 are selectively adsorbed, the effluent 1 is a wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 1 is less than or equal to 2%, the feed of the fixed bed 1 is changed from the wax oil fraction to a desorption solvent for desorption, meanwhile, the wax oil fraction is switched into the fixed bed 2 for selective adsorption of the unsaturated components, the effluent 2 is a wax oil fraction rich in the saturated components, when the unsaturated component content in the effluent 2 is less than or equal to 2%, the feed of the fixed bed 2 is changed from the wax oil fraction to the desorption solvent for desorption, meanwhile, the wax oil fraction is switched into the fixed bed 3 for selective adsorption of the unsaturated components, the feed of the fixed bed 3 is changed from the wax oil fraction to the desorption solvent for desorption, and meanwhile, the wax oil fraction is switched into the fixed bed 1 for selective adsorption of the unsaturated components. When the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent to desorb unsaturated components, the desorption process is finished when the content of the unsaturated components is not more than 20%, and the obtained product is rectified to recover the desorption solvent, so that wax oil fractions rich in the unsaturated components are obtained. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, so that the continuous separation of unsaturated components and saturated components of wax oil fractions is realized.
(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, then sending 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, and carrying out hydrocracking reaction by the reaction system with 2 reactors, wherein the reaction system is connected in seriesIn the form, the reaction materials sequentially pass through 2 reactors, the first reactor is filled with FBN series protective agent and FF-36 refined catalyst, the reaction temperature of the refining section is 330 ℃, and the volume space velocity is 4.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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 The method comprises the steps of carrying out a first treatment on the surface of the The effluent after the reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower to carry out fraction separation to obtain naphtha fraction, aviation kerosene fraction, diesel fraction, high-viscosity index tail oil fraction and the like respectively;
(3) The wax oil fraction rich in unsaturated components obtained in the step (1) is pressurized by a high-pressure pump and then is sent into a reaction system with the reaction system pressure of 15MPa and the hydrogen-oil volume ratio of 1000 together with high-pressure hydrogen, the reaction system is provided with 3 reaction systems for hydrocracking reaction, the reaction system adopts a serial connection mode, wherein the first reactor is independently filled with FBN series protective agent and FF-66 hydrofining catalyst, the upper and lower parts of the second reactor are respectively filled with FF-66 refining catalyst and FC-80 hydrocracking catalyst, the volume ratio of FF-66 refining catalyst to FC-80 hydrocracking catalyst is 3:1, and the third reactor is filled with FC-52 hydrocracking catalyst; the reaction effluent sequentially passes through a high-pressure separator, a low-pressure separator, a fractionating tower and the like, 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 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 370 ℃ and the volume space velocity is 1.5h -1 。
Specific surface area of FF-36 catalyst 215m 2 Per gram, pore volume 0.42ml/g, molybdenum oxide 21.4%, nickel oxide 4.4% and the balance alumina in weight percent of the catalyst; specific surface area of FF-66 catalyst 201m 2 Per gram, pore volume 0.39ml/g, molybdenum oxide 23.0 wt%, nickel oxide 4.9 wt% and alumina for the rest; specific surface area of FC-80 catalyst 215m 2 Per gram, pore volume 0.35ml/g, calculated by weight percent of catalyst, tungsten oxide 23.0%, nickel oxide 6.5%, silicon oxide 21% and the balance of aluminum oxide; specific surface area of FC-52 catalyst 422m 2 Per gram, pore volume 0.29ml/g, molybdenum oxide 16.0% by weight of catalyst, oxidationNickel 5.5%, silicon oxide 38%, and alumina the balance.
Example 2
(1) At normal pressure and adsorption temperature of 100deg.C, the liquid phase volume space velocity is 3h -1 Under the condition of adopting a switching fixed bed separation device to separate saturated components from unsaturated components, adopting manganese modified alumina as an adsorbent, wherein the manganese content is 3.5%, and adopting ethylene glycol monomethyl ether as an analytic solvent. The wax oil fraction is fed into a fixed bed 1, unsaturated components in the fixed bed 1 are selectively adsorbed, the effluent 1 is a wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 1 is less than or equal to 5%, the feed of the fixed bed 1 is changed from the wax oil fraction to a desorption solvent for desorption, meanwhile, the wax oil fraction is switched into the fixed bed 2 for selective adsorption of the unsaturated components, the effluent 2 is a wax oil fraction rich in the saturated components, when the unsaturated component content in the effluent 2 is less than or equal to 5%, the feed of the fixed bed 2 is changed from the wax oil fraction to the desorption solvent for desorption, meanwhile, the wax oil fraction is switched into the fixed bed 3 for selective adsorption of the unsaturated components, the feed of the fixed bed 3 is changed from the wax oil fraction to the desorption solvent for desorption, and meanwhile, the wax oil fraction is switched into the fixed bed 1 for selective adsorption of the unsaturated components. When the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent to desorb unsaturated components, the desorption process is finished when the content of the unsaturated components is not more than 15%, and the obtained product is rectified to recover the desorption solvent, so that wax oil fractions rich in the unsaturated components are obtained. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, so that the continuous separation of unsaturated components and saturated components of wax oil fractions is realized.
(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, then sending the wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 10MPa and the hydrogen-oil volume ratio of 800, arranging a reaction system of 1 reactor in the reaction system to carry out hydrocracking reaction, and respectively filling FBN series protective agent and FF-36 essence into the reactor from top to bottom in sequenceThe catalyst is prepared and the FC-80 hydrocracking catalyst, wherein 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 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 350 ℃ and the volume space velocity is 3.0h -1 . The effluent after the reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower to carry out fraction separation to obtain naphtha fraction, aviation kerosene fraction, diesel fraction, high-viscosity index tail oil fraction and the like respectively; the reaction temperature is 370 ℃; volume space velocity of 1.8 h -1 Between them;
(3) And (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 of 3 reactors for hydrocracking reaction, and the reaction system is in a two-stage form, wherein the first reactor is independently 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, and the volume ratio of the FF-66 refining catalysts to the FC-80 hydrocracking catalysts is 3:1; the reaction temperature of the refining section is 390 ℃ and the volume space velocity is 0.8h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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 through a booster pump and high-pressure hydrogen to carry out hydrocracking reaction, the pressure of a reaction system is 20MPa, the hydrogen-oil volume ratio is 1000, the third reactor is filled with FC-76 hydrocracking catalyst, and the reaction temperature is 340 ℃; the volume space velocity of the reaction process is 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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.
Specific surface area of FF-36 catalyst 215m 2 Per gram, pore volume 0.42ml/g, molybdenum oxide 21.4%, nickel oxide 4.4% and the balance alumina in weight percent of the catalyst; specific surface area of FF-66 catalyst 201m 2 Per gram, pore volume 0.39ml/g, in terms of weight percent of catalyst, oxidation23.0% of molybdenum, 4.9% of nickel oxide and the balance of aluminum oxide; specific surface area of FC-80 catalyst 215m 2 Per gram, pore volume 0.35ml/g, calculated by weight percent of catalyst, tungsten oxide 23.0%, nickel oxide 6.5%, silicon oxide 21% and the balance of aluminum oxide; specific surface area 372m of FC-76 catalyst 2 Per gram, pore volume 0.35ml/g, molybdenum oxide 15.2 wt%, nickel oxide 5.3 wt%, silicon oxide 31 wt% and alumina for the rest.
Example 3
(1) At normal pressure and adsorption temperature of 100deg.C, the liquid phase volume space velocity is 3h -1 Under the condition of adopting a switching fixed bed separation device to separate saturated components from unsaturated components, adopting nickel modified alumina as an adsorbent, wherein the nickel content is 4%, and adopting ethylene glycol monomethyl ether as an analytic solvent. The wax oil fraction is fed into a fixed bed 1, unsaturated components in the fixed bed 1 are selectively adsorbed, the effluent 1 is a wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 1 is less than or equal to 10%, the feed of the fixed bed 1 is changed from the wax oil fraction to a desorption solvent for desorption, meanwhile, the wax oil fraction is switched into the fixed bed 2 for selective adsorption of the unsaturated components, the effluent 2 is a wax oil fraction rich in the saturated components, when the unsaturated component content in the effluent 2 is less than or equal to 10%, the feed of the fixed bed 2 is changed from the wax oil fraction to the desorption solvent for desorption, meanwhile, the wax oil fraction is switched into the fixed bed 3 for selective adsorption of the unsaturated components, the feed of the fixed bed 3 is changed from the wax oil fraction to the desorption solvent for desorption, and meanwhile, the wax oil fraction is switched into the fixed bed 1 for selective adsorption of the unsaturated components. When the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent to desorb unsaturated components, the desorption process is finished when the content of the unsaturated components is not more than 20%, and the obtained product is rectified to recover the desorption solvent, so that wax oil fractions rich in the unsaturated components are obtained. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, so that the continuous separation of unsaturated components and saturated components of wax oil fractions is realized 。
(2) And (3) pressurizing the wax oil fraction rich in the saturated components obtained in the step (1) by a high-pressure pump, and then sending the wax oil fraction and high-pressure hydrogen into a reaction system with the pressure of 9MPa and the hydrogen-oil volume ratio of 900. The reaction system is provided with a reaction system with 1 reactor for hydrocracking reaction, the reactor is respectively filled with FBN series protective agent, FF-36 refined catalyst and FC-60 hydrocracking catalyst from top to bottom in sequence, 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 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 350 ℃ and the volume space velocity is 2.0h -1 . The effluent after the reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower to carry out fraction separation to obtain naphtha fraction, aviation kerosene fraction, diesel fraction, high-viscosity index tail oil fraction and the like respectively;
(3) And (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 14MPa and the hydrogen-oil volume ratio of 1500. The reaction system is provided with a reaction system of 3 reactors for hydrocracking reaction, and the reaction system is in two sections, wherein the first reactor is independently filled with FBN series protective agent and FF-66 hydrofining catalyst, the second reactor is sequentially filled with FF-66 refining catalyst and 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 the refining section is 390 ℃, and the volume space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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 enters a third reactor through a booster pump and high-pressure hydrogen to carry out hydrocracking reaction, the pressure of a reaction system is 14MPa, the volume ratio of hydrogen to oil is 1000, and the third reactor is filled with FC-52 hydrocracking catalyst; the reaction temperature is 350 ℃; the volume space velocity of the reaction process is 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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 can share high-pressure hydrogenAnd recycling hydrogen.
Specific surface area of FF-36 catalyst 215m 2 Per gram, pore volume 0.42ml/g, molybdenum oxide 21.4%, nickel oxide 4.4% and the balance alumina in weight percent of the catalyst; specific surface area of FF-66 catalyst 201m 2 Per gram, pore volume 0.39ml/g, molybdenum oxide 23.0 wt%, nickel oxide 4.9 wt% and alumina for the rest; specific surface area of FC-60 catalyst 223m 2 Per gram, pore volume 0.38ml/g, calculated by weight percent of catalyst, tungsten oxide 23.5%, nickel oxide 6.0%, silicon oxide 23% and the balance of aluminum oxide; specific surface area of FC-80 catalyst 215m 2 Per gram, pore volume 0.35ml/g, calculated by weight percent of catalyst, tungsten oxide 23.0%, nickel oxide 6.5%, silicon oxide 21% and the balance of aluminum oxide; specific surface area of FC-52 catalyst 422m 2 Per gram, pore volume 0.29ml/g, molybdenum oxide 16.0 wt%, nickel oxide 5.5 wt%, silicon oxide 38 wt% and aluminum oxide for the rest.
Example 4
(1) At a pressure of 0.3MPa, an adsorption temperature of 40 ℃ and a liquid phase volume space velocity of 2h -1 Under the condition of adopting a switching fixed bed separation device to separate saturated components from unsaturated components, adopting an iron modified 5A type molecular sieve as an adsorbent, wherein the iron content is 4.0%, and adopting dodecane as an analytic solvent. The wax oil fraction enters a fixed bed 1, unsaturated components in the fixed bed 1 are selectively adsorbed, an effluent 1 is a wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 1 is less than or equal to 3%, the feed of the fixed bed 1 is changed from the wax oil fraction to a desorption solvent for desorption, meanwhile, the wax oil fraction is switched to enter the fixed bed 2 for selective adsorption of the unsaturated components, an effluent 2 is a wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 2 is less than or equal to 3%, the feed of the fixed bed 2 is changed from the wax oil fraction to a desorption solvent for desorption, simultaneously, the wax oil fraction is switched to enter the fixed bed 3 for selective adsorption of the unsaturated components, the feed of the fixed bed 3 is changed from the wax oil fraction to the desorption solvent for desorption, and the same time, when the unsaturated component content in the effluent 3 is less than or equal to 3%, the feed of the fixed bed 3 is changed from the wax oil fraction to the desorption solvent for desorption When the wax oil fraction is switched to enter the fixed bed 1 with the end of desorption, the unsaturated component is selectively adsorbed. When the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent to desorb unsaturated components, the desorption process is finished when the content of the unsaturated components is not more than 20%, and the obtained product is rectified to recover the desorption solvent, so that wax oil fractions rich in the unsaturated components are obtained. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, so that the continuous separation of unsaturated components and saturated components of wax oil fractions is realized.
(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, then sending 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 2 reaction systems of reactors in the reaction system to carry out hydrocracking reaction, sequentially passing the reaction materials through 2 reactors in a serial manner, filling FBN series protective agent and FF-46 refining catalyst in a first reactor, wherein the reaction temperature of a refining section is 335 ℃, and the volume space velocity is 4.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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 The method comprises the steps of carrying out a first treatment on the surface of the The effluent after the reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower to carry out fraction separation to obtain naphtha fraction, aviation kerosene fraction, diesel fraction, high-viscosity index tail oil fraction and the like respectively; the method comprises the steps of carrying out a first treatment on the surface of the
(3) Pressurizing the wax oil fraction rich in unsaturated components obtained in the step (1) by a high-pressure pump, then sending the wax oil fraction and high-pressure hydrogen into a reaction system with the reaction system pressure of 16MPa and the hydrogen-oil volume ratio of 1100, wherein the reaction system is provided with 3 reaction systems for hydrocracking reaction, the reaction system adopts a serial connection mode, wherein the first reactor is independently 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-76 hydrocracking catalyst; the reaction effluent sequentially passes through a high-pressure separator, a low-pressure separator, a fractionating tower and the like, 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 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 380 ℃ and the volume space velocity is 1.5h -1 。
Specific surface area 211m of FF-46 catalyst 2 Per gram, pore volume 0.41ml/g, molybdenum oxide 21.6%, nickel oxide 4.3% and the balance alumina in weight percent of the catalyst; specific surface area of FF-66 catalyst 201m 2 Per gram, pore volume 0.39ml/g, molybdenum oxide 23.0 wt%, nickel oxide 4.9 wt% and alumina for the rest; specific surface area of FC-80 catalyst 215m 2 Per gram, pore volume 0.35ml/g, calculated by weight percent of catalyst, tungsten oxide 23.0%, nickel oxide 6.5%, silicon oxide 21% and the balance of aluminum oxide; specific surface area 372m of FC-76 catalyst 2 Per gram, pore volume 0.35ml/g, molybdenum oxide 15.2 wt%, nickel oxide 5.3 wt%, silicon oxide 31 wt% and alumina for the rest.
Example 5
(1) At normal pressure and adsorption temperature of 90 ℃ and liquid phase volume space velocity of 2.5h -1 Under the condition of adopting a switching fixed bed separation device to separate saturated components from unsaturated components, adopting manganese modified alumina as an adsorbent, wherein the manganese content is 3.0%, and adopting ethylene glycol monomethyl ether as an analytic solvent. The wax oil fraction is fed into a fixed bed 1, unsaturated components in the fixed bed 1 are selectively adsorbed, the effluent 1 is a wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 1 is less than or equal to 5%, the feed of the fixed bed 1 is changed from the wax oil fraction to a desorption solvent for desorption, meanwhile, the wax oil fraction is switched into a fixed bed 2 for selective adsorption of the unsaturated components, the effluent 2 is a wax oil fraction rich in the saturated components, when the unsaturated component content in the effluent 2 is less than or equal to 5%, the feed of the fixed bed 2 is changed from the wax oil fraction to a desorption solvent for desorption, simultaneously, the wax oil fraction is switched into a fixed bed 3 for selective adsorption of the unsaturated components, the effluent 3 is a wax oil fraction rich in the saturated components, when the unsaturated component content in the effluent 3 is less than or equal to 5%, the feed of the fixed bed 3 is changed from the wax oil fraction to the desorption solvent for desorption, and simultaneously, the wax oil fraction is switched into the fixed bed 1 for desorption The raw unsaturated components are selectively adsorbed. When the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent to desorb unsaturated components, the desorption process is finished when the content of the unsaturated components is not more than 10%, and the obtained product is rectified to recover the desorption solvent, so that wax oil fractions rich in the unsaturated components are obtained. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, so that the continuous separation of unsaturated components and saturated components of wax oil fractions is realized.
(2) Pressurizing the wax oil fraction rich in saturated components obtained in the step (1) by a high-pressure pump, then sending the wax oil fraction and high-pressure hydrogen into a reaction system with the reaction system pressure of 9MPa and the hydrogen-oil volume ratio of 850, arranging a reaction system of 1 reactor in the reaction system to carry out hydrocracking reaction, and sequentially filling FBN series protective agent, FF-46 refining catalyst and FC-60 hydrocracking catalyst into the reactor from top to bottom respectively, wherein the volume ratio of the FF-46 refining 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 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 360 ℃ and the volume space velocity is 3.0h -1 . The effluent after the reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower to carry out fraction separation to obtain naphtha fraction, aviation kerosene fraction, diesel fraction, high-viscosity index tail oil fraction and the like respectively; the reaction temperature is 370 ℃; volume space velocity of 1.8 h -1 Between them;
(3) And (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 18MPa and the hydrogen-oil volume ratio of 1100. The reaction system is provided with a reaction system of 3 reactors for hydrocracking reaction, and the reaction system is in a two-stage form, wherein the first reactor is independently 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, and the volume ratio of the FF-66 refining catalysts to the FC-80 hydrocracking catalysts is 3:1; the reaction temperature of the refining section is 390 ℃ and the volume space velocity is 0.8h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 390 ℃ and the volume space velocity is 1.5h -1 . The reaction effluent is in turnThe effluent of the fractionating tower enters a third reactor through a pressurizing pump and high-pressure hydrogen to carry out hydrocracking reaction through a high-pressure separator, a low-pressure separator, a fractionating tower and the like, the pressure of a reaction system is 18MPa, the volume ratio of hydrogen to oil is 1000, the third reactor is filled with FC-76 hydrocracking catalyst, and the reaction temperature is 350 ℃; the volume space velocity of the reaction process is 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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.
Specific surface area 211m of FF-46 catalyst 2 Per gram, pore volume 0.41ml/g, molybdenum oxide 21.6%, nickel oxide 4.3% and the balance alumina in weight percent of the catalyst; specific surface area of FF-66 catalyst 201m 2 Per gram, pore volume 0.39ml/g, molybdenum oxide 23.0 wt%, nickel oxide 4.9 wt% and alumina for the rest; specific surface area of FC-60 catalyst 223m 2 Per gram, pore volume 0.38ml/g, calculated by weight percent of catalyst, tungsten oxide 23.5%, nickel oxide 6.0%, silicon oxide 23% and the balance of aluminum oxide; specific surface area of FC-80 catalyst 215m 2 Per gram, pore volume 0.35ml/g, calculated by weight percent of catalyst, tungsten oxide 23.0%, nickel oxide 6.5%, silicon oxide 21% and the balance of aluminum oxide; specific surface area 372m of FC-76 catalyst 2 Per gram, pore volume 0.35ml/g, molybdenum oxide 15.2 wt%, nickel oxide 5.3 wt%, silicon oxide 31 wt% and alumina for the rest.
Example 6
(1) At normal pressure and adsorption temperature of 60 ℃ and liquid phase volume space velocity of 3h -1 Under the condition of adopting a switching fixed bed separation device to separate saturated components from unsaturated components, adopting nickel modified alumina as an adsorbent, wherein the nickel content is 3.5%, and adopting ethylene glycol monomethyl ether as an analytic solvent. The wax oil fraction enters a fixed bed 1, unsaturated components in the fixed bed 1 are selectively adsorbed, an effluent 1 is a wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 1 is less than or equal to 8%, the feeding of the fixed bed 1 is changed from the wax oil fraction into a desorption solvent for desorption, and meanwhile, the wax oil fraction is split The effluent 2 is wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 2 is less than or equal to 8%, the feed of the fixed bed 2 is changed from wax oil fraction to desorption solvent for desorption, meanwhile, the wax oil fraction is switched to enter the fixed bed 3 for unsaturated component selective adsorption, the effluent 3 is wax oil fraction rich in saturated components, when the unsaturated component content in the effluent 3 is less than or equal to 8%, the feed of the fixed bed 3 is changed from wax oil fraction to desorption solvent for desorption, and meanwhile, the wax oil fraction is switched to enter the fixed bed 1 after desorption for unsaturated component selective adsorption. When the fixed bed 1, the fixed bed 2 and the fixed bed 3 are switched to enter a desorption solvent to desorb unsaturated components, the desorption process is finished when the content of the unsaturated components is not more than 20%, and the obtained product is rectified to recover the desorption solvent, so that wax oil fractions rich in the unsaturated components are obtained. The fixed bed 1, the fixed bed 2 and the fixed bed 3 are periodically operated according to two steps of adsorption and desorption, so that the continuous separation of unsaturated components and saturated components of wax oil fractions is realized.
(2) And (3) pressurizing the wax oil fraction rich in the 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 10MPa and the hydrogen-oil volume ratio of 950. The reaction system is provided with a reaction system with 1 reactor for hydrocracking reaction, the reactor is respectively filled with FBN series protective agent, FF-46 refined catalyst and FC-80 hydrocracking catalyst from top to bottom in sequence, the volume ratio of the FF-46 refined catalyst to the FC-80 hydrocracking catalyst is 3:1, the reaction temperature of the refining section is 370 ℃, and the volume space velocity is 2.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 360 ℃ and the volume space velocity is 2.0h -1 . The effluent after the reaction is subjected to high-pressure separation heat exchange and low-pressure separation heat exchange, and enters a fractionating tower to carry out fraction separation to obtain naphtha fraction, aviation kerosene fraction, diesel fraction, high-viscosity index tail oil fraction and the like respectively;
(3) And (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. Reaction systemThe hydrocracking reaction is carried out by a reaction system with 3 reactors, wherein the first reactor is filled with FBN series protective agent and FF-46 hydrofining catalyst independently, the second reactor is filled with FF-36 refining catalyst and FC-60 hydrocracking catalyst respectively from top to bottom, the volume ratio of the FF-36 refining catalyst to the FC-60 hydrocracking catalyst is 2:1, the reaction temperature of the refining section is 380 ℃, and the volume space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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 enters a third reactor through a booster pump and high-pressure hydrogen to carry out hydrocracking reaction, the pressure of a reaction system is 14MPa, the volume ratio of hydrogen to oil is 1000, and the third reactor is filled with FC-52 hydrocracking catalyst; the reaction temperature is 350 ℃; the volume space velocity of the reaction process is 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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.
Specific surface area 211m of FF-46 catalyst 2 Per gram, pore volume 0.41ml/g, molybdenum oxide 21.6%, nickel oxide 4.3% and the balance alumina in weight percent of the catalyst; specific surface area of FF-66 catalyst 201m 2 Per gram, pore volume 0.39ml/g, molybdenum oxide 23.0 wt%, nickel oxide 4.9 wt% and alumina for the rest; specific surface area of FC-80 catalyst 215m 2 Per gram, pore volume 0.35ml/g, calculated by weight percent of catalyst, tungsten oxide 23.0%, nickel oxide 6.5%, silicon oxide 21% and the balance of aluminum oxide; specific surface area of FC-60 catalyst 223m 2 Per gram, pore volume 0.38ml/g, calculated by weight percent of catalyst, tungsten oxide 23.5%, nickel oxide 6.0%, silicon oxide 23% and the balance of aluminum oxide; specific surface area of FC-52 catalyst 422m 2 Per gram, pore volume 0.29ml/g, molybdenum oxide 16.0 wt%, nickel oxide 5.5 wt%, silicon oxide 38 wt% and aluminum oxide for the rest.
Comparative example 1
Pressurizing wax oil fraction with high pressure pump and high pressure hydrogen The mixture is fed 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 2 reactors for hydrocracking reaction, the reaction materials sequentially pass through the 2 reactors in a serial 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 refining section is 360 ℃, and the volume space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 358 ℃, and the volume space velocity is 1.5h -1 . And (3) performing high-pressure separation heat exchange and low-pressure separation heat exchange on the reacted effluent, and enabling the effluent to enter a fractionating tower for fraction separation to obtain naphtha fraction, aviation kerosene fraction, diesel fraction, high-viscosity index tail oil fraction and the like.
Specific surface area of FF-66 catalyst 201m 2 Per gram, pore volume 0.39ml/g, molybdenum oxide 23.0 wt%, nickel oxide 4.9 wt% and alumina for the rest; specific surface area of FC-80 catalyst 215m 2 Per gram, pore volume 0.35ml/g, calculated as weight percent of catalyst, tungsten oxide 23.0%, nickel oxide 6.5%, silicon oxide 21% and the balance alumina.
TABLE 1 wax oil fraction Properties
Figure SMS_1
TABLE 2 effect of technical application
Figure SMS_2
TABLE 3 high viscosity index lubricating base oil feedstock Properties
Figure SMS_3
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As can be seen from the implementation effects of the examples and the comparative examples, the heavy naphtha yield, the white oil yield and the yield of the high-viscosity index lubricating oil base oil raw material are greatly increased after the technology is adopted, particularly, the white oil and the lubricating oil base oil raw material which are high-added-value products are greatly increased, the utilization rate of wax oil fractions is greatly increased, the added value of the products is greatly increased, and the economic benefit is good.

Claims (7)

1. A wax oil processing method is characterized in that: the method comprises the following steps:
(1) Separating the wax oil fraction to generate 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 a product is separated to obtain a naphtha fraction, a aviation kerosene fraction, a diesel oil fraction and a high viscosity index tail oil fraction;
(3) Allowing the wax oil fraction rich in unsaturated components to enter a hydrofining reaction zone C and a hydrocracking reaction zone D for reaction, separating a resultant to obtain a naphtha fraction, and optionally obtaining a aviation kerosene fraction and a diesel fraction;
wherein, the wax oil fraction in the step (1) has the following properties: the distillation range is 260-650 ℃; density at 20 ℃ is 0.81g/cm 3 ~ 0.98g/cm 3 Between them; the sulfur content is between 0.05wt% and 4.0 wt%; the nitrogen content is 300-5000 mug/g; the mass content of saturated components in the wax oil fraction is 25% -85%, the mass content of saturated components in the wax oil fraction rich in saturated components is more than 80%, and the mass content of saturated components in the wax oil fraction rich in unsaturated components is less than 20%;
in step (2), the operating conditions of the hydrofining reaction zone A are as follows: the reaction pressure is 3-25 MPa; the reaction temperature is 220-450 ℃; the volume space velocity in the reaction process is 1.0-10.0 h -1 Between them; the volume ratio of hydrogen to oil is 200-3000; the operating conditions of hydrocracking reaction zone B are as follows: the reaction pressure is 3-25 MPa; the reaction temperature is 220-450 ℃; the volume space velocity in the reaction process is 1.0-10.0 h -1 Between them; the volume ratio of hydrogen to oil is 200-3000;
in step (3), the operating conditions of the hydrofining reaction zone C are as follows: the reaction pressure is between 6 and 25 MPa; the reaction temperature is 280-450 ℃; the volume space velocity of the reaction process is 0.2~5.0h -1 Between them; the volume ratio of hydrogen to oil is 500-3000; the hydrocracking reaction zone D is operated under the following conditions: the reaction pressure is between 6 and 25 MPa; the reaction temperature is 280-450 ℃; the volume space velocity in the reaction process is 0.4-5.0 h -1 Between them; the volume ratio of the hydrogen oil is 500-3000.
2. The method according to claim 1, characterized in that: in the step (1), the wax oil fraction raw material is at least one of straight-run wax oil, coker wax oil, deasphalted oil, catalytic cycle oil, coal tar, coal direct liquefied oil, coal indirect liquefied oil, synthetic oil and shale oil.
3. The method according to claim 1, characterized in that: in the step (1), the wax oil fraction is separated by adsorption separation, and the adsorption separation comprises two operations of adsorption and desorption: the pressure is normal pressure to 2MPa, the temperature is 25 ℃ to 200 ℃ and the liquid phase volume airspeed is 0.1 h to 5h -1 Contacting the wax oil fraction with an adsorbent to adsorb unsaturated components, wherein the obtained product is a wax oil fraction rich in saturated components; and after the adsorption is finished, the desorption solvent is contacted with the saturated adsorbent, and the obtained product is rectified to recover the solvent, so as to obtain the wax oil fraction rich in unsaturated components.
4. A method according to claim 3, characterized in that: the desorption solvent is one or more of alkane, alcohol, ether and ester, and the adsorbent is one or more of active carbon, alumina, silica gel, A-type molecular sieve and ZSM-series molecular sieve.
5. The method according to claim 1, characterized in that: 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).
6. The method according to claim 1, characterized in that: the mass content of silicon oxide of the hydrocracking catalyst in the step (3) is 5% -30% higher than that of the silicon oxide of the hydrocracking catalyst in the step (2); the mass content of the hydrogenation metal of the hydrogen adding cracking catalyst in the step (2) is 5% -40% higher than that of the hydrogenation metal of the hydrogen adding cracking catalyst in the step (3).
7. The method according to claim 1, characterized in that: in the step (2) and the step (3), the nitrogen content of the refined oil after hydrofining is less than 50 mug/g.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280221A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Hydrogenation conversion method for poor ignition quality fuel distillate
CN112143521A (en) * 2019-06-26 2020-12-29 中国石油化工股份有限公司 Hydrogenation method and system for producing catalytic reforming raw material
CN112143522A (en) * 2019-06-26 2020-12-29 中国石油化工股份有限公司 Hydrogenation method and system for production chemical material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280221A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Hydrogenation conversion method for poor ignition quality fuel distillate
CN112143521A (en) * 2019-06-26 2020-12-29 中国石油化工股份有限公司 Hydrogenation method and system for producing catalytic reforming raw material
CN112143522A (en) * 2019-06-26 2020-12-29 中国石油化工股份有限公司 Hydrogenation method and system for production chemical material

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