CN109988642B - Flexible hydrocracking process for producing lube base stock - Google Patents

Flexible hydrocracking process for producing lube base stock Download PDF

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CN109988642B
CN109988642B CN201711469386.0A CN201711469386A CN109988642B CN 109988642 B CN109988642 B CN 109988642B CN 201711469386 A CN201711469386 A CN 201711469386A CN 109988642 B CN109988642 B CN 109988642B
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hydrocracking
oil
product
catalyst
molecular sieve
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CN109988642A (en
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张学辉
刘涛
李宝忠
白振民
黄新露
方向晨
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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
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Abstract

The invention discloses a flexible hydrocracking method for producing lubricating oil base oil. The material of the wax oil raw material after hydrogenation pretreatment is divided into two parts; separating one part of materials by a hot high-pressure separator to obtain a gas phase and a liquid phase, mixing the other part of materials with the hot high-pressure gas phase and circulating hydrogen, and then passing through a hydrocracking catalyst bed layer containing a Y-type molecular sieve; mixing the hot high-liquid phase with hydrocracking tail oil and circulating hydrogen, and passing through a hydrocracking catalyst bed layer containing an isomeric cracking type molecular sieve; and respectively carrying out gas-liquid separation and fractionation on the hydrocracking reaction product and the hydroisomerization cracking reaction product to obtain distillate oil and tail oil with different specifications, and recycling part or all of the hydrocracking tail oil into the isomerization cracking reactor. The invention provides a flexible hydrocracking method for simultaneously producing more than two kinds of naphtha, aviation kerosene, diesel oil and tail oil products with different specifications on a set of hydrogenation process device, in particular producing high-quality lubricating oil base oil for the first time.

Description

Flexible hydrocracking process for producing lube base stock
Technical Field
The invention belongs to the field of petroleum refining, and particularly relates to a hydrocracking method for flexibly producing high-quality naphtha, aviation kerosene, diesel oil and tail oil products with different properties, in particular to high-quality lubricating oil base oil.
Background
The hydrogenation technology is an important processing means for the lightening of heavy oil and the upgrading of the quality of light oil. The hydrocracking technology has the advantages of strong raw oil adaptability, good product flexibility, high liquid product yield, high product quality and the like, and is developed quickly. The existing hydrocracking technology can be divided into three types according to the processing flow: a one-stage series hydrocracking process flow, a single-stage hydrocracking process flow and a two-stage hydrocracking process flow. The operation can be divided into three types according to whether the tail oil is circulated or not: a single-pass once-through process flow, a partial circulation process flow and a full circulation process flow. The hydrocracking technology uses two types of catalysts, namely a hydrocracking pretreatment catalyst and a hydrocracking catalyst, wherein the hydrocracking catalyst can be divided into different types of catalysts according to different cracking components, and the main cracking components comprise amorphous silica-alumina, a Y-type molecular sieve, a beta-type molecular sieve, an SAPO-series molecular sieve, a ZSM-5 molecular sieve and the like. When different types of hydrocracking components are used, the composition and the property of the obtained light oil are greatly different, and the composition and the property of tail oil are also greatly different.
CN103055922B discloses a preparation method of a bulk phase hydrocracking catalyst, and CN105018139B, CN001293228A, CN001508225A and CN104611020B all disclose a method for grading two different Y-type molecular sieves in a hydrocracking method of low energy consumption high yield high quality chemical raw materials. The technology can produce high-quality products by using a hydrocracking method containing a Y-type molecular sieve hydrocracking catalyst by using wax oil as raw oil, wherein the tail oil has high alkane content and low BMCI value and is a raw material for preparing ethylene by high-quality steam cracking, but the product of each fraction obtained by hydrocracking has only one specification.
CN105582992A discloses a hydroisomerization catalyst, a preparation method and application thereof, and a hydrocracking tail oil hydroisomerization method, which can produce high-quality products by using a hydrocracking method containing an isomerization type molecular sieve hydrocracking catalyst by using wax oil as raw oil, wherein the tail oil has high isomerization content, low condensation point and high viscosity index and is a raw material of high-quality lubricating oil base oil, but the product of each fraction obtained by hydrocracking only has one specification.
CN103394368B discloses a light oil type hydrocracking catalyst containing a composite molecular sieve, a preparation method and an application thereof, CN103551186B discloses a medium oil type hydrocracking catalyst containing a composite molecular sieve, a preparation method and an application thereof, and US4837396A discloses a preparation of a composite molecular sieve catalyst. The technology can produce various high-quality hydrocracking products by using a hydrocracking method of a hydrocracking catalyst containing a Y-type molecular sieve and an isomeric molecular sieve composite molecular sieve by using wax oil as raw oil, but the product of each fraction has only one specification.
CN001169919C discloses a method for increasing the yield of high-quality diesel oil by distillate oil. The technology can produce various high-quality hydrocracking products by using wax oil as raw oil and simultaneously using a hydrocracking method containing two catalysts, namely a Y-type molecular sieve catalyst and an isomeric molecular sieve hydrocracking catalyst, but the product of each fraction has only one specification.
In conclusion, compared with the existing hydrocracking technology using two different types of molecular sieve catalysts and the hydrocracking technology using the Y-type molecular sieve hydrocracking catalyst, the obtained heavy naphtha product has low sulfur content, relatively high aromatic hydrocarbon potential, relatively high smoke point of aviation kerosene products, low sulfur content of diesel oil products, high cetane number, but relatively high condensation point, low aromatic hydrocarbon content of tail oil products, relatively low density, relatively low BMCI value, but very high condensation point which is usually more than 30 ℃; by using a hydrocracking technology of an isomeric molecular sieve hydrocracking catalyst, the obtained heavy naphtha product has low sulfur content, slightly low aromatic hydrocarbon potential, low sulfur content and low condensation point of a diesel product, but has relatively slightly low cetane number and relatively high tail oil density, but has high content of isomeric hydrocarbon and very low condensation point which is usually less than 0 ℃; the hydrocracking technology using the Y-heterogeneous compound molecular sieve-containing catalyst or the hydrocracking technology using the Y-heterogeneous compound molecular sieve-containing hydrocracking catalyst and the heterogeneous molecular sieve-containing hydrocracking catalyst in a grading manner, and the property of the obtained tail oil is between that of the Y-heterogeneous compound molecular sieve-containing hydrocracking catalyst and that of the heterogeneous molecular sieve-containing hydrocracking catalyst. The hydrocracking process technology has the advantages that the hydrocracking tail oil products produced at the same conversion rate are greatly different, wherein the tail oil using the Y-type molecular sieve catalyst is a high-quality raw material for preparing ethylene through steam cracking, the tail oil using the heterogeneous molecular sieve catalyst is a raw material capable of directly producing high-quality lubricating oil base oil or serving as the high-quality lubricating oil base oil, and the tail oil obtained by using the Y-heterogeneous compound molecular sieve-containing catalyst or grading the Y-type molecular sieve-containing hydrocracking catalyst and the heterogeneous molecular sieve-containing hydrocracking catalyst can be used as a raw material for preparing ethylene through steam cracking or serving as a raw material for the high-quality lubricating oil base oil. Therefore, when the above hydrocracking processes are used alone, different types of hydrocracking catalysts can be selected according to requirements, or two molecular sieve composite catalysts are used, or two hydrocracking catalysts are selected for use in a grading manner, but the processes can only produce tail oil products with one property, namely, the operation flexibility is relatively poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a flexible hydrocracking method for producing lubricating oil base oil, which is characterized in that a hydrogenation pretreatment product flow is divided into two parts, one part of the gas enters a hot high-pressure separator, the separated gas is mixed with the rest part of the gas for hydrocracking, the separated liquid is mixed with hydrocracking tail oil and hydrogen for hydroisomerization cracking, and the wax oil raw oil is subjected to hydrocracking by a Y-type hydrocracking catalyst and hydroisomerization cracking by an isomerization type hydrocracking catalyst to flexibly produce high-quality steam cracking ethylene preparation raw material, high-quality lubricating oil base oil raw material, naphtha products with various specifications and high-quality motor fuel products.
The flexible hydrocracking method for producing the lubricating oil base oil comprises the following steps:
a. the method comprises the following steps that raw wax oil enters a hydrogenation pretreatment reactor under a hydrogenation pretreatment condition and passes through a hydrogenation pretreatment catalyst bed layer to obtain a hydrogenation pretreatment material flow, the hydrogenation pretreatment material flow is divided into two parts, and one part of the hydrogenation pretreatment material flow enters a thermal high-pressure separator to be separated to obtain a gas phase and a liquid phase;
b. b, passing the other part of the hydrogenation pretreatment material flow obtained in the step a and the gas phase material flow obtained by separating the hot high-pressure separator through a hydrocracking catalyst bed layer containing a Y-shaped molecular sieve catalyst in a hydrocracking reactor under a hydrocracking condition to obtain a hydrocracking material flow; separating and fractionating the hydrocracking product to obtain hydrocracking high-pressure hydrogen-rich gas, a hydrocracking gas product, a hydrocracking distillate oil product and a hydrocracking tail oil product;
c. and b, mixing the liquid phase material flow obtained in the step a, the hydrocracking tail oil obtained in the step b and circulating hydrogen, passing through a hydroisomerization cracking catalyst bed layer containing an isomerization type molecular sieve catalyst under a hydroisomerization cracking condition to obtain a hydroisomerization cracking material flow, and separating and fractionating the hydroisomerization cracking material flow to obtain a hydroisomerization cracking high-pressure hydrogen-rich gas, a hydroisomerization cracking gas product, a hydroisomerization cracking distillate oil product and a hydroisomerization cracking tail oil product.
The hydrocracking process according to the present invention may further comprise a step d: and c, mixing the hydrocracking high-pressure hydrogen-rich gas obtained in the step b with the hydroisomerization cracking high-pressure hydrogen-rich gas obtained in the step c for recycling.
In the present invention, the hydrocracked distillate product in step b typically comprises a hydrocracked light naphtha product, a hydrocracked heavy naphtha product, a hydrocracked aviation kerosene product and a hydrocracked diesel oil product. Likewise, the hydroisomerized cracked distillate product as described in step c typically comprises a hydroisomerized cracked light naphtha product, a hydroisomerized cracked heavy naphtha product, a hydroisomerized cracked aviation kerosene product and a hydroisomerized cracked diesel oil product
S, N, O and other impurities in the wax oil raw oil are effectively removed when passing through a hydrogenation pretreatment catalyst, aromatic hydrocarbon is subjected to hydrogenation saturation to a certain extent, a gas phase material flow obtained by gas-liquid separation of a part of hydrogenation pretreatment material flow is mixed with another part of hydrogenation pretreatment material flow, and then the mixture continues to pass through a hydrocracking catalyst bed layer containing a Y-shaped molecular sieve catalyst, wherein cyclic hydrocarbon is subjected to partial ring-opening reaction, macromolecules are cracked into small molecules, the Y-shaped molecular sieve has the characteristic of preferentially cracking macromolecular polycyclic cyclic hydrocarbon, and aviation kerosene products, diesel oil products and tail oil products with high normal hydrocarbon content and low aromatic hydrocarbon content can be obtained; the liquid phase material flow obtained by the gas-liquid separator is mixed with the hydrocracking tail oil, and then passes through the hydroisomerization cracking catalyst containing the isomerization type molecular sieve catalyst to continue the isomerization hydrocracking, and because the isomerization type molecular sieve has the characteristics of isomerization and cracking, the isomerization cracking product with high content of isomerization hydrocarbon can be obtained, in particular, the condensation point of diesel oil product is low, the condensation point of tail oil product is low, the viscosity index is high, the hydrocracking tail oil continues to carry out the hydroisomerization cracking, and the content of isoparaffin in the tail oil product can be increasedAnd reducing the content of aromatics and polycyclic naphthenes, further increasing the viscosity index of the hydroisomerized cracked tail oil, and additionally reducing the NH content due to the hydroisomerized cracking reaction3And low H2The method is carried out in an S environment, the required reaction temperature is very low, and the requirement of the hydroisomerization cracking reaction temperature can be met only by cooling the recycle hydrogen.
Compared with the prior art, the flexible hydrocracking method for producing the lubricating oil base oil has the advantages that:
1. in the invention, the hydrogenation pretreatment material flow obtained by the hydrogenation pretreatment reactor is directly divided into two parts in a pipeline, and effective distribution of the hydrogenation pretreatment material strand can be realized without special operation, wherein one part can obtain a gas phase and a liquid phase after passing through a thermal high-pressure separator, and then the obtained liquid phase material and a mixed material of the gas phase material and the other part of the hydrogenation treatment material are respectively subjected to different hydrocracking processes, so that target products with different specifications can be flexibly produced, and particularly, high-quality lubricating oil base oil products can be obtained after hydrocracking tail oil passes through a hydroisomerization catalyst containing an isomeric molecular sieve in a hydroisomerization cracking reactor. In the prior art, although a plurality of light products can be obtained by adjusting the conversion rate and the distillation range of the products, the same distillation range of a set of hydrocracking units can only be used for one type of light naphtha, heavy naphtha products, aviation kerosene products, diesel oil products and tail oil products because only one hydrocracking reactor outlet is arranged; if different specifications of hydrocracking products are required, more than two sets of hydrocracking units are required. Therefore, the invention provides a hydrocracking process for simultaneously producing more than two same-fraction ranges, but different specifications of tail oil products, more than two different specifications of aviation kerosene products, more than two different specifications of diesel oil products and a plurality of different specifications of naphtha products on one hydrocracking process device for the first time.
2. According to the invention, the hydrogenation pretreatment material flow at the outlet of the hydrogenation pretreatment reactor is directly separated to obtain two part material flows, the two part material flows are separated by the heat high-pressure separator to obtain a gas phase and a liquid phase, the liquid phase material flow is used as a raw material, a mixed material flow of the gas phase material flow and the other part of hydrogenation treatment material flow is used as a raw material, the mixed material flow is respectively sent to the independently arranged hydrocracking reactor for hydrocracking reaction and entering the hydrocracking reactor for hydroisomerization cracking reaction, and the hydrocracking tail oil partially or completely enters the hydroisomerization cracking reactor, so that naphtha products, aviation kerosene products, diesel oil products and tail oil products with different aromatic hydrocarbon contents, different isomeric hydrocarbon contents and different condensation points can be flexibly produced by the method.
3. In the invention, heavy naphtha obtained by hydrocracking a product obtained by fractionating the material flows of two cracking reactors by using a catalyst containing a Y-type molecular sieve has relatively high aromatic hydrocarbon potential, a aviation kerosene product has relatively high smoke point, a diesel oil product has relatively high cetane number, a tail oil product has high paraffin content and a BMCI value is relatively low; after partial hydroisomerization cracking of the catalyst containing the heterogeneous molecular sieve, particularly, the hydrocracking tail oil is subjected to the hydroisomerization cracking of the catalyst containing the heterogeneous molecular sieve to obtain naphtha with high content of heterogeneous hydrocarbons, low freezing point of a aviation kerosene product, low condensation point of a diesel oil product, high content of heterogeneous hydrocarbons of the tail oil product, large viscosity index and low condensation point; the hydrocracking tail oil has low aromatic hydrocarbon content, and the viscosity index of the hydrocracking tail oil can be improved after the hydrocracking is continuously carried out; therefore, the process can respectively meet the requirements of producing naphtha, aviation kerosene products, diesel oil products and tail oil products with different specifications.
4. In the invention, the liquid obtained by the hydrogenation pretreatment reactor has very high temperature and pressure and is divided into two parts of materials, wherein the gas phase and the liquid phase obtained by separating one part of the materials by the hot high-pressure separator also have very high temperature and pressure, the influence obtained by the other part of the hydrogenation pretreatment material and the hot high-pressure separator can directly enter the hydrocracking reactor for reaction, the hydrocracking tail oil has higher temperature after passing through the fractionating tower, the hydrocracking tail oil can enter the hydroisomerization cracking reactor for reaction only by pumping and pressurizing the hydrocracking tail oil, and the liquid phase and the hydrocracking tail oil obtained by separating by the hot high-pressure separator do not contain NH3Thus greatly reducing the hydrocracking reaction stationThe required temperature, namely the mixed liquid material is mixed with the recycle hydrogen to meet the requirement of the hydrogenation isomerization cracking reaction temperature, so that the coupling operation of the hydrogenation pretreatment reactor, the hydrogenation cracking reactor and the hydrogenation isomerization cracking reactor can be realized.
Drawings
Fig. 1 is a schematic flow chart of the principle of the present invention.
Wherein: 1-raw oil, 2-hydrotreating reactor, 3-hydrotreating stream, 4-hydrocracking feed stream, 5-hot high-pressure separator feed stream, 6-hydrocracking reactor, 7-hydrocracking stream, 8-hydrocracking reactor, 9-hydrocracking stream, 10-hydrocracking high-pressure separator, 11-hydrocracking high-pressure separator, 12-hydrocracking fractionator, 13-hydrocracking fractionator, 14-hydrocracking light naphtha product, 15-hydrocracking heavy naphtha product, 16-hydrocracking aviation kerosene product, 17-hydrocracking diesel product, 18-hydrocracking tail oil product, 19-hydrocracking light naphtha product, 20-hydrocracking heavy naphtha product, 21-hydroisomerized cracked aviation kerosene product, 22-hydroisomerized cracked diesel oil product, 23-hydroisomerized cracked tail oil product, 24-hydrocracking high-pressure separator hydrogen-rich gas, 25-hydroisomerized cracking high-pressure separator hydrogen-rich gas, 26-make-up hydrogen, 27-thermal high-pressure separator, 28-thermal high-pressure separator liquid phase and 29-thermal high-pressure separator gas phase.
Detailed Description
The initial boiling point of the wax oil raw material in the step a is 100-400 ℃, and the final boiling point is 400-650 ℃. The wax oil raw material oil can be one of straight-run wax oil, coking wax oil, deasphalted oil, catalytic cycle oil and the like obtained by petroleum processing, one of coal tar, coal direct liquefaction oil, coal indirect liquefaction oil, synthetic oil, shale oil and the like obtained from coal, and can also be mixed oil of a plurality of the coal tar, the coal direct liquefaction oil, the coal indirect liquefaction oil, the synthetic oil and the shale oil.
The hydrogenation pretreatment catalyst in the step a is a conventional wax oil hydrogenation pretreatment catalyst. Generally, metals in VIB group and/or VIII group are used as active components, alumina or silicon-containing alumina is used as a carrier, metals in VIB group are generally Mo and/or W, metals in VIII group are generally usedIs Co and/or Ni. Based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, and the properties are as follows: the specific surface area is 100 to 650m2The pore volume is 0.15 to 0.6 mL/g. The main catalysts comprise hydrogenation pretreatment catalysts such as 3936, 3996, FF-16, FF-26, FF-36, FF-46 and FF-56 series developed by the petrochemical research institute, and can also be similar catalysts with functions developed by domestic and foreign catalyst companies, such as HC-K, HC-P of UOP company, TK-555 and TK-565 of Topsoe company, KF-847 and KF-848 of Akzo company, and the like. The operating conditions can be conventional and are generally: the reaction pressure is 3.0MPa to 19.0MPa, the reaction temperature is 300 ℃ to 450 ℃, and the liquid hourly volume space velocity is 0.2h-1～6.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
The weight percentage of the liquid phase material flow obtained in the step a in the raw oil is 5-95%, preferably 10-90%.
The hot high-pressure separator in the step a is a conventional separator, the operating pressure is the reaction pressure, and the temperature is the outlet temperature of the hydrogenation pretreatment material flow or is not more than 50 ℃ lower than the outlet temperature.
The hydrocracking catalyst in the step b is a conventional wax oil hydrocracking catalyst. Generally, metals in a VIB group and/or a VIII group are used as active components, the metals in the VIB group are generally Mo and/or W, and the metals in the VIII group are generally Co and/or Ni. The carrier of the catalyst contains one or more of alumina, siliceous alumina and molecular sieve, preferably contains molecular sieve, and the molecular sieve can be Y-type molecular sieve. Based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, and the content of the molecular sieve is 5-80 wt%. The main catalysts are 3824, 3825, 3976, FC-12, FC-24, FC-26, FC-32, FC-50 catalysts and the like developed by the petrochemical research institute, HC-12, HC-14, HC-24, HC-39 and the like of UOP company. For hydrocracking catalysts, a certain hydrogenation activity and a certain cracking activity are required, which are both ensured for the oil produced by hydrotreating and for the olefins and aromatics in the fractions produced in the hydrocracking processThe hydrogenation saturation of (2) also requires ring-opening reaction of the saturated aromatic hydrocarbon. The hydrocracking operating conditions may be conventional and are generally: the reaction pressure is 3.0MPa to 19.0MPa, the reaction temperature is 300 ℃ to 450 ℃, and the liquid hourly volume space velocity is 0.2h-1～6.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
The separation described in step b generally comprises separating two parts, a hydrocracking high-pressure separator and a low-pressure separator. Wherein the high-pressure separator separates to obtain the hydrocracking high-pressure hydrogen-rich gas and liquid, and the liquid separated by the high-pressure separator enters the low-pressure separator. The low pressure separator separates the high pressure liquid product to yield a hydrocarbon-rich gas and a low pressure liquid product. The hydrocarbon-rich gas is separated to obtain the required hydrocracking gas product.
The fractionation described in step b is carried out in a hydrocracking fractionator system. And fractionating the low-pressure liquid product in a fractionating tower to obtain a hydrocracking light naphtha product, a hydrocracking heavy naphtha product, a hydrocracking aviation kerosene product, a hydrocracking diesel oil product and a hydrocracking tail oil product.
And c, allowing the hydrocracking tail oil product obtained in the step b to completely enter a hydroisomerization cracking reactor, or allowing part of the hydrocracking tail oil product to enter the hydroisomerization cracking reactor, wherein the weight of the tail oil entering the hydroisomerization cracking reactor is 10-100%, preferably 20-100% of the weight of the obtained hydrocracking tail oil.
The hydroisomerization cracking catalyst in the step c is a conventional wax oil hydroisomerization cracking catalyst. Generally, metals in a VIB group and/or a VIII group are used as active components, the metals in the VIB group are generally Mo and/or W, and the metals in the VIII group are generally Co and/or Ni. The carrier of the catalyst contains one or more of alumina, silicon-containing alumina and molecular sieve, preferably contains molecular sieve, and the molecular sieve can be beta type molecular sieve, Sapo type molecular sieve and the like. Based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, and the content of the molecular sieve is 5-80 wt%. The main catalysts comprise FC-14, FC-20 and the like developed by the petrochemical research institute. For hydrocracking catalysts, certain requirements are imposedHydrogenation activity and certain cracking activity, namely, the hydrogenation saturation of olefin and aromatic hydrocarbon in reaction materials is ensured, and the isomerization reaction of straight-chain alkane is also required. The hydroisomerization cracking may be carried out under conventional operating conditions, which are generally: the reaction pressure is 3.0MPa to 19.0MPa, the reaction temperature is 300 ℃ to 450 ℃, and the liquid hourly volume space velocity is 0.2h-1～6.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
The separation described in step c is carried out in a hydroisomerization cracking high pressure separator and a low pressure separator. Wherein, the hydroisomerization cracking high-pressure separator separates to obtain the hydroisomerization cracking high-pressure hydrogen-rich gas and liquid, and the liquid separated by the high-pressure separator enters the low-pressure separator. The low pressure separator separates the high pressure liquid product to yield a hydrocarbon-rich gas and a low pressure liquid product. The hydrocarbon-rich gas is separated to obtain the required hydroisomerized cracked gas product.
The fractionation described in step c is carried out in a hydroisomerization cracking fractionator system. And fractionating the low-pressure liquid product in a fractionating tower to obtain a hydroisomerized cracked light naphtha product, a hydroisomerized cracked heavy naphtha product, a hydroisomerized cracked aviation kerosene product, a hydroisomerized cracked diesel oil product and a hydroisomerized cracked tail oil product.
The hydrocracking gas product and the hydroisomerization cracking gas product in the steps b and c can be used as products independently or can be mixed into a mixed gas product.
The hydrocracked light naphtha product and the hydroisomerized cracked light naphtha product in the step b and the step c can be used as the products independently or can be mixed into a mixed light naphtha product.
The hydrocracked heavy naphtha product and the hydroisomerized cracked heavy naphtha product in step b and step c may be used as separate products or may be mixed into a mixed heavy naphtha product.
The hydrocracking aviation kerosene product and the hydroisomerization cracking aviation kerosene product in the step b and the step c can be used as products independently or can be mixed into a mixed aviation kerosene product.
The hydrocracking diesel oil product and the hydroisomerization diesel oil product in the step b and the step c can be used as products independently or can be mixed into a mixed diesel oil product.
Part of the hydrocracked tail oil in step b may be used as a product alone.
And d, independently using the hydroisomerized cracked tail oil in the step c as a product.
And d, mixing the high-pressure hydrogen-rich gas in the step d, and then directly using the mixed gas as recycle hydrogen, or recycling the mixed gas after hydrogen sulfide is removed by a recycle hydrogen desulfurization system.
With reference to fig. 1, the method of the present invention is as follows: raw oil 1 is firstly mixed with recycle hydrogen and enters a hydrogenation pretreatment reactor 2, a hydrogenation pretreatment stream 3 is divided into two parts, a hydrocracking raw material stream 4 and a hot high-pressure separator feed stream 5, the hot high-pressure separator feed stream 5 is separated in a hot high-pressure separator 27 to obtain a hot high-pressure separator liquid phase 28 and a hot high-pressure separator gas phase 29, the hydrocracking raw material stream 4, the hot high-pressure separator gas phase 29 and the recycle hydrogen are mixed and enter a hydrocracking reactor 6, a hydrocracking material stream 7 is obtained by passing through a hydrocracking catalyst bed layer, the hydrocracking material stream 7 enters a hydrocracking high-pressure separator 10 for gas-liquid separation, the liquid obtained by separation enters a fractionating tower 12 for fractionating to obtain a hydrocracking light naphtha product 14, a hydrocracking heavy naphtha product 15, a hydrocracking aviation kerosene product 16, a hydrocracking diesel product 17 and a hydrocracking tail oil product 18, mixing the thermal high-pressure separator liquid phase 28 with the hydrocracking tail oil 18 and the recycle hydrogen, entering a hydroisomerization cracking reactor 8, passing through a hydroisomerization cracking catalyst bed to obtain a hydroisomerization cracked stream 9, entering the hydroisomerization cracked stream 9 into a hydroisomerization cracking high-pressure separator 11 for gas-liquid separation, entering the separated liquid into a fractionating tower 13 for fractionation to obtain a hydroisomerization cracked light naphtha product 19, a hydroisomerization cracked heavy naphtha product 20, a hydroisomerization cracked aviation kerosene product 21, a hydroisomerization cracked diesel product 22 and a hydroisomerization cracked tail oil product 23, wherein the hydrocracking light naphtha product 14 and the hydroisomerization cracked light naphtha product 19 can be used as products independently or mixed to obtain a mixed light naphtha product, and the hydrocracking heavy naphtha product 15 and the hydroisomerization cracked heavy naphtha product 20 can be used as products independently, or mixed to obtain a mixed heavy naphtha product, the hydrocracking aviation kerosene product 16 and the hydroisomerization cracking aviation kerosene product 21 can be used as products independently or mixed to obtain a mixed aviation kerosene product, the hydrocracking diesel oil product 17 and the hydroisomerization cracking diesel oil product 22 can be used as products independently or mixed to obtain a mixed diesel oil product, and the gas 24 obtained by separating the hydrocracking high-pressure separator 10 and the gas 25 obtained by separating the hydroisomerization cracking high-pressure separator 11 are mixed and then are pressurized by a recycle hydrogen compressor and then are mixed with make-up hydrogen 26 to obtain recycle hydrogen.
The embodiments and effects of the present invention are described below by way of examples.
Examples 1 to 3
The protective agents FZC-100, FZC-105 and FZC106 are hydrogenation protective agents developed and produced by the smooth petrochemical research institute of the China petrochemical industry, Inc.; the catalyst FF-56 is a hydrotreating catalyst developed and produced by the smooth petrochemical research institute of China petrochemical company Limited; the catalyst FC-32 is a hydro-upgrading catalyst developed and produced by China petrochemical company Limited, compliant petrochemical research institute, and contains a Y-type molecular sieve; the catalyst FC-20 is a hydroisomerization cracking catalyst which is developed and produced by the smooth petrochemical research institute of China petrochemical company Limited and contains a beta-type molecular sieve.
TABLE 1 essential Properties of wax oil base stocks
Figure 736157DEST_PATH_IMAGE002
Table 2 example process conditions
Figure 731926DEST_PATH_IMAGE004
Table 3 example test results
Figure 511663DEST_PATH_IMAGE006
It can be seen from the examples that, by using the hydrocracking coupling process of the present invention, the hydrogenation pretreatment stream is divided into two parts, wherein one part of the stream enters the thermal high-pressure separator for separation to obtain a gas phase and a liquid phase, the liquid phase of the thermal high-pressure separator and the other part of the hydrogenation pretreatment stream pass through the hydrocracking catalyst, the liquid phase of the thermal high-pressure separator passes through the hydroisomerization cracking catalyst, and simultaneously, the hydrocracking tail oil partially or completely passes through the hydroisomerization cracking catalyst, i.e., different types of hydrocracking catalysts are used to achieve the purpose of producing hydrocracking products with different properties, especially high-quality lube base oil, and the production mode is flexible.

Claims (16)

1. A flexible hydrocracking process for producing a lubricant base oil comprising the steps of:
a. the method comprises the following steps that raw wax oil enters a hydrogenation pretreatment reactor under a hydrogenation pretreatment condition and passes through a hydrogenation pretreatment catalyst bed layer to obtain a hydrogenation pretreatment material flow, the hydrogenation pretreatment material flow is divided into two parts, and one part of the hydrogenation pretreatment material flow enters a thermal high-pressure separator to be separated to obtain a gas phase and a liquid phase;
b. b, passing the other part of the hydrogenation pretreatment material flow obtained in the step a and the gas phase material flow obtained by separating the hot high-pressure separator through a hydrocracking catalyst bed layer containing a Y-shaped molecular sieve catalyst in a hydrocracking reactor under a hydrocracking condition to obtain a hydrocracking material flow; separating and fractionating the hydrocracking product to obtain hydrocracking high-pressure hydrogen-rich gas, a hydrocracking gas product, a hydrocracking distillate oil product and a hydrocracking tail oil product;
c. and b, mixing the liquid phase material flow obtained in the step a, the hydrocracking tail oil obtained in the step b and circulating hydrogen, passing through a hydroisomerization cracking catalyst bed layer containing an isomerization type molecular sieve catalyst under a hydroisomerization cracking condition to obtain a hydroisomerization cracking material flow, and separating and fractionating the hydroisomerization cracking material flow to obtain a hydroisomerization cracking high-pressure hydrogen-rich gas, a hydroisomerization cracking gas product, a hydroisomerization cracking distillate oil product and a hydroisomerization cracking tail oil product.
2. The flexible hydrocracking process of claim 1, further comprising step d: and c, mixing the hydrocracking high-pressure hydrogen-rich gas obtained in the step b with the hydroisomerization cracking high-pressure hydrogen-rich gas obtained in the step c for recycling.
3. The flexible hydrocracking process according to claim 1, wherein the wax oil feedstock has an initial boiling point of 100 to 400 ℃ and an end boiling point of 405 to 650 ℃.
4. The flexible hydrocracking process of claim 3, wherein said wax oil feedstock is at least one selected from the group consisting of virgin wax oil, coker wax oil, deasphalted oil, catalytic cycle oil, coal tar, direct coal liquefaction oil, indirect coal liquefaction oil, synthetic oil and shale oil.
5. The flexible hydrocracking process of claim 1, wherein said hydrotreating catalyst has a group vib and/or group viii metal as an active component and an alumina or siliceous alumina as a carrier; based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, and the content of the VIII group metal is 3-15 wt% calculated by oxide; the properties are as follows: the specific surface area is 100 to 650m2The pore volume is 0.15 to 0.6 mL/g.
6. The flexible hydrocracking process of claim 1, wherein said pretreatment by hydrogenation is carried out under the operating conditions: the reaction pressure is 3.0MPa to 19.0MPa, the reaction temperature is 300 ℃ to 450 ℃, and the liquid hourly volume space velocity is 0.2h-1～6.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
7. The flexible hydrocracking process according to claim 1, wherein the liquid stream obtained in step a is 5 to 95 wt.% based on the feed oil.
8. The flexible hydrocracking process of claim 7, wherein the hydrocracking tail oil entering the hydrocracking reactor in step c is 10 to 100% by weight of the hydrocracking tail oil obtained in step b.
9. The flexible hydrocracking process of claim 1, wherein said hydrocracking catalyst comprises a group VIB and/or group VIII metal as an active component; the catalyst carrier contains a Y molecular sieve; based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, and the content of the Y molecular sieve is 5-80 wt%.
10. The flexible hydrocracking process of claim 1, wherein said hydrocracking conditions are: the reaction pressure is 3.0MPa to 19.0MPa, the reaction temperature is 300 ℃ to 450 ℃, and the liquid hourly volume space velocity is 0.2h-1～6.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
11. The flexible hydrocracking process of claim 1, wherein the hydroisomerization catalyst comprises a group VIB and/or group VIII metal as an active component, and the catalyst support comprises a molecular sieve, wherein the molecular sieve is a beta-type molecular sieve or a Sapo-type molecular sieve; based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, and the content of the molecular sieve is 5-80 wt%.
12. The flexible hydrocracking process of claim 1, wherein said hydroisomerization cracking conditions are: the reaction pressure is 3.0MPa to 19.0MPa, the reaction temperature is 300 ℃ to 450 ℃, and the liquid hourly volume space velocity is 0.2h-1～6.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
13. The flexible hydrocracking process of claim 1, wherein said hydrocracked distillate product of step b comprises a hydrocracked light naphtha product, a hydrocracked heavy naphtha product, a hydrocracked aviation kerosene product and a hydrocracked diesel product.
14. The flexible hydrocracking process of claim 1, wherein said hydroisomerized cracked distillate product of step c comprises a hydroisomerized cracked light naphtha product, a hydroisomerized cracked heavy naphtha product, a hydroisomerized cracked aviation kerosene product and a hydroisomerized cracked diesel product.
15. The flexible hydrocracking process of claim 7, wherein the liquid stream obtained in step a is 10 to 90 wt.% of the feed oil.
16. The flexible hydrocracking process according to claim 7 or 8, wherein the hydrocracking tail oil entering the hydroisomerization reactor in step c is 20 to 100% by weight of the hydrocracking tail oil obtained in step b.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104611018A (en) * 2013-11-05 2015-05-13 中国石油化工股份有限公司 Process method for producing lubricating oil base oil through poor-quality raw material

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