CN118440728B - Processing method for producing more chemical raw materials from vacuum residue - Google Patents
Processing method for producing more chemical raw materials from vacuum residueInfo
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- CN118440728B CN118440728B CN202310055029.9A CN202310055029A CN118440728B CN 118440728 B CN118440728 B CN 118440728B CN 202310055029 A CN202310055029 A CN 202310055029A CN 118440728 B CN118440728 B CN 118440728B
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
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Abstract
本发明公开了一种减压渣油多产化工原料的加工方法。所述方法包括：减压渣油原料与氢气混合进入沸腾床加氢反应区进行临氢热裂化反应，经分离分馏得到气体馏分、轻质馏分油、蜡油和尾油；轻质馏分油初馏点为50℃～80℃，终馏点为280℃～340℃；在氢气存在下，轻质馏分油与氢气混合依次进入第一加氢裂化反应区和第二加氢裂化反应区进行反应，得到的第二加氢裂化产物经分离、分馏得到气体、轻石脑油、重石脑油和尾油；尾油与氢气混合进入第三加氢裂化反应区，得到的第三加氢裂化产物经分离和分馏得到气体、轻石脑油、重石脑油；第一加氢裂化反压力第三加氢裂化反应压力高0.5～5.0MPa。该方法能够大幅提高化工原料的收率和质量。
The present invention discloses a method for processing vacuum residue to produce more chemical raw materials. The method comprises: mixing the vacuum residue raw material with hydrogen and entering an ebullated bed hydrogenation reaction zone for hydrothermal cracking, followed by separation and fractionation to obtain a gas fraction, light distillate oil, wax oil, and tail oil; the light distillate oil has an initial boiling point of 50°C to 80°C and a final boiling point of 280°C to 340°C; in the presence of hydrogen, the light distillate oil and hydrogen are mixed and sequentially introduced into a first hydrocracking reaction zone and a second hydrocracking reaction zone for reaction; the obtained second hydrocracking product is separated and fractionated to obtain gas, light naphtha, heavy naphtha, and tail oil; the tail oil is mixed with hydrogen and entered into a third hydrocracking reaction zone; the obtained third hydrocracking product is separated and fractionated to obtain gas, light naphtha, and heavy naphtha; the first hydrocracking back pressure is 0.5 to 5.0 MPa higher than the third hydrocracking reaction pressure. This method can significantly improve the yield and quality of chemical raw materials.
Description
Technical Field
The invention belongs to the field of heavy oil processing, and particularly relates to a processing method combining ebullated bed hydrogenation and hydrocracking, in particular to a processing method for producing high-quality chemical raw materials by taking inferior heavy oil as a raw material.
Background
In recent years, with the gradual decrease of light crude oil resources and the continuous rising of the price thereof, the processing of low-quality heavy oil with abundant reserves, wide sources and low price has become a global trend. Meanwhile, the market demand for light oil products is continuously increased, and the requirements of environmental protection regulations on the quality of oil products are increasingly strict. The above situation forces refineries to carefully face the worldwide technical problem of deep processing of inferior heavy oils. The boiling bed residual oil hydrogenation technology can be used for processing high-sulfur, high-carbon residue and high-metal heavy crude oil, has the advantages of uniform temperature in a reactor, long operation period, flexible device operation and the like, can solve the problems of low space velocity, quick catalyst deactivation, large system pressure drop and the like of a fixed bed residual oil hydrogenation device, and has obvious advantages.
CN201580070326.4 discloses a process for producing LPG and BTX comprising a) subjecting a mixed hydrocarbon stream to a first hydrocracking in the presence of a first hydrocracking catalyst to produce a first hydrocracking product stream, b) separating the first hydrocracking product stream to provide at least one light hydrocarbon stream comprising at least C2 and C3 hydrocarbons, an intermediate hydrocarbon stream consisting of C4 and/or C5 hydrocarbons, and a heavy hydrocarbon stream comprising at least C6+ hydrocarbons, and C) subjecting the heavy hydrocarbon stream to a second hydrocracking in the presence of a second hydrocracking catalyst to produce a second hydrocracking product stream comprising BTX, wherein the second hydrocracking is more severe than the first hydrocracking, d) wherein at least part of the intermediate hydrocarbon stream is subjected to C4 hydrocracking in the presence of the C4 hydrocracking catalyst to produce a C4 hydrocracking product stream, the C4 hydrocracking being optimized for converting C4 hydrocarbons into C3 hydrocarbons.
CN201480037272.7 discloses a process for producing light olefin compounds from a hydrocarbon feedstock comprising the steps of (a) feeding a hydrocarbon feedstock to a reaction zone for ring opening, (b) separating the reaction products produced by said reaction zone into a top stream and a side stream, (c) feeding the side stream from (b) to a Gasoline Hydrocracker (GHC) unit, (d) separating the reaction products of said GHC of step (c) into a top stream comprising hydrogen, methane, ethane and liquefied petroleum gas and a stream comprising aromatic hydrocarbon compounds and minor amounts of hydrogen and non-aromatic hydrocarbon compounds, (e) feeding the top stream from the Gasoline Hydrocracker (GHC) unit to a steam cracker unit.
In summary, petroleum hydrocarbons are complex in composition and mainly comprise paraffins, naphthenes and aromatics, where paraffins, especially small molecular paraffins, are good ethylene feeds and naphthenes and aromatics are good reforming feeds. Boiling bed hydrogenation is to make heavy raw material produce hydro-thermal cracking reaction under the hydro-environment, and follow the free radical reaction mechanism, its product has high normal hydrocarbon and cyclic hydrocarbon content, in the prior art, the conversion effect of 'should be alkene, should be aromatic' cannot be realized efficiently aiming at boiling bed residual oil hydrogenation distillate oil. Therefore, the development of a processing method suitable for producing high-quality chemical raw materials by boiling bed hydrogenation and hydrocracking by taking inferior heavy oil as a raw material has great significance.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a processing method of a vacuum residue multi-production chemical raw material, which takes inferior heavy oil such as vacuum residue and the like as a raw material, and can greatly improve the yield and quality of the chemical raw material.
The invention provides a processing method of a vacuum residuum productive chemical raw material, which comprises the following steps:
(1) Mixing a vacuum residuum raw material with hydrogen, entering a fluidized bed hydrogenation reaction zone for hydro-thermal cracking reaction, and separating and fractionating to obtain a gas fraction, light fraction oil, wax oil and tail oil, wherein the initial distillation point of the light fraction oil is 50-80 ℃, and the final distillation point is 280-340 ℃;
(2) In the presence of hydrogen, mixing the light distillate oil obtained in the step (1) with the hydrogen, entering a first hydrocracking reaction zone for first hydrocracking, and controlling the mass content of C 7 + normal paraffins in a first hydrocracking product to be 0.1% -5.0%;
(3) The reaction effluent of the step (2) enters a second hydrocracking reaction zone, and cyclic hydrocarbon with more than double rings is subjected to selective ring opening cracking to obtain a second hydrocracking product, wherein hydrogen-rich gas obtained after the second hydrocracking product is subjected to gas-liquid separation by a separator is used as circulating hydrogen, and liquid phase enters a fractionation system to be fractionated to obtain gas, light naphtha, heavy naphtha and tail oil;
(4) Mixing the tail oil and hydrogen in the step (3) and entering a third hydrocracking reaction zone to obtain a third hydrocracking product containing monocyclic cyclic hydrocarbon, and entering a separation and fractionation system to obtain gas, light naphtha and heavy naphtha;
wherein the reaction pressure of the first hydrocracking reaction zone in the step (2) is 0.5-5.0 MPa higher than that of the third hydrocracking reaction zone in the step (4).
According to the invention, the vacuum residuum in the step (1) has the properties of initial distillation point of 420-620 ℃, preferably 450-550 ℃, sulfur content of 2-10%, preferably 4-8%, nitrogen content of 0.2-1.0%, preferably 0.3-0.5%, and metal content of 100-500 mg/kg, preferably 200-300 mg/kg.
According to the invention, the reaction conditions of the ebullated bed hydrogenation reaction zone in the step (1) are that the reaction pressure is 10-25 MPa, preferably 15-20 MPa, the reaction temperature is 350-500 ℃, preferably 400-450 ℃, the hydrogen-oil volume ratio is 100:1-2000:1, preferably 300:1-1000:1, and the volume space velocity is 0.1h -1～1.5h-1, preferably 0.2h -1～1.0h-1.
According to the invention, the conversion rate of the vacuum residuum in the fluidized bed hydrogenation reaction zone in the step (1) is controlled to be 60% -90%, preferably 70% -80%, and the conversion rate is defined as the sum of the mass percentages of gas fraction, light fraction oil and wax oil in the fluidized bed hydrogenation product relative to the fresh raw materials.
According to the invention, the initial distillation point of the light distillate oil in the step (1) is 60-70 ℃ and the final distillation point is 290-320 ℃.
According to the invention, preferably, the mass content of C 7 + normal alkane in the first hydrocracking product in the step (2) is 1.0% -3.0%.
According to the invention, the chemical raw materials mainly comprise ethane, propane, butane and light naphtha and can also comprise heavy naphtha, wherein the heavy naphtha is used as a reforming raw material to produce BTX, the ethane, propane, butane and light naphtha are used as raw materials for producing low-carbon olefin, such as ethylene by being used as a steam cracking raw material, and the propane and butane can also be directly dehydrogenated to produce propylene and butene. Wherein, the low-carbon olefin refers to olefin with four or less carbon atoms, in particular ethylene, propylene and butadiene.
According to the invention, preferably, the reaction pressure of the first hydrocracking reaction zone in the step (2) is 0.5-4.0 MPa higher than the reaction pressure of the third hydrocracking reaction zone in the step (4).
According to the invention, the reaction conditions of the first hydrocracking reaction zone in the step (2) are as follows, wherein the reaction pressure is 6-10 MPa, preferably 7-9 MPa.
According to the invention, the reaction conditions of the first hydrocracking reaction zone in the step (2) are that the average reaction temperature is 250-450 ℃, preferably 300-400 ℃, the liquid hourly space velocity is 0.1-15.0 h -1, preferably 1.0-5.0 h -1, and the hydrogen-oil volume ratio is 100:1-2500:1, preferably 400:1-2000:1.
According to the present invention, in step (2), the light fraction oil may contain impurities such as sulfur, nitrogen, etc. According to actual needs, a hydrofining catalyst may be disposed upstream of the first hydrocracking catalyst to remove sulfur, nitrogen and other impurities. Wherein the nitrogen content in the reactant stream contacted with the first hydrocracking catalyst is preferably below 50mg/kg, more preferably below 20 mg/kg.
According to the present invention, the first hydrocracking reaction zone in step (2) is charged with a first hydrocracking catalyst. The first hydrocracking catalyst may be one or more catalysts.
According to the present invention, in the step (2), a conventional hydrofining catalyst may be used as the hydrofining catalyst disposed upstream of the first hydrocracking catalyst, mainly for hydrodesulfurization, nitrogen and other impurities. The hydrofining catalyst comprises a carrier and hydrogenation active metals, wherein the carrier is inorganic refractory oxide and is generally selected from one or more of alumina, amorphous silica-alumina, silica or titanium oxide, and the hydrogenation active metals comprise VIB and/or VIII metal components. In the hydrofining catalyst, the VIB group is preferably selected from tungsten and/or molybdenum, the content of the VIB group in the catalyst is 5% -30%, preferably 10% -20% based on the amount of an oxidized substance, the VIII group is preferably selected from nickel and/or cobalt, and the content of the VIB group in the catalyst is 1% -6%, preferably 1.5% -5% based on the amount of the oxidized substance. The content of the carrier in the catalyst is 64% -94%, preferably 75% -88.5% based on the amount of the oxidized substance.
According to the present invention, in step (2), the first hydrocracking catalyst comprises an active metal component and a support comprising a molecular sieve having selectively cracked normal paraffins, preferably one or more selected from the group consisting of ZSM-5 molecular sieve, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieves, preferably ZSM-5 molecular sieve. The molar ratio of SiO 2/Al2O3 of the ZSM-5 molecular sieve is 20-60. The carrier may also include a binder. Preferably, the binder is alumina. The active metal component comprises at least one of a group VIB metal, preferably molybdenum and/or tungsten, and a group VIII metal, preferably cobalt and/or nickel.
According to the present invention, in the step (2), preferably, the first hydrocracking catalyst has a content of group VIB metal (calculated as oxide) of 5.0% to 15.0%, a content of group VIII metal (calculated as oxide) of 2.0% to 5.0%, and a content of carrier of 80.0% to 93.0% based on the weight of the catalyst.
According to the present invention, in the step (2), preferably, in the carrier of the first hydrocracking catalyst, the content of the binder is 8% -60% and the content of the molecular sieve is 40% -92% based on the weight of the carrier.
According to the invention, in the step (2), the specific surface area of the first hydrocracking catalyst is 200-400 m 2/g, and the pore volume is 0.25-0.45 mL/g.
According to the present invention, the preparation method of the first hydrocracking catalyst in the step (2) may be prepared according to a conventional method in the art. The preparation method comprises the steps of preparing a carrier and loading active metal components, wherein the carrier is prepared by mechanically mixing a shape selective cracking molecular sieve and a binder, molding, drying and roasting. Conventional conditions may be used for drying and calcining the support. The drying condition is that the drying is carried out for 1-12 hours at 100-150 ℃. The roasting condition is that the roasting is carried out for 2.5-6.0 hours at 450-550 ℃.
According to the present invention, in the preparation method of the first hydrocracking catalyst in the step (2), the method of supporting the active metal component is a conventional method such as a kneading method, an impregnation method or the like, and the impregnation method is preferable. The impregnation method may be a saturated impregnation method, an excessive impregnation method or a complex impregnation method, i.e., impregnating the catalyst support with a solution containing the desired active component, followed by drying and calcination to obtain the first hydrocracking catalyst. The drying condition is that the drying is carried out for 1-12 hours at 100-150 ℃. The roasting condition is that the roasting is carried out for 2.5-6.0 hours at 450-550 ℃.
According to the present invention, the separation and fractionation of the second hydrocracking product of step (3) and the third hydrocracking product of step (4) preferably share a common separation and fractionation system.
According to the invention, in the step (3), the reaction conditions of the second hydrocracking reaction zone are as follows, wherein the reaction pressure is 6-10 MPa, preferably 7-9 MPa.
According to the invention, the reaction conditions of the second hydrocracking reaction in the step (3) are that the average reaction temperature is 250-450 ℃, preferably 300-400 ℃, the liquid hourly space velocity is 0.1-15.0 h -1, preferably 1.0-5.0 h -1, and the hydrogen-oil volume ratio is 100:1-2500:1, preferably 400:1-2000:1.
According to the present invention, it is preferred that the first hydrocracking reaction zone and the second hydrocracking reaction zone employ the same reaction pressure.
According to the invention, the second hydrocracking reaction zone in step (3) is charged with a second hydrocracking catalyst. The second hydrocracking catalyst may be one or more catalysts.
According to the invention, the third hydrocracking reaction zone in step (4) is charged with a third hydrocracking catalyst. The third hydrocracking catalyst may be one or more catalysts.
According to the present invention, the second hydrocracking catalyst in step (3) has the function of ring-opening cracking of polycyclic cyclic hydrocarbons.
According to the present invention, the third hydrocracking catalyst in step (4) has a function of selectively cracking side chains of the heterogeneous hydrocarbon or the cyclic hydrocarbon and retaining the monocyclic cyclic hydrocarbon.
According to the present invention, the second hydrocracking catalyst in step (3) and/or the third hydrocracking catalyst in step (4) comprises a cracking component, a hydrogenation component and a binder. The second hydrocracking catalyst and/or the third hydrocracking catalyst may be commercially available or prepared according to the prior art. The hydrogenation component is at least one of metal, metal oxide and metal sulfide of an active metal component, wherein the active metal component comprises VIB and/or VIII group metal, and the active metal component is more preferably at least one of iron, chromium, molybdenum, tungsten, cobalt and nickel. The binder is alumina and/or silica, and the cracking component comprises at least one of acidic molecular sieve, preferably Beta molecular sieve and Y molecular sieve.
According to the present invention, it is further preferred that the cracking component of the second hydrocracking catalyst in step (3) is a Y molecular sieve.
According to the present invention, it is further preferred that the third hydrocracking catalyst cracking component in step (4) is a Beta molecular sieve.
According to the invention, in the second hydrocracking catalyst in the step (3) and/or the third hydrocracking catalyst in the step (4), the content of the hydrogenation component in terms of oxide is 5wt% to 40wt%, preferably 10wt% to 30wt%, the content of the cracking component is 10wt% to 80wt%, preferably 20wt% to 60wt%, and the content of the binder is 5wt% to 85wt%, preferably 10wt% to 50wt%, based on the mass of the catalyst.
According to the present invention, the second hydrocracking catalyst in step (3) and/or the third hydrocracking catalyst in step (4) may be prepared according to a conventional method in the art. The preparation method comprises the steps of preparing a carrier and loading a hydrogenation component, wherein the carrier is prepared by mechanically mixing a cracking component and a binder, molding, drying and roasting. Conventional conditions may be used for drying and calcining the support. The drying condition is that the drying is carried out for 1-12 hours at 100-150 ℃. The roasting condition is that the roasting is carried out for 2.5-6.0 hours at 450-550 ℃.
According to the present invention, in the preparation method of the second hydrocracking catalyst in the step (3) and/or the third hydrocracking catalyst in the step (4), the method of supporting the hydrogenation component is a conventional method such as a kneading method, an impregnation method or the like, and the impregnation method is preferable. The impregnation method can be a saturated impregnation method, an excessive impregnation method or a complex impregnation method, namely, impregnating the catalyst carrier with a solution containing the required hydrogenation component, and then drying and roasting to obtain the hydrocracking catalyst. The drying condition is that the drying is carried out for 1-12 hours at 100-150 ℃. The roasting condition is that the roasting is carried out for 2.5-6.0 hours at 450-550 ℃.
According to the invention, in the third hydrocracking product of step (4), the ratio of the mass of the C 6～C8 monocyclic cyclic hydrocarbon to the total mass of the cyclic hydrocarbon in the light distillate feedstock is 0.35 to 0.55, preferably 0.44 to 0.50.
According to the invention, the reaction conditions of the third hydrocracking reaction zone in the step (4) are as follows, wherein the reaction pressure is 3-7 MPa, preferably 4-6 MPa.
According to the invention, the reaction conditions of the third hydrocracking reaction zone in the step (4) are that the average reaction temperature is 250-450 ℃, preferably 300-400 ℃, the liquid hourly space velocity is 0.1-15.0 h -1, preferably 1.0-5.0 h -1, and the hydrogen-oil volume ratio is 100:1-2500:1, preferably 400:1-2000:1.
Petroleum hydrocarbons have complex compositions and mainly comprise alkane, naphthene and arene, while high-quality ethylene raw materials are small-molecular normal alkane, and reforming raw materials are monocyclic naphthene and arene. The inventor finds that the diesel oil raw material sequentially passes through the shape selective cracking of linear alkane and the ring-opening cracking of polycyclic cyclic hydrocarbon, the selective hydrocracking of long side chains on heterogeneous hydrocarbon or cyclic hydrocarbon to keep monocyclic cyclic hydrocarbon as much as possible, and can generate micromolecular normal alkane with high selectivity, thereby realizing the efficient enrichment of micromolecular normal alkane in the low-carbon olefin raw material, and simultaneously keeping monocyclic cyclic hydrocarbon in heavy naphtha as much as possible, thereby realizing the efficient enrichment of high-quality reforming raw material, and thus realizing the aim of greatly improving the yield of chemical raw materials (namely the low-carbon olefin raw material and the reforming raw material) and the quality of the low-carbon olefin raw material and the reforming raw material.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) In the prior art, when the boiling bed diesel is used as a raw material for hydrocracking to produce chemical raw materials, the final distillation point of the boiling bed diesel obtained by fractionation of the boiling bed fraction is generally 350-380 ℃, so that the content of tricyclic aromatic hydrocarbon in the boiling bed diesel fraction is higher, the hydrocracking of the tricyclic aromatic hydrocarbon can be realized only by higher reaction pressure, and part of monocyclic aromatic hydrocarbon can be cracked by ring opening in the hydrocracking process by higher reaction pressure, thereby causing the loss of aromatic hydrocarbon. In the processing method of the vacuum residuum productive chemical raw materials, after the boiling bed distillate enters the fractionating tower, the content of tricyclic aromatic hydrocarbon in the top oil (light distillate) of the fractionating tower is controlled to be not higher than 1%, and proper reaction pressure is selected, so that the mixed processing of monocyclic aromatic hydrocarbon and bicyclic aromatic hydrocarbon is realized, the aromatic hydrocarbon loss of the raw materials in the hydrogenation process is reduced, and the aromatic hydrocarbon content in the hydrogenation product is improved. Specifically, the boiling bed hydrogenation light fraction oil and hydrogen enter a first hydrocracking reaction zone, mainly n-alkanes and long straight-chain cracking containing long straight-chain isoparaffins and naphthenes in the raw materials are selectively cracked to generate small molecular n-alkanes, the content of C 7 + n-alkanes in the first hydrocracking reaction effluent is 0.1% -5.0%, the first hydrocracking reaction effluent enters a second hydrocracking reaction zone, mainly polycyclic cyclic hydrocarbons are cracked in a ring opening way, single cyclic hydrocarbons are reserved, and side chains in the hydrocarbons are further subjected to chain scission to generate small molecular hydrocarbons, so that a large amount of chain alkanes in the raw materials can be converted into gas and light naphtha components, namely enriched in ethylene raw materials, the single cyclic hydrocarbons are reserved in heavy naphtha fractions, namely enriched in reforming raw materials, high-efficiency separation of the paraffins and the cyclic hydrocarbons can be realized through simple fractionation, and the quality of naphtha serving as catalytic reforming raw materials is improved while the high-quality ethylene cracking feeding is increased.
(2) The heavy naphtha obtained by the method has high content of monocyclic cyclic hydrocarbon, can be used as a catalytic reforming device for feeding, can cancel alkane cyclization and dehydrogenation units in the catalytic reforming device, can greatly reduce investment and energy consumption of the catalytic reforming device, and simultaneously can selectively realize side chain breaking reaction of the cyclic hydrocarbon with more than C 9 by following a positive carbon ion reaction mechanism in the hydrocracking reaction, so that the C 6～C8 cyclic hydrocarbon in the product has higher enrichment degree, and can greatly improve BTX yield after catalytic reforming and aromatic hydrocarbon extraction.
(3) The invention selectively converts the paraffin in the light distillate oil into the micromolecular paraffin, a certain amount of hydrogen is consumed in the process, but the light hydrocarbon is used as the raw material of the ethylene device, the hydrogen yield is high, the lower the carbon number is, the higher the hydrogen yield is, so that most of hydrogen consumed in the hydrogenation process can be recovered after the light hydrocarbon passes through the ethylene device, and meanwhile, the yield of ethylene, propylene and butadiene can be greatly improved, the gel cleaning period of the ethylene device is prolonged, and the economic benefit of the device is obviously improved.
Drawings
FIG. 1 is a schematic illustration of a process flow of the process of the present invention;
The main reference numerals illustrate:
1-heavy oil raw material, 2-hydrogen, 3-ebullated bed hydrogenation reaction zone, 4-ebullated bed hydrogenation reaction effluent, 5-separator, 6-gas phase stream, 7-liquid phase stream, 8-fractionating tower, 9-gas fraction, 10-light fraction oil, 11-wax oil, 12-tail oil, 13-hydrogen 14-first hydrocracking reaction zone, 15-first hydrocracking reaction effluent, 16-second hydrocracking reaction zone, 17-second hydrocracking reaction effluent, 18-separator, 19-gas phase stream hydrogen rich gas, 20-liquid phase stream, 21-fractionating tower, 22-gas fraction, 23-light naphtha, 24-heavy naphtha, 25-tail oil, 26-third hydrocracking reaction zone, 27-third hydrocracking reaction zone effluent.
Detailed Description
The operation and effect of the present invention will be further illustrated by the following examples, which are not to be construed as limiting the process of the present invention.
In the present invention, unless explicitly indicated otherwise, all percentages, parts, ratios, etc. referred to in this specification are by weight unless otherwise indicated, as such are not in accordance with the ordinary knowledge of one skilled in the art.
In the present invention, the total volume space velocity in both the examples and comparative examples is the ratio of fresh feed volume to total catalyst volume.
The method is shown in figure 1, and comprises the steps that heavy oil raw materials 1 and hydrogen 2 are mixed and enter a fluidized bed hydrogenation reaction zone 3, an obtained fluidized bed hydrogenation reaction effluent 4 enters a separator 5, a gas phase material flow 6 obtained through separation is recycled, a liquid phase material flow 7 enters a fractionating tower 8, gas fractions 9, light fraction oil 10, wax oil 11 and tail oil 12 are obtained through fractionation, the light fraction oil 10 and the hydrogen 13 are mixed and enter a first hydrocracking reaction zone 14 for hydrocracking reaction, a first hydrocracking reaction effluent 15 enters a second hydrocracking reaction zone 16, a second hydrocracking reaction effluent 17 enters a separator 18, a gas phase material flow hydrogen-rich gas 19 obtained through separation is recycled, a liquid phase material flow 20 enters a fractionating tower 21, gas fractions 22, light naphtha 23, heavy naphtha 24 and tail oil 25 are obtained through fractionation, the tail oil 25 and the hydrogen 13 are mixed and enter a third hydrocracking reaction zone 26, and the third hydrocracking reaction effluent 27 enters the separator 18 for separation and fractionation.
In the present invention, the first hydrocracking catalyst in each case is denoted by Cat-A plus a number, such as Cat-A1, cat-A2, cat-A3, cat-A4. The first hydrocracking catalyst was prepared by conventional active metal saturation impregnation, and the physicochemical properties of the obtained catalyst are shown in table 1.
In the present invention, the second hydrocracking catalyst in each case is shown as Cat-B, and the physical and chemical properties of the catalyst are shown in Table 2.
In the present invention, the third hydrocracking catalyst in each example is shown as Cat-C, and the physical and chemical properties of the catalyst are shown in Table 2.
In the present invention, the second hydrocracking catalyst and the third hydrocracking catalyst in each case are prepared by a conventional active metal saturation impregnation method.
Wherein, the Beta molecular sieve used in the catalyst Cat-C has the characteristics of SiO 2/Al2O3 mol ratio of 30, specific surface area of 350m 2/g and pore volume of 0.32cm 3/g. The Y molecular sieve used in catalyst Cat-B has the following properties of SiO 2/Al2O3 mol ratio of 15, specific surface area of 400m 2/g, pore volume of 0.30cm 3/g, and physicochemical properties of the obtained catalyst are shown in Table 2.
In the present invention, the raw oil in each example was a vacuum residue raw material, and the main properties thereof are shown in Table 3.
In the present invention, the nitrogen content of the reactant stream contacted with the first hydrocracking catalyst in step (2) in each example is 20mg/kg or less.
In the present invention, the ethylene raw material in each case refers to ethane, propane, butane and light naphtha obtained in the step (3), and the ethane, propane, butane and light naphtha can be directly used as raw materials for preparing ethylene by steam cracking.
In the invention, the distillation range of the light naphtha is liquid components with the temperature of less than 60 ℃, and the distillation range of the heavy naphtha is 60-175 ℃.
In the present invention, the yield of ethylene feedstock refers to the mass ratio of ethane, propane, butane and light naphtha in the hydrocracked product to the hydrocracked fresh feedstock (light distillate), and the yield of heavy naphtha refers to the mass ratio of heavy naphtha in the hydrocracked product to the hydrocracked fresh feedstock (light distillate).
Examples 1 to 4
The processing method of the vacuum residuum productive chemical raw materials adopts the flow as shown in figure 1, and comprises the following steps:
(1) Mixing vacuum residuum raw material with hydrogen, entering a fluidized bed hydrogenation reaction zone for hydro-thermal cracking reaction, entering a separator from an obtained fluidized bed hydrogenation reaction effluent, recycling a gas phase material flow obtained by separation, entering a fractionating tower from a liquid phase material flow, and fractionating to obtain gas fraction, light fraction oil, wax oil and tail oil;
(2) The light distillate oil and hydrogen are mixed and enter a first hydrocracking reaction zone, the first hydrocracking reaction zone is filled with a first hydrocracking catalyst, and the content of C 7 + normal paraffins in the effluent of the first hydrocracking reaction is controlled in the step (2).
(3) And (2) introducing the first hydrocracking reaction effluent obtained in the step (2) into a second hydrocracking reaction zone, filling a second hydrocracking catalyst in the second hydrocracking reaction zone, and reacting under the action of the catalyst to obtain a second hydrocracking catalyst. The hydrogen-rich gas obtained after the separation and fractionation of the second hydrocracking product is used as recycle hydrogen, and the liquid phase enters a fractionating tower to be fractionated to obtain gas, light naphtha, heavy naphtha and tail oil;
(4) And (3) introducing tail oil from the step (3) into a third hydrocracking reaction zone, wherein the third hydrocracking reaction zone is filled with a third hydrocracking catalyst, and the third hydrocracking reaction effluent and the second hydrocracking reaction effluent share a set of separation and fractionation system.
The process conditions and hydrogenation effects of each example are shown in Table 5.
Comparative example 1
The difference from example 1 is that the ebullated-bed light distillate oil is directly fed to the second hydrocracking reaction zone without first hydrocracking.
The process conditions and hydrogenation effects in this example are shown in Table 5.
Comparative example 2
The difference from example 1 is that the C 7 + normal alkane content in the first hydrocracking reaction effluent was controlled to be 6% in step (1).
The process conditions and hydrogenation effects in this example are shown in Table 5.
Comparative example 3
The difference from example 1 is that the catalysts of the second and third hydrocracking reaction zones are exchanged. Specifically, the second hydrocracking reaction zone is filled with a catalyst Cat-C, and the third hydrocracking reaction zone is filled with a catalyst Cat-B.
The process conditions and hydrogenation effects in this example are shown in Table 5.
Comparative example 4
The difference from example 1 is that the reaction pressure in the first hydrocracking reaction zone is the same as the reaction pressure in the third hydrocracking reaction zone.
The process conditions and hydrogenation effects in this example are shown in Table 5.
Comparative example 5
The difference from example 1 is that the mass content of the tricyclic aromatic hydrocarbon in the boiling bed light distillate is 3.5%.
The process conditions and hydrogenation effects in this example are shown in Table 5.
TABLE 1 physicochemical Properties of the first hydrocracking catalyst
| Catalyst | Cat-A1 | Cat-A2 | Cat-A3 | Cat-A4 |
| Pore volume, cm 3/g | 0.35 | 0.45 | 0.25 | 0.30 |
| Specific surface area, m 2/g | 300 | 200 | 400 | 350 |
| Content by weight percent based on the weight of the carrier | ||||
| ZSM-5 | 58 | 42 | 85 | 75 |
| Alumina oxide | 42 | 58 | 15 | 25 |
| Active metal content in the catalyst, wt% | ||||
| MoO3 | 10.0 | 15.0 | 5.0 | 12.5 |
| NiO | 3.5 | 2.0 | 5.0 | 4.0 |
| SiO 2/Al2O3 molar ratio of ZSM-5 | 40 | 60 | 20 | 50 |
TABLE 2 physicochemical Properties of the second hydrocracking catalyst and the third hydrocracking catalyst
| Catalyst Properties | Cat-C | Cat-B |
| Pore volume, cm 3/g | 0.35 | 0.35 |
| Specific surface area, m 2/g | 300 | 300 |
| Catalyst composition and content | ||
| Beta,wt% | 50 | - |
| Y,wt% | - | 30 |
| MoO3,wt% | 10 | 20 |
| NiO,wt% | 5 | 5 |
| Alumina, wt% | 35 | 45 |
TABLE 3 principal Properties of the feedstock
| Raw oil name | Vacuum residuum |
| Density (20 ℃ C.)/kg.m -3 | 1.032 |
| Distillation range/° C | |
| IBP/10% | 464/558 |
| 30%/50% | 606/646 |
| 70%/90% | 749/973 |
| 95%/EBP | 1025/1055 |
| Sulfur content, wt% | 5.61 |
| Nitrogen content, wt% | 0.38 |
| Ni+V,mg/kg | 200 |
TABLE 4 boiling bed hydrogenation process conditions and boiling bed light distillate main Properties
Continuous table 4
TABLE 5 hydrogenation effect
Continuous table 5
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
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| CN1352231A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Hydrogenating and pour point depressing catalyst and its preparing method |
| WO2006032989A1 (en) * | 2004-09-22 | 2006-03-30 | Indian Oil Corporation Limited | Hydrocracking process and catalyst composition |
| CN110938466A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Wax oil hydrocracking method |
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| CN101210198B (en) * | 2006-12-27 | 2012-03-21 | 中国石油化工股份有限公司 | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material |
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| CN1352231A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Hydrogenating and pour point depressing catalyst and its preparing method |
| WO2006032989A1 (en) * | 2004-09-22 | 2006-03-30 | Indian Oil Corporation Limited | Hydrocracking process and catalyst composition |
| CN110938466A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Wax oil hydrocracking method |
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