WO2012142723A1 - 一种渣油加氢处理和催化裂化组合方法 - Google Patents

一种渣油加氢处理和催化裂化组合方法 Download PDF

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Publication number
WO2012142723A1
WO2012142723A1 PCT/CN2011/000683 CN2011000683W WO2012142723A1 WO 2012142723 A1 WO2012142723 A1 WO 2012142723A1 CN 2011000683 W CN2011000683 W CN 2011000683W WO 2012142723 A1 WO2012142723 A1 WO 2012142723A1
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Prior art keywords
catalytic cracking
residue
hydrogenation
oil
hydrotreating
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PCT/CN2011/000683
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English (en)
French (fr)
Inventor
关明华
刘铁斌
耿新国
张学萍
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Priority to PCT/CN2011/000683 priority Critical patent/WO2012142723A1/zh
Publication of WO2012142723A1 publication Critical patent/WO2012142723A1/zh
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • 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
    • C10G2300/42—Hydrogen of special source or of special composition
    • 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
    • C10G2400/02—Gasoline

Definitions

  • the invention relates to a method for purifying a residue, in particular to a method for organically combining residue hydrotreating and catalytic cracking, and mainly producing gasoline products using residual oil as a raw material.
  • the processing of heavy and residual oil is not only to crack it into low-boiling products, such as naphtha, intermediate oil and vacuum gas oil, but also to increase their hydrogen-to-carbon ratio. Carbon or hydrogenation methods are used to achieve this.
  • the decarburization process includes coking, solvent deasphalting, heavy oil catalytic cracking, etc.; hydrogenation includes hydrocracking, hydrorefining, and the like.
  • the hydrogenation process can hydrogenate the residue to improve the yield of the liquid product, and can also remove the hetero atoms therein, and the product quality is good.
  • the hydrogenation process is a catalytic process, and there is a problem of deactivation of the hydrogenation catalyst.
  • the residual oil cracking rate of the residue hydrotreating technology is low, and the main purpose is to provide raw materials for downstream raw material lightening equipment such as catalytic cracking or coking.
  • the content of impurities such as sulfur, nitrogen, metal and the residual carbon in the inferior residue are significantly reduced, thereby obtaining a feed acceptable to the downstream lightening device, especially the catalytic cracking device, so the current heavy and slag
  • the combined technology of residual oil hydrotreating and catalytic cracking of residual oil is the mainstream technology.
  • the existing residue hydrotreating and catalytic cracking combined process firstly hydrotreats the residue, hydrolyzes the oil to separate the naphtha and the diesel fraction, and the hydrogenated tail oil acts as a heavy oil catalytic cracking feed for catalytic cracking.
  • the reaction is a dry gas, a liquefied gas, a gasoline, a diesel oil and a coke, a reductive oil is subjected to catalytic refining or a recirculating oil refining device is mixed with a residue hydrotreating raw material for hydrotreating, and the catalytic oil slurry is externally or partially Catalytic refining or recycling back to residual oil Hydrogenation unit.
  • the combination process of the above-mentioned residue hydrotreating and catalytic cracking has disadvantages such as low gasoline yield, large heat energy loss, and high equipment investment.
  • No. 4,713,221 discloses the recycling of catalytically cracked heavy cycle oil to a residue hydrotreating unit on the basis of a combination of conventional residue hydrogenation and catalytic cracking, mixing with the residue, hydrogenation, and then entering the catalytic cracking unit.
  • the catalytic cracking slurry has not been effectively utilized, and the method has a limited yield for reducing coke yield and increasing product yield.
  • CN1119397C discloses a residue hydrotreating-catalytic cracking combined process, in which a residue and a clarified oil are fed together into a residue hydrogenation unit, and reacted in the presence of hydrogen and a hydrogenation catalyst, and the heavy cycle oil is catalyzed.
  • the inside of the cracking unit is circulated; the oil slurry obtained by the reaction is separated by a separator to obtain a clarified oil, and is returned to the hydrogenation unit.
  • the slurry enters the residue hydrotreating unit, and the cokes in the slurry will increase the carbon deposition of the hydrogenation catalyst, reduce the hydrogenation activity and operation cycle of the hydrogenation catalyst, and the heavy cycle oil is in the catalytic cracking. Inside the device. Therefore, this method is limited in reducing coke yield and improving product quality.
  • CN1382776A discloses a combined method of residue hydrotreating and heavy oil catalytic cracking, which comprises hydrogenating a residue in a hydrotreating unit, separating the reaction product to obtain a gas, hydrogenating naphtha, hydrogenated diesel and adding Hydrogen residue.
  • the resulting hydrocracked oil enters a catalytic cracking unit for cracking reaction together with an optional vacuum gas oil, and the catalytically cracked heavy cycle oil is returned to the hydrotreating unit, and the distillate obtained by distilling the slurry is returned to the hydrotreating unit.
  • the method organically combines two units to convert residual oil, heavy cycle oil and slurry into light oil.
  • the method has a fractionation system in both the hydrotreating and the catalytic cracking process, which increases the investment cost; the heat energy loss is more due to the process heat exchange; meanwhile, the hydrotreating device and the catalytic cracking device have diesel products, relatively speaking, , the total yield of gasoline and gas products will be reduced.
  • the residual oil cracking rate of the residue hydrotreating unit is low, and the yield of naphtha and diesel oil obtained by fractionating the hydrogenated oil is limited, and the diesel fraction obtained by the hydrotreating process of the residue still cannot satisfy the high quality.
  • Catalytic cracking diesel sulfur and other impurities are high in content and poor in nature, and further hydrotreating is required to be a qualified diesel product.
  • the present invention provides a residue hydrotreating and catalytic cracking
  • the combined method can produce gasoline products in the largest amount, and the process is simple and the overall energy consumption is reduced.
  • the combination method of the residue hydrotreating and catalytic cracking of the present invention comprises: the residue raw material is subjected to hydrogenation reaction in the presence of hydrogen and a hydrotreating catalyst, and the hydrogenation reaction effluent is gas-liquid separated to obtain a gas phase and a liquid phase, and the gas phase cycle is used for In the hydrogenation reaction, the liquid phase directly enters the catalytic cracking unit without fractionation, and the catalytic cracking heavy fraction after the catalytic cracking reaction effluent separates the dry gas, the liquefied gas and the catalytic cracked gasoline is mixed with the residue raw material for hydrogenation reaction.
  • the residue raw material comprises atmospheric residue or vacuum residue, and may also be a residue raw material of other sources, and the residue raw material may also contain partial coking wax oil, deasphalted oil, heavy distillate oil.
  • the hydrogenation reaction effluent is first subjected to gas-liquid separation, and the gas-liquid separation is carried out under the same conditions as the reaction pressure level to obtain a gas phase and a liquid phase, the gas phase is mainly hydrogen gas, and is subjected to selective dehydrogenation treatment and then recycled.
  • the hydrogenation reaction process needs to be supplemented with new hydrogen to supplement the consumption of the reaction process.
  • the pressure separator controls the pressure of the low pressure separator at the pressure of the catalytic cracking unit and then directly enters the catalytic cracking unit, and the equipment such as the feed pump of the catalytic cracking unit can be eliminated.
  • the low pressure separator can flash a small amount of light hydrocarbons and dissolve. Hydrogen sulfide, hydrogen, etc.
  • the gas-liquid separation of the present invention employs conventional separation means, and includes, for example, the use of a conventional gas-liquid separation tank, a hydrocyclone, and the like. However, it does not include a fractionation unit, which greatly reduces equipment investment and reduces energy consumption.
  • the residue hydrogenation technology can be any technology suitable for the present invention, such as fixed bed residue hydrotreating technology, suspended bed residue hydrotreating technology, fluidized bed residue hydrotreating technology, moving bed residue hydrotreating Technology, etc.
  • the residual hydrotreating catalyst used has the functions of hydrodemetallization, hydrodesulfurization, hydrodenitrogenation and hydrocracking of residual oil. Single catalyst or combined catalyst. These catalysts are generally supported by a porous refractory inorganic oxide such as alumina, and an oxide of Group VIB and/or Group VIII metals such as W, Mo, Co, Ni, etc. as an active component, optionally added to each other.
  • the sulfur catalyst and the hydrodenitrogenation catalyst are generally loaded in such a manner that the feedstock oil is sequentially contacted with a protective agent, a hydrodemetallization, a hydrodesulfurization, and a hydrodenitrogenation catalyst.
  • a protective agent e.g., a hydrodemetallization, a hydrodesulfurization, and a hydrodenitrogenation catalyst.
  • Hydrotreating generally requires multiple reactors to increase throughput. It is usually operated at an absolute pressure of from about 5 MPa to about 35 MPa, preferably from about 10 MPa to about 20 MPa, at a temperature of from about 300 ° C to about 500 ° C, preferably from about 350 ° C to about 450 ° C.
  • the liquid hour volumetric space velocity and hydrogen partial pressure are selected according to the characteristics of the material to be treated and the required conversion rate and depth of refining.
  • the volumetric space velocity of the fresh residue raw material liquid is generally in the range of about 0.1 h - about 5.01 T 1 , preferably about 0.15 h - about S. Oh, and the total hydrogen oil volume ratio is from about 100 to about 5,000, preferably About 300 - about 3000.
  • the invention is suitable for hydrocracking of atmospheric and vacuum residue, and is especially suitable for hydroconversion of heavy hydrocarbon oil.
  • the specific conditions of the residue hydrotreating process can be specifically determined based on the nature of the feedstock and the requirements of the feed to the catalytic cracking unit.
  • catalytic cracking can employ conventional techniques in the art.
  • the catalytic cracking unit may be one or more than one set, and each unit shall include at least one reactor and one regenerator.
  • the catalytic cracking reaction effluent can be separated into dry gas, liquefied gas, catalytically cracked gasoline, and catalytically cracked heavy ends using conventional techniques in the art.
  • the catalytic cracking unit may be provided with a fractionator, which may be set separately or shared for each set of catalytic cracking units.
  • the catalytic cracking fractionation column fractionates the catalytic cracking reaction effluent into dry gas, liquefied gas, catalytically cracked gasoline, and catalytically cracked heavy ends.
  • the catalytic cracking fractionation column used in the present invention can be simply designed in comparison with a conventional catalytic cracking fractionation tower, and only fractionated dry gas, liquefied gas and catalytically cracked gasoline, and the catalytic cracking heavy fraction is divided into an initial boiling point of 170 - 220 °C.
  • the fractions include catalytic cracking diesel, catalytic cracking heavy cycle oil and slurry.
  • the catalytic cracking heavy fraction is filtered to remove the trace catalytic cracking catalyst powder before being recycled to the hydrotreating unit.
  • the catalytic cracking unit is operated under the general conditions of the art: a reaction temperature of from about 450 to about 600 ° C, preferably from about 480 to about 550 ° C; a regeneration temperature of from about 600 to about 800 ° C, preferably from about 650 to about At 750 ° C, the weight ratio of the extender oil is from about 2 to about 30, preferably from about 4 to about 10; the contact time with the catalyst is from about 0.1 to about 15 seconds, preferably from about 0.5 to about 5 seconds; and the pressure is about 0.1. ⁇ about 0.5MPa.
  • the catalytic cracking catalysts used include catalysts commonly used for catalytic cracking, such as silica-alumina catalysts, silico-magnesium catalysts, acid-treated clays, and molecular sieve cracking catalysts such as X-type, Y-type, ZSM-5, M-type, and pillar columns. It is a molecularly cleavable catalyst', because the molecular cleavage catalyst has high activity, less coke formation, high gasoline yield and high conversion rate.
  • Catalytic cracking unit The reactor may be of various types of catalytic cracking reactors, preferably riser reactors or riser extra bed reactors.
  • the process flow is generally as follows:
  • the feedstock oil is injected from the bottom of the riser reactor, and is contacted with a high-temperature regenerated catalyst from the regenerator, and the catalyst mixture formed by the cracking reaction and the coke-deposited catalyst moves upward along the riser reactor to complete the catalysis of the whole feedstock oil.
  • Cracking reaction Material ⁇ and production ⁇ .
  • Quality indicators are obtained through simple experiments. P , , , and the advantages of the present invention are:
  • the hydrotreating unit does not have a fractionation system
  • the hydrogenated oil directly enters the catalytic cracking reactor, and the catalytic cracking produces oil.
  • the remaining mixed oil is filtered and recycled to the hydrogenation unit. Both processes greatly reduce heat loss and achieve hot feed, which reduces energy consumption throughout the process.
  • the main products are high-octane catalytic cracking gasoline, liquefied petroleum gas and a small amount of dry gas, so as to ensure the maximum production of gasoline.
  • the gasoline obtained by the present invention has a high octane number and a marked improvement in quality.
  • the catalytic cracking of diesel fuel obtained by the prior scheme has a high content of aromatic hydrocarbons, a low cetane number, a high content of impurities such as sulfur, and poor properties, and further hydrotreating is required as a qualified diesel product.
  • the separation system of the catalytic cracking reaction effluent of the present invention does not carry out the separation of the catalytically cracked diesel fraction, eliminating the need for repeated processing steps.
  • the catalytic cracking fractionation column of the present invention can be greatly simplified, reducing equipment investment and operating energy consumption.
  • the catalytic cracking reaction effluent does not separate the catalytic cracking oil slurry, and solves the problem that the oil slurry is difficult to separate the catalyst solid powder due to the large viscosity.
  • the catalytic cracking heavy distillate contains a diesel fraction. Due to the dilution effect of the diesel split, the viscosity of the catalytic cracking slurry is greatly reduced, making the catalyst solid powder filtration easier.
  • the utilization rate is low, and the method of the invention does not separate the catalytic cracking slurry, and does not generate an efflux portion, thereby improving the utilization rate of the raw materials and the intended production. The yield of the product.
  • the catalytic cracking heavy fraction dilutes the fresh residue raw material, improves the oil properties, reduces the difficulty of hydrogenation reaction and the processing severity of the residue hydrotreating mixed feed; in addition, the catalytic cracking heavy fraction can be reduced
  • the viscosity of the raw materials improve the distribution of the raw materials in the reaction system and the transmission shield, reduce the influence of diffusion in the hydrotreating process of the residue, improve the deposition distribution of harmful metals such as nickel and vanadium in the catalytic reaction system, and prolong the catalyst. Service life; At the same time, the reduction in viscosity makes it easier to transport and filter the mixed feedstock.
  • the catalytic cracking diesel oil fraction and the above heavy fraction can remove impurities during the residue hydrogenation process, and the aromatic hydrocarbons are saturated, which becomes a better catalyzed, chemically cracked raw material composition, further improving the yield of high value-added products of catalytic cracking, The low value coke yield is significantly reduced.
  • FIG. 1 is a schematic view showing the process flow of a combined method of residue hydrotreating and catalytic cracking according to the present invention. detailed description
  • the residue raw material 1 and the filtered catalytically cracked heavy fraction 17 are mixed, and after being pressurized, mixed with the circulating hydrogen 2 to enter the hydrotreating reactor 3, and the metal and sulfur in the raw material oil are removed by contact with the hydrotreating catalyst bed. Impurities such as nitrogen, while reducing the residual carbon of the raw materials to meet the feed requirements of the downstream catalytic cracking unit.
  • Hydrogenation reactor 3 The outlet reaction effluent 4 enters the high pressure separator 5 for gas-liquid separation, and the separated gas phase stream is subjected to dehydrogenation treatment or the like, and then the compressor 8 is pressurized and recycled to the inlet of the hydrotreating reactor 3.
  • the supplemented new hydrogen can also be introduced after the recycle compressor 8, and the separated liquid phase stream is further separated into the helium separator 6, and the separated liquid phase stream is not subjected to heat exchange and fractionation to adjust the pressure of the low pressure separator.
  • the liquid phase stream is passed through line 7 to reaction system 9 of the catalytic cracking unit without the use of a feed pump.
  • the hydrogenated oil from line 7 enters the reaction system 9 of the catalytic cracking unit, contacts and reacts with the high temperature regenerated catalytic cracking catalyst, and the reacted oil and gas stream 10 enters the fractionation column 13 of the catalytic unit to separate the gas 11 and catalytic cracking.
  • Gasoline 12, gas 11 and catalytic cracking gasoline 12 discharge device, and the remaining catalytic cracking heavy fraction 14 of the fractionation column enters the separator 15.
  • the catalyst powder, impurities and solid particles 16 are filtered off, and the filtered catalytically cracked heavy fraction 17 is recycled to the hydrotreating unit.
  • the reaction is carried out on a small riser tubular catalytic cracking unit and a pilot residue oil hydrotreating unit.
  • the feedstock oil used in the examples and comparative examples was a normal crude oil of Saudi medium crude oil, the properties of which are shown in Table 1.
  • the type and volume of the residue hydrotreating catalyst used in the examples and the comparative examples are identical, and both are CEN, FZC, ZTN, ZTS series residue hydrogenation catalysts produced by the Catalyst Branch of China Petroleum & Chemical Corporation, including Protecting agent, demetallization catalyst, desulfurization catalyst, denitrification catalyst, etc., the filling sequence is generally to make the raw material oil in contact with the protective agent, hydrodemetallization, hydrodesulfurization, hydrodenitrogenation catalyst, of course, there are also these catalysts Hybrid loading technology.
  • the above catalyst loading technique is well known to those skilled in the art.
  • the catalytic cracking catalysts used in the examples and the comparative examples were the same as those used in the Dalian Petrochemical Company's 3.5 million tons/year heavy oil catalytic cracking unit, and were industrial equilibrium catalysts.
  • the composition of the freshener is: 95wt% LBO-16 hydroquinone catalyst + 5wt% LBO-A to increase the octane auxiliary.
  • This comparative example employs a conventional residue hydrotreating-catalytic cracking method in which a residue is subjected to a hydrogenation reaction in a hydrogenation treatment apparatus to separate a reaction product to obtain a gas, a hydrogenated naphtha, a hydrogenated diesel oil, and a hydrogenated residue.
  • the obtained hydrocracking oil enters a catalytic cracking unit for cracking reaction, and the catalytic cracking heavy-cycle oil is circulated in the catalytic cracking unit.
  • Table 2, Table 3 and Table 4 are the process conditions, product distribution and main product properties.
  • This embodiment adopts the combination method of residue hydrotreating and catalytic cracking provided by the invention, and all the liquid phase products of the hydrotreating process are directly into the catalytic cracking unit without fractionation, and the catalytic cracking reaction effluent fractionation system is simplified, and only the dry gas is fractionated.
  • the liquefied gas and the gasoline fraction, and the remaining catalytically cracked heavy fractions are filtered to the solid impurities and recycled to the hydrotreating unit for further processing.
  • Table 2, Table 3, and Table 5 are the process conditions, product distribution, and main product properties.

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Description

一种渣油加氢处理和催化裂化组合方法 技术领域
本发明涉及一种渣油轾质化方法， 具体地说是将渣油加氢处理和 催化裂化有机组合， 以渣油为原料主要生产汽油产品的工艺方法。 背景技术
随着原油日益变重、 变劣， 越来越多的渣油需要加工处理。 重、 渣油的加工处理不但是要将其裂化为低沸点的产物， 如石脑油、 中间 镏分油及减压瓦斯油等， 而且还要提高它们的氢碳比， 这就需要通过 脱碳或加氢的方法来实现。 其中脱碳工艺包括焦化、 溶剂脱沥青、 重 油催化裂化等； 加氢包括加氢裂化、 加氢精制等。 加氢法即能加氢转 化渣油， 提高液体产品的产率， 而且还能脱除其中的杂原子， 产品质 量还好。 但加氢法为催化加工工艺， 存在加氢催化剂失活问题， 尤其 加工劣质、 重盾烃类原料时， 催化剂失活问题更加严重。 目前， 为了 降低重质、 劣质渣油加工的成本， 增加炼油企业利润， 加工重质、 劣 质渣油妁工艺仍以脱碳工艺为主， 但其产品质量差， 需要进行后处理 才能利用， 其中脱沥青油和焦化蜡油馏分尤其需要进行加氢处理， 才 能继续使用催化裂化或加氢裂化等轻质化装置进行加工， 因此， 各炼 油企业均另建有脱沥青油和焦化蜡油的加氢处理装置。
渣油加氢处理技术的渣油裂化率较低， 主要目的是为下游原料轻 质化装置如催化裂化或焦化等装置提供原料。 通过加氢处理， 使劣质 渣油中的硫、 氮、 金属等杂质含量及残炭值明显降低， 从而获得下游 轻质化装置能够接受的进料， 尤其是催化裂化装置， 因此目前重、 渣 油加氢改质工艺技术中以渣油固定床加氢处理与催化裂化组合技术为 主流技术。
现有的渣油加氢处理与催化裂化组合工艺， 首先是将渣油进行加 氢处理， 加氢生成油分离出石脑油和柴油馏分， 加氢尾油作为重油催 化裂化进料， 进行催化裂化反应， 产物为干气、 液化气、 汽油、 柴油 和焦炭， 回炼油进行催化回炼或循环回渣油加氢装置与渣油加氢处理 原料混合进行加氢处理， 催化油浆外甩或部分催化回炼或循环回渣油 加氢装置。 上述渣油加氢处理与催化裂化组合工艺存在汽油收率低， 热能损耗大， 设备投资高等不利因素。
US4,713,221公开了在常规的渣油加氢和催化裂化联合的基础上， 将催化裂化的重循环油循环至渣油加氢装置， 与渣油混合后进行加氢， 再进入催化裂化装置。 但是催化裂化油浆没有得到有效利用， 该方法 对降低焦炭产率、 提高产品收率有限。
CN1119397C公开了一种渣油加氢处理 -催化裂化组合工艺方法， 该方法中， 渣油和澄清油一起进入渣油加氢装置， 在氢气和加氢催化 剂存在下进行反应， 重循环油在催化裂化装置内部进行循环； 反应所 得的油浆经分离器分离得到澄清油， 返回至加氢装置。 但油浆进入渣 油加氢处理装置， 油浆中的易生焦物将会增加加氢催化剂的积炭， 降 低了加氢催化剂的加氢活性和操作周期， 且重循环油是在催化裂化装 置内部。 因此， 此方法对降低焦炭产率、 提高产品质量是有限的。
CN1382776A公开了一种渣油加氢处理与重油催化裂化联合的方 法， 该方法将渣油在加氢处理装置进行加氢反应， 分离反应产物得到 气体， 加氢石脑油、 加氢柴油和加氢渣油。 所得的加氢渣油与任选的 减压瓦斯油一起进入催化裂化装置进行裂化反应 , 催化裂化的重循环 油返回加氢处理装置， 蒸馏油浆得到的蒸出物返回加氢处理装置。 该 方法将两个装置有机地联合起来， 能将渣油、 重循环油和油浆转化为 轻质油品。 但该方法在加氢处理和催化裂化过程中均设置分馏系统， 增加了投资费用； 由于过程换热， 热能损失较多； 同时， 加氢处理装 置和催化裂化装置都有柴油产品， 相对而言， 汽油和气体产品的总收 率将减少。 另外， 渣油加氢处理装置的渣油裂化率较低， 加氢生成油 进行分馏得到的石脑油、 柴油产率有限， 并且， 渣油加氢处理过程得 到的柴油馏分仍不能满足高质量柴油产品的要求。 催化裂化柴油硫等 杂质含量较高， 性质较差， 还需要进一步加氢处理才可作为合格的柴 油产品。
渣油加氢处理和催化裂化组合工艺中， 分馏装置的能耗占较大的 比例， 如何减少分馏装置的能耗也是需要重点考虑的内容。 发明内容
针对现有技术的不足， 本发明提供一种渣油加氢处理和催化裂化 组合方法， 可以最大量生产汽油产品， 同时工艺过程简单， 整体能耗 降低。
本发明渣油加氢处理和催化裂化组合方法包括： 渣油原料在氢气 和加氢处理催化剂存在下进行加氢反应， 加氢反应流出物经气液分离 得到气相和液相， 气相循环用于加氢反应， 液相不经分馏直接进入催 化裂化装置， 催化裂化反应流出物分离出干气、 液化气和催化裂化汽 油后的催化裂化重馏分与渣油原料混合进行加氢反应。
本发明方法中， 渣油原料包括常压渣油或减压渣油， 也可以是其 它来源的渣油原料， 渣油原料中也可以同时含有部分焦化蜡油、 脱沥 青油、 重质馏分油中的一种或者几中。 加氢反应流出物首先进行气液 分离， 该气液分离在与反应压力等级相同的条件下进行， 得到气相和 液相， 所述气相主要为氢气， 经过可选择的脱硫化氢处理后循环用于 加氢反应， 加氢反应过程同时需要补充新氢以补充反应过程的消耗。 压分离器， 控制低压分离器的压力 于催化裂化装置压力， 然后直接 进入催化裂化装置， 可以取消催化裂化装置的进料泵等设备， 低压分 离器可以闪蒸出少量轻质烃类和溶解的硫化氢及氢气等。
本发明的气液分离采用常规分离手段， 例如包括采用普通气液分 离罐、 旋液分离器等。 但不包括分馏装置， 从而大大减少设备投资并 降低大量能耗。
渣油加氢技术可以是任何适用于本发明的技术， 如固定床渣油加 氢处理技术、 悬浮床渣油加氢处理技术、 沸腾床渣油加氢处理技术、 移动床渣油加氢处理技术等。 以目前工业上较成熟的固定床渣油加氢 处理技术为例， 采用的渣油加氢处理催化剂是指具有渣油加氢脱金属、 加氢脱硫、 加氢脱氮和加氢裂化等功能的单一催化剂或组合催化剂。 这些催化剂一般都是以多孔耐熔无机氧化物如氧化铝为载体， 第 VIB 族和 /或 VIII族金属如 W、 Mo、 Co、 Ni等的氧化物为活性组分， 选择 性地加入其它各种助剂如 P、 Si、 F、 B等元素的催化剂， 例如由中国 石油化工股份有限公司催化剂分公司生产的 CEN、 FZC、 ZTN、 ZTS 系列渣油加氢催化剂， 由齐鲁石化公司第一化肥厂生产的 ZTN、 ZTS 系列催化剂就属于这类催化剂。 目前在固定床渣油加氢技术中， 经常 是多种催化剂配套使用， 其中有保护剂、 加氢脱金属催化剂、 加氢脱 硫催化剂、 加氢脱氮催化剂， 装填顺序一般是使原料油依次与保护剂、 加氢脱金属、 加氢脱硫、 加氢脱氮催化剂接触。 当然也有将这几种催 化剂混合装填的技术。 加氢处理一般设置多个反应器， 以提高加工量。 通常是在绝对压力为大约 5MPa -大约 35MPa，优选是大约 lOMPa -大 约 20MPa、 温度为大约 300 °C -大约 500 °C， 优选是大约 350°C -大约 450 °C下操作。 液时体积空速和氢分压是根据待处理物料的特性和要求 的转化率及精制深度进行选择的。 新鲜渣油原料液时体积空速一般在 大约 O. lh -大约 5.01T1 , 最好是大约 0.15h -大约 S.Oh 的范围内， 总氢油体积比为大约 100 -大约 5000 , 优选为大约 300 -大约 3000。 本发明适用于常压和减压渣油加氢处理， 尤其适用于重质烃类油的加 氢转化。 渣油加氢处理过程的具体条件可以根据原料的性质以及催化 裂化装置进料的要求具体确定。
本发明方法中， 催化裂化可以采用本领域常规技术。 催化裂化装 置可以是一套或一套以上， 每套装置至少应包括一个反应器、 一个再 生器。 催化裂化反应流出物可以采用本领域常规技术分离为干气、 液 化气、 催化裂化汽油和催化裂化重馏分。 例如， 催化裂化装置设置分 馏塔， 可以每套催化裂化装置分别设定， 也可以共用。 催化裂化分馏 塔将催化裂化反应流出物分馏为干气、 液化气、 催化裂化汽油和催化 裂化重馏分。 本发明所用的催化裂化分馏塔与常规催化裂化分馏塔相 比可以简 设计， 仅分馏出干气、 液化气和催化裂化汽油， 所述催化 裂化重馏分为初馏点在 170 - 220 °C的馏分， 包括催化裂化柴油、 催化 裂化重循环油和油浆。 所述催化裂化重馏分循环回加氢处理装置之前 先过滤出含有的微量催化裂化催化剂粉末。
催化裂化装置按本领域一般条件操作：反应温度为大约 450 ~大约 600 °C , 最好是大约 480 -大约 550°C ; 再生温度为大约 600 -大约 800 °C , 最好为大约 650 -大约 750°C , 剂油重量比为大约 2 ~大约 30， 最 好是大约 4 ~大约 10; 与催化剂接触时间为大约 0.1 ~大约 15秒， 最 好为大约 0.5 ~大约 5秒； 压力为大约 0.1 ~大约 0.5MPa。 所采用的催 化裂化催化剂包括通常用于催化裂化的催化剂， 如硅铝催化剂、 硅镁 催化剂、 酸处理的白土及 X型、 Y型、 ZSM - 5、 M型、 层柱等分子筛 裂化催化剂， 最好是分子歸裂化催化剂'， 这是因为分子歸裂化催化剂 的活性高， 生焦少， 汽油产率高， 转化率高。 所述的催化裂化装置的 反应器可以是各种型式的催化裂化反应器， 最好是提升管反应器或提 升管加床层反应器。 工艺流程一般为： 原料油从提升管反应器底部注 入， 与来自再生器的高温再生催化剂接触， 裂化反应生成的油气和沉 积焦炭的催化剂混合物沿提升管反应器向上移动， 完成整个原料油的 催化裂化反应。 料性 ^和产 ί。质量指标通过简单实验获得。 P 、 、 、 本发明的优点在于：
1、 从整个组合工艺来看， 加氢处理装置中不需设分馏系统， 大大 减少了分馏过程所需的能量。 加氢处理生成油直接进入催化裂化反应 器， 催化裂化系统不需设进料泵， 同时减少了大量换热设备。 催化裂 化反应流出物的分离系统仅分馏出汽油馏分等轻质产品， 分馏塔所需 的理论分离塔板数大大降低。 以上几个方面可以减少大量的动设备和 静设备， 使设备投资有了很大的降低。
2、 由于加氢处理装置不设分馏系统， 加氢生成油直接进入催化裂 化反应器， 催化裂化生成油在分离出气体产品和催化汽油后， 剩余混 合油经过滤后循环回加氢装置， 上述两个过程大大降低了热量的损失， 实现热进料， 从而降低了整个工艺过程的能耗。
3、 在整个组合工艺中， 主要产品是高辛烷值催化裂化汽油、 液化 石油气和少量干气， 从而可以保证最大量地生产汽油。 而且本发明获 得的汽油辛烷值高， 品质得到显著改善。 现有方案得到的催化裂化柴 油芳烃含量高， 十六烷值低， 硫等杂质含量高， 性质差， 还需要进一 步加氢处理才可作为合格的柴油产品。 本发明中催化裂化反应流出物 的分离系统不进行催化裂化柴油馏分的分离， 省去重复加工步骤。 同 时.， 在使用分馏塔的情况下， 本发明的催化裂化分馏塔可以大大简化， 降低设备投资和操作能耗。
4、 催化裂化反应流出物不分离出催化裂化油浆， 解决了油浆因粘 度大不易分离出催化剂固体粉末的问题。 催化裂化重馏分油中含有柴 油馏分， 由于柴油镏分的稀释作用， 催化裂化油浆粘度大幅降低， 使 得其中的催化剂固体粉末过滤更加容易。 在常规催化裂化油浆分离时， 虽然可以通过澄清而部分利用， 但利用率较低， 本发明方法由于不分 离出催化裂化油浆， 不产生外排部分， 提高了原料的利用率和目的产 品的收率。
5、 催化裂化重馏分对新鲜渣油原料起到稀释作用， 油品性质得到 改善， 降低了渣油加氢处理混合进料的加氢反应难度和加工苛刻度； 另外， 催化裂化重馏分可降低原料的粘度， 改善原料在反应系统中的 物流分布以及传盾， 减小扩散在渣油加氢处理过程中的影响， 改善镍、 钒等有害金属在催化反应系统中的沉积分布， 延长催化剂的使用寿命； 同时 , 粘度的降低使混合原料油的输送和过滤更加容易。
6、 催化裂化柴油馏分及以上重馏分可在渣油加氢工艺过程中脱除 杂质， 芳烃饱和， 成为更好的催,化裂化原料组成， 进一步提高了催化 裂化高附加值产品收率， 同时低价值的焦炭产率明显降低。 附图说明
图 1是本发明渣油加氢处理和催化裂化组合方法工艺流程示意图。 具体实施方式
下面结合附图对本发明所提供的方法进行进一步的说明， 但不因 此而限制本发明。
工艺流程详细描述如下：
渣油原料 1和过滤后的催化裂化重馏分 17混合， 升压后与循环氢 2混合进入加氢处理反应器 3 , 通过与加氢处理催化剂床层接触， 脱除 原料油中的金属、 硫、 氮等杂质， 同时降低原料的残炭来满足下游催 化裂化装置的进料要求。 加氢处理反应器 3 出口反应流出物 4进入高 压分离器 5 进行气液分离， 分离出的气相物流进行脱硫化氢等处理后 进循环压缩机 8升压后循环到加氢处理反应器 3的入口， 补充的新氢 也可以在循环压缩机 8之后引入，分离出的液相物流再到氐压分离器 6 进一步分离， 分离出的液相物流不经换热和分馏， 调整低压分离器的 压力， 使液相物流在不使用原料泵的情况下通过管线 7 进入催化裂化 装置的反应系统 9。
来自管线 7的加氢生成油进入催化裂化装置的反应系统 9 ,与高温 再生催化裂化催化剂接触并进行反应， 反应后的油气物流 10进入催化 装置的分馏塔 13 , 分离出气体 1 1和催化裂化汽油 12 , 气体 11和催化 裂化汽油 12排出装置， 分馏塔剩余的催化裂化重馏分 14进入分离器 15 , 过滤出催化剂粉末、 杂质及固体颗粒 16， 过滤后的催化裂化重馏 分 17循环到加氢处理装置。
下面的实施例将对本发明提供的方法进一步说明， 但并不因此而 限制本发明。 反应是在小型提升管式催化裂化装置和中试渣油加氢处 理装置上进行。 实施例和对比例中所用的原料油为沙特中质原油的常 压渣油， 其性质列于表 1。 实施例和对比例中所用的渣油加氢处理催化 剂的类型和体积完全相同， 均是中国石油化工股份有限公司催化剂分 公司生产的 CEN、 FZC、 ZTN、 ZTS 系列渣油加氢催化剂， 具体包括 保护剂， 脱金属催化剂， 脱硫催化剂， 脱氮催化剂等， 装填顺序一般 是使原料油依次与保护剂、 加氢脱金属、 加氢脱硫、 加氢脱氮催化剂 接触， 当然也有将这几种催化剂混合装填的技术。 上述催化剂装填技' 术为本领域技术人员所熟知的技术内容。 实施例和对比例中所用的催 化裂化催化剂相同， 均为大连石化分公司 350万吨 /年重油催化裂化装 置使用的催化剂， 为工业平衡催化剂。其新鲜剂组成为： 95wt%LBO-16 降浠烃催化剂 +5wt%LBO-A提高辛烷值助剂。
于比例
该对比例采用常规的渣油加氢处理 -催化裂化方法， 即渣油在加 氢处理装置进行加氢反应， 分离反应产物得到气体， 加氢石脑油、 加 氢柴油和加氢渣油。 所得的加氢渣油进入催化裂化装置进行裂化反应， 催化裂化重循环油在催化裂化装置内循环处理。 表 2、 表 3、 表 4分别 为工艺条件、 产品分布和主要产品性质。
实施例
该实施例采用本发明提供的渣油加氢处理和催化裂化组合方法， 加氢处理所有液相产物不经分馏直接进入催化裂化装置， 催化裂化反 应流出物分馏系统简化设计， 仅分馏出干气、 液化气和汽油馏分， 其 余的催化裂化重馏分经过滤出固体杂质后循环至加氢处理装置中进一 步加工。 表 2、 表 3、 表 5分别为工艺条件、 产品分布、 和主要产品性 质。
对比结果表明， 将催化裂化重馏分油与新鲜渣油原料混合加氢处 理后， 催化裂化汽油收率增加 22.49个百分点， 液化气产率增加了 9.23 百分点， 焦炭产率有所下降， 干气收率略有增加。 本发明方法可以很 好地满足希望增产汽油的企业。 表 1 原料油性盾
Figure imgf000010_0001
表 2 加氢处理和催化裂化工艺条件
Figure imgf000010_0002
以装置进料量计算。 实施例中新鲜原料的进料量与对比例相 同。
表 3 产品分布
Figure imgf000011_0001
以装置进料量为 100%计算， * ·以新鲜原料为 100%计算。 表 4 常规加氢处理 -催化裂化主要产品性质
Figure imgf000012_0001
• 在本发明中加氢常渣、 催化裂化重循环油均为中间产品 表 5 本发明主要产品性质
Figure imgf000012_0002

Claims

权 利 要 求
1. 一种渣油加氢处理和催化裂化组合方法， 其特征在于： 渣油原 料在氢气和加氢处理催化剂存在下进行加氢反应， 加氢反应流出物经 气液分离得到气相和液相， 气相循环用于加氢反应， 液相不经分馏直 接进入催化裂化装置， 催化裂化反应流出物分离出干气、 液化气和催 化裂化汽油后的催化裂化重馏分与渣油原料混合进行加氢反应。
2. 按照权利要求 1所述的方法， 其特征在于： 渣油原料包括常压 法油或减压; '查油。
3. 按照权利要求 1所述的方法， 其特征在于： 渣油原料加氢采用 固定床渣油加氢处理技术、 悬浮床渣油加氢处理技术、 沸腾床渣油加 氢处理技术或移动床渣油加氢处理技术。
4. 按照权利要求 1或 3所述的方法， 其特征在于： 渣油原料加氢 过程条件为： 绝对压力为大约 5MPa -大约 35MPa， 温度为大约 300°C -大约 500°C ,新鲜液时体积空速为大约 O. lh -大约 5. Oh , 总氢油体 积比为大约 100 -大约 5000。
5. 按照权利要求 1或 3所述的方法， 其特征在于： 渣油原料加氢 过程条件为： 绝对压力为大约 lOMPa -大约 20MPa, 温度为大约 350 °C -大约 450°C下， 新鲜液时体积空速为大约 0.15^ -大约 2.0h , 总 氢油体积比为大约 300 -大约 3000。
6. 按照权利要求 1所述的方法， 其特征在于： 催化裂化装置为一 套或一套以上， 每套催化裂化装置至少应包括一个反应器和一个再生 器。
7. 按照权利要求 6所述的方法， 其特征在于： 催化裂化装置设置 分馏塔， 催化裂化分馏塔将催化裂化反应流出物分馏为干气、 液化气、 催化裂化汽油和催化裂化重馏分。
8. 按照权利要求 1或 7所述的方法， 其特征在于： 催化裂化重馏 分循环回加氢处理装置之前先过滤出含有的微量催化裂化催化剂粉 末。
9. 按照权利要求 1或 6所述的方法， 其特征在于： 催化裂化装置 操作条件为： 反应温度为大约 450 ~大约 600°C , 再生温度为大约 600 -大约 800 °C , 剂油重量比为大约 2 ~大约 30 , 与催化剂接触时间为大 约 0.1 ~大约 15秒， 压力为大约 0.1 ~大约 0.5MPa。
10. 按照权利要求 1所述的方法， 其特征在于： 催化裂化装置操作 条件为: 反应温度为大约 490 ~大约 550°C, 再生温度为大约 50二 约 750°C, 剂油重量比为大约 4~大约 10, 与催化剂接触时间为大约 0.5 ~大约 5秒。
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