Gasoline production apparatus and gasoline production method

Abstract

This invention relates to the field of petroleum refining and discloses a gasoline preparation apparatus and method. The apparatus includes a membrane mixing unit (300), an olefin removal unit (400), and an S-Zorb desulfurization unit (500) connected in sequence. This invention can be modified from an existing S-Zorb desulfurization unit by adding at least one olefin removal unit before or after the original S-Zorb desulfurization unit. This allows for the reduction of olefins while maximizing the retention of octane number, ultimately yielding a low-sulfur, low-olefin gasoline fraction.

Description

Technical Field

[0001] This invention relates to the field of petroleum refining, specifically to gasoline preparation apparatus and gasoline preparation methods. Background Technology

[0002] Currently, gasoline used in vehicles is mainly catalytic cracking gasoline (FCC gasoline), with up to 80% of the gasoline in the gasoline pool coming from catalytic cracking gasoline, and 88% of the olefin content in finished gasoline coming from catalytic cracking gasoline. Although olefins have a high octane rating, they are chemically reactive and react with NO in the atmosphere after volatilization. x When mixed together and exposed to ultraviolet radiation from the sun, olefins form toxic photochemical smog, primarily composed of ozone, causing severe air pollution. Furthermore, olefins, especially dienes with conjugated structures, are particularly unstable and easily form gum and carbon deposits in engines and their intake systems, affecting normal engine operation. Therefore, the reduction of olefins in gasoline has become a global trend in fuel development, and upgrading gasoline product quality has become a common goal of the refining industries worldwide.

[0003] With increasingly stringent emission standards for motor vehicles, higher requirements have been placed on multiple indicators, including sulfur content, gasoline olefins, aromatics, benzene, and distillation range. Among these, the volume fraction of olefins in gasoline is subject to even lower requirements. Therefore, how to significantly reduce olefins while maximizing the preservation of octane rating is a crucial issue facing the upgrading of China VI gasoline quality.

[0004] S-Zorb gasoline adsorption desulfurization technology desulfurizes gasoline based on the principle of adsorption. Specifically, this technology uses an adsorbent to adsorb sulfur-containing molecules and removes sulfur atoms from the adsorbed molecules, retaining the sulfur atoms on the adsorbent. Simultaneously, the hydrocarbon components in the molecules are released and returned to the gasoline. No H2S is produced during this reaction, thus avoiding the re-reaction of H2S with olefins to form thiols. Compared with hydrodesulfurization technology, this technology is more effective at removing thiophene sulfur compounds that are difficult to remove through hydrotreating, achieving deep desulfurization. Furthermore, the olefin content (20-30% by weight) of the gasoline remains essentially unchanged after treatment, and the octane number loss is minimal.

[0005] However, the S-Zorb unit currently faces the following problems during operation: The catalytic gasoline contains olefins and a small amount of dienes. The adsorption desulfurization reaction temperature in the S-Zorb unit (≥400℃) is relatively high, and olefins polymerize under these high-temperature conditions, causing the gasoline's dry point to rise and reducing gasoline production. Furthermore, the small amount of dienes in the gasoline readily polymerizes, leading to coking on the walls of heat exchange equipment (such as feedstock heat exchangers and preheating furnaces), reducing heat exchange efficiency and increasing processing energy consumption. On the other hand, since the volume fraction of olefins in gasoline needs to be reduced to below 18% (China VI A) or 15% (China VI B), under the existing S-Zorb unit production conditions, the reduction in gasoline olefin content is limited. To meet the China VI standard's requirements for olefin content, the olefin content of the feedstock gasoline, i.e., the gasoline from the catalytic cracking unit (FCC gasoline), needs to be significantly reduced, resulting in a decrease in the overall efficiency of the catalytic unit and even the refining unit.

[0006] CN107686745A discloses a light gasoline etherification system and its process. The process includes: mixing methanol and light gasoline in a static mixer, then introducing the mixture into a fixed-bed reactor containing a sulfonic acid series macroporous cation exchange resin catalyst for a pre-etherification reaction, followed by deep etherification via catalytic distillation in a catalytic distillation column. While this process improves the conversion rate of etherifiable C5 and C6 hydrocarbons, it suffers from problems such as process complexity, low total olefin removal rate, and unacceptable oxygen content in the gasoline.

[0007] CN102839014A discloses a reactor and method for enhancing heavy oil conversion and reducing olefin content in gasoline. The method involves designing a riser reactor as a two-stage variable-diameter riser reactor. This reactor can increase the catalyst density and oil-catalyst contact efficiency within the riser, control operating conditions to improve the conversion rate of heavy oil in the second stage, and further reduce the olefin content of gasoline. While this method can increase the catalyst density and oil-catalyst contact efficiency within the riser, improve the conversion rate of heavy oil in the second stage, and further reduce the olefin content of gasoline, the total olefin content of the catalytic gasoline obtained by this method is above 30% by volume, which is relatively high.

[0008] CN1488728A discloses a catalytic gasoline aromatization catalyst and its application. Specifically, after adding an appropriate amount of potassium salt aqueous solution to K-type zeolite and a binder, the catalyst is obtained through molding, drying, and calcination. Integrating this catalyst into the FCC gasoline hydrodesulfurization / aromatication combined process technology, the FCC gasoline desulfurization rate can reach 90%, the olefin saturation rate reaches 51%, the gasoline yield remains essentially unchanged, and the anti-knock index loss is 1.7-2.0. Although this method results in a large amount of olefin removal and relatively little octane number loss in gasoline, the aromatic content of the resulting gasoline will exceed the standard.

[0009] In summary, existing catalytic cracking gasoline olefin reduction technologies primarily improve the olefin content of gasoline components through gasoline etherification, aromatization, isomerization, and improvements in the activity and selectivity of catalytic cracking processes, catalysts, and catalytic additives. These methods and technologies suffer from several problems: some processes are complex and require significant investment; some methods have uncontrollable olefin removal rates, excessive removal amounts, and substantial octane number losses; some processes offer limited olefin reduction, failing to meet gasoline quality standards; and some technologies are still immature and cannot be applied on a large scale industrially. Summary of the Invention

[0010] The purpose of this invention is to meet stricter vehicle emission standards and overcome the problems of existing technologies, such as complex gasoline preparation processes, high investment, insufficient olefin reduction to meet standards, or excessive olefin reduction and excessive octane number loss. This invention provides two gasoline preparation apparatuses and methods. The gasoline preparation method is easy to operate, allows for flexible adjustment of the olefin content in gasoline to obtain gasoline that meets the standards, and requires less investment, is easily improved and implemented, and produces gasoline with significantly reduced olefin content and minimal octane number loss.

[0011] To achieve the above objectives, the present invention provides a gasoline preparation apparatus comprising a membrane mixing unit, an olefin removal unit, and an S-Zorb desulfurization unit connected in sequence.

[0012] Preferably, the apparatus further includes: a feedstock oil unit connected to the membrane mixing unit; a gas supply unit connected to the feedstock oil unit and the membrane mixing unit; a gas-liquid separation unit disposed after the S-Zorb desulfurization unit; and a fractionation unit disposed after the gas-liquid separation unit.

[0013] Preferably, the S-Zorb desulfurization unit further includes a heating unit; more preferably, the heating unit is disposed between the olefin removal unit and the body of the S-Zorb desulfurization unit.

[0014] Preferably, the membrane mixing unit includes at least one liquid channel for containing feedstock oil or desulfurization products and a gas channel for containing hydrogen, wherein the liquid channel and the gas channel are adjacent to each other by a membrane tube having through-pores with an average pore size of nanometers; preferably, the membrane tube is formed of a porous material.

[0015] A second aspect of the present invention provides a gasoline preparation apparatus comprising an S-Zorb desulfurization unit, a membrane mixing unit, and an olefin removal unit connected in sequence.

[0016] Preferably, the apparatus further includes: a feedstock oil unit connected to the S-Zorb desulfurization unit; a gas supply unit connected to the feedstock oil unit and the membrane mixing unit; a gas-liquid separation unit disposed after the deolefins unit; and a fractionation unit disposed after the gas-liquid separation unit.

[0017] Preferably, the S-Zorb desulfurization unit further includes a heating unit; more preferably, the heating unit is disposed between the feedstock unit and the main body of the S-Zorb desulfurization unit.

[0018] Preferably, the membrane mixing unit includes at least one liquid channel for containing feedstock oil or desulfurization products and a gas channel for containing hydrogen, wherein the liquid channel and the gas channel are adjacent to each other by a membrane tube having through-pores with an average pore size of nanometers; preferably, the membrane tube is formed of a porous material.

[0019] A third aspect of the present invention provides a method for preparing gasoline, the method using the preparation apparatus described in the first aspect of the present invention, comprising the following steps:

[0020] 1) The step of mixing the feedstock oil and hydrogen in the membrane mixing unit;

[0021] 2) The feedstock oil mixed in step 1) is subjected to a first hydrogenation step in the deolefination unit;

[0022] 3) The step of desulfurizing the first hydrogenation product obtained in step 2) in the S-Zorb desulfurization unit to obtain the first desulfurization product.

[0023] The conditions for the first hydrogenation include: a pressure of 2.5-4 MPa, a temperature of 140-180°C, and a liquid hourly space velocity of 0.5-12 h⁻¹. -1 The hydrogen-to-oil volume ratio is 3-45:1.

[0024] Preferably, the first hydrogenation step is carried out in the presence of a hydrogenation catalyst, the hydrogenation catalyst comprising a support and an active component supported on the support, wherein the support comprises at least one of alumina, USY and silicon oxide, and the active component comprises at least two of the metal elements Mo, Ni and Co.

[0025] Preferably, the conditions for the first hydrogenation include: a pressure of 2.5-3.2 MPa, a temperature of 160-170°C, and a liquid hourly space velocity of 4-8 h⁻¹. -1 The hydrogen-to-oil volume ratio is 30-45:1.

[0026] Preferably, the method further includes the steps of gas-liquid separation and fractionation of the first desulfurization product.

[0027] Preferably, the feedstock is one or more of catalytic cracking gasoline, coking gasoline, and pyrolysis gasoline; more preferably, the feedstock is catalytic cracking gasoline.

[0028] Preferably, the feedstock oil has a distillation range of 35-210°C and an olefin content of 18-35% by volume; more preferably, the feedstock oil has a distillation range of 39-205°C and an olefin content of 18-27% by volume.

[0029] Preferably, the prepared gasoline has an olefin content of less than 18% by volume and a sulfur content of less than 10 ppm; more preferably, the prepared gasoline has an olefin content of less than 15% by volume and a sulfur content of less than 8 ppm.

[0030] A fourth aspect of the present invention provides a method for preparing gasoline, the method using the preparation apparatus described in the second aspect of the present invention, comprising the following steps:

[0031] 1) The step of desulfurizing the feedstock oil in the S-Zorb desulfurization unit;

[0032] 2) The step of subjecting the second desulfurization product obtained in step 1) to a second hydrogenation in the deolefination unit to obtain a second hydrogenation product;

[0033] The conditions for the second hydrogenation include: a pressure of 2-4 MPa, a temperature of 140-180 °C, and a liquid hourly space velocity of 0.5-12 h⁻¹. -1 The hydrogen-to-oil volume ratio is 3-45:1.

[0034] Preferably, the second hydrogenation step is carried out in the presence of a hydrogenation catalyst, the hydrogenation catalyst comprising a support and an active component supported on the support, wherein the support comprises at least one of alumina, USY and silicon oxide, and the active component comprises at least two of the metal elements Mo, Ni and Co.

[0035] Preferably, the conditions for the second hydrogenation include: a pressure of 2.4-2.8 MPa, a temperature of 160-170 °C, and a liquid hourly space velocity of 4-10 h⁻¹. -1 The hydrogen-to-oil volume ratio is 5-15:1.

[0036] Preferably, the method further includes the steps of gas-liquid separation and fractionation of the second hydrogenation product.

[0037] Preferably, the feedstock is one or more of catalytic cracking gasoline, coking gasoline, and pyrolysis gasoline; more preferably, the feedstock is catalytic cracking gasoline.

[0038] Preferably, the feedstock oil has a distillation range of 35-210°C and an olefin content of 18-35% by volume; more preferably, the feedstock oil has a distillation range of 39-205°C and an olefin content of 18-27% by volume.

[0039] Preferably, the prepared gasoline has an olefin content of less than 18% by volume and a sulfur content of less than 10 ppm; more preferably, the prepared gasoline has an olefin content of less than 15% by volume and a sulfur content of less than 8 ppm.

[0040] Through the above technical solution, the present invention can flexibly adjust the olefin content in gasoline while desulfurizing, and at the same time reduce octane number loss, so as to obtain gasoline fractions that meet the standards with low olefin content and little octane number loss.

[0041] In addition, by placing the deolefin removal unit before the S-Zorb desulfurization unit, coking of the feed heat exchanger of the S-Zorb desulfurization unit can be effectively prevented, thereby extending the operating cycle of the unit.

[0042] This invention can be modified from an existing S-Zorb desulfurization unit by adding at least one olefin removal unit before or after the original S-Zorb desulfurization unit. This can reduce olefins while maximizing the retention of octane number, ultimately yielding a low-sulfur (down to 4 ppm) and low-olefin (down to below 15% by volume) gasoline fraction. It results in lower operating costs, less investment, and easier unit modification, thereby increasing gasoline production and quality while reducing production costs. Attached Figure Description

[0043] Figure 1 This is a schematic diagram of a gasoline preparation apparatus according to a preferred embodiment of the present invention;

[0044] Figure 2 This is a schematic diagram of a gasoline preparation apparatus in another preferred embodiment of the present invention.

[0045] Explanation of reference numerals in the attached figures

[0046] 100: Raw material feed unit; 200: Gas supply unit

[0047] 300: Membrane mixing unit; 400: De-olefination unit

[0048] 500: S-Zorb desulfurization unit; 510: heating unit.

[0049] 700: Gas-liquid separation unit; 800: Fractionation unit

[0050] 610, 620, 630, 640, 650: Heat exchange units

[0051] A: Raw material oil B: Hydrogen

[0052] B1: Partial hydrogen gas; B2: The remaining hydrogen gas.

[0053] C: First hydrogenation product; E: First desulfurization product

[0054] F: First liquid phase; G, G': Reaction tail gas

[0055] H, H': Gasoline fraction; I, I': Dry gas

[0056] M: Second desulfurization product; N: Second hydrogenation product

[0057] F': Second liquid phase Detailed Implementation

[0058] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0059] In this invention, it should be understood that the terms "center," "inner," "outer," "upper," "lower," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or unit referred to must have a specific orientation, or a specific orientational structure and operation. Therefore, they should not be construed as limitations on this invention.

[0060] In this invention, the catalytic cracking gasoline refers to gasoline produced through a catalytic cracking process.

[0061] In this invention, the coking gasoline refers to gasoline produced through a delayed coking process.

[0062] In this invention, the pyrolytic gasoline refers to gasoline produced during the process of producing ethylene through high-temperature cracking in the presence of steam, using light hydrocarbons, naphtha, diesel oil, or vacuum gas oil as raw materials.

[0063] In this invention, the volume ratio of the gas (such as hydrogen) to the liquid (such as raw oil and desulfurization products) is the ratio at 25°C and 1 standard atmosphere.

[0064] In this invention, it should be noted that after obtaining gasoline fractions using the gasoline preparation apparatus and method described in this invention, the final gasoline product can be obtained by further adding additives and other materials to the obtained gasoline fractions using conventional apparatus and methods. The subsequent apparatus and methods are all common knowledge in the field. In order not to obscure the main idea of ​​this invention, this invention will not describe the subsequent blending steps in detail.

[0065] The first aspect of the present invention provides an apparatus for preparing gasoline, such as... Figure 1 As shown, the device includes a membrane mixing unit 300, an olefin removal unit 400, and an S-Zorb desulfurization unit 500 connected in sequence.

[0066] In this invention, by providing the membrane mixing unit 300 and the olefin removal unit 400 before the S-Zorb desulfurization unit 500, some olefins in the feedstock oil can be removed before desulfurization, thereby reducing the olefin content of the obtained gasoline fraction and maximizing the retention of octane in the feedstock oil, thus controlling the quality of the obtained gasoline fraction.

[0067] Hereinafter, the various units of the gasoline preparation apparatus described in the first aspect of the present invention will be described in detail.

[0068] In this invention, the membrane mixing unit 300 is used to mix liquid materials such as feedstock oil with hydrogen, so that the two are evenly distributed, thereby better controlling the concentration of hydrogen in the subsequent hydrodeolefin reaction and further improving the deolefin reaction effect.

[0069] Preferably, the membrane mixing unit is a membrane mixer, which may include at least one liquid channel for containing the feedstock oil and a gas channel for containing hydrogen. The liquid channel and the gas channel are adjacent to each other by a membrane tube having through-pores with an average pore size of nanometers. More preferably, the membrane tube is formed of a porous material.

[0070] Preferably, the membrane mixing unit has two concentric tubular channels, one of which is a liquid channel for containing liquids such as raw material oil, and the other is a gas channel for containing gas such as hydrogen. The liquid channel is inside the gas channel, and the wall of the liquid channel (i.e. the inner wall of the gas channel) is the membrane tube with through-pores having an average pore size of nanometers.

[0071] According to the present invention, the number of membrane mixing units 300 can be one or more. The number can be determined based on the processing capacity of the feedstock oil and the number of deolefinization units 400, as long as it ensures that the feedstock oil and hydrogen are mixed through the membrane mixing units 300; there are no particular limitations. Preferably, the number of membrane mixing units 300 is the same as the number of deolefinization units 400.

[0072] The number of membrane mixing units 300 can be, for example, 1, 2, 3, 3, 5, etc.

[0073] In this invention, the deolefin removal unit 400 can be any conventional reactor capable of removing olefins from feedstock oil, without particular limitation. It is acceptable as long as the olefins contained in the feedstock oil can be reacted within it. For example, the deolefin removal unit 400 can be an axial reactor and / or a radial reactor.

[0074] According to the present invention, the number of the deolefination units 400 can be one or more, and can be flexibly set according to the processing capacity of the feed oil and the deolefination capacity of a single deolefination unit 400, without any particular limitation.

[0075] The number of the deolefination units 400 can be, for example, 1, 2, 3, 3, 5, etc.

[0076] In this invention, the S-Zorb desulfurization unit 500 can be any conventional reactor in the art that utilizes S-Zorb adsorption desulfurization technology for desulfurization, without any particular limitation. It is acceptable as long as it can adsorb sulfur contained in the feedstock oil to obtain desulfurized feedstock oil. For example, the S-Zorb desulfurization unit 500 can be a moving bed reactor and / or a fluidized bed reactor.

[0077] Furthermore, in this invention, there is no particular limitation on the number of S-Zorb desulfurization units 500, as long as it can meet production requirements. Preferably, the number of S-Zorb desulfurization units 500 is at least one; more preferably, the number of S-Zorb desulfurization units 500 is one.

[0078] The number of the -Zorb desulfurization units 500 can be, for example, 1, 2, 3, 3, 5, etc.

[0079] Furthermore, according to a preferred embodiment of the present invention, the S-Zorb desulfurization unit 500 further includes a heating unit 510, which is preferably disposed between the olefin removal unit 400 and the main body of the S-Zorb desulfurization unit 500. The heating unit 510 is used to heat the material before it enters the S-Zorb desulfurization unit 500, thereby achieving desulfurization more efficiently.

[0080] In this invention, the heating unit 510 can be any of the various structures commonly used in the art for heating materials containing raw oil, without any particular limitation. For example, the heating unit 510 can be a heating furnace.

[0081] In this invention, the gasoline preparation apparatus may further include a feedstock unit 100, a gas supply unit 200, a gas-liquid separation unit 700, and a fractionation unit 800. The above units will be briefly described below.

[0082] In this invention, the gas supply unit 200 can be connected to the feedstock oil unit 100 and the membrane mixing unit 300, and is used to supply hydrogen to the feedstock oil A and the membrane mixing unit 300.

[0083] The gas-liquid separation unit 700 can be connected to the S-Zorb desulfurization unit 500 and is located after the S-Zorb desulfurization unit 500 to separate the reaction tail gas G and the first liquid phase F.

[0084] The fractionation unit 800 can be connected to the gas-liquid separation unit 700 and is located after the gas-liquid separation unit 700. It is used to fractionate the first liquid phase F obtained from gas-liquid separation to obtain gasoline fraction H.

[0085] According to the present invention, the crude oil feeding unit 100 may include an oil storage component and various crude oil conveying pipelines, power components, and valves that can transport crude oil from the oil storage component to a designated location, without particular limitation. For example, in a preferred embodiment of the present invention, the crude oil feeding unit 100 includes an oil storage tank, a crude oil conveying pipeline, a pump, and valves.

[0086] In this invention, the gas supply unit 200 can be any conventional structure capable of stably supplying gas, without particular limitation. For example, the gas supply unit 200 may include a gas pipeline for gas transmission, a power device such as a pump for providing power, and valves for regulating flow and controlling opening and closing, thereby supplying hydrogen to the feedstock unit 100 and the membrane mixing unit 300, etc., through the gas pipeline.

[0087] In this invention, preferably, the gas supply unit 200 has a branch pipeline for transporting a portion of hydrogen B1 to the pipeline behind the oil storage tank of the feedstock oil unit 100 to mix with the feedstock oil A, and for transporting another portion of hydrogen B2 to the membrane mixing unit 300 for hydrogenation of the feedstock oil A.

[0088] In this invention, the gas-liquid separation unit 700 can be any of the commonly used structures in the art for separating gas and liquid phases, and can be provided with a gas phase outlet and a liquid phase outlet. For example, the gas-liquid separation unit can be a vertical high-pressure separator and / or a horizontal high-pressure separator; there are no particular limitations, as long as the gas and liquid phase oil can be separated.

[0089] In this invention, the fractionation unit 800 can be any structure commonly used in the art that enables fractionation, as long as it can fractionate the first liquid phase F and separate it into gasoline fractions as needed. For example, the fractionation unit 800 can be a plate column and / or a packed column. In a preferred embodiment of this invention, the fractionation unit is a plate fractionation column.

[0090] In addition, the gasoline preparation apparatus described in the first aspect of the present invention may further include one or more heat exchange units, various valves, and pipelines that connect the above-mentioned units to each other. The above-mentioned components are conventional structures in the art and will not be described in detail here.

[0091] Furthermore, in this invention, such as Figure 1 The gasoline preparation apparatus shown may further include heat exchange units 610, 620, and 630. The heat exchange units 610, 620, and 630 can be any heat exchange component conventional in the art, without particular limitation. Preferably, the heat exchange units 610, 620, and 630 are heat exchangers.

[0092] When heat exchangers are used as heat exchange units 610, 620, and 630, each heat exchange unit may contain one or more sets of heat exchangers, as long as they are set according to the heat exchange requirements, without any particular limitation.

[0093] Preferably, the heat exchange unit 610 is disposed on the connecting pipeline between the feed oil unit 100 and the membrane mixing unit 300, and is used to heat the feed oil A to increase the reaction rate of the feed oil in the deolefin reaction unit 400 and improve the deolefin effect.

[0094] Preferably, the heat exchange unit 620 is disposed on the connecting pipeline between the olefin removal unit 400 and the S-Zorb desulfurization unit 500, and is used to heat the first hydrogenation product C, thereby improving the overall working efficiency of the device.

[0095] Preferably, the heat exchange unit 630 is disposed on the connecting pipeline between the S-Zorb desulfurization unit 500 and the gas-liquid separation unit 700, and is used to cool the first desulfurization product E, thereby improving the rate of subsequent gas-liquid separation.

[0096] The following, combined with Figure 1A particularly preferred embodiment of the first aspect of the present invention will be described below. In a particularly preferred embodiment, the gasoline preparation apparatus includes a feedstock unit 100, a gas supply unit 200, a membrane mixing unit 300, an olefin removal unit 400, an S-Zorb desulfurization unit 500, a gas-liquid separation unit 700, a fractionation unit 800, and three heat exchange units 610, 620, and 630. The feedstock unit 100 includes a storage tank for storing feedstock, a feedstock pipeline for transporting feedstock, and a pump for providing power. Figure 1 (Not shown in the image), the heat exchange unit 610 is installed on the connecting pipeline between the feedstock unit 100 and the membrane mixer 300. The gas supply unit 200 is connected to the feedstock unit 100 and the membrane mixer 300. Specifically, the gas supply unit 200 sends a portion of hydrogen B1 into the pipeline behind the oil storage tank of the feedstock unit 100 and before the branch pipeline through a branch gas supply pipeline, so that a portion of hydrogen B1 mixes with the feedstock A; in addition, another portion of hydrogen B2 is sent into the membrane mixer 300 through the branch gas supply pipeline, so that the other portion of hydrogen B2 mixes with the feedstock A mixed with a portion of hydrogen B1 in the membrane mixer 300. This can further prevent coking in the S-Zorb desulfurization unit 500 and improve the deolefin reaction efficiency. The membrane mixing unit 300 is followed by the olefin removal unit 400, the heat exchange unit 620, the heating unit 510, the S-Zorb desulfurization unit 500, the heat exchange unit 630, the gas-liquid separation unit 700, and the fractionation unit 800.

[0097] According to the present invention, in such Figure 1 In the preferred embodiment shown, by placing the deolefin removal unit 400 before the S-Zorb desulfurization unit 500, not only can some olefins in the feedstock be effectively removed and the sulfur content reduced, but coking can also be effectively prevented in the heat exchange unit 620, the heating unit 510 and the S-Zorb desulfurization unit 500, extending the unit's operating cycle and reducing operating costs. At the same time, while retaining the octane number to the maximum extent, the olefin content of the obtained gasoline fraction is reduced, thereby improving the quality of the obtained gasoline fraction.

[0098] Next, combined Figure 2 The gasoline preparation apparatus of the second aspect of the present invention will be described in detail.

[0099] like Figure 2 As shown, the gasoline preparation apparatus according to the second aspect of the present invention includes an S-Zorb desulfurization unit 500, a membrane mixing unit 300, and an olefin removal unit 400 connected in sequence.

[0100] In this invention, by providing the membrane mixing unit 300 and the olefin removal unit 400 after the S-Zorb desulfurization unit 500, some of the olefins in the second desulfurization product can be removed after desulfurization, thereby reducing the olefin content of the obtained gasoline fraction, while retaining the octane number of the feed oil to the maximum extent, thereby improving the quality of the obtained gasoline fraction.

[0101] In the second aspect of the present invention, the S-Zorb desulfurization unit 500, the membrane mixing unit 300, and the deolefin removal unit 400, and the number thereof, can be the same as those in the gasoline preparation apparatus described in the first aspect of the present invention. To avoid obscuring the main points of the present invention, further details are omitted here.

[0102] Furthermore, according to a preferred embodiment of the present invention, the S-Zorb desulfurization unit 500 further includes a heating unit 510, which is disposed between the feed oil inlet unit 100 and the main body of the S-Zorb desulfurization unit 500. The heating unit 510 is used to heat the feed oil A entering the S-Zorb desulfurization unit 500, thereby achieving desulfurization more efficiently and improving the overall working efficiency of the device.

[0103] In this invention, the heating unit 510 may be the same as the heating unit described in the first aspect of this invention, without any particular limitation.

[0104] In addition to the units described above, the gasoline preparation apparatus according to the second aspect of the present invention may further include: a feedstock oil unit 100 connected to the S-Zorb desulfurization unit 500 for supplying feedstock oil A to the S-Zorb desulfurization unit 500; a gas supply unit 200 connected to the feedstock oil unit 100 and the membrane mixing unit 300 for supplying hydrogen to the feedstock oil A and the membrane mixing unit 300; a gas-liquid separation unit 700 connected to the olefin removal unit 400 and disposed after the olefin removal unit 400 for separating the reaction tail gas G' and the second liquid phase F'; and a fractionation unit 800 connected to the gas-liquid separation unit 700 and disposed after the gas-liquid separation unit 700 for fractionating the second liquid phase F' obtained from the gas-liquid separation to obtain gasoline fraction H'.

[0105] The feedstock unit 100, gas supply unit 200, gas-liquid separation unit 700, and fractionation unit 800 described in the second aspect of the present invention can all be the same as those described in the first aspect of the present invention, and will not be described again here.

[0106] In addition, the gasoline preparation apparatus described in the second aspect of the present invention may further include one or more heat exchange units, various valves, and pipelines that connect the above-mentioned units to each other. The above-mentioned components are conventional structures in the art and will not be described in detail here.

[0107] In this invention, preferably, as shown in the example Figure 2 The gasoline preparation apparatus shown further includes heat exchange units 640 and 650.

[0108] Preferably, the heat exchange unit 640 is disposed on the connecting pipeline between the raw oil feeding unit 100 and the S-Zorb desulfurization unit 500, and is used to heat the raw oil A to improve the desulfurization effect of the raw oil in the S-Zorb desulfurization unit 500.

[0109] Preferably, the heat exchange unit 650 is disposed on the connecting pipeline between the S-Zorb desulfurization unit 500 and the membrane mixing unit 300, and is used to heat the second desulfurization product M, thereby increasing the rate of subsequent deolefin reaction and improving the overall working efficiency of the device.

[0110] Next, combined Figure 2 A particularly preferred embodiment of the gasoline preparation apparatus described in the second aspect of the present invention will be described below. For example... Figure 2 The gasoline preparation apparatus shown includes a feedstock unit 100, a gas supply unit 200, an S-Zorb desulfurization unit 500, a membrane mixing unit 300, a deolefin removal unit 400, a gas-liquid separation unit 700, a fractionation unit 800, and two heat exchange units 640 and 650. The feedstock unit 100 includes a storage tank for storing feedstock, a feedstock delivery pipeline for transporting feedstock, and a pump for providing power. Figure 2 (Not shown in the image) etc., which transport the feed oil A to the S-Zorb desulfurization unit 500, and the heat exchange unit 640 is provided on the connecting pipeline between the feed oil feeding unit 100 and the S-Zorb desulfurization unit 500. The gas supply unit 200 is connected to the feed oil feeding unit 100 and the membrane mixing unit 300. Specifically, the gas supply unit 200 sends part of the hydrogen B1 into the pipeline behind the oil storage tank of the feed oil feeding unit 100 through a branch gas transmission pipeline, so that part of the hydrogen B1 mixes with the feed oil A; in addition, another part of the hydrogen B2 is sent into the membrane mixing unit 300 through a branch gas transmission pipeline, and mixes with the desulfurized feed oil (second desulfurization product M) in the membrane mixing unit 300. The S-Zorb desulfurization unit 500 includes a heating unit 510 and is connected to the membrane mixing unit 300. The membrane mixing unit 300 is subsequently connected to the olefin removal unit 400, the gas-liquid separation unit 700, and the fractionation unit 800.

[0111] According to the present invention, in such Figure 2In the preferred embodiment shown, by placing the deolefin reaction unit 400 after the S-Zorb desulfurization unit 500, the olefin content in the feedstock can be effectively reduced while reducing the sulfur content, and the quality of the obtained gasoline fraction can be improved while retaining the octane number to the maximum extent.

[0112] According to the first and second aspects of the present invention, the feedstock oil may be one or more of catalytic cracking gasoline, coking gasoline and pyrolysis gasoline; preferably, the feedstock oil is catalytic cracking gasoline.

[0113] In addition, the distillation range of the feedstock oil can be 35-210℃, and the olefin content in the feedstock oil can be 18-35% by volume; preferably, the distillation range of the feedstock oil is 39-205℃, and the olefin content in the feedstock oil is 18-27% by volume.

[0114] A third aspect of the present invention provides a method for preparing gasoline, wherein the method is carried out using the apparatus described in the first aspect of the present invention, and includes the following steps:

[0115] 1) The step of mixing feedstock oil (A) with hydrogen in the membrane mixing unit (300);

[0116] 2) The feedstock oil mixed in step 1) is subjected to a first hydrogenation step in the deolefination unit (400);

[0117] 3) The first hydrogenation product (C) obtained in step 2) is desulfurized in the S-Zorb desulfurization unit (500) to obtain the first desulfurization product (E).

[0118] The conditions for the first hydrogenation include: a pressure of 2.5-4 MPa, a temperature of 140-180°C, and a liquid hourly space velocity of 0.5-12 h⁻¹. -1 The hydrogen-to-oil volume ratio is 3-45:1.

[0119] According to a third aspect of the invention, the feedstock A can be any of the feedstocks commonly used in the art for preparing gasoline. Preferably, the feedstock A is one or more of catalytic cracking gasoline, coking gasoline, and pyrolysis gasoline; more preferably, the feedstock A is catalytic cracking gasoline.

[0120] In this invention, the distillation range of the feedstock oil A can be 35-210℃, and the olefin content in the feedstock oil A is 18-35% by volume; preferably, the distillation range of the feedstock oil A is 39-205℃, and the olefin content in the feedstock oil A is 18-27% by volume.

[0121] In this invention, the selection of the first hydrogenation condition is crucial. By controlling the first hydrogenation condition within the above-mentioned range, the olefin content in the prepared gasoline can be reduced while retaining the octane number to the maximum extent, so that it meets the China VI gasoline standard.

[0122] Preferably, the conditions for the first hydrogenation include: a pressure of 2.5-3.2 MPa, a temperature of 160-170°C, and a liquid hourly space velocity of 4-8 h⁻¹. -1 The hydrogen-to-oil volume ratio is 30-45:1. By controlling the first hydrogenation conditions within this range, the quality of the resulting gasoline can be further improved.

[0123] According to a third aspect of the present invention, preferably, the feedstock oil A and a portion of hydrogen B1 are contacted in the pipeline of the feedstock oil feeding unit 100, and the volume ratio of the feedstock oil A to the portion of hydrogen B1 is 1:1-25; more preferably, the volume ratio of the feedstock oil A to the portion of hydrogen B1 is 1:5-15. This can slow down the coking of gasoline in the heat exchange unit and extend the service life of the device.

[0124] Furthermore, preferably, another portion of hydrogen B2 is mixed with feedstock oil A in the membrane mixing unit 300. In this invention, the volume ratio of the other portion of hydrogen B2 to the feedstock oil A is not particularly limited, as long as the final hydrogen-oil volume ratio can be adjusted to the hydrogenation conditions for the first hydrogenation reaction in the hydrogenation unit 400 described later, taking into account the volume ratio of feedstock oil A to the hydrogen B1.

[0125] For example, in this invention, the volume ratio of the feedstock oil A to the other component hydrogen B2 can be 1:1-45, more preferably, the volume ratio of the feedstock oil A to the other component hydrogen B2 is 1:10-30. This allows for better hydrogenation and improves the quality of the resulting gasoline fraction.

[0126] Furthermore, before step 1) in which feedstock oil A and hydrogen are mixed in the membrane mixing unit 300, feedstock oil A can be preheated in the heat exchange unit 610 to facilitate subsequent hydrogenation in the deolefination unit 400. Preferably, the preheating temperature is 100-200°C, and more preferably, the preheating temperature is 140-180°C.

[0127] According to the present invention, after the feedstock oil A is mixed with hydrogen in the membrane mixing unit 300, the mixed feedstock oil is hydrogenated in the deolefination unit 400 in the presence of a hydrogenation catalyst.

[0128] In addition, in this invention, there is no particular restriction on the direction in which feedstock oil A enters the catalyst bed in the deolefination unit 400 during hydrogenation. For example, feedstock oil A can enter from the bottom of the catalyst bed from bottom to top for hydrogenation, or feedstock oil A can enter from the top of the catalyst bed from top to bottom for hydrogenation.

[0129] In this invention, the selection of the hydrogenation catalyst is crucial. Preferably, the hydrogenation catalyst can both reduce the olefin content in the feedstock through hydrogenation and retain the high-octane portion of the feedstock to the maximum extent.

[0130] In this invention, preferably, the hydrogenation catalyst comprises a support and an active component supported on the support. The support may contain at least one of alumina, USY, and silicon dioxide; the active component may contain at least two of the metal elements Mo, Ni, and Co. Preferably, Mo and Ni are selected as the active components, thereby enabling the removal of some olefins while further retaining high-octane olefins during the hydrogenation process.

[0131] Examples of hydrogenation catalysts include: HDD-2 (active components are metal elements Mo and Ni) or HGO-2 (active components are metal elements Mo and Co) from Hunan Changling Petrochemical Technology Development Co., Ltd., with HDD-2, whose active components are Mo and Ni, being more preferred. Using this catalyst can reduce the olefin content in the overall feedstock oil while retaining some olefins with high octane numbers, thereby reducing the production cost of gasoline and obtaining high-quality gasoline fractions.

[0132] According to a third aspect of the present invention, in order to improve the efficiency and effect of subsequent desulfurization, the first hydrogenation product C is preferably preheated at the heat exchange unit 620. The preheating temperature can vary within a wide range, for example, the preheating temperature can be 300-420°C, and preferably, the preheating temperature is 380-420°C.

[0133] Before the first hydrogenation product C enters the S-Zorb desulfurization unit 500 for desulfurization, it is preferably heated in the heating furnace 510 to further improve the desulfurization efficiency. Preferably, the heating temperature is 410-420°C.

[0134] In this invention, when desulfurization is carried out in the S-Zorb desulfurization unit 500, the desulfurization conditions can be conventional conditions commonly used in the field for desulfurization of feedstock oil, without any particular limitation. For example, the desulfurization conditions may include: a temperature of 410-435℃ and a pressure of 2.0-3.5MPa. Preferably, the desulfurization conditions include: a temperature of 420-430℃ and a pressure of 2.5-3.0MPa.

[0135] According to the present invention, after desulfurization in the S-Zorb desulfurization unit 500, a first desulfurization product E is obtained. In order to separate the reaction tail gas G and the first liquid phase F in the first desulfurization product E, preferably, the method of the third aspect of the present invention further includes the step of performing gas-liquid separation of the first desulfurization product E in the gas-liquid separation unit 700.

[0136] To improve the gas-liquid separation effect and increase the processing speed, preferably, the first desulfurization product is cooled by the heat exchange unit 630 before entering the gas-liquid separation unit 700. Preferably, the cooling temperature is 130-200℃; more preferably, the cooling temperature is 130-170℃.

[0137] In this invention, the first liquid phase F after separation is obtained through the gas-liquid separation unit 700.

[0138] To improve the quality of the prepared gasoline, the method according to the third aspect of the present invention further includes the step of fractionating the first liquid phase F in the fractionation unit 800.

[0139] In this invention, the fractionation can be carried out using various methods and conditions commonly used in the art for separation, without particular limitations. Preferably, gasoline fraction is obtained by removing C3 and lower components from the first liquid phase through fractionation.

[0140] The gasoline prepared by the method described in the third aspect of the present invention has an olefin content of less than 18% by volume and a sulfur content of less than 10 ppm; preferably, the gasoline prepared has an olefin content of less than 15% by volume and a sulfur content of less than 8 ppm; more preferably, the gasoline prepared has a sulfur content of less than 6 ppm.

[0141] A fourth aspect of the present invention provides a method for preparing gasoline, the method using the preparation apparatus described in the second aspect of the present invention, comprising the following steps:

[0142] 1) The step of desulfurizing the feedstock oil (A) in the S-Zorb desulfurization unit (500);

[0143] 2) The step of subjecting the second desulfurization product (M) obtained in step 1) to a second hydrogenation in the deolefination unit (400) to obtain a second hydrogenation product (N);

[0144] The conditions for the second hydrogenation include: a pressure of 2-4 MPa, a temperature of 140-180 °C, and a liquid hourly space velocity of 0.5-12 h⁻¹. -1 The hydrogen-to-oil volume ratio is 3-45:1.

[0145] The raw material oil A used in the method described in the fourth aspect of the present invention can be the same as that in the third aspect of the present invention, and will not be repeated here.

[0146] According to a fourth aspect of the invention, the feedstock oil A is first completely desulfurized, and then the second desulfurization product M obtained from the desulfurization is hydrogenated to obtain a second hydrogenation product N, thereby removing some olefins while removing sulfur from the feedstock oil and retaining the octane number to the maximum extent.

[0147] According to a fourth aspect of the present invention, by controlling the conditions of the second hydrogenation within the above-mentioned range, it can be ensured that the olefin content in the prepared gasoline meets the China VI gasoline standard and that the octane number is retained to the maximum extent.

[0148] Preferably, the conditions for the second hydrogenation include: a pressure of 2.4-2.8 MPa, a temperature of 160-170 °C, and a liquid hourly space velocity of 4-10 h⁻¹. -1 The hydrogen-to-oil volume ratio is 5-15:1. By controlling the second hydrogenation conditions within this range, the quality of the prepared gasoline can be further improved.

[0149] According to a fourth aspect of the invention, prior to step 1) in which the feedstock oil A is desulfurized in the S-Zorb desulfurization unit 500, a portion of hydrogen B1 is mixed with the feedstock oil A to prevent coking in the heat exchange unit and the S-Zorb desulfurization unit 500.

[0150] In this invention, the volume ratio of the raw material oil A to the partial hydrogen B1 can be 1:1-30, and more preferably, the volume ratio of the raw material oil A to the partial hydrogen B1 is 1:5-15.

[0151] In addition, the feedstock oil A can be preheated in advance by heat exchange unit 640 and heating unit 510 to facilitate subsequent desulfurization treatment in S-Zorb desulfurization unit 500. Preferably, the preheating temperature is 300-420℃, more preferably, the preheating temperature is 410-420℃.

[0152] In this invention, the preheating process is carried out in two steps by heat exchange unit 640 and heating unit 510. There are no particular restrictions on the temperature of each step. For example, the raw material oil mixed with hydrogen can be heated to 300-400°C first by heat exchange unit 640, and then heated to 300-420°C by heating unit 510.

[0153] Furthermore, in this invention, the second desulfurized product M obtained after desulfurizing the raw material oil A can be cooled by the heat exchange unit 650, which can facilitate subsequent steps. For example, the temperature of the second desulfurized product M can be reduced to 100-200°C by the heat exchanger 650, preferably to 130-170°C by the heat exchange unit 650.

[0154] Next, the second desulfurization product M is mixed with another portion of hydrogen B2 in a membrane mixing unit 300. The volume ratio of the second desulfurization product M to the other portion of hydrogen B2 can be 1:1-25, more preferably, the volume ratio is 1:10-15. By mixing the other portion of hydrogen B2 with the second desulfurization product M in the membrane mixing unit 300, the effect of the subsequent hydrogenation reaction can be further improved, thereby improving the quality of the obtained gasoline fraction.

[0155] After the second desulfurization product M is mixed with another portion of hydrogen B2 in the membrane mixing unit 300, a second hydrogenation is carried out in the deolefination unit 400 to obtain the second hydrogenation product N.

[0156] Preferably, the method according to the fourth aspect of the present invention further includes the steps of separating the second hydrogenation product N into a second liquid phase F' in the gas-liquid separation unit 700, and fractionating the second liquid phase F' in the fractionation unit 800 to obtain a gasoline fraction H'.

[0157] The conditions for desulfurization, gas-liquid separation, and fractionation as described in the fourth aspect of this invention, as well as the hydrogenation catalyst used in the hydrogenation reaction, can be the same as those described in the third aspect of this invention, and will not be repeated here.

[0158] The gasoline prepared by the method described in the fourth aspect of the present invention has an olefin content of less than 18% by volume and a sulfur content of less than 10 ppm; preferably, the gasoline prepared has an olefin content of less than 15% by volume and a sulfur content of less than 8 ppm; more preferably, the gasoline prepared has a sulfur content of less than 6 ppm.

[0159] The present invention will be described in detail below through embodiments.

[0160] In the following examples and comparative examples, the feedstock used was catalytic cracked gasoline, the basic properties of which are shown in Table 1.

[0161] Table 1

[0162]

[0163] Example 1

[0164] use Figure 1 The device shown performs the operation, as follows: Figure 1 As shown, the gasoline preparation device includes a feedstock unit 100, a gas supply unit 200, a membrane mixing unit 300, an olefin removal unit 400, an S-Zorb desulfurization unit 500, a gas-liquid separation unit 700, a fractionation unit 800, and three heat exchange units 610, 620, and 630.

[0165] The crude oil feeding unit 100 includes an oil storage tank for storing crude oil, a crude oil conveying pipeline for conveying crude oil, and a pump for providing power. Figure 1 (Not shown in the image), the feed oil conveying pipeline is connected to the membrane mixing unit 300, and the heat exchange unit 610 is provided on the connecting pipeline between the feed oil feeding unit 100 and the membrane mixer 300.

[0166] The gas supply unit 200 is connected to the feedstock oil unit 100 and the membrane mixing unit 300. Specifically, the gas supply unit 200 sends a portion of hydrogen B1 into the pipeline behind the oil storage tank of the feedstock oil unit 100 through a branch gas pipeline, so that a portion of hydrogen B1 mixes with the feedstock oil A; in addition, another portion of hydrogen B2 is sent into the membrane mixing unit 300 through a branch gas pipeline.

[0167] The membrane mixing unit 300 is subsequently connected via pipelines to the olefin removal unit 400, the heat exchange unit 620, the heating unit 510, the S-Zorb desulfurization unit 500, the heat exchange unit 630, the gas-liquid separation unit 700, and the fractionation unit 800.

[0168] The membrane mixing unit 300 is a membrane mixer with two concentric tubular channels. One channel is a liquid channel for containing raw material oil, and the other is a gas channel for containing hydrogen. The liquid channel is located inside the gas channel. The wall of the liquid channel (i.e., the inner wall of the gas channel) is a membrane tube with through-pores of an average pore size of nanometers (the membrane tube was purchased from Beijing Zhongtianyuan Environmental Engineering Co., Ltd., with a pore size of 0.05 μm). The outer wall of the gas channel is made of porous ceramic material.

[0169] The deolefin removal unit 400 is an axial reactor, the S-Zorb desulfurization unit 500 is a fluidized bed reactor, the heating unit 510 is a heater, the gas-liquid separation unit 700 is a horizontal high-efficiency separator, the fractionation unit 800 is a plate fractionation tower, and the heat exchange units 610, 620, and 630 are heat exchangers.

[0170] The method for preparing gasoline fractions using the above-mentioned apparatus is as follows:

[0171] 1) The feedstock oil A and a portion of hydrogen B1 are mixed in a volume ratio of 1:5 and then heated to 160°C and 3.0 MPa by heat exchange unit 610.

[0172] 2) The feedstock oil A obtained in step 1) after being mixed with hydrogen and heated is mixed with another portion of hydrogen B2 at a volume ratio of 1:35 in the membrane mixing unit 300. Then, it undergoes a hydrogenation reaction with the hydrogenation catalyst in the deolefination unit 400 from bottom to top. The conditions for the hydrogenation reaction include: pressure of 3 MPa, temperature of 160 °C, and liquid hourly space velocity of 6 h⁻¹. -1 The hydrogen-to-oil volume ratio is 40:1. The hydrogenation catalyst used is the commercial catalyst HDD-2 (produced by Hunan Changling Petrochemical Technology Development Co., Ltd.), whose support is γ-Al2O3, and whose active components are Mo and Ni, to obtain the first hydrogenation product C.

[0173] 3) The first hydrogenation product C obtained in step 2) is heated to 380°C through heat exchange unit 620, and then heated to 420°C through heating unit 510. After that, it enters the S-Zorb desulfurization unit 500 for desulfurization to obtain the first desulfurization product E. The desulfurization conditions include: temperature of 422°C and pressure of 2.7 MPa.

[0174] 4) The first desulfurization product E obtained in step 3) is subjected to gas-liquid separation in gas-liquid separation unit 700 to obtain the first liquid phase F, wherein the conditions for gas-liquid separation include: temperature of 135-140℃ and pressure of 2.57MPa.

[0175] 5) The first liquid phase F obtained in step 4) is fractionated through fractionation unit 800 to separate gasoline fraction H from the bottom of the column. The fractionation conditions include: pressure of 0.5-0.6 MPa, feed temperature of 130°C, and bottom temperature of 136°C.

[0176] The properties of the first hydrogenation product C, the first desulfurization product E, and the gasoline fraction H obtained in this way are shown in Table 2.

[0177] Example 2

[0178] The apparatus described in Example 1 is used, and the method described in Example 1 is followed, except that:

[0179] In step 2), the conditions for the hydrogenation reaction include: a pressure of 3.2 MPa, a temperature of 165 °C, and a liquid hourly space velocity of 8 h⁻¹. -1 The volume ratio of hydrogen to oil is 35:1 (adjusting the volume ratio of feedstock oil A obtained in step 1) to another part of hydrogen B2 (the same applies below);

[0180] The properties of the first hydrogenation product C, the first desulfurization product E, and the gasoline fraction H obtained in this way are shown in Table 2.

[0181] Example 3

[0182] The apparatus described in Example 1 is used, and the method described in Example 1 is followed, except that:

[0183] In step 2), the conditions for the hydrogenation reaction include: a pressure of 2.5 MPa, a temperature of 170 °C, and a liquid hourly space velocity of 4 h⁻¹. -1 The hydrogen-to-oil volume ratio is 45:1;

[0184] The properties of the first hydrogenation product C, the first desulfurization product E, and the gasoline fraction H obtained in this way are shown in Table 2.

[0185] Example 4

[0186] The apparatus described in Example 1 is used, and the method described in Example 1 is followed, except that:

[0187] In step 2), the conditions for the hydrogenation reaction include: a pressure of 4 MPa, a temperature of 140 °C, and a liquid hourly space velocity of 3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 20:1;

[0188] The properties of the first hydrogenation product C, the first desulfurization product E, and the gasoline fraction H obtained in this way are shown in Table 2 (continued).

[0189] Example 5

[0190] The apparatus described in Example 1 is used, and the method described in Example 1 is followed, except that:

[0191] In step 2), the hydrogenation catalyst HGO-2 is used to replace the hydrogenation catalyst HDD-2. The support for this catalyst is γ-Al2O3, and the active components are Mo and Co.

[0192] The properties of the first hydrogenation product C, the first desulfurization product E, and the gasoline fraction H obtained in this way are shown in Table 2 (continued).

[0193] Comparative Example 1

[0194] The apparatus described in Example 1 is used, and the method described in Example 1 is followed, except that:

[0195] In step 2), the conditions for the hydrogenation reaction include: a pressure of 2 MPa, a temperature of 120 °C, and a liquid hourly space velocity of 15 h⁻¹. -1 The hydrogen-to-oil volume ratio is 2:1;

[0196] The properties of the first hydrogenation product C, the first desulfurization product E, and the gasoline fraction H obtained in this way are shown in Table 2 (continued).

[0197] Table 2

[0198]

[0199] Table 2 (continued)

[0200]

[0201] As can be seen from the results in Tables 2 and 2 (continued), by performing hydrogenation (de-olefinization) treatment under the first hydrogenation conditions specified in this invention before desulfurization, the olefin content in gasoline fractions can be effectively reduced while the octane number is well preserved.

[0202] In addition, by setting up a de-olefins unit before the S-zorb desulfurization unit, coking of the heat exchange unit and the S-Zorb desulfurization unit can be effectively prevented, thus extending the unit's operating cycle.

[0203] Example 6

[0204] Adopting such Figure 2 The device shown performs the operation, as follows: Figure 2 As shown, the gasoline preparation device includes a feedstock unit 100, an air supply unit 200, an S-Zorb desulfurization unit 500, a membrane mixing unit 300, an olefin removal unit 400, a gas-liquid separation unit 700, a fractionation unit 800, and two heat exchange units 640 and 650.

[0205] The crude oil feeding unit 100 includes an oil storage tank for storing crude oil, a crude oil conveying pipeline for conveying crude oil, and a pump for providing power. Figure 2 (Not shown in the image), which transports the feed oil A to the S-Zorb desulfurization unit 500, and the heat exchange unit 640 is provided on the connecting pipeline between the feed oil feeding unit 100 and the S-Zorb desulfurization unit 500.

[0206] The gas supply unit 200 is connected to the feedstock oil unit 100 and the membrane mixing unit 300. Specifically, the gas supply unit 200 sends a portion of hydrogen B1 into the pipeline behind the oil storage tank of the feedstock oil unit 100 through a branch gas pipeline, so that a portion of hydrogen B1 mixes with the feedstock oil A; in addition, another portion of hydrogen B2 is sent into the membrane mixing unit 300 through a branch gas pipeline.

[0207] The S-Zorb desulfurization unit 500 is connected to the membrane mixing unit 300, and the second desulfurization product M is fed into the membrane mixing unit 300. The membrane mixing unit 300 is subsequently connected to the olefin removal unit 400, the gas-liquid separation unit 700, and the fractionation unit 800.

[0208] The membrane mixing unit 300, the deolefin removal unit 400, the S-Zorb desulfurization unit 500, the heating unit 510, the gas-liquid separation unit 700, the fractionation unit 800, and the heat exchange units 640 and 650 are all the same as in Example 1.

[0209] The method for preparing gasoline fractions using the above-mentioned apparatus is as follows:

[0210] 1) The feedstock oil A and a portion of hydrogen B1 are mixed in a volume ratio of 1:5 and then heated to 400°C and 3.0 MPa by heat exchange unit 640;

[0211] 2) The feedstock oil A obtained in step 1) and mixed with hydrogen is heated to 420°C through heating unit 510, and then enters S-Zorb desulfurization unit 500 for desulfurization. The desulfurization conditions include: temperature of 420°C and pressure of 3MPa, to obtain the second desulfurization product M.

[0212] 3) After the second desulfurization product M is cooled to 160°C through heat exchange unit 650, it is mixed with another portion of hydrogen B2 at a volume ratio of 1:10 in membrane mixer 300. Then, it undergoes a hydrogenation reaction from bottom to top with the hydrogenation catalyst in the deolefination unit 400 to obtain the second hydrogenation product N. The conditions for the hydrogenation reaction include: pressure of 2.8 MPa, temperature of 160°C, and liquid hourly space velocity of 4.0 h⁻¹. -1 The hydrogen-to-oil volume ratio was 15:1, and the hydrogenation catalyst was the same as in Example 1.

[0213] 4) The second hydrogenation product N obtained in step 3) is subjected to gas-liquid separation in gas-liquid separation unit 700 to obtain the second liquid phase F', wherein the conditions for gas-liquid separation include: temperature of 135-140℃ and pressure of 2.57MPa;

[0214] 5) The second liquid phase F' obtained in step 4) is fractionated through fractionation unit 800 to separate gasoline fraction H' from the bottom of the column. The fractionation conditions include: pressure 0.5-0.6 MPa, feed temperature 130°C, and bottom temperature 136°C.

[0215] The properties of the second desulfurization product M, the second hydrogenation product N, and the gasoline fraction H' obtained in this way are shown in Table 3.

[0216] Example 7

[0217] The apparatus described in Example 6 is used, and the method described in Example 6 is followed, except that:

[0218] In step 3), the conditions for the hydrogenation reaction include: a pressure of 2.6 MPa, a temperature of 170 °C, and a liquid hourly space velocity of 8 h⁻¹. -1 The hydrogen-to-oil volume ratio is 10:1 (adjusting the volume ratio of the second desulfurization product M to another part of hydrogen B2, the same below);

[0219] The properties of the second desulfurization product M, the second hydrogenation product N, and the gasoline fraction H' obtained in this way are shown in Table 3.

[0220] Example 8

[0221] The apparatus described in Example 6 is used, and the method described in Example 6 is followed, except that:

[0222] In step 3), the conditions for the hydrogenation reaction include: a pressure of 2.4 MPa, a temperature of 165 °C, and a liquid hourly space velocity of 10 h⁻¹. -1 The hydrogen-to-oil volume ratio is 5:1;

[0223] The properties of the second desulfurization product M, the second hydrogenation product N, and the gasoline fraction H' obtained in this way are shown in Table 3.

[0224] Example 9

[0225] The apparatus described in Example 6 is used, and the method described in Example 6 is followed, except that:

[0226] In step 3), the conditions for the hydrogenation reaction include: a pressure of 2 MPa, a temperature of 150 °C, and a liquid hourly space velocity of 1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 20:1;

[0227] The properties of the second desulfurization product M, the second hydrogenation product N, and the gasoline fraction H' obtained in this way are shown in Table 3 (continued).

[0228] Example 10

[0229] The apparatus described in Example 6 is used, and the method described in Example 6 is followed, except that:

[0230] In step 3), the hydrogenation catalyst HGO-2 is used to replace the hydrogenation catalyst HDD-2. The support for this catalyst is γ-Al2O3, and the active components are Mo and Co.

[0231] The properties of the second desulfurization product M, the second hydrogenation product N, and the gasoline fraction H' obtained in this way are shown in Table 3 (continued).

[0232] Comparative Example 2

[0233] The apparatus described in Example 6 is used, and the method described in Example 6 is followed, except that:

[0234] In step 3), the conditions for the hydrogenation reaction include: a pressure of 1 MPa, a temperature of 120°C, and a liquid hourly space velocity of 15 h⁻¹. -1 The hydrogen-to-oil volume ratio is 2:1;

[0235] The properties of the second desulfurization product M, the second hydrogenation product N, and the gasoline fraction H' obtained in this way are shown in Table 3 (continued).

[0236] Table 3

[0237]

[0238] Table 3 (continued)

[0239]

[0240] As can be seen from Tables 3 and 3 (continued), after desulfurizing the feedstock oil, hydrodeolefinization under the second hydrotreating conditions specified in this invention can effectively reduce the olefin content in the resulting gasoline fraction and retain the octane number to the maximum extent.

[0241] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A gasoline preparation apparatus, characterized in that, The device comprises a membrane mixing unit (300), an olefin removal unit (400), and an S-Zorb desulfurization unit (500) connected in sequence. The device further includes: The feedstock oil unit (100) is connected to the membrane mixing unit (300); An air supply unit (200) is connected to the feedstock oil unit (100) and the membrane mixing unit (300); A gas-liquid separation unit (700) is disposed after the S-Zorb desulfurization unit (500); and A fractionation unit (800) is disposed after the gas-liquid separation unit (700). The gas supply unit (200) delivers a portion of hydrogen (B1) to the pipeline behind the oil storage tank and before the branch pipeline of the feedstock oil unit (100) through a branch gas pipeline, so that a portion of hydrogen (B1) mixes with the feedstock oil; in addition, another portion of hydrogen (B2) is delivered to the membrane mixing unit (300) through the branch gas pipeline, so that the other portion of hydrogen (B2) mixes with the feedstock oil mixed with a portion of hydrogen (B1) in the membrane mixing unit (300).

2. The gasoline preparation apparatus according to claim 1, wherein the S-Zorb desulfurization unit (500) further comprises a heating unit (510), the heating unit (510) being disposed between the olefin removal unit (400) and the body of the S-Zorb desulfurization unit (500).

3. A gasoline preparation apparatus, characterized in that, The device comprises an S-Zorb desulfurization unit (500), a membrane mixing unit (300), and an olefin removal unit (400) connected in sequence. The device further includes: The feedstock unit (100) is connected to the S-Zorb desulfurization unit (500); An air supply unit (200) is connected to the feedstock oil unit (100) and the membrane mixing unit (300); A gas-liquid separation unit (700) is disposed after the deolefin removal unit (400); and A fractionation unit (800) is disposed after the gas-liquid separation unit (700). The gas supply unit (200) sends a portion of hydrogen (B1) into the pipeline behind the oil storage tank of the feedstock oil unit (100) through a branch gas pipeline, so that a portion of hydrogen (B1) mixes with the feedstock oil; another portion of hydrogen (B2) is sent into the membrane mixing unit (300) through a branch gas pipeline, and is mixed with the desulfurized feedstock oil in the membrane mixing unit (300).

4. The preparation apparatus according to claim 3, wherein, The S-Zorb desulfurization unit (500) further includes a heating unit (510), which is disposed between the feedstock oil unit (100) and the main body of the S-Zorb desulfurization unit (500).

5. The preparation apparatus according to any one of claims 1-4, wherein, The membrane mixing unit (300) includes at least one liquid channel for containing feedstock oil or desulfurization products and a gas channel for containing hydrogen, wherein the liquid channel and the gas channel are adjacent to each other by a membrane tube having through-holes with an average pore size of nanometers.

6. The preparation apparatus according to claim 5, wherein, The membrane tube is formed of a porous material.

7. A method for preparing gasoline, characterized in that, This method uses the preparation apparatus according to any one of claims 1, 2, 5, and 6, and includes the following steps: 1) The step of mixing the feedstock oil (A) with hydrogen in the membrane mixing unit (300); 2) The feedstock oil mixed in step 1) is subjected to a first hydrogenation step in the deolefination unit (400); 3) The step of desulfurizing the first hydrogenation product (C) obtained in step 2) in the S-Zorb desulfurization unit (500) to obtain the first desulfurization product (E), The first hydrogenation conditions include a pressure of 2.5-3.2 MPa, a temperature of 160-170℃, a liquid hourly space velocity of 4-8 h -1 , and a hydrogen to oil volume ratio of 30-45:

1.

8. A method for preparing gasoline, characterized in that, This method uses the preparation apparatus according to any one of claims 3-6 and includes the following steps: 1) The step of desulfurizing the feedstock oil (A) in the S-Zorb desulfurization unit (500); 2) The step of subjecting the second desulfurization product (M) obtained in step 1) to a second hydrogenation in the deolefination unit (400) to obtain a second hydrogenation product (N); The second hydrogenation conditions include: pressure 2.4-2.8 MPa, temperature 160-170℃, liquid hourly space velocity 4-10 h -1 , hydrogen to oil volume ratio 5-15:

1.

9. The preparation method according to claim 7 or 8, wherein, The first and second hydrogenation steps are carried out in the presence of a hydrogenation catalyst, the hydrogenation catalyst containing a support and an active component supported on the support, wherein the support contains at least one of alumina, USY and silicon oxide, and the active component contains at least two of the metal elements Mo, Ni and Co.

10. The preparation method according to claim 9, wherein, The active components are the metallic elements Mo and Ni.

11. The preparation method according to claim 7 or 8, wherein, The method further includes the steps of gas-liquid separation and fractionation of the first desulfurization product (E) or the second hydrogenation product (N).

12. The preparation method according to claim 7 or 8, wherein, The feedstock is one or more of catalytic cracking gasoline, coking gasoline, and pyrolysis gasoline; The feedstock oil has a distillation range of 35-210℃ and an olefin content of 18-35% by volume.

13. The preparation method according to claim 7 or 8, wherein, The feedstock is catalytically cracked gasoline; The feedstock oil has a distillation range of 39-205℃ and an olefin content of 18-27% by volume.

14. The preparation method according to claim 7 or 8, wherein, The prepared gasoline has an olefin content of less than 18% by volume and a sulfur content of less than 10ppm.

15. The preparation method according to claim 14, wherein, The prepared gasoline has an olefin content of less than 15% by volume and a sulfur content of less than 8 ppm.

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