CN111073687B - Preparation method of clean gasoline - Google Patents

Preparation method of clean gasoline Download PDF

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CN111073687B
CN111073687B CN201811211807.4A CN201811211807A CN111073687B CN 111073687 B CN111073687 B CN 111073687B CN 201811211807 A CN201811211807 A CN 201811211807A CN 111073687 B CN111073687 B CN 111073687B
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zsm
gasoline
molecular sieve
content
reaction
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CN111073687A (en
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赵乐平
尹晓莹
尤百玲
郭振东
房莹
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7276—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • 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

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

Abstract

The invention discloses a preparation method of clean gasoline. The method takes rich gas and crude gasoline from the top of a fractionating tower of a catalytic cracking unit as reaction raw materials, and the preparation method comprises the following steps: cutting crude gasoline from a fractionating tower of a catalytic cracking unit to obtain light fraction gasoline and heavy fraction gasoline; carrying out alkali-free deodorization treatment on the light fraction gasoline, and then sending the light fraction gasoline and rich gas into a first fluidized reactor to carry out aromatization reaction with an aromatization catalyst to obtain an aromatization product; sending the heavy fraction gasoline into a hydrodesulfurization reactor to perform selective hydrodesulfurization reaction with a selective hydrodesulfurization catalyst to obtain a heavy fraction gasoline desulfurization product; and mixing the aromatization product with the heavy fraction gasoline desulfurization product to obtain a clean gasoline product. The method can save an absorption-stabilization system in a conventional catalytic cracking device, can produce clean gasoline with low sulfur and low olefin, and improves the yield and octane number of the gasoline.

Description

Preparation method of clean gasoline
Technical Field
The invention relates to a preparation method of clean gasoline, in particular to a method for preparing low-sulfur low-olefin clean gasoline.
Background
With the high-speed increase of Chinese economy, the keeping quantity of automobiles is continuously increased, and the keeping quantity of household automobiles reaches 2.05 hundred million by 6 months of 2017, which also causes the gasoline demand in China to show a continuously increasing state in recent years. Meanwhile, in order to reduce the discharge of harmful substances in the automobile exhaust, China sets increasingly strict clean gasoline standards. From 2017, the national V standard of sulfur-free gasoline (GB 17930-2016) is comprehensively implemented in China, the sulfur content is required to be no more than 10 mu g/g, the olefin content is no more than 24.0V%, and the aromatic hydrocarbon content is no more than 40V%. From 2019, the national VI clean gasoline standard implemented in stages in China is divided into A, B two stages, the national VIA standard requires that the sulfur content is no more than 10 mu g/g, the olefin content is no more than 18.0v%, the aromatic hydrocarbon content is no more than 35v%, and the olefin content in the national VIB standard is further limited to be less than 15 v%. The requirements of Chinese gasoline standards on the contents of sulfur, particularly olefin and aromatic hydrocarbon in gasoline are increasingly severe. Therefore, how to increase the yield of gasoline components and produce finished gasoline meeting national clean gasoline standards of V and VI is a difficult problem to be solved urgently by oil refining enterprises.
China is a catalytic cracking big country, more than 150 sets of catalytic cracking devices of different types are built and put into production, and the total processing capacity of the catalytic cracking devices reaches nearly 150 Mt/a. The catalytic cracking process generally consists of three parts, namely a reaction-regeneration system, a fractionation system and an absorption-stabilization system. The so-called absorption-stabilization system aims at separating the overhead gas (C) from the fractionation section1~C4Hydrocarbons) and a small amount of C3、C4The crude gasoline of the components is analyzed and separated to obtain dry gas, liquefied gas and catalytic cracking stable gasoline with qualified vapor pressure. In the product produced by the catalytic cracking device, the gas accounts for 10-20%, the gasoline component accounts for 40-60%, the diesel oil accounts for 20-40%, and the coke accounts for 5-10%. Liquefied gas component (C) in gas product of catalytic cracking unit3、C4Hydrocarbons) about 90% of the total mass of the gas, the balance being dry gas (C)1、C2Hydrocarbons). At present, most refineries sell dry gas and liquefied gas directly as fuels, the economic benefit is low, and C in the tower top gas is generally used in refineries with MTBE units4The hydrocarbons are separated as feedstock for the production of MTBE. China will realize the popularization and use of ethanol gasoline in 2020, and the promotion is to use E10 vehicle ethanol gasoline without adding MTBE, and after the development of MTBE is hindered, the production raw material C is4The export of hydrocarbons is a problem that oil refineries need to solve.
The gasoline component produced by the catalytic cracking unit accounts for about 70 percent of the total amount of the gasoline finished product. The sulfur content of the catalytic cracking gasoline is generally 200-1000 mug/g, and the olefin content is generally 20.0v% -45.0 v%. The sulfur and olefin contents in the catalytically cracked gasoline are high, and the reduction of the sulfur and olefin contents in the catalytically cracked gasoline is the key to meeting the increasingly strict clean gasoline standard.
In the existing catalytic cracking gasoline desulfurization technology, France Prime-G is mainly used+Selectivity isHydrodesulfurization process and Chinese petrochemical S zorb adsorption desulfurization process. Prime-G+The selective hydrodesulfurization process adopts the processes of full-fraction pre-hydrogenation, light and heavy gasoline fractionation and selective hydrodesulfurization of heavy fraction gasoline, the octane number loss is large when clean gasoline with the sulfur content not more than 10 mu g/g is produced, and the octane number loss of the product is further increased due to the hydrogenation saturation of olefin when national VI standard gasoline with the olefin content not more than 15v% is produced. The S zorb adsorption desulfurization process adopts an adsorption desulfurization method to treat the full-range catalytic cracking gasoline. Compared with the raw material, the product has the advantages of greatly reduced sulfur content, basically unchanged density, distillation range and other properties, slightly reduced olefin, slightly increased alkane and (RON + MON)/2 loss of less than 1.0 unit. However, the method can not greatly reduce the olefin content in the gasoline product, and the problem of olefin reduction can not be solved for the catalytic cracking gasoline with higher olefin content.
CN107974279A discloses a gasoline treatment method. The method comprises the step of feeding a gasoline raw material into a fluidized reactor to perform desulfurization and aromatization reactions with a mixed catalyst of an adsorption desulfurization catalyst and an aromatization catalyst to obtain a desulfurization and aromatization gasoline product. The raw materials treated by the method are gasoline components such as catalytic cracking gasoline, catalytic cracking gasoline and the like, the octane number loss of the obtained gasoline product is small, but the contents of sulfur and olefin cannot meet the national VI clean gasoline standard that the sulfur content is not more than 10 mu g/g and the olefin content is not more than 15.0v%, and the octane number loss is increased if the removal rate of sulfur and olefin is increased.
CN104673377B discloses a method for upgrading catalytically cracked gasoline. The method comprises the steps of cutting a gasoline raw material into light, medium and heavy gasoline fractions, respectively treating the light fraction gasoline, performing sweetening treatment on the light fraction gasoline, performing adsorption desulfurization on the medium fraction gasoline, performing aromatization/isomerization reaction on the medium fraction gasoline, performing selective hydrodesulfurization reaction on the heavy fraction gasoline, and mixing the reaction products to obtain the modified gasoline. The raw material treated by the method is catalytic cracking gasoline, although the sulfur content and the olefin content in the product can be effectively reduced, the method has excessively complex process flow and higher energy consumption.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of clean gasoline. The method can save an absorption-stabilization system in a conventional catalytic cracking device, can produce clean gasoline with low sulfur and low olefin, and improves the yield and octane number of the gasoline.
The invention provides a preparation method of clean gasoline, which takes rich gas and crude gasoline from the top of a fractionating tower of a catalytic cracking unit as reaction raw materials, and the preparation method comprises the following steps: cutting crude gasoline from a fractionating tower of a catalytic cracking unit to obtain light fraction gasoline and heavy fraction gasoline; carrying out alkali-free deodorization treatment on the light fraction gasoline, and then sending the light fraction gasoline and rich gas into a first fluidized reactor to carry out aromatization reaction with an aromatization catalyst to obtain an aromatization product; sending the heavy fraction gasoline into a hydrodesulfurization reactor to perform selective hydrodesulfurization reaction with a selective hydrodesulfurization catalyst to obtain a heavy fraction gasoline desulfurization product; and mixing the aromatization product with the heavy fraction gasoline desulfurization product to obtain a clean gasoline product.
In the reaction raw material, the rich gas from the top of the fractionating tower of the catalytic cracking unit is generally C1~C4Hydrocarbons, naphtha, typically C3~C12The hydrocarbons may be from the top of the fractionating tower of the same catalytic cracking unit, or may be from the top of the fractionating tower of a different catalytic cracking unit.
Among said rich gases, the liquefied gas component (i.e. C)3~C4Hydrocarbons) in a proportion of 80 to 90v%, preferably 85 to 90v%, of the total amount of the rich gas. In the rich gas, the sulfur content is not more than 200 mug/g, preferably 20 mug/g-180 mug/g.
The rich gas is preferably subjected to amine liquid absorption and alkali washing pretreatment to remove hydrogen sulfide, mercaptan and the like in the rich gas, and then is sent to a fluidized reactor to perform aromatization reaction with an aromatization catalyst.
In the crude gasoline, the volume content of olefin is not less than 20v%, preferably 20v% to 45v%, the volume content of aromatic hydrocarbon is not more than 30v%, preferably 15v% to 25v%, and the mass content of sulfur is not more than 500 mu g/g, preferably 100 mu g/g to 500 mu g/g.
The cutting point of the crude gasoline for cutting is 60-80 ℃.
The mass ratio of rich gas to light fraction gasoline in the reaction raw materials is 1: 3-1: 1, preferably 1: 2-1: 1.
the light distillate gasoline may be subjected to alkali-free deodorization using techniques well known in the art. If the conditions adopted by the alkali-free deodorization are as follows: the operating pressure of the reactor is 0.1-1.0 MPa, the reaction temperature is 20-70 ℃, and the feeding airspeed is 0.5h-1~2.0h-1The volume ratio of the air flow to the feeding flow is 0.1-1.0. The catalyst and cocatalyst are those commonly used in the art, and may be selected from commercially available products or prepared according to the knowledge in the art.
The first fluidized reactor is a riser reactor or a fluidized bed reactor.
The fluidized bed reactor can be one or more selected from a fixed fluidized bed, a bulk fluidized bed, a bubbling bed, a turbulent bed, a fast bed, a conveying bed and a dense-phase fluidized bed; the riser reactor can be one or more selected from the group consisting of an equal-diameter riser, an equal-linear-speed riser and various variable-diameter risers.
When a fluidized reactor is adopted, an aromatization catalyst circulation regeneration process is preferably adopted, and the method comprises the following specific steps:
firstly, in a reaction zone, carrying out aromatization reaction on reaction raw materials and a catalyst;
secondly, separating a reaction product from the reacted catalyst;
thirdly, the catalyst after reaction is subjected to carbon burning activation in an oxidation regenerator;
fourthly, reducing and regenerating the activated catalyst by using hydrogen;
and step five, returning the regenerated catalyst to the reaction zone for the next circulation.
Wherein, the condition for the carbon burning activation in the regenerator in the step three is as follows: the pressure is 0.5MPa to 1.5MPa, the volume ratio of the air agent is 500:1 to 1000:1, the temperature is kept constant at 400 ℃ to 550 ℃ for 3.0 to 10.0 hours, and the activated air is air.
The aromatization catalyst comprises a ZSM-5/ZSM-22 composite molecular sieve, an active metal component and a binder.
Based on the weight of the catalyst, the content of the ZSM-5/ZSM-22 composite molecular sieve is 60.0wt% -80 wt%, preferably 65.0wt% -75.0 wt%, the content of the active metal oxide is 2.5wt% -5.0 wt%, preferably 3.0wt% -5.0 wt%, and the content of the binder is 15.0wt% -35.0 wt%, preferably 20.0wt% -30.0 wt%; wherein, in the ZSM-5/ZSM-22 composite molecular sieve, the weight content of the ZSM-5 molecular sieve is 30wt% -75 wt%, preferably 40wt% -70 wt%.
The aromatization catalyst preferably further comprises an auxiliary agent, wherein the auxiliary agent is preferably P, and the content of the auxiliary agent P is 0.5wt% -2.5 wt%, preferably 1.0wt% -2.0 wt% based on the weight of the catalyst.
The precursor of the aromatization catalyst and the auxiliary agent P can be one or a mixture of more of phosphoric acid, ammonium phosphate, ammonium metaphosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
In the ZSM-5/ZSM-22 composite molecular sieve, the ZSM-5 molecular sieve is preferably a zinc isomorphous substituted nano ZSM-5 molecular sieve, the molar ratio of silicon oxide to aluminum oxide is 50-200, preferably 100-200, and the particle size is 10-100 nm. Zinc in the isomorphously substituted zinc nano ZSM-5 molecular sieve is introduced into a molecular sieve framework structure in the preparation process of the molecular sieve and is synthesized by a hydrothermal method. In the zinc isomorphously substituted nano ZSM-5 molecular sieve, zinc accounts for 0.5wt% -4.0 wt%, preferably 1.0wt% -3.8 wt% of the weight of the zinc isomorphously substituted nano ZSM-5 molecular sieve calculated by elements.
In the ZSM-5/ZSM-22 composite molecular sieve, the ZSM-22 molecular sieve is preferably a microporous-mesoporous ZSM-22 molecular sieve, and the molar ratio of silica to alumina is 30-180, preferably 60-150. In the ZSM-5/ZSM-22 composite molecular sieve, the most probable pore diameter of mesopores is 3.5-10 nm, and the pore volume of the mesopores accounts for 30-75%, preferably 40-65% of the total pore volume.
The aromatization catalyst comprises the active metal component which is the combination of at least one metal element in IIIB group and at least one metal element in VIII group, wherein the IIIB group metal is preferably La, and the VIII group metal element is preferably one or more of Ni and Co. Based on the weight of the catalyst, the content of the IIIB group metal in terms of oxide is 0.5wt% -2.0 wt%, and the content of the VIII group metal in terms of oxide is 0.5wt% -4.5 wt%. In the aromatization catalyst, the binder is a binder used in the preparation process of the conventional catalyst, and one or more of alumina and silica are generally used.
The aromatization catalyst used in the process of the present invention may be prepared by the following method:
(1) preparing a ZSM-5/ZSM-22 composite molecular sieve;
(2) loading the active metal component on a ZSM-5/ZSM-22 composite molecular sieve, drying and roasting;
(3) and (3) mixing the molecular sieve obtained in the step (2) with a binder, and molding to obtain the catalyst.
The preferred preparation method of the ZSM-5/ZSM-22 composite molecular sieve in the step (1) is as follows:
dispersing the zinc isomorphously substituted nano ZSM-5 molecular sieve in a synthesis system of the ZSM-22 molecular sieve, performing crystallization reaction for 24-72 hours at 140-180 ℃, washing, filtering and drying a product, and roasting for 3-12 hours at 400-600 ℃ to obtain the ZSM-5/ZSM-22 composite molecular sieve.
In the preparation method of the ZSM-5/ZSM-22 composite molecular sieve in the step (1), the synthesis system of the ZSM-22 molecular sieve is preferably as follows:
and uniformly mixing the reaction raw materials of a silicon source, an aluminum source, a template agent, a pore-expanding agent and water in proportion to obtain a ZSM-22 synthesis system. The pore-enlarging agent is preferably starch. Silicon source of SiO2The aluminum source is A12O3Calculated as C for starch6H10O5The molar ratio of each component in the synthesis system is calculated as follows: SiO 22：A12O3: template agent: starch: water = 1: 0.005-0.03: 0.1-0.6: 0.05-0.2: 20-60.
The silicon source is one or a mixture of tetraethyl orthosilicate, silica sol and water glass; the aluminum source is one or a mixture of more than two of pseudo-boehmite, aluminum sulfate, aluminum chloride and aluminum isopropoxide; the template agent is one or a mixture of more than two of 1, 6-hexamethylene diamine, 1-ethyl pyridine bromide and N-methyl imidazole biquaternary ammonium salt.
Loading the active metal component on the ZSM-5/ZSM-22 composite molecular sieve in the step (2) can be carried out by adopting a conventional impregnation method, such as an excess impregnation method, a saturated impregnation method, a spraying method and the like; or solid oxide and/or its precursor-metal salt or its hydroxide is mechanically mixed with molecular sieve, or precipitation method, sol treatment method, gelation method, etc. The preferred method of loading the metal active component of the present invention is impregnation. Then drying and roasting are carried out to obtain the ZSM-5/ZSM-22 composite molecular sieve loaded with the active metal component. The drying is carried out for 3 to 15 hours at the temperature of 100 to 150 ℃, and the roasting is carried out for 3 to 10 hours at the temperature of 400 to 600 ℃.
Wherein, the step (2) can load the auxiliary agent at the same time of loading the active metal component. The auxiliary agent is preferably P.
The method for loading the auxiliary agent in the step (2) is to carry out the precursor containing the auxiliary agent and the active metal component together by adopting a conventional impregnation method.
The molding in the step (3) is preferably performed by adopting a spray drying mode, and the particle size of the molded catalyst is 20-100 mu m. The temperature of the spray drying is 100-200 ℃.
In the method of the present invention, the aromatization reaction employs the following reaction conditions: the reaction pressure is 1.0MPa to 4.5MPa, the reaction temperature is 300 ℃ to 500 ℃, and the liquid hourly volume space velocity is 4.0 h-1~10.0h-1The volume ratio of hydrogen to oil is 50: 1-200: 1; preferred reaction conditions are as follows: the reaction pressure is 1.5MPa to 3.0MPa, the reaction temperature is 320 ℃ to 400 ℃, and the liquid hourly volume space velocity is 5.0h-1~8.0h-1The volume ratio of hydrogen to oil is 50: 1-150: 1.
In the method, the heavy fraction gasoline and a selective hydrodesulfurization catalyst are subjected to selective hydrodesulfurization reaction in a hydrodesulfurization reactor to obtain a heavy fraction gasoline desulfurization product. The selective hydrodesulfurization catalyst is amorphous Al2O3And/or aluminum silicate carrier, and/or non-noble metal catalyst of VIB group metal such as Mo and/or W, and/or VIII group metal such as Co and/or Ni, and conventional gasoline selective hydrodesulfurization catalyst in various prior art, such as FGH-21/FGH-31 combination developed by China petrochemical industry research instituteCatalysts, ME-1 catalysts, etc., or prepared according to methods known in the art.
In the method of the invention, the reaction conditions adopted by the hydrodesulfurization reaction are as follows: the reaction pressure is 1.0-3.0 MPa, the reaction temperature is 200-300 ℃, and the liquid hourly volume space velocity is 1.0h-1~5.0h-1The volume ratio of hydrogen to oil is 150: 1-450: 1; preferred reaction conditions are as follows: the reaction pressure is 1.5MPa to 2.0MPa, the reaction temperature is 250 ℃ to 280 ℃, and the liquid hourly volume space velocity is 2.0 h-1~4.0h-1The volume ratio of the hydrogen to the oil is 250: 1-350: 1. The sulfur content of the product after hydrodesulfurization treatment of the heavy fraction gasoline can generally reach not more than 10 mu g/g.
In the method, the sulfur content in the clean gasoline is not more than 10 mu g/g, and the olefin content is not more than 15.0 v%.
In the method, the yield of the clean gasoline relative to the crude gasoline is more than 103%, preferably 109-115%, and the RON (research octane number) is increased by 0-0.6 unit, preferably 0.1-0.4 unit relative to the crude gasoline.
Compared with the prior art, the invention has the following advantages:
1. the method of the invention uses the tower top rich gas of a catalytic cracking device and the raw gasoline as reaction raw materials, cuts the raw gasoline, utilizes the light fraction gasoline rich in olefin and the rich gas to perform aromatization and other various reactions, effectively reduces the olefin content in the gasoline, improves the octane number of the gasoline, simultaneously improves the yield of the gasoline, and effectively reduces the sulfur content in the gasoline by performing deep hydrodesulfurization reaction on the heavy fraction gasoline.
2. The method directly uses rich gas and crude gasoline at the top of the fractionating tower in the catalytic cracking device as reaction raw materials, saves an absorption-stabilization system in the catalytic cracking device, reduces the process flow, reduces the energy consumption and improves the economic benefit.
3. The method effectively utilizes the low-added-value and low-added-value clean gasoline component for increasing the yield of the rich gas and the high added value in the catalytic cracking unit, has high yield of the gasoline component, and obviously improves the economic benefit; meanwhile, the problem of the outlet of the carbon-four hydrocarbon raw material in the catalytic cracking liquefied gas caused by the hindered development of MTBE due to the popularization of the ethanol gasoline can be solved.
4. The method combines the characteristics of rich gas and light fraction gasoline, preferably adopts a specific aromatization functional catalyst, leads the olefin in the reaction raw material to generate a plurality of reactions such as proper aromatization and the like, has higher octane number while reducing the content of aromatic hydrocarbon and olefin, reduces the cracking of gasoline components, promotes the conversion of olefin in the rich gas, and thus improves the gasoline yield.
5. The aromatization catalyst of the invention preferably uses a micropore-mesopore ZSM-22 molecular sieve to compound with a zinc isomorphously substituted nanometer ZSM-5 molecular sieve to obtain a ZSM-5/ZSM-22 composite molecular sieve, and the catalyst prepared by the composite molecular sieve can improve the octane number of clean gasoline and reduce the olefin content; in addition, in the preparation method of the aromatization catalyst, the zinc isomorphous substituted nanometer ZSM-5 molecular sieve is dispersed in a synthesis system of the ZSM-22 molecular sieve, and the composite molecular sieve obtained by the specific preparation method is more beneficial to producing clean gasoline.
6. The invention can utilize the existing catalytic gasoline hydrodesulfurization device, only needs to add a light hydrocarbon aromatization reactor and an auxiliary system thereof, and can produce clean gasoline products with low sulfur, low olefin and high octane number.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention, wherein:
the system comprises an A-fractionating tower, a B-alkali-free deodorization treatment unit, a C-fluidization reactor, a D-hydrodesulfurization reactor, an E-mixer, an F-high-pressure gas-liquid separator, a G-hydrogen sulfide removal unit processor, an H-stripping tower, 1-crude gasoline, 2-light fraction gasoline, 3-heavy fraction gasoline, 4-desulfurized light fraction gasoline, 5-hydrogen, 6-rich gas, 7-aromatization product, 8-heavy fraction gasoline hydrodesulfurization product, 9-gasoline mixed product, 10-gas, 11-light hydrocarbon-containing gasoline, 12-recycle hydrogen, 13-liquefied gas and 14-clean gasoline product.
Figure 2 is an XRD diffractogram of different molecular sieves, wherein:
a-ZSM-5 in example 3, b-ZSM-22 in example 3, c-ZSM-5/ZSM-22 composite molecular sieve CM-1 in example 1, d-ZSM-5, ZSM-22 mixed molecular sieve in example 3.
FIG. 3 is a mesoporous distribution diagram of the ZSM-5/ZSM-22 composite molecular sieve CM-1 synthesized in example 1 of the present invention.
Detailed Description
The method and effect of the present invention will be further described with reference to the accompanying drawings and examples, but the present invention is not limited thereto.
The process of the present invention is described in detail below with reference to FIG. 1.
Crude gasoline 1 from a fractionating tower of a catalytic cracking unit enters a fractionating tower A and is cut into light fraction gasoline 2 and heavy fraction gasoline 3; after the light fraction gasoline is treated by the alkali-free deodorization treatment unit B, the obtained desulfurized light fraction gasoline 4 and desulfurized rich gas 6 and hydrogen 5 (fresh hydrogen and circulating hydrogen 12) from a fractionating tower of a catalytic cracking unit enter a fluidized reactor C for aromatization reaction to generate an aromatization product 7; the heavy fraction gasoline 3 and hydrogen 5 (new hydrogen + recycle hydrogen 12) enter a hydrodesulfurization reactor D to generate a heavy fraction gasoline hydrodesulfurization product 8; the gasoline aromatization product 7 and the heavy fraction gasoline hydrodesulfurization product 8 enter a mixer E to obtain a gasoline mixed product 9; the gasoline mixed product 9 enters a high-pressure gas-liquid separator F, gas 10 is separated from the top, and gasoline 11 containing light hydrocarbon is separated from the bottom; after passing through a hydrogen sulfide removal unit processor G, the gas 10 is taken as recycle hydrogen 8 and enters a fluidized reactor C and a hydrodesulfurization reactor D together with new hydrogen; the light hydrocarbon gasoline 11 passes through a stripping tower H, liquefied gas 13 is separated at the top of the tower, and a clean gasoline product 14 with low sulfur and low olefin is obtained at the bottom of the tower.
The present invention will be described in detail with reference to examples.
The properties of the catalytic cracking overhead gas-rich feedstock and the naphtha feedstock used in the examples and comparative examples are shown in tables 1 and 2.
Distilling the crude gasoline in a fractionating tower, and cutting into light fraction gasoline (LCN) and heavy fraction gasoline (HCN), wherein the cutting temperature of the light fraction gasoline (LCN) and the heavy fraction gasoline (HCN) is controlled at 70 ℃. The properties of the light fraction gasoline LCN and the heavy fraction gasoline HCN are shown in table 3.
The heavy fraction gasoline HCN is subjected to hydrodesulfurization reaction in a small fixed bed reactor, and the used catalyst is commercial CoMo/Al2O3The type ME-1 hydrodesulfurization catalyst has the reaction process conditions: the reaction pressure is 1.5MPa, the reaction temperature is 270 ℃, and the liquid hourly space velocity is 3.0h-1The volume ratio of hydrogen to oil is 300: 1. After running for 200h, the properties of the obtained heavy distillate gasoline desulfurization product HCN-P are shown in Table 3.
In the invention, XRD analysis adopts a Japanese physical D/max2500 type X-ray diffractometer, a Cu target, a Ka radiation source, a graphite monochromator, a voltage of 40kV, a current of 80mA, a step length of 0.1 ︒ and a scanning speed of 1 ︒/min. The pore volume and pore size distribution of the molecular sieve are measured by adopting a American Mike ASAP2400 type physical adsorption instrument and adopting a low-temperature liquid nitrogen adsorption method.
Example 1
The aromatization catalyst OTA-F-1 of the embodiment adopts a ZSM-5/ZSM-22 composite molecular sieve CM-1, and in the ZSM-5/ZSM-22 composite molecular sieve CM-1, zinc isomorphously replaces a nanometer ZSM-5 molecular Sieve (SiO)2/Al2O3The mol ratio is 120, the Zn content is 3.5wt%, the grain diameter is 80 nm) accounts for 60wt% of the total weight of the composite molecular sieve, and the ZSM-22 molecular Sieve (SiO) with a micropore-mesopore structure2/Al2O3The molar ratio is 90) accounts for 40wt% of the total weight of the composite molecular sieve. In the ZSM-5/ZSM-22 composite molecular sieve CM-1, the most probable pore diameter of mesopores is 4.5nm, and the pore volume of the mesopores accounts for 60 percent of the total pore volume.
The composition of the aromatization catalyst OTA-F-1 is as follows: the content of the ZSM-5/ZSM-22 composite molecular sieve CM-1 is 65.0wt percent, the content of P is 2.0wt percent, and the content of La is2O32.0wt%, NiO 3.0wt%, and alumina as adhesive.
The preparation method of the OTA-F-1 catalyst comprises the following steps:
0.8g of pseudo-boehmite, 100g of silica sol (30 wt% of silicon dioxide aqueous solution), 11.6g of 1, 6-hexanediamine, 8.1g of starch and 110g of deionized water are stirred and mixed for 1 hour to form uniform precursor solution. Uniformly dispersing 45.8g of zinc isomorphously substituted nano ZSM-5 molecular sieve into the precursor solution, stirring for 30min to form a uniform mixed solution, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining for sealing, statically crystallizing for 48h at 150 ℃, washing, filtering and drying to obtain solid powder, and roasting for 8h at 550 ℃ to obtain CM-1. As can be seen from XRD diffraction analysis (see figure 2) of CM-1, CM-1 has typical diffraction peaks of ZSM-5 and ZSM-22, and is basically free of heterocrystal, and is a ZSM-5/ZSM-22 composite molecular sieve. The analysis of the low-temperature liquid nitrogen adsorption method shows that the CM-1 has a micropore-mesopore structure, wherein the mesopore diameter distribution is shown in figure 3.
Putting ZSM-5/ZSM-22 composite molecular sieve CM-1 into a spray-leaching tank, spraying a solution containing phosphoric acid, lanthanum nitrate and nickel nitrate onto the composite molecular sieve CM-1 within 30 minutes, drying at room temperature, drying for 10 hours at 120 ℃, and roasting at 500 ℃ for 8 hours to obtain the molecular sieve loaded with the active metal and the auxiliary agent; adding the molecular sieve loaded with active metal into the alumina sol, and spray drying at 120 ℃ to prepare the microspheric aromatization catalyst OTA-F-1.
Example 2
The ZSM-5/ZSM-22 composite molecular sieve CM-1 used in the aromatization catalyst OTA-F-2 in this example was the same as in example 1.
The composition of the catalyst OTA-F-2 is as follows: the content of the ZSM-5/ZSM-22 composite molecular sieve CM-1 is 70.0wt percent, the content of P is 2.0wt percent, and the content of La is2O3The content was 1.0wt%, the CoO content was 3.5wt%, and the balance was binder alumina.
The preparation method of the OTA-F-2 catalyst comprises the following steps:
placing ZSM-5/ZSM-22 composite molecular sieve CM-1 into a spray-leaching tank, spraying a solution containing phosphoric acid, hydrogen phosphate, lanthanum nitrate and cobalt nitrate onto the composite molecular sieve within 30 minutes, drying at room temperature, drying for 10 hours at 120 ℃, and roasting at 500 ℃ for 8 hours to obtain the molecular sieve loaded with active metal; adding the molecular sieve loaded with active metal into the alumina sol, and spray drying at 120 ℃ to prepare the microspheric catalyst OTA-F-2.
Example 3
This example differs from example 1 in that a ZSM-5, ZSM-22 mixed molecular sieve was used, and the product obtained in example 1 was identified as ZSM-22 molecular sieve by XRD diffraction analysis (see FIG. 2) without adding ZSM-5 molecular sieve in the preparation of CM-1. By cryogenic liquid nitrogenThe adsorption method analysis shows that the ZSM-5 and ZSM-22 mixed molecular sieve has a micropore-mesopore structure. The aromatization catalyst OTA-F-3 of this example had the following composition: the content of the zinc isomorphously substituted nano ZSM-5 molecular sieve (same as example 1) was 39wt%, and the ZSM-22 molecular Sieve (SiO)2/Al2O3Molar ratio of 90) of 26wt%, P of 2.0wt%, La2O32.0wt%, NiO 3.0wt%, and alumina as adhesive.
The preparation method of the OTA-F-3 catalyst comprises the following steps:
uniformly mixing a zinc isomorphously substituted nano ZSM-5 molecular sieve and a ZSM-22 molecular sieve, putting the mixture into a spray-leaching tank, spraying a solution containing phosphoric acid, lanthanum nitrate and nickel nitrate onto a composite molecular sieve within 30 minutes, drying the composite molecular sieve at room temperature, drying the composite molecular sieve for 10 hours at 120 ℃, and roasting the composite molecular sieve for 8 hours at 500 ℃ to obtain an active metal-loaded molecular sieve; adding the molecular sieve loaded with active metal into the alumina sol, and spray drying at 120 ℃ to prepare the microspheric aromatization catalyst OTA-F-3.
Example 4
Compared with example 1, ZSM-5/ZSM-22 composite molecular sieve CM-2 is adopted for preparing the catalyst OTA-F-4 in the example. The difference between the ZSM-5/ZSM-22 composite molecular sieve CM-2 and the CM-1 is that starch is not added in a ZSM-22 molecular sieve powder synthesis system to obtain the CM-2, the XRD diffraction analysis of the CM-2 can be known as that in the ZSM-5/ZSM-22 composite molecular sieve, the analysis of a low-temperature liquid nitrogen adsorption method shows that the CM-2 only has a micropore structure, and the rest is the same as the example 1 to obtain the OTA-F-4 with the aromatization catalyst.
Example 5
The reaction raw materials are rich gas at the top of the industrial catalytic cracking unit and light fraction gasoline (LCN), and the mass ratio of the rich gas at the top of the tower to the light fraction gasoline is 1: 1.5, the raw material properties are shown in tables 1 and 2.
Performing alkali-free deodorization treatment on the light fraction gasoline, performing amine liquid absorption and alkali washing pretreatment on the rich gas, and controlling the sulfur content in the treated light fraction gasoline and the treated rich gas to be reduced to below 10 mug/g. Loading 40mL of OTA-F-1 aromatization catalyst into a small-sized continuous fluidized bed reactor, carrying out aromatization reaction on the treated rich gas and light fraction gasoline in a fluidized bed, and carrying out reactionThe process conditions are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 350 ℃, and the liquid hourly space velocity is 7.0h-1The volume ratio of hydrogen to oil is 120: 1. The conditions for the charcoal-fired activation of the aromatization catalyst were as follows: the pressure is 1.0MPa, the volume ratio of the gas agent is 800:1, the temperature is kept for 6 hours at 520 ℃, the activated gas is air, the activated catalyst is reduced and regenerated by hydrogen, and the regenerated catalyst returns to the small-sized continuous fluidized bed reactor for recycling. After 200h of operation, the properties of the resulting aromatization product are shown in table 4. The properties of the clean gasoline product obtained by mixing the aromatization product and the heavy fraction desulfurized gasoline product HCN-P are shown in table 5.
Example 6
Compared with example 5, the difference is that the aromatization catalyst used is OTA-F-2 and the properties of the resulting aromatization product are shown in Table 4. The properties of the clean gasoline product obtained by mixing the aromatization product and the heavy fraction desulfurized gasoline product HCN-P are shown in table 5.
Example 7
Compared with example 5, the difference is that the aromatization catalyst used is OTA-F-3 and the properties of the resulting aromatization product are shown in Table 4. The properties of the clean gasoline product obtained by mixing the aromatization product and the heavy fraction desulfurized gasoline product HCN-P are shown in table 5.
Example 8
Compared with example 5, the difference is that the aromatization catalyst used is OTA-F-4, and the properties of the resulting aromatization product are shown in Table 4. The properties of the clean gasoline product obtained by mixing the aromatization product and the heavy fraction desulfurized gasoline product HCN-P are shown in table 5.
Comparative example 1
Compared with example 5, the difference is that only light fraction gasoline is used as the raw material for aromatization reaction, the reaction raw material does not contain rich gas, and the aromatization products obtained in the experiment are shown in table 4. The properties of the clean gasoline product obtained by mixing the obtained aromatization product with the heavy fraction desulfurized gasoline product HCN-P are shown in table 5.
Comparative example 2
Compared with example 5, the difference is that the aromatization catalyst used is OTAZ-C-3 aromatization catalyst used in example 1 in CN107974279A, and the aromatization products obtained by the experiment are shown in Table 4. The properties of the clean gasoline product obtained by mixing the obtained aromatization product with the heavy fraction desulfurized gasoline product HCN-P are shown in table 5.
It can be seen from table 5 that, in example 5, the yield of the obtained clean gasoline product is improved by 13.2% compared with the raw gasoline raw material, the octane number is improved by 0.3 unit, and both the sulfur content and the olefin content in the product meet the clean gasoline standard of sulfur content no more than 10 [ mu ] g/g and olefin content no more than 15.0 v%. In example 6, the yield of the obtained clean gasoline product is improved by 12.9% compared with the raw gasoline material, the octane number is improved by 0.2 unit, and both the sulfur and olefin contents in the product meet the clean gasoline standard of sulfur content no more than 10 mu g/g and olefin content no more than 15.0 v%. In example 7, the yield of the obtained clean gasoline product is improved by 4.8% compared with the raw gasoline material, the octane number is not reduced, and the sulfur and olefin contents in the product both meet the clean gasoline standard with sulfur content no more than 10 μ g/g and olefin content no more than 15.0 v%. In example 8, the yield of the obtained clean gasoline product is improved by 4.5% compared with the raw gasoline material, the octane number is not reduced, and both the sulfur and olefin contents in the product meet the clean gasoline standard with sulfur content no more than 10 μ g/g and olefin content no more than 15.0 v%. Compared with raw gasoline, the yield of the gasoline product in the comparative example 1 is 96.8%, gasoline components are not increased, the octane number is reduced by 0.1 unit, and the sulfur and olefin contents in the product both meet the clean gasoline standard with the sulfur content of not more than 10 mu g/g and the olefin content of not more than 15.0 v%. Compared with raw gasoline, the yield of the gasoline product in the comparative example 2 is 96.5%, gasoline components are not increased, the octane number is reduced by 0.3 unit, the sulfur content in the product is not more than 10 mu g/g, but the reduction amplitude of the olefin content is limited, the olefin content in the product is 17.5v%, and the clean gasoline standard with the olefin content not more than 15.0v% cannot be met.
It can be seen from the above that the invention can effectively reduce the sulfur and olefin content in the gasoline, improve the octane number of the gasoline, meet the increasingly severe standards for clean gasoline, and increase the yield of gasoline components.
TABLE 1 raw material overhead gas enrichment Properties
Composition of By volume content of%
Hydrogen gas 3.32
Methane 3.64
Ethane (III) 2.10
Ethylene 1.44
Propane 8.78
Propylene (PA) 35.57
Isobutane 15.13
N-butane 3.69
N-butene 8.42
Isobutene 6.45
Trans butylAlkene(s) 6.69
Cis-butenediol 4.52
C5 and C5 or above components 0.24
Total of 100
Sulphur, microgram/g 85
TABLE 2 raw gasoline Properties
Properties of Raw gasoline feedstock
Density, g/cm3 0.732
Sulphur, microgram/g 412
RON 91.1
FIA process gasoline composition
Alkane content, v% 45.4
Olefin content, v% 34.1
Aromatic content, v% 20.5
Distillation range, deg.C
Initial boiling point 25
10% 44
50% 103
90% 172
End point of distillation 195
TABLE 3 Properties of the light and heavy cut gasolines and the desulfurized products of the heavy cut gasolines after cutting
Gasoline type Light fraction gasoline LCN Heavy fraction gasoline HCN Heavy fraction gasoline desulfurization product HCN-P
In the proportion of the whole fraction gasoline% 34.1 65.9 65.6
Density, g/cm3 0.658 0.772 0.772
Sulphur, microgram/g 27.8 616 6.5
RON 92.8 90.1 89.7
FIA process gasoline composition
Alkane content, v% 47.8 44.2 54.7
Olefin content, v% 52.2 24.7 14.1
Aromatic content, v% 0 31.1 31.2
TABLE 4 aromatization reaction product Properties
Experimental protocol Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2
Density, g/cm3 0.683 0.683 0.683 0.683 0.663 0.662
Sulphur, microgram/g 9.5 9.5 9.5 9.5 9.5 9.5
RON 93.8 93.7 93.4 93.4 93.4 92.9
FIA process gasoline composition
Alkane content, v% 59.5 59.4 63.1 63.3 66.4 64.1
Olefin content, v% 13.4 13.8 15.1 15.3 15.3 24.1
Aromatic content, v% 27.1 26.8 21.8 21.4 18.3 11.8
TABLE 5 gasoline product Properties after reaction
Experimental protocol Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2
Yield relative to raw crude gasoline as raw material% 113.2 112.9 104.8 104.5 96.8 96.5
Density, g/cm3 0.735 0.735 0.735 0.735 0.735 0.735
Sulphur, microgram/g 7.8 7.8 7.6 7.6 7.5 7.5
RON 91.4 91.3 91.1 91.1 91.0 90.8
FIA process gasoline composition
Alkane content, v% 56.7 57.4 57.8 57.9 58.7 57.9
Olefin content, v% 13.8 13.5 14.5 14.7 14.5 17.5
Aromatic content, v% 29.5 29.1 27.7 27.4 26.8 24.6
Distillation range, deg.C
Initial boiling point 36 36 36 36 36 36
10% 51 50 51 50 49 50
50% 109 108 108 109 106 108
90% 179 179 179 178 177 178
End point of distillation 198 198 198 198 197 198

Claims (28)

1. A method for preparing clean gasoline by taking rich gas and crude gasoline from the top of a fractionating tower of a catalytic cracking unit as reaction raw materials comprises the following steps: cutting crude gasoline from a fractionating tower of a catalytic cracking unit to obtain light fraction gasoline and heavy fraction gasoline; carrying out alkali-free deodorization treatment on the light fraction gasoline, and then sending the light fraction gasoline and rich gas into a first fluidized reactor to carry out aromatization reaction with an aromatization catalyst to obtain an aromatization product; sending the heavy fraction gasoline into a hydrodesulfurization reactor to perform selective hydrodesulfurization reaction with a selective hydrodesulfurization catalyst to obtain a heavy fraction gasoline desulfurization product; mixing an aromatization product and a heavy fraction gasoline desulfurization product to obtain a clean gasoline product, wherein the aromatization catalyst comprises a ZSM-5/ZSM-22 composite molecular sieve, an active metal component and a binder;
the aromatization reaction adopts the following reaction conditions: the reaction pressure is 1.0MPa to 4.5MPa, the reaction temperature is 300 ℃ to 500 ℃, and the liquid hourly volume space velocity is 4.0 h-1~10.0h-1The volume ratio of hydrogen to oil is 50: 1-200: 1; the reaction conditions adopted by the selective hydrodesulfurization reaction are as follows: the reaction pressure is 1.0-3.0 MPa, the reaction temperature is 200-300 ℃, and the liquid hourly volume space velocity is 1.0h-1~5.0h-1The volume ratio of hydrogen to oil is 150: 1-450: 1;
the aromatization catalyst takes the weight of the catalyst as a reference, the content of the ZSM-5/ZSM-22 composite molecular sieve is 60.0wt% -80 wt%, the content of the active metal oxide is 2.5wt% -5.0 wt%, and the content of the binder is 15.0wt% -35.0 wt%; wherein in the ZSM-5/ZSM-22 composite molecular sieve, the weight content of the ZSM-5 molecular sieve is 30wt% -75 wt%; in the ZSM-5/ZSM-22 composite molecular sieve, the ZSM-5 molecular sieve is a zinc isomorphous substituted nano ZSM-5 molecular sieve, the molar ratio of silicon oxide to aluminum oxide is 50-200, and the particle size is 10-100 nm; in the zinc isomorphously substituted nano ZSM-5 molecular sieve, zinc accounts for 0.5 to 4.0 weight percent of the weight of the zinc isomorphously substituted nano ZSM-5 molecular sieve in terms of elements; in the ZSM-5/ZSM-22 composite molecular sieve, the ZSM-22 molecular sieve is a microporous-mesoporous ZSM-22 molecular sieve, and the molar ratio of silicon oxide to aluminum oxide is 30-180; in the ZSM-5/ZSM-22 composite molecular sieve, the most probable pore diameter of mesopores is 3.5-10 nm, and the pore volume of the mesopores accounts for 30-75% of the total pore volume.
2. The method of claim 1, wherein: in the rich gas, the content of the liquefied gas component accounts for 80-90 v% of the total amount of the rich gas; in the rich gas, the sulfur content is not more than 200 mu g/g.
3. The method of claim 2, wherein: in the rich gas, the content of the liquefied gas component accounts for 85-90 v% of the total amount of the rich gas; in the rich gas, the sulfur content is 20 to 180 mug/g.
4. The method of claim 1, wherein: the rich gas is firstly subjected to amine liquid absorption and alkali washing pretreatment and then is sent into a fluidized reactor to carry out aromatization reaction with an aromatization catalyst.
5. The method of claim 1, wherein: in the crude gasoline, the volume content of olefin is not less than 20v%, the volume content of aromatic hydrocarbon is not more than 30v%, and the mass content of sulfur is not more than 500 mu g/g.
6. The method of claim 5, wherein: in the crude gasoline, the volume content of olefin is 20v% -45 v%, the volume content of aromatic hydrocarbon is 15v% -25 v%, and the mass content of sulfur is 100 mug/g-500 mug/g.
7. The method of claim 1, wherein: the cutting point of the crude gasoline for cutting is 60-80 ℃.
8. The method of claim 1, wherein: the mass ratio of rich gas to light fraction gasoline in the reaction raw materials is 1: 3-1: 1.
9. the method of claim 8, wherein: the mass ratio of rich gas to light fraction gasoline in the reaction raw materials is 1: 2-1: 1.
10. the method of claim 1, wherein: the first fluidized reactor is a riser reactor or a fluidized bed reactor.
11. The method of claim 1, wherein: the aromatization catalyst takes the weight of the catalyst as a reference, the content of the ZSM-5/ZSM-22 composite molecular sieve is 65.0wt% -75.0 wt%, the content of the active metal oxide is 3.0wt% -5.0 wt%, and the content of the binder is 20.0wt% -30.0 wt%; wherein in the ZSM-5/ZSM-22 composite molecular sieve, the weight content of the ZSM-5 molecular sieve is 40wt% -70 wt%.
12. The method of claim 1, wherein: the aromatization catalyst also comprises an auxiliary agent, wherein the auxiliary agent is P, and the content of the auxiliary agent P is 1.0wt% -2.0 wt% based on the weight of the catalyst.
13. The method of claim 12, wherein: based on the weight of the catalyst, the content of the assistant P is 1.0wt% -2.0 wt%.
14. The method of claim 1, wherein: the molar ratio of silicon oxide to aluminum oxide of the ZSM-5 molecular sieve is 100-200, and in the zinc isomorphously substituted nano ZSM-5 molecular sieve, zinc accounts for 1.0-3.8 wt% of the weight of the zinc isomorphously substituted nano ZSM-5 molecular sieve in terms of elements.
15. The method of claim 1, wherein: the molar ratio of silicon oxide to aluminum oxide of the ZSM-22 molecular sieve is 60-150, and the mesoporous volume of the ZSM-5/ZSM-22 composite molecular sieve accounts for 40-65% of the total pore volume.
16. The method of claim 1, wherein: the active metal component is a combination of at least one metal element in a IIIB group and at least one metal element in a VIII group, wherein the IIIB group metal element La, the VIII group metal element Ni and/or Co; based on the weight of the catalyst, the content of the IIIB group metal in terms of oxide is 0.5wt% -2.0 wt%, and the content of the VIII group metal in terms of oxide is 0.5wt% -4.5 wt%.
17. The method of claim 1, wherein: the preparation method of the aromatization catalyst comprises the following steps:
(1) preparing a ZSM-5/ZSM-22 composite molecular sieve;
(2) loading the active metal component on a ZSM-5/ZSM-22 composite molecular sieve, drying and roasting;
(3) and (3) mixing the molecular sieve obtained in the step (2) with a binder, and molding to obtain the catalyst.
18. The method of claim 17, wherein: the preparation method of the ZSM-5/ZSM-22 composite molecular sieve in the step (1) comprises the following steps: dispersing the zinc isomorphously substituted nano ZSM-5 molecular sieve in a synthesis system of the ZSM-22 molecular sieve, performing crystallization reaction for 24-72 hours at 140-180 ℃, washing, filtering and drying a product, and roasting for 3-12 hours at 400-600 ℃ to obtain the ZSM-5/ZSM-22 composite molecular sieve.
19. Push buttonThe method of claim 18, wherein: the synthesis system of the ZSM-22 molecular sieve is as follows: uniformly mixing reaction raw materials including a silicon source, an aluminum source, a template agent, a pore-expanding agent and water in proportion to obtain a ZSM-22 synthesis system; the pore-expanding agent is starch, and the silicon source is SiO2The aluminum source is A12O3Calculated as C for starch6H10O5The molar ratio of each component in the synthesis system is calculated as follows: SiO 22：A12O3: template agent: starch: water = 1: 0.005-0.03: 0.1-0.6: 0.05-0.2: 20-60.
20. The method of claim 19, wherein: the silicon source is one or a mixture of tetraethyl orthosilicate, silica sol and water glass; the aluminum source is one or a mixture of more than two of pseudo-boehmite, aluminum sulfate, aluminum chloride and aluminum isopropoxide; the template agent is one or a mixture of more than two of 1, 6-hexamethylene diamine, 1-ethyl pyridine bromide and N-methyl imidazole biquaternary ammonium salt.
21. The method of claim 17, wherein: and (3) drying at 100-150 ℃ for 3-15 h, and roasting at 400-600 ℃ for 3-10 h.
22. The method of claim 17, wherein: and (2) loading an auxiliary agent P while loading the active metal component.
23. The method of claim 17, wherein: the molding in the step (3) is performed by adopting a spray drying mode, the particle size of the molded catalyst is 20-100 mu m, and the temperature of spray drying is 100-200 ℃.
24. The method of claim 1, wherein: the aromatization reaction adopts the following reaction conditions: the reaction pressure is 1.5MPa to 3.0MPa, the reaction temperature is 320 ℃ to 400 ℃, and the liquid hourly volume space velocity is 5.0h-1~8.0h-1The volume ratio of hydrogen to oil is 50: 1-150: 1.
25. The method of claim 1, wherein: the reaction conditions adopted by the selective hydrodesulfurization reaction are as follows: the reaction pressure is 1.5MPa to 2.0MPa, the reaction temperature is 250 ℃ to 280 ℃, and the liquid hourly volume space velocity is 2.0 h-1~4.0h-1The volume ratio of the hydrogen to the oil is 250: 1-350: 1.
26. The method of claim 1, wherein: the sulfur content in the clean gasoline is not more than 10 mu g/g, and the olefin content is not more than 15.0 v%.
27. The method of claim 1, wherein: the yield of the clean gasoline relative to the crude gasoline is more than 103%, and the RON is increased by 0-0.6 unit relative to the crude gasoline.
28. The method of claim 27, wherein: the yield of the clean gasoline relative to the crude gasoline is 109-115%, and the RON is increased by 0.1-0.4 unit relative to the crude gasoline.
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