CN117861715A - Aromatic-enriched refined heavy distillate hydrocracking catalyst, preparation method thereof and aromatic-enriched heavy distillate hydrocracking method - Google Patents

Aromatic-enriched refined heavy distillate hydrocracking catalyst, preparation method thereof and aromatic-enriched heavy distillate hydrocracking method Download PDF

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CN117861715A
CN117861715A CN202211236741.0A CN202211236741A CN117861715A CN 117861715 A CN117861715 A CN 117861715A CN 202211236741 A CN202211236741 A CN 202211236741A CN 117861715 A CN117861715 A CN 117861715A
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aromatic
heavy distillate
hours
molecular sieve
catalyst
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钱斌
马宇春
刘师前
韩亚梅
王燕波
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • 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
    • B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
    • C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
    • C07C4/18—Catalytic processes
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7869—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalysts, in particular to an aromatic-rich refined heavy distillate oil hydrocracking catalyst which comprises the following components in percentage by weight: a) 10 to 30 percent of MoO 3 The method comprises the steps of carrying out a first treatment on the surface of the b) 0.01-5% lanthanide metal oxide; c) 89.99 to 65 percent of acid carrier. The catalyst has the characteristic of increasing the yield of BTX by high-selectivity aromatic-rich heavy distillate oil. The invention provides a preparation method of an aromatic-rich heavy distillate oil hydrocracking catalyst. The invention also provides a hydrocracking method of the aromatic-rich heavy distillate oil. The book is provided withThe method of the invention can ensure that the total content of the polycyclic aromatic hydrocarbon<10% by volume, total aromatics>85% by volume of the refined oil is converted into chemical materials with a xylene content of more than 20% by volume, an ethylbenzene content of less than 1% by volume and a BTX yield of more than 60% by volume.

Description

Aromatic-enriched refined heavy distillate hydrocracking catalyst, preparation method thereof and aromatic-enriched heavy distillate hydrocracking method
Technical Field
The invention relates to the field of catalysts, in particular to an aromatic-rich refined heavy distillate hydrocracking catalyst, a preparation method thereof and an aromatic-rich refined heavy distillate hydrocracking method.
Background
The aromatic-rich heavy distillate oil, such as Light Cycle Oil (LCO), has a high proportion in the diesel pool of China, about 30 percent, is a main secondary processing diesel component, the total aromatic hydrocarbon content of the diesel component is up to 80 percent, the naphthalene-based double-ring aromatic hydrocarbon accounts for about 70 percent, and the single-ring aromatic hydrocarbon and the tricyclic aromatic hydrocarbon respectively account for about 15 percent.
The ethylene tar is also a heavy distillate oil (higher than 205 ℃) rich in aromatic oil (the aromatic hydrocarbon content is higher than 90%), is a product of raw material and high-temperature condensation of products after steam cracking of ethylene cracking raw materials, and mainly comprises monocyclic and polycyclic aromatic hydrocarbon compounds, which have short side chains, high carbon-hydrogen ratio, heavy metals and low ash content, and meanwhile, the ethylene tar also contains heterocyclic compounds of N, S, O and other elements. The yield of ethylene tar varies depending on the cracking feedstock, and generally accounts for about 1/5 of the ethylene yield, which tends to increase with the heavies of the ethylene feedstock.
The ethylene tar has higher yield of each distillation section between 205 ℃ and 300 ℃ and is nearly 60 percent, and then the ethylene tar is extremely heavy colloid asphaltene component. Meanwhile, the ethylene tar has high sulfur content, high content of polycyclic aromatic hydrocarbon and high density. The primary distillation point-205 deg.c fraction has indene and its homolog as main component, the 205-225 deg.c fraction is naphthalene, the 225-245 deg.c fraction is methyl naphthalene, the 245-300 deg.c fraction is dimethyl naphthalene, the 300-360 deg.c fraction contains great amount of anthraquinone, acenaphthene, phenanthrene, etc. and the material of >360 deg.c is colloid and asphaltene with high hydrocarbon ratio. Wherein the naphthalene and the above polycyclic aromatic hydrocarbon account for more than 60 percent.
Foreign ethylene tar is mainly used as a raw material for producing carbon black. There are also many industries beginning to produce aromatic hydrocarbon solvent oils from pyrolysis fuel oils, and major manufacturers are the U.S. Exxon, netherlands Shell, japan Bolus Petroleum, and so on. At present, most of ethylene tar in China is used as fuel or is only subjected to primary processing, so that the utilization rate is low, and the economic benefit is poor.
Cleavage C 9 + Fraction mainly derived from pyrolysis gasoline C separated after passing through BTX column 9 + The aromatic hydrocarbon content of the fraction is up to more than 70 percent (the aromatic hydrocarbon content after dicyclopentadiene is removed can be more than 90 percent), and the fraction accounts for 11 to 22 percent of the yield of ethylene. Most of the pyrolysis C9+ in China is only used as cheap primary raw material and fuel oil or sold after preliminary processing.
How to utilize these low added value LCO, ethylene tar, cracking C 9 + And the like are urgent problems placed in front of petrochemical technology workers. Benzene (B), toluene (T) and xylene (X) are important basic organic chemical raw materials, are widely used for producing products such as polyester, chemical fiber and the like, are closely related to people's clothing and eating, and are in strong demand and rapid increase in recent years. Considering the abundant arene resources in LCO, ethylene tar and cracked C9+, how to crack LCO, ethylene tar and cracked C with low added value by the catalytic conversion technology 9 + Conversion to BTX would be a great opportunity and challenge.
In the field of heavy distillate hydrotreating, the catalytic cracking raw material hydrotreating technology has been industrially applied from the beginning of the 70 th century, and has been applied to many refineries for processing sulfur-containing or high sulfur crude oil. At present, mature catalytic cracking raw material pretreatment technology is already owned at home and abroad, and mainly comprises the following steps: VGO Union and APCU (partial conversion hydrocracking) technology, haldor, UOP IncAroshift technology, VGO Hydrotreating technology, chevron, VGO Hydrodesulfurization technology, exxon, T-star technology, IFP, mobil, AKZO, kellogg MAKfining technology, etc. In order to further improve the product quality and conversion rate, the catalytic raw material hydrogenation pretreatment process is gradually changed from the traditional hydrodesulfurization refining (HDS) to the Mild Hydrocracking (MHC) to improve the denitrification, carbon residue and polycyclic aromatic hydrocarbon saturation capacity.
The aromatic-rich heavy distillate oil has high carbon-hydrogen ratio, the gasoline octane number and diesel cetane number obtained by hydrogenation are lower, the hydrogen consumption is high, and the economy is poor. As reported in CN120034542, the aromatic-rich oil product is added into the heavy distillate oil to be subjected to hydrocracking treatment to produce diesel oil; CN102234539a is also produced by hydrocracking aromatic hydrocarbon in aromatic-rich oil after being fully saturated, and has high production cost and no economy.
The catalyst in the prior art is used for aromatic-rich heavy distillate, and generally adopts hydrogenation saturation and cracking, so that the catalyst has high hydrogen consumption for aromatic-rich heavy distillate with aromatic content of more than 80 percent, and valuable aromatic resources in the aromatic-rich heavy distillate are wasted.
The aromatic-rich heavy distillate oil can be selectively hydrofined by adopting the selective hydrogenation catalyst, and then the refined product is selectively hydrocracked to produce benzene (B), toluene (T) and xylene (X) aromatic hydrocarbon raw materials, so that the added value of the aromatic hydrocarbon raw materials is improved.
Disclosure of Invention
The invention aims to solve the problems that the existing catalyst has high hydrogen consumption and valuable aromatic hydrocarbon resources are wasted in the hydrotreating process of aromatic-rich heavy distillate with high aromatic hydrocarbon content, and provides an aromatic-rich refined heavy distillate hydrocracking catalyst which has the characteristic of increasing the yield of BTX of aromatic-rich heavy distillate with high selectivity.
In order to achieve the above purpose, the invention provides an aromatic-rich refined heavy distillate hydrocracking catalyst, which comprises the following components in percentage by weight:
a)10～30％MoO 3 ；
b) 0.01-5% lanthanide metal oxide;
c) 89.99 to 65 percent of acid carrier.
The second aspect of the invention provides a preparation method of the aromatic-enriched refined heavy distillate hydrocracking catalyst, which comprises the following steps: and (3) carrying out immersion contact on an immersion liquid prepared by the molybdenum source and the lanthanide metal source and an acidic carrier, and then drying and roasting.
The third aspect of the invention provides a method for hydrocracking aromatic-rich refined heavy distillate, comprising the following steps: after the catalyst of the invention is vulcanized, the aromatic-rich refined heavy distillate oil is hydrocracked in a hydrogen atmosphere.
Through the technical scheme, the catalyst is used for hydrocracking the aromatic-rich heavy distillate oil, and has the advantages of high xylene content in the product, low ethylbenzene content and high yields of benzene, toluene and xylene.
Drawings
FIG. 1 is an XRD pattern of the multifunctional acidic support and catalyst of example 1;
FIG. 2 is a graph showing the evaluation results of the catalyst of example 1;
FIG. 3 is a graph showing the evaluation results of the catalyst of comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the aromatic-rich refined heavy distillate refers to the hydrofined product of aromatic-rich heavy distillate raw material.
The invention provides an aromatic-rich refined heavy distillate hydrocracking catalyst, which comprises the following components in percentage by weight:
a)10～30％MoO 3 ；
b) 0.01-5% lanthanide metal oxide;
c) 89.99 to 65 percent of acid carrier.
The hydrocracking catalyst for the aromatic-rich heavy distillate oil provided by the invention has the characteristics of increasing the yield of BTX (benzene-toluene-xylene) from the aromatic-rich heavy distillate oil with high selectivity.
According to a preferred embodiment of the present invention, the lanthanide metal species is optionally broader, and according to a preferred embodiment of the present invention, the lanthanide metal is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and neodymium, preferably from one or more of lanthanum, cerium, praseodymium, and europium, preferably from lanthanum and praseodymium. With the preferred embodiment described above, the selectivity of BTX can be greatly improved.
In the present invention, the acidic carrier may be a commonly used acidic carrier, and for the present invention, it is preferable that the acidic carrier contains a hydrogen-type molecular sieve, the molecular sieve is at least one of H-ZSM-5, H-Y, H-beta, MCM-22, MOR and ZSM-12, and preferably the molecular sieve is at least two of H-ZSM-5, H-Y, H-beta, MCM-22, MOR and ZSM-12.
According to a preferred embodiment of the present invention, the acidic support contains H-ZSM-5, H-Y, H-beta, preferably H-ZSM-5, H-Y and H-beta molecular sieves in a weight ratio of 5 to 50:5 to 60:10 to 80, preferably 5 to 30:10 to 50:10 to 75; thereby further improving the yield and the xylene selectivity of the target product of the invention.
In the present invention, siO of the H-ZSM-5 type molecular sieve is used as long as the purpose of the present invention is achieved 2 /Al 2 O 3 The molar ratio is not particularly critical, and according to a preferred embodiment of the present invention, the H-ZSM-5 type molecular sieve is SiO 2 /Al 2 O 3 The molar ratio is 50-300. By adopting the foregoing preferred embodiment, the BTX yield can be further improved.
In the present invention, siO of the H-Y type molecular sieve is reduced as long as the object of the present invention is achieved 2 /Al 2 O 3 The molar ratio is not particularly critical, and according to a preferred embodiment of the present invention, the H-Y molecular sieve is SiO 2 /Al 2 O 3 The molar ratio is 3-30. By adopting the above preferred embodiment, the BTX yield and the xylene yield can be further improved.
In the present invention, as long as the object of the present invention can be achieved,SiO on the H-beta molecular sieve 2 /Al 2 O 3 The molar ratio is not particularly critical, and according to a preferred embodiment of the present invention, the H-. Beta.type molecular sieve is SiO 2 /Al 2 O 3 The molar ratio is 10-100. By adopting the above preferred embodiment, the BTX yield and the xylene yield can be further improved.
According to a preferred embodiment of the present invention, the acidic support contains the molecular sieve composition and a binder, preferably the molecular sieve composition is present in an amount of 70 to 95% by weight and the binder is present in an amount of 5 to 30% by weight. By adopting the above preferred embodiment, the BTX yield and the xylene yield can be further improved.
In the present invention, the object of the present invention can be achieved by an acidic support having the aforementioned characteristics, and there is no particular limitation on the method for producing the acidic support, and according to a preferred embodiment of the present invention, the method for producing the acidic support comprises:
(1) Uniformly mixing a binder source, H-ZSM-5, H-Y, H-beta powder and optional matrix to obtain a mixture I;
(2) And (3) kneading the mixture I with an acidic aqueous solution, forming, drying and roasting.
According to a preferred embodiment of the invention, the kneading time is 20 to 50 minutes.
According to a preferred embodiment of the present invention, step (1) and/or step (2) is carried out in the presence of an alkali metal salt and/or alkaline earth metal salt, preferably at least one selected from sodium, potassium, calcium, magnesium salt, preferably calcium salt.
According to a preferred embodiment of the invention, the alkali metal salt and/or alkaline earth metal salt is present in a weight ratio to the acidic aqueous solution of from 1:40 to 1:80, calculated as metal oxide.
According to a preferred embodiment of the invention, the weight ratio of the mixture I to the acidic aqueous solution is from 100:5 to 100:150, preferably from 100:50 to 100:100.
According to a preferred embodiment of the invention, the mixture I is kneaded with an acidic aqueous solution, shaped and dried after 5 to 15 hours.
In the present invention, the conditions for drying in the step (2) may be conventional choices in the art, and according to a preferred embodiment of the present invention, the conditions for drying in the step (2) include: the temperature is 80-150 ℃ and the time is 5-10 h.
In the present invention, the conditions for firing in step (2) may be conventional choices in the art, and according to a preferred embodiment of the present invention, the conditions for firing in step (2) include: the temperature is 450-700 ℃, and the time is 0.5-24 h, preferably 3-10 h. By adopting the above preferred embodiment, the BTX yield and the xylene yield can be further improved.
In the present invention, the binder source may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the binder source is selected from at least one of silicon-containing pseudo-boehmite, water glass, white carbon black and alumina sol.
According to a preferred embodiment of the invention, the pseudoboehmite comprises 1 to 30% by weight, preferably 5 to 20% by weight, of silicon on a dry basis (weight of the pseudoboehmite raw powder after dehydration).
In the embodiment of the invention, the silicon-containing 8% pseudo-boehmite is taken as the pseudo-boehmite for illustrating the advantages of the invention, but the invention is not limited to the example.
According to a preferred embodiment of the invention, the matrix content in the mixture I is from 0 to 5% by weight, preferably from 2 to 4% by weight.
In the present invention, the matrix may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the matrix is selected from at least one of methylcellulose, sesbania powder, polyethylene glycol, calcium nitrate, potassium nitrate and hydroxymethyl cellulose, preferably a mixture of methylcellulose and sesbania powder, and the weight ratio of methylcellulose to sesbania powder is 0.5-2:1.
In the present invention, the acidic substance in the acidic aqueous solution may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the acidic substance in the acidic aqueous solution is selected from at least one of nitric acid, phosphoric acid, acetic acid, citric acid, and tartaric acid.
According to a preferred embodiment of the invention, the concentration of the acidic aqueous solution is 1 to 6% by weight.
By adopting the above preferred embodiment, the BTX yield and the xylene yield can be further improved.
In the present invention, the catalyst having the aforementioned characteristics can achieve the object of the present invention, and there is no particular limitation on the preparation method of the catalyst, and according to a preferred embodiment of the present invention, the preparation method of the catalyst includes: and (3) carrying out immersion contact on an immersion liquid prepared by the molybdenum source and the lanthanide metal source and an acidic carrier, and then drying and roasting.
According to a preferred embodiment of the present invention, the impregnating solution contains 0.01 to 10 wt% of an organic additive, preferably 0.5 to 5 wt% of an organic additive.
In the present invention, the organic auxiliary agent may be selected conventionally in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the organic auxiliary agent is selected from one or more of diethyl aminomalonate, urea, citric acid and tartaric acid.
According to a preferred embodiment of the present invention, the organic additive is selected from at least one of diethyl aminomalonate, urea, citric acid. By adopting the foregoing preferred embodiment, the solubility of the active component and the dispersibility of the active component of the subsequent catalyst can be further improved.
In order to further improve the solubility of the active component and the dispersibility of the active component of the subsequent catalyst, according to a preferred embodiment of the invention, the organic auxiliary agent is urea and diethyl aminomalonate, and the weight ratio of urea to diethyl aminomalonate is 0.5-2:1.
According to a preferred embodiment of the present invention, the method for preparing the material, wherein the means of immersion contact comprises: the spray method is adopted for isovolumetric impregnation.
In the present invention, the conditions of the impregnation contact may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the conditions of the impregnation contact include: the dipping temperature is 10-60 ℃, and the dipping is carried out for 0.5-24 h. By adopting the foregoing preferred embodiment, the stability of the catalyst can be further improved.
In the present invention, the conditions for drying in the catalyst preparation method may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the conditions for drying include: the temperature is 30 to 130 ℃, and the drying time is determined according to the temperature, for example, the time is 1 to 6 hours. By adopting the foregoing preferred embodiment, the stability of the catalyst can be further improved.
In the present invention, the conditions of the calcination in the catalyst preparation method may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the conditions of the calcination include: the temperature is 200-600 ℃ and the time is 0.5-24 h; preferably, the temperature is 300-500 ℃ and the time is 1-10 h. By adopting the preferable scheme, the stability and activity of the catalyst can be further improved.
The invention provides a hydrocracking method of aromatic-rich refined heavy distillate oil, which comprises the following steps: the catalyst of the invention is vulcanized, and the aromatic-rich refined heavy distillate oil is hydrocracked in the presence of the vulcanized catalyst under the hydrogen atmosphere.
The oxidation catalyst is converted to the sulfided catalyst prior to use, as is well known to those skilled in the art, e.g., at 350 ℃,3MPa, volume space velocity v=0.8 h -1 ；H 2 Oil (v/v) =600, and sulfur-containing 2000ppm vulcanized Oil is vulcanized on line for 24-60 hours.
The method is particularly suitable for hydrocracking the aromatic-rich heavy distillate oil.
According to a preferred embodiment of the invention, the aromatic hydrocarbon content in the aromatic enriched refined heavy distillate is more than 85 volume percent, the final distillation point is lower than 380 ℃, the initial distillation point is higher than 160 ℃, the content of double-ring and above polycyclic aromatic hydrocarbon is less than 10 volume percent, the nitrogen content is less than 10ppm, and the sulfur content is higher than 50ppm.
The object of the invention is achieved by the process according to the invention, without special requirements on the hydrocracking conditions, which according to a preferred embodiment of the invention comprise: the pressure is 5-8 Mpa and the airspeed is 0.8-6 h -1 The inlet temperature is 260-500 ℃, and the volume ratio of hydrogen to distillate oil is 500-3000:1.
the prior art has low BTX yield, generally only 30-40 vol%, low dimethylbenzene content and high ethylbenzene content.
The present invention will be described with reference to specific examples, but the scope of the present invention is not limited to the examples.
XRD spectrum of the catalyst was measured by RIGAKU D/MAX 2550VB/PC type trans-target X-ray polycrystalline diffractometer (XRD), cu target K α The radiation source, the tube voltage is 40kV, the tube current is 100mA, and the scanning step length is 0.02 degree.
Example 1
Selecting hydrogen type SiO 2 /Al 2 O 3 130 g of ZSM-5 molecular sieve powder (the molar ratio is the same as the rest) with 130, and hydrogen type SiO is selected 2 /Al 2 O 3 145 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 625 g of 20 beta molecular sieve powder, 100 g of silicon-containing 8% pseudoboehmite dry basis weight (143 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal nitrate 3 58 g, la 2 O 3 2 g of impregnating solution, will dissolveThe volume of the solution is controlled at 140 ml, 1 g of urea and 1 g of diethyl aminomalonate are added into the impregnating solution, stirring and dissolving are uniform, 140 g of the multifunctional acid carrier is taken, the impregnating solution is loaded on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, ageing is carried out for 16 hours, drying is carried out for 4 hours at 100 ℃, and roasting is carried out for 3 hours at 450 ℃. Thus obtaining the oxidation catalyst.
The XRD pattern of the multifunctional acid carrier and the catalyst is shown in figure 1. As can be seen from FIG. 1, no significant MoO of the active ingredient is present 3 And the characteristic diffraction peak of the lanthanide metal oxide, the particle size of the active component is small, and the dispersibility is good.
The aromatic-rich heavy distillate feedstock and hydrofined product (referred to as aromatic-rich refined heavy distillate of the present invention) are shown in table 1.
Evaluation conditions: inlet temperature t=450 ℃; volume space velocity v=0.8 h -1 ；H 2 Oil (v/v) =1000; pressure = 6.5MPa.
The evaluation results are shown in Table 2 and FIG. 2. Wherein B refers to benzene, T refers to toluene, X refers to xylene, EB refers to ethylbenzene, and BTX refers to benzene, toluene, and xylene.
As can be seen from FIG. 2, the yield of xylene and BTX was high.
It can be seen from Table 2 that the ethylbenzene yield is low, the xylenes and BTX yields are high, the additional value is low, and the other products are low, so that the economic benefit is remarkable.
Example 2
Selecting hydrogen type SiO 2 /Al 2 O 3 200 g of 130 ZSM-5 molecular sieve powder, and selecting hydrogen type SiO 2 /Al 2 O 3 350 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 300 g of 20 beta molecular sieve powder, 150 g of silicon-containing 8% pseudoboehmite dry basis weight (214 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the above mixed powder, kneading for 35 min, extruding to form strips, and standing for 12 hrAnd after drying for 6 hours at 110 ℃, placing the mixture into a muffle furnace for roasting for 5 hours at 600 ℃ to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, aging for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours to obtain the oxidation catalyst. The XRD spectrum of the oxidation catalyst has no obvious characteristic diffraction peak of active components, which indicates that the active components have small granularity and good dispersibility.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 3
Selecting hydrogen type SiO 2 /Al 2 O 3 200 g of ZSM-5 molecular sieve powder of 250, and selecting hydrogen type SiO 2 /Al 2 O 3 350 g of Y molecular sieve powder of 15, and selecting hydrogen type SiO 2 /Al 2 O 3 300 g of 85 beta molecular sieve powder, 150 g of silicon-containing 8% pseudoboehmite dry basis weight (214 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 700 ℃ for 4 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, adopting a rotary pot spraying method, and adding the impregnating solution into the same volume as the impregnating solution at 40 DEG CThe product is loaded on a multifunctional acid carrier, aged for 16 hours, dried for 4 hours at 100 ℃, and baked for 3 hours at 450 ℃. Thus obtaining the oxidation catalyst. The XRD spectrum of the oxidation catalyst has no obvious characteristic diffraction peak of active components, which indicates that the active components have small granularity and good dispersibility.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 4
Selecting hydrogen type SiO 2 /Al 2 O 3 130 g of 130 ZSM-5 molecular sieve powder and selecting hydrogen type SiO 2 /Al 2 O 3 145 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 625 g of 20 beta molecular sieve powder, 100 g of silicon-containing 8% pseudoboehmite dry basis weight (143 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, eu 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, aging for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours. Thus obtaining the oxidation catalyst.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 5
Selecting hydrogen type SiO 2 /Al 2 O 3 500 g of 130 ZSM-5 molecular sieve powder, and selecting hydrogen type SiO 2 /Al 2 O 3 320 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 80 g of 20 beta molecular sieve powder, 100 g of silicon-containing 8% pseudoboehmite dry basis weight (143 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, aging for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours. Thus obtaining the oxidation catalyst. The XRD spectrum of the oxidation catalyst has no obvious characteristic diffraction peak of active components, which indicates that the active components have small granularity and good dispersibility.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 6
Selecting hydrogen type SiO 2 /Al 2 O 3 130 g of 130 ZSM-5 molecular sieve powder and selecting hydrogen type SiO 2 /Al 2 O 3 145 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 625 g of 20 beta molecular sieve powder, 100 g of silicon-containing 8% pseudoboehmite dry basis weight (143 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the above mixed powder, kneading for 35 min, extruding to obtain the invented productPlacing for 12 hours, drying for 6 hours at 110 ℃, and then placing into a muffle furnace for roasting for 5 hours at 600 ℃ to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of tartaric acid into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, ageing for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours. Thus obtaining the oxidation catalyst. The XRD spectrum of the oxidation catalyst has no obvious characteristic diffraction peak of active components, which indicates that the active components have small granularity and good dispersibility.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 7
Selecting hydrogen type SiO 2 /Al 2 O 3 130 g of 130 ZSM-5 molecular sieve powder and selecting hydrogen type SiO 2 /Al 2 O 3 145 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 625 g of 20 beta molecular sieve powder, 100 g of silicon-containing 8% pseudoboehmite dry basis weight (143 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing compositions from soluble metal precursors 3 58 g, la 2 O 3 1 g, pr 2 O 3 1 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, adopting a rotary pot spraying method, and adding the solution into the solution at 4The impregnating solution is loaded on a multifunctional acid carrier in an equal volume at the temperature of 0 ℃, aged for 16 hours, dried for 4 hours at the temperature of 100 ℃ and baked for 3 hours at the temperature of 450 ℃. Thus obtaining the oxidation catalyst.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 8
Selecting hydrogen type SiO 2 /Al 2 O 3 130 g of MCM-22 molecular sieve powder of 130, and hydrogen type SiO is selected 2 /Al 2 O 3 145 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 625 g of 20 beta molecular sieve powder, 100 g of silicon-containing 8% pseudoboehmite dry basis weight (143 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, aging for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours. Thus obtaining the oxidation catalyst. The XRD spectrum of the oxidation catalyst has no obvious characteristic diffraction peak of active components, which indicates that the active components have small granularity and good dispersibility.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 9
Selecting hydrogen type SiO 2 /Al 2 O 3 ZSM-5 molecules of (molar ratio, balance) 130130 g of sieve powder, hydrogen-type SiO is selected 2 /Al 2 O 3 145 g of MOR molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 625 g of 20 beta molecular sieve powder, 100 g of silicon-containing 8% pseudoboehmite dry basis weight (143 g of water-containing 30% pseudoboehmite raw powder) and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, aging for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours. Thus obtaining the oxidation catalyst. The XRD spectrum of the oxidation catalyst has no obvious characteristic diffraction peak of active components, which indicates that the active components have small granularity and good dispersibility.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 10
Selecting hydrogen type SiO 2 /Al 2 O 3 130 g of ZSM-5 molecular sieve powder with 130 (molar ratio, rest is the same) and selecting hydrogen type SiO 2 /Al 2 O 3 145 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 625 g of ZSM-12 molecular sieve powder of 20, 100 g of siliceous 8% pseudo-boehmite dry basis weight (143 g of water 30% pseudo-boehmite raw powder) and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, then adding the water containing 10 g of calcium oxideThe calcium nitrate is dissolved uniformly, the solution is poured into the mixed powder for kneading for 35 minutes, the mixture is extruded and shaped, the mixture is placed for 12 hours, dried for 6 hours at 110 ℃, and then placed into a muffle furnace for roasting for 5 hours at 600 ℃ to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, aging for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours. Thus obtaining the oxidation catalyst. The XRD spectrum of the oxidation catalyst has no obvious characteristic diffraction peak of active components, which indicates that the active components have small granularity and good dispersibility.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 11
Selecting hydrogen type SiO 2 /Al 2 O 3 200 g of 130 ZSM-5 molecular sieve powder, and selecting hydrogen type SiO 2 /Al 2 O 3 350 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 300 g of 20 beta molecular sieve powder, 150 g of silicon-containing 8 wt% pseudo-boehmite, 15 g of methylcellulose and 15 g of sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of citric acid into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, adopting a rotary pot spraying method,and loading the impregnating solution on a multifunctional acid carrier in an equal volume at 40 ℃, aging for 16 hours, drying for 4 hours at 100 ℃, and roasting for 3 hours at 450 ℃ to obtain the oxidation catalyst. The XRD spectrum of the oxidation catalyst has no obvious characteristic diffraction peak of active components, which indicates that the active components have small granularity and good dispersibility.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
Example 12
Selecting hydrogen type SiO 2 /Al 2 O 3 850 g of ZSM-5 molecular sieve powder of 130, 150 g of silicon-containing 8 wt% pseudo-boehmite, and 15 g of methylcellulose and sessile turnkey powder respectively are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g, la 2 O 3 2 g of impregnating solution, controlling the volume of the solution to 140 ml, adding 1 g of urea and 1 g of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 140 g of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, aging for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours. Thus obtaining the oxidation catalyst.
The evaluation materials and the evaluation conditions were the same as in example 1.
The evaluation results are shown in Table 2.
Comparative example 1
Selecting hydrogen type SiO 2 /Al 2 O 3 200 g of 130 ZSM-5 molecular sieve powder, and selecting hydrogen type SiO 2 /Al 2 O 3 350 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 20 g of beta molecular sieve powder, 150 g of silicon-containing 8% pseudoboehmite dry basis weight (30 g of water214 g of pseudo-boehmite raw powder with the weight percent), and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 16 g, la 2 O 3 The method comprises the steps of controlling the volume of the impregnating solution to be 180 milliliters, adding 1 gram of urea and 1 gram of diethyl aminomalonate into the impregnating solution, stirring and dissolving uniformly, taking 180 grams of multifunctional acid carrier, loading the impregnating solution on the multifunctional acid carrier in an equal volume manner by adopting a rotary pot spraying method at 40 ℃, aging for 16 hours, drying at 100 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours to obtain the oxidation catalyst.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2 and FIG. 3, and it can be seen from FIG. 3 that the yields of xylene and BTX are low, which is far lower than that of example 1.
Comparative example 2
Selecting hydrogen type SiO 2 /Al 2 O 3 200 g of 130 ZSM-5 molecular sieve powder, and selecting hydrogen type SiO 2 /Al 2 O 3 350 g of Y molecular sieve powder of 7, and selecting hydrogen type SiO 2 /Al 2 O 3 300 g of 20 beta molecular sieve powder, 150 g of silicon-containing 8 wt% pseudo-boehmite (214 g of water-containing 30 wt% pseudo-boehmite raw powder) and 15 g of methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake at 600 ℃ for 5 hours to obtain the multifunctional acid carrier.
Preparation of MoO-containing precursor from soluble metal salt 3 58 g of the solutionThe product is controlled at 140 milliliters, 1 gram of urea and 1 gram of diethyl aminomalonate are added into the impregnating solution, stirring and dissolving are carried out uniformly, 140 grams of multifunctional acid carrier is taken, the impregnating solution is loaded on the multifunctional acid carrier in an equal volume manner under the condition of 40 ℃ by adopting a rotary pot spraying method, ageing is carried out for 16 hours, drying is carried out for 4 hours at 100 ℃, and roasting is carried out at 450 ℃ to obtain the oxidation catalyst.
The raw materials and conditions were evaluated in the same manner as in example 1.
The evaluation results are shown in Table 2.
TABLE 1
Fraction hydrocarbon composition (vol%) Raw materials Hydrofined product
Paraffin hydrocarbons 5.3 7.1
Cycloparaffin 0.4 0.8
Di-cycloalkane 1.2 2.1
Tricycloalkanes 0.8 1.7
Total cycloalkane 2.4 4.6
Total saturated hydrocarbons 7.7 11.7
Alkylbenzene 7.5 19.5
Indane or tetrahydronaphthalene 7.7 42.4
Indene type 1.3 17.2
Total monocyclic aromatic hydrocarbons 16.5 79.1
Naphthalene (naphthalene) 0.7 1.0
Naphthalene type 39.9 2.7
Acenaphthene type 15.6 1.7
Acenaphthylenes 9.5 3.2
Total bicyclic aromatic hydrocarbons 65.7 8.6
Tricyclic aromatic hydrocarbons 10.1 0.6
Total aromatic hydrocarbon 92.3 88.3
Colloid 0 0
Total volume of 100 100
Initial point of distillation, DEG C 171 165
End point, DEG C 375 370
S/ppm 3650 100
N/ppm 420 3
The above composition was measured by multidimensional chromatography. From the results of table 1, it can be seen that the hydrofinished product had a total content of polycyclic aromatic hydrocarbons of < 10% by volume and a total aromatic hydrocarbon content of > 85% by volume.
TABLE 2
(vol%) B T X EB C8* BTX** Others
Example 1 9.3 28.6 26.9 0.7 27.6 64.8 34.5
Example 2 10.5 26.3 25.2 0.6 25.8 62.0 37.4
Example 3 10.2 27.0 25.9 0.6 26.5 63.1 36.3
Example 4 11.5 23.6 21.3 1.0 22.3 56.1 42.9
Example 5 28.0 18.5 9.3 0.9 10.2 55.8 43.3
Example 6 8.5 23.8 22.6 1.0 23.6 54.9 44.1
Example 7 10.7 27.5 27.1 0.8 27.9 65.3 33.9
Example 8 12.1 22.3 17.5 2.3 19.8 51.9 45.8
Example 9 13.5 22.3 16.9 3.5 20.4 52.7 43.8
Example 10 16.2 21.9 14.1 2.8 16.9 52.2 45.0
Example 11 6.3 18.6 17.7 1.4 19.1 42.6 56.0
Example 12 18.1 17.7 7.8 2.4 10.2 43.6 54.0
Comparative example 1 18.6 14.7 4.9 0.8 5.7 38.2 61.0
Comparative example 2 14.4 9.6 7.7 1.6 9.3 31.7 66.7
* C8 is the sum of X and EB; * Data for 400 hours on-line reaction.
Wherein B refers to benzene. Measured by chromatographic analysis;
t refers to toluene. Measured by chromatographic analysis;
x refers to xylene. Measured by chromatographic analysis;
EB refers to ethylbenzene. Measured by chromatographic analysis;
BTX refers to benzene, toluene, xylene. Measured by chromatographic analysis;
other means that the non-BTX and EB components were measured by chromatographic analysis;
the above composition was measured by chromatographic analysis. From the results of Table 2, it can be seen that the yield of BTX obtained by selective hydrocracking of the purified product was high.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, the endpoints of each of the ranges, and the individual points are combinable with each other to provide one or more new numerical ranges, which are to be considered as specifically disclosed herein.

Claims (10)

1. The aromatic-rich refined heavy distillate hydrocracking catalyst is characterized by comprising the following components in percentage by weight:
a)10～30％MoO 3 ；
b) 0.01-5% lanthanide metal oxide;
c) 89.99 to 65 percent of acid carrier.
2. The catalyst according to claim 1, wherein,
the lanthanide metal is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and neodymium, preferably from one or more of lanthanum, cerium, praseodymium, and europium, preferably from lanthanum and praseodymium.
3. The catalyst according to claim 1 or 2, wherein,
the acidic carrier contains a hydrogen type molecular sieve, wherein the molecular sieve is at least one of H-ZSM-5, H-Y, H-beta, MCM-22, MOR and ZSM-12, and preferably at least two of H-ZSM-5, H-Y, H-beta, MCM-22, MOR and ZSM-12;
preferably, the acidic support comprises an H-ZSM-5, H-Y, H-beta molecular sieve composition;
preferably, the weight ratio of H-ZSM-5, H-Y and H-beta molecular sieve is 5-50:5-60:10-80, preferably 5-30:10-50:10-75;
preferably, the SiO of H-ZSM-5 2 /Al 2 O 3 The molar ratio is 50-300;
preferably, the SiO of the H-Y 2 /Al 2 O 3 The molar ratio is 3-30;
preferably, the SiO of H-beta 2 /Al 2 O 3 The molar ratio is 10-100;
preferably, the acidic support comprises the molecular sieve composition and a binder, preferably the molecular sieve composition is present in an amount of from 70 to 95% by weight and the binder is present in an amount of from 5 to 30% by weight.
4. A catalyst according to any one of claims 1 to 3, wherein the process for preparing the acidic support comprises:
(1) Uniformly mixing a binder source, H-ZSM-5, H-Y, H-beta powder and optional matrix to obtain a mixture I;
(2) And (3) kneading the mixture I with an acidic aqueous solution, forming, drying and roasting.
5. The catalyst according to claim 4, wherein,
the weight ratio of the mixture I to the acidic aqueous solution is 100:5-100:150, preferably 100:50-100:100; and/or
The roasting conditions include: the temperature is 450-700 ℃, and the time is 0.5-24 h, preferably 3-10 h;
and/or
The adhesive source is at least one selected from silicon-containing pseudo-boehmite, water glass, white carbon black and alumina sol;
preferably, the pseudo-boehmite comprises 1-30% by weight of silicon on a dry basis, preferably 5-20%; and/or
The amount of matrix in the mixture I is 0 to 5 wt.%, preferably 2 to 4 wt.%; and/or
The matrix is selected from at least one of methyl cellulose, sesbania powder, polyethylene glycol and hydroxymethyl cellulose, preferably a mixture of methyl cellulose and sesbania powder, and the weight ratio of the methyl cellulose to the sesbania powder is 0.5-2:1; and/or
The acidic substance in the acidic aqueous solution is at least one selected from nitric acid, phosphoric acid, acetic acid, citric acid and tartaric acid;
preferably, the concentration of the acidic aqueous solution is 1 to 6% by weight.
6. A process for preparing an aromatic-rich heavy distillate hydrocracking catalyst as claimed in any one of claims 1 to 5, wherein the process comprises: and (3) carrying out immersion contact on an immersion liquid prepared by the molybdenum source and the lanthanide metal source and an acidic carrier, and then drying and roasting.
7. The preparation method according to claim 6, wherein,
the impregnating solution contains 0.01 to 10 weight percent of organic auxiliary agent, preferably 0.5 to 5 weight percent of organic auxiliary agent; and/or
Preferably, the organic additive is selected from one or more of diethyl aminomalonate, urea, citric acid and tartaric acid;
more preferably, the organic additive is selected from at least one of diethyl aminomalonate, urea, and citric acid;
particularly preferably, the organic auxiliary agent is urea and diethyl aminomalonate, and the weight ratio of the urea to the diethyl aminomalonate is 0.5-2:1.
8. The production method according to claim 6 or 7, wherein the manner of immersion contact comprises:
soaking with spray method to obtain uniform volume; and/or
The conditions of the immersion contact include: the dipping temperature is 10-60 ℃, and the dipping is carried out for 0.5-24 h; and/or
The drying conditions included: the temperature is 30-130 ℃ and the time is 1-6 h; and/or
The roasting conditions include: the temperature is 200-600 ℃, preferably 300-500 ℃; the time is 0.5 to 24 hours, preferably 1 to 10 hours.
9. A method for hydrocracking aromatic-rich refined heavy distillate oil, which is characterized by comprising the following steps: after sulfiding the catalyst of any one of claims 1-5, hydrocracking the aromatic-enriched refined heavy distillate in the presence of sulfided catalyst under hydrogen atmosphere.
10. The method of claim 9, wherein,
in the aromatic-rich refined heavy distillate oil, the total aromatic hydrocarbon content is more than 85 volume percent, the final distillation point is lower than 380 ℃, the initial distillation point is more than 160 ℃, the content of double-ring and above polycyclic aromatic hydrocarbons is less than 10 volume percent, the nitrogen content is less than 10ppm, and the sulfur content is more than 50ppm;
the hydrocracking conditions included: the pressure is 5-8 Mpa, the volume airspeed is 0.8-6 h -1 The inlet temperature is 260-500 ℃, and the volume ratio of hydrogen to distillate oil is 500-3000:1.
CN202211236741.0A 2022-10-10 2022-10-10 Aromatic-enriched refined heavy distillate hydrocracking catalyst, preparation method thereof and aromatic-enriched heavy distillate hydrocracking method Pending CN117861715A (en)

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