CN117085729A - Catalyst for lightening heavy aromatic hydrocarbon and preparation method and application thereof - Google Patents

Catalyst for lightening heavy aromatic hydrocarbon and preparation method and application thereof Download PDF

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CN117085729A
CN117085729A CN202210516657.8A CN202210516657A CN117085729A CN 117085729 A CN117085729 A CN 117085729A CN 202210516657 A CN202210516657 A CN 202210516657A CN 117085729 A CN117085729 A CN 117085729A
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molecular sieve
catalyst
hzsm
aromatic hydrocarbon
silicon source
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张学军
高卓然
胡亚琼
康宏敏
马健波
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Petrochina Co Ltd
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Petrochina Co Ltd
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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
    • B01J29/40—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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

The invention relates to a catalyst for lightening heavy aromatic hydrocarbon, a preparation method and application thereof, wherein the catalyst comprises an HZSM-5 molecular sieve, and the preparation method of the HZSM-5 molecular sieve comprises the following steps: step 1, mixing a silicon source, a molecular sieve, water and inorganic alkali, and reacting to obtain a reaction product; step 2, mixing a silicon source, an aluminum source, water and inorganic alkali to form a mixture, adding the reaction product obtained in the step 1, crystallizing, washing, drying and roasting the crystallized product to obtain the ZSM-5 molecular sieve; and 3, carrying out ion exchange on the ZSM-5 molecular sieve to obtain the HZSM-5 molecular sieve. The catalyst prepared by adopting the small-grain B-acid-rich HZSM-5 molecular sieve has good activity and selectivity in the heavy aromatic hydrocarbon lightening reaction.

Description

Catalyst for lightening heavy aromatic hydrocarbon and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalytic chemistry, and relates to a catalyst for lightening heavy aromatic hydrocarbon, a preparation method thereof and application of the catalyst in lightening the heavy aromatic hydrocarbon.
Background
The ZSM-5 molecular sieve is a molecular sieve with an MFI topological structure, and has a ten-membered ring two-dimensional pore canal system which is vertically crossed, wherein the sizes of ten-membered ring pore canals are respectively 0.55x0.51 nm and 0.56x0.53 nm. ZSM-5 molecular sieve has been widely used in the fields of catalytic cracking, alkylation, aromatization, isomerization, disproportionation of hydrocarbons, petroleum refining of methanol to ethylene, propylene, aromatic hydrocarbon and the like, and petrochemical industry.
CN201910786071.1 discloses a high-activity heavy aromatic hydrocarbon lightening catalyst and a preparation method thereof. The high-activity heavy aromatic hydrocarbon light catalyst is prepared by loading a noble metal precursor on a composite carrier and drying and roasting the noble metal precursor; the noble metal precursor is a platinum (IV) complex prepared by dissolving at least one of sponge platinum or chloroplatinic acid serving as a raw material.
CN201810672063.X discloses a catalyst for selective hydrogenation ring opening of C10+ heavy aromatic hydrocarbon and a preparation method thereof. The catalyst comprises the following components in percentage by mass: 50-80% of HY molecular sieve, 0.05-0.35% of platinum metal and the balance of alumina; siO of the catalyst 2 /Al 2 O 3 The molar ratio is 8-13, the specific surface area is 450-600 m 2 Per gram, the pore volume is 0.35-0.7 cm 3 /g；
CN201810153543.5 relates to a catalyst and its use in c11+ heavy aromatics lightening reactions. The catalyst comprises the following components in parts by weight: a) 5-80 parts of solid acid zeolite; b) 0.05 to 8 parts of a group VIII metal; c) 3 to 25 parts of a group VIB metal oxide; d) 0.1-2 parts of a group VIB metal sulfide; e) 20-95 parts of binder. The catalyst can be used for producing light aromatic hydrocarbon from full fraction C11+ inferior heavy aromatic hydrocarbon.
CN201710461288.6 discloses a process for producing BTX-rich high octane gasoline from heavy aromatics, which cuts heavy aromatics feedstock into monocyclic heavy aromatics and polycyclic aromatics; the selective hydrogenation saturation of the polycyclic aromatic hydrocarbon is carried out to obtain the monocyclic heavy aromatic hydrocarbon, the monocyclic heavy aromatic hydrocarbon is subjected to ring opening reaction of a naphthene ring, and then the monocyclic heavy aromatic hydrocarbon is mixed with the polycyclic aromatic hydrocarbon to carry out hydrocracking and transalkylation reaction, so that the BTX-rich high-octane gasoline is generated. The invention can not only improve the conversion rate of the polycyclic aromatic hydrocarbon in the heavy aromatic hydrocarbon raw material, but also ensure the liquid yield, reduce the yield of dry gas and liquefied gas, reduce the hydrogen consumption and the aromatic hydrocarbon loss, and achieve the purpose of producing BTX-rich high-octane gasoline.
CN201710461283.3 relates to a method for preparing a non-noble metal catalyst for lightening C10+ heavy aromatics. The catalyst of the invention uses simple substance nickel and nickel phosphide (Ni 2 P) is an active phase and takes molecular sieve and alumina as carriers. The competitive adsorbent is adopted to solve the problem that the reaction activity of the catalyst is greatly reduced because aluminum oxide and phosphorus element in the carrier react to generate aluminum phosphate; the low boiling point organic matter with strong reducibility is adopted to reduce the generation temperature of the nickel phosphide phase, reduce the aggregation of nickel phosphide particles and greatly improve the activity of the catalyst; the non-noble metal hydrogenation active phase is adopted to replace noble metal so as to greatly reduce the cost of the catalyst.
CN 201710284445.0A C9+ heavy aromatic hydrocarbon lightening catalyst comprises a carrier and active components with the following content calculated by taking the carrier as a reference, wherein the carrier comprises 5-90 mass percent of EU-1 molecular sieve and 10-95 mass percent of binder, the pore volume of the EU-1 molecular sieve is 0.30-0.70 ml/g, and the specific surface area is 360-500 m 2 And/g. The catalyst is used for the light reaction of C9+ heavy aromatic hydrocarbon and has higher light aromatic hydrocarbon yield.
CN201410642325.X relates to a C10+ heavy aromatic hydrocarbon hydro-transalkylation catalyst and a preparation method, wherein the C10+ heavy aromatic hydrocarbon refers to single/polycyclic aromatic hydrocarbon with carbon number more than or equal to 10 and final distillation point not more than 300 ℃; is characterized in that the catalyst can treat C10+ heavy aromatics under the condition of hydrogen, has higher conversion rate of C10+ heavy aromatics, higher selectivity of mixed xylene and selectivity of C9 aromatics, and realizes the lightening of C10+ heavy aromatics.
CN201410202045.7 relates to a method for increasing yield of aromatic hydrocarbon raw material by inferior heavy aromatic hydrocarbon, which mainly solves the problem that the prior art cannot increase yield of monocyclic aromatic hydrocarbon raw material by inferior heavy aromatic hydrocarbon containing polycyclic aromatic hydrocarbon.
CN201310512276.3 relates to a heavy aromatic hydrocarbon lightening catalyst and a preparation method thereof, which mainly solves the problems of low heavy aromatic hydrocarbon conversion depth, low monocyclic aromatic hydrocarbon yield and selectivity, and fast catalyst deactivation rate in the prior art. The invention solves the problems better by adopting the technical proposal that the catalyst comprises 30 to 70 percent of MCM-41 molecular sieve containing BEA zeolite structural units by weight percent, 29.5 to 69.9 percent of at least one metal selected from gamma-alumina, eta-alumina or pseudo-boehmite as a binder and 0.1 to 0.5 percent of at least one metal selected from Pt, pd or Ir.
CN200910057233.4 relates to a method for lightening heavy aromatic hydrocarbon and transferring alkyl, which mainly solves the problem of low activity when the traditional catalyst is used for lightening heavy aromatic hydrocarbon and transferring alkyl. The invention adopts a novel method for lightening and transalkylation of heavy aromatic hydrocarbon, wherein the catalyst comprises the following components in parts by weight: a) 5-95 parts of core-shell molecular sieve material, b) 95-5 parts of binder, wherein the core phase of the core-shell molecular sieve is ZSM-5, and the shell layer is the technical scheme of beta zeolite crystal grains with the coverage of 50-100%, so that the problem is well solved, and the method can be used in the industrial production of heavy aromatic hydrocarbon lightening and transalkylation.
Molecular sieves are a class of crystalline catalysts that have a high degree of shape selective properties. The grain size and acid content of the molecular sieve are key factors for the excellent performance of various molecular sieve materials. The acid quantity of the existing ZSM-5 is generally lower than that of HY and Hbeta molecular sieves, and the application of the existing ZSM-5 in partial catalytic reaction is limited. Therefore, the HZSM-5 molecular sieve with rich B acid is synthesized, and the HZSM-5 molecular sieve is further prepared into a catalyst for lightening heavy aromatic hydrocarbon.
Disclosure of Invention
The invention mainly aims to provide a catalyst for lightening heavy aromatic hydrocarbon, a preparation method and application thereof, and aims to solve the problems of low acid content and low reaction conversion rate of a catalyst mainly comprising an HZSM-5 molecular sieve in the prior art.
In order to achieve the aim, the invention provides a catalyst for lightening heavy aromatic hydrocarbon, which comprises an HZSM-5 molecular sieve, wherein the particle size of the HZSM-5 molecular sieve is less than 500nm, and the acid amount of the HZSM-5 molecular sieve B is more than 0.8mmol/g.
The HZSM-5 molecular sieve accounts for more than 80 percent of the total weight of the catalyst, and the acid amount of the catalyst B is more than 0.7mmol/g.
The HZSM-5 molecular sieve has the particle size smaller than 200nm and the B acid amount larger than 1.0mmol/g.
The HZSM-5 molecular sieve has the particle size smaller than 100nm and the B acid amount larger than 1.2mmol/g.
The catalyst for lightening heavy aromatic hydrocarbon disclosed by the invention has the advantage that the acid amount of the catalyst B is more than 1.1mmol/g.
In order to achieve the above object, the present invention also provides a method for preparing a catalyst for lightening heavy aromatic hydrocarbon, the catalyst comprising an HZSM-5 molecular sieve, the method for preparing the HZSM-5 molecular sieve comprising:
step 1, mixing a silicon source, a molecular sieve, water and inorganic alkali, and reacting for 4-16 hours at a reaction temperature of 100-150 ℃ to obtain a reaction product; wherein the silicon source is SiO 2 Based on SiO as molecular sieve 2 Calculated by the weight of inorganic base in OH - The molar ratio of the silicon source to the molecular sieve is 0.05-0.5, the molar ratio of the inorganic base to the silicon source is 0.1-1.0, and the molar ratio of the water to the silicon source is 10-100;
step 2, mixing a silicon source, an aluminum source, water and inorganic alkali to form a mixture, adding the reaction product obtained in the step 1, crystallizing for 36-96 hours at 120-180 ℃ in a crystallization kettle, washing the crystallized product, and drying for 4-8 hours at 120-140 ℃ to obtain a 500-phase materialRoasting at 550 ℃ for 4-8 hours to obtain a ZSM-5 molecular sieve; wherein the silicon source is SiO 2 The aluminum source is Al 2 O 3 Calculated by the weight of inorganic base in OH - The mole ratio of the silicon source to the aluminum source is 20-100, the mole ratio of the inorganic base to the silicon source is 0.1-1.0, and the mole ratio of the water to the silicon source is 10-100; the reaction product of the step 1 accounts for 0.05 to 0.50 weight percent of the mixture;
step 3, exchanging the ZSM-5 molecular sieve obtained in the step 2 with 5-10% ammonium salt solution according to the liquid-solid mass ratio of 5-10 and the temperature of 50-80 ℃, for example, exchanging for 3 times; washing the exchanged ZSM-5 molecular sieve with deionized water according to a liquid-solid mass ratio of 5-10, for example, 3 times; drying at 120-140 deg.c for 4-8 hr, and roasting at 450-500 deg.c for 4-8 hr to obtain small grain, B-acid-rich HZSM-5 molecular sieve.
In one embodiment, the ammonium salt in step 3 is a soluble ammonium salt, i.e., a water-soluble ammonium salt such as ammonium chloride, ammonium nitrate, and the like.
In the preparation method, part of ZSM-5 molecular sieve can generate hydrolysis reaction in the step 1, the silicon species and aluminum species dissolved from the molecular sieve can generate rearrangement reaction to generate secondary or intermediate structural units of the molecular sieve, and the dissolved or newly generated secondary or intermediate structural units of the molecular sieve can play a guiding role in the crystallization reaction of the molecular sieve in the step 2 to induce the generation of small-grain and B-acid-rich ZSM-5 molecular sieve. The reason for the small size of the crystallites is that in step 2, the reaction product of step 1 is able to provide a greater number of nucleation centers, increasing the rate of formation of the crystallites of the molecular sieve and thus reducing the size of the crystallites of the molecular sieve. The high acid content of the ZSM-5 molecular sieve B is caused by the fact that the reaction product of the step 1 induces the molecular sieve of high-skeleton aluminum or high-tetra-coordination aluminum in the crystallization reaction of the step 2, so that the acid content of the molecular sieve B is improved.
It has also been found in the study that the addition of a small amount of silicon source in step 1 makes the guiding of the reaction product of step 1 in step 2 more pronounced, which is related to the fact that the addition of silicon-containing compounds favors the dissolution or re-crystallization of new secondary or intermediate building blocks.
The invention relates to a preparation method of a catalyst for lightening heavy aromatic hydrocarbon, wherein the silicon source in the step 1 and the silicon source in the step 2 are respectively at least one of solid silica gel, silica sol and white carbon black; the inorganic base in the step 1 and the inorganic base in the step 2 are respectively at least one of sodium hydroxide and potassium hydroxide; the molecular sieve in the step 1 is a ZSM-5 molecular sieve, and the aluminum source is at least one of sodium metaaluminate and aluminum sulfate.
The invention also provides the HZSM-5 molecular sieve prepared by the preparation method. In a specific embodiment, the HZSM-35 molecular sieve obtained by the method has crystal grains smaller than 500nm, and the HZSM-5 molecular sieve has very high B acid quantity, and the B acid quantity is larger than 0.8mmol/g;
the invention also provides the small-grain B-acid-rich HZSM-5 molecular sieve prepared by the preparation method. In a specific embodiment, HZSM-35 molecular sieve grains obtained by the method are smaller than 200nm, and the amount of B acid is larger than 1.0mmol/g.
The invention also provides the small-grain B-acid-rich HZSM-5 molecular sieve prepared by the preparation method. In a specific embodiment, the HZSM-35 molecular sieve obtained by the method has crystal grains smaller than 100nm and the B acid amount larger than 1.2mmol/g.
The invention relates to a preparation method of a catalyst for lightening heavy aromatic hydrocarbon, which comprises the following steps:
and mixing the HZSM-5 molecular sieve with water, a binder, acid and an extrusion aid, extruding for molding, drying and roasting to obtain the catalyst.
In order to achieve the above purpose, the invention further provides an application of the catalyst obtained by the preparation method in the light weight of heavy aromatics.
The application of the invention, wherein the reaction conditions are as follows: the pressure is 2.0-6.0MPa, the airspeed is 1.0-3.0h -1 The temperature is 300-550 ℃, and the hydrogen-oil ratio is 500-1000:1; the heavy aromatic hydrocarbon is C9+ or C10+ aromatic hydrocarbon.
The invention has the beneficial effects that:
the HZSM-5 molecular sieve with small particle size and high B acid content can be obtained through specific reaction process, molar ratio of reaction raw materials, reaction condition, molar ratio of raw materials and crystallization condition adjustment, and the catalyst prepared by the molecular sieve shows high heavy aromatic hydrocarbon conversion rate and light aromatic hydrocarbon selectivity in a heavy aromatic hydrocarbon lightening experiment.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of the HZSM-5 molecular sieve of example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the HZSM-5 molecular sieve of example 1.
FIG. 3 is an X-ray diffraction (XRD) spectrum of the HZSM-5 molecular sieve of example 2.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the HZSM-5 molecular sieve of example 2.
FIG. 5 is an X-ray diffraction (XRD) pattern of the HZSM-5 molecular sieve of example 3.
FIG. 6 is a Scanning Electron Microscope (SEM) image of the HZSM-5 molecular sieve of example 3.
FIG. 7 is a flow chart of the heavy aromatics light ends process of example 4.
Wherein, the reference numerals:
r1 hydrogenation reactor
R2 light reactor
V2 primary gas-liquid separator
V3 secondary gas-liquid separator
Detailed Description
The following describes embodiments of the present invention in detail: the present examples are carried out on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and the following examples do not specify experimental methods of specific conditions, generally according to conventional conditions, and the following contents refer to weight contents unless otherwise specified.
The invention provides a preparation method of a catalyst for lightening heavy aromatic hydrocarbon, which comprises an HZSM-5 molecular sieve, and the preparation method of the HZSM-5 molecular sieve comprises the following steps:
step 1, mixing a silicon source, a molecular sieve, water and inorganic alkali, and reacting for 4-16 hours at a reaction temperature of 100-150 ℃ to obtain a reaction product; wherein the silicon source is SiO 2 Based on SiO as molecular sieve 2 Calculated by the weight of inorganic base in OH - Molar ratio of the silicon source to the molecular sieve0.05-0.5, wherein the molar ratio of the inorganic base to the silicon source is 0.1-1.0, and the molar ratio of the water to the silicon source is 10-100; preferably, the molar ratio of the silicon source to the molecular sieve is 0.1-0.3, the molar ratio of the inorganic base to the silicon source is 0.2-0.5, and the molar ratio of the water to the silicon source is 20-50; preferably, the reaction temperature is 120-140 ℃ and the time is 8-12 hours.
Step 2, mixing a silicon source, an aluminum source, water and inorganic alkali to form a mixture, adding the reaction product obtained in the step 1, crystallizing for 36-96 hours at 120-180 ℃ in a crystallization kettle, washing the crystallized product, drying for 4-8 hours at 120-140 ℃, and roasting for 4-8 hours at 500-550 ℃ to obtain the ZSM-5 molecular sieve; wherein the silicon source is SiO 2 The aluminum source is Al 2 O 3 Calculated by the weight of inorganic base in OH - The mole ratio of the silicon source to the aluminum source is 20-100, the mole ratio of the inorganic base to the silicon source is 0.1-1.0, and the mole ratio of the water to the silicon source is 10-100; the crystallization product in the step 1 accounts for 0.05 to 0.50 weight percent of the mixture; preferably, the molar ratio of the silicon source to the aluminum source is 30-70, the molar ratio of the inorganic base to the silicon source is 0.2-0.6, the molar ratio of the water to the silicon source is 20-50, and the crystallization product in the step 1 accounts for 0.1-0.3 of the weight of the mixture; preferably, the crystallization temperature is 140-160 ℃ and the crystallization time is 48-72 hours. And washing, drying and roasting the ZSM-5 molecular sieve, wherein the drying temperature is 120-140 ℃, and the roasting temperature is 500-550 ℃.
Step 3, exchanging the ZSM-5 molecular sieve obtained in the step 2 with 5-10% ammonium nitrate solution for 3 times according to the mass ratio of liquid to solid of 5-10 at 50-80 ℃; washing the exchanged ZSM-5 molecular sieve with deionized water for 3 times according to the liquid-solid mass ratio of 5-10; drying at 120-140 deg.c for 4-8 hr, and roasting at 450-500 deg.c for 4-8 hr to obtain small grain, B-acid-rich HZSM-5 molecular sieve.
The small-grain molecular sieve has short pore canal and high accessibility of active site. Thus, small-grain molecular sieves typically have relatively high catalytic activity. In addition, because the molecular sieve pore canal is short, the reaction product can rapidly leave the reaction zone, thereby avoiding the occurrence of secondary reaction and improving the selectivity of the reaction. The number of the apertures of the small-grain molecular sieve is far more than that of the common molecular sieve, and the small-grain molecular sieve is not easy to be blocked by carbon deposition generated by side reaction, so that the carbon deposition resistance of the molecular sieve is improved. Therefore, small-grain molecular sieves tend to exhibit better activity, selectivity, and activity stability than catalysts prepared from conventional particle size molecular sieves.
The B acid site on the molecular sieve is a main catalytic active site, and a high B acid amount tends to show higher catalytic reaction activity. The catalytic activity of the HZSM-5 molecular sieve is lower than that of HY and Hbeta molecular sieves in a plurality of catalytic reactions, but the pore structure of the HZSM-5 molecular sieve often shows good selectivity of target products. Therefore, increasing the amount of B acid in the HZSM-5 molecular sieve is an important direction for increasing the catalyst activity and improving the catalyst performance.
The method can obtain the HZSM-5 molecular sieve with small particle size and high B acid content through the adjustment of specific reaction process, reaction raw material molar ratio, reaction condition, raw material molar ratio and crystallization condition.
In one embodiment, in step 1, the silicon source is at least one of solid silica gel, silica sol, and white carbon black. The molecular sieve is ZSM-5 molecular sieve, and the inorganic base is at least one of sodium hydroxide and potassium hydroxide.
In the step 2, the silicon source is at least one of solid silica gel, silica sol and white carbon black. The aluminum source is at least one of sodium metaaluminate and aluminum sulfate, and the inorganic base is at least one of sodium hydroxide and potassium hydroxide.
The HZSM-5 molecular sieve obtained by the method shows that the particle size of the molecular sieve is less than 500nm by a scanning electron microscope, preferably the grain size of the molecular sieve is less than 200nm, and more preferably the grain size of the molecular sieve is less than 100nm; pyridine infrared analysis shows that the molecular sieve has an amount of B acid greater than 0.8mmol/g, preferably an amount of B acid greater than 1.0mmol/g, and more preferably an amount of B acid greater than 1.2mmol/g.
In one embodiment, the invention also provides a method for preparing a catalyst for lightening heavy aromatics, comprising:
mixing the HZSM-5 molecular sieve with water, a binder, acid and an extrusion aid, extruding for molding, drying and roasting to obtain the catalyst.
The kind and amount of the binder, acid and extrusion aid are not particularly limited in the present invention, and may be adjusted as required by those skilled in the art.
In one embodiment, the catalyst preparation process, steps 2 and 3 have a drying temperature of 120-140 ℃ and a calcination temperature of 450-500 ℃. In another embodiment, the acid is an organic acid or/and an inorganic acid, wherein the organic acid is preferably one or more of acetic acid and citric acid, and the inorganic acid is preferably nitric acid. The invention is not particularly limited in the type of the binder and the extrusion aid, and the binder and the extrusion aid commonly used in the prior art can be, for example, pseudo-boehmite, and the extrusion aid can be sesbania powder and/or methylcellulose.
In one embodiment, the weight content of the HZSM-5 molecular sieve in the heavy aromatics light catalyst is not less than 80%, preferably not less than 90%; the weight content of the binder such as pseudo-boehmite is 5-20%. Too low a content of HZSM-5 in the catalyst can affect product conversion and stability of the catalyst over long periods of operation.
The amount of B acid for the heavy aromatics lights catalyst obtained by the above method is greater than 0.7mmol/g, in one embodiment greater than 0.9mmol/g, and in another embodiment greater than 1.1mmol/g.
The HZSM-5 molecular sieve has small particle size and high B acid content, is used for lightening heavy aromatic hydrocarbon, particularly for selective ring opening of the heavy aromatic hydrocarbon, and has higher reaction conversion rate and higher product selectivity.
In one embodiment, the invention also provides the application of the catalyst in the light weight of heavy aromatics. For example, under hydrogen conditions, C9+ or C10+ heavy aromatics are added to the reactor and the heavy aromatics are lighter to produce lighter aromatics or high octane gasoline blending components in the presence of a catalyst comprising a small-grained B-rich acid HZSM-5 molecular sieve. In another embodiment, the heavy aromatics light weight reaction conditions are: pressure is 2.0-6.0MPa, airspeed is 1.0-3.0h -1 The temperature is 300-550 ℃, and the hydrogen-oil ratio is 500-1000:1. In the invention, the heavy aromatic hydrocarbon can be C9+ or C10+ aromatic hydrocarbon, for example, the heavy aromatic hydrocarbon can be C9+ or C10+ aromatic hydrocarbon of a reforming device, and also can be naphtha crackingThe device is composed of C9+ or C10+ heavy aromatic hydrocarbon. In yet another embodiment, the heavy aromatics light weight reaction conditions are: pressure is 3.0-5.0MPa, airspeed is 1.0-2.0h -1 The temperature is 350-500 ℃, and the hydrogen-oil ratio is 800-1000:1.
The invention can lighten heavy aromatic hydrocarbon to produce light aromatic hydrocarbon or high-octane gasoline blending component by adopting a fixed bed reactor, and can also adopt a moving bed, a fluidized bed and other reaction devices.
The technical scheme of the invention is further described in detail through specific embodiments.
Related test methods in various embodiments:
XRD characterization was performed using a smartlab type X-ray diffractometer from Rigaku Co. The CuK alpha line is used as a radiation source, the tube voltage is 40KV, the tube current is 50mA, the scanning speed is 5 DEG/min, and the scanning range is 2 theta=5-85 deg.
SEM characterization was performed using a type 200F field emission scanning electron microscope from Quanta chrome. The test high voltage was 200KV. The size of the molecular sieve grains was measured by a 200F type field emission scanning electron microscope.
Pyridine adsorption characterization was performed using a Nicolet-6700 Fourier transform infrared spectrometer from Nicolet corporation. The B and L acids of the molecular sieve were determined. The sample is pressed into tablets and then fixed in a reaction tank, and the temperature of the sample is 1 multiplied by 10 -3 purifying for 2 hours at pa and 450 ℃, cooling to 90 ℃, enabling the sample to be saturated and adsorb probe molecular pyridine, then programming to be heated to a specified temperature, carrying out vacuum desorption for 20 minutes, and recording Py-FTIR spectrogram.
There are two important indexes for evaluating the performance of the heavy aromatic hydrocarbon lightening catalyst: the first is the heavy aromatics conversion; the second is light aromatics selectivity, which is defined as:
comparative example 1
1000g of HZSM-5 molecular sieve (supplied by national medicine group chemical reagent Co., ltd., grain size of more than 1 μm, B acid amount of 0.521 mmol/g) was mixed with 100g of pseudo-boehmite (specific surface area 288 m) 2 Mixing evenly per gram, dry basis mass 68 percent and 30g sesbania powder. 50g of nitric acid was added to 850g of deionized water and stirred well. Then adding the mixture into the above mixed material, kneading by a kneader, and extruding and molding by a strip extruder. Dried in an oven at 120℃for 4 hours and transferred to a muffle furnace. Heating to 450 ℃ for 4 hours, keeping the temperature for 4 hours, and roasting to obtain the heavy aromatic hydrocarbon light catalyst A, wherein the infrared analysis of the pyridine of the catalyst A shows that the acid quantity of the catalyst B is 0.472mmol/g.
Comparative example 2
1000g of HZSM-5 molecular sieve (supplied by Shandong aluminium Co., ltd., grain size of less than 1 μm, B acid content of 0.436 mmol/g) was mixed with 100g of pseudo-boehmite (specific surface area 288 m) 2 Mixing uniformly per gram, dry basis 68%), 30g sesbania powder. 30g of nitric acid and 50g of acetic acid are added into 850g of deionized water and stirred uniformly. Then adding the mixture into the above mixed material, kneading by a kneader, and extruding and molding by a strip extruder. Dried in an oven at 120℃for 4 hours and transferred to a muffle furnace. Heating to 500 ℃ for 4 hours, keeping the temperature for 4 hours, and roasting to obtain the heavy aromatic hydrocarbon light catalyst B, wherein the infrared analysis of the pyridine of the catalyst B shows that the acid quantity of the catalyst B is 0.376mmol/g.
Example 1
(1) 200g of deionized water and silica Sol (SiO) were added to a stainless steel reactor at a time 2 100g of sodium hydroxide solution (sodium hydroxide mass content 30%), 100g of ZSM-5 molecular Sieve (SiO) 2 /Al 2 O 3 Molar ratio 20) 90g, stirring uniformly, sealing, and reacting at 140 ℃ for 12 hours.
(2) 300g of deionized water and silica Sol (SiO) were sequentially added to a stainless steel reaction vessel 2 220g of sodium hydroxide solution (mass content of sodium hydroxide is 30%) 30g of aluminum sulfate solution (Al 2 O 3 The mass content is 8.0 percent) of 25g. Stirring was continued while adding. 120g of the reaction product obtained in the step (1) is added, the mixture is stirred uniformly and then sealed, and crystallization is carried out at 175 ℃ for 48 hours. Cooling, filtering and washing after crystallizationAnd drying to obtain the ZSM-5 molecular sieve.
(3) The ZSM-5 molecular sieve is baked for 4 hours at 530 ℃ to remove the template agent, and then exchanged by an ammonium chloride solution with the mass concentration of 10%, wherein the mass ratio of exchanged liquid to solid is 5:1, and the temperature is 80 ℃. After 3 times of exchange, washing with deionized water for 3 times, drying at 120 ℃ for 4 hours, and roasting at 500 for 4 hours to obtain the HZSM-5 molecular sieve.
FIG. 1 is an X-ray diffraction (XRD) spectrum of the HZSM-5 molecular sieve of example 1. As can be seen from FIG. 1, the product obtained in example 1 is the HZSM-5 molecular sieve. FIG. 2 is a Scanning Electron Microscope (SEM) image of the HZSM-5 molecular sieve of example 1, and the particle size of the HZSM-5 molecular sieve obtained from FIG. 2 is less than 500nm. Pyridine infrared analysis of the HZSM-5 molecular sieve of example 1 showed an acid level of 0.832mmol/g B.
(4) 1000g of the small-grain B-acid-rich HZSM-5 molecular sieve (particle size is less than 500nm, B acid content is 0.832 mmol/g) and 100g of pseudo-boehmite (specific surface area 288 m) 2 Mixing evenly per gram, dry basis mass 68 percent and 30g sesbania powder. 50g of nitric acid is added into 850g of deionized water, stirred uniformly, then added into the mixed material, kneaded by a kneader, and extruded by a strip extruder to be molded. Dried in an oven at 120℃for 4 hours and transferred to a muffle furnace. Heating to 450 ℃ for 4 hours, keeping the temperature for 4 hours, and roasting to obtain the heavy aromatic hydrocarbon light catalyst C, wherein the infrared analysis of the pyridine of the catalyst C shows that the acid quantity of B is 0.761mmol/g.
Example 2
(1) 400g of deionized water and white carbon black (SiO) were added to a stainless steel reactor at a time 2 95% by mass, 40g of potassium hydroxide solution (potassium hydroxide mass content: 30%) 200g of ZSM-5 molecular Sieve (SiO) 2 /Al 2 O 3 Molar ratio 20) 120g, stirring uniformly, sealing, and reacting at 120 ℃ for 8 hours.
(2) 300g of deionized water and silica Sol (SiO) were sequentially added to a stainless steel reaction vessel 2 30% by mass, 250g of potassium hydroxide solution (30% by mass of potassium hydroxide) 30g of aluminum sulfate solution (in terms of Al) 2 O 3 The mass content is 8.0 percent) of 50g. Stirring was continued while adding. Then 150g of the reaction product of the step (1) is added, the mixture is stirred uniformly and then sealed, and the mixture is crystallized at 150 DEG CAnd the treatment is carried out for 60 hours. And cooling, filtering, washing and drying after crystallization to obtain the ZSM-5 molecular sieve.
(3) The ZSM-5 molecular sieve is baked for 4 hours at 530 ℃ to remove the template agent, and then exchanged by 5% ammonium chloride solution with the mass concentration, wherein the mass ratio of exchange liquid to solid is 10:1, and the temperature is 60 ℃. After 3 times of exchange, washing with deionized water for 3 times, drying at 120 ℃ for 4 hours, and roasting at 530 for 4 hours to obtain the HZSM-5 molecular sieve.
FIG. 3 is an X-ray diffraction (XRD) spectrum of the HZSM-5 molecular sieve of example 2. As can be seen from FIG. 3, the product obtained in example 2 is the HZSM-5 molecular sieve. FIG. 4 is a Scanning Electron Microscope (SEM) image of the HZSM-5 molecular sieve of example 2, and the particle size of the HZSM-5 molecular sieve obtained from FIG. 4 is less than 200nm. Pyridine infrared analysis of the HZSM-5 molecular sieve of example 2 showed an amount of B acid of 1.015mmol/g.
(4) 1000g of the small-grain B-acid-rich HZSM-5 molecular sieve (the grain diameter is less than 200nm and the B acid content is 1.015 mmol/g) and 100g of pseudo-boehmite (the specific surface area is 288 m) 2 Mixing evenly per gram, dry basis mass content 68 percent and 30g sesbania powder. Adding 30g of nitric acid and 50g of acetic acid into 850g of deionized water, uniformly stirring, adding into the mixed material, kneading by a kneader, and extruding by a strip extruder to form. Dried in an oven at 120℃for 4 hours and transferred to a muffle furnace. Heating to 500 ℃ for 4 hours, keeping the temperature for 4 hours, and roasting to obtain the heavy aromatic hydrocarbon light catalyst D, wherein the infrared analysis of the pyridine of the catalyst D shows that the acid quantity of the B is 0.911mmol/g.
Example 3
(1) 300g of deionized water, 100g of sodium hydroxide solution (sodium hydroxide mass content is 30%) and solid silica gel (SiO) are added into a stainless steel reaction kettle at one time 2 12g of ZSM-5 molecular Sieve (SiO) 2 /Al 2 O 3 Molar ratio 20) 100g, stirring uniformly, sealing, and reacting at 120 ℃ for 12 hours.
(2) 300g of deionized water and silica Sol (SiO) were sequentially added to a stainless steel reaction vessel 2 250g of sodium hydroxide solution (mass content of sodium hydroxide is 30%), 40g of potassium hydroxide solution (mass content of potassium hydroxide is 30%), 10g of aluminum sulfate solution (Al 2 O 3 Quality of meterThe content of the components is 8.0 percent) of 70g. Stirring was continued while adding. 180g of the reaction product obtained in the step (1) is added, the mixture is uniformly stirred and then sealed, and crystallization is carried out at 120 ℃ for 96 hours. And cooling, filtering, washing and drying after crystallization to obtain the ZSM-5 molecular sieve.
(3) The ZSM-5 molecular sieve is baked for 4 hours at 530 ℃ to remove the template agent, and then exchanged by an ammonium chloride solution with the mass concentration of 6%, wherein the mass ratio of exchanged liquid to solid is 5:1, and the temperature is 80 ℃. After 3 times of exchange, washing with deionized water for 3 times, drying at 120 ℃ for 4 hours, and roasting at 500 for 4 hours to obtain the HZSM-5 molecular sieve.
FIG. 5 is an X-ray diffraction (XRD) spectrum of the HZSM-5 molecular sieve of example 3. As can be seen from FIG. 5, the product obtained in example 3 is the HZSM-5 molecular sieve. FIG. 6 is a Scanning Electron Microscope (SEM) image of the HZSM-5 molecular sieve of example 3, and the particle size of the HZSM-5 molecular sieve obtained from FIG. 6 is less than 100nm. Pyridine infrared analysis of the HZSM-5 molecular sieve of example 3 showed an acid level of 1.232mmol/g B. .
(4) 1000g of the small-grain B-acid-rich HZSM-5 molecular sieve (the grain diameter is smaller than 100nm and the B acid content is 1.232 mmol/g) and 100g of pseudo-boehmite (the specific surface area is 288 m) 2 And mixing uniformly per gram, dry basis mass content of 68 percent and 50g of methyl cellulose. 50g of nitric acid is added into 900g of deionized water, stirred uniformly, then added into the mixed material, kneaded by a kneader, and extruded by a strip extruder to be molded. Dried in an oven at 140℃for 4 hours and transferred to a muffle furnace. Heating to 500 ℃ for 4 hours, keeping the temperature for 4 hours, and roasting to obtain the heavy aromatic hydrocarbon light catalyst E, wherein infrared analysis of the pyridine of the catalyst E shows that the acid quantity of B is 1.116mmol/g.
Example 4
The application effect of the catalyst is illustrated by carrying out heavy aromatic hydrocarbon lightening reaction by taking mixed C10+ heavy aromatic hydrocarbon as a raw material.
The heavy aromatic hydrocarbon lightening experimental device is a high-pressure reaction device, an isothermal fixed bed reactor is adopted, and a heavy aromatic hydrocarbon lightening process flow chart is shown in fig. 7.
The hydrogenation reactor R1 was charged with a heavy aromatic hydrocarbon hydrogenation catalyst in which 6wt% of molybdenum oxide and 12wt% of nickel oxide were supported on alumina, and the light aromatic hydrocarbon lightening catalyst of comparative examples 1 to 2 and A, B, C, D, E of examples 1 to 3 were charged in the lightening reactor R2, respectively.
The catalyst is packed in the constant temperature section of the reactor. And loading quartz sand with 20-30 meshes on the upper part and the lower part of the catalyst, and connecting the reactor into a system after the loading is completed. Nitrogen was introduced for the gas tightness test. The airtight pressure was gradually increased to 6.0MPa. The pressure drop is not more than 0.1MPa after the constant time is 2 hours, and the device is qualified in airtight.
The heavy aromatic hydrocarbon raw material with the set flow rate enters a hydrogenation reactor R1 after being metered by a metering pump, enters a hydrogenation reactor R1 bed layer after being heated to a certain temperature in the upper section of the hydrogenation reactor R1 to carry out desulfurization, denitrification and aromatic hydrocarbon saturation reaction, then enters a light-weight reactor R2 after being heated to a certain temperature, and carries out reactions such as aromatic hydrocarbon selective ring opening, dealkylation and the like under the action of a heavy aromatic hydrocarbon light-weight catalyst, the reaction product enters a primary gas-liquid separator V2, the gas product is discharged from the upper part of the primary gas-liquid separator V2, is separated by a secondary gas-liquid separator V4, and is discharged after being metered by a gas flowmeter; the liquid product is discharged from the bottom of the primary gas-liquid separator V2, and is sampled and analyzed after being separated by the secondary gas-liquid separators V3 and V5.
The raw materials for the heavy aromatic hydrocarbon lightening experiment are C10+ heavy aromatic hydrocarbons of a continuous reforming device of a refinery, and the compositions of the C10+ heavy aromatic hydrocarbons are shown in the following table 1.
TABLE 1 C10+ heavy aromatics composition analysis
The C10+ heavy aromatic hydrocarbon is heated under the pressure of 5.0MPa and the space velocity of 2.0h -1 Heavy aromatics hydrogenation reaction (performed in hydrogenation reactor R1) is performed at 320 ℃ and hydrogen-oil ratio of 1000:1, and then the hydrogenation reaction is performed at 5.0MPa and space velocity of 2.0h -1 Carrying out heavy aromatic hydrocarbon lightening reaction (in a lightening reactor R2) at 380 ℃ under the condition of hydrogen-oil ratio of 1000:1, carrying out gas-liquid separation on a liquid product by a primary separator V2, then carrying out further gas-liquid separation on the liquid product by a secondary separator V3 and V5, and then sampling and analyzing the hydrocarbon composition of the liquid product at the bottoms of the secondary separators V3 and V5.
The hydrogenation reactor R1 was charged with heavy aromatic hydrogenation catalyst, and then the light aromatic hydrogenation reactor R2 was charged with the light aromatic hydrogenation catalyst of comparative examples 1 to 2 and light aromatic hydrogenation catalyst of examples 1 to 3, respectively, to conduct evaluation experiments, and the obtained experimental results are shown in table 2.
TABLE 2 evaluation results of catalysts of different comparative examples and examples
As shown in Table 2, in the heavy aromatic hydrocarbon lightening experiment, the catalyst provided by the invention has higher heavy aromatic hydrocarbon conversion rate and light aromatic hydrocarbon selectivity.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. The catalyst for lightening heavy aromatic hydrocarbon is characterized by comprising an HZSM-5 molecular sieve, wherein the particle size of the HZSM-5 molecular sieve is less than 500nm, and the acid content of the HZSM-5 molecular sieve B is more than 0.8mmol/g.
2. The catalyst for the light weight of heavy aromatics according to claim 1, wherein said HZSM-5 molecular sieve has a particle size of less than 100nm and said HZSM-5 molecular sieve has an acid content of greater than 1.2mmol/g.
3. The catalyst for the lightening of heavy aromatics according to claim 1, wherein said catalyst B has an acid content greater than 0.7mmol/g.
4. The catalyst for the lightening of heavy aromatics according to claim 1, wherein said catalyst B has an acid content greater than 1.1mmol/g.
5. The preparation method of the catalyst for lightening heavy aromatic hydrocarbon is characterized in that the catalyst comprises an HZSM-5 molecular sieve, and the preparation method of the HZSM-5 molecular sieve comprises the following steps:
step 1, mixing a silicon source, a molecular sieve, water and inorganic alkali, and reacting for 4-16 hours at the temperature of 100-150 ℃ to obtain a reaction product; wherein the silicon source is SiO 2 Based on SiO as molecular sieve 2 The molar ratio of the inorganic base to the molecular sieve is 0.05-0.5, the molar ratio of the inorganic base to the silicon source is 0.1-1.0:1, and the molar ratio of the water to the silicon source is 10-100;
step 2, mixing a silicon source, an aluminum source, water and inorganic alkali to form a mixture, adding the reaction product obtained in the step 1, crystallizing for 36-96 hours at 120-180 ℃, washing the crystallized product, drying for 4-8 hours at 120-140 ℃, and roasting for 4-8 hours at 500-550 ℃ to obtain the ZSM-5 molecular sieve; wherein the silicon source is SiO 2 The aluminum source is Al 2 O 3 Calculated by the weight of inorganic base in OH - The mole ratio of the silicon source to the aluminum source is 20-100, the mole ratio of the inorganic base to the silicon source is 0.1-1.0, and the mole ratio of the water to the silicon source is 10-100; the reaction product of the step 1 accounts for 0.05 to 0.50 weight percent of the mixture;
step 3, exchanging the ZSM-5 molecular sieve obtained in the step 2 with an ammonium salt solution with the mass concentration of 5-10% according to the liquid-solid mass ratio of 5-10 and the temperature of 50-80 ℃; washing the ZSM-5 molecular sieve subjected to exchange with deionized water according to a liquid-solid mass ratio of 5-10; drying at 120-140 deg.c for 4-8 hr, and roasting at 450-500 deg.c for 4-8 hr to obtain small grain, B-acid-rich HZSM-5 molecular sieve.
6. The method for preparing a heavy aromatics light catalyst according to claim 5, wherein said silicon source in step 1 and said silicon source in step 2 are at least one of solid silica gel, silica sol, and white carbon black, respectively; the inorganic base in the step 1 and the inorganic base in the step 2 are at least one of sodium hydroxide and potassium hydroxide respectively; the molecular sieve in the step 1 is a ZSM-5 molecular sieve, and the aluminum source is at least one of sodium metaaluminate and aluminum sulfate.
7. The method for preparing a catalyst for light weight conversion of heavy aromatics according to claim 5, wherein said method comprises:
and mixing the HZSM-5 molecular sieve with water, a binder, acid and an extrusion aid, extruding for molding, drying and roasting to obtain the catalyst.
8. Use of the catalyst obtained by the preparation method of any one of claims 5 to 7 in the lightening of heavy aromatics.
9. The use according to claim 8, wherein the reaction conditions are: the pressure is 2.0-6.0MPa, the airspeed is 1.0-3.0h -1 The temperature is 300-550 ℃, and the hydrogen-oil ratio is 500-1000:1; the heavy aromatic hydrocarbon is C9+ or C10+ aromatic hydrocarbon.
CN202210516657.8A 2022-05-11 2022-05-11 Catalyst for lightening heavy aromatic hydrocarbon and preparation method and application thereof Pending CN117085729A (en)

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