CN112439447B - Heavy aromatic hydrocarbon lightening catalyst and preparation method and application thereof - Google Patents
Heavy aromatic hydrocarbon lightening catalyst and preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- 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
- B01J29/7023—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/26—Fuel gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A heavy aromatic hydrocarbon lightening catalyst comprises a composite carrier and a VA element oxide with the content of 0.5-10.0 mass percent calculated by taking the composite carrier as a reference, wherein the composite carrier comprises 10-45 mass percent of ZSM-5 zeolite, 10-45 mass percent of EU-1 zeolite and 10-80 mass percent of alumina. The catalyst is used for C 9 ～C 12 The non-hydrogenation light reaction of heavy aromatics can obtain higher light aromatics yield and high-quality liquefied gas rich in propane as a byproduct.
Description
Technical Field
The invention relates to a hydrocarbon conversion catalyst and a preparation method thereof, in particular to a heavy aromatic hydrocarbon lightening catalyst and a preparation method thereof.
Background
Heavy aromatics refer to C as a byproduct in petroleum and coal processing 9 The main sources of the aromatic hydrocarbon are as follows: byproduct C of catalytic reforming device of oil refinery 9 Heavy aromatics; wide cut fraction C of terylene material plant 10 Heavy aromatics; byproduct C of ethylene unit 9 Or C 10 Heavy aromatics; ethylene tar is a byproduct of an ethylene device; the coal is Wen Lianjiao and the byproduct heavy aromatics-coal tar. With the increase of domestic oil refining and coal chemical industry capacities, the capacities of a reforming device and an ethylene device are continuously expanded, and the heavy aromatic hydrocarbon yield is continuously increased. For a long time, heavy aromatic resources are not reasonably utilized, and a small amount of heavy aromatic resources are removed to be used as a solvent and extracted C 9 And C 10 Essentially all of the monomeric aromatic hydrocarbon is incorporated into the fuel for use. However, with the increasing perfection of environmental regulations, the content of heavy aromatics in fuel oils must be severely limited. Thus, howThe effective use of heavy aromatic resources is an important research topic.
In recent years, many research progress on the use of heavy aromatics has been reported at home and abroad. The development and utilization routes are mainly divided into two types, wherein one type is that heavy aromatic hydrocarbon is separated according to different components to obtain chemical products with higher utilization value, such as pseudocumene, mesitylene, durene, naphthalene, methylnaphthalene, high aromatic solvent and the like, and then the chemical products are further processed into fine chemical products; another method is to make it undergo the process of lightening reaction to produce light aromatic hydrocarbon (benzene, toluene and xylene, BTX for short) with high added value, and make it be used as basic petrochemical product, then separate out durene, etc. which can not be converted. The heavy aromatic hydrocarbon light-weight process route has the advantages of less investment, reasonable product structure and high added value, can effectively make up the gap with continuously increased light aromatic hydrocarbon demand, and has strong market competitiveness.
Heavy aromatics light weight mainly includes hydrodealkylation technology and transalkylation technology. Wherein the heavy aromatics hydrodealkylation includes thermal hydrodealkylation and catalytic hydrodealkylation. The main product of the thermal hydrogenation dealkylation is benzene, a catalyst is not used in the reaction process, the process is simple, hydrogen is consumed uniformly, but the reaction temperature is high, the requirements on the material of equipment are high, the energy consumption is high, and the control is not facilitated. The catalytic hydrodealkylation is carried out in the presence of a catalyst, and has the advantages of high efficiency, low hydrogen consumption, good selectivity, low operating temperature and high liquid yield. The main modes of the heavy aromatic transalkylation reaction are as follows: one is toluene disproportionation and transalkylation, and the other is a combination of aromatic transalkylation and dealkylation. The above processes all need to react in the hydrogen-contacting state, the hydrogen consumption is high, the catalyst mostly uses noble metal as an active center, and the investment is high.
USP4341622 discloses a process for converting heavy aromatics produced by reforming to BTX using a bifunctional catalyst comprising an HZSM-5 molecular sieve and an active component of a group VIII metal, either platinum or nickel, siO of the HZSM-5 molecular sieve 2 /Al 2 O 3 The molar ratio is 660-1600.
CN1117404a discloses a heavy aromatic hydrocarbon lightening catalyst and lightening method, the catalyst uses HZSM-5 zeolite and alumina as carriers, rhenium, tin and platinum (palladium) are loaded to prepare a bifunctional catalyst, and the catalyst is used for heavy aromatic hydrocarbon lightening reaction.
CN1082539C discloses a heavy aromatic hydrocarbon lightening catalyst and a method for separating lightening products, wherein the catalyst carrier consists of MOR zeolite, MFI zeolite and alumina, and is loaded with platinum or palladium. The catalyst is used for the light reaction of heavy aromatic hydrocarbon, and the product has more toluene and xylene.
CN101811063a adopts hydrogen nano zeolite and binder to prepare heavy aromatic hydrocarbon light catalyst, avoiding loading noble metal into the catalyst. The hydrogen-type nano zeolite includes at least one of beta zeolite, mordenite and ZSM-5. The catalyst can reduce the diffusion resistance of molecules by using nano zeolite, but the preparation difficulty and economic cost of the catalyst are obviously increased by using nano zeolite, for example, the nano zeolite is difficult to separate in production, so that the production efficiency is low and the cost is increased.
Disclosure of Invention
The invention aims to provide a heavy aromatic hydrocarbon lightening catalyst, a preparation method and application thereof, and the catalyst is used for C 9 ～C 12 The non-hydro light reaction of heavy aromatics can obtain higher light aromatics yield and high-quality liquefied gas rich in propane as a byproduct.
The heavy aromatic hydrocarbon lightening catalyst provided by the invention comprises a composite carrier and V A group element oxide with the content of 0.5-10.0 mass percent calculated by taking the composite carrier as a reference, wherein the composite carrier comprises 10-45 mass percent of ZSM-5 zeolite, 10-45 mass percent of EU-1 zeolite and 10-80 mass percent of alumina.
The catalyst of the invention takes ZSM-5 zeolite and EU-1 zeolite as active components, and is mixed with alumina to prepare a composite carrier, then the carrier is loaded with VA element oxide, and then the catalyst is prepared by steam treatment. The catalyst is used for the non-hydrogenation light reaction of heavy aromatic hydrocarbon, can produce light aromatic hydrocarbon (BTX) and byproducts of liquefied gas components, and has long single-pass reaction period and good regeneration performance.
Detailed Description
The invention takes hydrogen ZSM-5 zeolite and hydrogen EU-1 zeolite as main active components, uses alumina as a binder to form a composite carrier, loads VA element oxide, and carries out steam treatment to obtain the catalyst. The hydrogen type ZSM-5 zeolite can promote the dealkylation of heavy aromatic hydrocarbon to generate benzene, and has the function of benzene alkylation to produce dimethylbenzene, the hydrogen type EU-1 zeolite can provide larger molecular sieve pore channels, has stronger acidity, is easy for dealkylation of macromolecular aromatic hydrocarbon in raw materials, increases the generation of benzene, and has a large number of interactions of ZSM-5 zeolite with VA family elements in middle and small pore channels, so that the benzene alkylation reaction can be obviously improved, the generation of dimethylbenzene is increased, and the BTX yield in a light product is improved. The yield of the liquid phase product of the reaction is high, and liquefied gas and C are byproducts 1 ～C 2 The dry gas yield is low. In addition, the supported VA element oxide and the water vapor treatment can also reduce the carbon deposition of the catalyst and increase the stability and the regeneration performance of the catalyst.
The composite carrier of the catalyst of the present invention preferably comprises 15 to 38 mass% of ZSM-5 zeolite, 15 to 40 mass% of EU-1 zeolite and 22 to 70 mass% of alumina.
The ZSM-5 zeolite and EU-1 zeolite are preferably hydrogen form, and SiO of ZSM-5 zeolite 2 /Al 2 O 3 SiO of EU-1 zeolite with a molar ratio of 20 to 100, preferably 30 to 80 2 /Al 2 O 3 The molar ratio is 50 to 120, preferably 50 to 90.
The content of the group VA element oxide in the catalyst of the present invention is preferably 1.0 to 8.0 mass%. The VA group element is phosphorus, antimony or bismuth.
The alumina in the composite carrier is preferably gamma-Al 2 O 3 . The shape of the composite carrier is preferably a pellet shape, and the particle size range of the composite carrier is 1.2-2.5 mm.
The alpha value of the catalyst according to the invention is preferably 60 to 100, more preferably 60 to 80. The method for measuring the alpha value is described in "petrochemical analysis method (RIPP Experimental method)", et al, by Yang Cuiding, published by science Press, P255 "constant temperature method for measuring the alpha value of an acid catalyst.
The heavy aromatic hydrocarbon is C 9 ～C 12 Is a hydrocarbon aromatic hydrocarbon.
Preferably, the preparation method of the catalyst comprises the following steps:
(1) Fully mixing pseudo-boehmite and an acid solution, peptizing to obtain alumina sol with alumina content of 8-16 mass%, adding hydrogen ZSM-5 and hydrogen EU-1 zeolite, uniformly stirring to obtain slurry containing zeolite, drop-forming the slurry in an oil ammonia column, drying wet balls obtained by drop-forming at 30-100 ℃ for 5-30 hours, activating at 500-650 ℃ for 2-6 hours to obtain a spherical composite carrier,
(2) The spherical composite carrier prepared in the step (1) is immersed in a compound solution containing VA element, dried and roasted at 500-700 ℃ to obtain a spherical catalyst, and then treated by water vapor at 400-600 ℃ for 0.5-8 hours.
The step (1) of the method is to prepare a small spherical composite carrier, and the mass ratio of the acid used for peptization to the alumina contained in the pseudo-boehmite is preferably 0.02-0.20, more preferably 0.04-0.10.
The acid may be an inorganic acid and/or an organic acid. The inorganic acid is preferably nitric acid or hydrochloric acid, more preferably nitric acid, and the organic acid is preferably acetic acid or formic acid. The acid used for preparing the aluminum sol should be an acid solution, and the concentration of the acid solution is preferably 0.5 to 2.0 mass%.
(1) The time for peptizing pseudo-boehmite with an acid solution is preferably 1 to 10 hours, more preferably 1 to 6 hours.
(1) After adding hydrogen ZSM-5 zeolite and hydrogen EU-1 zeolite into aluminum colloid solution, the solid content of the obtained slurry containing zeolite is 18-22 mass%. The solid content is the sum of the zeolite and the alumina contained in the alumina peptization.
After the slurry containing zeolite is obtained, the slurry is formed by dripping balls in an oil ammonia column, wherein the oil phase of the oil ammonia column is kerosene, the concentration of an ammonia water phase is preferably 5-8 mass percent, and the temperature of the dripping balls is preferably 10-30 ℃. The kerosene is preferably C 10 ～C 16 Is an alkane of (a).
After the formation of the pellets, the wet pellets are taken out of the aqueous ammonia phase, dried preferably at 50 to 80℃for 8 to 24 hours and then activated, preferably at 550 to 600℃for 3 to 5 hours.
The step (2) of the method is to impregnate and introduce the VA element into the spherical composite carrier and carry out steam treatment, wherein the compound containing the VA element is an oxyacid or a water-soluble salt thereof, such as phosphoric acid, antimony nitrate or bismuth nitrate.
(2) The temperature of impregnating the spherical composite support with the group VA element-containing compound solution is 10 to 40 ℃, preferably 1 to 4 hours, more preferably 2 to 3 hours. The mass ratio of the impregnated liquid to the solid is preferably 0.5 to 1.2, the drying temperature of the impregnated solid is preferably 90 to 120 ℃, the time is preferably 4 to 20 hours, the roasting temperature after drying is preferably 500 to 600 ℃, the roasting time is preferably 2 to 8 hours, and more preferably 4 to 6 hours.
(2) The mass space velocity of the spherical catalyst treated by the water vapor is preferably 1.0 to 5.0h -1 The water vapor treatment temperature is preferably 450-550 ℃, and the water vapor treatment time is preferably 2-4 hours.
The method for non-hydrogenation light-weight of heavy aromatic hydrocarbon provided by the invention comprises the step of contacting the heavy aromatic hydrocarbon with the catalyst of the invention at 300-600 ℃ and 0.1-2.0 MPa to perform the non-hydrogenation light-weight reaction.
The space velocity of the feeding mass of the light reaction is 0.05 to 5.0h -1 Preferably 0.1 to 2.0h -1 The reaction temperature is preferably 400-500 ℃, and the pressure is preferably 0.2-1.0 MPa.
The catalyst of the invention can be repeatedly used through regeneration after being deactivated. The catalyst regeneration method comprises the following steps: the deactivated catalyst is treated with an inert gas containing oxygen, preferably nitrogen, having an oxygen content of 0.5 to 5.0% by volume. The proper regeneration temperature is 380-500 deg.c, pressure is 0.1-3.0 MPa and gas/agent volume ratio is 250-1000.
The catalyst of the invention is suitable for C 9 ～C 12 The heavy aromatic fraction is converted under the non-hydrogen condition, and the heavy aromatic fraction is dealkylated, alkylated and the like under the action of a catalyst to generate a liquid product containing light aromatic hydrocarbons (benzene, toluene and xylene), and simultaneously, a part of liquefied gas component rich in propane can be produced as a byproduct.
The heavy aromatic hydrocarbon light reaction raw material does not need to be pre-refined. The heavy aromatic hydrocarbon light reaction can adopt a moving bed and fixed bed reactor. Preferably, a moving bed reactor is adopted, so that the light reaction can be ensured to be carried out smoothly and continuously, frequent switching of the reactor for catalyst regeneration is avoided, and a plurality of moving bed reactors are preferably adopted for reaction.
The invention is further illustrated by the following examples, but is not limited thereto.
Example 1
The following examples prepare the catalysts of the present invention
(1) Preparation of pellet composite carrier
67.6 g of pseudo-boehmite (manufactured by Sasol company,
SB powder, alumina content of 75% by mass) was added with stirring to 270 g of 1.1% by mass nitric acid aqueous solution, peptized for 2 hours to obtain an alumina sol having an alumina content of 10% by mass, to which 25 g of SiO was added 2 /Al 2 O 3 Hydrogen type ZSM-5 molecular sieve with a molar ratio of 50 and 25 g of SiO 2 /Al 2 O 3 The zeolite-containing slurry was obtained by stirring a hydrogen form EU-1 molecular sieve having a molar ratio of 60 at a high speed for 3 hours, and the solid content of the slurry was 20 mass%.
The slurry is formed by dripping balls in an oil ammonia column, the temperature of the dripping balls is 15 ℃, the oil phase of the oil ammonia column is kerosene, the thickness is 10cm, the thickness of an ammonia water phase is 200cm, and the concentration of the ammonia water is 6 mass percent. The wet pellets were taken out from the bottom of the ammonia water layer, dried at 60℃for 10 hours, and activated at 550℃for 3 hours to obtain a pellet-shaped composite carrier d containing 25 mass% of a hydrogen-form ZSM-5 molecular sieve, 25 mass% of a hydrogen-form EU-1 molecular sieve and 50 mass% of gamma-alumina, the particle diameter of which was in the range of 1.6 to 2.0mm.
(2) Preparation of the catalyst
Taking 50 g of the composite carrier d prepared in the step (1), soaking the composite carrier d in 50 g of 5.5 mass% phosphoric acid solution at 25 ℃ for 2 hours, drying the soaked solid at 110 ℃ for 12 hours, roasting at 550 ℃ for 4 hours, treating the solid at 500 ℃ for 3 hours by using water vapor, and steamingThe mass space velocity of the steam treatment is 2.0h -1 . The composition and alpha values of the resulting catalyst D are shown in Table 1.
Example 2
A catalyst was prepared as in example 1, except that 32 g of hydrogen form ZSM-5 molecular sieve was added to the alumina sol in step (1), 18 g of hydrogen form EU-1 molecular sieve was added to obtain a slurry containing zeolite with a solid content of 20% by mass, and the slurry was subjected to dropping, drying and calcination to obtain a composite carrier e containing 32% by mass of hydrogen form ZSM-5 molecular sieve, 18% by mass of hydrogen form EU-1 molecular sieve and 50% by mass of gamma-alumina. The composite carrier E is immersed in a phosphoric acid solution, and the composition and alpha value of the catalyst E obtained after drying, roasting and steam treatment are shown in Table 1.
Example 3
A catalyst was prepared as in example 1, except that (1) 18 g of hydrogen form ZSM-5 molecular sieve was added to the alumina sol, 32 g of hydrogen form EU-1 molecular sieve was added, a slurry containing zeolite with a solid content of 20% by mass was obtained, and a composite carrier f comprising 18% by mass of hydrogen form ZSM-5 molecular sieve, 32% by mass of hydrogen form EU-1 molecular sieve and 50% by mass of gamma-alumina was obtained by dropping the slurry, drying and calcining. The composite carrier F is impregnated with a phosphoric acid solution, and the composition and alpha value of the catalyst F obtained after drying, roasting and steam treatment are shown in Table 1.
Example 4
A catalyst was prepared as in example 1, except that (1) 35 g of hydrogen form ZSM-5 molecular sieve was added to the alumina sol, 35 g of hydrogen form EU-1 molecular sieve was added, a slurry containing zeolite with a solid content of 20% by mass was obtained, and a composite carrier g comprising 35% by mass of hydrogen form ZSM-5 molecular sieve, 35% by mass of hydrogen form EU-1 molecular sieve and 50% by mass of gamma-alumina was obtained by dropping the slurry, drying and calcining. The composite carrier G is immersed in a phosphoric acid solution, and the composition and alpha value of the catalyst G obtained after drying, roasting and steam treatment are shown in Table 1.
Example 5
50 g of the composite support d prepared as in example 1 were immersed in 50 g of 11.0% strength by mass phosphoric acid solution at 25℃for 2 hours, and the immersed solid was dried at 110℃for 12 hours and calcined at 550℃for 4 hoursAt 500 deg.C, steam treatment is carried out for 3 hours, the mass space velocity of the steam treatment is 2.0h -1 . The composition and alpha values of the resulting catalyst H are shown in Table 1.
Comparative example 1
HZSM-5 zeolite-containing alumina pellets were prepared as in example 1 (1) except that 50 g of SiO was added to the alumina sol 2 /Al 2 O 3 The HZSM-5 molecular sieve with the molar ratio of 50 is subjected to ball dripping, drying and roasting to obtain the alumina balls a containing HZSM-5 zeolite, wherein the alumina balls a contain 50 mass percent of the HZSM-5 molecular sieve and 50 mass percent of gamma-alumina.
50 g of the alumina pellets a were taken and treated with water vapor at 500℃for 3 hours at a mass space velocity of 2.0 hours -1 The composition and alpha values of the catalyst A obtained are shown in Table 1.
Comparative example 2
Alumina pellets of EU-1 zeolite in hydrogen form were prepared as in example 1 (1) except that 50 g of SiO was added to the alumina sol 2 /Al 2 O 3 The alumina pellets b of the EU-1 zeolite containing hydrogen are obtained by dropping, drying and roasting the EU-1 molecular sieve containing hydrogen with a molar ratio of 60, wherein the alumina pellets b contain 50 mass percent of the EU-1 molecular sieve containing hydrogen and 50 mass percent of gamma-alumina.
50 g of the alumina pellets b were taken and treated with water vapor at 500℃for 3 hours at a mass space velocity of 2.0 hours -1 The composition and alpha values of the resulting catalyst B are shown in Table 1.
Comparative example 3
Alumina pellets containing HZSM-5 zeolite and hydrogen mordenite were prepared as in example 1 (1) except that 25 grams of SiO was added to the alumina sol 2 /Al 2 O 3 HZSM-5 molecular sieve having a molar ratio of 50 and 25 g SiO 2 /Al 2 O 3 The hydrogen mordenite with the molar ratio of 10 is subjected to ball dripping, drying and roasting to obtain zeolite-containing alumina balls c, wherein the zeolite-containing alumina balls c contain 25 mass percent of HZSM-5 molecular sieve, 25 mass percent of hydrogen mordenite and 50 mass percent of gamma-alumina.
50 g of the alumina pellets c were taken and treated with steam at 500℃for 3 hours, the mass space velocity of the steam treatmentFor 2.0h -1 The composition and alpha values of the resulting catalyst C are shown in Table 1.
TABLE 1
* Calculated based on the carrier.
Examples 6 to 13
The performance of the catalyst of the present invention and the comparative catalyst was evaluated on a small fixed bed reactor using the reformed heavy aromatic fraction having the composition shown in table 2 as a raw material. The evaluation conditions were: 420 ℃, 0.3MPa, 0.3hr of raw material feeding mass airspeed -1 The reaction time was 48 hours, and the catalyst and the reaction results used in each example are shown in Table 3.
As can be seen from Table 3, compared with comparative catalyst A, B, C, the catalyst D, E, F, G, H of the present invention has significantly improved raw material conversion and light aromatic hydrocarbon yield, significantly reduced carbon deposition, and by-product C 3 And C 4 Hydrocarbons, said C 3 And C 4 The hydrocarbon is a liquefied gas.
TABLE 2
| Carbon number | Alkanes | Cycloalkane (CNS) | Aromatic hydrocarbons | Totalizing |
| 6 | 0.01 | - | - | 0.01 |
| 7 | - | - | - | - |
| 8 | - | - | 0.02 | 0.02 |
| 9 | 0.01 | 0.00 | 35.82 | 35.83 |
| 10 | 0.07 | 0.75 | 61.72 | 62.54 |
| 11 | 0.00 | 0.17 | 1.40 | 1.57 |
| 12 | 0.03 | - | - | 0.03 |
| Totalizing | 0.12 | 0.92 | 98.96 | 100.00 |
TABLE 3 Table 3
Example 14
This example examines the stability of the catalysts of the present invention.
Catalyst D was packed in a reactor of a small fixed bed reactor, and the reformed heavy aromatic fraction shown in Table 2 was used as a raw material, and the reaction temperature was 420℃and the pressure was 0.3MPa, and the raw material feed mass space velocity was 0.3hr -1 The results of the continuous reaction under the conditions of (3) for 120 hours are shown in Table 4.
As can be seen from table 4, the conversion of the raw material and BTX yield were maintained at higher levels all the time, the total BTX yield was reduced from 33.41 mass% at the beginning to 30.38 mass% at the end of the reaction, and the average yield was greater than 31.71 mass%, indicating that the catalyst of the present invention had good heavy aromatics light activity, light aromatics selectivity and reaction stability.
TABLE 4 Table 4
Example 15
This example examines the regeneration performance of the catalyst of the present invention.
Filling catalyst D into reactor of small fixed bed reactor, taking reformed heavy aromatic fraction shown in Table 2 as raw material, reacting at 420 deg.C under 0.3MPa for 0.3hr at raw material feeding mass space velocity -1 The reaction was continued for 120 hours under the conditions of (2) and then the catalyst was regenerated.
The regeneration method comprises the following steps: nitrogen with oxygen content of 0.5-2.0 vol% is introduced into the catalyst bed, and the catalyst is regenerated under the conditions of 400 ℃ and 0.8MPa and gas/agent volume ratio of 500, and the regeneration time is 10 hours. The regenerated catalyst was reused for the reaction for 120 hours. The catalyst thus regenerated several times, each time after 120 hours of reaction, the results are shown in Table 5.
As can be seen from Table 5, the activity of catalyst D of the present invention after 5 and 10 regenerations was very close to that before regeneration, indicating that the catalyst of the present invention had very good regeneration performance.
TABLE 5
| Catalyst regeneration times | 0 | 5 | 10 |
| Conversion of raw material, mass% | 35.41 | 34.86 | 34.51 |
| (H 2 +CH 4 +C 2 Hydrocarbon) yield, mass% | 2.70 | 2.65 | 2.61 |
| (C 3 +C 4 ) Hydrocarbon yield, mass% | 4.82 | 4.50 | 4.13 |
| (C 3 +C 4 ) Propane content in hydrocarbon, mass% | 74.01 | 73.82 | 73.55 |
| C 5 + Gasoline yield, mass% | 92.48 | 92.85 | 93.26 |
| Benzene yield, mass% | 1.54 | 1.51 | 1.46 |
| Toluene yield, mass% | 8.56 | 8.27 | 8.01 |
| Xylene yield, mass% | 21.62 | 21.09 | 20.56 |
Claims (14)
1. A method for lightening heavy aromatic hydrocarbon is characterized by comprising the step of contacting heavy aromatic hydrocarbon with a catalyst at 300-600 ℃ and 0.1-2.0 MPa to perform non-hydrogenation lightening reaction, wherein the catalyst comprises a composite carrier and VA group elements with the content of 0.5-10.0 mass% calculated by taking the composite carrier as a referenceThe composite carrier comprises 10-45 mass% of ZSM-5 zeolite, 10-45 mass% of EU-1 zeolite and 10-80 mass% of alumina, wherein the SiO of the ZSM-5 zeolite 2 /Al 2 O 3 SiO of EU-1 zeolite with a molar ratio of 20-100 2 /Al 2 O 3 The molar ratio is 50-120, the heavy aromatic hydrocarbon is C9-C12 aromatic hydrocarbon, and the VA group element is phosphorus, antimony or bismuth.
2. The method according to claim 1, wherein the composite carrier comprises 15 to 38 mass% of ZSM-5 zeolite, 15 to 40 mass% of EU-1 zeolite, and 22 to 70 mass% of alumina.
3. The method according to claim 1 or 2, wherein the group va element oxide content is 1.0 to 8.0 mass%.
4. A method according to claim 1 or 2, characterized in that the alumina is gamma-Al 2 O 3 。
5. The method according to claim 1 or 2, characterized in that the catalyst has an alpha value of 60 to 100.
6. The method according to claim 1, characterized in that the preparation of the catalyst comprises the steps of:
(1) Fully peptizing pseudo-boehmite with an acid solution to obtain alumina sol with the alumina content of 8-16 mass percent, adding hydrogen ZSM-5 and hydrogen EU-1 zeolite, uniformly stirring to obtain slurry containing zeolite, performing drop ball forming in an oil ammonia column, drying wet balls obtained by drop ball forming at 30-100 ℃ for 5-30 hours, activating at 500-650 ℃ for 2-6 hours to obtain a spherical composite carrier,
(2) And (3) impregnating the spherical composite carrier prepared in the step (1) with a compound solution containing VA group elements, drying, roasting at 500-700 ℃ to obtain a spherical catalyst, and treating with water vapor at 400-600 ℃ for 0.5-8 hours.
7. The method according to claim 6, wherein the mass ratio of the acid used in peptization in the step (1) to alumina contained in pseudo-boehmite is 0.02 to 0.20, and the acid is an inorganic acid or an organic acid.
8. The method of claim 7, wherein the mineral acid is nitric acid or hydrochloric acid and the organic acid is acetic acid or formic acid.
9. The method of claim 6, wherein the peptizing of the pseudo-boehmite by the acid solution in the step (1) is performed for 1 to 10 hours.
10. The method according to claim 6, wherein the solid content of the slurry containing zeolite obtained in the step (1) is 18 to 22 mass%.
11. The process according to claim 6, wherein the group VA-containing compound of step (2) is an oxyacid or water-soluble salt thereof.
12. The method according to claim 6, wherein the temperature of impregnating the spherical composite support with the group VA element-containing compound solution in the step (2) is 10 to 40 ℃ for 2 to 3 hours.
13. The process according to claim 6, wherein the catalyst is treated with water vapor in step (2) at a mass space velocity of 1.0 to 5.0 hours -1 。
14. The process according to claim 1, wherein the weight space velocity of the feed material for the light-weight reaction is 0.05 to 5.0 hours -1 The reaction temperature is 400-500 ℃ and the pressure is 0.2-1.0 MPa.
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