CN114433207B - Hydrocracking catalyst for producing ethylene raw material, and preparation method and application thereof - Google Patents

Hydrocracking catalyst for producing ethylene raw material, and preparation method and application thereof Download PDF

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CN114433207B
CN114433207B CN202011115284.0A CN202011115284A CN114433207B CN 114433207 B CN114433207 B CN 114433207B CN 202011115284 A CN202011115284 A CN 202011115284A CN 114433207 B CN114433207 B CN 114433207B
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molecular sieve
silicon source
crystallization
sba
catalyst
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CN114433207A (en
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于正敏
孙晓艳
樊宏飞
王继锋
陈玉晶
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • 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
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/633—Pore volume less than 0.5 ml/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 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
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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
    • B01J29/08—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
    • 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
    • C10G2300/1074—Vacuum distillates
    • 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
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/20—C2-C4 olefins
    • 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
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    • 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
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Abstract

The invention discloses a preparation method of a hydrocracking catalyst for producing high-quality ethylene raw materials, which comprises the following steps: mixing Al-SBA-15/Y shell-core composite molecular sieve, macroporous alumina and adhesive, shaping, drying, roasting to obtain catalyst carrier and loading hydrogenation active metal on the catalyst carrier. The hydrocracking catalyst prepared by the method has the characteristics of high tail oil yield and low BMCI value of the tail oil, and can be used for producing high-quality ethylene cracking raw materials in a maximum amount.

Description

Hydrocracking catalyst for producing ethylene raw material, and preparation method and application thereof
Technical Field
The invention relates to a hydrocracking catalyst for producing ethylene raw materials and a preparation method and application thereof, in particular to a hydrocracking catalyst for producing high-quality ethylene raw materials and a preparation method and application thereof.
Background
Ethylene is a tap product in petrochemical industry, with rapid development of petrochemical industry, the market demand of basic chemical raw materials such as domestic triphenyl, triene and the like is growing increasingly, and according to statistics, the gap of the basic chemical raw materials in China reaches 2600x10 by 2020 4 t will become the bottleneck for restricting the development of the chemical industry in China. Compared with ethylene cracking raw materials such as straight-run naphtha, light hydrocarbon and the like, the hydrocracking tail oil is used as an ethylene raw material, the ethylene single pass yield can reach about 27 percent, and the ethane recycle ethylene yield of an industrial device can reach more than 31 percentStraight run naphtha is basically equivalent and is a good cracking raw material. Because crude oil in China is heavier, naphtha raw materials for preparing ethylene are few, a plurality of enterprises use hydrocracking tail oil as ethylene cracking raw materials, particularly recently built ethylene devices all adopt the hydrocracking tail oil as the cracking raw materials, the domestic ethylene productivity in thirteen-five' end stages breaks through the increase of 3000 ten thousand tons/year demand and drives the development of domestic ethylene industry, and simultaneously, higher requirements are also provided for the supply and optimization of ethylene cracking raw materials. In view of the pressure, ethylene production enterprises not only need to increase the supply amount of ethylene raw materials, but also need to improve the quality of the ethylene raw materials, and the high-quality ethylene raw materials can improve the yield of ethylene, prolong the running period of a cracking furnace, and achieve the purposes of increasing the yield of ethylene and reducing the material and energy consumption.
The hydrocracking catalyst is a double-function catalyst consisting of a hydrogenation function and a cracking function, wherein the hydrogenation function is provided by hydrogenation active metal, so that the hydrogenation performance of the hydrocracking catalyst is improved, and the saturation of aromatic hydrocarbon is facilitated; currently, the cracking centers in most hydrocracking catalysts are provided by molecular sieves, and the cracking centers in most hydrocracking catalysts are provided by molecular sieves, so improving the performance of the catalyst by improving the performance of the molecular sieves is a viable approach.
CN201310114414.2 describes a modification method of USY molecular sieve, and the specific surface area, secondary pore volume and proportion of medium and strong acid of the modified molecular sieve are obviously improved. CN201310240740.8 and CN201410131823.8 describe a binding modification method of a mesoporous-rich ultrastable Y molecular sieve, the secondary pore content of the modified molecular sieve is remarkably improved, the silicon-aluminum ratio is increased, and the unit cell constant is reduced. CN201410131458.0 describes a modification method of USY molecular sieve, which uses mixed solution of ammonium fluosilicate and citric acid to make modification treatment, and finally obtains the modified USY molecular sieve with rich secondary pore structure, high crystallinity and rich medium strong acid. CN201610288625.1 discloses a hydrocracking catalyst for producing high-quality ethylene raw material, its preparation method and application, adding Y-type molecular sieve into a pressure-resistant container of one or several organic alkali solutions, constant-temperature treating for 0.5-3 hr, adding white carbon black and active metal component into the above-mentioned mixture, uniformly mixing, then fully rolling and forming, then drying and roasting so as to obtain the invented hydrocracking catalyst. The hydrocracking catalyst prepared by the method has the characteristics of high hydrocracking property and good product selectivity, and can be used for producing high-quality ethylene cracking raw materials.
As a raw material for preparing ethylene by steam cracking, high-quality hydrocracking tail oil is required to have high paraffin content, low naphthene and arene content, especially low arene content and low BMCI value, so that higher ethylene and triene yield can be obtained, and the T90, T95 and dry point and thick-ring hydrocarbon content are required to be reduced, so that the coke generation is reduced and the running period of a cracking furnace is prolonged.
The above research can change the molecular sieve pore channel structure and adjust the acid property of the molecular sieve by adopting different modification methods, but has poor process adaptability to the composition and structure change of reactant hydrocarbons, poor selectivity of hydrocarbon conversion reaction, and incapacity of converting cyclic hydrocarbon in raw materials into single-ring hydrocarbon components completely and preferentially, and part of chain hydrocarbon which needs to be reserved is also converted into light hydrocarbon components, so that the yield and quality of hydrogenated tail oil cannot be considered.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrocracking catalyst for producing ethylene raw materials, a preparation method and application thereof. The hydrocracking catalyst prepared by the method has the characteristics of high tail oil yield and low BMCI value of the tail oil, and can be used for producing high-quality ethylene cracking raw materials in a maximum amount.
A method of preparing a hydrocracking catalyst for producing a premium ethylene feedstock, said method comprising: mixing Al-SBA-15/Y shell-core composite molecular sieve, macroporous alumina and adhesive, shaping, drying, roasting to obtain catalyst carrier and loading hydrogenation active metal on the catalyst carrier.
In the method of the invention, the macroporous alumina has the following properties: pore volume of 0.6-1.2 mL/g, preferably 0.8-1.0 mL/g, specific surface area of 300-600 m 2 Preferably 400 to 500 and m per gram 2 /g。
In the method of the invention, the binder is small pore alumina, and the small pore aluminaThe pore volume of the aluminum is 0.3-0.5 mL/g, and the specific surface area is 200-400 m 2 /g。
In the method, the carrier can be molded according to actual needs, the carrier can be in the shape of a cylindrical strip, clover and the like, and in the molding process, molding aids such as peptizing acid, extrusion aids and the like can be added, and the peptizing agent can generally adopt inorganic acid and/or organic acid, and the extrusion aids such as sesbania powder.
In the method of the invention, the carrier is dried and roasted by a conventional method, and the method comprises the following steps: drying at 80-120 deg.c for 3-10 hr and roasting at 400-600 deg.c for 3-10 hr.
In the method of the invention, the hydrogenation active metal is VIB metal and/or VIII metal, the VIB metal is molybdenum and/or tungsten, and the VIII metal is cobalt and/or nickel.
In the method of the invention, the loading of the hydrogenation active metal can adopt a loading method which is conventional in the prior art, preferably an impregnation method, and can be saturated impregnation, excessive impregnation or complexation impregnation, namely, the catalyst carrier is impregnated with a solution containing the required active components, the impregnated carrier is dried for l-12 hours at 100-120 ℃, and then the carrier is baked for 3-10 hours at 400-600 ℃ to prepare the final catalyst.
In the method of the invention, the preparation of the Al-SBA-15/Y shell-core composite molecular sieve comprises the following steps:
(1) Mixing a template agent, a silicon source and a Y-type molecular sieve for reaction, and carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase;
(2) Taking 10% -50%, preferably 15% -30% of the volume fraction of the liquid phase obtained in the step (1), adjusting the mass content of the template agent in the taken liquid phase to be 0.05-0.8, preferably 0.1-0.6, further preferably 0.25-0.5, adding the template agent into the solid phase separated in the step (1) for crystallization, and carrying out solid-liquid separation, drying and roasting after the crystallization is finished to obtain the SBA-15/Y shell-core composite molecular sieve;
(3) And (3) treating the SBA-15/Y shell-core composite molecular sieve obtained in the step (2) by adopting an acidic aluminum salt solution, and drying and roasting to obtain the final composite carrier.
In the step (1) of the method, the silicon source is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate and butyl orthosilicate.
In the method step (1), the silicon source is prepared by prehydrolysis, and the prehydrolysis process of the silicon source is as follows: adding a silicon source into an acidic solution, and aging to obtain the silicon source, wherein the acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
In the step (1) of the method, a specific process of prehydrolysis of the silicon source is as follows: and adding the silicon source into a dilute acid solution with the pH value of 1-4, preferably, stirring for 1-12 h at room temperature, standing and ageing for 4-120 h to obtain the silicon source, preferably, adding the silicon source into a dilute acid solution with the pH value of 2.5-3.5, stirring for 6-8 h at room temperature, and standing and ageing for 24-96 h to obtain the silicon source.
In the step (1) of the method, the template agent is P123, and the template agent P123 can be dissolved in an acidic aqueous solution first and then mixed with materials such as a silicon source, a Y-type molecular sieve and the like for reaction.
In the step (1) of the method, the Y-type molecular sieve is a modified Y-type molecular sieve, the particle size of the Y-type molecular sieve is 200 nm-5000 nm, and the silicon-aluminum molar ratio is SiO 2 /Al 2 O 3 The molar ratio of silicon to aluminum is 10-30; preferably 15-20.
In the step (1) of the method, the molar concentration of the acid solution in the template agent, the silicon source and the Y-type molecular sieve mixture is 0.1-1.0 mol/L, preferably 0.2-0.4 mol/L, and the mass content of the template agent is 0.2-3%, preferably 0.2-2%; the mass content of the silicon source is 1% -10%, preferably 3% -8%; the mass content of the Y-type molecular sieve is 1% -15%, preferably 3% -10%.
In the step (1) of the method, the reaction temperature is 20-40 ℃, preferably 25-30 ℃; the reaction time is 2-12 hours, preferably 4-8 hours.
In the step (1) of the method, a specific template agent, a silicon source and a Y-type molecular sieve are mixed and reacted as follows: and dissolving a certain amount of template agent (such as P123) in an acidic aqueous solution, adding water into Y, adding into the solution, stirring for 10-15 min, adding a prehydrolyzed silicon source, and stirring at a constant temperature for 2-12 h.
In the step (2), the crystallization process is to add alkaline substances or alkaline solutions into the crystallization system to adjust the pH of the system to be 3-11, preferably pH to be 7.5-10, and more preferably 8-9.5; the crystallization temperature is 80-140 ℃, preferably 100-120 ℃; the crystallization time is 4 to 48 hours, preferably 24 to 30 hours.
In the step (2), one or more of centrifugal separation and filtering separation are adopted, preferably, the solid content of the separated liquid phase is controlled to be 0.05-3 wt%, preferably 0.1-2.5 wt%, and more preferably 0.3-0.2 wt%; at this time, part of the liquid is the same as the solid phase mixture in the step (1) for crystallization; the rest liquid phase can be mixed with the template agent, the silicon source and the Y-type molecular sieve to repeat the operation process of the step (1); the mass content of the template agent added into the mixed system is 0.2% -3%, preferably 0.2% -2%; the mass content of the added silicon source in the system is 1% -10%, preferably 3% -8%; the mass content of the added Y-type molecular sieve in the system is 1% -15%, preferably 3% -10%, and the mass fraction of the rest liquid phase is 10% -50%; the process can be repeatedly carried out, the repeated times are not limited, and the optimization adjustment can be carried out according to the actual production condition.
In the step (2) of the method, the drying temperature is 80-120 ℃, the drying time is 4-10h, the roasting temperature is 450-600 ℃, and the roasting time is 4-8h.
In the step (3) of the method, the aluminum salt is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate, the pH value of the acidic aluminum salt solution is 1-4, preferably 2-3, and the mass content of the aluminum salt in the acidic aluminum salt solution is 0.1% -1%, preferably 0.2% -0.8%; the treatment time is 3-10, and the treatment temperature is 25-35 ℃.
In the step (3) of the method, a specific operation process is as follows: dissolving a certain amount of aluminum source in an acidic solution, wherein the pH value of the acidic aluminum salt solution is 1-4, preferably 2-3, adding the SBA-15/Y shell-core composite molecular sieve prepared in the step (2), stirring for 10-20h at 28-32 ℃, washing, drying for 4-10h at 80-120 ℃, and roasting for 4-6h at 500-560 ℃ to obtain the Al-SBA-15/Y molecular sieve.
The method adopts proper crystallization conditions such as controlling the content of the template agent, crystallizing under alkaline conditions and the like, ensures the stability of the Y molecular sieve in the crystallization process, avoids collapse of the molecular sieve, synthesizes a composite carrier with more uniform morphology and complete SBA-15/Y of 'core shell', and obviously improves the performance of the catalyst when the carrier is used for hydrocracking.
A hydrocracking catalyst for producing high-quality ethylene raw materials comprises the following components in percentage by weight: the Al-SBA-15/Y shell-core composite molecular sieve is generally 20-70%, preferably 30-50%; the macroporous alumina is generally 10% -40%, the small-pore alumina is generally 10% -20%, and the VIB group metal is generally 6% -20%, preferably 8% -14% in terms of oxide; the group VIII metal is generally 2% to 8%, preferably 3% to 6% by oxide.
In the catalyst, the Al-SBA-15/Y shell-core type composite molecular sieve is characterized in that a shell is the SBA-15 molecular sieve, a core is the Y-type molecular sieve, the mass ratio of the shell to the core is 10:90-50:50, preferably 20:80-40:60, and the composite molecular sieve contains non-framework aluminum (aluminum introduced later) with the content of 0.5% -5%, preferably 1% -3.5% of the composite carrier calculated by oxide.
In the catalyst of the invention, the catalyst has the following properties: the pores with the pore distribution of 4-15nm account for 70-90 percent of the total pore volume, preferably 75-85 percent, and the specific surface area is 300-550 m 2 Per gram, the pore volume is 0.40-0.7 mL/g.
A hydrocracking method for producing high-quality ethylene raw materials, which adopts the hydrocracking catalyst, and the reaction conditions are as follows: in the presence of hydrogen, the reaction pressure is 10-18MPa, the reaction temperature is 350-400 ℃, the hydrogen-oil volume ratio is 500-1500, and the liquid hourly space velocity is 0.5-3.0h -1 。
In the hydrocracking process of the present invention, the feedstock comprises a heavy hydrocarbon material, preferably VGO, as feedstock, typically hydrocarbons having a boiling point of 250 to 600 ℃, typically having a nitrogen content of 500 to 2000ppm.
The hydrocracking reaction of the catalyst for producing ethylene material prepared by the method of the invention can be carried out gradually according to order, the ring opening selectivity of the catalyst is enhanced, macromolecular cyclic hydrocarbon in raw oil is selectively cracked into monocyclic hydrocarbon to naphtha fraction, macromolecular chain hydrocarbon is remained in tail oil fraction, the improvement of the product quality of the tail oil yield is facilitated, the BMCI value is low, and the yield of triene in steam cracking process can be improved.
Detailed Description
The specific surface area and pore volume of the product are measured by adopting an ASAP2405 low-temperature liquid nitrogen adsorption method. The acid amount was measured by infrared spectrometer, and the adsorbent used was pyridine. Relative crystallinity was measured by XRD, with standard NaY of 100. In the invention, the mass fraction is as follows unless otherwise specified. The solid content of the liquid phase in the process according to the invention is defined as the ratio of the weight of the solid after evaporation of the water removed to the total mass of the liquid phase.
Example 1:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.5g of P123 surfactant was dissolved in 130g of a 0.3mol/L hydrochloric acid solution, and 2.8g of a modified Y-1 molecular sieve (specific surface area 815 m) 2 Per gram, pore volume 0.54 mL/g, siO 2 /Al 2 O 3 The molar ratio is 18, the relative crystallinity is 104, the acid quantity is 0.615 mmol/g), after being dissolved by adding water, stirring for 5min, adding the pre-hydrolysis solution of TEOS prepared in advance in the step (1), stirring for 6h at the constant temperature of 30 ℃ and separating, thus obtaining a solid phase and a liquid phase. The solid content of the liquid phase was controlled to be 0.5%.
2. The liquid phase obtained in step (1) was added to 1.0g of P123, 15.8g of concentrated HCL and 37g of water. Repeating the step 1; and (3) carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase, and controlling the solid content of the liquid phase to be 0.5%.
3. And (3) hydrothermal crystallization: adding the solid obtained in the step 2 into 30g of the liquid phase obtained in the step (1), uniformly stirring, adjusting the pH of the reaction liquid of the step (2) to 8.0 by using ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-1 material.
4. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-1 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with the AlSBA-15/Y-1 mesoporous shell layer. The physical parameters of the composite molecular sieve are shown in Table 1.
Example 2:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.4g of P123 surfactant was dissolved in 120g of 0.3mol/L hydrochloric acid solution, and 3.5g of the modified Y-1 molecular sieve (specific surface area 815 m) 2 Per gram, pore volume 0.54 mL/g, siO 2 /Al 2 O 3 The molar ratio is 18, the relative crystallinity is 104, the acid quantity is 0.615 mmol/g), after being dissolved by adding water, stirring for 5min, adding the pre-hydrolysis solution of TEOS prepared in advance in the step (1), stirring for 4h at the constant temperature of 30 ℃ and separating, thus obtaining a solid phase and a liquid phase. The solid content of the liquid phase was controlled to be 0.5%.
2. The liquid phase obtained in step (1) was added to 0.96P123, 12.1g of concentrated HCl and 34g of water. Repeating the step 1; and (3) carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase, and controlling the solid content of the liquid phase to be 0.5%.
3. And (3) hydrothermal crystallization: adding 28g of the liquid phase obtained in the step (1) into the solid obtained in the step (2), uniformly stirring, adjusting the pH of the reaction solution of the step (2) to 4.5 by using ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-2 material.
4. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-2 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with the AlSBA-15/Y-2 mesoporous shell layer. The physical parameters of the composite molecular sieve are shown in Table 1.
Example 3:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.3g of P123 surfactant was dissolved in 110g of a 0.3mol/L hydrochloric acid solution, and 4.4g of a modified Y-1 molecular sieve (specific surface area 815 m) 2 Per gram, pore volume 0.54 mL/g, siO 2 /Al 2 O 3 Molar ratio of 18, relative crystallinity of 104, acid content of 0.615 mmol/g) is dissolved in water, and stirredStirring for 5min, adding the pre-hydrolysis solution of TEOS prepared in the step (1), stirring at 30 ℃ for 4h, and separating to obtain a solid phase and a liquid phase. The solid content of the liquid phase was controlled to be 0.8%.
2. The liquid phase obtained in step (1) was added to 0.88P123, 12.1g of concentrated HCl and 31g of water. Repeating the step 1; and (3) carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase, and controlling the solid content of the liquid phase to be 0.8%.
3. And (3) hydrothermal crystallization: adding the solid obtained in the step 2 into 22g of the liquid phase obtained in the step (1), uniformly stirring, adjusting the pH of the reaction liquid of the step (2) to 9.0 by ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-3 material.
4. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-3 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with an AlSBA-15/Y-3 mesoporous shell layer, wherein the physical parameters of the composite molecular sieve are shown in the table 1.
Example 4:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.2g of P123 surfactant was dissolved in 100g of 0.3mol/L hydrochloric acid solution, and 5.6g of the modified Y-1 molecular sieve (specific surface area 815 m) 2 Per gram, pore volume 0.54 mL/g, siO 2 /Al 2 O 3 The molar ratio is 18, the relative crystallinity is 104, the acid quantity is 0.615 mmol/g), after being dissolved by adding water, stirring for 5min, adding the pre-hydrolysis solution of TEOS prepared in advance in the step (1), stirring for 4h at the constant temperature of 30 ℃ and separating, thus obtaining a solid phase and a liquid phase. The solid content of the liquid phase was controlled to be 1.0%.
2. The liquid phase obtained in step (1) was added to 0.66P123, 9.3g of concentrated HCl and 24g of water. Repeating the step 1; and (3) carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase, and controlling the solid content of the liquid phase to be 1.0%.
3. And (3) hydrothermal crystallization: adding 18g of the liquid phase obtained in the step (1) into the solid obtained in the step (2), uniformly stirring, adjusting the pH of the reaction solution of the step (2) to 9.5 by using ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-1 material.
4. 1.0g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-4 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with an AlSBA-15/Y-4 mesoporous shell layer, wherein the physical parameters of the composite molecular sieve are shown in the table 1.
Example 4-1:
1. (a) 5.0g of teos was added to 15.0g of 15.0gpH =3 HCl solution with stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left stand for 24 hours for use. (b) 1.2g of P123 surfactant was dissolved in 100g of 0.3mol/L hydrochloric acid solution, and 5.6g of the modified Y-1 molecular sieve (specific surface area 815 m) 2 Per gram, pore volume 0.54 mL/g, siO 2 /Al 2 O 3 The molar ratio is 18, the relative crystallinity is 104, the acid quantity is 0.615 mmol/g) is dissolved in water, and then is stirred for 5min, and the pre-hydrolysis solution of TEOS prepared in advance in the step (1) is added and is stirred for 4h at the constant temperature of 30 ℃.
2. And (3) hydrothermal crystallization: adjusting the pH of the reaction solution in the step 1 to 4.5 by ammonia water, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the core-shell structure SBA-15/Y-4-1 material.
3. 1.5g of aluminum isopropoxide is dissolved in 200ml of 0.2mol/LHCl solution, 30g of SBA-15/Y-4-1 material with a core-shell structure is added, the mixture is stirred for 20 hours at 30 ℃, and the mixture is washed, dried and roasted for 5 hours at 550 ℃ to obtain the aluminum supplementing material with an AlSBA-15/Y-4-1 mesoporous shell layer, wherein the physical parameters of the composite molecular sieve are shown in Table 1.
Example 5
78.1 g of AlSBA-15/Y-1 molecular sieve and 26.3 g of macroporous alumina (pore volume 0.82mL/g, specific surface area 410 m) 2 And/g), 27 g of small-pore alumina and dilute nitric acid (the molar ratio of nitric acid to small-pore alumina is 0.25), adding water, grinding into paste, extruding, drying the extruded strip at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-1.
The carrier is immersed in immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at 500 ℃ with a programmed temperature, thus obtaining the catalyst CAT-1, and the properties of the corresponding catalyst are shown in Table 2.
Example 6
70.3 g of AlSBA-15/Y-2 molecular sieve and 35.7 g of macroporous alumina (pore volume 0.82mL/g, specific surface area 410 m) 2 And/g), 35 g of small-pore alumina and dilute nitric acid (the molar ratio of nitric acid to small-pore alumina is 0.25), adding water, grinding into paste, extruding, drying the extruded strip at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-2.
The carrier is immersed in the impregnating solution containing molybdenum and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at 500 ℃ with a programmed temperature, thus obtaining the catalyst CAT-2, and the properties of the corresponding catalyst are shown in Table 2.
Example 7
65.5 g AlSBA-15/Y-3 molecular sieve, 44.6 g macroporous alumina (pore volume 0.82mL/g, specific surface area 410 m) 2 And/g), 27 g of small-pore alumina and dilute nitric acid (the molar ratio of nitric acid to small-pore alumina is 0.25), adding water, grinding into paste, extruding, drying the extruded strip at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-3.
The carrier is immersed in immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at 500 ℃ with a programmed temperature, thus obtaining catalyst CAT-3, and the properties of the corresponding catalyst are shown in Table 2.
Example 8
57.7 g AlSBA-15/Y-4 molecular sieve, 53.6 g macroporous alumina (pore volume 0.82mL/g, specific surface area 410 m) 2 And/g), 35 g of small-pore alumina and dilute nitric acid (the molar ratio of nitric acid to small-pore alumina is 0.25), adding water, grinding into paste, extruding, drying the extruded strip at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier TCAT-4.
The carrier is immersed in immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at 500 ℃ with a programmed temperature, thus obtaining catalyst CAT-4, and the properties of the corresponding catalyst are shown in Table 2.
Example 8-1
The preparation method of the catalyst is the same as that of example 8, and AlSBA-15/Y-4-1 is used for replacing AlSBA-15/Y-4 to obtain the catalyst CCAT-4.
Table 1 physicochemical properties of composite molecular sieves
TABLE 2 physicochemical Properties of the catalysts
The above catalysts of the present invention CAT-1, CAT-2, CAT-3, CAT-4 and comparative example CCAT-4 were subjected to activity evaluation tests. The tests were carried out on a 200mL small hydrogenation unit using a one-stage serial hydrocracking process with the properties of the feedstock oil as shown in table 4. The operating conditions were as follows: the reaction pressure is 15.7MPa, and the hydrogen oil volume ratio is 1000:1, liquid hourly space velocity 1.0h －1， Reaction temperature 363 deg.c, refined oil nitrogen content<10ppm. The results of the catalyst activity test are shown in Table 4.
TABLE 3 Properties of raw oil
TABLE 4 evaluation results of catalyst Activity
As can be seen from the evaluation results of the catalysts in Table 4, the catalyst prepared by the invention has high yield, the tail oil product has high linear alkane content, and the alkane content of more than two rings and the BMCI value of the tail oil are lower than those of the comparative example. The catalyst prepared by the method has the characteristics of high tail oil yield and good ring opening performance.

Claims (26)

1. A preparation method of a hydrocracking catalyst for producing high-quality ethylene raw materials is characterized by comprising the following steps of: the method comprises the following steps: mixing Al-SBA-15/Y shell-core composite molecular sieve, macroporous alumina and adhesive, shaping, drying, roasting to obtain carrier and loading hydrogenation active metal on the carrier;
the preparation method of the Al-SBA-15/Y shell-core type composite molecular sieve comprises the following steps:
(1) Mixing a template agent, a silicon source and a Y-type molecular sieve for reaction, and carrying out solid-liquid separation on the reacted materials to obtain a solid phase and a liquid phase;
(2) Taking 10% -50% of the volume fraction of the liquid phase obtained in the step (1), adjusting the mass content of the template agent in the taken liquid phase to be 0.05% -0.8%, adding the template agent into the solid phase separated in the step (1) for crystallization, and carrying out solid-liquid separation, drying and roasting after the crystallization is finished to obtain the SBA-15/Y shell-core composite molecular sieve;
(3) Treating the SBA-15/Y shell-core composite molecular sieve obtained in the step (2) by adopting an acidic aluminum salt solution, and drying and roasting to obtain a final composite carrier;
in the step (2), controlling the solid content of the separated liquid phase to be 0.05-3wt%; at this time, part of the liquid is the same as the solid phase mixture in the step (1) for crystallization; and (3) mixing the rest liquid phase with the template agent, the silicon source and the Y-type molecular sieve, and repeating the operation process of the step (1).
2. The method according to claim 1, characterized in that: the macroporous alumina has the following properties: pore volume is 0.6-1.2 mL/g, specific surface area is 300-600 m 2 /g。
3. The method according to claim 1, characterized in that: the adhesive is small-pore alumina with pore volume of 0.3-0.5 mL/g and specific surface area of 200-400 m 2 /g。
4. The method according to claim 1, characterized in that: the carrier can be molded according to actual needs, and one or more of a molding auxiliary agent, a peptizing agent and an extrusion aid are optionally added in the molding process.
5. The method according to claim 1, characterized in that: the carrier is dried for 3-10 hours at the temperature of 80-120 ℃ and baked for 3-10 hours at the temperature of 400-600 ℃.
6. The method according to claim 1, characterized in that: the hydrogenation active metal is VIB metal and/or VIII metal, the VIB metal is molybdenum and/or tungsten, and the VIII metal is cobalt and/or nickel.
7. The method according to claim 1, characterized in that: the loading of hydrogenation active metal adopts an impregnation method, the impregnated carrier is dried for l-12 hours at 100-120 ℃, and then baked for 3-10 hours at 400-600 ℃ to prepare the final catalyst.
8. The method according to claim 1, characterized in that: and (2) taking 15-30% of the volume fraction of the liquid phase obtained in the step (1), adjusting the mass content of the template agent in the taken liquid phase to be 0.1-0.6%, adding the template agent into the solid phase separated in the step (1) for crystallization, and carrying out solid-liquid separation, drying and roasting after the crystallization is finished to obtain the SBA-15/Y shell-core composite molecular sieve.
9. The method according to claim 8, wherein: in the step (1), the silicon source is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate and butyl orthosilicate.
10. The method according to claim 8, wherein: in the step (1), the silicon source is prepared by prehydrolysis, and the prehydrolysis process of the silicon source is as follows: adding a silicon source into an acidic solution, and aging to obtain the silicon source, wherein the acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
11. The method according to claim 8, wherein: in the step (1), the prehydrolysis process of the silicon source is as follows: and adding a silicon source into a dilute acid solution with pH=1-4, stirring for 1-12 hours at room temperature, and standing and aging for 4-120 hours to obtain the silicon source.
12. The method according to claim 8, wherein: in the step (1), the template agent is P123, and the template agent P123 is firstly dissolved in an acidic aqueous solution and then mixed with a silicon source and a Y-type molecular sieve for reaction.
13. The method according to claim 8, wherein: in the step (1), the Y-type molecular sieve is a modified Y-type molecular sieve, the particle size of the Y-type molecular sieve is 200 nm-5000 nm, and the silicon-aluminum molar ratio is SiO 2 /Al 2 O 3 The molar ratio of silicon to aluminum is 10-30.
14. The method according to claim 10, wherein: in the step (1), the molar concentration of the acidic solution in the template agent, the silicon source and the Y-type molecular sieve mixture is 0.1-1.0 mol/L, and the mass content of the template agent is 0.2% -3%; the mass content of the silicon source is 1% -10%; the mass content of the Y-type molecular sieve is 1% -15%.
15. The method according to claim 8, wherein: in the step (1), the reaction temperature is 20-40 ℃; the reaction time is 2-12 h.
16. The method according to claim 8, wherein: in the step (1), the mixing reaction process of the template agent, the silicon source and the Y-type molecular sieve is as follows: and dissolving a certain amount of template agent in an acidic aqueous solution, adding water into the solution after adding the Y-type molecular sieve, stirring for 10-15 min, adding a prehydrolyzed silicon source, and stirring at a constant temperature for 2-12 h.
17. The method according to claim 8, wherein: in the step (2), the crystallization process is to add alkaline substances or alkaline solutions into a crystallization system to adjust the pH value of the system to be 3-11; the crystallization temperature is 80-140 ℃; the crystallization time is 4-48 h.
18. The method according to claim 17, wherein: in the step (2), the crystallization process is to add alkaline substances or alkaline solution into the crystallization system to adjust the pH=7.5-10; the crystallization temperature is 100-120 ℃; the crystallization time is 24-30 h.
19. The method according to claim 8, wherein: in the step (2), the drying temperature is 80-120 ℃, the drying time is 4-10h, the roasting temperature is 450-600 ℃, and the roasting time is 4-8h.
20. The method according to claim 8, wherein: in the step (3), the aluminum salt is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate, the pH value of the acidic aluminum salt solution is 1-4, and the mass content of the aluminum salt in the acidic aluminum salt solution is 0.1% -1%; the treatment time is 3-10, and the treatment temperature is 25-35 ℃.
21. The method according to claim 8, wherein: in the step (3), a certain amount of aluminum source is dissolved in an acidic solution, the pH value of the acidic aluminum salt solution is 1-4, the SBA-15/Y shell-core composite molecular sieve prepared in the step (2) is added, stirring is carried out for 10-20h at 28-32 ℃, washing is carried out, drying is carried out for 4-10h at 80-120 ℃, and roasting is carried out for 4-6h at 500-560 ℃ to obtain the Al-SBA-15/Y molecular sieve.
22. A hydrocracking catalyst for producing high quality ethylene feedstock prepared by any one of the methods 1-21, characterized in that: the catalyst comprises the following components in percentage by weight: 20-70% of Al-SBA-15/Y shell-core composite molecular sieve; 10% -40% of macroporous alumina, 10% -20% of small-pore alumina and 6% -20% of VIB group metal calculated by oxide; the group VIII metal is 2% -8% in terms of oxide.
23. The catalyst of claim 22, wherein: the Al-SBA-15/Y shell-core type composite molecular sieve comprises an SBA-15 molecular sieve shell and a Y-type molecular sieve core, wherein the mass ratio of the shell to the core is 10:90-50:50, and the composite molecular sieve contains non-framework aluminum with the content of 0.5% -5% of oxide in a composite carrier.
24. The catalyst of claim 22, wherein: the catalyst has the following properties: the pores with the pore distribution of 4-15nm account for 70-90 percent of the total pore volume, and the specific surface area is 300-550 m 2 Per gram, the pore volume is 0.40-0.7 mL/g.
25. A hydrocracking process for producing a high quality ethylene feedstock characterized by: the catalyst prepared by the process of any one of claims 1 to 21 or the catalyst of any one of claims 22 to 24, under the following reaction conditions: in the presence of hydrogen, the reaction pressure is 10-18MPa, the reaction temperature is 350-400 ℃, the hydrogen-oil volume ratio is 500-1500, and the liquid hourly space velocity is 0.5-3.0h -1 。
26. The method according to claim 25, wherein: the raw materials adopted comprise heavy hydrocarbon materials, the raw materials are hydrocarbons with the boiling point of 250-600 ℃ and the nitrogen content of 500-2000 ppm.
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