WO2024041636A1 - 金属修饰分子筛、及其制备和应用 - Google Patents

金属修饰分子筛、及其制备和应用 Download PDF

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WO2024041636A1
WO2024041636A1 PCT/CN2023/114925 CN2023114925W WO2024041636A1 WO 2024041636 A1 WO2024041636 A1 WO 2024041636A1 CN 2023114925 W CN2023114925 W CN 2023114925W WO 2024041636 A1 WO2024041636 A1 WO 2024041636A1
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molecular sieve
metal
modified
exchange
roasting
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PCT/CN2023/114925
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English (en)
French (fr)
Inventor
张成喜
李永祥
周顺利
付强
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中国石油化工股份有限公司
中石化石油化工科学研究院有限公司
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Priority claimed from CN202211033765.6A external-priority patent/CN117654588A/zh
Priority claimed from CN202211033764.1A external-priority patent/CN117654587A/zh
Priority claimed from CN202211035148.XA external-priority patent/CN117658755A/zh
Application filed by 中国石油化工股份有限公司, 中石化石油化工科学研究院有限公司 filed Critical 中国石油化工股份有限公司
Publication of WO2024041636A1 publication Critical patent/WO2024041636A1/zh

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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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes

Definitions

  • the present application relates to the field of catalysts, and specifically to a metal-modified molecular sieve, its preparation and application.
  • Long-chain alkylbenzene is an important raw material for the preparation of synthetic detergent sodium alkylbenzene sulfonate.
  • Long-chain alkylbenzenes are mainly produced by the alkylation reaction of long-chain olefins and monocyclic aromatic hydrocarbons.
  • Current commercial technology mainly uses hydrofluoric acid or aluminum trichloride as catalysts, but these two catalytic systems have greater
  • the safety and environmental protection risks are gradually being eliminated as the safety and environmental protection requirements gradually increase.
  • the development of new corrosion-free and pollution-free solid acid alkylation methods as an alternative technology has become an inevitable development trend in long-chain alkylbenzene production technology.
  • the industrial solid acid process uses the fluorine-containing SiO 2 -Al 2 O 3 solid acid catalyst (ZL93104573.8) jointly developed by UOP Company of the United States and Petresa Company of Spain.
  • This catalyst needs to be restored to activity through regular benzene flushing. Achieve long-term stable operation.
  • the catalyst itself contains fluorine, it is corrosive to the equipment and still poses certain safety and environmental risks.
  • CN107867699A discloses a Y zeolite containing regular ultra-large micropores. By subjecting selected Y zeolite to template agent and acid-base treatment, a Y zeolite with 1-2nm regular ultra-large micropores is constructed. Due to the regular ultra-large micropores, it provides The rich acid sites and suitable reaction channels result in higher conversion rate and selectivity.
  • CN110562995A discloses a synthesis method of nanometer Y zeolite and its application in the synthesis of linear alkylbenzene. Due to the catalyst grains, the diffusion resistance is small and the activity of alkylation of long-chain olefins is high. Performance and stability are improved.
  • CN102639471A discloses a method for producing linear alkylbenzene. This method uses a combination of two zeolites to limit framework isomerization and improve the linearity of the product.
  • the purpose of this application is to provide a metal-modified molecular sieve, its preparation and application.
  • the metal-modified molecular sieve contains a certain amount of extra-framework modified metal, which can better inhibit the skeletal isomerization of long-chain hydrocarbon-based aromatic compound products and improve the product accuracy. chain degree and product selectivity, and its catalytic cycle life has also been greatly extended.
  • the present application provides a metal-modified molecular sieve, including a silica-aluminum molecular sieve and a modified metal selected from alkaline earth metals, Group IIIB metals, Group IIIA metals, or combinations thereof, at least a part of which
  • the modified metal exists in the form of compensating cations outside the molecular sieve framework, and based on the total amount of the metal modified molecular sieve, the content of the modified metal is 8-30wt% in terms of elements;
  • the mass fraction of the surface-modified metal measured by X-ray photoelectron spectroscopy (XPS) is the same as the bulk phase measured by X-ray fluorescence spectrometry (XRF).
  • the ratio of mass fractions of modifying metals shall not exceed 1.45.
  • the product of the second ion exchange is subjected to a second roasting, optionally repeating the second ion exchange and the second roasting one or more times to obtain a second exchanged molecular sieve;
  • the first roasting and/or the second roasting are performed in an alkaline atmosphere.
  • a solid acid catalyst including the metal-modified molecular sieve of the present application and a heat-resistant inorganic oxide.
  • a method for preparing long-chain hydrocarbyl aromatic compounds which includes the step of reacting long-chain olefins and aromatic hydrocarbons in the presence of the metal-modified molecular sieve of the present application.
  • the method is carried out in the presence of the solid acid catalyst of the present application, and further includes the step of regenerating the solid acid catalyst in the presence of oxygen-containing mixed gas.
  • the metal-modified molecular sieve provided by this application can better suppress the skeleton of the target long-chain hydrocarbon-based product during the preparation process of long-chain hydrocarbon-based aromatic compounds through the modification of a certain amount of extra-skeleton metal with a specific surface layer and distribution in the molecular sieve channels. Isomerization improves product linearity and product selectivity, and its catalytic cycle life is also greatly extended.
  • the preparation method of metal-modified molecular sieves provided by this application can realize the modification of a specific amount of extra-framework metal with a specific surface layer and distribution in the molecular sieve channels through multiple ion exchanges and multiple roastings, while ensuring the stability of the unit cells of the molecular sieve before and after the reaction. Stable to prevent molecular sieve structure from being destroyed due to repeated roasting.
  • the solid acid catalyst provided in this application through the combination of metal-modified molecular sieves and heat-resistant inorganic oxides, can achieve shape selection of the reaction product during the preparation process of long-chain alkylbenzene, significantly improving the linearity of the product. and product selectivity is improved; at the same time, the solid acid catalyst provided by this application is suitable for reactor forms such as fixed bed, fluidized bed, and moving bed in industrial production, and can realize large-scale industrial applications.
  • the preparation method of long-chain hydrocarbon aromatic compounds provided by this application uses the metal-modified molecular sieve and/or solid acid catalyst of this application. Due to the shape selection of the reaction product after the modification of the molecular sieve, the linearity of the product is significantly improved, and the product The selectivity is improved, and the catalytic cycle life of the metal-modified molecular sieve is also significantly extended.
  • the catalyst can also be regenerated conveniently, achieving long-term continuous operation through reaction-regeneration, and achieving continuous and stable preparation of long-chain hydrocarbon aromatic compounds, especially long-chain alkylbenzenes.
  • Figure 1 shows a comparison of the XRD spectra of the metal-modified molecular sieve and HY molecular sieve obtained in Preparation Example I-1;
  • Figure 2 shows the pyridine adsorption infrared spectrum of the molecular sieves obtained in Preparation Example I-1 and Preparation Comparative Examples I-1 to I-3;
  • Figure 3 shows a comparison of the XRD spectra of the metal-modified molecular sieve and H ⁇ molecular sieve obtained in Preparation Example I-2;
  • Figure 4 shows the evaluation results of continuous operation for 300 hours when the metal-modified molecular sieve obtained in Preparation Example I-1 was used in the preparation of long linear alkyl benzene;
  • Figure 5 shows the evaluation results of continuous operation for 260 hours using the solid acid catalyst obtained in Preparation Example II-1 in the preparation of long linear alkyl benzene;
  • Figure 6 shows the evaluation results of applying the solid acid catalyst obtained in Preparation Example II-1 to the continuous preparation of long linear alkylbenzene through a continuous reaction-regeneration method.
  • any specific numerical value disclosed herein is not limited to the precise value of the numerical value, but is to be understood to also encompass values close to the precise value, such as within ⁇ 5% of the precise value. all possible values.
  • one or more new values can be obtained by any combination between the endpoint values of the range, between the endpoint value and the specific point value within the range, and between each specific point value. Numerical ranges, these new numerical ranges should also be deemed to be specifically disclosed herein.
  • the term "outside the molecular sieve framework” means that the modified metal exists in the cationic position of the molecular sieve in the form of ions and/or is loaded on the surface of the molecular sieve in the form of oxides.
  • the peak position of the characteristic peak of the metal-modified molecular sieve is the same as the peak position of the diffraction peak of the unmodified molecular sieve, that is, there is no shift in the characteristic peak, which can prove that the modified metal is located outside the molecular sieve framework.
  • the mass fraction of surface modified metal refers to the mass fraction of modified metal elements measured by The mass fraction of the modified metal element. It can be understood that the XRF test first obtains the mass fraction of the bulk modified metal in terms of oxides, and then calculates the mass fraction of the corresponding element.
  • dry basis mass is defined as the mass of the material after roasting at 600°C for 3 hours.
  • any matters or matters not mentioned shall directly apply to those known in the art without any changes.
  • any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of this application and shall not be It is regarded as new content that has not been disclosed or expected in this article, unless those skilled in the art believe that the combination is obviously unreasonable.
  • the application provides a metal-modified molecular sieve, including a silica-aluminum molecular sieve and a modified metal selected from alkaline earth metals, Group IIIB metals, Group IIIA metals, or combinations thereof, wherein at least a portion of the modified metal Exists in the form of compensating cations outside the molecular sieve framework, and based on the total amount of the metal-modified molecular sieve, the content of the modified metal is 8-30wt% in terms of elements;
  • the mass fraction of the surface-modified metal measured by X-ray photoelectron spectroscopy (XPS) is the same as the bulk phase measured by X-ray fluorescence spectrometry (XRF).
  • the ratio of mass fractions of modifying metals shall not exceed 1.45.
  • the inventor of this application has discovered through extensive research that when the interior of the molecular sieve contains a certain amount of extra-skeleton modified metal, and the modified metal has a specific surface layer and distribution within the molecular sieve pores, it can be used in the alkylation reaction of long-chain olefins and aromatic hydrocarbons. It can effectively inhibit the occurrence of side reactions such as olefin isomerization and polyalkylation reactions that lead to the generation of by-products and catalyst deactivation, and achieve shape-selective catalysis, thus improving the linearity of the product and the catalytic cycle life of the molecular sieve.
  • the ratio of the mass fraction of the surface-modified metal measured by XPS to the mass fraction of the bulk-modified metal measured by XRF does not exceed 1.35. , preferably 0.9-1.35, for example, it can be 0.95, 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35 or any value within the range of any two points. Under the above preferred distribution conditions, it is beneficial to improve the catalytic cycle life of the molecular sieve and the linearity of the product. If the ratio of the mass fraction of the surface modified metal to the mass fraction of the bulk modified metal is too high, it may shorten the catalytic cycle life of the molecular sieve. If the ratio is too low, the linearity of the product may decrease.
  • the content of the modified metal is 12-23 wt% in terms of elements.
  • the content of the modifying metal may be 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt% or Any value within the range of values formed by any two points. Under the above preferred conditions, it is helpful to ensure that the metal distribution is in the best position, thereby achieving shape-selective catalysis and improving the catalytic cycle life of the catalyst and the linearity of the product.
  • the atomic radius of the modified metal is 120-270pm, preferably 160-240pm.
  • the modified metal is selected from Mg, Ca, Sr, Ba, La, Ce, Pr, Rd, Sm, Eu, Yb, Sc, Y, Al, Ga, In, or a combination thereof; even further preferably is La, Ce, Sr, Y, or their combination.
  • the molar ratio of silica/alumina in the metal-modified molecular sieve is 1-100:1, more preferably 3-20:1.
  • the metal-modified molecules are selected from X-type molecular sieves, Y-type molecular sieves, MCM-22-type molecular sieves, Beta-type molecular sieves, MOR-type molecular sieves, or combinations thereof, preferably X-type molecular sieves and/or Y-type molecular sieves. type molecular sieve.
  • X-type molecular sieves preferably X-type molecular sieves and/or Y-type molecular sieves. type molecular sieve.
  • the use of the above-mentioned preferred molecular sieve types is beneficial to further improving the catalytic activity of the molecular sieve.
  • the pyridine adsorption infrared spectrum of the metal-modified molecular sieve has two absorption peaks in the range of 1440-1460 cm -1 . Further preferably, the ratio of the absorption peak area at the lower wave number position to the total area of the two absorption peaks is 0.3-0.7, more preferably 0.4-0.6.
  • the pyridine adsorption infrared spectrum of silica-aluminum molecular sieve will show an infrared absorption peak near 1450cm -1 , which is the absorption peak of L acid on the surface of the molecular sieve.
  • the original absorption peak near 1450cm -1 is split into two absorption peaks in the range of 1440-1460cm -1 .
  • the absorption peak at the lower wave number position is the modification within the molecular sieve channels.
  • the absorption peak of strong L acid induced by metal cations is calculated by calculating the proportion of the strong L acid, that is, the absorption peak area at the lower wave number position accounts for the total of the two absorption peaks in the range of 1440-1460 cm -1
  • the ratio of the areas can be used to determine the location and content of modified metals in the molecular sieve.
  • a method for preparing the metal-modified molecular sieve of the present application including the following steps:
  • the product of the second ion exchange is subjected to a second roasting, optionally repeating the second ion exchange and the second roasting to obtain a second exchanged molecular sieve;
  • the first roasting and/or the second roasting are performed in an alkaline atmosphere.
  • the preparation method of metal-modified molecular sieves provided by this application can realize the modification of specific extra-framework metals through at least two cross-bakings, while ensuring the stability of the unit cell size of the molecular sieve before and after the reaction, and avoiding the destruction of the molecular sieve structure due to multiple roastings. .
  • the number of repetitions of the second ion exchange and the second roasting is not particularly limited. It can be determined according to the effect of ion exchange.
  • the purpose is to make the metal content in the molecular sieve meet the above range requirements. For example, it can Repeat 1-3 times.
  • the molecular sieve precursor is a silica-alumina molecular sieve, and the molar ratio of silicon oxide/alumina in the molecular sieve is preferably 1-100:1, more preferably 3-20:1.
  • the molar ratio of silicon oxide and alumina of the molecular sieve before and after metal modification remains basically unchanged, and both meet the above molar ratio range requirements.
  • the molecular sieve precursor is selected from at least one of X-type molecular sieve, Y-type molecular sieve, MCM-22-type molecular sieve, Beta-type molecular sieve and MOR-type molecular sieve, preferably X-type molecular sieve and/or Y-type molecular sieve. type molecular sieve.
  • the molecular sieve precursor is a hydrogen-form or sodium-form molecular sieve.
  • the molecular sieve precursor is a sodium-type molecular sieve
  • the first exchange liquid and/or the second exchange liquid further includes an ammonium salt.
  • the first exchange liquid also includes an ammonium salt.
  • step 1) includes ion co-exchange of the sodium-type molecular sieve with a first exchange liquid containing a soluble compound of the modified metal and an ammonium salt.
  • the preparation process can be shortened by using ion co-exchange. Na + is exchanged into metal cations and NH 4 + in one step, and the exchanged NH 4 + can be decomposed and removed in the subsequent roasting process, retaining the molecular sieve. of acidic hydrogen protons.
  • the ammonium salt can be a conventional choice in the art, preferably selected from ammonium nitrate, ammonium chloride, ammonium sulfate, or combinations thereof.
  • the ammonium salt concentrations in the first and second exchange liquids are independently 50-200g/L, preferably 70-150g/L.
  • the preparation method further includes ammonium exchange of the second exchange molecular sieve with a third exchange liquid containing ammonium salt, and then The heat treatment.
  • the Na + content in the molecular sieve can be further reduced by the ammonium exchange to ensure that the molecular sieve has a higher acid content.
  • the ammonium exchange and drying can be carried out using conventional methods and conditions in the art.
  • the second exchange molecular sieve is contacted with the third exchange liquid containing ammonium salt, and then filtered and dried as a primary Ammonium exchange process, the ammonium exchange process can be optionally repeated 1-3 times, so that the Na mass fraction in the molecular sieve is less than 0.2%.
  • the concentration range of the ammonium salt in the third exchange liquid may be the same as the concentration range in the above-mentioned first exchange liquid or second exchange liquid, which will not be described again here.
  • the soluble compound of the modified metal is selected from the group consisting of chlorides, nitrates, phosphates, sulfates of the modified metal, or combinations thereof.
  • the concentration of the metal-modified soluble compound in the first exchange liquid and/or the second exchange liquid there are no special requirements for the concentration of the metal-modified soluble compound in the first exchange liquid and/or the second exchange liquid, as long as the content of the modified metal element in the metal-modified molecular sieve meets the above range requirements. Routine adjustments can be made by those skilled in the art.
  • the concentrations of the metal-modifying soluble compounds in the first exchange liquid and the second exchange liquid are each independently 100-500g/L, and further preferably 130-400g/L. Using the above preferred embodiment, it can be On the basis of meeting the above content requirements, shorten the preparation process.
  • the first exchange liquid and the second exchange liquid also independently include a solvent, and the solvent is preferably water.
  • the mass ratio of the first exchange liquid to the molecular sieve precursor is 2-8:1, more preferably 3-6:1.
  • the mass ratio of the second exchange liquid to the first exchange molecular sieve is 3-6:1, more preferably 3-5:1.
  • the conditions for the first ion exchange include: the exchange temperature is 50-90°C, preferably 70-90°C; the exchange time is 0.5-2h, preferably 0.8-1.5h.
  • the conditions for the second ion exchange may be the same as or different from the conditions for the first ion exchange.
  • the conditions for the second ion exchange include: the exchange temperature is 50-120°C, preferably 70-100°C. °C; the exchange time is 0.5-2h, preferably 0.8-1.5h. Further preferably, the exchange temperature of the second ion exchange is 0-15°C higher than the exchange temperature of the first exchange, preferably 1-10°C higher. Adopting the above preferred embodiment is beneficial to optimizing the metal distribution and further improving the catalytic activity of the molecular sieve.
  • the amount of the modified metal is such that in the obtained metal-modified molecular sieve, based on the total amount of the molecular sieve, the content of the modified metal is 8-30wt% in terms of elements, preferably 8-30wt%. 12-23wt%.
  • the content of the modifying metal may be 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt% or Any value within the range of values formed by any two points.
  • the first roasting and/or the second roasting are carried out in an alkaline atmosphere.
  • the first roasting and the second roasting are both carried out in an alkaline atmosphere.
  • Adopting the above preferred embodiments helps protect the molecular sieve structure and further improves the catalytic cycle life of the metal-modified molecular sieve.
  • the alkaline atmosphere is provided by an aqueous solution of an alkaline compound. It can be understood that the aqueous solution of the basic compound vaporizes rapidly at the roasting temperature, thereby providing an alkaline atmosphere for the roasting process.
  • the selection range for the basic compound is relatively wide.
  • the alkaline compound is selected from ammonia, ammonium carbonate, urea, or a combination thereof, preferably ammonia.
  • the concentration of the basic compound is 0.01-2mol/L, preferably 0.01-0.5mol/L, further preferably 0.05- 0.3 mol/L, under the above preferred conditions, is beneficial to the stability of the molecular sieve structure and prolongs the catalytic cycle life of the molecular sieve.
  • the introduction rate of the alkaline atmosphere is each independently 0.01- 0.5mL/min, more preferably 0.05-0.2mL/min. It can be understood that when the processing amount of the molecular sieve precursor increases, the introduction rate of the alkaline atmosphere can be increased proportionally.
  • the first calcination conditions include: calcination temperature is 400-600°C, calcination time is 0.5-3h, and pressure is 0.01-0.1MPa (gauge pressure).
  • the conditions for the second calcination include: calcination temperature is 400-600°C, calcination time is 0.5-3h, and pressure is 0.01-0.1MPa (gauge pressure).
  • the first roasting and the second roasting do not refer to the operation sequence, but are only used to distinguish the roasting conditions in different steps.
  • the conditions for the first roasting and the second roasting may be the same or different, as long as the above conditions are met.
  • the first roasting or the second roasting before the first roasting or the second roasting, it also includes solid-liquid separation and drying of the product of the first ion exchange or the second ion exchange respectively, and the solid-liquid Separation and drying can be performed by conventional operations in the art, and will not be described again.
  • the oxygen-containing atmosphere in step 5) is air or a mixture of oxygen and an inert gas; the inert gas is preferably nitrogen.
  • the oxygen content in the oxygen-containing atmosphere is 16-30 vol%, preferably 18-25 vol%.
  • the temperature of the heat treatment in step 5) is 50-100°C higher than the temperature of the second roasting in step 4).
  • the use of higher temperature oxygen-containing atmosphere heat treatment allows the modified metal to further migrate and anchor under high temperature conditions to ensure that the metal remains stable in repeated reaction-regeneration high temperature environments.
  • the heat treatment conditions include: a temperature of 500-700°C, preferably 550-650°C, and a treatment time of 2-12h, preferably 4-8h.
  • a metal-modified molecular sieve prepared by the method of the present application is provided.
  • a solid acid catalyst which catalyst includes a metal-modified molecular sieve and a heat-resistant inorganic oxide, wherein the metal-modified molecular sieve is gold according to the present application. It is a modified molecular sieve.
  • metal-modified molecular sieve is used as an active component.
  • the inventor of this application discovered through extensive research that when the solid acid catalyst is used in the alkylation reaction of long-chain olefins and aromatic hydrocarbons, , through the combination of the metal-modified molecular sieve of the present application and the heat-resistant inorganic oxide, the linearity of the product can be further improved, and its catalytic cycle life is also greatly extended, making it suitable for industrial production.
  • the content of each component in the solid acid catalyst is based on the feed ratio.
  • the content of each component in the solid acid catalyst has a wide selection range and can be adjusted according to actual application needs.
  • the dry basis mass ratio of the metal-modified molecular sieve to the heat-resistant inorganic oxide is 99:1 to 20:80, preferably 95:5 to 25:75, and more preferably 90:10 to 50:50.
  • the heat-resistant inorganic oxide is selected from alumina, zirconia, silica, titanium dioxide, clay, kaolin, montmorillonite, magnesia alumina crystal, amorphous silica alumina, or a combination thereof, more preferably from alumina, zirconia, silica, titanium dioxide, or combinations thereof.
  • the use of the above-mentioned preferred heat-resistant inorganic oxides is beneficial to bringing into play the synergistic effect of the metal-modified molecular sieve and the heat-resistant inorganic oxides, further improving the catalytic performance of the catalyst.
  • the particle size of the heat-resistant inorganic oxide is 0.005-200 ⁇ m, more preferably 0.01-100 ⁇ m. Under the above preferred circumstances, it is beneficial to enhance the interaction between the molecular sieve and the inorganic oxide and improve the catalyst performance and strength.
  • a method for preparing the solid acid catalyst of the present application including: combining the metal modified molecular sieve of the present application, heat-resistant inorganic oxide and/or its precursor, water, optional extrusion aid, and any The selected peptizer is mixed, shaped and calcined to obtain the solid acid catalyst.
  • the precursor of the heat-resistant inorganic oxide is a substance that can be roasted to obtain the heat-resistant inorganic oxide, which is a common choice in this field, and this application has no special requirements for this.
  • the precursor of alumina may be pseudoboehmite.
  • the particle size of the heat-resistant inorganic oxide and/or its precursor is 0.005-200 ⁇ m, more preferably 0.01-100 ⁇ m. Under the above preferred circumstances, it is beneficial to enhance the interaction between the molecular sieve and the inorganic oxide and improve the catalyst performance and strength.
  • the type of extrusion aid is not particularly limited, and all conventional extrusion aids in this field are suitable for this application.
  • the extrusion aid is selected from sesbania powder, cellulose, starch, or a combination thereof.
  • the selection range of the amount of extrusion aid is wide.
  • the amount of the extrusion aid is 0-20 wt% of the total dry weight of the metal modified molecular sieve, the heat-resistant inorganic oxide and/or its precursor, and further preferably, the amount of the extrusion aid is It is 1-5 wt% of the total dry weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide.
  • the type of peptizing agent is not particularly limited, and all peptizing agents conventionally defined in this field are applicable to this application.
  • the peptizer is selected from citric acid, nitric acid, phosphoric acid, or combinations thereof.
  • the amount of peptizing agent is not particularly limited.
  • the amount of the peptizing agent is 0-20 wt% of the total dry weight of the metal modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor.
  • the amount of the peptizing agent is 0-20 wt%. 1-8 wt% of the total weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor on a dry basis.
  • the selection range of the amount of water is wide, as long as the above components can be mixed evenly, and can be adjusted according to actual needs.
  • the ratio of the amount of water to the total dry weight of the metal modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor is 0.2-1.2:1. Further preferably, the amount of water is 0.2-1.2:1.
  • the ratio of the total dry basis weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor is 0.3-1:1.
  • the method further includes drying or shaping and drying the shaped product to obtain a mixed shaped product, and then performing the roasting.
  • the drying or molding drying can be carried out using conventional operations in the art, such as oven drying or spray drying, so that the dry basis weight of the mixed molded product is 40-85wt% of the weight of the molded product, preferably 60-75wt. %.
  • the drying or molding drying temperature is 100-250°C, preferably 100-150°C, and the drying or molding drying time is 1-24h, preferably 2-10h.
  • the temperature of the primary roasting is 400-650°C, preferably 500-600°C, and the time of primary roasting is 0.5-8h, preferably 2-6h.
  • a solid acid catalyst prepared by the method of the present application is provided.
  • the metal-modified molecular sieve or solid acid catalyst of the present application in the preparation of long-chain hydrocarbyl aromatic compounds, wherein the long-chain hydrocarbyl aromatic compound It is prepared by the reaction of long-chain olefins and aromatic hydrocarbons.
  • the present application provides a method for preparing long-chain hydrocarbyl aromatic compounds, including the step of reacting long-chain olefins and aromatic hydrocarbons in the presence of the metal-modified molecular sieve of the present application.
  • the long-chain olefins obtained through paraffin dehydrogenation, cracking, and oligomerization of small molecule olefins or commercially available long-chain olefins can be used in this application.
  • the long chain olefin is a long chain alpha olefin having a double bond at the end.
  • the long-chain olefin is a C7-C27 long-chain olefin, further preferably a C8-C15 long-chain olefin, and more preferably a C10-C14 long-chain olefin.
  • the aromatic hydrocarbon may be a monocyclic or bicyclic aromatic hydrocarbon, preferably a benzene aromatic hydrocarbon, more preferably selected from benzene, toluene, ethylbenzene, or a combination thereof, and benzene is particularly preferred.
  • the reaction conditions of the long-chain olefins and aromatic hydrocarbons can be carried out using conventional conditions in the art. It is preferable to ensure that the reaction is carried out in a liquid phase and the pressure is always sufficient to ensure that the reaction is carried out in a single liquid phase.
  • the single liquid phase means that the reactants put in are all in liquid phase, and the reaction conditions are such that the reactants will not vaporize during the reaction process.
  • the reaction pressure is higher than the saturated vapor pressure of long-chain olefins and aromatic hydrocarbons at corresponding reaction temperatures, so that the reaction materials are all in liquid phase for contact reaction.
  • reaction conditions include: reaction temperature is 50-250°C, preferably 70-200°C; reaction pressure is 0.1-7MPa, preferably 2-4MPa; aromatic hydrocarbon/ene molar ratio is 3- 70:1, preferably 4-60:1; the space velocity of long-chain olefins is 0.1-5h -1 , preferably 0.3-3h -1 .
  • reaction temperature is 50-250°C, preferably 70-200°C
  • reaction pressure is 0.1-7MPa, preferably 2-4MPa
  • aromatic hydrocarbon/ene molar ratio is 3- 70:1, preferably 4-60:1
  • the space velocity of long-chain olefins is 0.1-5h -1 , preferably 0.3-3h -1 .
  • the reaction of the long-chain olefins and aromatic hydrocarbons can be carried out in a conventional reactor in the art.
  • the reaction can be carried out in a fixed bed reactor, a fluidized bed reactor, a moving bed reactor or a slurry bed reactor.
  • the reaction of the long-chain olefins and aromatic hydrocarbons is carried out in the presence of the solid acid catalyst of the present application, and the method further includes: performing the reaction on the solid acid catalyst under oxygen-containing mixed gas. Regeneration steps.
  • the catalyst can be regenerated conveniently through regeneration, and long-term continuous operation can be achieved through reaction-regeneration.
  • the oxygen content in the oxygen-containing mixed gas is 1-50 vol%, preferably 10-25 vol%.
  • the oxygen-containing mixed gas is a mixed gas of oxygen and a protective gas;
  • the protective gas can be selected from any gas that does not participate in the reaction.
  • the protective gas is nitrogen, helium, At least one of the argon gases.
  • the regeneration temperature is 400-700°C
  • the regeneration time is 4-18h
  • the volume space velocity of the oxygen-containing mixed gas is 500-6000h -1
  • the regeneration pressure is 0.01-0.1MPa ( Gauge).
  • the regeneration temperature is 450-600°C, for example, it can be 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, Typical but not limiting temperatures such as 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C; preferably, the regeneration time is 5-12h, and the volume space velocity of the oxygen-containing mixed gas is 500 -5000h -1 , regeneration pressure is 0.01-0.05MPa (gauge pressure). Adopting the above preferred regeneration conditions is beneficial to improving the regeneration effect of the solid acid catalyst.
  • the timing of the regeneration is selected by detecting the reaction progress. For example, the regeneration is performed when the long-chain olefin conversion rate is lower than 95%. More preferably, the regeneration is performed when the long-chain olefin conversion rate is lower than 98%.
  • this application provides the following technical solutions:
  • a metal-modified molecular sieve characterized in that the metal-modified molecular sieve includes a molecular sieve and a metal outside the molecular sieve skeleton; based on the total amount of the metal-modified molecular sieve, in terms of elements, the content of the modified metal is 8 -30wt%;
  • the ratio of the mass fraction of the surface-modified metal measured by XPS to the mass fraction of the bulk-modified metal measured by XRF does not exceed 1.45.
  • the metal-modified molecular sieve according to item A1 wherein in the metal-modified molecular sieve, in terms of the mass fraction of the element, the mass fraction of the surface-modified metal measured by XPS is the same as the mass fraction of the bulk-modified metal measured by XRF.
  • the ratio of mass fractions does not exceed 1.35, preferably 0.9-1.35;
  • the content of the modified metal is 12-23wt% in terms of elements
  • the atomic radius of the modified metal is 120-270pm, preferably 160- 240pm;
  • the modified metal is selected from at least one of alkaline earth metals, Group IIIB metals and Group IIIA metals; further preferably, it is at least one of La, Ce, Sr and Y.
  • metal-modified molecular sieve according to item A1 or A2, wherein the metal-modified molecular sieve is a silica-aluminum molecular sieve;
  • the molar ratio of silica/alumina in the metal-modified molecular sieve is 1-100:1, preferably 3-20:1;
  • the metal-modified molecules are selected from at least one of X-type molecular sieves, Y-type molecular sieves, MCM-22-type molecular sieves, Beta-type molecular sieves and MOR-type molecular sieves, preferably X-type molecular sieves and/or Y-type molecular sieves.
  • a method for preparing metal-modified molecular sieves which is characterized in that it includes the following steps:
  • the product of the second ion exchange is subjected to a second roasting, optionally repeating the second ion exchange and the second roasting to obtain a second exchanged molecular sieve;
  • the first roasting and/or the second roasting are carried out in an alkaline atmosphere
  • the content of the modified metal is 8-30 wt% in terms of elements.
  • the molecular sieve precursor is a silica-alumina molecular sieve, and the molar ratio of silicon oxide/alumina in the molecular sieve is preferably 1-100:1, preferably 3-20:1;
  • the molecular sieve precursor is selected from at least one of X-type molecular sieve, Y-type molecular sieve, MCM-22-type molecular sieve, Beta-type molecular sieve and MOR-type molecular sieve, preferably X-type molecular sieve.
  • X-type molecular sieve Molecular sieve and/or Y-type molecular sieve;
  • the molecular sieve precursor is a sodium-type molecular sieve, and the first exchange liquid and/or the second exchange liquid further includes an ammonium salt;
  • the ammonium salt is selected from ammonium nitrate, ammonium chloride, ammonium sulfate, or a combination thereof;
  • the concentration of ammonium salt in the first exchange liquid and/or the second exchange liquid is independently 50-200 g/L.
  • A7 The preparation method according to any one of items A4-A6, wherein the soluble compound of the modified metal is selected from the group consisting of chloride, nitrate, phosphate, sulfate of the modified metal, or a combination thereof;
  • the concentration of the soluble compound modifying the metal is each independently 100-500g/L;
  • the first exchange liquid and the second exchange liquid also each independently include a solvent, and the solvent is preferably water;
  • the atomic radius of the modified metal is 120-270pm, preferably 160-240pm;
  • the modified metal is selected from at least one of alkaline earth metals, Group IIIB metals and Group IIIA metals; further preferably at least one of La, Ce, Sr and Y;
  • the mass ratio of the first exchange liquid to the molecular sieve precursor is 2-8:1;
  • the mass ratio of the second exchange liquid to the first exchange molecular sieve is 3-6:1;
  • the conditions for the first ion exchange include: exchange temperature is 50-90°C, preferably 70-90°C; exchange time is 0.5-2h, preferably 0.5-1.5h;
  • the exchange temperature of the second ion exchange is 0-15°C higher than the exchange temperature of the first ion exchange, preferably 1-10°C.
  • the alkaline compound is selected from ammonia, ammonium carbonate, urea, or a combination thereof;
  • the concentration of the basic compound in the aqueous solution of the basic compound is 0.01-2mol/L;
  • the introduction rate of the alkaline atmosphere is 0.01-0.5 mL/min based on the volume of the aqueous alkaline compound solution;
  • the conditions for the first roasting include: roasting temperature of 400-600°C, roasting time of 0.5-3h, and pressure of 0.01-0.1MPa (gauge pressure);
  • the conditions for the second calcination include: calcination temperature is 400-600°C, calcination time is 0.5-3h, and pressure is 0.01-0.1MPa (gauge pressure).
  • A9 The preparation method according to any one of items A4-A8, wherein the oxygen-containing atmosphere is air or a mixture of oxygen and inert gas;
  • the oxygen content in the oxygen-containing atmosphere is 16-30 vol%, preferably 18-25 vol%;
  • the temperature of the heat treatment is 50-100°C higher than the second roasting temperature
  • the heat treatment conditions include: a temperature of 500-700°C, preferably 550-650°C, and a treatment time of 2-12h, preferably 4-8h.
  • a long-chain olefin alkylation method which method includes: contacting long-chain olefins and aromatic hydrocarbons with a catalyst under alkylation reaction conditions to perform an alkylation reaction;
  • the catalyst is the metal-modified molecular sieve described in any one of items A1-A3 and A10.
  • the long-chain olefin is a C8-C28 long-chain olefin, further preferably a C8-C15 long-chain olefin, and more preferably a C10-C14 long-chain olefin;
  • the aromatic hydrocarbon is selected from benzene, toluene, ethylbenzene, or a combination thereof, preferably benzene;
  • the conditions for the alkylation reaction include: reaction temperature is 50-250°C, preferably 70-200°C; reaction pressure is 0.1-7MPa, preferably 2-4MPa; benzene/ene molar ratio is 3-70 :1, preferably 4-60:1; the mass space velocity of long-chain olefins is 0.1-5h -1 , preferably 0.3-3h -1 .
  • a solid acid catalyst characterized in that the catalyst includes a metal-modified molecular sieve and a heat-resistant inorganic oxide;
  • the metal-modified molecular sieve includes molecular sieves and metals outside the molecular sieve framework; based on the total amount of the metal-modified molecular sieve, the content of the modified metal is 8-30wt% in terms of elements;
  • the mass fraction of the element in terms of the mass fraction of the element, the mass fraction of the surface-modified metal measured by XPS and the mass fraction of the bulk-modified metal measured by XRF The ratio of scores does not exceed 1.45.
  • the particle size of the heat-resistant inorganic oxide is 0.005-200 ⁇ m, more preferably 0.01-100 ⁇ m.
  • the content of the modified metal is 12-23wt% in terms of elements
  • the atomic radius of the modified metal is 120-270pm, preferably 160-240pm;
  • the modified metal is selected from at least one of alkaline earth metals, Group IIIB metals and Group IIIA metals; further preferably, it is at least one of La, Ce, Sr and Y.
  • the molar ratio of silica/alumina in the metal-modified molecular sieve is 1-100:1, preferably 3-20:1;
  • the metal-modified molecules are selected from at least one of X-type molecular sieves, Y-type molecular sieves, MCM-22-type molecular sieves, Beta-type molecular sieves and MOR-type molecular sieves, preferably X-type molecular sieves and/or Y-type molecular sieves.
  • a method for preparing a solid acid catalyst characterized in that the preparation method includes: combining metal modified molecular sieves, heat-resistant inorganic oxides and/or their precursors, water, optional extrusion aids, and optional The peptizer is mixed, shaped and roasted to obtain the solid acid catalyst;
  • the metal-modified molecular sieve includes molecular sieves and metals outside the molecular sieve framework; based on the total amount of the metal-modified molecular sieve, the content of the modified metal is 8-30wt% in terms of elements;
  • the ratio of the mass fraction of the surface-modified metal measured by XPS to the mass fraction of the bulk-modified metal measured by XRF does not exceed 1.45.
  • the product of the second ion exchange is subjected to a second roasting, optionally repeating the second ion exchange and the second roasting to obtain a second exchanged molecular sieve;
  • the first roasting and/or the second roasting are performed in an alkaline atmosphere.
  • the molecular sieve precursor is a silica-alumina molecular sieve, and the molar ratio of silicon oxide/alumina in the molecular sieve is preferably 1-100:1, preferably 3-20:1;
  • the molecular sieve precursor is selected from at least one of X-type molecular sieve, Y-type molecular sieve, MCM-22-type molecular sieve, Beta-type molecular sieve and MOR-type molecular sieve, preferably X-type molecular sieve and/or Y-type molecular sieve;
  • the molecular sieve precursor is a sodium-type molecular sieve, and the first exchange liquid and/or the second exchange liquid further includes an ammonium salt;
  • the ammonium salt is selected from ammonium nitrate, ammonium chloride, ammonium sulfate, or a combination thereof;
  • the concentration of ammonium salt in the first exchange liquid and/or the second exchange liquid is independently 50-200 g/L.
  • the first exchange liquid and the second exchange liquid also each independently include a solvent, and the solvent is preferably water;
  • the concentration of the soluble compound modifying the metal is each independently 100-500g/L;
  • the atomic radius of the modified metal is 120-270pm, preferably 160-240pm;
  • the modified metal is selected from at least one of alkaline earth metals, Group IIIB metals and Group IIIA metals; further preferably at least one of La, Ce, Sr and Y;
  • the mass ratio of the first exchange liquid to the molecular sieve precursor is 2-8:1;
  • the mass ratio of the second exchange liquid to the first exchange molecular sieve is 3-6:1;
  • the conditions for the first ion exchange include: exchange temperature is 50-90°C, preferably 70-90°C; exchange time is 0.5-2h, preferably 0.5-1.5h;
  • the exchange temperature of the second ion exchange is 0-15°C higher than the exchange temperature of the first ion exchange, preferably 1-10°C;
  • the content of the modified metal is 12-23 wt% in terms of elements.
  • the alkaline compound is selected from ammonia, ammonium carbonate, urea, or a combination thereof;
  • the concentration of the basic compound in the aqueous solution of the basic compound is 0.01-2mol/L;
  • the introduction rate of the alkaline atmosphere is 0.01-0.5 mL/min based on the volume of the aqueous alkaline compound solution;
  • the conditions for the first roasting include: roasting temperature of 400-600°C, roasting time of 0.5-3h, and pressure of 0.01-0.1MPa (gauge pressure);
  • the conditions for the second calcination include: calcination temperature is 400-600°C, calcination time is 0.5-3h, and pressure is 0.01-0.1MPa (gauge pressure).
  • the oxygen content in the oxygen-containing atmosphere is 16-30 vol%, preferably 18-25 vol%;
  • the temperature of the heat treatment is 50-100°C higher than the second roasting temperature
  • the heat treatment conditions include: a temperature of 500-700°C, preferably 550-650°C, and a treatment time of 2-12h, preferably 4-8h.
  • the particle size of the heat-resistant inorganic oxide and/or its precursor is 0.005-200 ⁇ m, more preferably 0.01-100 ⁇ m;
  • the extrusion aid is selected from sesbania powder, cellulose, starch, or a combination thereof;
  • the amount of the extrusion aid is 0-20 wt% of the total dry weight of the metal modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor. Further preferably, the amount of the extrusion aid is It is 1-5wt% of the total dry basis weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor;
  • the peptizing agent is selected from citric acid, nitric acid, phosphoric acid, or a combination thereof;
  • the amount of the peptizing agent is 0-20 wt% of the total dry weight of the metal modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor. Further preferably, the amount of the peptizing agent is 0-20 wt%. 1-8wt% of the total dry weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor;
  • the ratio of the amount of water to the total dry weight of the metal modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor is 0.2-1.2:1. Further preferably, the amount of water is 0.2-1.2:1. The ratio of the total dry basis weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide and/or its precursor is 0.3-1:1;
  • the roasting temperature is 400-650°C, and the roasting time is 1-12 hours.
  • a method for preparing long-chain alkylbenzene which is characterized in that the method includes: contacting a mixture of long-chain olefins and aromatic hydrocarbons with a solid acid catalyst under alkylation reaction conditions to obtain long-chain alkylbenzene;
  • the method also optionally includes: regenerating the solid acid catalyst under oxygen-containing mixed gas;
  • the solid acid catalyst includes metal modified molecular sieves and heat-resistant inorganic oxides
  • the metal-modified molecular sieve includes molecular sieves and metals outside the molecular sieve framework; based on the total amount of the metal-modified molecular sieve, calculated as elements, the content of the modified metal is 8-30wt%; calculated as the mass fraction of elements , the ratio of the mass fraction of the surface modified metal measured by XPS to the mass fraction of the bulk modified metal measured by XRF does not exceed 1.45.
  • the particle size of the heat-resistant inorganic oxide is 0.005-200 ⁇ m, more preferably 0.01-100 ⁇ m.
  • the content of the modified metal is 12-23wt% in terms of elements
  • the atomic radius of the modified metal is 120-270pm, preferably 160-240pm;
  • the modified metal is selected from at least one of alkaline earth metals, Group IIIB metals and Group IIIA metals; further preferably, it is at least one of La, Ce, Sr and Y.
  • the molar ratio of silica/alumina in the metal-modified molecular sieve is 1-100:1, preferably 3-20:1;
  • the metal-modified molecules are selected from at least one of X-type molecular sieves, Y-type molecular sieves, MCM-22-type molecular sieves, Beta-type molecular sieves and MOR-type molecular sieves, preferably X-type molecular sieves and/or Y-type molecular sieves.
  • preparation method according to any one of items C1-C5, wherein the preparation method of the solid acid catalyst includes: combining metal modified molecular sieves, heat-resistant inorganic oxides and/or The precursor, water, optional extrusion aid, and optional peptizing agent are mixed, shaped and calcined to obtain the solid acid catalyst.
  • the product of the second ion exchange is subjected to a second roasting, optionally repeating the second ion exchange and the second roasting to obtain a second exchanged molecular sieve;
  • the first roasting and/or the second roasting are performed in an alkaline atmosphere.
  • the molecular sieve precursor is a silica-alumina molecular sieve, and the molar ratio of silicon oxide/alumina in the molecular sieve is preferably 1-100:1, preferably 3-20:1;
  • the molecular sieve precursor is selected from at least one of X-type molecular sieve, Y-type molecular sieve, MCM-22-type molecular sieve, Beta-type molecular sieve and MOR-type molecular sieve, preferably X-type molecular sieve and/or Y-type molecular sieve;
  • the molecular sieve precursor is a sodium-type molecular sieve, and the first exchange liquid and/or the second exchange liquid further includes an ammonium salt;
  • the ammonium salt is selected from ammonium nitrate, ammonium chloride, ammonium sulfate, or a combination thereof;
  • the concentration of the ammonium salt in the first exchange liquid and/or the second exchange liquid is independently 50-200 g/L.
  • the first exchange liquid and the second exchange liquid also each independently include a solvent, and the solvent is preferably water;
  • the modified metal in the first exchange liquid and/or the second exchange liquid, can be the modified metal.
  • concentration of soluble compounds is each independently 100-500g/L;
  • the mass ratio of the first exchange liquid to the molecular sieve precursor is 2-8:1;
  • the mass ratio of the second exchange liquid to the first exchange molecular sieve is 3-6:1;
  • the conditions for the first ion exchange include: exchange temperature is 50-90°C, preferably 70-90°C; exchange time is 0.5-2h, preferably 0.5-1.5h;
  • the exchange temperature of the second ion exchange is 0-15°C higher than the exchange temperature of the first ion exchange, preferably 1-10°C.
  • the alkaline compound is selected from ammonia, ammonium carbonate, urea, or a combination thereof;
  • the concentration of the basic compound in the aqueous solution of the basic compound is 0.01-2mol/L;
  • the introduction rate of the alkaline atmosphere is 0.01-0.5 mL/min based on the volume of the aqueous alkaline compound solution;
  • the conditions for the first roasting include: roasting temperature of 400-600°C, roasting time of 0.5-3h, and pressure of 0.01-0.1MPa (gauge pressure);
  • the conditions for the second calcination include: calcination temperature is 400-600°C, calcination time is 0.5-3h, and pressure is 0.01-0.1MPa (gauge pressure).
  • the oxygen content in the oxygen-containing atmosphere is 16-30 vol%, preferably 18-25 vol%;
  • the temperature of the heat treatment is 50-100°C higher than the second roasting temperature
  • the heat treatment conditions include: a temperature of 500-700°C, preferably 550-650°C, and a treatment time of 2-12h, preferably 4-8h.
  • the amount of the extrusion aid is 0-5 wt% of the total weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide on a dry basis;
  • the peptizing agent is selected from citric acid, nitric acid, phosphoric acid, or a combination thereof;
  • the amount of the peptizing agent is 0-8 wt% of the total weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide on a dry basis;
  • the ratio of the amount of water to the total weight of the metal-modified molecular sieve and the heat-resistant inorganic oxide on a dry basis is 0.1-1:1;
  • the roasting temperature is 400-700°C, and the roasting time is 2-12 hours.
  • the long-chain olefins are selected from C7-C27 long-chain olefins
  • the aromatic hydrocarbon is selected from benzene, toluene, ethylbenzene, or a combination thereof, preferably benzene;
  • the alkylation reaction conditions include: reaction temperature of 50-250°C, pressure of 0.1-7MPa, benzene/ene molar ratio of 3-80:1, and mass space velocity of feed olefins of 0.1-5h -1 ;
  • the alkylation reaction conditions include: reaction temperature is 70-200°C, pressure is 2-4MPa, benzene/ene molar ratio is 4-60:1, and the mass space velocity of the feed olefin is 0.3-3h -1 .
  • the oxygen content in the oxygen-containing mixed gas is 1-50 vol%, preferably 10-25 vol%;
  • the protective gas is selected from nitrogen, helium, argon, or a combination thereof;
  • the regeneration temperature is 400-700°C
  • the regeneration time is 4-18h
  • the volume space velocity of the oxygen-containing mixed gas is 500-6000h -1
  • the regeneration pressure is 0.01-0.1MPa (gauge pressure).
  • the mass fraction of the bulk-modifying metal was tested by XRF.
  • the mass fraction of surface modification metal is measured by XPS test.
  • the ESCALAB 250 X-ray photoelectron spectrometer (Thermo Fisher Scientific Company) was used for XPS testing.
  • the test conditions include: monochromatic Al K ⁇ eV) corrected charge displacement.
  • the XRF test was conducted using the 3271 X-ray fluorescence spectrometer of Rigaku Electric Industrial Co., Ltd.; the test conditions include: the anode target material of the X-ray tube is a rhodium target; The laser voltage is 50kV; the laser current is 50mA.
  • an American Bruker Tensor II Fourier transform infrared spectrometer was used to conduct pyridine adsorption infrared testing.
  • the testing process was as follows: the sample was made into a self-supporting sheet and placed in the in-situ pool of the infrared spectrometer to be sealed. The temperature was increased to 450°C, and the vacuum was evacuated to about 10 -6 Pa for 2 hours to desorb water molecules and other impurities physically adsorbed by the molecular sieve.
  • the molecular sieves used in the following series of Preparation Examples I were purchased from Sinopec Catalyst Co., Ltd.
  • the molecular sieve is filtered and dried and then roasted for 1h at 550°C under a pressure of 0.02MPa. During the roasting process Pour 0.1M ammonia water into the solution at 0.1mL/min; after roasting, the first exchange molecular sieve is obtained, and the mass fraction of lanthanum metal is calculated to be 10.65% by XRF detection.
  • step 2 2) Perform the second ion exchange and the second roasting on the first exchange molecular sieve to obtain the second exchange molecular sieve.
  • the conditions are the same as step 1.
  • the mass fraction of lanthanum metal calculated by XRF detection of the second exchange molecular sieve is 17.33%.
  • the XRD spectrum of the metal-modified molecular sieve Y1 is shown in Figure 1.
  • the characteristic peaks at 11.9° and 12.4° are attributed to the metal ions on the cationic site, and the characteristic peak at 29.0° is attributed to the metal on the surface of the molecular sieve. oxide; at the same time, by comparing the diffraction peaks of HY molecular sieve, it can be seen that the peak position of the corresponding characteristic peak of molecular sieve Y1 is the same as the peak position of the diffraction peak of HY molecular sieve, that is, there is no shift, which proves that the modified metal Lanthanum is located outside the molecular sieve framework.
  • the number of the prepared metal-modified molecular sieve is Y2.
  • the XRD spectrum of the metal-modified molecular sieve Y2 is shown in Figure 3.
  • the peak position of the corresponding characteristic peak of the molecular sieve Y2 is the same as the peak position of the diffraction peak of the H ⁇ molecular sieve.
  • Preparation Example I-1 The method in Preparation Example I-1 was followed, except that the lanthanum nitrate solution was replaced with a cerium nitrate solution.
  • the number of the prepared metal-modified molecular sieve is Y3.
  • Preparation Example I-1 The method in Preparation Example I-1 was followed, except that the lanthanum nitrate solution was replaced with a strontium nitrate solution.
  • the number of the prepared metal-modified molecular sieve is Y4.
  • the difference is that in the first and second ion exchanges, the mass ratio of the lanthanum nitrate solution and the HY molecular sieve is 2.5:1.
  • the number of the prepared metal-modified molecular sieve is Y5.
  • the difference is that in the first and second ion exchanges, the mass ratio of the lanthanum nitrate solution to the HY molecular sieve is 3.8:1.
  • the number of the prepared metal-modified molecular sieve is Y6.
  • step 2 2) Perform the second ion exchange and the second roasting on the first exchanged molecular sieve to obtain the second exchanged molecular sieve.
  • the conditions are the same as step 1.
  • the difference is that the concentration of the lanthanum nitrate solution is 400g/L.
  • the number of the prepared metal-modified molecular sieve is Y9.
  • the difference is that the concentration of the lanthanum nitrate solution is 200g/L.
  • the number of the prepared metal-modified molecular sieve is Y10.
  • the number of the prepared metal-modified molecular sieve is Y11.
  • the molecular sieve is filtered and dried and then roasted for 1h at 550°C under a pressure of 0.02MPa. During the roasting process Pour in 0.1M ammonia water at 0.1mL/min to obtain the first exchange molecular sieve;
  • the second ion exchange temperature is 90°C; after roasting, the second exchange molecular sieve is obtained.
  • the molecular sieve is filtered and dried and then roasted at 550°C for 1h under a pressure of 0.02MPa. At the same time, the temperature is 0.1mL/min during the roasting process. Pour in 0.1M ammonia water; obtain the first exchange molecular sieve after roasting, and calculate the mass fraction of lanthanum metal to be 5.83% through XRF detection.
  • step 2 2) Perform a second ion exchange and a second roasting on the first exchanged molecular sieve to obtain a second exchanged molecular sieve.
  • the conditions are the same as step 1.
  • the second exchanged molecular sieve is calculated by XRF detection and has a lanthanum metal mass fraction of 6.97%.
  • step 2 2) Perform the second ion exchange and the second roasting on the first exchange molecular sieve to obtain the second exchange molecular sieve.
  • the method is the same as step 1.
  • the mass fraction of lanthanum metal of the second exchange molecular sieve is calculated by XRF detection to be 31.80%.
  • the difference is that during the first roasting and the second roasting process, an equal amount of water is introduced to replace the ammonia water.
  • the obtained molecular sieve is marked as DY4.
  • the measured physical and chemical properties of the molecular sieve DY4 As shown in continued Table I-1.
  • This comparative example illustrates the process of preparing molecular sieves using a vacuum impregnation method to load metals.
  • lanthanum nitrate solution to carry out the treatment on the HY molecular sieve.
  • the loading of lanthanum is 20%
  • the mass ratio of lanthanum nitrate solution and HY molecular sieve is 2:1
  • rotary impregnation at 80°C for 3 hours on a rotary evaporator, followed by vacuum dehydration and the impregnated catalyst is dried at 120°C for 12 hours.
  • the catalyst was calcined at 600°C for 4 hours in an air atmosphere in a muffle furnace.
  • the obtained molecular sieve was recorded as DY5.
  • the measured physical and chemical properties of the molecular sieve DY5 are as shown in the continued Table I-1.
  • the molecular sieve sample Y1 of Preparation Example I-1 was subjected to an alkylation reaction of benzene and 1-dodecene under the reaction conditions of 120°C and 2.5MPa.
  • the olefin feed space velocity was 0.354h -1 and the benzene/ene mole The ratio is 60.
  • the conversion rate and product selectivity results under this reaction condition are shown in Table I-2.
  • Conversion rate of 1-dodecene (%) (Amount of 1-dodecene material before reaction - Amount of 1-dodecene material after reaction)/Amount of 1-dodecene material before reaction ⁇ 100%;
  • Monoalkylbenzene selectivity (%) the amount of monoalkylbenzene substances after the reaction/the amount of substances in all reaction products ⁇ 100%;
  • Degree of linearity (%) Amount of linear alkylbenzene substances after reaction/Amount of monoalkylbenzene substances after reaction ⁇ 100%.
  • 3wt% nitric acid (based on the total weight of molecular sieve and silica on a dry basis), based on the dry basis of molecular sieve and silica, based on the mass ratio of Add deionized water to 0.5:1, mix evenly, then extrusion molding, dry at 150°C for 6 hours, so that the dry weight of the mixed molded product after drying is 70wt%, and then air-calcined at 600°C for 6 hours to obtain a solid Acid catalyst G13.
  • the difference is that the molecular sieves DY1-DY4 obtained in Preparation Comparative Examples I-1 to I-4 are used to replace Y1, respectively, to obtain solid acid catalysts DG1-DG4.
  • the solid acid catalyst G1 obtained in Preparation Example II-1 was used to carry out the alkylation reaction of benzene and 1-dodecene under the reaction conditions of 120°C and 3MPa.
  • the olefin feed space velocity was 0.354h -1 and the benzene feed was The amount ratio of alkenes is 60:1.
  • the calculated conversion rate of 1-dodecene and selectivity of monoalkylbenzene are shown in Table II-1.
  • the results of the stable operation evaluation are shown in Figure 5. From Figure 5, it can be seen that in the stable operation evaluation of 260 hours, the selectivity of monoalkylbenzene has been close to 100%, and the linearity of alkylbenzene has also been above 94%.
  • the conversion rate of 1-dodecene (%) (the amount of 1-dodecene before the reaction - the amount of 1-dodecene after the reaction) / the amount of 1-dodecene before the reaction Amount ⁇ 100%;
  • Monoalkylbenzene selectivity (%) the amount of monoalkylbenzene substances after the reaction/the amount of substances in all reaction products ⁇ 100%;
  • Degree of linearity (%) Amount of linear alkylbenzene substances after reaction/Amount of monoalkylbenzene substances after reaction ⁇ 100%.
  • the solid acid catalyst is regenerated using the regeneration method in Application Example II-1, and a total of two reaction-regeneration processes are performed.
  • the reaction results of fresh agent, primary regenerant and secondary regenerant are shown in Table II-2.
  • the solid acid catalyst prepared in the series of Preparation Examples II of the present application has high catalytic activity in the alkylation reaction of 1-dodecene and benzene. , the conversion rate of the reactants is high, the selectivity of monoalkylbenzene is more than 98%, and the linearity of alkylbenzene reaches more than 94%. In the stable operation evaluation of 260 hours, the selectivity of monoalkylbenzene and the stability of alkylbenzene and linearity are good, and it can be suitable for large-scale industrial applications.

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Abstract

公开了一种金属修饰分子筛、及其制备和应用，所述金属修饰分子筛包括硅铝分子筛和选自碱土金属、第IIIB族金属、第IIIA族金属，或者它们的组合的修饰金属，其中至少一部分所述修饰金属以分子筛骨架外的补偿阳离子的形式存在，并且以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％；所述金属修饰分子筛中，以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量分数的比值不超过1.45。用在长链烃基芳香化合物的制备中时，所述分子筛能够较好地抑制目标长链烃基产品的骨架异构，提高产品直链度和产物选择性，同时其催化周期寿命也获得了大幅延长。

Description

金属修饰分子筛、及其制备和应用 技术领域
本申请涉及催化剂领域，具体涉及一种金属修饰分子筛、及其制备和应用。
背景技术
长链烷基苯是制备合成洗涤剂烷基苯磺酸钠的重要原料。长链烷基苯主要由长链烯烃与单环芳烃发生烷基化反应来制备，目前的商业化工艺技术主要采用氢氟酸或三氯化铝作为催化剂，但这两种催化体系具有较大的安全和环保隐患，随着安全和环保要求的逐渐提高而逐渐被淘汰。开发无腐蚀无污染的固体酸烷基化新方法作为替代技术，成为长链烷基苯生产技术的必然发展趋势。
目前，工业化的固体酸工艺中用到美国UOP公司和西班牙Petresa公司合作开发的含氟的SiO2-Al2O3固体酸催化剂(ZL93104573.8)，该催化剂需要通过定期的苯冲洗恢复活性以实现长周期稳定运行，同时由于该催化剂本身含氟，对设备具有一定的腐蚀性，仍具有一定的安全环保隐患。
国内外研究较多的是沸石分子筛的催化剂体系。由于长链烷基苯分子相对较大，十元环及以下孔道无法进入，只有具有十二元环以上孔道的MOR、Y、Beta等分子筛才具有较好的苯与长链烯烃的烷基化反应催化性能(Catal Surv Asia(2014)18:1-12；Catal Today(2017)298:109-116)。另一方面由于支链烷基苯不容易降解，国标对烷基苯产品的直链度有严格的要求。分子筛催化长链烷基苯合成时最大的问题是较短的使用寿命问题和较低的直链度。
CN107867699A公开了一种含规整超大微孔的Y沸石，通过对选定Y沸石进行模板剂和酸碱处理，构筑了一种具有1-2nm规整超大微孔的Y沸石，由于规整超大微孔提供的丰富的酸中心和适宜的反应孔道，从而得到了更高的转化率和选择性。
CN110562995A公开了一种纳米Y沸石的合成方法及在直链烷基苯合成中的应用，由于催化剂晶粒，扩散阻力小，长链烯烃烷基化的活 性和稳定性都得到提高。
CN102639471A公开了一种生产直链烷基苯的方法，该方法采用两种沸石组合以限制骨架异构化，来提高产品的直链度。
但是，现有技术中，长链烷基苯的制备中，由于长链烯烃的长度较大，长链烯烃的活化和骨架异构对反应的活性和选择性依然存在巨大挑战。另一方面，现有技术中催化剂的催化周期寿命依然较短，产品直链度较低，同时制备流程长，成本高。
发明内容
本申请的目的是提供一种金属修饰分子筛、及其制备和应用，该金属修饰分子筛包含一定量的骨架外修饰金属，可以较好地抑制长链烃基芳香化合物产品的骨架异构，提高产品直链度和产物选择性，同时其催化周期寿命也获得了大幅延长。
为了实现上述目的，一方面，本申请提供了一种金属修饰分子筛，包括硅铝分子筛和选自碱土金属、第IIIB族金属、第IIIA族金属，或者它们的组合的修饰金属，其中至少一部分所述修饰金属以分子筛骨架外的补偿阳离子的形式存在，并且以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％；
其中，所述金属修饰分子筛中，以元素的质量分数计，通过X射线光电子能谱分析(XPS)测得的表层修饰金属的质量分数与通过X射线荧光光谱分析(XRF)测得的体相修饰金属的质量分数的比值不超过1.45。
另一方面，提供了本申请的金属修饰分子筛的制备方法，包括以下步骤：
1)将分子筛前体与含有修饰金属的可溶性化合物的第一交换液进行第一次离子交换；
2)将第一次离子交换的产物进行第一焙烧，得到第一交换分子筛；
3)将第一交换分子筛与含有修饰金属的可溶性化合物的第二交换液进行第二次离子交换；
4)将第二次离子交换的产物进行第二焙烧，任选地重复一次或多次所述第二次离子交换和第二焙烧，得到第二交换分子筛；
5)在含氧气氛下，对第二交换分子筛进行热处理，得到所述金属 修饰分子筛；
其中，所述第一焙烧和/或第二焙烧在碱性气氛下进行。
另一方面，提供了一种固体酸催化剂，包括本申请的金属修饰分子筛和耐热无机氧化物。
另一方面，提供了本申请的金属修饰分子筛和固体酸催化剂在制备长链烃基芳香化合物中的应用。
另一方面，提供了一种长链烃基芳香化合物的制备方法，包括在本申请的金属修饰分子筛存在下，使长链烯烃和芳烃反应的步骤。
优选地，所述方法在本申请的固体酸催化剂存在下进行，并且还包括在含氧混合气存在下，对所述固体酸催化剂进行再生的步骤。
本申请提供的金属修饰分子筛，通过一定量的具有特定的表层和分子筛孔道内分布的骨架外金属的修饰，能够在长链烃基芳香化合物的制备过程中较好地抑制目标长链烃基产品的骨架异构，提高产品直链度和产物选择性，同时其催化周期寿命也获得了大幅延长。
本申请提供的金属修饰分子筛的制备方法，通过多次离子交换和多次焙烧能够实现特定量的具有特定的表层和分子筛孔道内分布的骨架外金属的修饰，同时保证反应前后分子筛的晶胞的稳定，避免分子筛结构由于多次焙烧而被破坏。
本申请提供的固体酸催化剂，通过金属修饰分子筛和耐热无机氧化物的配合，在长链烷基苯的制备过程中，能够实现对反应产物的择形，使得产品的直链度显著提高，和产物选择性提高；同时，本申请提供的固体酸催化剂适用于工业化生产中固定床、流化床以及移动床等反应器形式，能够实现大规模的工业应用。
本申请提供的长链烃基芳香化合物的制备方法，使用了本申请的金属修饰分子筛和/或固体酸催化剂，由于分子筛修饰后对反应产物的择形，使得产品的直链度显著提高，和产物选择性提高，同时也使得金属修饰分子筛的催化周期寿命明显延长。当使用本申请的固体酸催化剂时，还可以便捷地使催化剂再生，通过反应-再生实现长周期连续运行，实现长链烃基芳香化合物，特别是长链烷基苯的连续稳定制备。
本申请的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本申请的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本申请，但并不构成对本申请的限制。在附图中：
图1显示了制备实施例I-1所得的金属修饰分子筛和HY分子筛的XRD谱图比较；
图2显示了制备实施例I-1和制备对比例I-1至I-3所得分子筛的吡啶吸附红外谱图；
图3显示了制备实施例I-2所得的金属修饰分子筛和Hβ分子筛的XRD谱图比较；
图4显示了制备实施例I-1所得的金属修饰分子筛应用在长直链烷基苯制备中连续运行300h的评价结果；
图5显示了制备实施例II-1所得的固体酸催化剂应用在长直链烷基苯制备中连续运行260h的评价结果；以及
图6显示了制备实施例II-1所得的固体酸催化剂通过连续反应-再生方式应用于长直链烷基苯的连续制备的评价结果。
具体实施方式
以下结合附图对本申请的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值，而应当理解为还涵盖了接近该精确值的值，例如在该精确值±5％范围内的所有可能的数值。并且，对于所披露的数值范围而言，在该范围的端点值之间、端点值与范围内的具体点值之间，以及各具体点值之间可以任意组合而得到一个或多个新的数值范围，这些新的数值范围也应被视为在本文中具体公开。
除非另有说明，本文所用的术语具有与本领域技术人员通常所理解的相同的含义，如果术语在本文中有定义，且其定义与本领域的通常理解不同，则以本文的定义为准。
在本申请中，所述“分子筛骨架外”指的是修饰金属以离子形态存在于分子筛阳离子位和/或以氧化物形态负载在分子筛表面，通过XRD测 试金属修饰分子筛的特征峰的出峰位置，与未修饰的分子筛的衍射峰的出峰位置相同，即特征峰没有产生偏移，则可以证明修饰金属均位于分子筛骨架外。
在本申请中，表层修饰金属的质量分数指通过XPS测得的修饰金属元素的质量分数，XPS探测深度为分子筛表面0-10nm范围，体相修饰金属的质量分数指通过XRF测试并计算得到的修饰金属元素的质量分数。可以理解的是，XRF测试首先得到以氧化物计的体相修饰金属的质量分数，再经过计算得到对应的元素的质量分数。
在本申请中，所述“干基质量”定义为材料在600℃焙烧3小时后的物质质量。
本申请中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本申请原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
在本文中提及的所有专利和非专利文献，包括但不限于教科书和期刊文章等，均通过引用方式全文并入本文。
在第一方面，本申请提供了一种金属修饰分子筛，包括硅铝分子筛和选自碱土金属、第IIIB族金属、第IIIA族金属，或者它们的组合的修饰金属，其中至少一部分所述修饰金属以分子筛骨架外的补偿阳离子的形式存在，并且以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％；
其中，所述金属修饰分子筛中，以元素的质量分数计，通过X射线光电子能谱分析(XPS)测得的表层修饰金属的质量分数与通过X射线荧光光谱分析(XRF)测得的体相修饰金属的质量分数的比值不超过1.45。
本申请的发明人经过大量研究发现，当分子筛内部包含一定量的骨架外修饰金属，并且该修饰金属具有特定的表层和分子筛孔道内分布时，其用在长链烯烃与芳烃的烷基化反应中能够有效抑制烯烃异构化和多烷基化反应等导致副产品生成和催化剂失活的副反应发生，实现择形催化，从而提高产品直链度和分子筛的催化周期寿命。
在优选的实施方式中，所述金属修饰分子筛中，以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量分数的比值不超过1.35，优选为0.9-1.35，例如可以为0.95、1、1.05、1.1、1.15、1.2、1.25、1.3、1.35或任意两点构成的数值范围内的任意数值。在上述优选的分布情况下，有利于提高分子筛的催化周期寿命以及产品直链度，表层修饰金属的质量分数与体相修饰金属的质量分数的比值过高，可能导致分子筛的催化周期寿命缩短，比值过低，可能导致产品直链度下降。
在优选的实施方式中，以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为12-23wt％。例如，以元素计，所述修饰金属的含量可以为12wt％、13wt％、14wt％、15wt％、16wt％、17wt％、18wt％、19wt％、20wt％、21wt％、22wt％、23wt％或任意两点构成的数值范围内的任意数值。在上述优选的情况下，有利于确保金属分布处于最佳位置，进而实现择形催化，提高催化剂的催化周期寿命和产品直链度。
在优选的实施方式中，所述修饰金属的原子半径为120-270pm，优选为160-240pm。进一步优选地，所述修饰金属选自Mg、Ca、Sr、Ba、La、Ce、Pr、Rd、Sm、Eu、Yb、Sc、Y、Al、Ga、In，或者它们的组合；更进一步优选为La、Ce、Sr、Y，或者它们的组合。采用上述优选的金属，有利于与分子筛孔道实现匹配，达到最佳的择形催化效果，保护分子筛结构，提高其催化周期寿命和产品直链度。
在优选的实施方式中，所述金属修饰分子筛中氧化硅/氧化铝的摩尔比为1-100：1，进一步优选为3-20：1。
在优选的实施方式中，所述金属修饰分子筛选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛、MOR型分子筛，或者它们的组合，优选为X型分子筛和/或Y型分子筛。采用上述优选的分子筛种类，有利于进一步提高分子筛的催化活性。
在优选的实施方式中，所述金属修饰分子筛的吡啶吸附红外谱图在1440-1460cm-1范围内存在两个吸收峰。进一步优选地，在较低波数位置的吸收峰面积占所述两个吸收峰的总面积的比值为0.3-0.7，更优选为0.4-0.6。通常，硅铝分子筛的吡啶吸附红外谱图会在1450cm-1附近显示出红外吸收峰，其为分子筛表面的L酸的吸收峰。在本申请的 金属修饰分子筛的吡啶吸附红外谱图中，原本在1450cm-1附近的吸收峰会分裂为在1440-1460cm-1范围内的两个吸收峰，其中在较低波数位置的吸收峰为分子筛孔道内修饰金属阳离子诱导产生的强L酸的吸收峰，通过计算所述强L酸的占比，即在较低波数位置的吸收峰面积占1440-1460cm-1范围内的所述两个吸收峰的总面积的比值，即可判断分子筛中修饰金属的位置和含量。
第二方面，提供了制备本申请的金属修饰分子筛的方法，包括以下步骤：
1)将分子筛前体与含有修饰金属的可溶性化合物的第一交换液进行第一次离子交换；
2)将第一次离子交换的产物进行第一焙烧，得到第一交换分子筛；
3)将第一交换分子筛与含有修饰金属的可溶性化合物的第二交换液进行第二次离子交换；
4)将第二次离子交换的产物进行第二焙烧，任选地重复第二次离子交换和第二焙烧，得到第二交换分子筛；
5)在含氧气氛下，对第二交换分子筛进行热处理，得到所述金属修饰分子筛；
其中，所述第一焙烧和/或第二焙烧在碱性气氛下进行。
本申请提供的金属修饰分子筛的制备方法，通过至少两交两焙能够实现特定的骨架外金属的修饰，同时保证反应前后分子筛的晶胞大小的稳定，能够避免分子筛结构由于多次焙烧而被破坏。
在本申请中，对于第二次离子交换和第二焙烧的重复次数，本申请不做特别的限定，可以根据离子交换的效果确定，目的是使得分子筛中的金属含量满足上述范围要求，例如可以重复1-3次。
在优选的实施方式中，所述分子筛前体为硅铝分子筛，所述分子筛中氧化硅/氧化铝的摩尔比优选为1-100：1，进一步优选为3-20：1。
在本申请中，金属修饰前后分子筛的氧化硅和氧化铝的摩尔比基本保持不变，均满足上述摩尔比范围要求。
在优选的实施方式中，所述分子筛前体选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛和MOR型分子筛中的至少一种，优选为X型分子筛和/或Y型分子筛。
在优选的实施方式中，所述分子筛前体为氢型或钠型的分子筛。
在某些优选的实施方式中，所述分子筛前体为钠型分子筛，且所述第一交换液和/或第二交换液中还包括铵盐，例如，所述第一交换液中还包括铵盐。在这种情况下，步骤1)包括将钠型分子筛与含有修饰金属的可溶性化合物和铵盐的第一交换液进行离子共交换。在此类优选实施方式中，采用离子共交换可以缩短制备流程，一步将Na+交换为金属阳离子和NH4 +，而交换的NH4 +又可在后续的焙烧过程中分解脱除，保留分子筛的酸性氢质子。
在此类优选实施方式中，所述铵盐可以为本领域常规的选择，优选选自硝酸铵、氯化铵、硫酸铵，或者它们的组合。
在进一步优选的实施方式中，所述第一和第二交换液中的铵盐的浓度相互独立地为50-200g/L，优选为70-150g/L。
根据本申请，当所述分子筛前体为钠型分子筛时，在优选的实施方式中，所述制备方法还包括将第二交换分子筛采用含有铵盐的第三交换液进行铵交换，然后再进行所述热处理。在此类优选实施方式中，通过所述铵交换可以进一步降低分子筛中的Na+含量，以确保分子筛具有较高的酸量。
在此类优选实施方式中，所述铵交换和干燥可以采用本领域常规的方法和条件进行，例如，将第二交换分子筛与含有铵盐的第三交换液进行接触，然后过滤干燥，作为一次铵交换过程，所述铵交换过程可以任选地重复1-3次，使得分子筛中Na质量分数低于0.2％即可。
在本申请中，所述第三交换液中铵盐浓度可以和上述第一交换液或第二交换液中的浓度范围相同，在此不再赘述。
在本申请中，对于所述修饰金属的可溶性化合物的具体种类没有特殊的要求，可以根据实际需要进行选择。优选地，所述修饰金属的可溶性化合物选自所述修饰金属的氯化物、硝酸盐、磷酸盐、硫酸盐，或者它们的组合。
根据本申请，对于所述第一交换液和/或第二交换液中修饰金属的可溶性化合物的浓度没有特殊的要求，只要使得金属修饰分子筛中的修饰金属元素含量满足上述范围要求即可，本领域技术人员可以进行常规调整。优选地，第一交换液和第二交换液中所述修饰金属的可溶性化合物的浓度各自独立地为100-500g/L，进一步优选为130-400g/L，采用上述优选的实施方式，可以在满足上述含量要求的基础上，缩短制备 流程。
在优选的实施方式中，所述第一交换液和第二交换液中还各自独立地包括溶剂，所述溶剂优选为水。
在优选的实施方式中，为了第一次离子交换更充分，所述第一交换液与所述分子筛前体的质量比为2-8：1，进一步优选为3-6：1。
在优选的实施方式中，所述第二交换液与第一交换分子筛的质量比3-6：1，进一步优选为3-5：1。
在优选的实施方式中，所述第一次离子交换的条件包括：交换温度为50-90℃，优选为70-90℃；交换时间为0.5-2h，优选为0.8-1.5h。
在本申请中，第二次离子交换的条件可以和第一次离子交换的条件相同或不同，优选地，第二次离子交换的条件包括：交换温度为50-120℃，优选为70-100℃；交换时间为0.5-2h，优选为0.8-1.5h。进一步优选地，所述第二次离子交换的交换温度比第一交换的交换温度高0-15℃，优选高1-10℃。采用上述优选的实施方式，有利于优化金属分布，进一步提高分子筛的催化活性。
在本申请的方法中，所述修饰金属的用量使得在所得金属修饰分子筛中，以所述分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％，优选地为12-23wt％。例如，以元素计，所述修饰金属的含量可以为12wt％、13wt％、14wt％、15wt％、16wt％、17wt％、18wt％、19wt％、20wt％、21wt％、22wt％、23wt％或任意两点构成的数值范围内的任意数值。
在本申请中，为了能够进一步调控金属的分布，所述第一焙烧和/或第二焙烧在碱性气氛下进行，优选地，所述第一焙烧和第二焙烧均在碱性气氛下进行。采用上述优选的实施方式，有助于保护分子筛结构，进一步提高金属修饰分子筛的催化周期寿命。
在优选的实施方式中，所述碱性气氛由碱性化合物的水溶液提供。可以理解的是，碱性化合物的水溶液在焙烧温度下迅速汽化，从而为焙烧过程提供碱性气氛。
在本申请中，对于所述碱性化合物的选择范围较宽。优选地，所述碱性化合物选自氨、碳酸铵、尿素，或者它们的组合，优选为氨。
在进一步优选的实施方式中，所述碱性化合物的水溶液中，碱性化合物的浓度为0.01-2mol/L，优选为0.01-0.5mol/L，进一步优选为0.05- 0.3mol/L，在上述优选的情况下，有利于分子筛结构的稳定，延长分子筛的催化周期寿命。
在优选的实施方式中，相对于50g分子筛前体，所述第一和第二焙烧过程中，所述碱性气氛的通入速率，以碱性化合物水溶液的体积计，各自独立地为0.01-0.5mL/min，进一步优选为0.05-0.2mL/min。可以理解的是，当分子筛前体的处理量增大时，碱性气氛的通入速率可以呈比例提高。
在优选的实施方式中，所述第一焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)。
在优选的实施方式中，所述第二焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)。
在本申请中，所述第一焙烧和第二焙烧并非指操作顺序，仅用于区分不同的步骤中的焙烧条件。所述第一焙烧和第二焙烧的条件可以相同或不同，只要满足上述条件要求即可。
在本申请的具体实施方式中，所述第一焙烧或第二焙烧之前，还分别包括将第一次离子交换的产物或第二次离子交换的产物进行固液分离和干燥，所述固液分离和干燥可以采用本领域常规的操作进行，在此不再赘述。
在优选的实施方式中，步骤5)的所述含氧气氛为空气或氧气和惰性气体的混合气；所述惰性气体优选为氮气。
在优选的实施方式中，所述含氧气氛中，氧气的含量为16-30vol％，优选为18-25vol％。
在优选的实施方式中，步骤5)的所述热处理的温度比步骤4)的所述第二焙烧的温度高50-100℃。采用更高温度的含氧气氛热处理，使得修饰金属进一步迁移，并在高温条件下锚定，以确保金属在反复的反应-再生高温环境中保持稳定。
在优选的实施方式中，所述热处理的条件包括：温度为500-700℃，优选为550-650℃，处理时间为2-12h，优选为4-8h。
在第三方面，提供了通过本申请的方法制备得到的金属修饰分子筛。
在第四方面，提供了一种固体酸催化剂，该催化剂包括金属修饰分子筛和耐热无机氧化物，其中所述金属修饰分子筛为根据本申请的金 属修饰分子筛。
在本申请中，所述固体酸催化剂中，金属修饰分子筛作为活性组元，本申请的发明人经过大量研究发现，当所述固体酸催化剂用在长链烯烃与芳烃的烷基化反应中时，通过本申请的金属修饰分子筛和耐热无机氧化物的配合，能够进一步提高产品直链度，同时其催化周期寿命也获得了大幅延长，适用于工业化生产。
在本申请中，对于所述固体酸催化剂中各组份的含量按照投料比计，对于所述固体酸催化剂中各组份的含量选择范围较宽，可以根据实际应用需要进行调整。优选地，所述金属修饰分子筛与耐热无机氧化物的干基质量比为99：1至20：80，优选为95：5至25：75，更优选为90：10至50：50。
在本申请中，对于所述耐热无机氧化物的选择没有特殊的要求，可以采用本领域常规的具体物质种类。优选地，所述耐热无机氧化物选自氧化铝、氧化锆、二氧化硅、二氧化钛、粘土、高岭土、蒙脱土、镁铝结晶石、无定型硅铝，或者它们的组合，更优选选自氧化铝、氧化锆、二氧化硅、二氧化钛，或者它们的组合。采用上述优选的耐热无机氧化物，有利于发挥金属修饰分子筛和耐热无机氧化物的配合作用，进一步提高催化剂的催化性能。
在优选的实施方式中，所述耐热无机氧化物的粒径为0.005-200μm，进一步优选为0.01-100μm。在上述优选的情况下，有利于增强分子筛与无机氧化物的相互作用，提高催化剂性能和强度。
在第五方面，提供了制备本申请的固体酸催化剂的方法，包括：将本申请的金属修饰分子筛、耐热无机氧化物和/或其前驱体、水、任选的助挤剂、以及任选的胶溶剂进行混合、成型和焙烧，得到所述固体酸催化剂。
在本申请中，所述耐热无机氧化物的前驱体为可以通过焙烧得到所述耐热无机氧化物的物质，其为本领域的常规选择，本申请对此没有特殊的要求。例如，氧化铝的前驱体可以为拟薄水铝石。
优选地，所述耐热无机氧化物和/或其前驱体的粒径为0.005-200μm，进一步优选为0.01-100μm。在上述优选的情况下，有利于增强分子筛与无机氧化物的相互作用，提高催化剂性能和强度。
根据本申请，所述混合过程中可以选择加入或不加入助挤剂和/或 胶溶剂，可以根据实际成型需要进行选择。
在本申请中，对助挤剂的种类没有特别限定，本领域常规的助挤剂均适用于本申请。优选地，所述助挤剂选自田菁粉、纤维素、淀粉，或者它们的组合。
本申请中，对助挤剂的用量的选择范围较宽。优选地，所述助挤剂的用量为所述金属修饰分子筛、耐热无机氧化物和/或其前驱体的干基总重量的0-20wt％，进一步优选地，所述助挤剂的用量为所述金属修饰分子筛以及耐热无机氧化物的干基总重量的1-5wt％。
本申请中，对胶溶剂的种类没有特别限定，本领域常规定义的胶溶剂均适用于本申请。优选地，所述胶溶剂选自柠檬酸、硝酸、磷酸，或者它们的组合。本申请中，对胶溶剂的用量没有特别限定。优选地，所述胶溶剂的用量为所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的0-20wt％，进一步优选地，所述胶溶剂的用量为所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的1-8wt％。
本申请中，对水的用量的选择范围较宽，只要能够使以上各组分混合均匀即可，可以根据实际需要进行调整。优选地，所述水的用量与所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的比值为0.2-1.2：1，进一步优选地，所述水的用量与所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的比值为0.3-1：1。
在本申请中，根据需要，所述方法还包括将成型后的产物进行干燥或成型干燥，得到混合成型物，然后再进行所述焙烧。所述干燥或成型干燥可以采用本领域常规的操作进行，例如烘干或喷雾干燥，使得所述混合成型物的干基重量为成型后的产物的重量的40-85wt％，优选为60-75wt％。
在优选的实施方式中，所述干燥或成型干燥的温度为100-250℃，优选为100-150℃，干燥或成型干燥的时间为1-24h，优选为2-10h。
在优选的实施方式中，所述一次焙烧的温度为400-650℃，优选为500-600℃，一次焙烧的时间为0.5-8h，优选为2-6h。
在第六方面，提供了通过本申请的方法制备得到的固体酸催化剂。
在第七方面，提供了本申请的金属修饰分子筛或固体酸催化剂在长链烃基芳香化合物的制备中的应用，其中所述长链烃基芳香化合物 的制备通过长链烯烃与芳烃的反应实现。
在第八方面，本申请提供了一种长链烃基芳香化合物的制备方法，包括：在本申请的金属修饰分子筛存在下，使长链烯烃和芳烃反应的步骤。
在本申请的长链烃基芳香化合物制备方法中，由于分子筛修饰后对反应产物的择形，使得产品的直链度显著提高，和产物选择性提高，而产物选择性的提高也使得金属修饰分子筛的催化周期寿命明显延长。
在本申请中，对所述长链烯烃的来源没有特殊的要求，例如通过链烷烃脱氢、裂化以及小分子烯烃低聚方式获得的或者商购的长链烯烃均可用于本申请。优选地，所述长链烯烃为末端具有双键的长链α烯烃。优选地，所述长链烯烃为C7-C27的长链烯烃，进一步优选为C8-C15的长链烯烃，更优选为C10-C14的长链烯烃。
根据本申请，所述芳烃可以为单环或双环芳烃，优选为苯系芳烃，更优选选自苯、甲苯、乙苯，或者它们的组合，特别优选为苯。
在本申请中，所述长链烯烃与芳烃的反应条件可以采用本领域常规的条件进行，优选保证所述反应在液相中进行且压力总是足够确保反应在单液相下进行。在本申请中，所述单液相指的是投入的反应物均为液相，且反应条件满足反应物在反应过程中不会汽化。优选地，反应压力高于相应反应温度下长链烯烃和芳烃的饱和蒸汽压，使得反应物料均处于液相下进行接触反应。在优选的实施方式中，所述反应的条件包括：反应温度为50-250℃，优选为70-200℃；反应压力为0.1-7MPa，优选为2-4MPa；芳烃/烯摩尔比为3-70：1，优选为4-60：1；长链烯烃的空速为0.1-5h-1，优选为0.3-3h-1。采用上述优选的反应条件，有助于降低烷基的异构化并使苯(或其他芳基化合物的芳族结构部分)的聚烷基化最小化，同时使烯烃的消耗最大化以使产物最大化。
根据本申请，所述长链烯烃和芳烃的反应可以在本领域常规的反应器中进行。例如，所述反应可以在固定床反应器、流化床反应器、移动床反应器或浆态床反应器中进行。
在某些优选的实施方式中，所述长链烯烃和芳烃的反应在本申请的固体酸催化剂存在下进行，并且所述方法还包括：在含氧混合气下，对所述固体酸催化剂进行再生的步骤。在此类优选实施方式中，通过再生可以便捷地再生催化剂，通过反应-再生实现长周期连续运行。
在进一步优选的实施方式中，所述含氧混合气中，氧气的含量为1-50vol％，优选为10-25vol％。
在进一步优选的实施方式中，所述含氧混合气为氧气和保护气体的混合气；所述保护气体可以选自任意不参与反应的气体，优选地，所述保护气体为氮气、氦气、氩气中的至少一种。
在进一步优选的实施方式中，所述再生的温度为400-700℃，再生的时间为4-18h，含氧混合气的体积空速为500-6000h-1，再生压力为0.01-0.1MPa(表压)。
在更进一步优选的实施方式中，所述再生的温度为450-600℃，例如可以为450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃等典型而非限制性的温度；优选地，再生的时间为5-12h，含氧混合气的体积空速为500-5000h-1，再生压力为0.01-0.05MPa(表压)。采用上述优选的再生条件，有利于提高固体酸催化剂的再生效果。
根据本申请，通过周期性地对所述固体酸催化剂进行再生，能够实现反应的长周期运行。通过检测反应进度选择所述再生的时机，例如，在长链烯烃转化率低于95％时进行所述再生，进一步优选地，在长链烯烃转化率低于98％时进行所述再生。
在某些优选的实施方式中，本申请提供了如下的技术方案：
A1、一种金属修饰分子筛，其特征在于，所述金属修饰分子筛包括分子筛和分子筛骨架外的金属；以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％；
其中，所述金属修饰分子筛中，以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量分数的比值不超过1.45。
A2、根据项目A1所述的金属修饰分子筛，其中，所述金属修饰分子筛中，以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量分数的比值不超过1.35，优选为0.9-1.35；
优选地，以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为12-23wt％；
优选地，所述修饰金属的原子半径为120-270pm，优选为160- 240pm；
优选地，所述修饰金属选自碱土金属、第IIIB族金属和第IIIA族金属中的至少一种；进一步优选为La、Ce、Sr和Y中的至少一种。
A3、根据项目A1或A2所述的金属修饰分子筛，其中，所述金属修饰分子筛为硅铝分子筛；
优选地，所述金属修饰分子筛中氧化硅/氧化铝的摩尔比为1-100：1，优选为3-20：1；
优选地，所述金属修饰分子筛选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛和MOR型分子筛中的至少一种，优选为X型分子筛和/或Y型分子筛。
A4、一种金属修饰分子筛的制备方法，其特征在于，包括以下步骤：
1)将分子筛前体与含有修饰金属的可溶性化合物的第一交换液进行第一次离子交换；
2)将第一次离子交换的产物进行第一焙烧，得到第一交换分子筛；
3)将第一交换分子筛与含有修饰金属的可溶性化合物的第二交换液进行第二次离子交换；
4)将第二次离子交换的产物进行第二焙烧，任选地重复第二次离子交换和第二焙烧，得到第二交换分子筛；
5)在含氧气氛下，对第二交换分子筛进行热处理，得到所述金属修饰分子筛；
其中，所述第一焙烧和/或第二焙烧在碱性气氛下进行；
其中，以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％。
A5、根据项目A4所述的制备方法，其中，以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为12-23wt％。
A6、根据项目A4或A5所述的制备方法，其中，所述分子筛前体为氢型或钠型的分子筛；
优选地，所述分子筛前体为硅铝分子筛，所述分子筛中氧化硅/氧化铝的摩尔比优选为1-100：1，优选为3-20：1；
优选地，所述分子筛前体选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛和MOR型分子筛中的至少一种，优选为X型 分子筛和/或Y型分子筛；
优选地，所述分子筛前体为钠型分子筛，所述第一交换液和/或第二交换液中还包括铵盐；
优选地，所述铵盐选自硝酸铵、氯化铵、硫酸铵，或者它们的组合；
优选地，所述第一交换液和/或第二交换液中，铵盐的浓度各自独立地为50-200g/L。
A7、根据项目A4-A6中任一项所述的制备方法，其中，所述修饰金属的可溶性化合物选自所述修饰金属的氯化物、硝酸盐、磷酸盐、硫酸盐，或者它们的组合；
优选地，所述第一交换液和/或第二交换液中，所述修饰金属的可溶性化合物的浓度各自独立地为100-500g/L；
优选地，所述第一交换液和第二交换液中还各自独立地包括溶剂，所述溶剂优选为水；
优选地，所述修饰金属的原子半径为120-270pm，优选为160-240pm；
优选地，所述修饰金属选自碱土金属、第IIIB族金属和第IIIA族金属中的至少一种；进一步优选为La、Ce、Sr和Y中的至少一种；
优选地，所述第一交换液与所述分子筛前体的质量比为2-8：1；
优选地，所述第二交换液与第一交换分子筛的质量比为3-6：1；
优选地，所述第一次离子交换的条件包括：交换温度为50-90℃，优选为70-90℃；交换时间为0.5-2h，优选为0.5-1.5h；
优选地，所述第二次离子交换的交换温度比第一次离子交换的交换温度高0-15℃，优选为1-10℃。
A8、根据项目A4-A7中任一项所述的制备方法，其中，所述碱性气氛由碱性化合物的水溶液提供；
优选地，所述碱性化合物选自氨、碳酸铵、尿素，或者它们的组合；
优选地，所述碱性化合物的水溶液中，碱性化合物的浓度为0.01-2mol/L；
优选地，相对于50g分子筛前体，所述碱性气氛的通入速率，以碱性化合物水溶液的体积计，为0.01-0.5mL/min；
优选地，所述第一焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)；
优选地，所述第二焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)。
A9、根据项目A4-A8中任一项所述的制备方法，其中，所述含氧气氛为空气或氧气和惰性气体的混合气；
优选地，所述含氧气氛中，氧气的含量为16-30vol％，优选为18-25vol％；
优选地，所述热处理的温度比第二焙烧温度高50-100℃；
优选地，所述热处理的条件包括：温度为500-700℃，优选为550-650℃，处理时间为2-12h，优选为4-8h。
A10、项目A4-A9中任一项所述的制备方法制得的金属修饰分子筛。
A11、一种长链烯烃烷基化方法，该方法包括：在烷基化反应条件下，将长链烯烃和芳烃与催化剂接触进行烷基化反应；
其特征在于，所述催化剂为项目A1-A3和A10中任一项所述的金属修饰分子筛。
A12、根据项目A11所述的方法，其中，所述长链烯烃为末端具有双键的长链α烯烃；
优选地，所述长链烯烃为C8-C28的长链烯烃，进一步优选为C8-C15的长链烯烃，更优选为C10-C14的长链烯烃；
优选地，所述芳烃选自苯、甲苯、乙苯，或者它们的组合，优选为苯；
优选地，所述烷基化反应的条件包括：反应温度为50-250℃，优选为70-200℃；反应压力为0.1-7MPa，优选为2-4MPa；苯/烯摩尔比为3-70：1，优选为4-60：1；长链烯烃的质量空速为0.1-5h-1，优选为0.3-3h-1。
B1、一种固体酸催化剂，其特征在于，该催化剂包括金属修饰分子筛和耐热无机氧化物；
其中，所述金属修饰分子筛包括分子筛和分子筛骨架外的金属；以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％；
其中，所述金属修饰分子筛中，以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量 分数的比值不超过1.45。
B2、根据项目B1所述的固体酸催化剂，其中，以干基质量计，所述金属修饰分子筛与耐热无机氧化物的质量比为99：1至20：80，优选为95：5至25：75，更优选为90：10至50：50。
B3、根据项目B1或B2所述的固体酸催化剂，其中，所述耐热无机氧化物选自氧化铝、氧化锆、二氧化硅、二氧化钛，或者它们的组合；
优选地，所述耐热无机氧化物的粒径为0.005-200μm，进一步优选为0.01-100μm。
B4、根据项目B1-B3中任一项所述的固体酸催化剂，其中，所述金属修饰分子筛中，以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量分数的比值不超过1.35，优选为0.9-1.35；
优选地，以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为12-23wt％；
优选地，所述修饰金属的原子半径为120-270pm，优选为160-240pm；
优选地，所述修饰金属选自碱土金属、第IIIB族金属和第IIIA族金属中的至少一种；进一步优选为La、Ce、Sr和Y中的至少一种。
B5、根据项目B1-B4中任一项所述的固体酸催化剂，其中，所述金属修饰分子筛为硅铝分子筛；
优选地，所述金属修饰分子筛中氧化硅/氧化铝的摩尔比为1-100：1，优选为3-20：1；
优选地，所述金属修饰分子筛选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛和MOR型分子筛中的至少一种，优选为X型分子筛和/或Y型分子筛。
B6、一种固体酸催化剂的制备方法，其特征在于，该制备方法包括：将金属修饰分子筛、耐热无机氧化物和/或其前驱体、水、任选的助挤剂、以及任选的胶溶剂进行混合、成型和焙烧，得到所述固体酸催化剂；
其中，所述金属修饰分子筛包括分子筛和分子筛骨架外的金属；以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％；
其中，所述金属修饰分子筛中，以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量分数的比值不超过1.45。
B7、根据项目B6所述的制备方法，其中，所述金属修饰分子筛通过以下方法制得，该方法包括：
1)将分子筛前体与含有修饰金属的可溶性化合物的第一交换液进行第一次离子交换；
2)将第一次离子交换的产物进行第一焙烧，得到第一交换分子筛；
3)将第一交换分子筛与含有修饰金属的可溶性化合物的第二交换液进行第二次离子交换；
4)将第二次离子交换的产物进行第二焙烧，任选地重复第二次离子交换和第二焙烧，得到第二交换分子筛；
5)在含氧气氛下，对第二交换分子筛进行热处理，得到所述金属修饰分子筛；
其中，所述第一焙烧和/或第二焙烧在碱性气氛下进行。
B8、根据项目B7所述的制备方法，其中，所述分子筛前体为氢型或钠型的分子筛；
优选地，所述分子筛前体为硅铝分子筛，所述分子筛中氧化硅/氧化铝的摩尔比优选为1-100：1，优选为3-20：1；
优选地，所述分子筛前体选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛和MOR型分子筛中的至少一种，优选为X型分子筛和/或Y型分子筛；
优选地，所述分子筛前体为钠型分子筛，所述第一交换液和/或第二交换液中还包括铵盐；
优选地，所述铵盐选自硝酸铵、氯化铵、硫酸铵，或者它们的组合；
优选地，所述第一交换液和/或第二交换液中，铵盐的浓度各自独立地为50-200g/L。
B9、根据项目B7或B8所述的制备方法，其中，所述修饰金属的可溶性化合物选自所述修饰金属的氯化物、硝酸盐、磷酸盐、硫酸盐，或者它们的组合；
优选地，所述第一交换液和第二交换液中还各自独立地包括溶剂，所述溶剂优选为水；
优选地，所述第一交换液和/或第二交换液中，所述修饰金属的可溶性化合物的浓度各自独立地为100-500g/L；
优选地，所述修饰金属的原子半径为120-270pm，优选为160-240pm；
优选地，所述修饰金属选自碱土金属、第IIIB族金属和第IIIA族金属中的至少一种；进一步优选为La、Ce、Sr和Y中的至少一种；
优选地，所述第一交换液与所述分子筛前体的质量比为2-8：1；
优选地，所述第二交换液与第一交换分子筛的质量比为3-6：1；
优选地，所述第一次离子交换的条件包括：交换温度为50-90℃，优选为70-90℃；交换时间为0.5-2h，优选为0.5-1.5h；
优选地，所述第二次离子交换的交换温度比第一次离子交换的交换温度高0-15℃，优选为1-10℃；
优选地，以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为12-23wt％。
B10、根据项目B7-B9中任一项所述的制备方法，其中，所述碱性气氛由碱性化合物的水溶液提供；
优选地，所述碱性化合物选自氨、碳酸铵、尿素，或者它们的组合；
优选地，所述碱性化合物的水溶液中，碱性化合物的浓度为0.01-2mol/L；
优选地，相对于50g分子筛前体，所述碱性气氛的通入速率，以碱性化合物水溶液的体积计，为0.01-0.5mL/min；
优选地，所述第一焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)；
优选地，所述第二焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)。
B11、根据项目B7-B10中任一项所述的制备方法，其中，所述含氧气氛为空气或氧气和惰性气体的混合气；
优选地，所述含氧气氛中，氧气的含量为16-30vol％，优选为18-25vol％；
优选地，所述热处理的温度比第二焙烧温度高50-100℃；
优选地，所述热处理的条件包括：温度为500-700℃，优选为550-650℃，处理时间为2-12h，优选为4-8h。
B12、根据项目B6-B11中任一项所述的制备方法，其中，以干基质量计，所述金属修饰分子筛和耐热无机氧化物和/或其前驱体的质量比为99：1至20：80，优选为95：5至25：75，更优选为90：10至50：50。
B13、根据项目B6-B12中任一项所述的制备方法，其中，所述的耐热无机氧化物选自氧化铝、氧化锆、二氧化硅、二氧化钛，或者它们的组合；
优选地，所述耐热无机氧化物和/或其前驱体的粒径为0.005-200μm，进一步优选为0.01-100μm；
优选地，所述助挤剂选自田菁粉、纤维素、淀粉，或者它们的组合；
优选地，所述助挤剂的用量为所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的0-20wt％，进一步优选地，所述助挤剂的用量为所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的1-5wt％；
优选地，所述胶溶剂选自柠檬酸、硝酸、磷酸，或者它们的组合；
优选地，所述胶溶剂的用量为所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的0-20wt％，进一步优选地，所述胶溶剂的用量为所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的1-8wt％；
优选地，所述水的用量与所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的比值为0.2-1.2：1，进一步优选地，所述水的用量与所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的比值为0.3-1：1；
优选地，所述焙烧的温度为400-650℃，焙烧的时间为1-12h。
B14、项目B6-B13中任一项所述的制备方法制得的固体酸催化剂。
B15、项目B1-B5和B14中任一项所述的固体酸催化剂在制备长链烷基苯中的应用。
C1、一种长链烷基苯的制备方法，其特征在于，该方法包括：在烷基化反应条件下，将长链烯烃和芳烃的混合物与固体酸催化剂接触，得到长链烷基苯；
该方法还任选地包括：在含氧混合气下，对所述固体酸催化剂进行再生；
其中，所述固体酸催化剂包括金属修饰分子筛和耐热无机氧化物；
其中，所述金属修饰分子筛包括分子筛和分子筛骨架外的金属；以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％；以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量分数的比值不超过1.45。
C2、根据项目C1所述的制备方法，其中，以所述固体酸催化剂的总量为基准，以干基质量计，所述金属修饰分子筛与耐热无机氧化物的质量比为99：1至20：80，优选为95：5至25：75，更优选为90：10至50：50。
C3、根据项目C1或C2所述的制备方法，其中，所述的耐热无机氧化物选自氧化铝、氧化锆、二氧化硅、二氧化钛，或者它们的组合；
优选地，所述耐热无机氧化物的粒径为0.005-200μm，进一步优选为0.01-100μm。
C4、根据项目C1-C3中任一项所述的制备方法，其中，所述金属修饰分子筛中，以元素的质量分数计，通过XPS测得的表层修饰金属的质量分数与通过XRF测得的体相修饰金属的质量分数的比值不超过1.35，优选为0.9-1.35；
优选地，以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为12-23wt％；
优选地，所述修饰金属的原子半径为120-270pm，优选为160-240pm；
优选地，所述修饰金属选自碱土金属、第IIIB族金属和第IIIA族金属中的至少一种；进一步优选为La、Ce、Sr和Y中的至少一种。
C5、根据项目C1-C4中任一项所述的制备方法，其中，所述金属修饰分子筛为硅铝分子筛；
优选地，所述金属修饰分子筛中氧化硅/氧化铝的摩尔比为1-100：1，优选为3-20：1；
优选地，所述金属修饰分子筛选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛和MOR型分子筛中的至少一种，优选为X型分子筛和/或Y型分子筛。
C6、根据项目C1-C5中任一项所述的制备方法，其中，所述固体酸催化剂的制备方法包括：将金属修饰分子筛、耐热无机氧化物和/或 其前驱体、水、任选的助挤剂、以及任选的胶溶剂进行混合、成型和焙烧，得到所述固体酸催化剂。
C7、根据项目C1-C6中任一项所述的制备方法，其中，所述金属修饰分子筛通过以下方法制得，该方法包括：
1)将分子筛前体与含有修饰金属的可溶性化合物的第一交换液进行第一次离子交换；
2)将第一次离子交换的产物进行第一焙烧，得到第一交换分子筛；
3)将第一交换分子筛与含有修饰金属的可溶性化合物的第二交换液进行第二次离子交换；
4)将第二次离子交换的产物进行第二焙烧，任选地重复第二次离子交换和第二焙烧，得到第二交换分子筛；
5)在含氧气氛下，对第二交换分子筛进行热处理，得到所述金属修饰分子筛；
其中，所述第一焙烧和/或第二焙烧在碱性气氛下进行。
C8、根据项目C7所述的制备方法，其中，所述分子筛前体为氢型或钠型的分子筛；
优选地，所述分子筛前体为硅铝分子筛，所述分子筛中氧化硅/氧化铝的摩尔比优选为1-100：1，优选为3-20：1；
优选地，所述分子筛前体选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛和MOR型分子筛中的至少一种，优选为X型分子筛和/或Y型分子筛；
优选地，所述分子筛前体为钠型分子筛，所述第一交换液和/或第二交换液中还包括铵盐；
优选地，所述铵盐选自硝酸铵、氯化铵、硫酸铵，或者它们的组合；
优选地，所述第一交换液和/或第二交换液中，所述铵盐的浓度各自独立地为50-200g/L。
C9、根据项目C7或C8所述的制备方法，其中，所述修饰金属的可溶性化合物选自所述修饰金属的氯化物、硝酸盐、磷酸盐、硫酸盐，或者它们的组合；
优选地，所述第一交换液和第二交换液中还各自独立地包括溶剂，所述溶剂优选为水；
优选地，所述第一交换液和/或第二交换液中，所述修饰金属的可 溶性化合物的浓度各自独立地为100-500g/L；
优选地，所述第一交换液与所述分子筛前体的质量比为2-8：1；
优选地，所述第二交换液与第一交换分子筛的质量比为3-6：1；
优选地，所述第一次离子交换的条件包括：交换温度为50-90℃，优选为70-90℃；交换时间为0.5-2h，优选为0.5-1.5h；
优选地，所述第二次离子交换的交换温度比第一次离子交换的交换温度高0-15℃，优选为1-10℃。
C10、根据项目C7-C9中任一项所述的制备方法，其中，所述碱性气氛由碱性化合物的水溶液提供；
优选地，所述碱性化合物选自氨、碳酸铵、尿素，或者它们的组合；
优选地，所述碱性化合物的水溶液中，碱性化合物的浓度为0.01-2mol/L；
优选地，相对于50g分子筛前体，所述碱性气氛的通入速率，以碱性化合物水溶液的体积计，为0.01-0.5mL/min；
优选地，所述第一焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)；
优选地，所述第二焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)。
C11、根据项目C7-C10中任一项所述的制备方法，其中，所述含氧气氛为空气或氧气和惰性气体的混合气；
优选地，所述含氧气氛中，氧气的含量为16-30vol％，优选为18-25vol％；
优选地，所述热处理的温度比第二焙烧温度高50-100℃；
优选地，所述热处理的条件包括：温度为500-700℃，优选为550-650℃，处理时间为2-12h，优选为4-8h。
C12、根据项目C6-C11中任一项所述的制备方法，其中，所述助挤剂选自田菁粉、纤维素、淀粉，或者它们的组合；
优选地，所述助挤剂的用量为所述金属修饰分子筛以及耐热无机氧化物的干基总重量的0-5wt％；
优选地，所述胶溶剂选自柠檬酸、硝酸、磷酸，或者它们的组合；
优选地，所述胶溶剂的用量为所述金属修饰分子筛以及耐热无机氧化物的干基总重量的0-8wt％；
优选地，所述水的用量与所述金属修饰分子筛以及耐热无机氧化物的干基总重量的比值为0.1-1：1；
优选地，所述焙烧的温度为400-700℃，焙烧的时间为2-12h。
C13、根据项目C1-C12中任一项所述的制备方法，其中，所述长链烯烃为末端具有双键的长链α烯烃；
优选地，所述长链烯烃选自C7-C27的长链烯烃；
优选地，所述芳烃选自苯、甲苯、乙苯，或者它们的组合，优选为苯；
优选地，所述烷基化反应条件包括：反应温度为50-250℃，压力为0.1-7MPa，苯/烯摩尔比3-80:1，进料烯烃的质量空速0.1-5h-1；
优选的，所述烷基化反应条件包括：反应温度为70-200℃，压力为2-4MPa，苯/烯摩尔比为4-60:1，进料烯烃的质量空速0.3-3h-1。
C14、根据项目C1-C13中任一项所述的制备方法，其中，所述含氧混合气为氧气和保护气体的混合气；
优选地，所述含氧混合气中，氧气的含量为1-50vol％，优选为10-25vol％；
优选地，所述保护气体选自氮气、氦气、氩气，或者它们的组合；
优选地，所述再生的温度为400-700℃，再生的时间为4-18h，含氧混合气的体积空速为500-6000h-1，再生压力为0.01-0.1MPa(表压)。
实施例
以下将通过实施例对本申请进行详细描述。
以下实施例中，在没有特别说明的情况下，使用的各种原料均可从商业渠道获得。
以下实施例中，体相修饰金属的质量分数通过XRF测试。表层修饰金属的质量分数通过XPS测试测得。
在本申请中，采用ESCALAB 250型X射线光电子能谱仪(Thermo Fisher Scientific公司)进行XPS测试，测试条件包括：单色Al KαX射线，能量1486.6eV，功率150W，采用污染碳的C1s峰(284.8eV)校正荷电位移。
在本申请中，采用日本理学电机工业株光会社3271型X射线荧光光谱仪进行XRF测试；测试条件包括：X光管的阳极靶材料为铑靶； 激光电压为50kV；激光电流为50mA。
在本申请中，采用美国Bruker Tensor II傅里叶变换红外光谱仪进行吡啶吸附红外测试，测试过程为：将样品制成自撑片置于红外光谱仪的原位池中密封，以10℃/min的速率升温至450℃，抽真空至10-6Pa左右保持2h，以脱附分子筛物理吸附的水分子等杂质。冷却至室温后，静态饱和吸附吡啶平衡10min，然后升温至200℃，再次抽真空至10-6Pa，保持30min，冷却至室温，扫描1000-4000cm-1范围内得红外谱图。
所述XRD的测试条件包括：所用仪器为荷兰PANalytical公司的X射线粉末衍射仪；测试条件包括：管电压40kV，管电流40mA，Cu靶Kα辐射，扫描速度2°/min，扫描范围2θ＝5°-35°。
以下制备实施例I系列中采用的分子筛均购自于中国石化催化剂有限公司。
制备实施例I-1
1)取50g的HY分子筛(氧化硅/氧化铝的摩尔比为6，w(Na2O)＝0.0628％)，采用硝酸镧溶液对HY分子筛进行第一次离子交换，硝酸镧的浓度为300g/L，交换温度80℃，交换时间1h，硝酸镧溶液与HY分子筛的质量比为3：1，交换后分子筛经过滤干燥后在0.02MPa压力下在550℃进行第一焙烧1h，在焙烧过程中以0.1mL/min通入0.1M氨水；焙烧后得到第一交换分子筛，经XRF检测计算得到镧金属质量分数为10.65％。
2)对第一交换分子筛进行第二次离子交换和第二焙烧得到第二交换分子筛，条件与步骤1相同，第二交换分子筛经XRF检测计算得到镧金属质量分数为17.33％。
3)将第二交换分子筛在马弗炉中空气气氛下在600℃焙烧4h，即为成品分子筛，编号为Y1。
通过XRD测试，金属修饰分子筛Y1的XRD谱图如图1所示，其中在11.9°、12.4°处的特征峰归属于阳离子位上的金属离子，29.0°处的特征峰归属于分子筛表面的金属氧化物；同时，通过和HY分子筛的衍射峰对比可以看出，分子筛Y1的相应特征峰的出峰位置与HY分子筛的衍射峰的出峰位置相同，即没有产生偏移，由此证明修饰金属镧均位于分子筛骨架外。
通过吡啶吸附红外测试，金属修饰分子筛Y1的吡啶吸附红外谱图如图2所示，其中在约1455cm-1和约1445cm-1处均显示出明显的吸收峰。
测得的分子筛Y1的理化性质如表I-1所示。
制备实施例I-2
按照制备实施例I-1中的方法，不同的是，将步骤1)中的HY型分子筛替换为等质量的Hβ型分子筛(氧化硅/氧化铝的摩尔比为19，w(Na2O)＝0.0171％)。制得的金属修饰分子筛的编号为Y2。
测得的分子筛Y2的理化性质如表I-1所示。
通过XRD测试，金属修饰分子筛Y2的XRD谱图如图3所示，通过和Hβ分子筛的衍射峰对比可以看出，分子筛Y2的相应特征峰的出峰位置与Hβ分子筛的衍射峰的出峰位置相同，即没有产生偏移，由此证明修饰金属镧均位于分子筛骨架外。
制备实施例I-3
按照制备实施例I-1中的方法，不同的是，将硝酸镧溶液替换为硝酸铈溶液。制得的金属修饰分子筛的编号为Y3。
测得的分子筛Y3的理化性质如表I-1所示。
制备实施例I-4
按照制备实施例I-1中的方法，不同的是，将硝酸镧溶液替换为硝酸锶溶液。制得的金属修饰分子筛的编号为Y4。
测得的分子筛Y4的理化性质如表I-1所示。
制备实施例I-5
按照制备实施例I-1中的方法，不同的是，在第一次和第二次离子交换中，硝酸镧溶液与HY分子筛的质量比均为2.5：1。制得的金属修饰分子筛的编号为Y5。
测得的分子筛Y5的理化性质如表I-1所示。
制备实施例I-6
按照制备实施例I-1中的方法，不同的是，在第一次和第二次离子交换中，硝酸镧溶液与HY分子筛的质量比均为3.8：1。制得的金属修饰分子筛的编号为Y6。
测得的分子筛Y6的理化性质如表I-1所示。
制备实施例I-7
按照制备实施例I-1中的方法，不同的是，将氨水的通入速率替换为0.03mL/min。制得的金属修饰分子筛的编号为Y7。
测得的分子筛Y7的理化性质如表I-1所示。
制备实施例I-8
1)取50g的NaY分子筛(氧化硅/氧化铝的摩尔比为5，w(Na2O)＝12.8％)，采用氯化铵和硝酸镧的混合溶液对NaY分子筛进行第一次离子交换，氯化铵的浓度为120g/L(单独计算)，硝酸镧的浓度为300g/L(单独计算)，交换温度为80℃，交换时间为1h，混合溶液与分子筛的质量比为3：1，交换后分子筛经过滤干燥后在0.02MPa压力下在550℃进行第一焙烧1h，在焙烧过程中以0.1mL/min通入0.1M氨水；焙烧后得到第一交换分子筛。
2)对第一交换分子筛进行第二次离子交换和第二焙烧得到第二交换分子筛，条件与步骤1相同。
3)对第二交换分子筛采用氯化铵溶液交换，氯化铵的浓度为120g/L，交换温度为80℃，交换时间为1h，氯化铵溶液与分子筛的质量比为3：1，交换后分子筛经过滤干燥后再次进行氯化铵溶液交换，条件与上述相同，重复2次，使得分子筛中Na质量分数低于0.2％，将第二交换分子筛在马弗炉中空气气氛下在600℃焙烧4h。
即为成品分子筛，编号为Y8。测得的分子筛Y8的理化性质如表I-1所示。
制备实施例I-9
按照制备实施例I-1中的方法，不同的是，硝酸镧溶液的浓度为400g/L。制得的金属修饰分子筛的编号为Y9。
测得的分子筛Y9的理化性质如续表I-1所示。
制备实施例I-10
按照制备实施例I-1中的方法，不同的是，硝酸镧溶液的浓度为200g/L。制得的金属修饰分子筛的编号为Y10。
测得的分子筛Y10的理化性质如续表I-1所示。
制备实施例I-11
按照制备实施例I-1中的方法，不同的是，将步骤1)中的HY型分子筛替换为等质量的HX型分子筛(氧化硅/氧化铝的摩尔比为2，w(Na2O)＝0.0156％)。制得的金属修饰分子筛的编号为Y11。
测得的分子筛Y11的理化性质如续表I-1所示。
制备实施例I-12
1)取50g的HY分子筛(氧化硅/氧化铝的摩尔比为6，w(Na2O)＝0.0628％)，采用硝酸镧溶液对HY分子筛进行第一次离子交换，硝酸镧的浓度为300g/L，交换温度80℃，交换时间1h，硝酸镧溶液与HY分子筛的质量比为3：1，交换后分子筛经过滤干燥后在0.02MPa压力下在550℃进行第一焙烧1h，在焙烧过程中以0.1mL/min通入0.1M氨水，得到第一交换分子筛；
2)对第一交换分子筛进行第二次离子交换，与第一次离子交换不同的是，第二次离子交换温度为90℃；经过焙烧，得到第二交换分子筛。
3)将第二交换分子筛在马弗炉中空气气氛下在600℃焙烧4h，即为成品分子筛，编号为Y12。
测得的分子筛Y12的理化性质如续表I-1所示。
制备对比例I-1
采用制备实施例I-1中未处理的HY分子筛，编号为DY1。测得的分子筛DY1的理化性质如续表I-1所示。
通过吡啶吸附红外测试，分子筛DY1的吡啶吸附红外谱图如图2所示，其中在1440-1460cm-1范围内仅显示出一个吸收峰。
制备对比例I-2
1)取50g的HY分子筛(氧化硅/氧化铝的摩尔比为6，w(Na2O)＝0.0628％)，采用硝酸镧溶液对HY分子筛进行第一次离子交换，硝酸镧的浓度为150g/L，交换温度80℃，交换时间1h，溶液与分子筛质量比为3：1，交换后分子筛经过滤干燥后在0.02MPa压力下在550℃焙烧1h，同时在焙烧过程中以0.1mL/min通入0.1M氨水；焙烧后得到第一交换分子筛，经XRF检测计算得到镧金属质量分数为5.83％。
2)对第一交换分子筛进行第二次离子交换和第二焙烧得到第二交换分子筛，条件与步骤1相同，第二交换分子筛经XRF检测计算得到镧金属质量分数为6.97％。
3)将第二交换分子筛在马弗炉中空气气氛下在600℃焙烧4h，即为成品分子筛，编号为DY2。
通过吡啶吸附红外测试，分子筛DY2的吡啶吸附红外谱图如图2 所示，其中仅在约1455cm-1处显示出明显的吸收峰。
测得的分子筛DY2的理化性质如续表I-1所示。
制备对比例I-3
1)取50g的HY分子筛(氧化硅/氧化铝的摩尔比为6，w(Na2O)＝0.0628％)，采用硝酸镧溶液对HY分子筛进行第一次离子交换，浓度为900g/L，交换温度80℃，交换时间1h，溶液与分子筛质量比为3：1，交换后分子筛经蒸发除水并干燥后在0.02MPa压力下在550℃焙烧1h，同时在焙烧过程中以0.1mL/min通入0.1M氨水；焙烧后分子筛经XRF检测计算得到镧金属质量分数为19.06％。
2)对第一交换分子筛进行第二次离子交换和第二焙烧得到第二交换分子筛，方法与步骤1相同，第二交换分子筛经XRF检测计算得到镧金属质量分数为31.80％。
3)将第二交换分子筛在马弗炉中空气气氛下在600℃焙烧4h，即为成品分子筛，编号为DY3。
通过吡啶吸附红外测试，分子筛DY3的吡啶吸附红外谱图如图2所示，其中仅在约1445cm-1处显示出明显的吸收峰。
测得的分子筛DY3的理化性质如续表I-1所示。
制备对比例I-4
按照制备实施例I-1中的方法，不同的是，在第一焙烧和第二焙烧过程中均通入等量的水替换氨水，得到的分子筛记为DY4，测得的分子筛DY4的理化性质如续表I-1所示。
制备对比例I-5
本对比例说明采用真空浸渍法负载金属制备分子筛过程，取50g的HY分子筛(氧化硅/氧化铝的摩尔比为6，w(Na2O)＝0.0628％)，采用硝酸镧溶液对HY分子筛进行过量真空浸渍，镧的负载量为20％，硝酸镧溶液与HY分子筛的质量比为2：1，在旋转蒸发仪上80℃旋转浸渍3h，之后真空脱水，浸渍后催化剂在120℃干燥12h，干燥后催化剂马弗炉中空气气氛下在600℃焙烧4h，得到的分子筛记为DY5，测得的分子筛DY5的理化性质如续表I-1所示。
表I-1制备实施例I-1至I-12和制备对比例I-1至I-5中所得催化剂的性质

*所述强L酸占比表征为吡啶吸附红外谱图中约1445cm- 1处的吸收峰面积与约1445cm-
1处和约1450cm-1处的吸收峰面积总和的比值(下同)。
续表I-1制备实施例I-1至I-12和制备对比例I-1至I-5中所得催化剂的性质
应用实施例I-1
将制备实施例I-1的分子筛样品Y1，在120℃、2.5MPa的反应条件进行苯与1-十二烯的烷基化反应，烯烃进料空速为0.354h-1，苯/烯摩尔比为60。在该反应条件下转化率与产物选择性结果见表I-2所示。
将制备实施例I-1分子筛进行稳定性评价，结果见图4，从图4可以看出，采用制备实施例I-1制备分子筛在1-十二烯与苯烷基化反应中的催化性能稳定，300h的评价中单烷基苯选择性一直接近100％，烷基苯的直链度也一直在94％以上。
1-十二烯的转化率(％)＝(反应前1-十二烯的物质的量-反应后1-十二烯的物质的量)/反应前1-十二烯的物质的量×100％；
单烷基苯选择性(％)＝反应后单烷基苯的物质的量/全部反应产物的物质的量×100％；
直链度(％)＝反应后直链烷基苯的物质的量/反应后单烷基苯的物质的量×100％。
应用实施例I-2至I-12
按照应用实施例I-1的方法，分别用制备实施例I-2至I-12中的分子筛替换Y1。烷基化反应结果如表I-2和续表I-2所示。
应用对比例I-1至I-5
按照应用对比例I-1的方法，分别用制备对比例I-1至I-5中的分子筛替换Y1。烷基化反应结果如续表I-2所示。
表I-2应用实施例I-1至I-12和应用对比例I-1至I-5的反应结果

续表I-2应用实施例I-1至I-12和应用对比例I-1至I-5的反应结果

从表I-2及续表I-2的结果可以看出，本申请制备实施例I系列制得的金属修饰分子筛催化1-十二烯与苯烷基化反应的活性、稳定性和选择性高，其中单烷基苯选择性98％以上，烷基苯的直链度达到94％以上。
通过制备实施例I-1和制备对比例I-1至I-3对比可以看出，不进行金属修饰、金属含量过高或过低时，不利于提高催化剂寿命和产品直链度，尤其是当金属含量超过30wt％时，烯烃转化率大幅降低，单烷基苯选择性差。通过制备实施例I-1和制备对比例I-4可以看出，当第一焙烧和第二焙烧均不采用碱性气氛时，表层修饰金属的质量分数占比更高，催化剂的活性降低，烷基苯的直链度降低，同时，随着反应进行，催化效果快速衰减，催化剂寿命短。
以下制备实施例II系列用于说明本申请中固体酸催化剂的制备。
制备实施例II-1
取分子筛样品Y1与拟薄水铝石(平均粒径为100μm)按照干基重量百分比为80：20混合，分别添加3wt％的田菁粉和3wt％的硝酸(以分子筛和拟薄水铝石的干基总重量为基准)，按照分子筛与拟薄水铝石的干基为基准按照质量比1：1加入去离子水，混合均匀后挤出成型，在110℃下干燥6h，以使得干燥后所述混合成型物的干基重量为65wt％，然后在550℃下空气焙烧4h，得到固体酸催化剂G1。
制备实施例II-2至II-12
按照制备实施例II-1中的方法，不同的是，采用制备实施例I-2至I-12中的金属修饰分子筛分别替换Y1，得到固体酸催化剂G2-G12。
制备实施例II-13
将制备实施例II-1中催化剂制备过程替换为：取分子筛样品Y1与二氧化硅(平均粒径为0.05μm)按照干基重量百分比为80：20混合，分别添加3wt％的田菁粉和3wt％的硝酸(以分子筛和二氧化硅的干基总重量为基准)，按照分子筛与二氧化硅的干基为基准，按照质量比为 0.5：1加入去离子水，混合均匀后挤出成型，在150℃下干燥6h，以使得干燥后所述混合成型物的干基重量为70wt％，然后在600℃下空气焙烧6h，得到固体酸催化剂G13。
制备实施例II-14
按照制备实施例II-1中的方法，不同的是，将分子筛样品Y1与拟薄水铝石按照干基重量百分比替换为60：40混合，得到固体酸催化剂G14。
制备对比例II-1至II-4
按照制备实施例II-1中的方法，不同的是，采用制备对比例I-1至I-4中得到的分子筛DY1-DY4分别替换Y1，得到固体酸催化剂DG1-DG4。
应用实施例II-1
用制备实施例II-1所得的固体酸催化剂G1，在120℃、3MPa的反应条件进行苯与1-十二烯的烷基化反应，烯烃进料空速为0.354h-1，进料苯烯物质的量比为60：1。计算得到的1-十二烯的转化率与单烷基苯的选择性等结果见表II-1。稳定运转评价结果见图5，从图5可以看出，在260h的稳定运转评价中单烷基苯选择性一直接近100％，烷基苯线性度也一直在94％以上。
当1-十二烯转化率低于98％时，采用含氧混合气(氧气含量20％，氮气含量80％)对催化剂在500℃下再生8h，再生压力为0.01MPa(表压)，混合气的体积空速为3000h-1；记为一次反应-再生过程，再生结束后以相同反应条件再次进行反应，共进行两次反应-再生过程。新鲜剂、一次再生剂和二次再生剂的反应结果见表II-2。
连续反应-再生运转评价结果见图6，从图6可以看出，在两次反应-再生评价中单烷基苯选择性一直接近100％，烷基苯直链度也一直在94％以上。
其中，1-十二烯的转化率(％)＝(反应前1-十二烯的物质的量-反应后1-十二烯的物质的量)/反应前1-十二烯的物质的量×100％；
单烷基苯选择性(％)＝反应后单烷基苯的物质的量/全部反应产物的物质的量×100％；
直链度(％)＝反应后直链烷基苯的物质的量/反应后单烷基苯的物质的量×100％。
应用实施例II-2至III-14
按照应用实施例II-1中的方法，不同的是，采用制备实施例II-2至II-14中的固体酸催化剂G2-G14替换G1，分别进行烷基化反应，结果见表II-1。
应用实施例II-15
按照应用实施例II-1中的方法，不同的是，再生温度替换为400℃。共进行两次反应-再生过程。新鲜剂、一次再生剂和二次再生剂的反应结果见续表II-2。
应用实施例II-16
按照应用实施例II-1中的方法，不同的是，将烷基化反应温度替换为220℃。共进行两次反应-再生过程。新鲜剂、一次再生剂和二次再生剂的反应结果见续表II-2。
应用对比例II-1
按照应用实施例II-1中的方法，不同的是，采用制备对比例II-1中的固体酸催化剂DG1替换G1，进行烷基化反应，结果见表II-1。
当1-十二烯转化率低于98％时，采用应用实施例II-1中的再生方法对固体酸催化剂进行再生，共进行两次反应-再生过程。新鲜剂、一次再生剂和二次再生剂的反应结果见续表II-2。
应用对比例II-2至III-4
按照应用实施例II-1中的方法，不同的是，采用制备对比例II-2至II-4中的固体酸催化剂DG2至DG4分别替换G1，进行烷基化反应，结果见表II-1。
表II-1应用实施例II-1至II-14和应用对比例II-1至II-4的反应结果
续表II-1应用实施例II-1至II-14和应用对比例II-1至II-4的反应结果
从表II-1及续表II-1的结果可以看出，本申请制备实施例II系列制得的固体酸催化剂具有较高的催化活性，在1-十二烯与苯烷基化反应中，反应物的转化率高、其中单烷基苯选择性98％以上，烷基苯的直链度达到94％以上。在260h的稳定运转评价中单烷基苯选择性和烷基苯和直链度的稳定性好，能够适用于大规模工业应用。
表II-2应用实施例II-1和应用对比例II-1的连续反应-再生的运转结果
续表II-2应用实施例II-15和II-16的连续反应-再生的运转结果
从表II-2及续表II-2的结果可以看出，采用本申请的固体酸催化剂，通过在含氧混合气下的再生可以实现长链烷基苯制备的长周期连续运行。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所发明的内容。

Claims (17)

  1. 一种金属修饰分子筛，包括硅铝分子筛和选自碱土金属、第IIIB族金属、第IIIA族金属，或者它们的组合的修饰金属，其中至少一部分所述修饰金属以分子筛骨架外的补偿阳离子的形式存在，并且以所述金属修饰分子筛的总量为基准，以元素计，所述修饰金属的含量为8-30wt％，优选为12-23wt％；
    其中，所述金属修饰分子筛中，以元素的质量分数计，通过X射线光电子能谱分析(XPS)测得的表层修饰金属的质量分数与通过X射线荧光光谱分析(XRF)测得的体相修饰金属的质量分数的比值不超过1.45，优选为0.9-1.45，更优选为0.9-1.35。
  2. 根据权利要求1所述的金属修饰分子筛，其中，所述修饰金属的原子半径为120-270pm，优选为160-240pm；
    优选地，所述修饰金属选自La、Ce、Sr、Y，或者它们的组合。
  3. 根据权利要求1或2所述的金属修饰分子筛，其中所述金属修饰分子筛的氧化硅/氧化铝摩尔比为1-100：1，优选为3-20：1；
    优选地，所述金属修饰分子筛选自X型分子筛、Y型分子筛、MCM-22型分子筛、Beta型分子筛、MOR型分子筛，或者它们的组合，更优选为X型分子筛和/或Y型分子筛。
  4. 根据权利要求1-3中任一项所述的金属修饰分子筛，其中所述金属修饰分子筛的吡啶吸附红外谱图在1440-1460cm-1范围内存在两个吸收峰，优选地，在较低波数位置的吸收峰面积占所述两个吸收峰的总面积的比值为0.3-0.7，更优选为0.4-0.6。
  5. 在先权利要求中任一项所述的金属修饰分子筛的制备方法，包括以下步骤：
    1)将分子筛前体与含有修饰金属的可溶性化合物的第一交换液进行第一次离子交换；
    2)将第一次离子交换的产物进行第一焙烧，得到第一交换分子筛；
    3)将第一交换分子筛与含有修饰金属的可溶性化合物的第二交换液进行第二次离子交换；
    4)将第二次离子交换的产物进行第二焙烧，任选地重复一次或多次所述第二次离子交换和第二焙烧，得到第二交换分子筛；
    5)在含氧气氛下，对第二交换分子筛进行热处理，得到所述金属修饰分子筛；
    其中，所述第一焙烧和/或第二焙烧在碱性气氛下进行，
    优选地，步骤5)的热处理在比步骤4)的第二焙烧更高的温度下进行，优选在比第二焙烧高50-100℃的温度下进行。
  6. 根据权利要求5所述的制备方法，其中所述分子筛前体为氢型或钠型的分子筛；
    优选地，所述分子筛前体为钠型分子筛，并且所述第一交换液和/或第二交换液中还包括铵盐，更优选地，所述铵盐选自硝酸铵、氯化铵、硫酸铵，或者它们的组合，进一步优选地，所述第一交换液和/或第二交换液中，所述铵盐的浓度各自独立地为50-200g/L。
  7. 根据权利要求5或6所述的制备方法，具有以下特征中的一个或多个：
    所述第一交换液和第二交换液中所含的所述修饰金属的可溶性化合物可以相同或不同，并且相互独立地选自所述修饰金属的氯化物、硝酸盐、磷酸盐、硫酸盐，或者它们的组合；
    所述第一交换液和/或第二交换液中，所述修饰金属的可溶性化合物的浓度各自独立地为100-500g/L；
    所述第一交换液与所述分子筛前体的质量比为2-8：1，且所述第二交换液与第一交换分子筛的质量比为3-6：1；
    所述第一次离子交换的条件包括：交换温度为50-90℃，优选为70-90℃；交换时间为0.5-2h，优选为0.5-1.5h，且所述第二次离子交换的交换温度比第一次离子交换的交换温度高0-15℃，优选高1-10℃，交换时间为0.5-2h，优选为0.5-1.5h。
  8. 根据权利要求5-7中任一项所述的制备方法，具有以下特征中的一个或多个：
    所述碱性气氛由碱性化合物的水溶液的蒸汽提供，优选地，所述碱性化合物选自氨、碳酸铵、尿素，或者它们的组合，更优选地，所述碱性化合物的水溶液中，碱性化合物的浓度为0.01-2mol/L；
    相对于50g分子筛前体，所述第一和第二焙烧过程中，所述碱性气氛的通入速率，以碱性化合物水溶液的体积计，相互独立地为0.01-0.5mL/min；
    所述第一焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)；以及
    所述第二焙烧的条件包括：焙烧温度为400-600℃，焙烧时间为0.5-3h，压力为0.01-0.1MPa(表压)。
  9. 根据权利要求5-8中任一项所述的制备方法，其中：
    步骤5)的所述含氧气氛为空气、或氧气和惰性气体的混合气，优选地，所述含氧气氛中，氧气的含量为16-30vol％，优选为18-25vol％；和/或
    步骤5)的热处理的条件包括：温度为500-700℃，优选为550-650℃，处理时间为2-12h，优选为4-8h。
  10. 一种固体酸催化剂，包括权利要求1-4中任一项所述的金属修饰分子筛和耐热无机氧化物，优选地，以干基质量计，所述金属修饰分子筛与耐热无机氧化物的质量比为99：1至20：80，优选为95：5至25：75，更优选为90：10至50：50。
  11. 根据权利要求10所述的固体酸催化剂，其中，所述耐热无机氧化物选自氧化铝、氧化锆、二氧化硅、二氧化钛、粘土、高岭土、蒙脱土、镁铝结晶石、无定型硅铝，或者它们的组合，优选选自氧化铝、氧化锆、二氧化硅、二氧化钛，或者它们的组合；
    优选地，所述耐热无机氧化物的粒径为0.005-200μm，进一步优选为0.01-100μm。
  12. 权利要求10所述的固体酸催化剂的制备方法，包括：将权利要求1-4中任一项所述的金属修饰分子筛、耐热无机氧化物和/或其前驱体、水、任选的助挤剂、以及任选的胶溶剂进行混合、成型和焙烧，得到所述固体酸催化剂。
  13. 根据权利要求12所述的制备方法，具有以下特征中的一个或多个：
    所述助挤剂选自田菁粉、纤维素、淀粉，或者它们的组合，优选地所述助挤剂的用量为所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的0-20wt％，更优选1-5wt％；
    所述胶溶剂选自柠檬酸、硝酸、磷酸，或者它们的组合，优选地所述胶溶剂的用量为所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的0-20wt％，更优选1-8wt％；
    所述水的用量与所述金属修饰分子筛以及耐热无机氧化物和/或其前驱体的干基总重量的比值为0.2-1.2：1，优选0.3-1：1；以及
    所述焙烧的温度为400-650℃，焙烧的时间为1-12h。
  14. 权利要求1-4中任一项所述的金属修饰分子筛或者权利要求10或11所述的固体酸催化剂在制备长链烃基芳香化合物中的应用。
  15. 一种长链烃基芳香化合物的制备方法，包括：在权利要求1-4中任一项所述的金属修饰分子筛存在下，使长链烯烃和芳烃反应的步骤，
    优选地，所述长链烯烃为末端具有双键的长链α烯烃，进一步优选地，所述长链烯烃为C7-C27的长链烯烃，更进一步优选为C8-C15的长链烯烃，特别优选为C10-C14的长链烯烃；
    优选地，所述芳烃为单环或双环芳烃，更优选为苯系芳烃，更进一步优选选自苯、甲苯、乙苯，或者它们的组合，特别优选为苯；
  16. 根据权利要求15所述的方法，其中所述反应的条件包括：反应温度为50-250℃，优选为70-200℃；反应压力为0.1-7MPa，优选为2-4MPa；芳烃/烯摩尔比为3-70：1，优选为4-60：1；长链烯烃的质量空速为0.1-5h-1，优选为0.3-3h-1。
  17. 根据权利要求15或16所述的方法，其中所述反应在权利要求10或11所述的固体酸催化剂存在下进行，优选地，所述方法还包括在含氧混合气存在下，对所述固体酸催化剂进行再生的步骤；
    进一步优选地，所述含氧混合气为氧气和保护气体的混合气，所述保护气体选自氮气、氦气、氩气，或者它们的组合，更优选地，所述含氧混合气中，氧气的含量为1-50vol％，优选为10-25vol％；
    更进一步优选地，所述再生的条件包括：再生温度为400-700℃，再生时间为4-18h，含氧混合气的体积空速为500-6000h-1，再生压力为0.01-0.1MPa(表压)。
PCT/CN2023/114925 2022-08-26 2023-08-25 金属修饰分子筛、及其制备和应用 WO2024041636A1 (zh)

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