WO2022089338A1 - 硅铝分子筛催化剂及其制备和应用 - Google Patents

硅铝分子筛催化剂及其制备和应用 Download PDF

Info

Publication number
WO2022089338A1
WO2022089338A1 PCT/CN2021/125964 CN2021125964W WO2022089338A1 WO 2022089338 A1 WO2022089338 A1 WO 2022089338A1 CN 2021125964 W CN2021125964 W CN 2021125964W WO 2022089338 A1 WO2022089338 A1 WO 2022089338A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
mixture
aluminum
molecular sieve
source
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/125964
Other languages
English (en)
French (fr)
Inventor
杨为民
王达锐
孙洪敏
刘威
宦明耀
薛明伟
何俊琳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to EP21885065.9A priority Critical patent/EP4234084A4/en
Priority to KR1020237017870A priority patent/KR20230097108A/ko
Priority to US18/250,320 priority patent/US20230398524A1/en
Priority to JP2023525051A priority patent/JP7812851B2/ja
Priority to CA3199797A priority patent/CA3199797A1/en
Publication of WO2022089338A1 publication Critical patent/WO2022089338A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/34—Mechanical properties
    • B01J35/36—Mechanical strength
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/77—Compounds characterised by their crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/073—Ethylbenzene
    • 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
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present application relates to the technical field of aromatic hydrocarbon alkylation catalysts, in particular to a silicon-alumina molecular sieve catalyst suitable for the alkylation of aromatic hydrocarbons and olefins, and a preparation method and application thereof.
  • Ethylbenzene is an important basic organic raw material, mainly used to produce styrene, and styrene is an important monomer for the synthesis of polystyrene, styrene-butadiene rubber, ABS and SBS, etc. It is also used in the pharmaceutical, coating and textile industries. very broad.
  • Ethylbenzene is mainly synthesized by the alkylation of benzene and ethylene.
  • the gas-phase alkylation of benzene and ethylene is a complex reaction system with side reactions coexisting in series and parallel.
  • By-products such as diethylbenzene, triethylbenzene, toluene, xylene, propylbenzene, methylethylbenzene and butylbenzene.
  • xylene and ethylbenzene have similar boiling points and are difficult to be effectively removed by fractional distillation. Therefore, it is particularly important to control the content of xylene in alkylation products.
  • polyethylbenzene diethylbenzene and triethylbenzene materials are separated from the alkylation reaction products in industrial production, and then ethylbenzene is generated by transalkylation reaction, reducing the alkylation products.
  • the medium polyethylbenzene content can reduce the load of the subsequent transalkylation reaction, which is of great significance to the energy saving and efficiency improvement of enterprises.
  • Benzene and ethylene alkylation catalysts used in industry have certain requirements on shape and mechanical strength. Therefore, a large amount of binder needs to be added during the molding process of molecular sieve catalyst. Although the addition of a large amount of binder increases the mechanical strength of the catalyst, However, it also brings some negative effects, such as diluting the active center of the catalyst, blocking the pores of the molecular sieve, and at the same time causing more side reactions, resulting in lower product purity. In order to solve the negative effects brought by the binder, the prior art discloses a method for preparing a binderless catalyst.
  • CN107512729B discloses a method for preparing a binder-free ZSM-5 molecular sieve, comprising the following steps: a) providing a synthetic ZSM-5 molecular sieve; b) combining the synthetic ZSM-5 molecular sieve with a binder and a pore-forming agent Mixing with an aqueous acid solution, molding, and drying to obtain a ZSM-5 molecular sieve precursor; the binder is selected from at least one of silica sol or alumina; wherein the silica sol provides the first silicon source, and the alumina provides the first silicon source.
  • an aluminum source c) crystallizing the mixture of the ZSM-5 molecular sieve precursor, the second silicon source, the second aluminum source, the alkali source, the organic templating agent and water, and separating and drying the solid product to obtain the Binderless ZSM-5 molecular sieve.
  • the purpose of this application is to provide a silicon-alumina molecular sieve catalyst suitable for the alkylation of aromatic hydrocarbons and olefins, and its preparation and application. , selectivity and stability, can significantly reduce the content of by-products.
  • the present application provides a silica-alumina molecular sieve catalyst
  • the desorption curve in the NH 3 -TPD spectrum of the catalyst shows three peaks P1, P2 and P3, the three peaks
  • the desorption temperatures corresponding to the peak top positions of P1, P2 and P3 were in the range of 180-220°C, 250-290°C and 370-410°C, respectively.
  • the peak heights H1, H2 and H3 of the three peaks P1, P2 and P3 satisfy H1>H2>H3.
  • the application provides a method for preparing a silica-alumina molecular sieve catalyst, comprising the steps of:
  • the fourth mixture is treated to obtain the silica-alumina molecular sieve catalyst, wherein the treatment includes calcination.
  • the silicon powder used in step 2) contains two different sizes of silica particles, the sizes of which are in the range of 0.1-2 ⁇ m and 4-12 ⁇ m respectively, and the mass ratio of the two is (0.5-2.0):1 .
  • the present application provides a method for the gas-phase alkylation of aromatic hydrocarbons and olefins, comprising contacting aromatic hydrocarbons and olefins in the presence of the catalyst of the present application or the catalyst prepared according to the method of the present application to carry out an alkylation reaction to obtain alkanes.
  • Aromatic hydrocarbons comprising contacting aromatic hydrocarbons and olefins in the presence of the catalyst of the present application or the catalyst prepared according to the method of the present application to carry out an alkylation reaction to obtain alkanes.
  • Aromatic hydrocarbons Aromatic hydrocarbons.
  • the inventors have found through research that the acidity distribution in the silica-alumina molecular sieve catalyst, especially the binder-free ZSM-5 molecular sieve catalyst, can catalyze the catalytic performance of the gas-phase alkylation of aromatics and olefins, especially the production of by-products. rate has a greater impact.
  • the inventor has further studied and found that when the desorption curve of the NH 3 -TPD spectrum of the silica-alumina molecular sieve catalyst presents three peaks, especially when the heights of the three peaks from low to high are in a specific proportional relationship according to the desorption temperature, It is beneficial to improve the catalytic performance of the gas-phase alkylation reaction of aromatic hydrocarbons and olefins, and is especially beneficial to reduce the content of by-products such as xylene and polyethylbenzene in the product.
  • the grain size of the catalyst when the grain size of the catalyst exhibits a bimodal distribution, it has a synergistic effect and a relay effect on the diffusion and reaction of reactant molecules, so that the diffusion performance and reaction performance of the catalyst are matched, and the activity and selectivity of the catalyst are improved at the same time. , which can significantly reduce the content of by-products in the product.
  • the preparation method of the catalyst of the present application does not need to add pre-prepared molecular sieve powder in the preparation process, but uses a polyhydroxy polymer compound regulator, preferably silicon powder with two particle sizes, and the prepared catalyst has specific properties. Acid distribution and grain distribution.
  • the catalyst prepared by the method of the present application is especially suitable for the process of gas-phase alkylation of aromatic hydrocarbons and olefins to produce alkyl aromatic hydrocarbons, and has high activity, selectivity and stability.
  • the content of xylene in the alkylation product can be below 500 ppm, and the mass content of diethylbenzene and triethylbenzene can be below 8%.
  • Fig. 1 is the XRD spectrum of the silica-alumina molecular sieve catalyst prepared in Example 1 of the application;
  • Fig. 2 is the SEM photo of the silica-alumina molecular sieve catalyst prepared in Example 1 of the application;
  • Fig. 3 is the NH 3 -TPD spectrum of the silica-alumina molecular sieve catalyst prepared in Example 1 of the application;
  • Fig. 4 is the XRD spectrum of the silica-alumina molecular sieve catalyst prepared in Example 2 of the application;
  • Fig. 6 is the SEM photograph of the silica-alumina molecular sieve catalyst prepared in Comparative Example 1;
  • FIG. 7 is the NH 3 -TPD spectrum of the silica-alumina molecular sieve catalyst prepared in Comparative Example 1.
  • FIG. 7 is the NH 3 -TPD spectrum of the silica-alumina molecular sieve catalyst prepared in Comparative Example 1.
  • any specific numerical value disclosed herein, including the endpoints of a numerical range, is not limited to the precise value of the numerical value, but is to be understood to encompass values approximating the precise value, such as within ⁇ 5% of the precise value. all possible values. And, for the disclosed numerical range, between the endpoint values of the range, between the endpoint values and the specific point values in the range, and between the specific point values, one or more new values can be obtained in any combination. Numerical ranges, these new numerical ranges should also be considered to be specifically disclosed herein.
  • polyhydroxy polymer compound refers to a polymer containing multiple hydroxyl groups in the molecular formula, including but not limited to hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose cellulose, casein or gum arabic.
  • acidic molecular sieve has the meaning commonly understood in the art and refers to a molecular sieve having B acid and/or L acid sites.
  • any matter or matter not mentioned is directly applicable to those known in the art without any change.
  • 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 should not be It is considered to be new content not disclosed or anticipated herein, unless a person skilled in the art considers that the combination is obviously unreasonable.
  • the first aspect of the present application provides a silica-alumina molecular sieve catalyst, and the desorption curve in the NH 3 -TPD spectrum of the catalyst shows three peaks P1, P2 and P3, and the three peaks P1, P2
  • the desorption temperatures corresponding to the peak top positions of P3 are in the range of 180-220°C, 250-290°C and 370-410°C, respectively, preferably, 190-210°C, 260-280°C and 380-400°C, respectively In the range.
  • the peak heights H1, H2 and H3 of the three peaks P1, P2 and P3 satisfy H1>H2>H3, and more preferably the peak heights H1, H2 and H3 satisfy the following relationship:
  • the desorption temperature in the NH 3 -TPD spectrum is divided into three intervals, 100-240°C, 240-300°C and 300-500°C, respectively, and the integral of the desorption curve in the three temperature intervals
  • the areas correspond to the weak acid amount S1, the medium strong acid amount S2 and the strong acid amount S3 of the catalyst, respectively.
  • the weak acid amount S1, the medium and strong acid amount S2 and the strong acid amount S3 of the catalyst satisfy the following relationship:
  • the weak acid amount S1 of the catalyst accounts for 40-50% of the total acid amount (that is, the total amount of weak acid amount, medium-strong acid amount and strong acid amount), and the medium-strong acid amount S2 accounts for the total acid amount.
  • the ratio is 15-25%, and the ratio of the strong acid content S3 to the total acid content is 35-45%, wherein the weak acid content S1, the medium strong acid content S2 and the strong acid content S3
  • the ratio of the total acid content is respectively determined by the NH of the catalyst.
  • the integrated area of the desorption curve in the 3 -TPD spectrum in the temperature range of 100-240°C, 240-300°C and 300-500°C is relative to the desorption curve in the NH3 -TPD spectrum of the catalyst at 100-
  • the ratio of the total integrated area in the temperature range of 500°C is calculated.
  • the ratio of the superacid content of the catalyst to the total acid content is less than 5%, preferably less than 3%, wherein the ratio of the superacid content to the total acid content is determined by the NH 3 of the catalyst -Calculation of the ratio of the integral area of the desorption curve in the temperature range above 500°C in the TPD spectrum to the total integral area of the desorption curve in the NH 3 -TPD spectrum of the catalyst in the temperature range of 100-500°C get.
  • the silica-alumina molecular sieve catalyst is a binder-free silica-alumina molecular sieve catalyst, more preferably, the silica-alumina molecular sieve is an acidic molecular sieve with a ten-membered ring or twelve-membered ring pore structure, especially Preferably, the silica-alumina molecular sieve is ZSM-5 molecular sieve.
  • the silica-alumina molecular sieve catalyst does not additionally support any modified metal components or non-metal components, such as zinc, magnesium, calcium, iron, cobalt, nickel, phosphorus, lanthanum, copper, zirconium , chromium, manganese, silver, ruthenium, palladium, platinum, titanium, tin, strontium, barium, vanadium, lithium, etc.
  • modified metal components or non-metal components such as zinc, magnesium, calcium, iron, cobalt, nickel, phosphorus, lanthanum, copper, zirconium , chromium, manganese, silver, ruthenium, palladium, platinum, titanium, tin, strontium, barium, vanadium, lithium, etc.
  • the silica-alumina molecular sieve catalyst has grains of two different sizes, the sizes of which are in the range of 10-300 nm and 400-1600 nm, respectively. More preferably, the number of crystal grains with a size within 10-300nm accounts for 5-60% of the total number of crystal grains, preferably 30-60%; the number of crystal grains within a size of 400-1600nm accounts for 40-95% of the total number of crystal grains %, preferably 40-70%.
  • the isolated aluminium content in the catalyst is 97.5-100%, preferably 99-100%.
  • the isolated aluminum content can be measured as follows:
  • Isolated aluminum content (1-2 ⁇ C cobalt /C aluminum ) ⁇ 100%
  • the Co-Na type catalyst was prepared by ion exchange, and C cobalt and C aluminum were the Co content and Al content in the catalyst obtained by ICP test, respectively.
  • the mechanical strength of the silica-alumina molecular sieve catalyst is 100-170 N/cm, more preferably 110-160 N/cm.
  • the SiO 2 /Al 2 O 3 molar ratio of the silica-alumina molecular sieve catalyst is 30-400.
  • a second aspect of the present application provides a method for preparing a silica-alumina molecular sieve catalyst, comprising the following steps:
  • the fourth mixture is treated to obtain the silica-alumina molecular sieve catalyst, wherein the treatment includes calcination.
  • the templating agent described in step 1) is selected from one of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, and tetraethylammonium bromide or
  • the silicon source is selected from one or more of silica sol, white carbon black, tetraethyl silicate, and silicon powder;
  • the first aluminum source is selected from aluminum chloride, aluminum nitrate, aluminum sulfate, One or more of aluminum isopropoxide and pseudo-boehmite.
  • the process of obtaining the first mixture by heating and mixing the template agent, the silicon source, the first aluminum source and the water in step 1) is as follows: the template agent, the silicon source, the first aluminum source and the water are placed in a closed container. Stir in medium, stirring time is 4h-20h, stirring temperature is 90-150 °C.
  • the silicon powder in step 2) contains two different sizes of silica particles, the sizes of which are in the range of 0.1-2 ⁇ m and 4-12 ⁇ m, respectively, and the mass ratio of the two is (0.5- 2.0): 1;
  • the second aluminum source is selected from one or more of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum alkoxide, pseudoboehmite, and aluminum hydroxide.
  • the ratios of the first mixture, the silicon powder and the second aluminum source in step 2) are respectively: the weight ratio of the first mixture to the silicon powder is (0.2-0.8):1; the silicon powder to the second aluminum
  • the molar ratio of the sources was (30-400):1, wherein the silicon powder was calculated as SiO 2 and the second aluminum source was calculated as Al 2 O 3 .
  • the third mixture in step 3), can be made into various shapes as required, for example, it can be made into a strip, and its cut surface can be a circle, a gear, a clover, a four-leaf clover, a honeycomb, etc. shape.
  • the third mixture has a diameter of 1.0-6.0 mm and a length of 3-10 mm.
  • the alkali source in step 4) is selected from tetrapropylammonium hydroxide, tetraethylammonium hydroxide, ammonia water, ethylamine, ethylenediamine, n-butylamine, hexamethylenediamine, cyclohexane One or more of amine, piperidine, hexamethyleneimine, homopiperazine, dicyclohexylamine.
  • the conditioning agent used in step 4) is selected from one of hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, casein, and gum arabic one or more.
  • step 4 the process of contacting the third mixture, the alkali source and the conditioner to obtain the fourth mixture is as follows: the alkali source and the conditioner are mixed and stirred at 30-60° C. for 3-10 hours for the first time, and then The third mixture was added and left to stand in an enclosed space at 30-60°C for 5-10 hours.
  • the process of treating the fourth mixture to obtain a silica-alumina molecular sieve catalyst in step 5) is as follows: the fourth mixture is left standing or stirred at 130-190° C. in a closed space for 12-72 hours, and then Including the steps of washing, drying, roasting and acid washing.
  • the washing for example, washing with deionized water until the pH value of the solution is 7-8
  • drying, and roasting can be carried out by conventional methods.
  • the drying conditions can be as follows: the drying temperature is 80-150° C., The drying time is 5-12 hours; the conditions that can be used for roasting are as follows: the roasting temperature is 500-600 ° C, and the roasting time is 4-10 hours; the conditions that can be used for pickling are as follows: the acid washing temperature is 30-90 ° C, the acid washing The time is 2-10 hours, the acid can be at least one of hydrochloric acid, sulfuric acid, oxalic acid or nitric acid, and the mass concentration of the acid solution can be 0.5%-5%.
  • the properties of the silica-alumina molecular sieve catalyst prepared by the method of the present application are as described in the first aspect above, which will not be described in detail here.
  • a third aspect of the present application provides a method for the gas-phase alkylation of aromatic hydrocarbons and olefins, comprising performing an alkylation reaction between aromatic hydrocarbons and olefins in the presence of the catalyst of the present application or the catalyst prepared by the method of the present application to obtain an alkyl group Aromatic hydrocarbons.
  • the aromatic hydrocarbons are selected from benzene, alkylbenzenes or combinations thereof, preferably selected from benzene, toluene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, i-butylbenzene, tert-butylbenzene Benzene or a combination thereof;
  • the olefin is selected from C2-C6 olefins, preferably selected from ethylene, propylene, n-butene, isobutylene or a combination thereof.
  • the conditions for the alkylation reaction include: a reaction temperature of 260-400° C., a reaction pressure of 0.1-3.0 MPa, an olefin mass space velocity of 0.1-10.0 h -1 , and a molar ratio of aromatic hydrocarbons to olefins. 2-20.
  • the fourth aspect of the present application provides the use of the catalyst according to the present application or the catalyst prepared by the method of the present application in catalyzing the gas-phase alkylation reaction of aromatic hydrocarbons and olefins.
  • the XRD spectrum of the catalyst was detected by using Ultima IV X-ray powder diffractometer of Rigaku Company, Japan.
  • the voltage was selected as 35kV
  • the current was selected as 30mA
  • the scanning speed was 1° ⁇ min ⁇ 1 .
  • the acidity distribution of the catalyst was obtained by NH 3 -TPD test, wherein the NH 3 -TPD spectrum was obtained by using the temperature programmed desorption device of Tianjin Pengxiang Technology Co., Ltd. 200906PX18.
  • the specific process is as follows: take 0.05-0.20g of the sample (20-40 mesh) after pressing and sieving, put it into a quartz sample tube, first heat up and activate it in a helium atmosphere for 1h to stabilize for 1h, then cool down to below 40°C, and then heat up again At 100 °C, the ammonia gas was adsorbed at 100 °C until saturation. Finally, after purging with helium gas for 1 h, the temperature-programmed desorption was started, and the temperature was increased to 600 °C at a heating rate of 10 °C/min, and the working curve was recorded.
  • the mechanical strength of the catalyst was obtained by using a smart particle strength tester, wherein the DLIII type smart particle strength tester of Dalian Penghui Technology Development Co., Ltd. was used to test the mechanical strength of the catalyst after calcination, and the tested catalyst was placed horizontally. On the measuring instrument, test the maximum pressure that the catalyst can withstand when crushing, and take the average value after testing the crushing strength of 20 catalysts.
  • SEM pictures were obtained by using Hitachi S-4800 cold field emission high-resolution scanning electron microscope of Hitachi Corporation.
  • the grain size distribution is obtained by counting the data of at least 300 grains in the corresponding SEM photos, and calculating the proportion of the number of grains in a certain grain distribution range to the total statistical number.
  • the molar ratio of SiO 2 /Al 2 O 3 of the catalyst was obtained by ICP test, and the ICP test was carried out by using a Kontron Model S-35 ICP-AES analyzer. Before the test, 50 mg of the sample was completely dissolved in 50g of hydrofluoric acid solution inside.
  • the test method for the isolated aluminum content of the catalyst is as follows: first, the synthesized catalyst is ion-exchanged into Na type, wherein the catalyst and the sodium chloride solution with a concentration of 0.5 mol/L are used according to the solid-liquid mass ratio of 1 Mix at : 100, stir at room temperature for 4h, drain the solution after finishing, wash the solid with deionized water, and detect the washing solution with silver nitrate solution, until no white precipitate is formed in the washing solution, then finish washing to obtain Na-type catalyst; Then, the Na-type catalyst was exchanged with Co 2+ ions, and the Na-type catalyst and cobalt nitrate solution with a concentration of 0.05mol/L were mixed according to the solid-liquid mass ratio of 1:200, stirred at room temperature for 10 hours, and the solution was drained after the end.
  • the solid was washed with deionized water, and the washing liquid was detected with an aqueous ammonia solution until no blue precipitate was formed in the washing liquid, then the washing was terminated to obtain a Co-type catalyst. After drying, use ICP to test the Co content and Al content in the Co-type catalyst, and calculate the isolated aluminum content according to the following formula:
  • Isolated aluminum content (1-2 ⁇ C cobalt /C aluminum ) ⁇ 100%
  • C cobalt and C aluminum are the Co content and Al content in the Co-type catalyst, respectively.
  • the raw materials and reagents used are all commercially available materials, and the purity is reagent pure.
  • mixture A1 Mix 27.7 grams of 40 wt% tetrapropylammonium hydroxide aqueous solution, 60 grams of white carbon black, 13.32 grams of aluminum sulfate octadecahydrate and 54 grams of water, and stir in a closed container at 90° C. for 20 hours to obtain mixture A1.
  • Mix 12 grams of mixture A1 60 grams of silicon powder (silicon powder contains two kinds of silica particles with sizes in the range of 0.3-1.2 ⁇ m and 5-9 ⁇ m, and the mass of the two are 20 grams and 40 grams respectively), 13.32 g of aluminum sulfate octadecahydrate was mixed to obtain a mixture B1.
  • the mixture B1 was extruded to obtain the mixture C1 (the mixture C1 was cylindrical, with a diameter of 1.8 mm and a length of 5 mm).
  • 5 g of ethylamine and 0.5 g of hydroxyethyl cellulose were mixed and stirred at 50° C. for 5 hours, then 50 g of mixture C1 was added, and the mixture was allowed to stand at 30° C. for 10 hours in a closed space to obtain mixture D1.
  • the mixture D1 was then left to stand at 130°C for 72 hours in a closed space, then washed with deionized water to a pH value of 8, dried at 80°C for 12 hours, calcined at 500°C for 10 hours, and 3% oxalic acid was used in the mixture.
  • the XRD pattern of the silica-alumina molecular sieve catalyst E1 is shown in Figure 1, which has a typical MFI topological structure diffraction peak, indicating that it is a ZSM-5 molecular sieve catalyst.
  • the SEM photo of the silica-alumina molecular sieve catalyst E1 is shown in Figure 2. It can be seen from the figure that the catalyst has two sizes of crystallites. According to statistics, the sizes of the two crystallites are in the range of 50-200nm and 400-1000nm respectively. , the proportion of the number of grains is 35% and 65%, respectively.
  • the NH 3 -TPD spectrum of the silica-alumina molecular sieve catalyst E1 is shown in Figure 3. There are three peaks in the spectrum.
  • the three peaks are numbered as P1, P2 and P3 according to the desorption temperature from low to high.
  • the mechanical strength of the silica-alumina molecular sieve catalyst E1 is 155 N/cm, the molar ratio of SiO 2 /Al 2 O 3 is 50.8, and the isolated aluminum content is 99.0%.
  • mixture B2 Mix 253 grams of tetrapropylammonium hydroxide aqueous solution with a concentration of 40wt%, 133 grams of tetrapropylammonium bromide, 208.3 grams of tetraethyl silicate, 2.22 grams of aluminum sulfate octadecahydrate and 60 grams of water. The mixture was stirred at 150 °C for 4 h to obtain mixture A2. Mix 48 grams of mixture A2, 60 grams of silicon powder (silicon powder contains two kinds of silica particles with sizes in the range of 1.2-2 ⁇ m and 9-12 ⁇ m, and the masses of the two are 30 grams and 30 grams respectively), 1.665 grams Aluminum sulfate octadecahydrate is mixed to obtain mixture B2.
  • the mixture B2 was extruded to obtain the mixture C2 (the mixture C2 was cylindrical, with a diameter of 2.2 mm and a length of 5 mm).
  • the mixture of 20 g of cyclohexylamine, 0.5 g of casein and 2 g of hydroxypropyl methylcellulose was mixed and stirred at 50 ° C for 5 hours, then 50 g of the mixture C2 was added, and it was left at 60 ° C in a closed space for 5 hours to obtain Mixture D2.
  • the mixture D2 was then left to stand at 190°C for 12 hours in a closed space, washed with deionized water to a pH of 7, dried at 150°C for 5 hours, calcined at 600°C for 4 hours, and 0.5% oxalic acid was used in the mixture. Pickled at 30°C for 10 hours to obtain a silica-alumina molecular sieve catalyst E2.
  • the XRD pattern of the silica-alumina molecular sieve catalyst E2 is shown in Figure 4, which has a typical MFI topological structure diffraction peak, indicating that it is a ZSM-5 molecular sieve catalyst.
  • the SEM photo of the silica-alumina molecular sieve catalyst E2 shows that the catalyst has two sizes of crystallites. According to statistics, the sizes of the two crystallites are in the range of 250-300nm and 1000-1600nm, respectively, and the proportion of the number of crystallites is 40%. % and 60%. There are three peaks in the NH 3 -TPD spectrum of the silica-alumina molecular sieve catalyst E2.
  • the three peaks are numbered as P1, P2 and P3 according to the desorption temperature from low to high.
  • the peak positions of the three peaks correspond to the desorption
  • the mechanical strength of the silica-alumina molecular sieve catalyst E2 is 112 N/cm, the molar ratio of SiO 2 /Al 2 O 3 is 398, and the isolated aluminum content is 99.6%.
  • mixture B3 The mixture B3 was extruded to obtain the mixture C3 (the mixture C3 was cylindrical, with a diameter of 1.2 mm and a length of 5 mm). 10 g of n-butylamine and 1.5 g of gum arabic were mixed and stirred at 50° C. for 5 hours, then 50 g of mixture C3 was added, and the mixture was allowed to stand at 40° C.
  • mixture D3 was left standstill at 170°C for 36 hours in a closed space, washed with deionized water until the pH value was 7.5, dried at 100°C for 8 hours, and calcined at 550°C for 6 hours. Pickled at 60°C for 6 hours to obtain a silica-alumina molecular sieve catalyst E3.
  • the XRD pattern of the silica-alumina molecular sieve catalyst E3 is shown in Figure 5, which has a typical MFI topological structure diffraction peak, indicating that it is a ZSM-5 molecular sieve catalyst.
  • the SEM photo of the silica-alumina molecular sieve catalyst E3 shows that the catalyst has two sizes of crystallites. According to statistics, the sizes of the two crystallites are in the range of 10-100nm and 400-700nm, respectively, and the proportion of the crystallites is 56%. % and 44%. There are three peaks in the NH 3 -TPD spectrum of the silica-alumina molecular sieve catalyst E3.
  • the three peaks are numbered as P1, P2 and P3 according to the desorption temperature from low to high.
  • the peak positions of the three peaks correspond to the desorption
  • the mechanical strength of the silica-alumina molecular sieve catalyst E3 is 145 N/cm, the molar ratio of SiO 2 /Al 2 O 3 is 125, and the isolated aluminum content is 99.2%.
  • the preparation of the catalyst is carried out with reference to the method of Example 3, the difference is that the silicon powder used contains only one size of silica particles, the size of which is in the range of 0.1-0.3 ⁇ m, and no addition is made in step 4). regulator.
  • the specific preparation process of the catalyst is as follows: 126 grams of tetrapropylammonium hydroxide aqueous solution with a concentration of 40wt%, 66 grams of tetrapropylammonium bromide, 208.3 grams of tetraethyl silicate, 6.66 grams of aluminum sulfate octadecahydrate and 50 grams of The water was mixed uniformly, and stirred at 120° C. for 12 h in an airtight container to obtain mixture A4.
  • mixture B4 Mix 24 grams of mixture A4, 60 grams of silicon powder (silicon powder contains only one size of silica particles, the size of which is in the range of 0.1-0.3 ⁇ m), and 6.66 grams of aluminum sulfate octadecahydrate to obtain mixture B4.
  • the mixture B4 was extruded to obtain the mixture C4 (the mixture C4 was cylindrical, with a diameter of 1.2 mm and a length of 5 mm).
  • 10 g of n-butylamine was stirred at 50° C. for 5 hours, then 50 g of mixture C4 was added, and the mixture was allowed to stand at 40° C. for 7 hours in a closed space to obtain mixture D4.
  • the mixture D4 was then left to stand at 170°C for 36 hours in a closed space, washed with deionized water until the pH value was 7.5, dried at 100°C for 8 hours, calcined at 550°C for 6 hours, and 3% hydrochloric acid was used in the mixture. Pickled at 60° C. for 6 hours to obtain a silica-alumina molecular sieve catalyst F1.
  • the SEM photograph of the silica-alumina molecular sieve catalyst F1 is shown in FIG. 6 . It can be seen from the figure that the catalyst has only one size of crystallites, and the size of the crystallites is in the range of 180-250 nm according to statistics.
  • the proportions of weak acid S1, medium and strong acid S2 and strong acid S3 to the total acid were 34%, 10% and 56%, respectively.
  • the mechanical strength of the silica-alumina molecular sieve catalyst F1 is 155 N/cm, the SiO 2 /Al 2 O 3 molar ratio is 128, and the isolated aluminum content is 95.8%.
  • the preparation of the catalyst was carried out with reference to the method of Example 1, except that the order of adding the regulator hydroxyethyl cellulose was changed.
  • the specific preparation process of the catalyst is as follows: 27.7 grams of tetrapropylammonium hydroxide aqueous solution with a concentration of 40 wt%, 60 grams of white carbon black, 13.32 grams of aluminum sulfate octadecahydrate, 54 grams of water and 0.5 grams of hydroxyethyl cellulose are mixed uniformly , and stirred at 90 °C for 20 h in a closed container to obtain mixture A5.
  • mixture B5 Mix 12 grams of mixture A5, 60 grams of silicon powder (silicon powder contains two kinds of silica particles with sizes in the range of 0.3-1.2 ⁇ m and 5-9 ⁇ m, and the masses of the two are 20 grams and 40 grams respectively), 13.32 g of aluminum sulfate octadecahydrate was mixed to obtain mixture B5.
  • the mixture B5 was extruded to obtain the mixture C5 (the mixture C5 was cylindrical, with a diameter of 1.8 mm and a length of 5 mm).
  • 5 g of ethylamine was stirred at 50°C for 5 hours, then 50 g of mixture C5 was added and left to stand at 30°C in a closed space for 10 hours to obtain mixture D5.
  • the mixture D5 was left standing at 130°C for 72 hours in a closed space, washed with deionized water to a pH value of 8, dried at 80°C for 12 hours, calcined at 500°C for 10 hours, and 3% oxalic acid was used in the mixture. Pickled at 60° C. for 5 hours to obtain a silica-alumina molecular sieve catalyst F2.
  • the SEM photo of the silica-alumina molecular sieve catalyst F2 shows that it has two sizes of crystallites, and the sizes of the two crystallites are in the range of 200-420 nm and 1500-2000 nm, respectively.
  • the mechanical strength of the silica-alumina molecular sieve catalyst F2 is 135 N/cm, the molar ratio of SiO 2 /Al 2 O 3 is 52.4, and the isolated aluminum content is 96.6%.
  • the preparation of the catalyst was carried out with reference to the method of Example 3, except that the silicon powder used contained only one size of silica particles, the size of which was in the range of 0.1-0.3 ⁇ m.
  • the specific preparation process of the catalyst is as follows: 126 grams of tetrapropylammonium hydroxide aqueous solution with a concentration of 40wt%, 66 grams of tetrapropylammonium bromide, 208.3 grams of tetraethyl silicate, 6.66 grams of aluminum sulfate octadecahydrate and 50 grams of The water was mixed uniformly, and the mixture was stirred at 120° C. for 12 h in an airtight container to obtain mixture A6.
  • mixture B6 Mix 24 grams of mixture A6, 60 grams of silicon powder (silicon powder contains only one size of silica particles, and the size is in the range of 0.1-0.3 ⁇ m) and 6.66 grams of aluminum sulfate octadecahydrate to obtain mixture B6.
  • the mixture B6 was extruded to obtain the mixture C6 (the mixture C6 was cylindrical, with a diameter of 1.2 mm and a length of 5 mm).
  • 10 g of n-butylamine and 1.5 g of gum arabic were stirred at 50° C. for 5 hours, then 50 g of mixture C6 was added, and the mixture was left at 40° C. for 7 hours in a closed space to obtain mixture D6.
  • the mixture D6 was left standstill at 170° C.
  • the SEM picture of the silica-alumina molecular sieve catalyst F3 shows that it has only one size of crystallites, and by statistics, the size of the crystallites is in the range of 170-245 nm. There are two peaks in the NH 3 -TPD spectrum of the silica-alumina molecular sieve catalyst F3.
  • the mechanical strength of the silica-alumina molecular sieve catalyst F3 is 142 N/cm, the SiO 2 /Al 2 O 3 molar ratio is 126, and the isolated aluminum content is 97.3%.
  • Catalyst is prepared according to the method for reference CN 107512729A, and the specific process is as follows:
  • ZSM-5 molecular sieve precursor 41.866 g of the above synthesized ZSM-5 molecular sieve, 37.5 g of alkaline silica sol (40.0 wt % SiO 2 content), 0.5616 g of methylcellulose, and nitric acid aqueous solution (with a concentration of 5 wt %) Mix uniformly, and prepare by extruding strips a ZSM-5 molecular sieve precursor with a ZSM-5 molecular sieve content of 70 wt% and a four-leaf clover-shaped cross-section, with a diameter of 1.2 mm and a length of 5 mm.
  • Preparation of the target catalyst 1.97 grams of sodium aluminate (Al 2 O 3 content of 43.0 wt %, Na 2 O content of 35.0 wt %), 247 grams of water, 8.865 grams of n-butylamine (concentration of 99.0 wt %) were mixed uniformly, It was then mixed with all the molecular sieve precursors prepared above, and the resulting mixture was placed at 150° C. for crystallization for 28 hours.
  • the SEM picture of catalyst F4 shows that it has only one size of crystallites, and the size of the crystallites is in the range of 300-450 nm by statistics.
  • the proportion of S3 to the total acid content was 29%, 11% and 60%, respectively.
  • the mechanical strength of catalyst F4 is 78 N/cm
  • the SiO 2 /Al 2 O 3 molar ratio is 145
  • the isolated aluminum content is 93.7%.
  • the grain size of the catalyst of the present application has a bimodal distribution, and the desorption curve in the NH 3 -TPD spectrum shows three distinct peaks.
  • the catalyst of the present application has a significantly different acidity distribution, in particular, the proportion of medium and strong acids is significantly increased, while the proportion of strong acids is reduced and the proportion of weak acids is increased.
  • the silicon-alumina molecular sieve catalysts E1-E3 prepared in Example 1-3 and the catalysts F1-F4 prepared in Comparative Example 1-4 were respectively applied to the gas-phase alkylation reaction of benzene and ethylene.
  • the reaction temperature was 380 ° C, and the reaction pressure was 1.5MPa, the mass space velocity of ethylene is 2.2h -1 , and the benzene to ethylene molar ratio is 5.5 for 10h, and the content of xylene, diethylbenzene and triethylbenzene in the alkylation product is detected, and the ethylene conversion rate is calculated. and ethyl selectivity.
  • the reaction results are shown in Table 2 below, wherein:
  • Ethylene conversion (total ethylene feed - ethylene in reactor effluent)/total ethylene feed x 100%
  • Ethyl selectivity (the number of moles of ethylbenzene produced by the reaction + the number of moles of diethylbenzene ⁇ 2 + the number of moles of triethylbenzene ⁇ 3) / the number of moles of ethylene consumed by the reaction ⁇ 100%
  • Silica-alumina molecular sieve catalysts E1-E3 prepared in Examples 1-3 and catalysts F1-F4 prepared in Comparative Examples 1-4 were tested in the gas-phase alkylation reaction of benzene and ethylene under ultra-high ethylene space velocity reaction conditions.
  • the specific test conditions are as follows: the reaction temperature is 400°C, the pressure is 2.0MPa, the mass space velocity of ethylene is 6h -1 , and the molar ratio of benzene and ethylene is 2. The time elapsed for 60% conversion, the reaction results are shown in Table 3 below.
  • the catalyst of the present application has higher activity and selectivity in the alkylation reaction of aromatic hydrocarbons and olefins, which can significantly reduce the content of by-products and improve the conversion of olefins. rate and product selectivity.
  • the mass content of the key impurity xylene in the obtained alkylation product can be below 500 ppm, and the mass content of diethylbenzene and triethylbenzene can be below 8%.
  • the catalyst of the present application has higher stability in the gas-phase alkylation reaction of benzene and ethylene under ultra-high ethylene space velocity reaction conditions, and the single-pass life obviously increase.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

公开了一种硅铝分子筛催化剂及其制备和应用，所述催化剂的NH 3-TPD谱图中脱附曲线显示出三个峰P1、P2和P3，所述三个峰P1、P2和P3的峰顶位置对应的脱附温度分别在180-220℃、250-290℃和370-410℃的范围内。所述催化剂用于芳烃与烯烃气相烷基化制备烷基芳烃的反应时具有较高的活性、选择性和稳定性。

Description

硅铝分子筛催化剂及其制备和应用
相关申请的交叉引用
本申请要求2020年10月26日提交的、申请号为202011158111.7、名称为“一种苯和乙烯烷基化的催化剂及其制备方法和应用”的专利申请的优先权，其内容经此引用全文并入本文。
技术领域
本申请涉及芳烃烷基化催化剂的技术领域，具体涉及一种适用于芳烃和烯烃烷基化的硅铝分子筛催化剂及其制备方法和应用。
背景技术
乙苯是重要的基础有机原料，主要用来生产苯乙烯，而苯乙烯是合成聚苯乙烯、丁苯橡胶、ABS和SBS等的重要单体，还应用于制药、涂料和纺织工业中，用途非常广泛。
乙苯主要是通过苯和乙烯经烷基化反应合成，实际催化反应过程中，苯与乙烯气相烷基化是一个串联和并联副反应共存的复杂反应体系，除了生成乙苯外，还会生成二乙苯、三乙苯、甲苯、二甲苯、丙苯、甲乙苯和丁苯等副产物。在副产物中，二甲苯与乙苯沸点相近，难以通过分馏有效去除，因此控制烷基化产物中二甲苯含量尤为重要。另外，为提高乙苯收率，工业生产中从烷基化反应产物中分离出多乙苯(二乙苯和三乙苯)物料，随后通过烷基转移反应生成乙苯，降低烷基化产物中多乙苯含量可以减少后续烷基转移反应的负荷，对企业节能增效具有重要的意义。
工业使用的苯和乙烯烷基化催化剂对形状和机械强度均有一定的要求，因此在分子筛催化剂成型过程中需要添加大量的粘结剂，大量粘结剂的加入虽然增加了催化剂的机械强度，但同时也带来一些负面影响，比如会稀释催化剂的活性中心，堵塞分子筛的孔道，同时引发较多的副反应，导致产品纯度降低。为了解决粘结剂带来的负面影响，现有技术中公开了制备无粘结剂催化剂的方法。
CN107512729B公开了一种无粘结剂ZSM-5分子筛的制备方法，包括以下步骤：a)提供合成态ZSM-5分子筛；b)将所述合成态ZSM-5分子 筛与粘结剂、造孔剂和酸的水溶液混合、成型、干燥以获得ZSM-5分子筛前体；所述粘结剂选自硅溶胶或氧化铝中的至少一种；其中，硅溶胶提供第一硅源，氧化铝提供第一铝源；c)将所述ZSM-5分子筛前体、第二硅源、第二铝源、碱源、有机模板剂和水的混合物晶化，并将固体产物分离、干燥以获得所述无粘结剂ZSM-5分子筛。
目前公开报道的制备无粘结剂分子筛催化剂的方法中，一般在成型过程中需要添加一定量的分子筛粉末，这就意味着需要提前制得这部分分子筛粉末，无疑增加了操作步骤及生产成本。
发明内容
本申请的目的是提供一种适用于芳烃和烯烃烷基化的硅铝分子筛催化剂及其制备和应用，所述催化剂用于芳烃和烯烃气相烷基化制备烷基芳烃时，具有较高的活性、选择性和稳定性，可明显降低副产物的含量。
为了实现上述目的，在一个方面，本申请提供了一种硅铝分子筛催化剂，所述催化剂的NH 3-TPD谱图中脱附曲线显示出三个峰P1、P2和P3，所述三个峰P1、P2和P3的峰顶位置对应的脱附温度分别在180-220℃、250-290℃和370-410℃的范围内。
优选地，所述三个峰P1、P2和P3的峰高H1、H2和H3满足H1＞H2＞H3。
更优选地，所述三个峰P1、P2和P3的峰高H1、H2和H3之间满足如下关系：
H2/H1＝(0.5-0.8)∶1；
H3/H2＝(0.8-0.9)∶1；以及
H3/H1＝(0.4-0.7)∶1。
在另一方面，本申请提供了一种制备硅铝分子筛催化剂的方法，包括如下步骤：
1)将模板剂、硅源、第一铝源和水加热混合得到第一混合物；
2)将第一混合物、硅粉和第二铝源混合得到第二混合物；
3)将第二混合物成型得到第三混合物；
4)将第三混合物、碱源和调节剂接触得到第四混合物，其中所述调节剂为多羟基高分子化合物；以及
5)对第四混合物进行处理得到所述硅铝分子筛催化剂，其中所述处理包括焙烧。
优选地，步骤2)中所用的硅粉中含有两种不同尺寸的二氧化硅颗粒，其尺寸分别在0.1-2μm和4-12μm范围内，两者的质量比为(0.5-2.0)∶1。
再一方面，本申请提供了一种芳烃与烯烃气相烷基化的方法，包括使芳烃与烯烃在本申请的催化剂或按照本申请方法制备得到的催化剂存在下接触进行烷基化反应，得到烷基芳烃。
本申请的硅铝分子筛催化剂具有如下有益效果：
1、发明人经研究发现，硅铝分子筛催化剂、特别是无粘结剂的ZSM-5分子筛催化剂中的酸性分布对其催化芳烃和烯烃气相烷基化反应的催化性能，尤其是副产物的产率影响较大。发明人进一步研究发现，当硅铝分子筛催化剂的NH 3-TPD谱图中，脱附曲线呈现出三个峰时，特别是按照脱附温度由低到高三个峰的高度呈特定比例关系时，有利于提高对芳烃和烯烃气相烷基化反应的催化性能，特别是有利于降低产物中副产物，如二甲苯和多乙苯的含量。进一步地，当催化剂的晶粒尺寸呈现双峰分布时，对于反应物分子的扩散和反应具有协同作用和接力作用，使催化剂的扩散性能和反应性能相配合，在提高催化剂活性和选择性的同时，能够明显降低产物中副产物的含量。
2、本申请催化剂的制备方法不需要在制备过程中添加预先准备的分子筛粉末，而采用了多羟基高分子化合物调节剂，优选采用两种颗粒尺寸的硅粉，所制得的催化剂具有特定的酸性分布和晶粒分布。本申请方法制备的催化剂特别适用于芳烃和烯烃气相烷基化制烷基芳烃的过程，具有较高的活性、选择性和稳定性。
3、本申请催化剂用于苯和乙烯气相烷基化反应中时，烷基化产物中二甲苯含量可至500ppm以下，二乙苯和三乙苯质量含量可至8％以下。
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为本申请实施例1制备的硅铝分子筛催化剂的XRD谱图；
图2为本申请实施例1制备的硅铝分子筛催化剂的SEM照片；
图3为本申请实施例1制备的硅铝分子筛催化剂的NH 3-TPD谱图；
图4为本申请实施例2制备的硅铝分子筛催化剂的XRD谱图；
图5为本申请实施例3制备的硅铝分子筛催化剂的XRD谱图；
图6为对比例1制备的硅铝分子筛催化剂的SEM照片；以及
图7为对比例1制备的硅铝分子筛催化剂的NH 3-TPD谱图。
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，术语“多羟基高分子化合物”是指分子式内含有多个羟基的高分子，包括但不限于羟乙基纤维素、羟甲基纤维素、羟丙基甲基纤维素、甲基纤维素、干酪素或阿拉伯树胶。
在本申请中，术语“酸性分子筛”具有本领域通常理解的含义，指具有B酸和/或L酸性位点的分子筛。
在本申请中，如无相反表示，所给压力均为表压。
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。
如上所述，本申请第一方面提供了一种硅铝分子筛催化剂，该催化剂的NH 3-TPD谱图中脱附曲线显示出三个峰P1、P2和P3，所述三个峰P1、P2和P3的峰顶位置对应的脱附温度分别在180-220℃、250-290℃和370-410℃的范围内，优选地，分别在190-210℃、260-280℃和380-400℃的范围内。
在优选的实施方式中，所述三个峰P1、P2和P3的峰高H1、H2和H3满足H1＞H2＞H3，更优选地所述峰高H1、H2和H3之间满足如下关系：
H2/H1＝(0.5-0.8)∶1；
H3/H2＝(0.8-0.9)∶1；以及
H3/H1＝(0.4-0.7)∶1。
根据本申请，将NH 3-TPD谱图中的脱附温度划分为三个区间，分别为100-240℃、240-300℃和300-500℃，脱附曲线在三个温度区间内的积分面积分别对应催化剂的弱酸量S1、中强酸量S2和强酸量S3。优选地，所述催化剂的弱酸量S1、中强酸量S2和强酸量S3之间满足如下关系：
S2/S1＝(0.38-0.52)∶1，更优选地，S2/S1＝(0.4-0.5)∶1；
S2/S3＝(0.32-0.58)∶1，更优选地，S2/S3＝(0.35-0.55)∶1；以及
S3/S1＝(0.8-1.2)∶1，更优选地，S3/S1＝(0.9-1.1)∶1，
在优选的实施方式中，所述催化剂的弱酸量S1占总酸量(即弱酸量、中强酸量和强酸量的总量)的比例为40-50％，中强酸量S2占总酸量的比例为15-25％，强酸量S3占总酸量的比例为35-45％，其中所述弱酸量S1、中强酸量S2和强酸量S3占总酸量的比例分别由所述催化剂的NH 3-TPD谱图中脱附曲线在100-240℃、240-300℃和300-500℃的温度区间内的积分面积相对于所述催化剂的NH 3-TPD谱图中脱附曲线在100-500℃温度区间内的总积分面积的比例计算得到。
在优选的实施方式中，所述催化剂的超强酸量相对于总酸量的比例 小于5％，优选小于3％，其中所述超强酸量相对于总酸量的比例由所述催化剂的NH 3-TPD谱图中脱附曲线在500℃以上的温度区间内的积分面积相对于所述催化剂的NH 3-TPD谱图中脱附曲线在100-500℃温度区间内的总积分面积的比例计算得到。
在优选的实施方式中，所述硅铝分子筛催化剂为无粘结剂的硅铝分子筛催化剂，更优选地，所述硅铝分子筛为具有十元环或十二元环孔结构的酸性分子筛，特别优选地，所述硅铝分子筛为ZSM-5分子筛。
在优选的实施方式中，所述硅铝分子筛催化剂上未额外负载任何的改性金属组分或者非金属组分，如锌、镁、钙、铁、钴、镍、磷、镧、铜、锆、铬、锰、银、钌、钯、铂、钛、锡、锶、钡、钒、锂等。
在优选的实施方式中，所述硅铝分子筛催化剂具有两种不同尺寸的晶粒，其尺寸分别在10-300nm和400-1600nm范围内。更优选地，尺寸在10-300nm内的晶粒数量占总晶粒数的5-60％，优选30-60％；尺寸在400-1600nm内的晶粒数量占总晶粒数的40-95％，优选为40-70％。
在优选的实施方式中，所述催化剂中孤立铝含量为97.5-100％，优选99-100％。根据本申请，所述孤立铝含量可以通过如下方式测量得到：
孤立铝含量＝(1-2×C 钴/C 铝)×100％，
其中通过离子交换制备Co-Na型催化剂，C 钴和C 铝分别为ICP测试得到的催化剂中Co含量和Al含量。
在优选的实施方式中，所述硅铝分子筛催化剂的机械强度为100-170N/cm，更优选为110-160N/cm。
在优选的实施方式中，所述硅铝分子筛催化剂的SiO 2/Al 2O 3摩尔比为30-400。
本申请第二方面提供了一种制备硅铝分子筛催化剂的方法，包括如下步骤：
(1)将模板剂、硅源、第一铝源和水加热混合得到第一混合物；
(2)将第一混合物、硅粉和第二铝源混合得到第二混合物；
(3)将第二混合物成型得到第三混合物；
(4)将第三混合物、碱源和调节剂接触得到第四混合物，所述调节剂为多羟基高分子化合物；
(5)对第四混合物进行处理得到所述硅铝分子筛催化剂，其中所 述处理包括焙烧。
在优选的实施方式中，步骤1)中所述的模板剂选自四丙基氢氧化铵、四丙基溴化铵、四乙基氢氧化铵、四乙基溴化铵中的一种或多种；所述硅源选自硅溶胶、白炭黑、硅酸四乙酯、硅粉中的一种或多种；所述第一铝源选自氯化铝、硝酸铝、硫酸铝、异丙醇铝、拟薄水铝石中的一种或多种。
在优选的实施方式中，步骤1)中所述模板剂、硅源、第一铝源和水的摩尔比分别为，模板剂∶硅源＝(0.05-1.0)∶1，硅源∶第一铝源＝(30-400)∶1，水∶硅源＝(3-12)∶1，其中硅源以SiO 2计算，第一铝源以Al 2O 3计算。
在优选的实施方式中，步骤1)中由模板剂、硅源、第一铝源和水加热混合得到第一混合物的过程为：将模板剂、硅源、第一铝源和水在密闭容器中搅拌，搅拌时间为4h-20h，搅拌温度为90-150℃。
在优选的实施方式中，步骤2)中所述硅粉中含有两种不同尺寸的二氧化硅颗粒，其尺寸分别在0.1-2μm和4-12μm范围内，两者的质量比为(0.5-2.0)∶1；第二铝源选自氯化铝、硝酸铝、硫酸铝、醇铝、拟薄水铝石、氢氧化铝中的一种或多种。
在优选的实施方式中，步骤2)中第一混合物、硅粉和第二铝源的比例分别为：第一混合物与硅粉重量比为(0.2-0.8)∶1；硅粉与第二铝源的摩尔比为(30-400)∶1，其中硅粉以SiO 2计算，第二铝源以Al 2O 3计算。
在本申请中，对于步骤3)的所述成型的具体方式没有严格的限制，可以采用本领域惯用的催化剂成型方式，例如可以采用挤出成型法来实施。
根据本申请，在步骤3)中，第三混合物可以根据需要制成各种形状，例如可以制成条状，其切面可以为圆形、齿轮状、三叶草状、四叶草状或蜂窝状等形状。在优选的实施方式中，第三混合物的直径为1.0-6.0mm，长度为3-10mm。
在优选的实施方式中，步骤4)中所述碱源选自四丙基氢氧化铵、四乙基氢氧化铵、氨水、乙胺、乙二胺、正丁胺、己二胺、环己胺、哌啶、六亚甲基亚胺、高哌嗪、二环己基胺中的一种或多种。
在优选的实施方式中，步骤4)中所用的调节剂选自羟乙基纤维素、 羟甲基纤维素、羟丙基甲基纤维素、甲基纤维素、干酪素、阿拉伯树胶中的一种或多种。
在优选的实施方式中，步骤4)中所述第三混合物、碱源和调节剂的质量比例为，碱源∶第三混合物＝(0.1-0.4)∶1，调节剂∶第三混合物＝(0.01-0.05)∶1。
在优选的实施方式中，步骤4)中将第三混合物、碱源和调节剂接触得到第四混合物的过程为：首次将碱源和调节剂在30-60℃混合搅拌3-10小时，然后加入第三混合物，在密闭空间中于30-60℃静置5-10小时。
在优选的实施方式中，步骤5)中将第四混合物处理得到硅铝分子筛催化剂的过程为：将第四混合物在密闭空间中于130-190℃静置或搅拌12-72小时，然后还可以包括洗涤、干燥、焙烧、酸洗的步骤。根据本申请，所述洗涤(比如用去离子水洗涤至溶液的pH值为7-8)、干燥、焙烧可以采用常规方法进行，比如干燥可以采用的条件如下：干燥温度为80-150℃，干燥时间为5-12小时；焙烧可以采用的条件如下：焙烧温度为500-600℃，焙烧时间为4-10小时；酸洗可以采用的条件如下：酸洗温度为30-90℃，酸洗时间为2-10小时，酸可以为盐酸、硫酸、草酸或者硝酸中的至少一种，酸溶液的质量浓度可以为0.5％-5％。
在优选的实施方式中，通过本申请方法制备得到的硅铝分子筛催化剂的性质如上文第一方面中所述，在此不再做具体描述。
本申请第三方面提供了一种芳烃与烯烃气相烷基化的方法，包括使芳烃与烯烃在本申请的催化剂或者通过本申请的方法制备得到的催化剂存在下进行烷基化反应，得到烷基芳烃。
在优选的实施方式中，所述芳烃选自苯、烷基苯或者它们的组合，优选选自苯、甲苯、乙苯、正丙苯、异丙苯、正丁苯、异丁苯、叔丁苯或者它们的组合；所述烯烃选自C2-C6烯烃，优选选自乙烯、丙烯、正丁烯、异丁烯或者它们的组合。
在优选的实施方式中，所述烷基化反应的条件包括：反应温度为260-400℃，反应压力为0.1-3.0MPa，烯烃质量空速为0.1-10.0h -1，芳烃和烯烃摩尔比为2-20。
本申请第四方面提供了根据本申请的催化剂或者通过本申请的方法制备得到的催化剂在催化芳烃和烯烃的气相烷基化反应中的应用。
实施例
下面通过具体实施例对本申请做进一步说明，但并不构成对本申请的限制。
以下实施例和对比例中，催化剂的XRD谱图采用日本Rigaku公司Ultima IV型X-射线粉末衍射仪检测得到，电压选作35kV，电流选作30mA，扫描速度为1°·min -1。
以下实施例和对比例中，催化剂的酸性分布通过NH 3-TPD测试得到，其中采用天津市鹏翔科技有限公司200906PX18型号的程序升温脱附装置获得NH 3-TPD谱图。具体过程如下：取压片过筛后(20-40目)的样品0.05-0.20g放入石英样品管，首先在氦气气氛中升温活化1h稳定1h，然后降温至40℃以下，随后再次升温到100℃，在100℃下吸附氨气直至饱和，最后氦气吹扫1h后开始程序升温脱附，以10℃/min的升温速率升温到600℃，并记录工作曲线。
以下实施例和对比例中，催化剂的机械强度采用智能颗粒强度测定仪得到，其中采用大连鹏辉科技开发有限公司DLIII型智能颗粒强度测定仪测试焙烧后催化剂的机械强度，将被测催化剂横放在测定仪上面，测试催化剂破碎时所承受的最大压力，测试20颗催化剂的压碎强度后取其平均值。
以下实施例和对比例中，采用日立公司的Hitachi S-4800冷场发射高分辨率扫描电子显微镜获得SEM照片。晶粒尺寸分布通过统计相应的SEM照片中至少300个晶粒的数据后得到，并计算某晶粒分布范围内的晶粒数量占总统计数量的占比。
以下实施例和对比例中，催化剂的SiO 2/Al 2O 3摩尔比例通过ICP测试得到，其中采用Kontron的Model S-35型ICP-AES分析仪进行ICP测试，测试之前取50mg样品完全溶解在50g氢氟酸溶液里面。
以下实施例和对比例中，催化剂的孤立铝含量的测试方法如下：首先将合成的催化剂离子交换成Na型，其中将催化剂和浓度为0.5mol/L的氯化钠溶液按照固液质量比例1∶100混合，在室温下搅拌4h，结束后沥干溶液，再用去离子水洗涤固体，并用硝酸银溶液检测洗涤液，直至洗涤液中无白色沉淀生成，则结束洗涤，得到Na型催化剂；然后对Na型催化剂进行Co 2+离子交换，将Na型催化剂和浓度为 0.05mol/L的硝酸钴溶液按照固液质量比例1∶200混合，在室温下搅拌10h，结束后沥干溶液，再用去离子水洗涤固体，并用氨水溶液检测洗涤液，直至洗涤液中无蓝色沉淀生成，则结束洗涤，得到Co型催化剂。烘干后采用ICP测试Co型催化剂中的Co含量和Al含量，并按如下公式计算孤立铝含量：
孤立铝含量＝(1-2×C 钴/C 铝)×100％，
其中C 钴和C 铝分别为Co型催化剂中的Co含量和Al含量。
以下实施例和对比例中，如无其它说明，所用原料和试剂均为市售材料，纯度为试剂纯。
【实施例1】
将27.7克浓度为40wt％的四丙基氢氧化铵水溶液、60克白炭黑、13.32克十八水硫酸铝和54克水混合均匀，在密闭容器中于90℃搅拌20h，得到混合物A1。将12克混合物A1、60克硅粉(硅粉中含有尺寸分别在0.3-1.2μm和5-9μm范围内的两种二氧化硅颗粒，两者的质量分别为20克和40克)、13.32克十八水硫酸铝混合得到混合物B1。将混合物B1挤出成型得到混合物C1(混合物C1为圆柱状，直径为1.8mm，长度为5mm)。将5克乙胺和0.5克羟乙基纤维素在50℃混合搅拌5小时，然后加入50克混合物C1，在密闭空间中于30℃静置10小时得到混合物D1。再将混合物D1在密闭空间中于130℃静置72小时，然后经过去离子水洗涤至pH值为8，80℃烘干12小时，500℃焙烧10小时，采用质量浓度为3％的草酸于60℃酸洗5小时，得到硅铝分子筛催化剂E1。
硅铝分子筛催化剂E1的XRD谱图如图1所示，其具有典型的MFI拓扑结构衍射峰，表明为ZSM-5分子筛催化剂。硅铝分子筛催化剂E1的SEM照片如图2所示，从图中可以看出所述催化剂具有两种尺寸的晶粒，通过统计，两种晶粒的尺寸分别在50-200nm和400-1000nm范围内，其晶粒数占比分别为35％和65％。硅铝分子筛催化剂E1的NH 3-TPD谱图如图3所示，谱图中出现三个峰，按照脱附温度由低到高将三个峰分别编号为P1，P2和P3，三个峰的峰顶位置对应的脱附温度分别为196℃、265℃和385℃，三个峰的高度H1、H2和H3之比分别为：H2/H1＝0.66，H3/H2＝0.82；H3/H1＝0.54；由脱附曲线在100-240 ℃、240-300℃和300-500℃三个温度区间内的积分面积计算得到催化剂的弱酸量S1、中强酸量S2和强酸量S3之比分别为：S2/S1＝0.46，S2/S3＝0.49，S3/S1＝0.94，相应地弱酸量S1、中强酸量S2和强酸量S3占总酸量的比例分别为42％，19％和39％。
通过测试，硅铝分子筛催化剂E1的机械强度为155N/cm，SiO 2/Al 2O 3摩尔比为50.8，孤立铝含量为99.0％。
【实施例2】
将253克浓度为40wt％的四丙基氢氧化铵水溶液、133克四丙基溴化铵、208.3克硅酸四乙酯、2.22克十八水硫酸铝和60克水混合均匀，在密闭容器中于150℃搅拌4h，得到混合物A2。将48克混合物A2、60克硅粉(硅粉中含有尺寸分别在1.2-2μm和9-12μm范围内的两种二氧化硅颗粒，两者的质量分别为30克和30克)、1.665克十八水硫酸铝混合得到混合物B2。将混合物B2挤出成型得到混合物C2(混合物C2为圆柱状，直径为2.2mm，长度为5mm)。将20克环己胺、0.5克干酪素和2克羟丙基甲基纤维素的混合物在50℃混合搅拌5小时，然后加入50克混合物C2，在密闭空间中于60℃静置5小时得到混合物D2。再将混合物D2在密闭空间中于190℃静置12小时，然后经过去离子水洗涤至pH值为7，150℃烘干5小时，600℃焙烧4小时，采用质量浓度为0.5％的草酸于30℃酸洗10小时，得到硅铝分子筛催化剂E2。
硅铝分子筛催化剂E2的XRD谱图如图4所示，其具有典型的MFI拓扑结构衍射峰，表明为ZSM-5分子筛催化剂。硅铝分子筛催化剂E2的SEM照片显示所述催化剂具有两种尺寸的晶粒，通过统计，两种晶粒的尺寸分别在250-300nm和1000-1600nm范围内，其晶粒数占比分别为40％和60％。硅铝分子筛催化剂E2的NH 3-TPD谱图中出现三个峰，按照脱附温度由低到高将三个峰分别编号为P1，P2和P3，三个峰的峰顶位置对应的脱附温度分别为191℃、260℃和381℃，三个峰的高度H1、H2和H3之比分别为：H2/H1＝0.51，H3/H2＝0.80，H3/H1＝0.41；由脱附曲线在100-240℃、240-300℃和300-500℃三个温度区间内的积分面积计算得到催化剂的弱酸量S1、中强酸量S2和强酸量S3之比分别为：S2/S1＝0.48，S2/S3＝0.52，S3/S1＝0.92，相应地弱酸量S1、中强 酸量S2和强酸量S3占总酸量的比例分别为42％，20％和38％。
通过测试，硅铝分子筛催化剂E2的机械强度为112N/cm，SiO 2/Al 2O 3摩尔比为398，孤立铝含量为99.6％。
【实施例3】
将126克浓度为40wt％的四丙基氢氧化铵水溶液、66克四丙基溴化铵、208.3克硅酸四乙酯、6.66克十八水硫酸铝和50克水混合均匀，在密闭容器中于120℃搅拌12h，得到混合物A3。将24克混合物A3、60克硅粉(硅粉中含有尺寸分别在0.1-0.3μm和4-7μm范围内的两种二氧化硅颗粒，两者的质量分别为40克和20克)、6.66克十八水硫酸铝混合得到混合物B3。将混合物B3挤出成型得到混合物C3(混合物C3为圆柱状，直径为1.2mm，长度为5mm)。将10克正丁胺和1.5克阿拉伯树胶在50℃混合搅拌5小时，然后加入50克混合物C3，在密闭空间中于40℃静置7小时得到混合物D3。再将混合物D3在密闭空间中于170℃静置36小时，然后经过去离子水洗涤至pH值为7.5，100℃烘干8小时，550℃焙烧6小时，采用质量浓度为3％的盐酸于60℃酸洗6小时，得到硅铝分子筛催化剂E3。
硅铝分子筛催化剂E3的XRD谱图如图5所示，其具有典型的MFI拓扑结构衍射峰，表明为ZSM-5分子筛催化剂。硅铝分子筛催化剂E3的SEM照片显示所述催化剂具有两种尺寸的晶粒，通过统计，两种晶粒的尺寸分别在10-100nm和400-700nm范围内，其晶粒数占比分别为56％和44％。硅铝分子筛催化剂E3的NH 3-TPD谱图中出现三个峰，按照脱附温度由低到高将三个峰分别编号为P1，P2和P3，三个峰的峰顶位置对应的脱附温度分别为208℃、277℃和399℃，三个峰的高度H1、H2和H3之比分别为：H2/H1＝0.79，H3/H2＝0.89，H3/H1＝0.70；由脱附曲线在100-240℃、240-300℃和300-500℃三个温度区间内的积分面积计算得到催化剂的弱酸量S1、中强酸量S2和强酸量S3比例分别为：S2/S1＝0.41，S2/S3＝0.38，S3/S1＝1.07，相应地弱酸量S1、中强酸量S2和强酸量S3占总酸量的比例分别为40％，17％和43％。
通过测试，硅铝分子筛催化剂E3的机械强度为145N/cm，SiO 2/Al 2O 3摩尔比为125，孤立铝含量为99.2％。
【对比例1】
参照实施例3的方法进行催化剂的制备，不同之处在于，所使用的硅粉中仅含一种尺寸的二氧化硅颗粒，其尺寸在0.1-0.3μm范围内，且步骤4)中未添加调节剂。催化剂的具体制备过程如下：将126克浓度为40wt％的四丙基氢氧化铵水溶液、66克四丙基溴化铵、208.3克硅酸四乙酯、6.66克十八水硫酸铝和50克水混合均匀，在密闭容器中于120℃搅拌12h，得到混合物A4。将24克混合物A4、60克硅粉(硅粉中仅含一种尺寸的二氧化硅颗粒，其尺寸在0.1-0.3μm范围内)、6.66克十八水硫酸铝混合得到混合物B4。将混合物B4挤出成型得到混合物C4(混合物C4为圆柱状，直径为1.2mm，长度为5mm)。将10克正丁胺在50℃搅拌5小时，然后加入50克混合物C4，在密闭空间中于40℃静置7小时得到混合物D4。再将混合物D4在密闭空间中于170℃静置36小时，然后经过去离子水洗涤至pH值为7.5，100℃烘干8小时，550℃焙烧6小时，采用质量浓度为3％的盐酸于60℃酸洗6小时，得到硅铝分子筛催化剂F1。
硅铝分子筛催化剂F1的SEM照片如图6所示，从图中可以看出所述催化剂仅具有一种尺寸的晶粒，通过统计，所述晶粒的尺寸在180-250nm范围内。硅铝分子筛催化剂F1的NH 3-TPD谱图如图7所示，谱图中出现两个峰，按照脱附温度由低到高将两个峰分别编号为P1和P2，两个峰的峰顶位置对应的脱附温度分别为194℃和396℃，两个峰的高度H1和H2之比为：H2/H1＝0.96，由脱附曲线在100-240℃、240-300℃和300-500℃三个温度区间内的积分面积计算得到催化剂的弱酸量S1、中强酸量S2和强酸量S3比例分别为：S2/S1＝0.28，S2/S3＝0.17，S3/S1＝1.63，相应地弱酸量S1、中强酸量S2和强酸量S3占总酸量的比例分别为34％，10％和56％。
通过测试，硅铝分子筛催化剂F1的机械强度为155N/cm，SiO 2/Al 2O 3摩尔比为128，孤立铝含量为95.8％。
【对比例2】
参照实施例1的方法进行催化剂的制备，不同之处在于，改变了调节剂羟乙基纤维素的加料顺序。催化剂的具体制备过程如下：将27.7克浓度为40wt％的四丙基氢氧化铵水溶液、60克白炭黑、13.32克十八 水硫酸铝、54克水和0.5克羟乙基纤维素混合均匀，在密闭容器中于90℃搅拌20h，得到混合物A5。将12克混合物A5、60克硅粉(硅粉中含有尺寸分别在0.3-1.2μm和5-9μm范围内的两种二氧化硅颗粒，两者的质量分别为20克和40克)、13.32克十八水硫酸铝混合得到混合物B5。将混合物B5挤出成型得到混合物C5(混合物C5为圆柱状，直径为1.8mm，长度为5mm)。将5克乙胺在50℃搅拌5小时，然后加入50克混合物C5，在密闭空间中于30℃静置10小时得到混合物D5。再将混合物D5在密闭空间中于130℃静置72小时，然后经过去离子水洗涤至pH值为8，80℃烘干12小时，500℃焙烧10小时，采用质量浓度为3％的草酸于60℃酸洗5小时，得到硅铝分子筛催化剂F2。
硅铝分子筛催化剂F2的SEM照片显示其具有两种尺寸的晶粒，通过统计，两种晶粒的尺寸分别在200-420nm和1500-2000nm范围内。硅铝分子筛催化剂F2的NH 3-TPD谱图中出现两个峰，按照脱附温度由低到高将两个峰分别编号为P1和P2，两个峰的峰顶位置对应的脱附温度分别为197℃和399℃，两个峰的高度H1和H2之比为：H2/H1＝0.76；由脱附曲线在100-240℃、240-300℃和300-500℃三个温度区间内的积分面积计算得到催化剂的弱酸量S1、中强酸量S2和强酸量S3比例分别为：S2/S1＝0.26，S2/S3＝0.16，S3/S1＝1.60，相应地弱酸量S1、中强酸量S2和强酸量S3占总酸量的比例分别为35％，9％和56％。
通过测试，硅铝分子筛催化剂F2的机械强度为135N/cm，SiO 2/Al 2O 3摩尔比为52.4，孤立铝含量为96.6％。
【对比例3】
参照实施例3的方法进行催化剂的制备，不同之处在于，所使用的硅粉中仅含一种尺寸的二氧化硅颗粒，其尺寸在0.1-0.3μm范围内。催化剂的具体制备过程如下：将126克浓度为40wt％的四丙基氢氧化铵水溶液、66克四丙基溴化铵、208.3克硅酸四乙酯、6.66克十八水硫酸铝和50克水混合均匀，在密闭容器中于120℃搅拌12h，得到混合物A6。将24克混合物A6、60克硅粉(硅粉中仅含一种尺寸的二氧化硅颗粒，尺寸在0.1-0.3μm范围内)、6.66克十八水硫酸铝混合得到混合物B6。将混合物B6挤出成型得到混合物C6(混合物C6为圆柱状， 直径为1.2mm，长度为5mm)。将10克正丁胺和1.5克阿拉伯树胶在50℃搅拌5小时，然后加入50克混合物C6，在密闭空间中于40℃静置7小时得到混合物D6。再将混合物D6在密闭空间中于170℃静置36小时，然后经过去离子水洗涤至pH值为7.5，100℃烘干8小时，550℃焙烧6小时，采用质量浓度为3％的盐酸于60℃酸洗6小时，得到硅铝分子筛催化剂F3。
硅铝分子筛催化剂F3的SEM照片显示其仅具有一种尺寸的晶粒，通过统计，所述晶粒的尺寸在170-245nm范围内。硅铝分子筛催化剂F3的NH 3-TPD谱图中出现两个峰，按照脱附温度由低到高将两个峰编号分别为P1和P2，两个峰的峰顶位置对应的脱附温度分别为189℃和366℃，两个峰的高度H1和H2之比为：H2/H1＝0.76；由脱附曲线在100-240℃、240-300℃和300-500℃三个温度区间内的积分面积计算得到催化剂的弱酸量S1、中强酸量S2和强酸量S3比例分别为：S2/S1＝0.43，S2/S3＝0.35，S3/S1＝1.23，相应地弱酸量S1、中强酸量S2和强酸量S3占总酸量的比例分别为38％，16％和46％。
通过测试，硅铝分子筛催化剂F3的机械强度为142N/cm，SiO 2/Al 2O 3摩尔比为126，孤立铝含量为97.3％。
【对比例4】
按照参考文献CN 107512729A的方法制备催化剂，具体流程如下：
制备合成态ZSM-5分子筛：采用碱性硅溶胶、十八水合硫酸铝、四丙基氢氧化铵(TPAOH)和水为合成原料，将上述原料按照物料配比(摩尔比)为：SiO 2/Al 2O 3＝180，TPAOH/SiO 2＝0.22，H 2O/SiO 2＝18，混合均匀后，装入不锈钢反应釜中，在搅拌情况下于150℃晶化3天。晶化结束后过滤、洗涤、干燥得到合成态的ZSM-5分子筛。
制备ZSM-5分子筛前体：将上述合成态ZSM-5分子筛41.866克、碱性硅溶胶(SiO 2含量为40.0wt％)37.5克、甲基纤维素0.5616克、硝酸水溶液(浓度为5wt％)混合均匀，通过挤条成型制备得到ZSM-5分子筛含量为70wt％、横截面为四叶草形的条状分子筛前体，其直径为1.2mm，长度为5mm。
制备目标催化剂：将1.97克铝酸钠(Al 2O 3含量为43.0wt％，Na 2O含量为35.0wt％)、247克水、8.865克正丁胺(浓度为99.0wt％)混合均 匀，再与上述制得的全部分子筛前体混合，将所得混合物置于150℃晶化28小时。晶化结束后过滤、洗涤、干燥、550℃空气中焙烧5小时、浓度为10wt％的硫酸铵溶液铵交换3次，再在550℃空气中焙烧5小时得到无粘结剂的ZSM-5分子筛催化剂F4。
催化剂F4的SEM照片显示其仅具有一种尺寸的晶粒，通过统计，所述晶粒的尺寸在300-450nm范围内。催化剂F4的NH 3-TPD谱图中出现两个峰，按照脱附温度由低到高将两个峰分别编号为P1和P2，两个峰的峰顶位置对应的脱附温度分别为193℃和390℃，两个峰的高度H1和H2之比为：H2/H1＝1.21；由脱附曲线在100-240℃、240-300℃和300-500℃三个温度区间内的积分面积计算得到催化剂的弱酸量S1、中强酸量S2和强酸量S3比例分别为：S2/S1＝0.37，S2/S3＝0.18，S3/S1＝2.03，相应地弱酸量S1、中强酸量S2和强酸量S3占总酸量的比例分别为29％，11％和60％。
通过测试，催化剂F4的机械强度为78N/cm，SiO 2/Al 2O 3摩尔比为145，孤立铝含量为93.7％。
表1 各实施例和对比例所得催化剂的性质
Figure PCTCN2021125964-appb-000001
由表1的数据可以看出，本申请催化剂的晶粒尺寸呈双峰分布，其NH 3-TPD谱图中脱附曲线显示出明显的三个峰。并且，与对比例所得的催化剂相比，本申请催化剂具有显著不同的酸性分布，特别是中强酸量占比显著提高，同时强酸量占比降低而弱酸量占比提高。
【测试例1】
将实施例1-3制备的硅铝分子筛催化剂E1-E3以及对比例1-4制备 的催化剂F1-F4分别应用到苯与乙烯的气相烷基化反应中，在反应温度380℃，反应压力为1.5MPa，乙烯质量空速为2.2h -1，苯和乙烯摩尔比为5.5的条件下反应10h，检测烷基化产物中二甲苯含量，二乙苯和三乙苯含量，并计算乙烯转化率和乙基选择性。反应结果见下表2，其中：
乙烯转化率＝(总乙烯进料量-反应器流出物中的乙烯量)/总乙烯进料量×100％
乙基选择性＝(反应生成的乙苯摩尔数+二乙苯摩尔数×2+三乙苯摩尔数×3)/反应消耗的乙烯摩尔数×100％
表2 苯和乙烯气相烷基化反应结果
Figure PCTCN2021125964-appb-000002
【测试例2】
将实施例1-3制备的硅铝分子筛催化剂E1-E3以及对比例1-4制备的催化剂F1-F4分别在超高乙烯空速反应条件下测试其在苯和乙烯的气相烷基化反应中的单程寿命，具体测试条件如下，反应温度400℃，压力为2.0MPa，乙烯质量空速为6h -1，苯和乙烯摩尔比为2，单程寿命是指从反应开始至乙烯转化率下降至初始转化率的60％所经过的时间，反应结果见下表3。
表3 超高空速反应条件下催化剂的单程寿命测试结果
催化剂编号 单程寿命，h
E1 240
E2 282
E3 256
F1 175
F2 146
F3 155
F4 123
如表2的数据所示，与对比例所得的催化剂相比，本申请的催化剂在芳烃与烯烃的烷基化反应中具有较高的活性和选择性，可以显著降低副产物含量，提高烯烃转化率和产物选择性。具体地，在苯和乙烯烷基化制乙苯的反应中，所得烷基化产物的关键杂质二甲苯质量含量可至500ppm以下，二乙苯和三乙苯质量含量可至8％以下。
如表3的数据所示，与对比例所得的催化剂相比，本申请的催化剂在超高乙烯空速反应条件下在苯和乙烯的气相烷基化反应中具有较高的稳定性，单程寿命明显增加。
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公开的内容。

Claims (13)

  1. 一种硅铝分子筛催化剂，所述催化剂的NH 3-TPD谱图中脱附曲线显示出三个峰P1、P2和P3，所述三个峰P1、P2和P3的峰顶位置对应的脱附温度分别在180-220℃、250-290℃和370-410℃的范围内，优选分别在190-210℃、260-280℃和380-400℃的范围内。
  2. 按照权利要求1所述的催化剂，其中所述三个峰P1、P2和P3的峰高H1、H2和H3满足H1＞H2＞H3，优选地所述峰高H1、H2和H3之间满足如下关系：
    H2/H1＝(0.5-0.8)∶1；
    H3/H2＝(0.8-0.9)∶1；以及
    H3/H1＝(0.4-0.7)∶1。
  3. 按照权利要求1或2所述的催化剂，其中所述催化剂的弱酸量S1、中强酸量S2和强酸量S3之间满足如下关系：
    S2/S1＝(0.38-0.52)∶1，优选地，S2/S1＝(0.4-0.5)∶1；
    S2/S3＝(0.32-0.58)∶1，优选地，S2/S3＝(0.35-0.55)∶1；以及
    S3/S1＝(0.8-1.2)∶1，优选地，S3/S1＝(0.9-1.1)∶1，
    其中所述弱酸量S1、中强酸量S2和强酸量S3之间的比例由所述催化剂的NH 3-TPD谱图中脱附曲线在100-240℃、240-300℃和300-500℃的温度区间内的积分面积的比例计算得到。
  4. 按照权利要求1-3中任一项所述的催化剂，其中所述催化剂的弱酸量S1占总酸量的比例为40-50％，中强酸量S2占总酸量的比例为15-25％，强酸量S3占总酸量的比例为35-45％，其中所述弱酸量S1、中强酸量S2和强酸量S3占总酸量的比例分别由所述催化剂的NH 3-TPD谱图中脱附曲线在100-240℃、240-300℃和300-500℃的温度区间内的积分面积相对于所述催化剂的NH 3-TPD谱图中脱附曲线在100-500℃温度区间内的总积分面积的比例计算得到。
  5. 按照权利要求1-4中任一项所述的催化剂，其中所述催化剂为无粘结剂的硅铝分子筛催化剂，优选地所述硅铝分子筛为具有十元环或十二元环孔结构的酸性分子筛，更优选为ZSM-5分子筛。
  6. 按照权利要求1-5中任一项所述的催化剂，其中所述催化剂具有以下特征中的一个或多个：
    所述催化剂的超强酸量相对于总酸量的比例小于5％，优选小于3％，其中所述超强酸量相对于总酸量的比例由所述催化剂的NH 3-TPD谱图中脱附曲线在500℃以上的温度区间内的积分面积相对于所述催化剂的NH 3-TPD谱图中脱附曲线在100-500℃温度区间内的总积分面积的比例计算得到；
    所述催化剂上未额外负载任何的改性金属组分或者非金属组分，例如锌、镁、钙、铁、钴、镍、磷、镧、铜、锆、铬、锰、银、钌、钯、铂、钛、锡、锶、钡、钒、锂等；
    所述催化剂具有两种不同尺寸的晶粒，其尺寸分别在10-300nm和400-1600nm范围内；优选地，尺寸在10-300nm内的晶粒数量占总晶粒数的5-60％，尺寸在400-1600nm内的晶粒数量占总晶粒数的40-95％；
    所述催化剂中孤立铝含量为97.5-100％，优选为99-100％；
    所述催化剂的机械强度为100-170N/cm，优选为110-160N/cm；以及
    所述催化剂的SiO 2/Al 2O 3摩尔比为30-400。
  7. 一种制备硅铝分子筛催化剂的方法，包括如下步骤：
    1)将模板剂、硅源、第一铝源和水加热混合得到第一混合物；
    2)将第一混合物、硅粉和第二铝源混合得到第二混合物；
    3)将第二混合物成型得到第三混合物；
    4)将第三混合物、碱源和调节剂接触得到第四混合物，其中所述调节剂为多羟基高分子化合物，优选选自羟乙基纤维素、羟甲基纤维素、羟丙基甲基纤维素、甲基纤维素、干酪素、阿拉伯树胶，或者它们的任意组合；以及
    5)对第四混合物进行处理得到所述硅铝分子筛催化剂，其中所述处理包括焙烧。
  8. 按照权利要求7所述的方法，其中所述步骤1)具有以下特征中的一个或多个：
    所述的模板剂选自四丙基氢氧化铵、四丙基溴化铵、四乙基氢氧化铵、四乙基溴化铵或者它们的组合，所述硅源选自硅溶胶、白炭黑、硅酸四乙酯、硅粉或者它们的组合，所述第一铝源选自氯化铝、硝酸铝、硫酸铝、异丙醇铝、拟薄水铝石或者它们的组合；
    所述模板剂、硅源、第一铝源和水的摩尔比满足模板剂∶硅源 ＝(0.05-1.0)∶1，硅源∶第一铝源＝(30-400)∶1，以及水∶硅源＝(3-12)∶1，其中硅源以SiO 2计算，第一铝源以Al 2O 3计算；以及
    步骤1)的所述加热混合包括将所述模板剂、硅源、第一铝源和水在密闭容器中搅拌，搅拌时间为4h-20h，搅拌温度为90-150℃。
  9. 按照权利要求7或8所述的方法，其中所述步骤2)具有以下特征中的一个或多个：
    所述硅粉中含有两种不同尺寸的二氧化硅颗粒，其尺寸分别在0.1-2μm和4-12μm范围内，两者的质量比为(0.5-2.0)∶1；
    所述第二铝源选自氯化铝、硝酸铝、硫酸铝、醇铝、拟薄水铝石、氢氧化铝或者它们的组合；以及
    所述第一混合物、硅粉和第二铝源的比例满足第一混合物与的硅粉重量比为(0.2-0.8)∶1；硅粉与第二铝源的摩尔比为(30-400)∶1；其中硅粉以SiO 2计算，第二铝源以Al 2O 3计算。
  10. 按照权利要求7-9中任一项所述的方法，其中所述步骤4)具有以下特征中的一个或多个：
    所述碱源选自四丙基氢氧化铵、四乙基氢氧化铵、氨水、乙胺、乙二胺、正丁胺、己二胺、环己胺、哌啶、六亚甲基亚胺、高哌嗪、二环己基胺或者它们的组合；
    所述第三混合物、碱源和调节剂的质量比满足碱源∶第三混合物＝(0.1-0.4)∶1；调节剂∶第三混合物＝(0.01-0.05)∶1；以及
    步骤4)的所述接触包括将碱源和调节剂于30-60℃混合搅拌3-10小时，然后加入第三混合物，在密闭空间中于30-60℃静置5-10小时。
  11. 按照权利要求7-10中任一项所述的方法，其中步骤5)的所述处理包括将第四混合物在密闭空间中于130-190℃下静置或搅拌12-72小时，然后再进行洗涤、干燥、焙烧和酸洗。
  12. 一种芳烃与烯烃气相烷基化的方法，包括使芳烃与烯烃在权利要求1-6中任一所述的催化剂或按照权利要求7-11中任一所述的方法制备得到的催化剂存在下接触进行烷基化反应，得到烷基芳烃。
  13. 按照权利要求12所述的方法，其中所述芳烃选自苯、烷基苯或者它们的组合，优选选自苯、甲苯、乙苯、正丙苯、异丙苯、正丁苯、异丁苯、叔丁苯，或者它们的组合；所述烯烃选自C2-C6烯烃，优选选自乙烯、丙烯、正丁烯、异丁烯，或者它们的组合；
    优选地，所述烷基化反应的条件包括：反应温度为260-400℃，反应压力为0.1-3.0MPa，烯烃质量空速为0.1-10.0h -1，芳烃和烯烃摩尔比为2-20。
PCT/CN2021/125964 2020-10-26 2021-10-25 硅铝分子筛催化剂及其制备和应用 Ceased WO2022089338A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP21885065.9A EP4234084A4 (en) 2020-10-26 2021-10-25 MOLECULAR SIEVE TYPE CATALYST BASED ON SILICON-ALUMINUM, ITS PREPARATION AND CORRESPONDING APPLICATION
KR1020237017870A KR20230097108A (ko) 2020-10-26 2021-10-25 규소-알루미늄 분자체 촉매, 이의 제조 및 적용
US18/250,320 US20230398524A1 (en) 2020-10-26 2021-10-25 Silicon-aluminum molecular sieve catalyst, and preparation and application thereof
JP2023525051A JP7812851B2 (ja) 2020-10-26 2021-10-25 ケイ素－アルミニウム分子篩触媒、ならびにその調製および利用
CA3199797A CA3199797A1 (en) 2020-10-26 2021-10-25 Silicon-aluminum molecular sieve catalyst, and preparation and application thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011158111.7A CN114471672B (zh) 2020-10-26 2020-10-26 一种苯和乙烯烷基化的催化剂及其制备方法和应用
CN202011158111.7 2020-10-26

Publications (1)

Publication Number Publication Date
WO2022089338A1 true WO2022089338A1 (zh) 2022-05-05

Family

ID=81383340

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/125964 Ceased WO2022089338A1 (zh) 2020-10-26 2021-10-25 硅铝分子筛催化剂及其制备和应用

Country Status (8)

Country Link
US (1) US20230398524A1 (zh)
EP (1) EP4234084A4 (zh)
JP (1) JP7812851B2 (zh)
KR (1) KR20230097108A (zh)
CN (1) CN114471672B (zh)
CA (1) CA3199797A1 (zh)
TW (1) TWI893234B (zh)
WO (1) WO2022089338A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471685A (zh) * 2020-10-26 2022-05-13 中国石油化工股份有限公司 一种无粘结剂Beta分子筛催化剂及其制备方法和应用
CN115894142A (zh) * 2022-10-19 2023-04-04 东南大学 适用于制备胺类化合物的催化剂、催化剂制备及催化方法
CN116618020A (zh) * 2023-07-24 2023-08-22 山东恒昌圣诚化工股份有限公司 一种净化空气的分子筛及其制备方法
CN119612540A (zh) * 2023-09-12 2025-03-14 中国石油化工股份有限公司 一种zsm-5分子筛及其制备和应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118005029B (zh) * 2022-11-08 2026-01-02 中国石油化工股份有限公司 Lsx分子筛、调控lsx分子筛晶簇大小的方法及其应用
CN120132895A (zh) * 2025-04-23 2025-06-13 成都锐逊科技有限公司 一种双功能二氧化碳加氢联产乙苯分子筛催化剂及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102441414A (zh) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 一种用于烷基化反应催化剂及其制备方法和应用
CN103007983A (zh) * 2012-10-08 2013-04-03 太原理工大学 一种用于甲醇制汽油的hzsm-5分子筛催化剂及其制备方法和应用
CN103818925A (zh) * 2014-03-17 2014-05-28 中国石油大学(华东) 酸碱耦合制备等级孔zsm-5分子筛的方法
CN103878013A (zh) * 2012-12-20 2014-06-25 中国石油化工股份有限公司 甲苯歧化与烷基转移催化剂及其制备方法和应用
CN104549437A (zh) * 2013-10-12 2015-04-29 中国石油化工股份有限公司 一种磷和稀土改性的zsm-5分子筛催化剂及其制备方法和应用
CN104646047A (zh) * 2013-11-22 2015-05-27 中国石油天然气股份有限公司 一种多级孔复合分子筛及其制备和应用
CN104759290A (zh) * 2015-04-29 2015-07-08 太原理工大学 Zn改性的多级孔HZSM-5催化剂及其在液化气芳构化中的应用
CN106807324A (zh) * 2015-12-02 2017-06-09 中国科学院大连化学物理研究所 一种分子筛酸性和孔结构的复合调变方法
CN107512729A (zh) 2016-06-18 2017-12-26 中国石油化工股份有限公司 无粘结剂zsm‑5分子筛的制备方法
FR3092104A1 (fr) * 2019-01-29 2020-07-31 Panjin Institute Of Industrial Technology, Dalian University Of Technology Procédé de préparation d'un tamis moléculaire composite sans liant et son usage dans la désulfuration par adsorption du pétrole

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009262098A (ja) * 2008-04-28 2009-11-12 Ne Chemcat Corp 選択還元触媒を用いた排気ガス浄化方法
CN101584993B (zh) * 2009-06-19 2011-11-16 中国科学院大连化学物理研究所 一种稀乙烯与苯烷基化制乙苯用催化剂及其制备方法
CN105271300B (zh) * 2014-07-02 2018-05-18 中国石油化工股份有限公司 一种分子筛催化剂、制备方法以及应用
CN107511170B (zh) * 2016-06-18 2020-12-29 中国石油化工股份有限公司 无粘结剂zsm-5分子筛催化剂的制备方法
KR20190101162A (ko) * 2018-02-22 2019-08-30 서울대학교산학협력단 벤젠 제조용 촉매 및 그 제조 방법
CN110882715B (zh) * 2018-09-07 2021-03-26 中国科学院大连化学物理研究所 一种乙醇与苯气相烷基化制备乙苯催化剂及其制备和应用

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102441414A (zh) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 一种用于烷基化反应催化剂及其制备方法和应用
CN103007983A (zh) * 2012-10-08 2013-04-03 太原理工大学 一种用于甲醇制汽油的hzsm-5分子筛催化剂及其制备方法和应用
CN103878013A (zh) * 2012-12-20 2014-06-25 中国石油化工股份有限公司 甲苯歧化与烷基转移催化剂及其制备方法和应用
CN104549437A (zh) * 2013-10-12 2015-04-29 中国石油化工股份有限公司 一种磷和稀土改性的zsm-5分子筛催化剂及其制备方法和应用
CN104646047A (zh) * 2013-11-22 2015-05-27 中国石油天然气股份有限公司 一种多级孔复合分子筛及其制备和应用
CN103818925A (zh) * 2014-03-17 2014-05-28 中国石油大学(华东) 酸碱耦合制备等级孔zsm-5分子筛的方法
CN104759290A (zh) * 2015-04-29 2015-07-08 太原理工大学 Zn改性的多级孔HZSM-5催化剂及其在液化气芳构化中的应用
CN106807324A (zh) * 2015-12-02 2017-06-09 中国科学院大连化学物理研究所 一种分子筛酸性和孔结构的复合调变方法
CN107512729A (zh) 2016-06-18 2017-12-26 中国石油化工股份有限公司 无粘结剂zsm‑5分子筛的制备方法
FR3092104A1 (fr) * 2019-01-29 2020-07-31 Panjin Institute Of Industrial Technology, Dalian University Of Technology Procédé de préparation d'un tamis moléculaire composite sans liant et son usage dans la désulfuration par adsorption du pétrole

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471685A (zh) * 2020-10-26 2022-05-13 中国石油化工股份有限公司 一种无粘结剂Beta分子筛催化剂及其制备方法和应用
CN115894142A (zh) * 2022-10-19 2023-04-04 东南大学 适用于制备胺类化合物的催化剂、催化剂制备及催化方法
CN116618020A (zh) * 2023-07-24 2023-08-22 山东恒昌圣诚化工股份有限公司 一种净化空气的分子筛及其制备方法
CN119612540A (zh) * 2023-09-12 2025-03-14 中国石油化工股份有限公司 一种zsm-5分子筛及其制备和应用
CN119612540B (zh) * 2023-09-12 2025-10-31 中国石油化工股份有限公司 一种zsm-5分子筛及其制备和应用

Also Published As

Publication number Publication date
EP4234084A4 (en) 2024-05-01
TW202216598A (zh) 2022-05-01
CN114471672A (zh) 2022-05-13
US20230398524A1 (en) 2023-12-14
TWI893234B (zh) 2025-08-11
JP7812851B2 (ja) 2026-02-10
JP2023547894A (ja) 2023-11-14
KR20230097108A (ko) 2023-06-30
EP4234084A1 (en) 2023-08-30
CN114471672B (zh) 2023-04-07
CA3199797A1 (en) 2022-05-05

Similar Documents

Publication Publication Date Title
TWI893234B (zh) 矽鋁分子篩催化劑及其製備和用途
TWI674148B (zh) Ｓｃｍ－１０分子篩、其製造方法及其用途
CN105727930A (zh) 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用
JP4744530B2 (ja) ジエチレントリアミンを使用したベータゼオライトの合成方法
CN115196650A (zh) 一种金属改性的介孔zsm-5分子筛及其制备方法
CN115140745B (zh) 一种金属改性的多级孔zsm-5分子筛及其制备方法
JP2002509477A (ja) アルキル化触媒およびその応用
KR20150056624A (ko) 저 제올라이트 촉매 조성물을 이용하는 고선택적 알킬화 방법
CN115999621B (zh) 一种硅铝分子筛催化剂及其制备和应用
US20250262612A1 (en) Solid acid alkylation catalyst, and preparation method therefor and use thereof
CN114425412A (zh) 烷基芳烃非临氢异构化催化剂及其制备方法与应用
CN115999622B (zh) 一种硅铝型分子筛催化剂及其制备和应用
CN113620766B (zh) 一种高选择性线性烷基苯的生产方法
RU2846032C1 (ru) Кремниево-алюминиевый молекулярно-ситовый катализатор, его приготовление и применение
CN108970636B (zh) 一种苯烷基化催化剂的制备方法
CN115650817A (zh) 一种采用纳米片状分子筛催化乙醇和苯制乙苯的方法
CN106032279B (zh) 硅铝分子筛及其制备方法和应用以及一种环酮转化的方法
CN100497176C (zh) 一种mww结构硅铝分子筛及其制备方法
CN119951572B (zh) 含Beta/Y复合分子筛的催化剂、制备方法及其应用和芳烃液相烷基转移的方法
CN119899073A (zh) 一种烷基化方法
WO2026086013A1 (zh) 一种催化剂组合物及其制备和应用
CA3304650A1 (en) Zsm-5 molecular sieve, catalyst for preparing ethylbenzene by means of alkylation of benzene, and preparation and use thereof
CN119972159A (zh) 无粘结剂zsm-5分子筛催化剂及其制备方法和应用
CN117920334A (zh) 一种mww结构分子筛催化剂及其制备方法和应用
CN115722256A (zh) 一种烷基化催化剂的制备方法、催化剂和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21885065

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3199797

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2023525051

Country of ref document: JP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112023007751

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 202347035631

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 20237017870

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021885065

Country of ref document: EP

Effective date: 20230526

ENP Entry into the national phase

Ref document number: 112023007751

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20230425

WWG Wipo information: grant in national office

Ref document number: 2023113394

Country of ref document: RU