WO2025119035A1 - 改性分子筛及其制备方法、催化剂及其应用、苯胺合成二苯胺的方法 - Google Patents

改性分子筛及其制备方法、催化剂及其应用、苯胺合成二苯胺的方法 Download PDF

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WO2025119035A1
WO2025119035A1 PCT/CN2024/134560 CN2024134560W WO2025119035A1 WO 2025119035 A1 WO2025119035 A1 WO 2025119035A1 CN 2024134560 W CN2024134560 W CN 2024134560W WO 2025119035 A1 WO2025119035 A1 WO 2025119035A1
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molecular sieve
modified molecular
catalyst
auxiliary component
group
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French (fr)
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王振宇
郑步梅
祁文博
王丽博
赵响宇
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • 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
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Definitions

  • the invention relates to the technical field of molecular sieve preparation, and in particular to a modified molecular sieve and a preparation method thereof, a catalyst and application thereof, and a method for synthesizing diphenylamine from aniline.
  • Diphenylamine is an important organic chemical raw material with a wide range of uses. It is mainly used in the industry as an antioxidant for synthetic rubber, a stabilizer for explosives, a fuel and pharmaceutical intermediate, azo dyes, a fruit preservative, etc. It can also be used as an analytical reagent for the identification of DNA, the colorimetric determination of nitrates, nitrites, chlorates, and magnesium, and as a redox indicator.
  • the catalysts for the synthesis of diphenylamine from aniline introduced in domestic and foreign patent technologies are mostly solid acid catalysts, such as patent applications US3118944A, US4454348A, US3944613A, CN1114240A, etc., which disclose the technology of using activated alumina, amorphous silica-alumina, and molecular sieves to prepare catalysts.
  • the continuous synthesis of diphenylamine from aniline and a matching special molecular sieve catalyst whose active component is H ⁇ molecular sieve.
  • the continuous synthesis of diphenylamine from aniline using H ⁇ molecular sieve catalyst generally has a conversion rate of 20-25% and a selectivity of 96-97 mol%.
  • CN105618106A proposed a multi-level pore ⁇ molecular sieve catalyst rich in a large amount of mesoporous pore volume; the thesis "Study on Catalyst for Preparation of Diphenylamine by Aniline Condensation” introduced halogens into ⁇ molecular sieves to increase acidity; “Acta Petrolei Sinica” (2017, Vol. 33, No.
  • the purpose of the present invention is to overcome the problems of low selectivity and short single-pass operation cycle of the catalyst for synthesizing diphenylamine from aniline in the prior art, and to provide a modified molecular sieve and a preparation method thereof, a catalyst and an application thereof, and a method for synthesizing diphenylamine from aniline.
  • the modified molecular sieve is applied to the catalyst for synthesizing diphenylamine from aniline and has high catalytic activity, high selectivity and long single-pass operation cycle.
  • the first aspect of the present invention provides a modified molecular sieve, wherein the modified molecular sieve comprises a ⁇ molecular sieve and an auxiliary component, wherein the auxiliary component is selected from at least one of alkali metals;
  • the index constant k of the modified molecular sieve is not less than 100.
  • Q is the standard meta-xylene adsorption capacity per 100 g of modified molecular sieve, in g; a is the molar ratio of silicon oxide to aluminum oxide in the modified molecular sieve; and c is the molar number of the auxiliary component in terms of oxide per 100 g of modified molecular sieve.
  • a second aspect of the present invention provides a method for preparing a modified molecular sieve, comprising:
  • the auxiliary agent component is selected from at least one of alkali metals
  • step (3) using an inactive fluid to purge and/or flush the product obtained in step (2) so that the organic salt of the auxiliary component reacts to form a macromolecular product containing the auxiliary component, and the molecular diameter of the macromolecular product containing the auxiliary component is larger than the pore diameter of the ⁇ molecular sieve, thereby obtaining a modified molecular sieve precursor;
  • the third aspect of the present invention provides another method for preparing a modified molecular sieve, comprising the following steps:
  • the auxiliary agent component is selected from at least one of alkali metals;
  • the organic solvent is a C6-C10 substituted or unsubstituted cyclic hydrocarbon compound;
  • the organic salt of the auxiliary agent component contains a cyclic structure in the molecule and contains an unsaturated functional group that can undergo addition reaction with the cyclic hydrocarbon compound;
  • step (3) using an inactive fluid having a temperature not lower than 80° C. to purge and/or rinse the product obtained in step (2), and then drying the product to obtain a modified molecular sieve precursor;
  • the fourth aspect of the present invention provides a modified molecular sieve obtained by the preparation method provided by the second aspect or the third aspect.
  • a fifth aspect of the present invention provides a catalyst, which comprises the modified molecular sieve described in the first aspect or the fourth aspect and a binder.
  • a sixth aspect of the present invention provides a method for synthesizing diphenylamine from aniline, the method comprising: contacting aniline with a catalyst under condensation reaction conditions;
  • the catalyst is the catalyst provided in the fifth aspect.
  • the catalyst for synthesizing diphenylamine from aniline in industry is a modified ⁇ molecular sieve catalyst.
  • ⁇ molecular sieve is a high-silicon molecular sieve with a twelve-membered ring pore structure, which has acidity and pore structure suitable for the reaction of aniline synthesizing diphenylamine.
  • the pore structure of ⁇ molecular sieve there are two types of pore space, namely straight pores and pore intersections.
  • the pore intersection is that two pores penetrate each other at a certain angle and communicate with each other internally.
  • This pore intersection has a wide space, and the acid center is denser than the non-intersection, which can catalyze the cyclization and condensation reactions of aniline molecules to generate macromolecules such as tricyclic linear acridine and bicyclic planar quinoline, and diffuse out from the pores, thereby making it impossible to fundamentally improve the selectivity of diphenylamine.
  • this pore intersection also becomes an active zone for the generation of carbon deposit precursors.
  • the index constant k of the beta molecular sieve modified by the additive metal in the prior art is lower than 100, usually 60-90, and the additive oxide is usually loaded in large quantities in the straight-through pores, which is not conducive to maintaining the pores unobstructed, affecting the diffusion of reactants and products in the pores, and it is difficult to achieve the modification of the acid center at the intersection of the pores, thereby resulting in a fast decay rate of the aniline conversion rate of the catalyst and a short single-pass operation cycle.
  • the initial extraction time of the industrial aniline synthesis diphenylamine catalyst is generally only 250 hours, and carbon burning regeneration is required after only 1500 hours, resulting in high operating costs for the device and few annual effective operating hours.
  • the modified molecular sieve provided by the present invention has an index constant k of not less than 100, and the auxiliary agent components in the modified molecular sieve are almost completely loaded at the intersection of the pores, and the acid centers at the intersections can be modified in a targeted manner without affecting the acid centers at the straight pores or the smooth flow of the pores.
  • the catalyst containing the modified molecular sieve has a higher diphenylamine selectivity and a longer single-pass operation cycle.
  • the first aspect of the present invention provides a modified molecular sieve, wherein the modified molecular sieve comprises a ⁇ molecular sieve and an auxiliary component, wherein the auxiliary component is selected from at least one of alkali metals;
  • the indicative constant k of the modified molecular sieve is not less than 100, preferably 100-550, and more preferably 101-500.
  • it can be 101, 110, 120, 130, 140, 150, 160, 180, 200, 250, 300, 350, 400, 450, 500 and other specific but non-limiting values.
  • the index constant k of the modified molecular sieve is not less than 100, and the auxiliary component in the modified molecular sieve is almost completely loaded at the intersection of the pores, and the acid center at the intersection can be modified in a targeted manner, without affecting the acid center at the straight-through pores, nor affecting the smooth flow of the pores, so that the catalyst made of the modified molecular sieve has a higher diphenylamine selectivity and a longer single-pass operation cycle.
  • Q is the standard meta-xylene adsorption capacity per 100 g of modified molecular sieve, in g; a is the molar ratio of silicon oxide to aluminum oxide in the modified molecular sieve; and c is the molar number of the auxiliary component in terms of oxide per 100 g of modified molecular sieve.
  • k is a dimensionless value calculated by formula (1).
  • the method for determining the standard meta-xylene adsorption of the modified molecular sieve is as follows: the intelligent gravimetric analyzer (Intelligent Gravimetric Analyser, IGA-002) is used for determination.
  • the molecular sieve is first subjected to impurity removal treatment to remove moisture and impurities such as residual template agents.
  • the impurity removal treatment is to raise the temperature of the sample to be tested from room temperature to 300°C at a rate of 5°C/minute under a vacuum state, and then return it to room temperature after its mass becomes constant, and then the determination of the meta-xylene adsorption is started.
  • meta-xylene vapor is passed into the sample chamber after impurity removal. After the sample is completely adsorbed and saturated (i.e., the weight is constant), the weight difference is recorded, which is the meta-xylene adsorption of the modified molecular sieve. The ratio of the meta-xylene adsorption to the initial mass of the modified molecular sieve is calculated to obtain the standard meta-xylene adsorption per 100g of the modified molecular sieve Q.
  • the standard meta-xylene adsorption capacity per 100g of the modified molecular sieve is 17-33g, preferably 18-31g.
  • meta-xylene is used as the target substance, which can reflect the pore structure of the modified molecular sieve.
  • the pore intersections in the modified molecular sieve have a suitable number of acid centers and a suitable pore size, and there are almost no auxiliary components in the straight pores, which is conducive to further improving the catalytic selectivity and single-pass operation cycle of the modified molecular sieve catalyst.
  • the silicon-aluminum ratio a of the modified molecular sieve refers to the molar ratio of silicon oxide and aluminum oxide in the modified molecular sieve
  • the "silicon-aluminum ratio" involved in the present invention refers to the molar ratio of silicon oxide to aluminum oxide, which is obtained by testing the XRF characterization method.
  • the molar ratio of silicon oxide to aluminum oxide in the modified molecular sieve is 20-250, preferably 25-200, for example, it can be 20, 25, 40, 60, 80, 100, 120, 150, etc., a specific but non-limiting molar ratio or a range between any two. In the above preferred case, it is beneficial for the modified molecular sieve to retain a suitable active center.
  • the modified molecular sieve does not contain non-framework silicon oxide and/or aluminum oxide.
  • the ⁇ molecular sieve is H ⁇ molecular sieve.
  • c is the molar number of the auxiliary component calculated as oxide in every 100 g of the modified molecular sieve, which is obtained by testing using an ICP characterization method.
  • 1.4909 is the fitting coefficient.
  • the auxiliary agent component is selected from sodium and/or potassium.
  • the auxiliary agent component exists in the form of an oxide.
  • the molar amount of the auxiliary component calculated as oxide is 0.01-0.12 mol, preferably 0.02-0.1 mol.
  • the one-way operation cycle of the catalyst for synthesizing diphenylamine from aniline in industry is relatively short, and the initial extraction time is generally about 250h, and carbon burning regeneration is required only after 1500 hours, the device operating cost is high, and the annual effective start-up hours are small.
  • the acid centers at the intersection of the molecular sieve channels can be regulated while avoiding the influence on the molecular sieve channel structure, so that the catalyst made of the modified molecular sieve has higher diphenylamine selectivity and longer single-pass operation cycle.
  • a second aspect of the present invention provides a method for preparing a modified molecular sieve, comprising:
  • the auxiliary agent component is selected from at least one of alkali metals
  • step (3) using an inactive fluid to purge and/or flush the product obtained in step (2) so that the organic salt of the auxiliary component reacts to form a macromolecular product containing the auxiliary component, and the molecular diameter of the macromolecular product containing the auxiliary component is larger than the pore diameter of the ⁇ molecular sieve, thereby obtaining a modified molecular sieve precursor;
  • the organic salt of the auxiliary component generates a macromolecular product with a complex spatial structure under the action of the beta molecular sieve acid center.
  • the molecular diameter of this macromolecular product is larger than the molecular sieve pore diameter.
  • the metal oxide is formed and attached to the intersection of the molecular sieve pores, which plays a role in modulating the acid center at the intersection of the pores and adjusting the size of the pores. It is understandable that in the absence of acid center catalysis, macromolecular products cannot be formed.
  • the pore diameter of the ⁇ molecular sieve refers to the maximum straight-through pore diameter of the ⁇ molecular sieve.
  • the longest diameter of the approximate ellipse of the radial cross section of the pore (perpendicular to the axial direction) is measured by transmission electron microscopy as the maximum straight-through pore diameter, and the maximum straight-through pore diameter of the ⁇ molecular sieve is generally 0.7 nm.
  • the composition of the liquid phase without purging or flushing at the same reaction temperature is analyzed by liquid chromatograph, and the composition of the liquid phase/gas phase after purging or flushing is analyzed by liquid chromatograph or gas chromatograph.
  • the organic salt reaction of the auxiliary component generates a macromolecular product containing the auxiliary component through composition comparison.
  • the molecular diameter of the macromolecular product refers to the molecular dynamics diameter, which is calculated by molecular dynamics simulation.
  • the inactive fluid may be any gas or liquid that does not participate in the reaction.
  • the present invention has no particular limitation on the type of the reaction, as long as a macromolecular product having a molecular diameter greater than the pore diameter of the ⁇ molecular sieve can be obtained.
  • the organic salt of the auxiliary component can be subjected to a self-polymerization reaction to form a macromolecular product containing the auxiliary component, or the organic salt of the auxiliary component can be subjected to an addition reaction with the organic solvent to form a macromolecular product containing the auxiliary component.
  • the third aspect of the present invention provides a method for preparing a modified molecular sieve, comprising the following steps:
  • the auxiliary agent component is selected from at least one of alkali metals;
  • the organic solvent is a C6-C10 substituted or unsubstituted cyclic hydrocarbon compound;
  • the organic salt of the auxiliary component contains a cyclic structure in its molecule and contains an unsaturated functional group capable of undergoing addition reaction with the cyclic hydrocarbon compound;
  • step (3) using an inactive fluid having a temperature not lower than 80° C. to purge and/or rinse the product obtained in step (2), and then drying the product to obtain a modified molecular sieve precursor;
  • the organic salt of the auxiliary component is first dissolved in the cyclic hydrocarbon compound to prepare an impregnation solution, and then the solution is filled with the ⁇ molecular sieve pores through an impregnation treatment, so that the organic salt of the auxiliary component and the cyclic hydrocarbon compound diffuse into the molecular sieve pores; further, by purging and/or flushing with an inactive fluid not less than 80°C, the unsaturated functional groups in the molecules of the organic salt of the auxiliary component and the cyclic hydrocarbon compound are added in situ at high temperature to generate a macromolecular salt product with a multi-ring structure.
  • the molecular size of the reaction product is larger than the diameter of the molecular sieve straight-through pore, even if there is an acid center required for the reaction in the straight-through pore, it cannot be generated in the straight-through pore, and can only be generated at the intersection of the pores, such as where there is sufficient space and an acid center.
  • the metal oxide is formed and attached to the intersection of the molecular sieve pores, which plays a role in modulating the acid center at the intersection of the pores and adjusting the size of the pores.
  • the modified molecular sieve prepared by the preparation method provided by the present invention has higher diphenylamine selectivity and longer single-pass operation cycle when used in catalysts.
  • the reason for this may be that the above preparation method can adjust the acid centers at the intersection of the ⁇ molecular sieve channels without affecting the acid centers at the straight channels or the smooth flow of the channels.
  • the cyclic structure is selected from at least one of a saturated or unsaturated five-membered ring and a six-membered ring.
  • the cyclic structure may be a carbocyclic ring composed entirely of carbon atoms, or may be a heterocyclic ring containing heteroatoms such as S, N, O, etc.
  • the saturated or unsaturated five-membered ring and the six-membered ring are composed entirely of carbon atoms.
  • the beta molecular sieve is an H beta molecular sieve.
  • the present invention has no particular limitation on the source of the beta molecular sieve, which can be purchased commercially or prepared by any method known in the art.
  • the molar ratio of silicon oxide to aluminum oxide in the beta molecular sieve is 20-250, preferably 25-200.
  • the organic salt of the auxiliary component contains at least one unsaturated six-membered ring in the molecule, preferably a benzene ring.
  • it is conducive to the generation of macromolecular salt products with a multi-ring structure.
  • the molecule of the organic salt of the auxiliary component also contains an unsaturated functional group that can undergo an addition reaction with the cyclic hydrocarbon compound.
  • the present invention has no particular limitation on the type of the unsaturated functional group, as long as it can undergo an addition reaction with the cyclic hydrocarbon compound.
  • the unsaturated functional group is selected from a carbon-carbon double bond and/or a carbon-carbon triple bond.
  • the present invention has no particular limitation on the position of the unsaturated functional group in the molecule, and it can be on the ring of the cyclic structure or in a substituent of the cyclic structure.
  • the addition reaction is carried out under certain temperature conditions and catalysis by the ⁇ molecular sieve acid center.
  • the molecular weight of the organic salt of the auxiliary component does not exceed 250 g/mol, preferably 50-220 g/mol. Controlling the molecular weight of the organic salt of the auxiliary component within the above preferred range is conducive to the generation of macromolecular salt products with a multi-ring structure of suitable molecular size at the intersection of the molecular sieve channels.
  • the structure of the organic salt of the auxiliary component is as shown in formula (i),
  • R1 is a C2-C4 alkenylene or alkynylene group, for example, it can be at least one of vinylene, ethynylene, propenylene, propynylene, butenylene and butynylene.
  • the position of the carbon-carbon double bond or carbon-carbon triple bond can be located in the middle of the group or at both ends of the group, and the present invention has no particular limitation.
  • the alkenylene or alkynylene group can be a straight chain or branched chain group, and the present invention has no particular limitation on this.
  • R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from at least one of a hydrogen atom and a C1-C3 hydrocarbon group, for example, at least one of a hydrogen atom, a methyl group and an ethyl group, more preferably a hydrogen atom.
  • a 1 is selected from -COO- or -SO 3 -, preferably -COO-.
  • M refers to an auxiliary metal ion, which is at least one selected from alkali metal ions, preferably K + or Na + .
  • the above preferred implementation is beneficial for the auxiliary component to modulate the acid centers at the intersection of the molecular sieve channels, and will not affect the smooth flow of the channels, so that the catalyst made of the modified molecular sieve has higher diphenylamine selectivity and longer single-pass operation cycle.
  • the cyclic hydrocarbon compound in the impregnation solution acts as a solvent, so that the organic salt of the auxiliary component is evenly dispersed in the cyclic hydrocarbon compound; on the other hand, the cyclic hydrocarbon compound and the organic salt of the auxiliary component can undergo addition reaction at the intersection of the pores of the molecular sieve under the condition of blowing or flushing of an inactive fluid with a temperature not lower than 80°C to generate a macromolecular organic salt.
  • the present invention has a wide selection range for the cyclic hydrocarbon compound, preferably a C6-C10 substituted or unsubstituted cyclic hydrocarbon compound, the substituent in the cyclic hydrocarbon compound can be, for example, a C1-C3 alkyl group, and further preferably, the cyclic hydrocarbon compound is selected from at least one of benzene, cyclohexane, toluene, methylcyclopentane and cyclohexene.
  • the organic salt of the auxiliary component is a cinnamate of the auxiliary component
  • the cyclic hydrocarbon compound is selected from at least one of benzene, cyclohexane, toluene, methylcyclopentane and cyclohexene, more preferably benzene.
  • the above preferred embodiment is conducive to the two components forming a liquid uniform phase and generating a macromolecular salt product with a multi-ring structure at the intersection of the molecular sieve pores.
  • the content of the organic salt of the auxiliary component is 0.1-10wt%, preferably 0.5-9wt%; the content of the cyclic hydrocarbon compound is 90-99.9wt%, preferably 90-99.5wt%.
  • the above preferred embodiments are conducive to the formation of a uniform liquid phase and the reaction to generate an appropriate amount of macromolecular salt products with a multi-ring structure to fill the intersection of the molecular sieve channels.
  • the amount of the impregnation solution is 4-10 mL, preferably 5-8 mL.
  • the present invention does not particularly limit the temperature of the impregnation, and those skilled in the art can adjust it according to actual needs.
  • the impregnation can be carried out at room temperature, and preferably, the impregnation time is 1-10 hours, preferably 1-5 hours.
  • the impregnation liquid fills the pores of the H ⁇ molecular sieve, so that the organic salt and cyclic hydrocarbon compound of the auxiliary component diffuse into the pores of the molecular sieve.
  • the inactive fluid may be any gas or liquid that does not participate in the reaction, for example, it may be at least one of nitrogen, argon, helium and neon. From the perspective of reducing the preparation cost, nitrogen is preferred.
  • high-temperature purging and/or flushing not only provides the required temperature for the addition reaction, but also can vaporize the excess small molecules in the pores and take them out of the molecular sieve, while the macromolecular products generated by the reaction cannot be taken out of the pores due to the molecular size limitation and continue to remain at the intersection of the pores.
  • the content of cyclic hydrocarbon compounds in the outlet inactive fluid is not higher than 1 ⁇ g/L.
  • the conditions for purging and/or flushing include: the temperature of the inactive fluid is 80-300°C, preferably 85-280°C, the volume space velocity is 100-3000h -1 , preferably 200-2000h -1 , and the purging and/or flushing time is 2-24h, preferably 3-20h.
  • the above preferred embodiment is adopted, which is conducive to the formation of macromolecular products to modulate the acid centers at the intersection of the H ⁇ molecular sieve pores, and can remove excess small molecules in the pores to avoid affecting the smooth flow of the pores, so that the catalyst made of the modified molecular sieve has higher diphenylamine selectivity and longer single-pass operation cycle.
  • the organic salts and cyclic hydrocarbon compounds of the remaining unreacted auxiliary components in the product can be further removed by an optional washing step.
  • the present invention does not specifically limit the operation mode and conditions of the washing, and those skilled in the art can select according to actual needs.
  • the washing detergent may be water, preferably, the liquid-to-solid ratio of water to the product obtained by the purge is 4-10 mL/g, preferably 5-8 mL/g; the washing temperature may be 20 to 80°C, preferably 20-70°C, and from the perspective of energy saving, it may be carried out at room temperature.
  • the present invention does not particularly limit the number of washings, and can be adjusted according to the actual washing situation. Preferably, the number of washings is 1-10 times, preferably 2-6 times.
  • the present invention has no particular limitation on the drying conditions.
  • the drying temperature is 60-150° C., preferably 80-120° C.
  • the drying time is 2-24 h, preferably 3-20 h.
  • the calcination in step (4) is performed so that the carbon and hydrogen components in the macromolecular product carried in the modified molecular sieve precursor are fully oxidized and burned to become carbon dioxide and water vapor and escape from the molecular sieve, and the remaining metal oxides continue to adhere to the intersection of the molecular sieve channels, playing a role in modulating the acid center at the intersection of the channels and adjusting the size of the intersection.
  • the calcination conditions include: a temperature of 300-800°C, preferably 400-700°C, and a calcination time of 2-24h, preferably 3-8h.
  • the present invention further provides a method for preparing a molecular sieve, comprising:
  • the organic salt of the auxiliary component contains a ring structure in the molecule and contains a carbon-carbon double bond and/or a carbon-carbon triple bond;
  • the auxiliary agent component is selected from at least one of alkali metals;
  • the cyclic hydrocarbon compound is a C6-C10 substituted or unsubstituted cyclic hydrocarbon compound;
  • step (3) purging the product obtained in step (2) with an inert gas having a temperature not lower than 80° C., and then optionally washing and drying to obtain a modified molecular sieve precursor;
  • the present invention provides a preferred method for preparing a modified molecular sieve, comprising:
  • the organic salt of the auxiliary component is meat silicate
  • the auxiliary component is selected from at least one of alkali metals
  • the cyclic hydrocarbon compound is at least one of benzene, cyclohexane, toluene, methylcyclopentane and cyclohexene;
  • step (3) purging the product obtained in step (2) with an inert gas having a temperature not lower than 80° C., and then optionally washing and drying to obtain a modified molecular sieve precursor;
  • the meat silicate and the above-mentioned cyclic hydrocarbon compound can undergo addition reaction under the catalytic action of the acid center of the beta molecular sieve at a certain temperature to obtain a compound containing a multi-ring macromolecule.
  • the metal oxide obtained after roasting is attached to the intersection of the molecular sieve channels, playing a role in modulating the acid center at the intersection of the channels and adjusting the size of the area.
  • a fourth aspect of the present invention provides a modified molecular sieve obtained by the above preparation method.
  • a fifth aspect of the present invention provides a catalyst, which comprises the modified molecular sieve described in the first aspect or the fourth aspect and a binder.
  • the present invention has a wide range of choices for the binder, and can be any conventional choice in the art, for example, it can be at least one of alumina, bentonite, spinel and silica, preferably alumina.
  • the content of the modified molecular sieve is 55-85wt%, preferably 58-83wt%, and the content of the binder is 15-45wt%, preferably 17-42wt%.
  • the catalyst further comprises a second auxiliary component, which can be any metal component and/or non-metal component that is beneficial to improving the catalytic activity of the catalyst in synthesizing diphenylamine from aniline.
  • a second auxiliary component can be any metal component and/or non-metal component that is beneficial to improving the catalytic activity of the catalyst in synthesizing diphenylamine from aniline.
  • the metal component is selected from at least one of the metal elements of Group IA, Group IIA, Group IIIB, Group IVB, Group VIII, Group IB, and Group IIB, for example, it can be at least one of Li, Na, K, Mg, Ca, Ti, Zr, La, Ce, Pr, Fe, Co, Ni, Cu and Zn, preferably at least one of Li, La, Ce, Mg, Ca, Ba, Cu, Zn, Zr, Fe, and more preferably at least one of La, Ce and Mg.
  • the non-metal component is selected from at least one of Group IIIA non-metal, Group IVA non-metal and Group VA non-metal elements, preferably at least one of Si, P, B and C.
  • the content of the second auxiliary component is 0.1-5wt%, preferably 1-4wt%, calculated as oxide.
  • the specific surface area of the catalyst is 250-650 m 2 /g, preferably 300-600 m 2 /g.
  • the specific pore volume of the catalyst is 0.2-0.55 mL/g, preferably 0.25-0.5 mL/g.
  • the specific surface area and specific pore volume of the catalyst are measured by a nitrogen physical adsorption method.
  • the present invention has no special requirements for the shape of the catalyst, which can be in the form of a bar or a sphere.
  • its cross-section can be cylindrical, three-leaf clover or four-leaf clover, etc.
  • the bar diameter is preferably 0.5-3mm (according to standard Q/SH 361 933), preferably 1-2mm; when in the form of a sphere, its diameter is preferably 0.5-5mm, preferably 1-3mm.
  • the present invention has no particular limitation on the preparation method of the above-mentioned catalyst, and the catalyst can be prepared by any conventional method in the art.
  • the modified molecular sieve and the binder can be molded first, and then the second auxiliary component can be loaded.
  • the present invention also has no particular limitation on the loading method of the second auxiliary component, and the catalyst can be loaded by a conventional loading method, such as an impregnation method, which is well known to those skilled in the art.
  • Another aspect of the present invention provides a method for preparing a catalyst, comprising:
  • the organic salt of the auxiliary component contains a cyclic structure in its molecule and an unsaturated functional group capable of undergoing addition reaction with the cyclic hydrocarbon compound;
  • the auxiliary agent component is selected from at least one of alkali metals;
  • the cyclic hydrocarbon compound is a C6-C10 substituted or unsubstituted cyclic hydrocarbon compound;
  • step (3) using an inactive fluid having a temperature not lower than 80° C. to purge and/or rinse the product obtained in step (2), and then optionally washing and drying to obtain a modified molecular sieve precursor;
  • step (1) to step (4) are the same as those defined in the second aspect and will not be repeated here.
  • the binder precursor refers to any substance that can be calcined to obtain the binder.
  • the precursor of aluminum oxide can be pseudo-boehmite, which is well known to those skilled in the art.
  • the present invention has no particular limitation on the extrusion aid and the peptizing agent, and both can be selected conventionally in the art.
  • the extrusion aid can be, for example, sesbania powder
  • the peptizing agent can be, for example, dilute nitric acid and/or citric acid.
  • the concentration of the dilute nitric acid can generally be 3-15wt%.
  • the mass ratio of the modified molecular sieve, the binder and/or the binder precursor, the extrusion aid and the peptizing agent is (60-85):(15-40):(3-20):(5-80), preferably (70-80):(20-30):(10-15):(20-50), wherein the weights of the modified molecular sieve, the binder and/or the binder precursor are all calculated on a dry basis.
  • the dry basis weight of the modified molecular sieve refers to the weight of the modified molecular sieve after being calcined at 600° C. and the adsorbed water and crystal water are burned off.
  • the dry weight of the binder and/or binder precursor refers to the weight of the binder and/or binder precursor after burning out adsorbed water and crystal water after calcining at 600°C.
  • the present invention has no particular limitation on the molding method, and those skilled in the art can select the molding method according to actual needs, for example, it can be extrusion molding, tablet molding, ball rolling molding, etc.
  • the conditions for the first drying and the second drying each independently include: a temperature of 60-150° C., preferably 80-120° C., and a time of 2-24 h, preferably 5-20 h.
  • the product obtained by the immersion is first naturally dried in the shade, for example, placed at room temperature for 10-48 hours for drying.
  • the conditions of the first calcination and the second calcination each independently include: a temperature of 300-800° C., preferably 400-700° C., and a calcination time of 2-24 h, preferably 3-8 h.
  • the present invention has no particular requirements for the specific operation and conditions of the impregnation in step (5), subject to the requirement of the loading amount of the second auxiliary component.
  • the content of the second auxiliary component is 0.1-5wt%, preferably 1-4wt%, calculated as oxide.
  • the soluble compound of the second auxiliary component may be a conventional inorganic salt and/or organic salt containing the second auxiliary component, and the solvent in the impregnation solution is preferably water.
  • a sixth aspect of the present invention provides use of the modified molecular sieve or the catalyst in an aniline condensation reaction.
  • a seventh aspect of the present invention provides a method for synthesizing diphenylamine from aniline, the method comprising: contacting aniline with a catalyst under condensation reaction conditions; wherein the catalyst is the catalyst described in the fifth aspect.
  • the condensation reaction conditions include: reaction pressure of 0.1-4MPa, preferably 0.15-3.5MPa; reaction temperature of 280-360°C, preferably 290-350°C; aniline volume space velocity of 0.1-0.3h -1 , preferably 0.15-0.25h -1 .
  • the pressure involved refers to the gauge pressure.
  • the raw materials used are all commercially available, and the weights of the modified molecular sieve and the alumina precursor in the material amounts are all weights on a dry basis.
  • step (3) The molecular sieve obtained in step (2) was washed with deionized water at a liquid-to-solid ratio of 6 mL/g, and the washed molecular sieve was dried at 110° C. for 5 hours and calcined at 550° C. for 5 hours to obtain a modified H ⁇ molecular sieve A1; the composition and physicochemical properties of the modified molecular sieve are shown in Table 1.
  • step (3) The molecular sieve obtained in step (2) was washed with deionized water at a liquid-to-solid ratio of 5 mL/g, and the washed molecular sieve was dried at 110° C. for 4 hours and calcined at 500° C. for 5 hours to obtain a modified H ⁇ molecular sieve A2; the composition and physicochemical properties of the modified molecular sieve are shown in Table 1.
  • step (3) The molecular sieve obtained in step (2) was washed with deionized water at a liquid-to-solid ratio of 8 mL/g, and the washed molecular sieve was dried at 110° C. for 3 hours and calcined at 550° C. for 3 hours to obtain a modified molecular sieve A3.
  • the composition and physicochemical properties of the modified molecular sieve are shown in Table 1.
  • step (3) The molecular sieve obtained in step (2) was washed with deionized water at a liquid-to-solid ratio of 5 mL/g, and the washed molecular sieve was dried at 120° C. for 6 hours and calcined at 540° C. for 4 hours to obtain a modified H ⁇ molecular sieve A4; the composition and physicochemical properties of the modified molecular sieve are shown in Table 1.
  • step (1) the mass percentage of potassium cinnamate was 2 wt%.
  • the obtained modified molecular sieve was denoted as A5, and the composition and physicochemical properties were shown in Table 1.
  • step (2) the filtered molecular sieve was purged with 80°C hot nitrogen at a space velocity of 150 h -1 for 3 hours.
  • the modified molecular sieve obtained was designated A6, and its composition and physicochemical properties are shown in Table 1.
  • the H ⁇ molecular sieve (the molar ratio of silicon oxide to aluminum oxide is 40) was impregnated with potassium nitrate aqueous solution as the impregnation solution by an equal volume impregnation method. After impregnation for 2 hours, the molecular sieve was filtered out, dried at 110°C for 5 hours and calcined at 550°C for 5 hours. The modified molecular sieve obtained was recorded as DA1. The composition and physicochemical properties of the modified molecular sieve are shown in Table 1.
  • the H ⁇ molecular sieve (the molar ratio of silicon oxide to aluminum oxide is 25) was impregnated with potassium cinnamate aqueous solution as the impregnation solution by an equal volume impregnation method. After impregnation for 2 hours, the molecular sieve was filtered out, dried at 110°C for 5 hours and calcined at 550°C for 5 hours. The modified molecular sieve obtained was recorded as DA2. The composition and physicochemical properties of the modified molecular sieve are shown in Table 1.
  • the H ⁇ molecular sieve (the molar ratio of silicon oxide to aluminum oxide is 80) was impregnated with potassium nitrate aqueous solution as the impregnation solution by an equal volume impregnation method. After impregnation for 3 hours, the molecular sieve was filtered out, dried at 120°C for 3 hours and calcined at 560°C for 5 hours. The modified molecular sieve obtained was recorded as DA3. The composition and physicochemical properties of the modified molecular sieve are shown in Table 1.
  • Unmodified H ⁇ molecular sieve (molar ratio of silicon oxide to aluminum oxide is 40) was used, denoted as DA4, and the composition and physicochemical properties are shown in Table 1.
  • the modified molecular sieve A1, alumina, sesbania powder and 10wt% nitric acid solution were fully kneaded in a mass ratio of 70:30:10:40, wherein the weight of the modified molecular sieve and alumina precursor were calculated on a dry basis, and then extruded into a clover-shaped strip with a strip diameter of 2 mm.
  • the catalyst precursor was then obtained by drying at 110°C for 5 hours and calcining at 550°C for 5 hours;
  • step (2) The catalyst precursor obtained in step (1) was loaded with La oxide by an equal volume impregnation method, and then dried at 110° C. for 5 hours and calcined at 550° C. for 5 hours to obtain a finished catalyst, which was recorded as CAT-1.
  • the composition and physicochemical properties of the catalyst are shown in Table 2.
  • the modified molecular sieve A2, alumina, sesbania powder and 12wt% nitric acid solution were fully mixed in a mass ratio of 77:23:11:38, wherein the weight of the modified molecular sieve and alumina precursor were calculated on a dry basis, and then extruded into a cylindrical shape with a cross section of 1.8 mm.
  • the catalyst precursor was then obtained by drying at 120°C for 4 hours and calcining at 510°C for 3 hours;
  • step (2) The catalyst precursor obtained in step (1) was loaded with Ce oxide by an equal volume impregnation method, and then dried at 120° C. for 5 hours and calcined at 500° C. for 4 hours to obtain a finished catalyst, which was recorded as CAT-2.
  • the composition and physicochemical properties of the catalyst are shown in Table 2.
  • the modified molecular sieve A3, alumina, sesbania powder and 15wt% nitric acid solution were fully mixed in a mass ratio of 72:28:13:35, wherein the weight of the modified molecular sieve and alumina precursor were calculated on a dry basis, and then extruded into a cylindrical shape with a cross section of 1.5 mm.
  • the catalyst precursor was then obtained by drying at 120°C for 5 hours and calcining at 550°C for 3 hours;
  • step (2) The catalyst precursor obtained in step (1) was loaded with Mg oxide by an equal volume impregnation method, and then dried at 120° C. for 5 hours and calcined at 550° C. for 4 hours to obtain a finished catalyst, which was recorded as CAT-3.
  • the composition and physicochemical properties of the catalyst are shown in Table 2.
  • the modified molecular sieve A4, alumina, sesbania powder and 10wt% nitric acid solution were fully mixed in a mass ratio of 60:40:15:40, wherein the weight of the modified molecular sieve and alumina precursor were calculated on a dry basis, and then extruded into a clover-shaped strip with a cross section of 2.2 mm.
  • the strip was then dried at 110°C for 6 hours and calcined at 550°C for 4 hours to obtain a catalyst precursor;
  • step (2) The catalyst precursor obtained in step (1) was loaded with Si oxide by an equal volume impregnation method, and then dried at 110° C. for 5 hours and calcined at 550° C. for 5 hours to obtain a finished catalyst, which was recorded as CAT-4.
  • the composition and physicochemical properties of the catalyst are shown in Table 2.
  • Example 2 The method of Example 1 was followed, except that modified molecular sieve A5 was used instead of A1.
  • the finished catalyst was recorded as CAT-5, and its composition and physicochemical properties are shown in Table 2.
  • Example 2 The method of Example 1 was followed, except that modified molecular sieve A6 was used instead of A1.
  • the finished catalyst was recorded as CAT-6, and its composition and physicochemical properties are shown in Table 2.
  • step (2) is not performed, and the catalyst precursor obtained in step (1) is directly used as the finished catalyst, which is recorded as CAT-7.
  • Example 2 The method of Example 1 was followed, except that modified molecular sieve DA1 was used instead of A1. The resulting finished catalyst was recorded as DCAT-1. The composition and physicochemical properties of the catalyst are shown in Table 2.
  • Example 2 The method of Example 2 was followed, except that modified molecular sieve DA2 was used instead of A2. The resulting finished catalyst was recorded as DCAT-2. The composition and physicochemical properties of the catalyst are shown in Table 2.
  • Example 3 The method of Example 3 was followed, except that modified molecular sieve DA3 was used instead of A3. The resulting finished catalyst was recorded as DCAT-3. The composition and physicochemical properties of the catalyst are shown in Table 2.
  • Example 2 The method of Example 1 was followed, except that modified molecular sieve DA4 was used instead of A1. The resulting finished catalyst was recorded as DCAT-4. The composition and physicochemical properties of the catalyst are shown in Table 2.
  • step (2) The catalyst precursor obtained in step (1) was contacted with an aqueous solution of molybdenum nitrate, and NaBH4 was added for reflux reduction at 100°C for 8 hours. The catalyst was filtered and vacuum dried to obtain a spherical catalyst with a particle diameter of 3 mm, which was recorded as DCAT-5.
  • composition and physicochemical properties of the catalyst are shown in Table 2.
  • the standard meta-xylene adsorption capacity of 100 g of DCAT-5 is 10.65 g, and the calculated index constant k is 36.
  • the catalysts of the above examples and comparative examples were used in a small evaluation device to evaluate the synthesis of diphenylamine from aniline.
  • Aniline was used as the raw material, the reaction temperature was 310°C, the reaction pressure was 3 MPa, the volumetric space velocity of aniline was 0.2 h -1 , the concentration of the product was analyzed by liquid chromatography, and the conversion rate and selectivity were calculated.
  • Table 3 where:
  • Initial extraction time (h) is the total operation time from the start of the reaction to when the aniline conversion rate drops to 20 mol%;
  • Aniline conversion (mol%) is the average aniline molar conversion during the initial extraction time.
  • Aniline conversion (mol%) mole number of aniline participating in the reaction/total mole number of aniline feed ⁇ 100%.
  • Diphenylamine selectivity (mol%) is the average diphenylamine molar selectivity during the initial extraction time.
  • Diphenylamine selectivity (mol%) mole number of diphenylamine in the product/total mole number of main and by-products ⁇ 100%.

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Abstract

一种改性分子筛及其制备方法、催化剂及其应用、苯胺合成二苯胺的方法，所述改性分子筛包含β分子筛以及助剂组分，所述助剂组分选自碱金属中的至少一种；其中，所述改性分子筛的指征常数k不低于100。该改性分子筛制成的催化剂具有较高的二苯胺选择性和更长的单程运转周期。

Description

改性分子筛及其制备方法、催化剂及其应用、苯胺合成二苯胺的方法
相关申请的交叉引用
本申请要求2023年12月06日提交的中国专利申请202311665591.X的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及分子筛制备技术领域，具体涉及一种改性分子筛及其制备方法、催化剂及其应用、苯胺合成二苯胺的方法。
背景技术
二苯胺是一种重要的有机化工原料，其用途非常广泛。工业上主要用于合成橡胶的防老剂、炸药稳定剂、燃料和医药中间体、偶氮类染料、水果保鲜剂等，也可以作为分析试剂用于鉴定DNA，硝酸盐、亚硝酸盐、氯酸盐、镁的比色测定及氧化还原指示剂。目前，国内外专利技术中介绍的苯胺合成二苯胺的催化剂多为固体酸催化剂，如专利申请US3118944A、US4454348A、US3944613A、CN1114240A等公开了采用活性氧化铝、无定型硅铝、分子筛来制备催化剂的技术。
20世纪90年代中期，研究人员开发出苯胺连续合成二苯胺新工艺及配套的专用分子筛催化剂，其活性组分为Hβ分子筛。目前使用Hβ分子筛催化剂的苯胺连续合成二苯胺工艺，转化率一般为20-25％，选择性一般为96-97mol％。
近年来本领域内研究人员对β分子筛催化剂进行了酸性和孔道的调变。如CN105618106A提出了一种富含大量介孔孔容的多级孔β分子筛催化剂；学位论文《苯胺缩合制备二苯胺催化剂的研究》向β分子筛中引入卤素以增加酸性；《石油学报》(2017年，第33卷，第1期)《碱处理对Hβ分子筛催化苯胺缩合制二苯胺性能的影响》采用碱处理的方式对β分子筛晶体进行刻蚀，以增加介孔孔容等。但是依然存在选择性较低、单程运转周期较短的问题。
发明内容
本发明的目的是为了克服现有技术存在的苯胺合成二苯胺催化剂选择性较低、单程运转周期较短的问题，提供一种改性分子筛及其制备方法、催化剂及其应用、苯胺合成二苯胺的方法，该改性分子筛应用于苯胺合成二苯胺催化剂中具有较高的催化活性，选择性高、单程运转周期长。
为了实现上述目的，本发明第一方面提供一种改性分子筛，所述改性分子筛包含β分子筛以及助剂组分，所述助剂组分选自碱金属中的至少一种；
其中，所述改性分子筛的指征常数k不低于100。
在本发明中，所述指征常数k按式(1)计算得到：
k＝Q/(1.4909×a-0.558-c)                       式(1)
其中，Q为每100g改性分子筛的标准间二甲苯吸附量，单位为g；a为改性分子筛中氧化硅与氧化铝的摩尔比；c为每100g改性分子筛中以氧化物计的助剂组分的摩尔数。
本发明第二方面提供一种改性分子筛的制备方法，包括：
(1)配制包含助剂组分的有机盐和有机溶剂的浸渍液；
所述助剂组分选自碱金属中的至少一种；
(2)采用上述浸渍液浸渍β分子筛；
(3)采用非活性流体对步骤(2)得到的产物进行吹扫和/或冲洗，以使助剂组分的有机盐发生反应形成含有助剂组分的大分子产物，且所述含有助剂组分的大分子产物的分子直径大于β分子筛的孔道直径，得到改性分子筛前驱体；
(4)将所述改性分子筛前驱体进行焙烧。
本发明第三方面提供另一种改性分子筛的制备方法，包括以下步骤：
(1)配制包含助剂组分的有机盐和有机溶剂的浸渍液；
其中，所述助剂组分选自碱金属中的至少一种；所述有机溶剂为C6-C10的取代或未取代的环烃化合物；所述助剂组分的有机盐的分子中含有环状结构，且含有能够与环烃化合物发生加成反应的不饱和官能团；
(2)采用上述浸渍液浸渍β分子筛；
(3)采用温度不低于80℃的非活性流体对步骤(2)得到的产物进行吹扫和/或冲洗，然后进行干燥，得到改性分子筛前驱体；
(4)将所述改性分子筛前驱体进行焙烧。
本发明第四方面提供上述第二方面或第三方面提供的制备方法制得的改性分子筛。
本发明第五方面提供一种催化剂，所述催化剂包含上述第一方面或第四方面所述的改性分子筛和粘结剂。
本发明第六方面提供一种苯胺合成二苯胺的方法，所述方法包括：在缩合反应条件下，将苯胺与催化剂接触；
其中，所述催化剂为第五方面提供的催化剂。
本发明的发明人在研究中发现，苯胺合成二苯胺反应是典型的酸催化反应，催化剂的酸性质和孔道结构影响产物的选择性和催化剂稳定性。目前工业上苯胺合成二苯胺的催化剂为改性的β分子筛催化剂。β分子筛是一种拥有十二元环孔道结构的高硅分子筛，具有适合苯胺合成二苯胺反应的酸性和孔道结构，在β分子筛的孔道结构中，有两类孔道空间，即直通孔道和孔道交叉点，孔道交叉点是两条孔道呈一定角度相互贯穿，内部相通。这种孔道交叉处空间开阔，酸中心较非交叉处更为密集，可以催化苯胺分子的环化、缩合反应，生成三环线性的吖啶、双环平面的喹啉这类大分子，并从孔道中扩散出去，从而导致无法从根本上提高二苯胺的选择性。此外，这种孔道交叉处也成为积碳前驱物生成的活跃地带。
现有技术中的助剂金属改性的β分子筛的指征常数k低于100，通常为60-90，助剂氧化物通常大量负载在直通孔道内，既不利于保持孔道的通畅，影响反应物和产物在孔道内的扩散，也难以实现孔道交叉处酸中心的修饰，从而导致催化剂的苯胺转化率衰减速率快，单程运转周期短，工业上苯胺合成二苯胺催化剂的初提时间一般仅250h，仅1500小时便需烧碳再生，装置操作费用高，年有效开工时数少。
与现有技术中的改性分子筛相比，本发明提供的改性分子筛的指征常数k不低于100，该改性分子筛中的助剂组分几乎完全负载在孔道交叉处，能够靶向地对交叉处的酸中心进行修饰，不会对直通孔道处的酸中心造成影响，亦不会影响孔道的畅通。含有该改性分子筛的催化剂具有较高的二苯胺选择性和更长的单程运转周期。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种改性分子筛，所述改性分子筛包含β分子筛以及助剂组分，所述助剂组分选自碱金属中的至少一种；
其中，所述改性分子筛的指征常数k不低于100，优选为100-550，进一步优选为101-500，例如可以为101、110、120、130、140、150、160、180、200、250、300、350、400、450、500等具体而非限定性的数值。
根据本发明，所述改性分子筛的指征常数k不低于100，该改性分子筛中的助剂组分几乎完全负载在孔道交叉处，能够靶向地对交叉处的酸中心进行修饰，不会对直通孔道处的酸中心造成影响，亦不会影响孔道的畅通，从而使得改性分子筛制成的催化剂具有较高的二苯胺选择性和更长的单程运转周期。现有技术中的改性β分子筛的指征常数k在100以下，用于改性的助剂氧化物通常大量负载在直通孔道内，既不利于保持孔道的通畅，影响反应物和产物在孔道内的扩散，也难以实现孔道交叉处酸中心的修饰，从而导致催化剂的苯胺转化率衰减速率快，单程运转周期短，工业上苯胺合成二苯胺催化剂的初提时间一般仅250h，仅1500小时便需烧碳再生，装置操作费用高，年有效开工时数少。
在本发明中，所述指征常数k按式(1)计算得到：
k＝Q/(1.4909×a-0.558-c)                    式(1)
其中，Q为每100g改性分子筛的标准间二甲苯吸附量，单位为g；a为改性分子筛中氧化硅与氧化铝的摩尔比；c为每100g改性分子筛中以氧化物计的助剂组分的摩尔数。
在本发明中，k为通过式(1)计算得到的数值，无量纲。
其中，改性分子筛的标准间二甲苯吸附量测定方法如下：采用智能重量分析仪(Intelligent Gravimetric Analyser，IGA-002)进行测定。测定间二甲苯吸附量前先进行分子筛脱杂处理，脱除水分以及残留的模板剂等杂质，脱杂处理即在抽真空状态下，将待测试样品从室温以5℃/分钟的速率升温至300℃，待其质量恒定后降回至室温，开始进行间二甲苯吸附量的测定。在室温下，将间二甲苯蒸气通入脱杂后的样品室，待样品完全吸附饱和(即重量恒定)后，记录重量差值，即为该改性分子筛的间二甲苯吸附量，计算间二甲苯吸附量与改性分子筛的初始质量的比值得到每100g改性分子筛的标准间二甲苯吸附量Q。
在进一步优选的实施方式中，每100g改性分子筛的标准间二甲苯吸附量为17-33g，优选为18-31g。在本发明中，采用间二甲苯作为标的物，能够反映改性分子筛的孔道结构，在上述优选的情况下，表明改性分子筛中的孔道交叉处具有适宜的酸中心数量以及适宜的孔道尺寸，且直通孔道内几乎没有助剂组分，有利于进一步提高改性分子筛催化剂的催化选择性和单程运转周期。
在本发明中，所述改性分子筛的硅铝比a指的是改性分子筛中氧化硅和氧化铝的摩尔比，本发明中涉及的“硅铝比”均指的是氧化硅与氧化铝的摩尔比，通过XRF表征方法测试得到。优选地，所述改性分子筛中氧化硅与氧化铝的摩尔比为20-250，优选为25-200，例如可以为20、25、40、60、80、100、120、150等具体而非限定性的摩尔比或任意两者之间的范围。在上述优选的情况下，有利于改性分子筛保有适宜的活性中心。
优选地，所述改性分子筛中不包含非骨架的氧化硅和/或氧化铝。
优选地，所述β分子筛为Hβ分子筛。
根据本发明，c为每100g改性分子筛中以氧化物计的助剂组分的摩尔数，通过ICP表征方法测试得到。
在本发明中，1.4909为拟合系数。
根据本发明一些优选的实施方式，所述助剂组分选自钠和/或钾。优选情况下，所述助剂组分以氧化物形式存在。
根据本发明，100g所述改性分子筛中，以氧化物计的助剂组分的摩尔量为0.01-0.12mol，优选为0.02-0.1mol。
现有分子筛改性手段如水蒸气处理、负载金属/非金属氧化物等，是一类不具针对性的普遍修饰手段，既对孔道交叉处进行修饰，也对直通孔道进行修饰。这种情况下，孔道交叉处仍有比较开阔的空间和较多数量的酸中心存在，能够继续催化副反应的发生，不但影响产物二苯胺选择性，还会进一步形成高碳氢比的积碳前体，直至形成积碳。且现有技术中为了达到修饰孔道交叉处酸中心的目的，需要增大改性组分负载量，这样一来则会影响反应物和产物在孔道内的扩散，增大了催化剂的苯胺转化率衰减速率，缩短了单程运转周期。故工业上苯胺合成二苯胺催化剂单程运转周期较短，初提时间一般在250h左右，仅1500小时便需烧碳再生，装置操作费用高，年有效开工时数少。
在本发明中，通过控制适量的改性组分负载量，并且控制改性分子筛的指征常数k在上述范围内，既能够对分子筛孔道交叉处的酸中心进行调控，同时避免对于分子筛孔道结构的影响，使得以改性分子筛制成的催化剂具有较高的二苯胺选择性和更长的单程运转周期。
本发明第二方面提供一种改性分子筛的制备方法，包括：
(1)配制包含助剂组分的有机盐和有机溶剂的浸渍液；
所述助剂组分选自碱金属中的至少一种；
(2)采用上述浸渍液浸渍β分子筛；
(3)采用非活性流体对步骤(2)得到的产物进行吹扫和/或冲洗，以使助剂组分的有机盐发生反应形成含有助剂组分的大分子产物，且所述含有助剂组分的大分子产物的分子直径大于β分子筛的孔道直径，得到改性分子筛前驱体；
(4)将所述改性分子筛前驱体进行焙烧。
根据本发明，通过步骤(3)，使得助剂组分的有机盐在β分子筛酸中心作用下生成具有复杂空间结构的大分子产物，这种大分子产物的分子直径大于分子筛孔道直径，即使在非活性流体的吹扫和/或洗涤下，该物质也将继续留在分子筛孔道交叉处，经过进一步焙烧后形成金属氧化物附着在分子筛孔道交叉处，起到调变孔道交叉处酸中心并调节该处尺寸的作用。可以理解的是，在无酸中心催化的情况下，无法形成大分子产物。
在本发明中，β分子筛的孔道直径指的是β分子筛的最大直通孔道直径，通过透射电子显微镜观察，测量孔道径向截面(与轴向垂直)的近似椭圆的最长径为最大直通孔道直径，β分子筛的最大直通孔道直径通常为0.7nm。采用液相色谱仪分析相同反应温度下未经吹扫或冲洗的液相组成，通过液相色谱仪或气相色谱仪分析吹扫或冲洗后的液相/气相组成，通过组成对比证明助剂组分的有机盐反应生成了含有助剂组分的大分子产物，大分子产物的分子直径指的是分子动力学直径，采用分子动力学模拟计算得到。
所述非活性流体可以为任意不参与反应的气体或液体。
本发明对于所述反应的类型没有特别的限定，只要能够得到分子直径大于β分子筛的孔道直径的大分子产物即可。例如可以使助剂组分的有机盐发生自聚反应形成含有助剂组分的大分子产物，或者也可以使助剂组分的有机盐与所述有机溶剂发生加成反应形成含有助剂组分的大分子产物。
本发明第三方面提供一种改性分子筛的制备方法，包括以下步骤：
(1)配制包含助剂组分的有机盐和有机溶剂的浸渍液；
其中，所述助剂组分选自碱金属中的至少一种；所述有机溶剂为C6-C10的取代或未取代的环烃化合物；
所述助剂组分的有机盐的分子中含有环状结构，且含有能够与环烃化合物发生加成反应的不饱和官能团；
(2)采用上述浸渍液浸渍β分子筛；
(3)采用温度不低于80℃的非活性流体对步骤(2)得到的产物进行吹扫和/或冲洗，然后进行干燥，得到改性分子筛前驱体；
(4)将所述改性分子筛前驱体进行焙烧。
现有分子筛改性手段如水蒸气处理、负载金属/非金属氧化物等，既对孔道交叉处进行修饰，也对直通孔道进行修饰，是一类不具针对性的普遍修饰手段。现有技术中如果要达到修饰孔道交叉处酸中心的目的，则需要较高的改性物负载量，不利于反应物和产物在孔道内的扩散，从而增大了催化剂的苯胺转化率衰减速率，缩短了单程运转周期。
本发明提供的改性分子筛的制备方法中，首先将助剂组分的有机盐溶于环烃化合物中制成浸渍液，再通过浸渍处理使该溶液充满β分子筛孔道，使得助剂组分的有机盐和环烃化合物扩散至分子筛孔道；进一步通过用不低于80℃的非活性流体进行吹扫和/或冲洗，在高温下使得助剂组分的有机盐的分子中不饱和官能团与环烃化合物原位发生加成反应，生成具有多环结构的大分子盐类产物。由于该反应产物分子尺寸大于分子筛直通孔道的直径，即使直通孔道内有反应所需的酸中心也无法在直通孔道内生成，只能在孔道交叉处这样既有足够空间又有酸中心的地点生成。经过进一步焙烧后形成金属氧化物附着在分子筛孔道交叉处，起到调变孔道交叉处酸中心并调节该处尺寸的作用。
本发明提供的制备方法制得的改性分子筛用于催化剂中具有较高的二苯胺选择性和更长的单程运转周期，究其原因可能是由于采用上述制备方法可以针对β分子筛孔道交叉处的酸中心进行调变，并不会对直通孔道处的酸中心造成影响，亦不会影响孔道的畅通。
根据本发明一些优选的实施方式，所述环状结构选自饱和或不饱和的五元环和六元环中的至少一种。所述环状结构可以是全部由碳原子组成的碳环，也可以含有例如S、N、O等杂原子的杂环。优选情况下，所述饱和或不饱和的五元环和六元环全部由碳原子组成。
根据本发明，优选地，所述β分子筛为Hβ分子筛。本发明对于所述β分子筛的来源没有特别的限定，可以来自于商购或采用本领域任意已知的方法制备得到。优选地，所述β分子筛中氧化硅与氧化铝的摩尔比为20-250，优选为25-200。
优选地，所述助剂组分的有机盐的分子中至少含有一个不饱和六元环，优选为苯环。在上述优选的情况下，有利于生成多环结构的大分子盐类产物。
根据本发明，所述助剂组分的有机盐的分子中还含有能够与环烃化合物发生加成反应的不饱和官能团。本发明对于所述不饱和官能团的种类没有特别的限定，只要能够与所述环烃化合物发生加成反应即可，优选地，所述不饱和官能团选自碳碳双键和/或碳碳三键。本发明对于所述不饱和官能团的位置在分子中的位置也没有特别的限定，可以在所述环状结构的环上，也可以为环状结构的取代基中。
在本发明中，所述加成反应在一定温度条件以及β分子筛酸中心催化下进行。
在进一步优选的实施方式中，所述助剂组分的有机盐的分子量不超过250g/mol，优选为50-220g/mol。控制助剂组分的有机盐的分子量在上述优选的范围内，有利于在分子筛孔道交叉处生成分子大小适宜的多环结构的大分子盐类产物。
根据本发明一种特别优选的实施方式，所述助剂组分的有机盐的结构如式(i)所示，
其中，R1为C2-C4的亚烯基或亚炔基，例如可以为亚乙烯基、亚乙炔基、亚丙烯基、亚丙炔基、亚丁烯基和亚丁炔基中的至少一种。有关碳碳双键或碳碳三键位置，可以位于基团的中间位置也可以位于基团的两端，本发明没有特别的限制。所述亚烯基或亚炔基可以为直链或支链的基团，本发明对此也没有特别的限定。
式(i)中，R2、R3、R4、R5、R6各自独立地选自氢原子、C1-C3的烃基中的至少一种，例如可以为氢原子、甲基和乙基中的至少一种，更优选为氢原子。
式(i)中，A1选自-COO-或者-SO3-，优选为-COO-。
式(i)中，M指的是助剂金属离子，选自碱金属离子中的至少一种，优选为K+或Na+。
采用上述优选的实施方式，既有利于助剂组分对分子筛孔道交叉处的酸中心进行调变，亦不会影响孔道的畅通，使得制得的改性分子筛制成的催化剂具有较高的二苯胺选择性和更长的单程运转周期。
在本发明中，所述环烃化合物在浸渍液中一方面起到溶剂的作用，使得助剂组分的有机盐在环烃化合物中均匀分散，另一方面环烃化合物与助剂组分的有机盐在温度不低于80℃的非活性流体的吹扫或冲洗条件下能够在分子筛的孔道交叉处发生加成反应，生成大分子有机盐。
本发明对于所述环烃化合物的选择范围较宽，优选为C6-C10的取代或未取代的环烃化合物，所述环烃化合物中的取代基例如可以为C1-C3的烷基，进一步优选地，所述环烃化合物选自苯、环己烷、甲苯、甲基环戊烷和环己烯中的至少一种。
根据本发明特别优选的一种实施方式，所述助剂组分的有机盐为助剂组分的肉桂酸盐，所述环烃化合物选自苯、环己烷、甲苯、甲基环戊烷和环己烯中的至少一种，更优选为苯。采用上述优选的实施方式，有利于两种组分形成液相均匀相，并在分子筛孔道交叉处生成多环结构的大分子盐类产物。
根据本发明一些优选的实施方式，以所述浸渍液的总量为基准，助剂组分的有机盐的含量为0.1-10wt％，优选为0.5-9wt％；环烃化合物的含量为90-99.9wt％，优选为90-99.5wt％。采用上述优选的实施方式，有利于二者形成液相均匀相并反应生成适量的多环结构的大分子盐类产物以填充分子筛孔道交叉处。
根据本发明一些优选的实施方式，相对于1g所述Hβ分子筛，所述浸渍液的用量为4-10mL，优选为5-8mL。
本发明对于所述浸渍的温度没有特别的限定，本领域技术人员可以根据实际需要进行调整，优选地，所述浸渍可以在常温下进行，优选地，所述浸渍的时间为1-10h，优选为1-5h。在上述优选的情况下，能够保证浸渍液充满Hβ分子筛孔道，使得助剂组分的有机盐和环烃化合物扩散至分子筛孔道中。
在本发明中，所述非活性流体可以为任意地不参与反应的气体或液体，例如可以为氮气、氩气、氦气和氖气中的至少一种，从降低制备成本的角度考虑，优选为氮气。
根据本发明，通过高温吹扫和/或冲洗，既为加成反应提供了所需的温度，同时能够将孔道内多余的小分子气化带出分子筛，而反应生成的大分子产物受分子尺寸限制，无法从孔道中被带出，继续留在孔道交叉处。优选地，吹扫和/或冲洗结束时，出口非活性流体中的环烃化合物的含量不高于1μg/L。
优选地，所述吹扫和/或冲洗的条件包括：非活性流体的温度为80-300℃，优选为85-280℃，体积空速为100-3000h-1，优选为200-2000h-1，吹扫和/或冲洗的时间为2-24h，优选为3-20h。采用上述优选的实施方式，既有利于形成大分子产物从而对Hβ分子筛孔道交叉处的酸中心进行调变，又能够去除孔道内多余的小分子，避免影响孔道的畅通，使得制得的改性分子筛制成的催化剂具有较高的二苯胺选择性和更长的单程运转周期。
在本发明中，通过任选的洗涤步骤可以进一步去除产物中剩余未反应的助剂组分的有机盐和环烃化合物，本发明对于所述洗涤的操作方式和条件没有特别的限定，本领域技术人员可以根据实际需要进行选择。
根据本发明一些优选的实施方式，所述洗涤采用的洗涤剂可以为水，优选地，水与所述吹扫得到的产物的液固比为4-10mL/g，优选5-8mL/g；洗涤温度可以为20至80℃，优选为20-70℃，从节能角度考虑，可以在常温下进行。本发明对于所述洗涤的次数也没有特别的限定，可以根据实际洗涤情况进行调整，优选地，洗涤次数为1-10次，优选为2-6次。
本发明对于所述干燥的条件也没有特别的限定，优选地，所述干燥的温度为60-150℃，优选为80-120℃，时间为2-24h，优选为3-20h。
在本发明中，通过步骤(4)所述焙烧，以使得所述改性分子筛前驱体中负载的大分子产物中的碳、氢组分充分氧化燃烧，变成二氧化碳和水蒸汽并逸出分子筛，余下的金属氧化物继续附着在分子筛孔道交叉处，起到调变孔道交叉处酸中心并调节该处尺寸的作用。优选地，所述焙烧的条件包括：温度为300-800℃，优选为400-700℃，焙烧时间为2-24h，优选为3-8h。
本发明另外提供一种分子筛的制备方法，包括：
(1)配制包含助剂组分的有机盐和环烃化合物的浸渍液；
其中，所述助剂组分的有机盐的分子中含有环状结构，且含有碳碳双键和/或碳碳三键；
所述助剂组分选自碱金属中的至少一种；所述环烃化合物为C6-C10的取代或未取代的环烃化合物；
(2)采用上述浸渍液浸渍β分子筛；
(3)采用温度不低于80℃的非活性气体对步骤(2)得到的产物进行吹扫，然后进行任选的洗涤和干燥，得到改性分子筛前驱体；
(4)将所述改性分子筛前驱体进行焙烧。
特别优选地，本发明提供一种优选的改性分子筛的制备方法，包括：
(1)配制包含助剂组分的有机盐和环烃化合物的浸渍液；
其中，所述助剂组分的有机盐为肉硅酸盐，所述助剂组分选自碱金属中的至少一种；所述环烃化合物为苯、环己烷、甲苯、甲基环戊烷和环己烯中的至少一种；
(2)采用上述浸渍液浸渍β分子筛；
(3)采用温度不低于80℃的非活性气体对步骤(2)得到的产物进行吹扫，然后进行任选的洗涤和干燥，得到改性分子筛前驱体；
(4)将所述改性分子筛前驱体进行焙烧。
根据本发明，肉硅酸盐与上述环烃化合物能够在一定温度下，在β分子筛酸中心的催化作用下，发生加成反应，得到含有多环大分子化合物。经焙烧后得到的金属氧化物附着在分子筛孔道交叉处，起到调变孔道交叉处酸中心并调节该处尺寸的作用。
本发明第四方面提供上述制备方法制得的改性分子筛。
本发明第五方面提供一种催化剂，所述催化剂包含第一方面或第四方面所述的改性分子筛和粘结剂。
本发明对于所述粘结剂的选择范围较宽，可以为本领域任意常规的选择，例如可以为氧化铝、膨润土、尖晶石和氧化硅中的至少一种，优选为氧化铝。
根据本发明一些优选的实施方式，以所述催化剂的总量为基准，所述改性分子筛的含量为55-85wt％，优选为58-83wt％，粘结剂的含量为15-45wt％，优选为17-42wt％。
根据本发明，优选地，所述催化剂还包括第二助剂组分，所述第二助剂组分可以为任意地有利于提高催化剂苯胺合成二苯胺催化活性的金属组分和/或非金属组分。
为了进一步提高催化剂的选择性和单程运转周期，优选地，所述金属组分选自IA族、IIA族、IIIB族、IVB族、VIII族、IB族、IIB族金属元素中的至少一种，例如可以为Li、Na、K、Mg、Ca、Ti、Zr、La、Ce、Pr、Fe、Co、Ni、Cu和Zn中的至少一种，优选为Li、La、Ce、Mg、Ca、Ba、Cu、Zn、Zr、Fe中的至少一种，更优选为La、Ce和Mg中的至少一种。
优选地，所述非金属组分选自IIIA族非金属、IVA族非金属和VA族非金属元素中的至少一种，优选为Si、P、B和C中的至少一种。
优选地，以所述催化剂的总量为基准，以氧化物计，所述第二助剂组分的含量为0.1-5wt％，优选为1-4wt％。在上述优选的情况下，有利于进一步调节催化剂酸性，从而进一步提高催化剂的活性。
根据本发明，优选地，所述催化剂的比表面积为250-650m2/g，优选为300-600m2/g。
根据本发明，优选地，所述催化剂的比孔容为0.2-0.55mL/g，优选为0.25-0.5mL/g。
在本发明中，催化剂的比表面积和比孔容通过氮气物理吸附方法测得。
本发明对于所述催化剂的形状也没有特别的要求，可以为条形或球型，为条形时其截面可以是圆柱形、三叶草或四叶草形状等，条径优选为0.5-3mm(根据标准Q/SH 361 933)，优选1-2mm；为球型时，其直径优选为0.5-5mm，优选1-3mm。
本发明对于上述催化剂的制备方法没有特别的限定，可以采用本领域任意常规的方式制备得到。例如可以先将改性分子筛与粘结剂进行成型，然后负载第二助剂组分。本发明对于所述第二助剂组分的负载方式也没有特别的限定，可以采用常规的负载方式进行，例如可以为浸渍法，为本领域技术人员所熟知。
本发明另一方面提供一种催化剂的制备方法，包括：
(1)配制包含助剂组分的有机盐和环烃化合物的浸渍液；
其中，所述助剂组分的有机盐的分子中含有环状结构，且含有能够与环烃化合物发生加成反应的不饱和官能团；
所述助剂组分选自碱金属中的至少一种；所述环烃化合物为C6-C10的取代或未取代的环烃化合物；
(2)采用上述浸渍液浸渍β分子筛；
(3)采用温度不低于80℃的非活性流体对步骤(2)得到的产物进行吹扫和/或冲洗，然后进行任选的洗涤和干燥，得到改性分子筛前驱体；
(4)将所述改性分子筛前驱体进行焙烧，得到改性分子筛；
(5)将改性分子筛、粘结剂和/或粘结剂前驱体以及可选的助挤剂和可选的胶溶剂进行混和成型，然后进行第一干燥和第一焙烧，得到催化剂前驱体；
(6)采用含有第二助剂组分的可溶性化合物的溶液浸渍所述催化剂前驱体，然后进行第二干燥和第二焙烧。
步骤(1)-步骤(4)的具体操作条件与第二方面的定义相同，在此不再赘述。
在本发明中，所述粘结剂前驱体指的是任意经焙烧能够得到所述粘结剂的物质。例如氧化铝的前驱体可以为拟薄水铝石，为本领域技术人员所熟知。
本发明对于所述助挤剂和胶溶剂没有特别的限定，均可以采用本领域常规的选择。所述助挤剂例如可以为田菁粉，所述胶溶剂例如可以为稀硝酸和/或柠檬酸。其中，所述稀硝酸的浓度一般可以为3-15wt％。
根据本发明一些优选的实施方式，所述改性分子筛、粘结剂和/或粘结剂前驱体、助挤剂和胶溶剂的质量比为(60-85)：(15-40)：(3-20)：(5-80)，优选为(70-80)：(20-30)：(10-15)：(20-50)，其中，改性分子筛、粘结剂和/或粘结剂前驱体的重量均是以干基计。
在本发明中，改性分子筛的干基重量指的是改性分子筛经过600℃焙烧后烧除吸附水和结晶水后的重量。
粘结剂和/或粘结剂前驱体的干基重量指的是粘结剂和/或粘结剂前驱体经过600℃焙烧后烧除吸附水和结晶水后的重量。
本发明对于所述成型的方式也没有特别的限定，本领域技术人员可以根据实际需要进行选择，例如可以为挤条成型、压片成型、滚球成型等。
根据本发明一些优选的实施方式，所述第一干燥和第二干燥的条件各自独立地包括：温度为60-150℃，优选为80-120℃，时间为2-24h，优选为5-20h。
根据本发明一些优选的实施方式，在进行所述第二干燥之前先将浸渍得到的产物进行自然阴干，例如在室温下放置10-48h进行干燥。
优选地，所述第一焙烧和第二焙烧的条件各自独立地包括：温度为300-800℃，优选为400-700℃，焙烧时间为2-24h，优选为3-8h。
本发明对于步骤(5)中所述浸渍的具体操作和条件没有特别的要求，以满足第二助剂组分的负载量要求为准。优选地，以所述催化剂的总量为基准，以氧化物计，所述第二助剂组分的含量为0.1-5wt％，优选为1-4wt％。
所述第二助剂组分的可溶性化合物可以为常规的含有第二助剂组分的无机盐和/或有机盐，所述浸渍液中的溶剂优选为水。
本发明第六方面提供上述改性分子筛或上述催化剂在苯胺缩合反应中的应用。
本发明第七方面提供一种苯胺合成二苯胺的方法，所述方法包括：在缩合反应条件下，将苯胺与催化剂接触；其中，所述催化剂为第五方面所述的催化剂。
根据本发明，优选地，所述缩合反应条件包括：反应压力为0.1-4MPa，优选为0.15-3.5MPa；反应温度为280-360℃，优选为290-350℃；苯胺体积空速为0.1-0.3h-1，优选为0.15-0.25h-1。在本发明中，如无特别说明，涉及的压力均指的是表压。
以下将通过实施例对本发明进行详细描述。
以下实施例中，如无特别说明，采用的原料均来自于商购，所述物料用量中，改性分子筛、氧化铝前驱体的重量均是以干基计的重量。
以下制备例用于说明改性分子筛的制备。
制备例1
(1)将适量肉桂酸钾溶于苯中，搅拌均匀，充分溶解，肉桂酸钾的质量百分含量为8.5wt％；用该溶液以5mL/g的液固比浸渍200g的Hβ分子筛(氧化硅与氧化铝摩尔比为40)，浸渍2小时后滤出分子筛；
(2)将滤出的分子筛用110℃热氮气以800h-1的空速吹扫4小时，至出口氮气中的苯含量不高于1μg/L；
吹扫结束后自然冷却至室温；
(3)用去离子水以6mL/g的液固比清洗步骤(2)所得到分子筛，将洗涤后分子筛于110℃干燥5小时并于550℃焙烧5小时，得到改性Hβ分子筛A1；改性分子筛的组成和物化性质如表1所示。
制备例2
(1)将适量肉桂酸钾溶于苯中，搅拌均匀，充分溶解，配制成质量百分含量为9％的溶液；用该溶液以7mL/g的液固比浸渍200g的Hβ分子筛(氧化硅与氧化铝的摩尔比为25)，浸渍4小时后滤出分子筛；
(2)将滤出的分子筛用120℃热氮气以1000h-1的空速吹扫4小时，吹扫结束后自然冷却至室温；
(3)用去离子水以5mL/g的液固比清洗步骤(2)所得到分子筛，将洗涤后分子筛于110℃干燥4小时并于500℃焙烧5小时，得到改性Hβ分子筛A2；改性分子筛的组成和物化性质如表1所示。
制备例3
(1)将适量肉桂酸钾溶于苯中，搅拌均匀，充分溶解，配制成质量百分含量为8％的溶液；用该溶液以7mL/g的液固比浸渍200g的Hβ分子筛(氧化硅与氧化铝的摩尔比为80)，浸渍3小时后滤出分子筛；
(2)将滤出的分子筛用120℃热氮气以1100h-1的空速吹扫3小时，吹扫结束后自然冷却至室温；
(3)用去离子水以8mL/g的液固比清洗步骤(2)所得到分子筛，将洗涤后分子筛于110℃干燥3小时并于550℃焙烧3小时，得到改性分子筛A3，改性分子筛的组成和物化性质如表1所示。
制备例4
(1)将适量肉桂酸钾溶于苯中，搅拌均匀，充分溶解，配制成质量百分含量为6％的溶液；用该溶液以5mL/g的液固比浸渍200g的Hβ分子筛(氧化硅与氧化铝的摩尔比为150)，浸渍4小时后滤出分子筛；
(2)将滤出的分子筛用110℃热氮气以900h-1的空速吹扫5小时，吹扫结束后自然冷却至室温；
(3)用去离子水以5mL/g的液固比清洗步骤(2)所得到分子筛，将洗涤后分子筛于120℃干燥6小时并于540℃焙烧4小时，得到改性Hβ分子筛A4；改性分子筛的组成和物化性质如表1所示。
制备例5
按照制备例1的方法，不同的是，步骤(1)中，肉桂酸钾的质量百分含量为2wt％。得到的改性分子筛记为A5，组成和物化性质如表1所示。
制备例6
按照制备例1的方法，不同的是，步骤(2)中，将滤出的分子筛用80℃热氮气以150h-1的空速吹扫3小时。得到的改性分子筛记为A6，组成和物化性质如表1所示。
对比制备例1
以硝酸钾水溶液为浸渍液，采用等体积浸渍的方法浸渍Hβ分子筛(氧化硅与氧化铝的摩尔比为40)，浸渍2小时后滤出分子筛，并于110℃干燥5小时并于550℃焙烧5小时，得到的改性分子筛记为DA1，改性分子筛的组成和物化性质如表1所示。
对比制备例2
以肉桂酸钾水溶液为浸渍液，采用等体积浸渍的方法浸渍Hβ分子筛(氧化硅与氧化铝的摩尔比为25)，浸渍2小时后滤出分子筛，并于110℃干燥5小时并于550℃焙烧5小时，得到的改性分子筛记为DA2，改性分子筛的组成和物化性质如表1所示。
对比制备例3
以硝酸钾水溶液为浸渍液，采用等体积浸渍的方法浸渍Hβ分子筛(氧化硅与氧化铝的摩尔比为80)，浸渍3小时后滤出分子筛，并于120℃干燥3小时并于560℃焙烧5小时，得到的改性分子筛记为DA3，改性分子筛的组成和物化性质如表1所示。
对比制备例4
采用未改性的Hβ分子筛(氧化硅与氧化铝的摩尔比为40)，记为DA4，组成和物化性质如表1所示。
表1

以下实施例用于说明催化剂的制备。
实施例1
(1)将改性分子筛A1、氧化铝、田菁粉与10wt％硝酸溶液按照质量比为70：30：10：40充分混捏，其中改性分子筛、氧化铝前驱体的重量均是以干基计，然后进行挤条成型截面为条径为2mm的三叶草形。再经110℃干燥5小时，550℃焙烧5小时制得催化剂前驱体；
(2)步骤(1)所得催化剂前驱体采用等体积浸渍法负载La氧化物，再经110℃干燥5小时，550℃焙烧5小时制得成品催化剂，该催化剂记作CAT-1。催化剂的组成和物化性质如表2所示。
实施例2
(1)将改性分子筛A2、氧化铝、田菁粉与12wt％硝酸溶液按照质量比为77：23：11：38充分混捏，其中改性分子筛、氧化铝前驱体的重量均是以干基计，然后进行挤条成型，截面为1.8mm的圆柱形。再经120℃干燥4小时，510℃焙烧3小时制得催化剂前驱体；
(2)步骤(1)所得催化剂前驱体采用等体积浸渍法负载Ce氧化物，再经120℃干燥5小时，500℃焙烧4小时制得成品催化剂，该催化剂记作CAT-2。催化剂的组成和物化性质如表2所示。
实施例3
(1)将改性分子筛A3、氧化铝、田菁粉与15wt％硝酸溶液按照质量比为72：28：13：35充分混捏，其中改性分子筛、氧化铝前驱体的重量均是以干基计，然后进行挤条成型，截面为1.5mm的圆柱形。再经120℃干燥5小时，550℃焙烧3小时制得催化剂前驱体；
(2)步骤(1)所得催化剂前驱体采用等体积浸渍法负载Mg氧化物，再经120℃干燥5小时，550℃焙烧4小时制得成品催化剂，该催化剂记作CAT-3。催化剂的组成和物化性质如表2所示。
实施例4
(1)将改性分子筛A4、氧化铝、田菁粉与10wt％硝酸溶液按照质量比为60：40：15：40充分混捏，其中改性分子筛、氧化铝前驱体的重量均是以干基计，然后进行挤条成型，截面为2.2mm的三叶草形。再经110℃干燥6小时，550℃焙烧4小时制得催化剂前躯体；
(2)步骤(1)所得催化剂前驱体采用等体积浸渍法负载Si氧化物，再经110℃干燥5小时，550℃焙烧5小时制得成品催化剂，该催化剂记作CAT-4。催化剂的组成和物化性质如表2所示。
实施例5
按照实施例1的方法，不同的是，采用改性分子筛A5替换A1，制得的成品催化剂记作CAT-5，组成和物化性质如表2所示。
实施例6
按照实施例1的方法，不同的是，采用改性分子筛A6替换A1，制得的成品催化剂记作CAT-6，组成和物化性质如表2所示。
实施例7
按照实施例1的方法，不同的是，不进行步骤(2)，将步骤(1)得到的催化剂前驱体直接作为成品催化剂，记为CAT-7。
对比例1
按照实施例1的方法，不同的是，采用改性分子筛DA1替换A1，得到的成品催化剂记为DCAT-1，催化剂的组成和物化性质如表2所示。
对比例2
按照实施例2的方法，不同的是，采用改性分子筛DA2替换A2，得到的成品催化剂记为DCAT-2，催化剂的组成和物化性质如表2所示。
对比例3
按照实施例3的方法，不同的是，采用改性分子筛DA3替换A3，得到的成品催化剂记为DCAT-3，催化剂的组成和物化性质如表2所示。
对比例4
按照实施例1的方法，不同的是，采用改性分子筛DA4替换A1，得到的成品催化剂记为DCAT-4，催化剂的组成和物化性质如表2所示。
对比例5
(1)将改性分子筛DA1、氧化铝、田菁粉与10wt％硝酸溶液按照质量比为70：30：10：40充分混捏，其中改性分子筛、氧化铝前驱体的重量均是以干基计，然后进行混捏，成型，再经110℃干燥5小时，550℃焙烧5小时制得催化剂前驱体；
(2)将步骤(1)所得催化剂前驱体与硝酸钼的水溶液接触，加入NaBH4在100℃下回流还原8h，过滤、真空干燥得到球形催化剂，颗粒直径3mm，记作DCAT-5。
催化剂的组成和物化性质如表2所示。每100g的DCAT-5的标准间二甲苯吸附量为10.65g，计算指征常数k为36。
表2
测试例
取上述实施例和比较例催化剂在小型评价装置中进行苯胺合成二苯胺评价实验，以苯胺为原料，反应温度为310℃，反应压力为3MPa，苯胺的体积空速为0.2h-1，采用液相色谱分析产物的浓度，并通过计算得到转化率和选择性，结果见表3，其中，
初提时间(h)为从反应起始至当苯胺转化率降至20mol％时的运转总时长；
苯胺转化率(mol％)为初提时间内的平均苯胺摩尔转化率，
苯胺转化率(mol％)＝参与反应的苯胺摩尔数/苯胺进料总摩尔数×100％。
二苯胺选择性(mol％)为初提时间内的平均二苯胺摩尔选择性，
二苯胺选择性(mol％)＝产物中二苯胺摩尔数/主副产物总摩尔数×100％。
表3
通过表3的结果可以看出，本发明制得的改性分子筛进一步制备得到的催化剂具有较高的二苯胺选择性和更长的单程运转周期。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (21)

  1. 一种改性分子筛，其特征在于，所述改性分子筛包含β分子筛以及助剂组分，所述助剂组分选自碱金属中的至少一种；
    其中，所述改性分子筛的指征常数k不低于100；
    所述指征常数k通过式(1)计算得到：
    k＝Q/(1.4909×a-0.558-c)                        式(1)
    其中，Q为每100g改性分子筛的标准间二甲苯吸附量，单位为g；a为改性分子筛中氧化硅与氧化铝的摩尔比；c为每100g改性分子筛中以氧化物计的助剂组分的摩尔数。
  2. 根据权利要求1所述的改性分子筛，其中，所述改性分子筛的指征常数k为100-550，优选为101-500；
    优选地，每100g改性分子筛的标准间二甲苯吸附量为17-33g，优选为18-31g。
  3. 根据权利要求1或2所述的改性分子筛，其中，所述助剂组分选自钠和/或钾；
    优选地，100g所述改性分子筛中，以氧化物计的助剂组分的摩尔量为0.01-0.12mol，优选为0.02-0.1mol。
  4. 根据权利要求1-3中任意一项所述的改性分子筛，其中，所述改性分子筛中氧化硅与氧化铝的摩尔比为20-250，优选为25-200。
  5. 一种改性分子筛的制备方法，其特征在于，包括：
    (1)配制包含助剂组分的有机盐和有机溶剂的浸渍液；
    所述助剂组分选自碱金属中的至少一种；
    (2)采用上述浸渍液浸渍β分子筛；
    (3)采用非活性流体对步骤(2)得到的产物进行吹扫和/或冲洗，以使助剂组分的有机盐发生反应形成含有助剂组分的大分子产物，且所述含有助剂组分的大分子产物的分子直径大于β分子筛的孔道直径，得到改性分子筛前驱体；
    (4)将所述改性分子筛前驱体进行焙烧。
  6. 根据权利要求5所述的制备方法，其中，步骤(3)中，采用非活性流体对步骤(2)得到的产物进行吹扫和/或冲洗，使助剂组分的有机盐发生自聚反应形成含有助剂组分的大分子产物；或者，
    使助剂组分的有机盐与所述有机溶剂发生加成反应形成含有助剂组分的大分子产物。
  7. 一种改性分子筛的制备方法，其特征在于，包括以下步骤：
    (1)配制包含助剂组分的有机盐和有机溶剂的浸渍液；
    其中，所述助剂组分选自碱金属中的至少一种；所述有机溶剂为C6-C10的取代或未取代的环烃化合物；
    所述助剂组分的有机盐的分子中含有环状结构，且含有能够与环烃化合物发生加成反应的不饱和官能团；
    (2)采用上述浸渍液浸渍β分子筛；
    (3)采用温度不低于80℃的非活性流体对步骤(2)得到的产物进行吹扫和/或冲洗，然后进行干燥，得到改性分子筛前驱体；
    (4)将所述改性分子筛前驱体进行焙烧。
  8. 根据权利要求7所述的制备方法，其中，所述环状结构选自饱和或不饱和的五元环和六元环中的至少一种；优选地，所述饱和或不饱和的五元环和六元环全部由碳原子组成；
    优选地，所述不饱和官能团选自碳碳双键和/或碳碳三键。
  9. 根据权利要求5-8中任意一项所述的制备方法，其中，所述助剂组分的有机盐的分子中至少含有一个不饱和六元环，优选为苯环；
    优选地，所述助剂组分的有机盐的分子量不超过250g/mol，优选为50-220g/mol；
    优选地，所述有机溶剂选自苯、环己烷、甲苯、甲基环戊烷和环己烯中的至少一种。
  10. 根据权利要求5-9中任意一项所述的制备方法，其中，所述助剂组分的有机盐的结构如式(i)所示；
    其中，R1为C2-C4的亚烯基或亚炔基，R2、R3、R4、R5、R6各自独立地选自氢原子、C1-C3的烃基中的至少一种；A1选自-COO-或者-SO3-；M选自碱金属离子中的至少一种。
  11. 根据权利要求10所述的制备方法，其中，所述R1为亚乙烯基、亚丙烯基、亚丁烯基中的至少一种；
    和/或，R2、R3、R4、R5、R6各自独立地选自氢原子、C1-C3的烃基中的至少一种；
    和/或，A1为-COO-；
    和/或，M选自K+或Na+。
  12. 根据权利要求5-11中任意一项所述的制备方法，其中，以所述浸渍液的总量为基准，助剂组分的有机盐的含量为0.1-10wt％，优选为0.5-9wt％；有机溶剂的含量为90-99.5wt％，优选为90-99.5wt％；
    优选地，相对于1g所述Hβ分子筛，所述浸渍液的用量为4-10mL，优选为5-8mL；
    优选地，所述浸渍的时间为1-10h，优选为1-5h。
  13. 根据权利要求5-12中任意一项所述的制备方法，其中，吹扫和/或冲洗结束时，出口非活性流体中的环烃化合物的含量不高于1μg/L；
    优选地，所述非活性流体选自气体或液体，优选选自氮气、氩气、氦气和氖气中的至少一种；
    优选地，所述吹扫和/或冲洗的条件包括：非活性流体的温度为80-300℃，优选为85-280℃，体积空速为100-3000h-1，优选为200-2000h-1，吹扫和/或冲洗的时间为2-24h，优选为3-20h。
  14. 根据权利要求5-13中任意一项所述的制备方法，其中，所述焙烧的条件包括：温度为300-800℃，优选为400-700℃，焙烧时间为2-24h，优选为3-8h。
  15. 权利要求5-14中任意一项所述的制备方法制得的改性分子筛。
  16. 一种催化剂，其特征在于，所述催化剂包含权利要求1-4和15中任意一项所述的改性分子筛和粘结剂。
  17. 根据权利要求16所述的催化剂，其中，所述粘结剂选自氧化铝、膨润土、尖晶石和氧化硅中的至少一种；
    优选地，以所述催化剂的总量为基准，所述改性分子筛的含量为55-85wt％，优选为58-83wt％，粘结剂的含量为15-45wt％，优选为17-42wt％；
    优选地，所述催化剂还包括第二助剂组分，所述第二助剂组分为金属组分和/或非金属组分；
    优选地，所述金属组分选自IA族、IIA族、IIIB族、IVB族、VIII族、IB族、IIB族金属元素中的至少一种，优选为Li、La、Ce、Mg、Ca、Ba、Cu、Zn、Zr、Fe中的至少一种；
    优选地，所述非金属组分选自IIIA族非金属、IVA族非金属和VA族非金属元素中的至少一种，优选为Si、P、B和C中的至少一种；
    优选地，以所述催化剂的总量为基准，以氧化物计，所述第二助剂组分的含量为0.1-5wt％。
  18. 根据权利要求16或17所述的催化剂，其中，所述催化剂的比表面积为250-650m2/g，优选为300-600m2/g；
    优选地，所述催化剂的比孔容为0.2-0.55mL/g，优选为0.25-0.5mL/g。
  19. 权利要求1-4和15中任意一项所述的改性分子筛或权利要求16-18中任意一项所述的催化剂在苯胺缩合反应中的应用。
  20. 一种苯胺合成二苯胺的方法，其特征在于，所述方法包括：在缩合反应条件下，将苯胺与催化剂接触；
    其中，所述催化剂为权利要求16-18中任意一项所述的催化剂。
  21. 根据权利要求20所述的方法，其中，所述缩合反应条件包括：反应压力为0.1-4MPa，优选为0.15-3.5MPa；反应温度为280-360℃，优选为290-350℃；苯胺体积空速为0.1-0.3h-1，优选为0.15-0.25h-1。
PCT/CN2024/134560 2023-12-06 2024-11-26 改性分子筛及其制备方法、催化剂及其应用、苯胺合成二苯胺的方法 Pending WO2025119035A1 (zh)

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