CN113509958B - Heteroatom-containing molecular sieve, modification method and application thereof - Google Patents

Heteroatom-containing molecular sieve, modification method and application thereof Download PDF

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CN113509958B
CN113509958B CN202010277923.7A CN202010277923A CN113509958B CN 113509958 B CN113509958 B CN 113509958B CN 202010277923 A CN202010277923 A CN 202010277923A CN 113509958 B CN113509958 B CN 113509958B
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molecular sieve
heteroatom
catalyst
molar ratio
phenol
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CN113509958A (en
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彭欣欣
林民
朱斌
夏长久
罗一斌
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • 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
    • 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

Abstract

A modification method of a molecular sieve containing hetero atoms is characterized in that the molecular sieve containing hetero atoms and a template agent are modified under the conditions of externally applied pressure, externally added liquid with pH value more than 6 and roasting treatment with apparent pressure of 0.01-1.0 Mpa. The method has the advantages of simple process, easy implementation, good effect, and high micropore specific surface area while removing part of template agent, and generates a new pore structure.

Description

Heteroatom-containing molecular sieve, modification method and application thereof
Technical Field
The invention relates to a molecular sieve, a modification method and application thereof, in particular to a heteroatom-containing molecular sieve, a modification method and application thereof in the fields of catalytic oxidation reaction, catalytic isomerization-esterification and catalytic MPV reaction.
Background
Molecular sieve has unique pore canal structure and active center, so that it has high activity and product selectivity in several reactions. The existing preparation methods of the molecular sieve mainly comprise a hydrothermal synthesis method, a dry gel conversion method, a post-synthesis method and the like. Among them, the dry gel conversion method and the post-synthesis method are less applied to industry due to complicated operation process, the need of using corrosive reagents and harsh operation conditions, and the hydrothermal synthesis method is mainly adopted in the production of most molecular sieves at present. The hydrothermal synthesis method mainly adopts liquid or solid raw materials, and the molecular sieve product is obtained by crystallization under certain temperature and pressure conditions in the kettle-type reactor, so that the operation condition is more mild, and the operation process is simpler and more convenient and is easy to industrialize.
Most molecular sieves are produced under the guiding action of expensive organic amine, and the organic amine can serve as a structure guiding agent and an organic base in the crystallization process of the molecular sieve. Prior to use of the molecular sieve, the usual method in industry is to remove the templating agent by high temperature calcination under oxygen.
CN1115296C discloses a method for removing template agent by mixing molecular sieve containing organic amine template agent with acid-containing solution, drying and roasting, the method has harsh treatment condition, the molecular sieve is easy to cause skeleton structure damage after being mixed with strong acid substance, and activity is reduced.
CN1117471a discloses a method for removing organic amine by roasting after treating a solution of a silicon-aluminum molecular sieve and hydrazine, hydroxylamine, hydrazine or hydrochloride of hydroxylamine, which requires the use of toxic reagents, and the operation process is mainly safe.
CN1138007a discloses a method for roasting and removing organic amine template agent after immersing super macroporous molecular sieve in hydrogen peroxide, the method uses strong oxidant, and there is a safety problem that the oxidant is decomposed violently when meeting alkali.
Chinese patent CN1219701C discloses a method for removing organic template agent by using microwave digestion and cheap oxidizing inorganic acid and hydrogen peroxide as solvent and self pressure, which is carried out under 5-20 atm, and the treatment condition is harsh.
CN1220301a discloses an organic template agent in MCM-41 super macroporous molecular sieve containing template agent by using straight-run gasoline, alcohol and inorganic acid composite extraction agent, and the method is only applicable to super macroporous molecular sieve, and has no ideal effect on medium and large pore molecular sieves.
CN1307097C discloses a method of using inorganic acid or inorganic base to regulate hydrogen peroxide solution, then placing the hydrogen peroxide solution and molecular sieve together in a photoreactor, and decomposing template agent under the irradiation of ultraviolet light, the treatment efficiency of this method is low.
In summary, the prior art methods for treating the templates of molecular sieves mainly decompose the templates in various ways under severe conditions, and the templates in the molecular sieves are not fully utilized and expensive templates are lost.
Disclosure of Invention
The invention aims at solving the problems that the template agent treatment method in the prior art is harsh in condition, only the template agent is simply decomposed or removed, the template agent is not fully utilized and expensive template agent is wasted, and provides a modification method of a molecular sieve which fully utilizes the template agent.
It is a further object of the present invention to provide a molecular sieve obtainable by the modification process, which molecular sieve has a particular pore distribution profile.
It is a further object of the present invention to provide the use of said molecular sieves.
In order to achieve one of the purposes of the invention, the invention provides a modification method of a molecular sieve containing hetero atoms, which is characterized in that the molecular sieve containing hetero atoms of a template agent is modified under the conditions of externally applied pressure, externally added liquid with pH value more than 6 and roasting treatment with apparent pressure of 0.01-1.0 Mpa.
In order to achieve the second object of the present invention, the present invention provides a deviceThe molecular sieve containing hetero atoms is characterized by that it contains one element of titanium, tin and zirconium, and its micropore specific surface area is 420-500m 2 And/g, the molecular sieve having a first pore distribution in the range of 2-2.8nm and a second pore distribution in the range of 2.8-4nm, the ratio of the second pore distribution to the maximum differential pore volume of the first pore distribution being (0.6-1.5): 1.
in order to achieve the third object of the present invention, the present invention provides the use of a molecular sieve in a catalytic reaction.
The modification method of the heteroatom-containing molecular sieve provided by the invention has the advantages of simple process, easiness in implementation, good effect, removal of part of template agent, and improvement of the specific surface area of micropores, so that a new pore structure is generated. The heteroatom-containing molecular sieve provided by the invention has the advantages of double-pore distribution and high micropore specific surface area, and is high in catalytic activity and high in target product yield when being used for preparing dihydroxybenzene by phenol hydroxylation reaction, lactic acid ester by dihydroxyacetone and alcohol reaction, and gamma-valerolactone by levulinic acid and secondary alcohol.
Drawings
FIG. 1 is a pore distribution diagram of a TS-1 molecular sieve obtained by the modification method of comparative example 1.
FIG. 2 is a pore distribution diagram of the TS-1 molecular sieve obtained by the modification method of example 1.
Detailed Description
The invention provides a modification method of a heteroatom-containing molecular sieve, which is characterized in that the heteroatom-containing molecular sieve containing a template agent is modified under the conditions of externally applied pressure, externally added liquid with pH value more than 6 and roasting treatment with apparent pressure of 0.01-1.0 Mpa.
In the process of the present invention, the apparent pressure is preferably 0.1 to 0.5MPa, more preferably 0.2 to 0.3MPa, and the temperature is 200 to 600℃and more preferably 250 to 400 ℃.
The molecular sieve containing the heteroatom and the template agent is prepared by adopting a hydrothermal synthesis method or a rearrangement method, and the molecular sieve containing the heteroatom and the template agent is filtered, dried and not baked. In the molecular sieve containing the heteroatom and the template agent, the content of the template agent accounts for 1-30% of the weight of the molecular sieve. The template agent comprises an organic amine compound, such as fatty amine, aromatic amine, alcohol amine, organic quaternary ammonium base, organic quaternary ammonium salt and/or long-chain alkyl ammonium compound.
The organic amine is one or more of fatty amine, aromatic amine and alcohol amine, and the fatty amine (also called fatty amine compound) has a general formula of R 1 (NH 2 ) n Wherein R is 1 Is an alkyl or alkylene group having 1 to 8 carbon atoms, n=1 or 2; the alcohol amine (also called alcohol amine compound in the invention) has a general formula (HOR) 2 ) m NH (3-m) Wherein R is 2 Is an alkyl group having 1 to 8 carbon atoms, m=1, 2 or 3. The aliphatic amine is one or more of ethylamine, n-butylamine, butanediamine or hexamethylenediamine. The aromatic amine refers to an amine with one aromatic substituent, such as one or more of aniline, toluidine and p-phenylenediamine. Such as one or more of monoethanolamine, diethanolamine, or triethanolamine.
The organic quaternary ammonium base is one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or tetraethylammonium hydroxide; such as one or more of tetrapropylammonium bromide, tetrabutylammonium bromide, tetraethylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium chloride, or tetraethylammonium chloride.
The long-chain alkyl ammonium compound has a general formula of R 3 NH 3 X or R 3 N(R 4 ) 3 X, wherein R is 3 Is alkyl with 12-18 carbon atoms, R 4 Is alkyl with 1-4 carbon atoms; x is a monovalent anion such as OH - 、Cl - 、Br - The method comprises the steps of carrying out a first treatment on the surface of the When X is OH - When the present invention is referred to as basic long chain alkyl ammonium compounds; the long-chain alkyl ammonium compound is exemplified by cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium hydroxide, and long-chain alkyl ammonium compound is exemplified by tetradecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium hydroxide, dodecyl trimethylammonium bromide, dodecyl ammonium chloride, dodecylOne or more of trimethylammonium hydroxide, octadecyltrimethylammonium bromide, octadecyl ammonium chloride, and octadecyl trimethylammonium hydroxide.
In the present invention, the molecular sieve containing the template agent may be a molecular sieve having a structure of AEL, AFI, AFN, BEC, CFI, CHA, CON, EUO, FAU, FER, IMF, LTA, MER, MFI, MEL, MOR, MWW, RHO, TON, BEA, EWT, two-dimensional hexagonal phase, preferably having an MFI structure. The molecular sieve framework containing the template agent can contain titanium, tin, zirconium, tantalum, niobium, molybdenum, tungsten, vanadium, manganese, chromium, iron, cobalt, nickel, copper and zinc elements, for example, TS-1, sn-MFI molecular sieve and Zr-MFI molecular sieve, wherein the molar ratio of the titanium, tin or zirconium element to the silicon element in the molecular sieve is preferably (0.001-0.04): 1, further preferably (0.01 to 0.03): 1.
in the present invention, the liquid with pH value higher than 6 is preferably water, ammonia water or organic amine water solution. The mass fraction of the alkaline substance in the liquid is preferably 0 to 30%, more preferably 5 to 10%. The organic amine is preferably fatty amine or organic quaternary ammonium base, and the fatty amine (also called fatty amine compound) has a general formula of R 1 (NH 2 ) n Wherein R is 1 Is an alkyl or alkylene group having 1 to 8 carbon atoms, n=1 or 2, such as one or more of ethylamine, n-butylamine, butanediamine or hexamethylenediamine, and the organic quaternary ammonium base comprises one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or tetraethylammonium hydroxide.
The modification treatment can lead the liquid to be contacted with the heteroatom-containing molecular sieve containing the template agent at the temperature and the pressure, and can lead the liquid to be contacted with the heteroatom-containing molecular sieve containing the template agent after being gasified. Preferably, this includes preheating the liquid to vaporise and contacting the gas produced with the molecular sieve. The contacting may be static or may be fluid passing through the molecular sieve. The amount of the liquid used in the modification treatment is preferably (0.1 to 1) g of liquid/(g of molecular sieve. Min), more preferably (0.2 to 0.6) g of liquid/(g of molecular sieve. Min).
The modification treatment also comprises roasting the molecular sieve after the modification treatment in an oxygen-containing atmosphere. That is, the molecular sieve after the modification treatment of the invention can achieve the effect of partially removing the template agent, and can be subjected to roasting operation after washing and/or drying. The roasting can be carried out under the condition of oxygen enrichment or oxygen deficiency, the roasting temperature is preferably 300-800 ℃, and the roasting time is preferably 0.5-12h.
The invention also provides a molecular sieve containing hetero atoms, which is characterized in that the specific surface area of micropores of the molecular sieve is 420-500m 2 /g, preferably 440-470m 2 The molecular sieve has a first pore distribution in the range of 2-2.8nm and a second pore distribution in the range of 2.8-4nm, the ratio of the second pore distribution to the maximum differential pore volume of the first pore distribution being (0.6-1.5): 1. preferably (0.8-1.2): 1.
the hetero atom is one of Ti, sn, zr, ta, nb, mo, W, V, mn, cr, fe, co, ni, cu and Zn, preferably Ti, sn and Zr. The crystal structure of the heteroatom-containing molecular sieve is selected from AEL, AFI, AFN, BEC, CFI, CHA, CON, EUO, FAU, FER, IMF, LTA, MER, MFI, MEL, MOR, MWW, RHO, TON, BEA, EWT, two-dimensional hexagonal phase structure, wherein the MFI structure is preferred. The heteroatom-containing molecular sieve is preferably a TS-1, sn-MFI molecular sieve or a Zr-MFI molecular sieve.
The invention further provides application of the heteroatom-containing molecular sieve obtained by the heteroatom-containing molecular sieve or the modification method. Preferably, the TS-1, sn-MFI molecular sieve and Zr-MFI molecular sieve which are claimed above are applied to catalytic reactions of phenol hydroxylation reaction for preparing benzenediol, dihydroxyacetone for preparing lactic acid ester by reacting with alcohol, levulinic acid for preparing gamma-valerolactone by reacting with secondary alcohol, and the like.
In addition, under the condition of hydroxylation reaction, TS-1 molecular sieve is used as a catalyst, phenol and hydrogen peroxide are contacted with a solvent to obtain a product containing the benzenediol, and the solvent is water or alcohol, ketone, ester and nitrile with the carbon number of 1-10. The molar ratio of the phenol to the hydrogen peroxide is preferably 1: (0.1 to 5), further preferably 1: (0.5-3), more preferably 1: (0.8-1.5), the molar ratio of phenol to solvent is preferably 1: (1-100), further preferably 1: (10-70), more preferably 1: (20-50), the weight ratio of the catalyst to phenol is preferably (0.01-0.3): 1, further preferably (0.05 to 0.15): 1, the solvent is preferably one or more of water, methanol, acetone, butanone and acetonitrile. The reaction temperature is preferably 50 to 90℃and more preferably 60 to 80 ℃. The reaction time is preferably 0.5 to 12 hours.
Further, the method for preparing methyl lactate provided by the invention is to contact dihydroxyacetone with alcohol to obtain a product containing the methyl lactate by using Sn-MFI molecular sieve as a catalyst. The alcohol is primary alcohol, secondary alcohol or tertiary alcohol with 1-10 carbon atoms, preferably methanol, ethanol, n-propanol, isopropanol, cyclopentanol or cyclohexanol. The molar ratio of dihydroxyacetone to alcohol is preferably 1: (5-100), further preferably 1: (20-80), more preferably 1: (30-60), the weight ratio of the catalyst to dihydroxyacetone is preferably (0.01-0.3): 1, further preferably (0.05 to 0.15): 1. the reaction temperature is preferably 50 to 80℃and more preferably 60 to 70 ℃. The reaction time is preferably 0.5 to 12 hours.
In addition, the method for preparing gamma-valerolactone provided by the invention takes Zr-MFI molecular sieve as a catalyst, and levulinic acid is contacted with secondary alcohol under the MPV reaction condition to obtain a product containing gamma-valerolactone. The secondary alcohol is a secondary alcohol with 3-10 carbon atoms, preferably isopropanol, sec-butanol, 2-pentanol and cyclohexanol. The molar ratio of levulinic acid to secondary alcohol is preferably 1: (10-200), further preferably 1: (30-130), more preferably 1: (50-80), the weight ratio of the catalyst to levulinic acid is preferably (0.01-0.3): 1, further preferably (0.05 to 0.15): 1. the reaction temperature is preferably 60 to 180℃and more preferably 80 to 140 ℃. The reaction time is preferably 1 to 24 hours.
In the application provided by the invention, the heteroatom-containing molecular sieve is used in the form of raw powder, can be used after being molded, and can be mixed with other catalysts for use; the application can be carried out in a plurality of reactors such as a kettle reactor, a slurry bed reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a micro-channel reactor and the like; the reaction raw materials and the catalyst can be fed at one time, intermittently and continuously, and the invention is not limited.
It will be appreciated by those skilled in the art that the separation of the product from the catalyst may be achieved in various ways, for example, in the case of using an original powdery molecular sieve as the catalyst, the separation of the product and the recovery and reuse of the catalyst may be achieved by sedimentation, filtration, centrifugation, evaporation, membrane separation, or the like, or the catalyst may be molded and then packed in a fixed bed reactor, and the catalyst is recovered after the reaction is completed, and various methods for separating and recovering the catalyst are generally involved in the prior art and are not repeated here.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the following examples and comparative examples:
the structure of the molecular sieve was determined by XRD analysis.
The content of the template agent in the molecular sieve is measured by a thermogravimetric method, and the weight loss from the temperature of more than 200 ℃ of the weight loss curve to the time when the weight loss curve is stable is calculated as the template agent content of the molecular sieve.
The chemical composition of the molecular sieve was determined using XRF analysis.
The specific surface area of the molecular sieve is measured by adopting a nitrogen low-temperature adsorption desorption method, and the micropore specific surface area is calculated according to a BET method; the pore volume and pore distribution were measured according to the method described in RIPP 151-90, written by Yang Cuiding et al, method for petrochemical analysis (first edition, published by science Press 1990, 9).
The morphology analysis of the molecular sieve adopts an SEM method to observe the particle size and morphology.
The acidity analysis was performed using pyridine infrared spectroscopy.
The state of the titanium species was analyzed by ultraviolet-visible light spectroscopy.
The starting materials used in the examples and comparative examples were analytically pure reagents unless otherwise specified.
The reaction product is analyzed by gas chromatography, and the analysis result is quantified by an external standard method. Wherein, the analysis conditions of the chromatograph are: agilent-6890 chromatograph, HP-5 capillary chromatographic column, sample injection amount 0.5 μl, sample inlet temperature 280 ℃. The column temperature was maintained at 100deg.C for 2min, then raised to 250deg.C at 15 ℃/min and maintained for 10min. FID detector, detector temperature 300 ℃.
Yield of benzenediol (%) = moles of catechol and hydroquinone in the product/moles of phenol in the feed x 100%.
Yield of methyl lactate (%) = mole of methyl lactate in product/mole of dihydroxyacetone in starting material x 100%.
Gamma valerolactone yield (%) = moles of gamma valerolactone in product/moles of levulinic acid in starting material x 100%.
Preparation example 1
The preparation example is used for preparing the TS-1 molecular sieve containing the template agent.
About 3/4 of a solution of tetrapropylammonium hydroxide (TPAOH, 20 wt%) was added to a solution of Tetraethylorthosilicate (TEOS) to obtain a liquid mixture having a pH of about 13, and then the desired amount of n-butyl titanate [ Ti (OBu) ] was added dropwise to the obtained liquid mixture with vigorous stirring 4 ]Is stirred for 15 minutes. Finally, the remaining TPAOH was slowly added to the mixture and stirred at 348-353K for about 3 hours to give a chemical composition of 0.02TiO 2 ∶SiO 2 ∶0.36TPA∶35H 2 O sol, crystallizing at 443K for 3 days, filtering the obtained solid, washing with distilled water, and drying at 373K for 5 hours to obtain molecular sieve sample with the number of TS-1-A.
The weight loss of TS-1-A measured by thermogravimetric method at 200-600deg.C is 15%.
Preparation example 2
The preparation example is used for preparing the TS-1 molecular sieve containing the template agent.
The difference from preparation example 1 is that a TiO having a chemical composition of 0.008 is obtained 2 ∶SiO 2 ∶0.36TPA∶35H 2 O sol and molecular sieve sample number is TS-1-B.
The weight loss of TS-1-B measured by thermogravimetric method at 200-600deg.C is 12%.
Preparation example 3
The preparation example is used for preparing the Sn-MFI molecular sieve containing the template agent.
About 3/4 of the tetrapropylammonium hydroxide (TPAOH, 20 wt%) solution was added to the tetraethyl orthosilicate (TEOS) solution to obtain a liquid mixture having a pH of about 13, and then a desired amount of SnCl was added dropwise to the obtained liquid mixture with vigorous stirring 4 ·5H 2 O, stir for 15 minutes. Finally, the remaining TPAOH was slowly added to the mixture and stirred at 348-353K for about 3 hours to give a chemical composition of 0.02SnO 2 ∶SiO 2 ∶0.36TPA∶35H 2 O sol, then crystallization at 443K temperature for 3 days, then filtering the obtained solid, washing with distilled water, and drying at 373K temperature for 5 hours to obtain a molecular sieve sample with the number of Sn-MFI-A.
The weight loss of Sn-MFI-A measured by thermogravimetric method is 13% at 200-600 ℃.
Preparation example 4
The preparation example is used for preparing the Sn-MFI molecular sieve containing the template agent.
The difference from preparation example 3 is that a chemical composition of 0.008SnO is obtained 2 ∶SiO 2 ∶0.36TPA∶35H 2 O sol and molecular sieve sample number is Sn-MFI-B.
The weight loss of Sn-MFI-B measured by thermogravimetric method is 11% at 200-600 ℃.
Preparation example 5
The preparation example is used for preparing the Zr-MFI molecular sieve containing the template agent.
About 3/4 of the tetrapropylammonium hydroxide (TPAOH, 20 wt%) solution was added to the tetraethyl orthosilicate (TEOS) solution to obtain a liquid mixture having a pH of about 13, and then a desired amount of zirconium n-propoxide (70 wt%) was added dropwise to the obtained liquid mixture with vigorous stirring, followed by stirring for 15 minutes. Finally, the remaining TPAOH was slowly added to the mixture and stirred at 348-353K for about 3 hours to give a chemical composition of 0.02ZrO 2 ∶SiO 2 ∶0.36TPA∶35H 2 O sol, then crystallizing at 443K for 3 days, and obtainingAfter washing with distilled water, drying at 373K for 5 hours, a molecular sieve sample was obtained, numbered Zr-MFI-A.
The weight loss of Zr-MFI-A measured by thermogravimetry at 200-600 ℃ was 12%.
Preparation example 6
The preparation example is used for preparing the Zr-MFI molecular sieve containing the template agent.
The difference from preparation example 3 is that a ZrO having a chemical composition of 0.008 was obtained 2 ∶SiO 2 ∶0.36TPA∶35H 2 O sol and molecular sieve sample number is Zr-MFI-B.
The weight loss of Zr-MFI-B measured by thermogravimetry at 200-600 ℃ was 8%.
Comparative example 1
This comparative example illustrates the preparation of TS-1 without templating agent using air calcination.
Roasting TS-1-A at 550 ℃ under the atmospheric pressure of air atmosphere for 6 hours to remove the template agent, and measuring the weight loss of the treated molecular sieve between 200 ℃ and 600 ℃ to be 0 by adopting a thermogravimetric method. The specific surface area of micropores of the molecular sieve and the ratio of the maximum differential pore volume of the second pores in the range of 2.8-4nm to the first pores in the range of 2-2.8nm are shown in Table 1, and the pore distribution diagram is shown in FIG. 1.
And (3) carrying out phenol hydroxylation reaction by taking the obtained molecular sieve as a catalyst. The mole ratio of phenol to hydrogen peroxide is 1:1, the molar ratio of phenol to acetone is 1:20, the weight ratio of the catalyst to phenol is 0.1:1, the reaction temperature is 80 ℃ and the reaction time is 4 hours, and the obtained product is subjected to gas chromatographic analysis.
The product yield results are shown in Table 1.
Comparative example 2
This comparative example illustrates the preparation of TS-1 without templating agent using pressurized air calcination.
Roasting TS-1-A at 350 deg.C and air pressure of 0.2MPa for 6 hr, and measuring the weight loss of the treated molecular sieve at 200-600 deg.C by thermogravimetric method to be 14%. Then roasting for 6 hours at 550 ℃ under normal pressure in an air atmosphere to remove the template agent. The micropore specific surface area of the molecular sieve and the ratio of the second pores in the range of 2.8-4nm to the maximum differential pore volume of the first pores in the range of 2-2.8nm are shown in Table 1.
And (3) carrying out phenol hydroxylation reaction by taking the obtained molecular sieve as a catalyst. The mole ratio of phenol to hydrogen peroxide is 1:1, the molar ratio of phenol to acetone is 1:20, the weight ratio of the catalyst to phenol is 0.1:1, the reaction temperature is 80 ℃ and the reaction time is 4 hours, and the obtained product is subjected to gas chromatographic analysis. The product yield results are shown in Table 1.
Example 1
This example illustrates the preparation of TS-1 without templating agent using the method of the present invention.
Introducing ammonia water with the mass fraction of 20% into TS-1-A at 350 ℃ and under the condition of N2 back pressure of 0.2Mpa, measuring the pH value of the solution to be 14, introducing the liquid/(g molecular sieve-min) with the rate of 0.2g, and carrying out pressure roasting treatment for 6h, wherein the loss weight of the treated molecular sieve is 8% at 200-600 ℃ by adopting a thermogravimetric method. And then roasting for 6 hours at 550 ℃ under normal pressure in an air atmosphere to remove the residual template agent.
The micropore specific surface area of the molecular sieve and the ratio of the second pores in the range of 2.8-4nm to the maximum differential pore volume of the first pores in the range of 2-2.8nm are shown in Table 1. The pore distribution diagram is shown in fig. 2.
And (3) carrying out phenol hydroxylation reaction by taking the obtained molecular sieve as a catalyst. The mole ratio of phenol to hydrogen peroxide is 1:1, the molar ratio of phenol to acetone is 1:20, the weight ratio of the catalyst to phenol is 0.1:1, the reaction temperature is 80 ℃ and the reaction time is 4 hours, and the obtained product is subjected to gas chromatographic analysis. The product yield results are shown in Table 1.
Example 2
This example illustrates the preparation of TS-1 without templating agent using the method of the present invention.
The difference from example 1 is that TS-1-A is introduced with ammonia water with a mass fraction of 5% under the conditions of 250 ℃ and N2 back pressure of 0.3Mpa, the pH value of the solution is measured to be 14, the introduction rate is 0.6g of liquid/(g of molecular sieve. Min), and the loss weight of the treated molecular sieve is measured to be 7% at 200-600 ℃ by adopting a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 3
This example illustrates the preparation of TS-1 without templating agent using the method of the present invention.
The difference from example 1 is that TS-1-A is introduced into an aqueous solution of ethylamine with a mass fraction of 12% under the conditions of 400 ℃ and an N2 back pressure of 0.25Mpa, the pH value of the solution is measured to be 13, the introduction rate is 0.4g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve is measured to be 9% at 200-600 ℃ by adopting a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 4
This example illustrates the preparation of TS-1 without templating agent using the method of the present invention.
The difference from example 1 is that TS-1-B is introduced into 30% by mass of aqueous solution of propylamine under the conditions of 600 ℃ and N2 back pressure of 0.1Mpa, the pH value of the solution is measured to be 13, the introduction rate is 0.8g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve at 200-600 ℃ is measured to be 6% by adopting a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 5
This example illustrates the preparation of TS-1 without templating agent using the method of the present invention.
The difference from example 1 is that TS-1-B is introduced into an ammonia water solution with the mass fraction of 25% under the condition of 200 ℃ and N2 back pressure of 0.5Mpa, the pH value of the solution is measured to be 14, the introduction rate is 0.1g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve is measured to be 5% at the temperature of 200-600 ℃ by adopting a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 6
This example illustrates the preparation of TS-1 without templating agent using the method of the present invention.
The difference from example 1 is that TS-1-B is introduced with water at 500℃and N2 backpressure of 0.4MPa, the pH value of the solution is determined to be 7, the introduction rate is 1g of liquid/(g of molecular sieve. Min), and the loss weight of the treated molecular sieve is determined to be 7% at 200-600℃by thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Comparative example 3
This comparative example illustrates the preparation of Sn-MFI without templating agent using air calcination.
Roasting Sn-MFI-A at 550 ℃ under the condition of air atmosphere and normal pressure for 6 hours to remove a template agent, and measuring the weight loss of the treated molecular sieve between 200 ℃ and 600 ℃ by adopting a thermogravimetric method to be 0.
The micropore specific surface area of the molecular sieve and the ratio of the second pores in the range of 2.8-4nm to the maximum differential pore volume of the first pores in the range of 2-2.8nm are shown in Table 1.
And (3) carrying out a reaction for preparing methyl lactate from dihydroxyacetone by taking the obtained molecular sieve as a catalyst. The molar ratio of dihydroxyacetone to methanol was set to 1:60, the weight ratio of catalyst to dihydroxyacetone is preferably 0.1:1, the reaction temperature is 60 ℃ and the reaction time is 6 hours, and the obtained product is subjected to gas chromatographic analysis. The product yield results are shown in Table 1.
Comparative example 4
This comparative example illustrates the preparation of Sn-MFI without templating agent using pressurized air calcination.
Roasting Sn-MFI-A at 350 ℃ and air pressure of 0.2Mpa for 6 hours, and measuring the weight loss of the treated molecular sieve between 200 and 600 ℃ by adopting a thermogravimetric method to be 12 percent. Then roasting for 6 hours at 550 ℃ under normal pressure in an air atmosphere to remove the template agent.
The micropore specific surface area of the molecular sieve and the ratio of the second pores in the range of 2.8-4nm to the maximum differential pore volume of the first pores in the range of 2-2.8nm are shown in Table 1.
And (3) carrying out a reaction for preparing methyl lactate from dihydroxyacetone by taking the obtained molecular sieve as a catalyst. The molar ratio of dihydroxyacetone to methanol was set to 1:60, the weight ratio of catalyst to dihydroxyacetone is preferably 0.1:1, the reaction temperature is 60 ℃ and the reaction time is 6 hours, and the obtained product is subjected to gas chromatographic analysis. The product yield results are shown in Table 1.
Example 7
This comparative example illustrates the preparation of Sn-MFI without templating agent according to the process of the present invention.
Introducing ammonia water with the mass fraction of 20% into Sn-MFI-A at 350 ℃ and under the condition of N2 back pressure of 0.2Mpa, measuring the pH value of the solution to be 14, introducing the liquid/(g molecular sieve-min) with the rate of 0.2g, and carrying out pressure roasting treatment for 6h, wherein the loss weight of the treated molecular sieve is 7% at 200-600 ℃ by adopting a thermogravimetric method. And then roasting for 6 hours at 550 ℃ under normal pressure in an air atmosphere to remove the residual template agent. The micropore specific surface area of the molecular sieve and the ratio of the second pores in the range of 2.8-4nm to the maximum differential pore volume of the first pores in the range of 2-2.8nm are shown in Table 1.
And (3) carrying out a reaction for preparing methyl lactate from dihydroxyacetone by taking the obtained molecular sieve as a catalyst. The molar ratio of dihydroxyacetone to methanol was set to 1:60, the weight ratio of catalyst to dihydroxyacetone is preferably 0.1:1, the reaction temperature is 60 ℃ and the reaction time is 6 hours, and the obtained product is subjected to gas chromatographic analysis. The product yield results are shown in Table 1.
Example 8
This example illustrates the preparation of Sn-MFI without templating agent according to the process of the present invention.
The difference from example 7 is that Sn-MFI-A is introduced with ammonia water with a mass fraction of 5% under the conditions of 250 ℃ and N2 back pressure of 0.3Mpa, the pH value of the solution is measured to be 14, the introduction rate is 0.6g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve is measured to be 5% at 200-600 ℃ by adopting a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 9
This example illustrates the preparation of Sn-MFI without templating agent according to the process of the present invention.
The difference from example 7 is that Sn-MFI-A is introduced into an aqueous solution of 12% by mass of ethylamine at 400℃and an N2 backpressure of 0.25MPa, the pH of the solution is determined to be 13, the rate of introduction is 0.4g of liquid/(g of molecular sieve. Min), and the loss weight of the treated molecular sieve is determined to be 7% at 200-600℃by thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 10
This example illustrates the preparation of Sn-MFI without templating agent according to the process of the present invention.
The difference from example 7 is that Sn-MFI-B is introduced into a 30% mass fraction aqueous solution of propylamine at 600℃and an N2 backpressure of 0.1MPa, the pH of the solution is measured to be 13, the introduction rate is 0.8g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve is measured to be 6% at 200-600℃by the thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 11
This example illustrates the preparation of Sn-MFI without templating agent according to the process of the present invention.
The difference from example 7 is that Sn-MFI-B is introduced into an ammonia solution with a mass fraction of 25% under the conditions of 200 ℃ and an N2 back pressure of 0.5Mpa, the pH value of the solution is measured to be 14, the introduction rate is 0.1g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve is measured to be 5% at 200-600 ℃ by a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 12
This example illustrates the preparation of Sn-MFI without templating agent according to the process of the present invention.
The difference from example 7 is that Sn-MFI-B is introduced with water at 500℃and an N2 backpressure of 0.4MPa, the pH value of the solution is determined to be 7, the introduction rate is 1g of liquid/(g of molecular sieve. Min), and the loss weight of the treated molecular sieve is determined to be 7% at 200-600℃by thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Comparative example 5
This comparative example illustrates the preparation of Zr-MFI without templating agent using air calcination.
The Zr-MFI-A is roasted for 6 hours at 550 ℃ under the atmospheric pressure of air atmosphere to remove the template agent, and the weight loss of the treated molecular sieve at 200-600 ℃ is measured to be 0 by adopting a thermogravimetric method. The micropore specific surface area of the molecular sieve and the ratio of the second pores in the range of 2.8-4nm to the maximum differential pore volume of the first pores in the range of 2-2.8nm are shown in Table 1.
And carrying out levulinic acid preparation gamma-valerolactone reaction by taking the obtained molecular sieve as a catalyst. The molar ratio of levulinic acid to isopropanol was set to 1:80, the weight ratio of catalyst to levulinic acid is preferably 0.12:1, reaction temperature 100 ℃ and reaction time 12h, and carrying out gas chromatographic analysis on the obtained product. The product yield results are shown in Table 1.
Comparative example 6
This comparative example illustrates the preparation of a template-free Zr-MFI by roasting with pressurized air.
The Zr-MFI-A is roasted for 6 hours under the condition of 350 ℃ and the air pressure of 0.2Mpa, and the weight loss of the treated molecular sieve is 11 percent between 200 and 600 ℃ measured by adopting a thermogravimetric method. Then roasting for 6 hours at 550 ℃ under normal pressure in an air atmosphere to remove the template agent. The micropore specific surface area of the molecular sieve and the ratio of the second pores in the range of 2.8-4nm to the maximum differential pore volume of the first pores in the range of 2-2.8nm are shown in Table 1.
And carrying out levulinic acid preparation gamma-valerolactone reaction by taking the obtained molecular sieve as a catalyst. The molar ratio of levulinic acid to isopropanol was set to 1:80, the weight ratio of catalyst to levulinic acid is preferably 0.12:1, reaction temperature 100 ℃ and reaction time 12h, and carrying out gas chromatographic analysis on the obtained product. The product yield results are shown in Table 1.
Example 13
This example illustrates the preparation of Zr-MFI without templating agent according to the process of the present invention.
Introducing 20% ammonia water by mass fraction into Zr-MFI-A at 350 ℃ under the condition of N2 back pressure of 0.2Mpa, measuring the pH value of the solution to be 14, introducing the liquid/(g molecular sieve-min) at the rate of 0.2g, and carrying out pressure roasting treatment for 6h, wherein the weight loss of the treated molecular sieve at 200-600 ℃ is 6% by adopting a thermogravimetric method. And then roasting for 6 hours at 550 ℃ under normal pressure in an air atmosphere to remove the residual template agent. The micropore specific surface area of the molecular sieve and the ratio of the second pores in the range of 2.8-4nm to the maximum differential pore volume of the first pores in the range of 2-2.8nm are shown in Table 1.
And carrying out levulinic acid preparation gamma-valerolactone reaction by taking the obtained molecular sieve as a catalyst. The molar ratio of levulinic acid to isopropanol was set to 1:80, the weight ratio of catalyst to levulinic acid is preferably 0.12:1, reaction temperature 100 ℃ and reaction time 12h, and carrying out gas chromatographic analysis on the obtained product. The product yield results are shown in Table 1.
Example 14
This example illustrates the preparation of Zr-MFI without templating agent according to the process of the present invention.
The difference from example 13 is that Zr-MFI-A is introduced with ammonia water with a mass fraction of 5% at 250℃and an N2 back pressure of 0.3MPa, the pH value of the solution is measured to be 14, the introduction rate is 0.6g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve is measured to be 5% at 200-600℃by a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 15
This example illustrates the preparation of Zr-MFI without templating agent according to the process of the present invention.
The difference from example 13 is that Zr-MFI-A is introduced into an aqueous solution of 12% by mass of ethylamine at 400℃and an N2 backpressure of 0.25MPa, the pH of the solution is determined to be 13, the rate of introduction is 0.4g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve is determined to be 6% at 200-600℃by thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 16
This example illustrates the preparation of Zr-MFI without templating agent according to the process of the present invention.
The difference from example 13 is that Zr-MFI-B is introduced into a 30% by mass aqueous solution of propylamine under the conditions of 600℃and an N2 back pressure of 0.1MPa, the pH value of the solution is measured to be 13, the introduction rate is 0.8g of liquid/(g of molecular sieve. Min), and the loss weight of the treated molecular sieve is measured to be 4% at 200-600℃by a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 17
This example illustrates the preparation of Zr-MFI without templating agent according to the process of the present invention.
The difference from example 13 is that Zr-MFI-B is introduced into an ammonia solution with a mass fraction of 25% under the conditions of 200℃and an N2 back pressure of 0.5MPa, the pH value of the solution is measured to be 14, the introduction rate is 0.1g of liquid/(g of molecular sieve. Min), and the weight loss of the treated molecular sieve is measured to be 5% at 200-600℃by a thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
Example 18
This example illustrates the preparation of Zr-MFI without templating agent according to the process of the present invention.
The difference from example 13 is that Zr-MFI-B is introduced with water at 500℃and an N2 backpressure of 0.4MPa, the pH value of the solution is determined to be 7, the introduction rate is 1g of liquid/(g of molecular sieve. Min), and the loss weight of the treated molecular sieve is determined to be 4% at 200-600℃by thermogravimetric method.
The results of the micropore specific surface area of the molecular sieve and the ratio of the second pore volume in the range of 2.8-4nm to the maximum differential pore volume of the first pore in the range of 2-2.8nm are shown in Table 1, and the results of the product yield are shown in Table 1.
TABLE 1
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As can be seen from examples 1-18 and comparative examples 1-6, the method for modifying the molecular sieve provided by the invention is simple to operate and easy to implement, and can be used for preparing the double-pore distribution molecular sieve with higher micropore specific surface area, first pores in the range of 2-2.8nm, second pores in the range of 2.8-4nm, and the ratio of the maximum differential pore volume of the second pores to the first pores is (0.6-1.5): 1. the TS-1, sn-MFI and Zr-MFI molecular sieves prepared by the method have high yield of target products and show excellent catalytic performance.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination of the various embodiments of the present disclosure may be made without departing from the spirit of the present disclosure, which should also be considered as the disclosure of the present invention.

Claims (18)

1. A molecular sieve containing hetero atoms is characterized by that its micropore specific surface area is 420-500m 2 /g; the molecular sieve has a first pore distribution in the range of 2-2.8nm and a second pore distribution in the range of 2.8-4nm, the ratio of the second pore distribution to the maximum differential pore volume of the first pore distribution being (0.6-1.5): 1, a step of;
the heteroatom-containing molecular sieve is obtained by modifying the following method: under the conditions of externally applied pressure, externally added liquid with pH value more than 6 and roasting treatment with apparent pressure of 0.01-1.0 Mpa, modifying the heteroatom-containing molecular sieve containing the template agent, and roasting the modified molecular sieve in oxygen-containing atmosphere; wherein the heteroatom-containing molecular sieve is a TS-1 molecular sieve, a Sn-MFI molecular sieve or a Zr-MFI molecular sieve; the liquid with the pH value more than 6 is water, ammonia water or aqueous solution of organic amine, and the mass fraction of alkaline substances in the liquid is 0-30%; in the roasting treatment condition, the roasting temperature is 200-600 ℃.
2. The heteroatom-containing molecular sieve according to claim 1, wherein the apparent pressure in the calcination treatment conditions is 0.1-0.5MPa.
3. The heteroatom-containing molecular sieve according to claim 1, wherein the heteroatom-containing molecular sieve containing a template agent comprises a heteroatom-containing molecular sieve containing a template agent prepared by a hydrothermal synthesis method or a rearrangement method, and subjected to filtration, drying, but not roasting treatment.
4. A heteroatom-containing molecular sieve according to claim 1 or claim 3 wherein the template agent comprises from 1 to 30% by weight of the molecular sieve.
5. The heteroatom-containing molecular sieve of claim 1, wherein the modification treatment comprises pre-heating the liquid to vaporize and contacting the gas produced thereby with the heteroatom-containing molecular sieve containing a templating agent.
6. The heteroatom-containing molecular sieve according to claim 1, wherein the liquid having a pH > 6 is introduced at a rate of (0.1-1) g liquid/(g molecular sieve-min) during the modification treatment.
7. A method for preparing benzenediol by phenol hydroxylation reaction, which is characterized in that under the condition of hydroxylation reaction, the heteroatom-containing molecular sieve as defined in any one of claims 1-6 is used as a catalyst, and phenol and hydrogen peroxide are contacted with a solvent to obtain a product containing benzenediol; the heteroatom-containing molecular sieve is a TS-1 molecular sieve.
8. The method of claim 7, wherein the molar ratio of phenol to hydrogen peroxide is 1: (0.1-5); the molar ratio of phenol to solvent is 1: (1-100); the weight ratio of the catalyst to the phenol is (0.01-0.3): 1.
9. the method of claim 8, wherein the molar ratio of phenol to hydrogen peroxide is 1: (0.5-3); the molar ratio of phenol to solvent is 1: (10-70); the weight ratio of the catalyst to the phenol is (0.05-0.15): 1.
10. the method of claim 9, wherein the molar ratio of phenol to hydrogen peroxide is 1: (0.8-1.5); the molar ratio of phenol to solvent is 1: (20-50).
11. A process for preparing methyl lactate, characterized in that dihydroxyacetone is contacted with an alcohol to obtain a product containing lactate, using the heteroatom-containing molecular sieve as defined in any one of claims 1 to 6 as a catalyst; the heteroatom-containing molecular sieve is a Sn-MFI molecular sieve.
12. The method of claim 11, wherein the dihydroxyacetone to alcohol molar ratio is 1: (5-100); the weight ratio of the catalyst to dihydroxyacetone is (0.01-0.3): 1.
13. the method of claim 12, wherein the dihydroxyacetone to alcohol molar ratio is 1: (20-80); the weight ratio of the catalyst to dihydroxyacetone is (0.05-0.15): 1.
14. the method of claim 13, wherein the dihydroxyacetone to alcohol molar ratio is 1: (30-60).
15. A process for preparing gamma valerolactone, characterized in that levulinic acid is contacted with a secondary alcohol under MPV reaction conditions using the heteroatom-containing molecular sieve as defined in any one of claims 1-6 as catalyst to obtain a gamma valerolactone-containing product; the heteroatom-containing molecular sieve is a Zr-MFI molecular sieve.
16. The method of claim 15, wherein the molar ratio of levulinic acid to secondary alcohol is 1: (10-200); the weight ratio of the catalyst to levulinic acid is (0.01-0.3): 1.
17. the method of claim 16, wherein the molar ratio of levulinic acid to secondary alcohol is 1: (30-130); the weight ratio of the catalyst to levulinic acid is (0.05-0.15): 1.
18. the method of claim 17, wherein the molar ratio of levulinic acid to secondary alcohol is 1: (50-80).
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