CN111253237B - Method for preparing methylglyoxal by catalyzing sugar - Google Patents

Method for preparing methylglyoxal by catalyzing sugar Download PDF

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CN111253237B
CN111253237B CN201811459271.8A CN201811459271A CN111253237B CN 111253237 B CN111253237 B CN 111253237B CN 201811459271 A CN201811459271 A CN 201811459271A CN 111253237 B CN111253237 B CN 111253237B
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molecular sieve
tin
titanium
silicon molecular
silicon
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CN111253237A (en
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夏长久
刘聿嘉
彭欣欣
朱斌
林民
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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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • 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
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • 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
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a method for preparing methylglyoxal by catalyzing sugar, which comprises the following steps: contacting sugar with a catalyst in a reactor in the presence of alcohol and carrying out a reaction to obtain a product containing methylglyoxal; wherein the molar ratio of sugar to alcohol is 1: (50-600), the reaction temperature is more than 100 ℃ and less than 150 ℃, the reaction time is 10-50h, the catalyst contains a tin-titanium-silicon molecular sieve, and the weight ratio of sugar to the tin-titanium-silicon molecular sieve based on the dry weight is 1: (1-6). The process of the present invention has high sugar conversion and methylglyoxal yield.

Description

Method for preparing methylglyoxal by catalyzing sugar
Technical Field
The invention relates to a method for preparing methylglyoxal by catalyzing sugar.
Background
Methylglyoxal is an aldehyde compound, also known as methylglyoxal, 2-oxopropanal. The product is yellow or yellow brown transparent liquid, has pungent smell, and is hygroscopic. Density 1.200g/cm 3 Melting point 25 ℃, boiling point 72 ℃ and refractive index 1.4209. The substance is easy to polymerize into viscous semisolid, is dissolved in water to release heat, and is recovered into monomer solution. Heating at 72 deg.C to form yellow green gas, and maintaining in closed tube for several days, wherein the product is generally 20% -40% water solution. It can be used as intermediate of medicine and pesticide and biochemical reagent, and also can be used as raw material of cimetidine, lactic acid, pyruvic acid, analgesic, anticancer, antihypertensive, desensitizer and cosmetic.
The traditional methods for producing methylglyoxal include acetone method, propylene glycol method, glycerin catalytic dehydrogenation method and hydroxyacetone catalytic dehydrogenation method. Acetone method is commonly used in industrial production to produce pyruvaldehyde, which usually contains acetone aldoxime, acetone hydroxylamine and other byproducts, and acetonitrile and other toxic reagents. Liquid phase oxidation of propylene glycol is also one of the possible processes, but the process results in low product yield and complex product. The product obtained by the gas-solid phase catalytic oxidation of propylene glycol has good quality and high yield, the process key lies in the development of the catalyst, a noble metal catalyst is required to be used, and the cost is higher. The catalytic dehydrogenation of glycerol also requires the use of costly noble metal catalysts. The yield of the product and the conversion rate of the reactant are both high in the gas-phase catalytic oxidation of the hydroxyacetone, but the hydroxyacetone reactant is not easy to obtain.
Disclosure of Invention
The invention aims to provide a method for preparing methylglyoxal by catalyzing sugar, which has high sugar conversion rate and methylglyoxal yield.
In order to achieve the above object, the present invention provides a method for preparing methylglyoxal by catalyzing sugar, which comprises:
contacting sugar with a catalyst in a reactor in the presence of alcohol and carrying out reaction to obtain a product containing methylglyoxal; wherein the molar ratio of sugar to alcohol is 1: (50-600), the reaction temperature is more than 100 ℃ and less than 150 ℃, the reaction time is 10-50h, the catalyst contains a tin-titanium-silicon molecular sieve, and the weight ratio of sugar to the tin-titanium-silicon molecular sieve based on the dry weight is 1: (1-6).
Optionally, the tin-titanium-silicon molecular sieve is selected from one or more of an MFI type tin-titanium-silicon molecular sieve, an MEL type tin-titanium-silicon molecular sieve, a BEA type tin-titanium-silicon molecular sieve, an MWW type tin-titanium-silicon molecular sieve, an MOR type tin-titanium-silicon molecular sieve, a hexagonal structure tin-titanium-silicon molecular sieve and an FAU type tin-titanium-silicon molecular sieve.
Optionally, the tin-titanium-silicon molecular sieve is selected from one or more of a Sn-Ti-MFI molecular sieve, a Sn-Ti-MEL molecular sieve, a Sn-Ti-Beta molecular sieve, a Sn-Ti-MCM-22 molecular sieve, a Sn-Ti-MOR molecular sieve, a Sn-Ti-MCM-41 molecular sieve, a Sn-Ti-SBA-15 molecular sieve and a Sn-Ti-USY molecular sieve.
Optionally, the tin-titanium-silicon molecular sieve contains a silicon element, a titanium element, a tin element and an oxygen element;
preferably, at least part of the crystal grains of the tin-titanium-silicon molecular sieve have a cavity structure;
preferably, the proportion of the external specific surface area of the tin-titanium-silicon molecular sieve in the total specific surface area is more than 10%, and the total specific surface area is 300m 2 More than g, and the external specific surface area is 20m 2 More than g;
preferably, the tin-titanium-silicon molecular sieve has a diffraction peak at 0.5-9 degrees in an XRD pattern at 2 theta;
preferably, the tin-titanium-silicon molecular sieve is 460cm in FT-IR spectrum -1 、975cm -1 、800cm -1 And 1080cm -1 Nearby absorption;
preferably, the tin-titanium-silicon molecular sieve has absorption at 200-300nm in a UV-Vis spectrum;
preferably, the ratio of the external specific surface area of the tin-titanium-silicon molecular sieve to the total specific surface area is 10-25%, and the total specific surface area is 310-600m 2 Per g, external specific surface area of 31-150m 2 /g；
Preferably, the tin-titanium-silicon molecular sieve is P/P at 25 DEG C 0 Strip with a sorption time of 1 hour of =0.10The benzene adsorption is at least 35mg/g measured under the conditions; at a relative pressure P/P 0 A difference between the nitrogen adsorption amount during desorption and the nitrogen adsorption amount during adsorption of the tin-titanium-silicon molecular sieve of about 0.60% is greater than 2% of the nitrogen adsorption amount during adsorption of the tin-titanium-silicon molecular sieve;
preferably, a hysteresis loop exists between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption of the tin-titanium-silicon molecular sieve;
preferably, the radial length of the cavity part of the cavity structure inside the crystal grains of the tin-titanium-silicon molecular sieve is 0.5-300nm;
preferably, the molar ratio of the tin element to the silicon element in the tin-titanium-silicon molecular sieve is 0.05-10.
Optionally, the preparation method of the tin-titanium-silicon molecular sieve comprises:
(1) Contacting a tin source, a titanium source and a template agent in the presence of an aqueous solvent to obtain a first mixture;
(2) Mixing the first mixture with a silicon molecular sieve to obtain a second mixture;
(3) Crystallizing the second mixture under hydrothermal crystallization conditions;
preferably, in step (1), the contacting conditions include: the contact temperature is 20-80 ℃, and the contact time is 1-240min;
preferably, the silicon molecular sieve and the tin source are used in such an amount that the molar ratio of tin element to silicon element in the prepared tin-titanium-silicon molecular sieve is 0.05-10; the dosage of the silicon molecular sieve and the titanium source ensures that the molar ratio of the titanium element to the silicon element in the prepared tin-titanium-silicon molecular sieve is 0.05-10;
preferably, the molar ratio of the silicon molecular sieve, the template agent, the titanium source, the tin source and the water is from 0.005 to 20 2 The tin source is calculated by tin element, and the titanium source is calculated by TiO 2 Counting;
preferably, the hydrothermal crystallization conditions include: the crystallization temperature is 80-200 ℃ under the closed condition, and the crystallization time is 6-150h;
preferably, the tin source is an inorganic tin compound and/or an organotin compound; the titanium source is an inorganic titanium compound and/or an organic titanium compound; the template agent is one or more of aliphatic amine compound, aliphatic alcohol amine compound and quaternary ammonium base compound; the silicon molecular sieve is one or more selected from S-1, S-2, BETA, MOR, MCM-22, MCM-41, SBA-15 and MCM-48;
preferably, at least part of the inner part of crystal grains of the tin-titanium-silicon molecular sieve has a cavity structure, and a diffraction peak is arranged at 0.5-9 degrees in 2 theta in an XRD pattern; 460cm in the FT-IR spectrum -1 、975cm -1 、800cm -1 、1080cm -1 Nearby absorption; the absorption is carried out at 200-300nm in a UV-Vis spectrum, and the total specific surface area of the tin-titanium-silicon molecular sieve is 300m 2 More than g, and the external specific surface area is 30m 2 More than g, and the proportion of the external specific surface area in the total specific surface area is more than 10 percent.
Optionally, the tin-titanium-silicon molecular sieve is obtained by performing secondary hydrothermal synthesis on a titanium-silicon molecular sieve and a compound containing a tin source, a template agent, alkali and water at 100-160 ℃, and performing filtering separation, drying and roasting operations, wherein the tin content in the molecular sieve is 1-5 wt% calculated by oxides;
preferably, the tin-titanium-silicon molecular sieve is a mixture of one or more of Sn-TS-1, sn-TS-2, sn-Ti-BETA, sn-Ti-MCM-22, sn-Ti-MCM-41 and Sn-Ti-MCM-48.
Optionally, the Sn-TS-1 is a titanium silicalite molecular sieve having an MFI crystal structure, crystal grains are hollow, and the radial length of a cavity portion of the hollow crystal grains is 5 to 300 nanometers; the molecular sieve sample is at 25 ℃ and P/P 0 =0.10, and the adsorption time is at least 70 mg/g, and a hysteresis loop exists between the adsorption isotherm and the desorption isotherm of low-temperature nitrogen adsorption of the molecular sieve.
Optionally, the sugar is one or more selected from pentose, hexose and disaccharide, the pentose is xylose, the hexose is one or more selected from glucose, fructose and mannose, and the disaccharide is sucrose;
the alcohol is one or more selected from monohydric alcohol, dihydric alcohol and polyhydric alcohol containing more than three hydroxyl groups; the monohydric alcohol is selected from one or more of methanol, ethanol, propanol, n-butanol, isobutanol and pentanol, the dihydric alcohol is selected from one or more of ethylene glycol, propylene glycol, butanediol and hexanediol, and the polyhydric alcohol is selected from one or more of glycerol, trimethylolethane, pentaerythritol, xylitol and sorbitol.
Optionally, the molar ratio of sugar to alcohol is 1: (100-500), the weight ratio of sugar to tin-titanium-silicon molecular sieve based on dry weight is 1: (1.2-3), the reaction temperature is 110-140 ℃, the reaction time is 12-40h, the reaction pressure is 0.1-6MPa, and the reaction pressure is preferably 0.1-4MPa.
Optionally, the reactor is a tank reactor, a fixed bed reactor, a moving bed, a suspended bed or a slurry bed reactor.
The method adopts the catalyst containing the binary tin-titanium-silicon molecular sieve, the framework titanium atoms and the framework tin atoms cooperate with the catalyst to catalyze the sugar to generate the aldol condensation reaction to generate the dihydroxyacetone, and the ketocarbonyl in the dihydroxyacetone is further activated to generate the pyruvaldehyde, so that the reaction efficiency is improved. Compared with the prior art, higher sugar conversion rate and methylglyoxal yield can be obtained in a short time under mild reaction conditions, the subsequent separation energy consumption of the product is lower, the process is safer and more efficient, and the method is suitable for large-scale industrial production and application.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a diagram of the reaction mechanism involved in the conversion of sugars to methylglyoxal according to the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present invention, the dry weight refers to the weight measured after the sample is baked at 550 ℃ for 3 hours.
The invention provides a method for preparing methylglyoxal by catalyzing sugar, which comprises the following steps: contacting sugar with a catalyst in a reactor in the presence of alcohol and carrying out a reaction to obtain a product containing methylglyoxal; wherein the molar ratio of sugar to alcohol is 1: (50-600), the reaction temperature is more than 100 ℃ and less than 150 ℃, the reaction time is 10-50h, the catalyst contains a tin-titanium-silicon molecular sieve, and the weight ratio of sugar to the tin-titanium-silicon molecular sieve based on the dry weight is 1: (1-6). The reaction mechanism is shown in figure 1.
According to the present invention, the tin-titanium-silicon molecular sieve refers to a molecular sieve obtained by substituting tin atoms and titanium atoms for a part of silicon atoms in a lattice framework of the molecular sieve, wherein the content of the tin atoms and the titanium atoms in the molecular sieve can be determined by using an XRF method which is conventional in the art, and the content of the tin atoms and the titanium atoms in the framework of the molecular sieve can be determined by using an ultraviolet spectrum or an infrared spectrum, for example, when a tin-titanium-silicon molecular sieve sample is analyzed by using an ultraviolet spectrum, a characteristic absorption peak of the framework tin atoms appears at a position near 190nm, and a characteristic absorption peak of the framework Ti atoms appears at a position near 210 nm. Pyridine infrared spectrum at 1450cm -1 The peaks around the molecular sieve show the L-acidic character of the molecular sieve and are provided by framework tin atoms and framework titanium atoms.
According to the present invention, the tin-titanium-silicon molecular sieve may be a product of replacing a part of framework silicon of various topological structure molecular sieves with tin atoms and titanium atoms, the topological structure of the molecular sieve may be referred to the website of International Zeolite Association (IZA), for example, the tin-titanium-silicon molecular sieve may be selected from one or more of MFI-type tin-titanium-silicon molecular sieve, such as Sn-Ti-MFI molecular sieve, MEL-type tin-titanium-silicon molecular sieve, BEA-type tin-titanium-silicon molecular sieve, MWW-type tin-titanium-silicon molecular sieve, such as Sn-Ti-MFI molecular sieve, MOR-type tin-titanium-silicon molecular sieve, such as Sn-Ti-MEL molecular sieve, BEA-type tin-titanium-silicon molecular sieve, such as Sn-Ti-Beta molecular sieve, MWW-type tin-titanium-silicon molecular sieve, such as Sn-Ti-MCM-22 molecular sieve, MOR-type tin-titanium-silicon molecular sieve, such as Sn-Ti-Beta molecular sieve, hexagonal structure, such as FAU-type tin-titanium-molecular sieve, such as Sn-Ti-ussi molecular sieve, such as FAU-molecular sieve, favi-Ti-molecular sieve, favi-type tin-titanium-molecular sieve; preferably, the tin-titanium-silicon molecular sieve is one or more of an MFI type tin-titanium-silicon molecular sieve, a BEA type tin-titanium-silicon molecular sieve and an FAU type tin-titanium-silicon molecular sieve, more preferably an MFI type tin-titanium-silicon molecular sieve, which can be obtained commercially or prepared by the methods disclosed in chinese patents CN105217645A and CN102452918A, and the following two specific embodiments of the tin-titanium-silicon molecular sieve are provided.
An embodiment of the first tin-titanium-silicon molecular sieve is from patent CN105217645A.
According to a first embodiment, the tin-titanium-silicon molecular sieve contains silicon, titanium, tin and oxygen, wherein at least part of the crystal grains of the tin-titanium-silicon molecular sieve have a cavity structure inside. The fact that at least part of the tin titanium silicalite molecular sieves have a cavity structure inside the crystal grains means that at least part of the tin titanium silicalite molecular sieves in a large number of the tin titanium silicalite molecular sieves have a cavity structure inside the crystal grains, preferably more than 50% of the tin titanium silicalite molecular sieves have a cavity structure inside the crystal grains, and more preferably 70-100% of the tin titanium silicalite molecular sieves have a cavity structure inside the crystal grains.
According to the first embodiment, the ratio of the external specific surface area of the tin-titanium-silicon molecular sieve to the total specific surface area is preferably 10% or more, preferably 10 to 25%, more preferably 10 to 20%, and still more preferably 12 to 18%. Preferably, the total specific surface area is 300m 2 More preferably 310 to 600 m/g 2 G, more preferably from 350 to 460m 2 (ii) in terms of/g. The external specific surface area is 20m 2 A ratio of at least 30 m/g, preferably 2 More preferably 31 to 150 m/g or more 2 Per g, more preferably 35 to 120m 2 Per g, most preferably from 40 to 70m 2 /g。
According to a first embodiment, the total specific surface area refers to the BET specific surface area; and the external specific surface area refers to the surface area of the external surface of the tin-titanium-silicon molecular sieve, and can also be referred to as the external surface area for short. The total specific surface area, the external specific surface area and the like can be measured according to the standard method of ASTM D4222-98.
According to a first embodiment, the crystalline tin-titanium-silicon molecular sieve with a cavity structure has the spectral properties of a conventional tin-titanium-silicon molecular sieve, and specifically, the tin-titanium-silicon molecular sieve has a diffraction peak at 0.5 to 9 degrees in 2 theta, preferably a diffraction peak at 5 to 9 degrees in 2 theta in an XRD pattern.
According to a first embodiment, the tin-titanium-silicon molecular sieve is preferably 460cm in the FT-IR spectrum -1 、975cm -1 、800cm -1 And 1080cm -1 There is absorption in the vicinity. Preferably, the tin-titanium-silicon molecular sieve has absorption at 200-300nm in a UV-Vis spectrum, and preferably has absorption at 200-260 nm.
According to the first embodiment, the molar ratio of the tin element to the silicon element in the tin titanium silicalite molecular sieve is preferably from 0.05 to 10, more preferably from 0.1 to 5, and particularly preferably from 0.2 to 2. Preferably, the molar ratio of the titanium element to the silicon element in the tin-titanium-silicon molecular sieve is 0.05-10, more preferably 0.1-5. The tin element, the titanium element and the silicon element in the proportion can further optimize the catalytic activity of the tin-titanium-silicon molecular sieve.
According to a first embodiment, the tin-titanium-silicon molecular sieve is preferably P/P at 25 ℃ 0 An amount of benzene adsorbed of at least 25mg/g, preferably at least 35mg/g, preferably from 40 to 100mg/g, as measured at 0.10 and an adsorption time of 1 hour.
According to a first embodiment, the tin-titanium-silicon molecular sieve is preferably at a relative pressure P/P 0 When the molar ratio is about 0.60, the difference between the nitrogen adsorption amount at the time of desorption and the nitrogen adsorption amount at the time of adsorption of the tin-titanium-silicon molecular sieve is greater than 2% of the nitrogen adsorption amount at the time of adsorption of the tin-titanium-silicon molecular sieve, preferably the difference between the nitrogen adsorption amount at the time of desorption and the nitrogen adsorption amount at the time of adsorption of the tin-titanium-silicon molecular sieve is greater than 5% of the nitrogen adsorption amount at the time of adsorption of the tin-titanium-silicon molecular sieve, and more preferably the difference between the nitrogen adsorption amount at the time of desorption and the nitrogen adsorption amount at the time of adsorption of the tin-titanium-silicon molecular sieve is 6% of the nitrogen adsorption amount at the time of adsorption of the tin-titanium-silicon molecular sieve-10％。
According to the first embodiment, a hysteresis loop is preferably present between the adsorption isotherm and the desorption isotherm of the low temperature nitrogen adsorption of the tin-titanium-silicon molecular sieve. Preferably, the radial length of the cavity part of the internal cavity structure of the crystal grains of the tin-titanium-silicon molecular sieve is 0.1-500nm, and the preferred length is 0.5-300nm.
According to a first embodiment, the method of making a tin-titanium-silicon molecular sieve comprises:
(1) Contacting a tin source, a titanium source and a template agent in the presence of an aqueous solvent to obtain a first mixture;
(2) Mixing the first mixture with a silicon molecular sieve to obtain a second mixture;
(3) And crystallizing the second mixture under the hydrothermal crystallization condition.
According to the first embodiment, the temperature of the contact is wide in a selectable range, and for the preferred step (1) of the invention, the contact conditions include: the contact temperature is 20 to 80 deg.C, more preferably 25 to 60 deg.C, and still more preferably 25 to 40 deg.C. Thus, the activity of the tin-titanium-silicon molecular sieve can be improved. The contacting time can be determined according to specific needs, and preferably in step (1), the contacting conditions further include: the contact time is 1-240min, more preferably 5-120min, and still more preferably 20-60min.
According to the first embodiment, the amount of the silicon molecular sieve and the tin source is preferably such that the molar ratio of the tin element to the silicon element in the prepared tin-titanium-silicon molecular sieve is from 0.05 to 100, preferably from 0.1 to 5, and more preferably from 0.5 to 2; the molar ratio of the titanium element to the silicon element in the prepared tin-titanium-silicon molecular sieve is from 0.05 to 100, preferably from 0.1 to 5, and more preferably from 0.5 to 4.
According to a first embodiment, to achieve the above object, the molar ratio of the silicalite, the templating agent, the titanium source, the tin source and the water is preferably from 100Silicon molecular sieve of SiO 2 The tin source is calculated by tin element, and the titanium source is calculated by TiO 2 And (6) counting.
According to the first embodiment, it is preferable that the conditions for mixing in the step (2) include: the mixing temperature is 25-60 deg.C, and the mixing time is 20-60min. Preferably, the hydrothermal crystallization conditions include: the crystallization temperature under a closed condition is 80 to 200 ℃, more preferably 100 to 180 ℃, still more preferably 110 to 175 ℃, and most preferably 160 to 170 ℃. The crystallization time is preferably 6 to 150 hours, more preferably 24 to 96 hours.
According to the first embodiment, the variety of the tin source can be widely selected, and any substance containing tin (for example, a compound containing tin element and/or a simple substance of tin) can achieve the object of the present invention. The inorganic tin compound is, for example, a water-soluble inorganic tin salt, which may be, for example, one or more of tin chloride, tin chloride pentahydrate, stannous chloride, tin nitrate, tin sulfate, tin phosphate, stannous chloride hydrate, metastannic acid, calcium stannate, potassium stannate, sodium stannate, lithium stannate, magnesium stannate, stannous sulfate, stannous pyrophosphate, and stannic pyrophosphate; the organic acid salt of tin is preferably a C2-C10 organic acid salt, including but not limited to one or more of tin acetate, stannous acetate and stannous octoate. The organotin compound may be an organic acid salt of tin and/or an organic ligand compound of tin, preferably a stannic acid ester. Among them, the most preferable organotin compound is tin acetate.
According to a first embodiment, the titanium source may be a conventional choice in the art, and may be an inorganic titanium compound and/or an organic titanium compound, preferably selected from inorganic titanium salts and/or organic titanates, preferably organic titanates, for the purposes of the present invention.
According to a first embodiment, the inorganic titanium salt is chosen from various hydrolysable titanium salts, such as may be chosen from TiX 4 、TiOX 2 Or Ti (SO) 4 ) 2 And various forms of titanium-containing salts, wherein X is halogen, preferably chlorine, of whichPreferably, the inorganic titanium salt is selected from titanium trichloride and TiCl 4 、Ti(SO 4 ) 2 And TiOCl 2 One or more of (a).
According to a first embodiment, the organic titanate is preferably of formula M 4 TiO 4 Wherein M is preferably an alkyl group having 1 to 4 carbon atoms, and 4M's may be the same or different, preferably the organotitanate is selected from one or more of isopropyl titanate, n-propyl titanate, tetrabutyl titanate and tetraethyl titanate being used as examples in the specific embodiments of the present invention, but not thereby limiting the scope of the present invention.
According to a first embodiment, preferably the titanium source is one or more of tetrabutyl titanate, titanium tetrachloride, tetraisopropyl titanate and titanium trichloride.
According to the first embodiment, the selection range of the template is wide, and the template can be specifically selected according to the type of the tin-titanium-silicon molecular sieve to be prepared, and those skilled in the art can know the type. For the present invention, it is preferable that the templating agent is one or more of an aliphatic amine compound, an aliphatic alcohol amine compound, and a quaternary ammonium base compound.
According to a first embodiment, the quaternary ammonium base can be any of various organic quaternary ammonium bases, and in particular, the quaternary ammonium base can be a quaternary ammonium base represented by the following formula:
Figure BDA0001888334960000081
in the above formula, R 5 、R 6 、R 7 And R 8 Each C1-C4 alkyl, including C1-C4 straight chain alkyls and C3-C4 branched chain alkyls, such as: r 5 、R 6 、R 7 And R 8 Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. More preferably, the quaternary ammonium base is one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide.
According to a first embodiment, the aliphatic amineCan be various NH 3 Is substituted with an aliphatic hydrocarbon group (preferably an alkyl group), and specifically, the aliphatic amine may be an aliphatic amine represented by the following formula: r 9 (NH 2 ) n (ii) a In the above formula, n is an integer of 1 or 2. When n is 1, R 9 Is C1-C6 alkyl, including C1-C6 straight-chain alkyl and C3-C6 branched-chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isoamyl, tert-amyl and n-hexyl. When n is 2, R 9 Is C1-C6 alkylene, including C1-C6 linear alkylene and C3-C6 branched alkylene, such as methylene, ethylene, n-propylene, n-butylene, n-pentylene, or n-hexylene. More preferably, the aliphatic amine compound is one or more of ethylamine, n-butylamine, butanediamine, and hexamethylenediamine.
According to a first embodiment, the aliphatic alcohol amine can be various NH 3 In the above formula (b), at least one hydrogen of the aliphatic alcohol amine is substituted by a hydroxyl group-containing aliphatic hydrocarbon group (preferably an alkyl group), and specifically, the aliphatic alcohol amine may be represented by the following formula: (HOR) 10 ) m NH (3-m) (ii) a In the above formula, m are R 10 Identical or different, are each C1-C4 alkylene, including C1-C4 linear alkylene and C3-C4 branched alkylene, such as methylene, ethylene, n-propylene and n-butylene; m is 1, 2 or 3. More preferably, the aliphatic alcohol amine compound is one or more of monoethanolamine, diethanolamine and triethanolamine.
According to a first embodiment, the templating agent is preferably tetrapropylammonium hydroxide and/or tetraethylammonium hydroxide.
According to a first embodiment, the silicalite may be at least one of an MFI structure (e.g., S-1), an MEL structure (e.g., S-2), a BEA structure (e.g., beta), an MWW structure (e.g., MCM-22), a two-dimensional hexagonal structure (e.g., MCM-41, SBA-15), an MOR structure (e.g., MOR), a TUN structure (e.g., TUN), and other structures of silicalite (e.g., ZSM-48, MCM-48). Preferably, the silicon molecular sieve is one or more of a silicon molecular sieve with an MFI structure, a silicon molecular sieve with an MEL structure and a silicon molecular sieve with a BEA structure, more preferably a silicon molecular sieve with an MFI structure, and preferably, the silicon molecular sieve is one or more of S-1, S-2 and Beta, preferably S-1.
According to the first embodiment, the silicon molecular sieve can be obtained commercially or prepared, and the method for preparing the silicon molecular sieve is well known to those skilled in the art and is not described herein again.
According to the first embodiment, it is preferred that the method further comprises: and filtering and washing the crystallized product to obtain a solid, and roasting the obtained solid after drying or not drying. The methods of filtering the product obtained by crystallization, drying the solid obtained by filtering, and calcining are well known to those skilled in the art, and in the present invention, the optional range of the drying conditions is wide, and the drying can be specifically performed with reference to the prior art. For the present invention, it is preferable that the drying conditions include: the temperature is between room temperature and 200 ℃, and more preferably between 80 and 120 ℃; the time is 1-24h, preferably 2-10h.
According to a first embodiment, the conditions of the calcination can be chosen within a wide range, and for the purposes of the present invention, it is preferred that the conditions of the calcination include: the roasting temperature is 300-800 ℃, preferably 450-550 ℃; the roasting time is 2-12h, preferably 2-4h; more preferably, the firing conditions include: firstly, roasting for 0.5-6h at 350-600 ℃ in nitrogen atmosphere, and then roasting for 0.5-12h at 350-600 ℃ in air atmosphere. Methods of filtration and washing are also well known to those skilled in the art and will not be described in detail herein.
An embodiment of the second tin titanium silicalite molecular sieve is from patent CN102452918A.
According to a second embodiment, the tin-titanium-silicon molecular sieve is obtained by performing a second hydrothermal synthesis on a titanium-silicon molecular sieve together with a compound containing a tin source, a template agent, alkali and water at 100-160 ℃, and performing filtering separation, drying and roasting operations, wherein the tin content in the molecular sieve is 1-5 wt% calculated by oxides, and a strong Lewis acid center is formed at a framework position, so that the activation of the molecular sieve on a substrate is enhanced in an organic reaction.
According to a second embodiment, the tin-titanium-silicon molecular sieve is a mixture of one or more of Sn-TS-1, sn-TS-2, sn-Ti-BETA, sn-Ti-MCM-22, sn-Ti-MCM-41 and Sn-Ti-MCM-48. TS-1 is preferred, and a synthesis method of the titanium silicalite TS-1 is disclosed for the first time in U.S. Pat. No. 4,4410501. As a more preferable embodiment, the invention adopts a TS-1 titanium silicalite molecular sieve with a hollow structure, the molecular sieve has a titanium silicalite molecular sieve with an MFI crystal structure, crystal grains have a hollow structure, and the radial length of a cavity part of each hollow crystal grain is 5-300 nanometers; the molecular sieve sample has a benzene adsorption capacity of at least 70 mg/g measured at 25 ℃, P/P0=0.10, and an adsorption time of 1 hour, and a hysteresis loop exists between an adsorption isotherm and a desorption isotherm of low temperature nitrogen adsorption of the molecular sieve. The TS-1 titanium silicalite molecular sieve with a hollow structure has larger mesoporous volume, which is usually more than 0.16mL/g, while the conventional TS-1 titanium silicalite molecular sieve has the mesoporous volume of about 0.084 mL/g. The TS-1 titanium silicalite molecular sieve with the hollow structure can be prepared by a method disclosed in Chinese patent ZL99126289.1, and is commercially available.
According to the present invention, the sugar and the alcohol are well known to those skilled in the art, for example, the sugar is one or more selected from the group consisting of a pentose, a hexose, and a disaccharide, the pentose is xylose, the hexose is one or more selected from the group consisting of glucose, fructose, and mannose, and the disaccharide is sucrose; the alcohol may be one or more selected from monohydric alcohol, dihydric alcohol and polyhydric alcohol containing more than three hydroxyl groups; the monohydric alcohol is selected from one or more of methanol, ethanol, propanol, n-butanol, isobutanol and pentanol, preferably methanol, the dihydric alcohol is selected from one or more of ethylene glycol, propylene glycol, butylene glycol and hexylene glycol, and the polyhydric alcohol is selected from one or more of glycerol, trimethylolethane, pentaerythritol, xylitol and sorbitol.
According to the invention, the molar ratio of sugar to alcohol is preferably 1: (100-500), the weight ratio of sugar to tin titanium silicalite molecular sieve, on a dry basis, is preferably 1: (1.2-3), the reaction temperature is preferably 110-140 ℃, the reaction time is preferably 12-40h, the reaction pressure (absolute pressure) is 0.1-6MPa, and the reaction pressure is preferably 0.1-4MPa.
The reaction according to the present invention may be carried out in a conventional catalytic reactor, and the present invention is not particularly limited, for example, the reaction according to the present invention may be carried out in a batch tank reactor, or in other suitable reactors such as fixed bed, moving bed, suspended bed, etc., preferably in a tank reactor, fixed bed reactor, moving bed, suspended bed or slurry bed reactor, the specific operation of which is well known to those skilled in the art, and the present invention will not be described in detail.
According to the present invention, it can be understood by those skilled in the art that, depending on the reactor used, the tin-titanium-silicon molecular sieve of the present invention may be a molecular sieve raw powder, or may be a molded catalyst formed by mixing a molecular sieve and a carrier. The separation of the product containing methylglyoxal from the catalyst can be achieved in various ways, for example, when the original powdery molecular sieve is used as the catalyst, the separation of the product and the recovery and reuse of the catalyst can be achieved by settling, filtering, centrifuging, evaporating, membrane separation, or the like, or the catalyst can be molded and then loaded into a fixed bed reactor, and the catalyst is recovered after the reaction is finished.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The starting materials used in the preparation examples, preparation comparative examples, examples and comparative examples were all chemically pure reagents, except where otherwise specified.
In the invention, the X-ray diffraction (XRD) crystal phase diagram of a sample is determined on a Siemens D5005 type X-ray diffractometer, the ray source is K alpha (Cu), and the test range 2 theta is 0.5-30 degrees. The Fourier infrared (FT-IR) spectrum of the sample is measured on a Nicolet8210 type Fourier infrared spectrometer, and the measuring range is 400-4000cm -1 . The solid ultraviolet-visible diffuse reflection spectrum (UV-vis) of the sample is measured on a SHIMADZU UV-3100 model ultraviolet-visible spectrometer, and the measuring range is 200-1000nm. The total specific surface area and the external specific surface area of the sample were measured on a Micromeritics ASAP2405 static nitrogen adsorption apparatusThe measurement was carried out according to ASTM D4222-98 standard method. TEM is a transmission electron microscope of the sample obtained on a transmission electron microscope of the type Tecnai G2F20S-TWIN from FEI.
In the present invention, the benzene adsorption amount is measured by a conventional static adsorption method, and the adsorption isotherm and desorption isotherm of low-temperature nitrogen adsorption are measured according to the ASTM D4222-98 standard method.
In the present invention, the molecular sieve yield refers to the percentage of the mass of the product actually obtained to the theoretically calculated mass (based on the total amount of the charged silicon dioxide, titanium dioxide and tin dioxide).
In the invention, in a transmission electron microscope test, a certain number of crystal grains in a certain visual field range are taken as representatives, such as 100 crystal grains, the proportion of the number of the crystal grains with the cavity structures in the crystal grains in the total number of the crystal grains is observed, and the proportion of the tin-titanium-silicon molecular sieves with the cavity structures in the crystal grains in the total number of the tin-titanium-silicon molecular sieves is calculated.
In the invention, the gas chromatography is adopted to analyze the methylglyoxal in the activity evaluation system, the liquid chromatography is adopted to analyze the sugar in the activity evaluation system, the analysis result is quantified by an internal standard method, and the internal standard substance is naphthalene. Wherein, the analysis conditions of the gas chromatography are as follows: agilent-6890 type chromatograph, HP-5 capillary chromatographic column, sample amount of 0.5 μ L, and sample inlet temperature of 280 deg.C. The column temperature was maintained at 100 ℃ for 2min, then ramped up to 200 ℃ at a rate of 15 ℃/min and maintained for 3min. FID detector, detector temperature 300 ℃. The analysis conditions of the liquid chromatography were: an Agilent-1200 type chromatograph, an AminexHPX-87H chromatographic column, a column temperature of 60 ℃, a differential refraction detector, 0.005M sulfuric acid as a mobile phase and a flow rate of 0.5mL/min.
In the invention:
percent sugar conversion = (moles of sugar in starting material-moles of sugar in product)/moles of sugar in starting material × 100%;
methylglyoxal selectivity% = mol of methylglyoxal in product/(mol of sugar in raw material-mol of sugar in product) × 100%;
the yield of methylglyoxal is% = mol of methylglyoxal in the product/mol of sugar in the raw material x 100%, namely the yield of methylglyoxal is% = selectivity of methylglyoxal x sugar conversion%.
Preparation examples and preparation comparative examples were used to provide catalysts used in the examples and comparative examples.
Preparation of example 1
The preparation example prepares the Sn-Ti-MFI-1 molecular sieve according to the method of the specification example 1 of the Chinese patent CN105217645A, and the specific preparation method is as follows:
(1) Stirring and contacting tetrapropylammonium hydroxide aqueous solution (with the concentration of 15 weight percent) with tetrabutyl titanate and stannic chloride pentahydrate for 30min at 25 ℃ to obtain a mixture;
(2) Adding the silicalite molecular sieve S-1 into the mixture at 60 ℃, stirring and contacting for 0.5h to obtain a mixture (in the contact process, water is added or not added according to the requirement, if the feeding of the step (1) can meet the feeding requirement of the water, the water is not added, if the feeding can not meet the feeding requirement of the water, the water can be additionally added when the mixture containing tetrapropylammonium hydroxide, tetrabutyl titanate and tin chloride is stirred and contacted with the silicalite molecular sieve, or the water is removed by distillation, and other preparation examples are similar and are not repeated); wherein, the feeding molar ratio of each substance is ensured as follows: silicon source (silicon molecular sieve), alkali source template agent (tetrapropylammonium hydroxide), titanium source (tetrabutyl titanate): tin source (crystalline tin tetrachloride): water =100 2 The titanium source is calculated as TiO 2 The tin source is calculated by the tin element;
(3) And transferring the mixture into a stainless steel sealed reaction kettle, crystallizing for 144 hours at the temperature of 170 ℃ and the autogenous pressure, filtering the obtained crystallized product, washing with water, drying for 120 minutes at the temperature of 110 ℃, and then roasting for 3 hours at the temperature of 550 ℃ to obtain the tin-titanium-silicon molecular sieve.
By XRF composition analysis, the tin-titanium-silicon molecular sieve has the tin content of 1.8 percent by mass and the titanium content of 0.9 percent by mass; TEM indicates that 100% of the tin-titanium-silicon molecular sieve grains have a cavity structure; in an XRD crystal phase diagram, a diffraction peak exists at the 2 theta position of 5-9 degrees; in FT-IR, 460cm -1 、800cm -1 、975cm -1 、1080cm -1 There is absorption nearby; in UV-Vis, there is an absorption at 220 nm; low temperature nitrogen absorptionA hysteresis loop exists between the adsorption isotherm and the desorption isotherm, the yield of the molecular sieve is 94 percent, the benzene adsorption capacity is 62mg/g, the ratio of the adsorption-desorption difference value to the adsorption capacity (the difference between the nitrogen adsorption capacity during desorption and the nitrogen adsorption capacity during adsorption of the tin-titanium-silicon molecular sieve is greater than the nitrogen adsorption capacity during adsorption of the tin-titanium-silicon molecular sieve) is 6 percent, and the total specific surface area is 440m 2 A specific surface area of 46m 2 The proportion of the external specific surface area to the total specific surface area was 10.5%.
Preparation of example 2
The preparation example prepares the Sn-Ti-MFI-2 molecular sieve according to the method of the specification example 2 of the Chinese patent CN105217645A, and the specific preparation method is as follows:
(1) Stirring and contacting tetrapropylammonium hydroxide aqueous solution (with the concentration of 20 weight percent) with tetrabutyl titanate and stannic chloride pentahydrate for 30min at 25 ℃ to obtain a mixture;
(2) Adding a silicon molecular sieve S-1 into the mixture at 25 ℃, and stirring and contacting for 0.5h to obtain a mixture; wherein, the feeding molar ratio of each substance is ensured as follows: silicon source (silicon molecular sieve), alkali source template agent (tetrapropylammonium hydroxide), titanium source (tetrabutyl titanate): tin source (tin tetrachloride): water =100 2 The titanium source is calculated as TiO 2 The tin source is calculated by the tin element;
(3) And transferring the mixture into a stainless steel sealed reaction kettle, crystallizing for 120 hours at the temperature of 160 ℃ and the autogenous pressure, filtering the obtained crystallized product, washing with water, drying for 120 minutes at the temperature of 110 ℃, and then roasting for 3 hours at the temperature of 550 ℃ to obtain the tin-titanium-silicon molecular sieve.
By XRF composition analysis, the Sn mass percent of the tin-titanium-silicon molecular sieve is 1.0, and the titanium mass percent is 2.6; in an XRD crystal phase diagram, diffraction peaks exist at 5-9 degrees of 2 theta; TEM indicates that the inside of 100% molecular sieve crystal grains is a cavity structure; in FT-IR, 460cm -1 、800cm -1 、975cm -1 、1080cm -1 Nearby absorption; in UV-Vis, there is an absorption at 220 nm; a hysteresis loop exists between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption, the yield of the molecular sieve is 93 percent, and the benzene adsorption capacity is 68mg/g, the ratio of the adsorption-desorption difference value to the adsorption amount (the difference between the nitrogen adsorption amount during desorption and the nitrogen adsorption amount during adsorption of the tin-titanium-silicon molecular sieve is larger than the nitrogen adsorption amount during adsorption of the tin-titanium-silicon molecular sieve) is 8 percent, and the total specific surface area is 424m 2 A specific surface area of 45 m/g 2 The proportion of the external specific surface area to the total specific surface area was 10.6%.
Preparation of example 3
The preparation example prepares the Sn-Ti-MFI-3 molecular sieve according to the method of the specification example 3 of the Chinese patent CN105217645A, and the specific preparation method is as follows:
(1) A mixture was obtained by contacting an aqueous tetraethylammonium hydroxide solution (concentration of 28% by weight) with titanium tetrachloride and tin nitrate at 35 ℃ for 30 minutes with stirring;
(2) Adding a silicon molecular sieve S-1 into the mixture at 50 ℃, and stirring and contacting for 0.5h to obtain a mixture; wherein, the feeding molar ratio of each substance is ensured as follows: silicon source (silicon molecular sieve), alkali source template (tetraethylammonium hydroxide), titanium source (titanium tetrachloride), tin source (tin nitrate), water =100 2 The titanium source is calculated as TiO 2 The tin source is calculated by the tin element;
(3) And transferring the mixture into a stainless steel sealed reaction kettle, crystallizing for 96 hours at the temperature of 170 ℃ under autogenous pressure, filtering the obtained crystallized product, washing with water, drying for 120 minutes at the temperature of 110 ℃, and roasting for 3 hours at the temperature of 550 ℃ to obtain the tin-titanium-silicon molecular sieve.
By XRF composition analysis, the Sn mass percent of the tin-titanium-silicon molecular sieve is 0.8, and the titanium mass percent is 0.3; in an XRD crystal phase diagram, diffraction peaks exist at 5-9 degrees of 2 theta; TEM indicates that the inside of 100% molecular sieve crystal grains is a cavity structure; in FT-IR, 460cm -1 、800cm -1 、975cm -1 、1080cm -1 There is absorption nearby; in UV-Vis, there is an absorption at 230 nm; a hysteresis loop exists between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption, the molecular sieve yield is 94 percent, the benzene adsorption capacity is 54mg/g, and the ratio of the adsorption and desorption difference value to the adsorption capacity (the difference value between the nitrogen adsorption capacity during desorption and the nitrogen adsorption capacity during adsorption of the tin-titanium-silicon molecular sieve is greater than that of the tin-titanium-silicon molecular sieveNitrogen adsorption amount of the tin-titanium-silicon molecular sieve during adsorption) is 5%, and the total specific surface area is 431m 2 Per g, external specific surface area 43m 2 The proportion of the external specific surface area to the total specific surface area is 10%.
Preparation of example 4
The preparation example prepares the Sn-Ti-MFI-4 molecular sieve according to the method of the specification example 4 of the Chinese patent CN105217645A, and the specific preparation method is as follows:
(1) Stirring and contacting tetrapropylammonium hydroxide aqueous solution (with the concentration of 15 weight percent) with tetraisopropyl titanate and stannic chloride for 30min at the temperature of 30 ℃ to obtain a mixture;
(2) Adding a silicon molecular sieve S-1 into the mixture at 60 ℃, and stirring and contacting for 0.5h to obtain a mixture; wherein, the feeding molar ratio of each substance is ensured as follows: silicon source (silicon molecular sieve), alkali source template (tetrapropylammonium hydroxide), titanium source (tetraisopropyl titanate), tin source (tin tetrachloride), water =100 2 The titanium source is calculated as TiO 2 The tin source is calculated by the tin element;
(3) And transferring the mixture into a stainless steel sealed reaction kettle, crystallizing for 72 hours at the temperature of 120 ℃ and the autogenous pressure, filtering the obtained crystallized product, washing with water, drying for 120 minutes at the temperature of 110 ℃, and then roasting for 3 hours at the temperature of 550 ℃ to obtain the tin-titanium-silicon molecular sieve.
By XRF composition analysis, the Sn mass percentage content of the tin-titanium-silicon molecular sieve is 6.6, and the titanium mass percentage content is 2.1; in an XRD crystal phase diagram, diffraction peaks exist at 5-9 degrees of 2 theta; TEM indicates that 96% of the molecular sieve crystal grains have a cavity structure; in FT-IR, 460cm -1 、800cm -1 、975cm -1 、1080cm -1 Nearby absorption; in UV-Vis, there is absorption around 240 nm; a hysteresis loop exists between the adsorption isotherm and the desorption isotherm of low-temperature nitrogen adsorption, the molecular sieve yield is 94 percent, the benzene adsorption capacity is 83mg/g, the ratio of the adsorption-desorption difference value to the adsorption capacity (the difference value between the nitrogen adsorption capacity during desorption and the nitrogen adsorption capacity during adsorption of the tin-titanium-silicon molecular sieve is greater than the nitrogen adsorption capacity during adsorption of the tin-titanium-silicon molecular sieve) is 9 percent, and the total specific surface area is 416m 2 In terms of per gram, having an external specific surface area of50m 2 The proportion of the external specific surface area to the total specific surface area was 12.1%.
Preparation of example 5
In the preparation example, the Sn-Ti-MFI-5 molecular sieve is prepared according to the method in the specification example 7 of the Chinese patent CN105217645A. The preparation method comprises the following steps:
(1) Stirring and contacting tetrapropylammonium hydroxide aqueous solution (with the concentration of 15 weight percent) with titanium trichloride and stannic chloride pentahydrate for 30min at the temperature of 25 ℃ to obtain a mixture;
(2) Adding a silicon molecular sieve S-1 into the mixture at 40 ℃, and stirring and contacting for 0.5h to obtain a mixture; wherein, the feeding molar ratio of each substance is ensured as follows: silicon source (silicon molecular sieve), alkali source template (tetrapropylammonium hydroxide), titanium source (titanium trichloride), tin source (crystalline tin tetrachloride), water =100 2 The titanium source is calculated as TiO 2 The tin source is calculated by the tin element;
(3) And transferring the mixture into a stainless steel sealed reaction kettle, crystallizing for 36 hours at the temperature of 170 ℃ and the autogenous pressure, filtering the obtained crystallized product, washing with water, drying for 120 minutes at the temperature of 110 ℃, and then roasting for 3 hours at the temperature of 550 ℃ to obtain the tin-titanium-silicon molecular sieve.
By XRF composition analysis, the Sn mass percentage content of the tin-titanium-silicon molecular sieve is 9.6, and the titanium mass percentage content is 2.5; in an XRD crystal phase diagram, diffraction peaks exist at 5-9 degrees of 2 theta; TEM indicates that 61% of the molecular sieve crystal grains have a cavity structure; in FT-IR, 460cm -1 、800cm -1 、975cm -1 、1080cm -1 Nearby absorption; in UV-Vis, there is absorption at 230-260 nm; a hysteresis loop exists between an adsorption isotherm and a desorption isotherm of low-temperature nitrogen adsorption, the yield of the molecular sieve is 93 percent, the benzene adsorption capacity is 41mg/g, the ratio of an adsorption-desorption difference value to an adsorption capacity (the difference value between the nitrogen adsorption capacity during desorption and the nitrogen adsorption capacity during adsorption of the tin-titanium-silicon molecular sieve is greater than the nitrogen adsorption capacity during adsorption of the tin-titanium-silicon molecular sieve) is 5 percent, and the total specific surface area is 356m 2 (g) an external specific surface area of 51m 2 The proportion of the external specific surface area to the total specific surface area was 14.3%.
Preparation of example 6
In this preparation example, a tin-titanium-silicon molecular sieve was prepared according to the method of preparation example 1 of CN102452918A catalyst, and the specific preparation method is as follows:
22.5 g tetraethyl orthosilicate and 7.0 g tetrapropylammonium hydroxide were mixed, 59.8 g distilled water was added, after mixing uniformly, hydrolysis was carried out at 60 ℃ for 1.0 hour under normal pressure to obtain a hydrolysis solution of tetraethyl orthosilicate, a solution consisting of 1.1 g tetrabutyl titanate and 5.0 g anhydrous isopropyl alcohol was slowly added with vigorous stirring, and the resulting mixture was stirred at 75 ℃ for 3 hours to obtain a clear transparent colloid. Placing the colloid into a stainless steel sealed reaction kettle, and standing at a constant temperature of 170 ℃ and a self-generated pressure for 6 days to obtain a mixture of crystallized products; the mixture was filtered, washed with water to pH 6-8, and dried at 110 ℃ for 60 minutes to give raw, unfired TS-1 powder. And roasting the TS-1 raw powder for 4 hours at 550 ℃ in an air atmosphere to obtain the TS-1 molecular sieve.
Then TS-1 is uniformly mixed in a system with tetrapropylammonium hydroxide as a template agent and anhydrous stannic chloride as a tin source according to the proportion of molecular sieve (g), anhydrous stannic chloride (mol), tetrapropylammonium hydroxide (mol) and water (mol) =100: 0.06 x: 0.15: 180, wherein the value of x is the mass percent of stannic oxide in the molecular sieve, the mixture is subjected to a closed high-pressure kettle, and 2.2wt percent of tin element calculated by oxide is introduced into an MFI framework of the mixture through a secondary hydrothermal synthesis method at 140 ℃, so as to obtain the catalyst which is Sn-TS-1, wherein SnO is expressed as Sn-TS-1, and SnO is oxidized and oxidized, and the catalyst is oxidized and the catalyst is prepared by the following steps of 2 2.2wt%, tiO 2 The mass percentage of (b) is 3.9wt%.
Preparation of example 7
The TS-1 molecular sieve obtained in the preparation example 6 is uniformly mixed according to the proportion of the molecular sieve (g) to the sulfuric acid (mol) to the water (mol) =100: 0.15: 15, the mixture reacts for 5.0 hours at the temperature of 90 ℃, and then the mixture is filtered, washed and dried according to a conventional method to obtain the acid-treated TS-1 molecular sieve.
Mixing the acid treated TS-1 molecular sieve uniformly according to the proportion of molecular sieve (g), triethanolamine (mol), tetrapropylammonium hydroxide (mol) and water (mol) =100: 0.20: 0.15: 180, placing the mixture into a stainless steel sealed reaction kettle, standing the mixture for 0.5 day at the constant temperature of 190 ℃ and the autogenous pressure, cooling and relieving the pressure, filtering, washing and drying the mixture according to a conventional method, and roasting the mixture for 3 hours at the temperature of 550 ℃ in an air atmosphere to obtain the hollow-structure molecular sieve.
The molecular sieve is analyzed to be a titanium-silicon molecular sieve with an MFI structure through X-ray diffraction, a hysteresis ring exists between an adsorption isotherm and a desorption isotherm of low-temperature nitrogen adsorption of the molecular sieve, the crystal grains are hollow crystal grains, and the radial length of a cavity part is 15-180 nanometers; the molecular sieve sample had a benzene adsorption of 78 mg/g measured at 25 ℃, P/P0=0.10, and an adsorption time of 1 hour.
Then, in a system with a hollow structure molecular sieve, at 140 ℃, tetrapropylammonium hydroxide as a template agent and anhydrous stannic chloride as a tin source, uniformly mixing the molecular sieve with anhydrous stannic chloride (mol), tetrapropylammonium hydroxide (mol) and water (mol) =100: 0.06 x: 0.15: 180 according to the proportion of the molecular sieve (g) to the anhydrous stannic chloride (mol), wherein the value of x is the mass percent of stannic oxide in the molecular sieve, subjecting the mixture to hydrothermal synthesis at 140 ℃ for 72 hours in a closed autoclave, introducing 2.1wt% of tin element (calculated by oxide) into an MFI framework of the mixture, and recording a catalyst as Sn-HTS, wherein SnO (stannic oxide) is calculated by oxide 2 2.1wt%, tiO 2 The mass percentage of (B) is 4.3wt%.
Preparation of comparative example 1
The preparation comparative example is used for preparing the Sn-MFI molecular sieve, and the specific preparation method comprises the following steps:
adding tin tetrachloride pentahydrate (SnCl) 4 .5H 2 O) was dissolved in water, the aqueous solution was added to tetraethyl orthosilicate (TEOS) and stirred, tetrapropylammonium hydroxide (TPAOH, 20% aqueous solution) and water were added with stirring, and stirring was continued for 30 minutes to obtain 0.03SnO 2 ：SiO 2 :0.45TPA：35H 2 And crystallizing the clear liquid of O at 433K for 2 days, filtering the obtained solid, washing the solid with distilled water, drying the solid for 5 hours at 393K, and roasting the solid for 10 hours at 823K to obtain a molecular sieve sample. Wherein the dosage of TEOS is 15.31g, the dosage of TPAOH is 33.67g 4 .5H 2 The amount of O was 0.38g and the amount of water was 39.64g.
Preparation of comparative example 2
The present preparation comparative example reference "Nemeth L, moscoso J, erdman N, et al. Synthesis and Catalysis of Sn-Beta as a selective oxidation catalyst [ J ]. Studies in Surface Science & Catalysis,2004,154 (04): 2626-2631" describes the preparation of a Sn-Beta molecular sieve by:
the pentahydrate stannic chloride (SnCl) 4 .5H 2 O) dissolving in water, adding tetraethyl orthosilicate (TEOS) into the water solution, stirring, adding tetraethyl ammonium hydroxide (TEAOH) while stirring, stirring until TEOS is evaporated to obtain alcohol, and adding Hydrogen Fluoride (HF) into the clear solution to form a paste thin layer. Finally, a suspension of dealuminized nano Beta seed crystals (20 nm) and water is added to obtain the product with a chemical composition of 0.03SnO 2 ：SiO 2 ：6TEA：15H 2 O:10HF, then crystallized at the temperature of 413K for 10 days, and then the obtained solid is filtered, washed by distilled water, dried at the temperature of 393K for 5 hours, and then roasted at the condition of 823K for 10 hours to obtain a molecular sieve sample. Wherein the dosage of TEOS is 20.81g, the dosage of TEAOH is 88.42g 4 .5H 2 The amount of O used was 1.05g, the amount of water used was 27.01g, and the amount of HF used was 20g.
Preparation of comparative example 3
The Sn-USY molecular sieve is prepared by the method of "Yang X, wu L, wang Z, et al. Conversion of dihydroxy monomer to methyl lactate catalyzed by high active Sn-USY at room temperature [ J ]. Catalysis Science & Technology,2016,6 (6): 1757-1763", and the Sn-USY molecular sieve is prepared by the following method:
mixing the H-USY molecular sieve with nitric acid, treating at 85 ℃ for 8H, filtering and washing a sample with deionized water, and drying at 120 ℃ for 12H to obtain a solid sample. This solid sample was mixed with tin tetrachloride pentahydrate (SnCl) 4 .5H 2 O) for 1h to obtain a chemical composition of 0.03SnO 2 ：100SiO 2 Drying the mixed liquid at 100 ℃ for 12h, and finally roasting at 550 ℃ for 3 hours to obtain a molecular sieve sample. Wherein the dosage of H-USY is 2.0g, the dosage of nitric acid is 50mL 4 .5H 2 The amount of O used was 0.6g.
Preparation of comparative example 4
The preparation comparative example is used for preparing the TS-1 molecular sieve, and the specific preparation method comprises the following steps:
tetrapropylammonium hydroxide (TPAOH, 20%) solution in an amount of about 3/4 was added to a tetraethyl orthosilicate (TEOS) solution to obtain a liquid mixture having a pH of about 13, and then a desired amount of n-butyl titanate [ Ti (OBu) ] was added dropwise to the obtained liquid mixture under vigorous stirring 4 ]Stirring for 15 min to obtain clear liquid, and slowly adding the rest TPAOH into the clear liquid, and stirring at 348-353K for about 3 hr to obtain 0.03TiO 2 ：SiO 2 ：0.36TPA：35H 2 And O sol, then crystallizing for 3 days at the temperature of 443K, filtering the obtained solid, washing with distilled water, drying for 5 hours at the temperature of 373K, and then roasting for 10 hours at the condition of 823K to obtain a molecular sieve sample. Wherein the amount of TEOS is 42g, the amount of TPAOH is 73g, ti (OBu) 4 The amount of (A) was 2g, the amount of anhydrous isopropyl alcohol was 10g, and the amount of water was 68g.
Preparation of comparative example 5
The preparation comparative example is used for preparing the TS-2 molecular sieve, and the specific preparation method comprises the following steps:
a certain amount of tetrabutylammonium hydroxide solution (TBAOH, 20%) was mixed with Tetraethoxysilane (TEOS), and then a desired amount of n-butyl titanate [ Ti (OBu) ] was added dropwise to the resulting transparent liquid mixture under vigorous stirring 4 ]Stirring for 30 minutes to obtain a clear liquid after hydrolysis. Finally, 2 times the amount of distilled water was added and the sol was stirred at 348-353K for 2h to remove the alcohol. The chemical composition of the sol obtained was 0.03TiO 2 ：SiO 2 :0.2TBA：20H 2 And O. And (3) crystallizing the sol at 443K for 3 days, filtering and washing the obtained crystallized product, drying for 6h under 373K, and roasting for 16h under 823K to obtain a molecular sieve sample. Wherein the amount of TEOS is 42g, the amount of TBAOH is 52g, ti (OBu) 4 The amount of (A) was 2g, the amount of anhydrous isopropyl alcohol was 10g, and the amount of water was 30g.
Preparation of comparative example 6
The preparation comparative example is used for preparing the Ti-Beta molecular sieve, and the specific preparation method comprises the following steps:
a certain amount of tetraethyl orthosilicate (TEOS) was added to a solution of metered tetraethylammonium hydroxide solution (TEAOH, 20%) and hydrogen peroxide and hydrolyzed under stirring for 2h. Then weighed tetrabutyl titanate [ Ti (OBu) 4 ]Adding the anhydrous isopropanol solution into hydrolysate of ethyl orthosilicate, continuously stirring for 3h to remove alcohol, and finally obtaining the chemical composition of TiO 2 ：60SiO 2 :33TEA：400H 2 O:20H 2 O 2 The sol of (4). Finally, adding dealuminized P-type molecular sieve seed crystals and stirring vigorously (the seed crystal adding amount is that the sol is calculated by silica, and 4g of seed crystals are added into 100g of silica). After the mixture is crystallized under 413K for 14 days, the obtained slurry is filtered, washed by water, dried under 373K for 6h, and then calcined under 823K for 12h to obtain a molecular sieve sample. Wherein the amount of TEOS is 42g, the amount of TEAOH is 81g, ti (OBu) 4 The dosage of the compound is 1.16g, the dosage of the anhydrous isopropanol is 10g, and the dosage of the hydrogen peroxide is 7.5g.
Preparation of comparative example 7
The hollow titanium silicalite molecular sieve HTS prepared by the preparation comparative example is prepared by the method described in the specification example 1 of the Chinese patent CN1301599A, and the specific preparation method is as follows:
tetraethyl orthosilicate 22.5 g and tetrapropylammonium hydroxide 7.0 g are mixed, and then distilled water 59.8 g is added, after uniform mixing, the mixture is hydrolyzed at 60 ℃ and normal pressure for 1.0 hour to obtain a tetraethyl orthosilicate hydrolyzed solution, a solution consisting of tetrabutyl titanate 1.1 g and anhydrous isopropanol 5.0 g is slowly added under vigorous stirring, and the obtained mixture is stirred at 75 ℃ for 3 hours to obtain a clear and transparent colloid. Placing the colloid into a stainless steel sealed reaction kettle, and standing at a constant temperature of 170 ℃ and a self-generated pressure for 6 days to obtain a mixture of crystallized products; the mixture was filtered, washed with water to pH 6-8, and dried at 110 ℃ for 60 minutes to give raw, unfired TS-1 powder. And roasting the TS-1 raw powder for 4 hours at 550 ℃ in an air atmosphere to obtain the TS-1 molecular sieve.
And (3) uniformly mixing the obtained TS-1 molecular sieve according to the proportion of molecular sieve (g) to sulfuric acid (mol) to water (mol) =100: 0.15: 150, reacting for 5.0 hours at 90 ℃, and then filtering, washing and drying according to a conventional method to obtain the acid-treated TS-1 molecular sieve.
Mixing the acid treated TS-1 molecular sieve uniformly according to the proportion of molecular sieve (g), triethanolamine (mol), tetrapropylammonium hydroxide (mol) and water (mol) =100: 0.20: 0.15: 180, placing the mixture into a stainless steel sealed reaction kettle, placing the stainless steel sealed reaction kettle at the constant temperature of 190 ℃ and the autogenous pressure for 0.5 day, cooling and releasing the pressure, filtering, washing and drying the mixture according to a conventional method, and roasting the mixture for 3 hours at the temperature of 550 ℃ in an air atmosphere to obtain the HTS molecular sieve.
The HTS molecular sieve has a hollow structure with the radial length of 5-100 nanometers, and the benzene adsorption quantity measured by a static adsorption method under the conditions of 25 ℃, P/P0=0.10 and 1 hour of adsorption time is 85 mg/g molecular sieve; the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption determined according to the standard method of astm d4222-98 show that there is a hysteresis loop between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption.
Preparation of comparative example 8
The preparation method of the tin-loaded titanium silicalite Sn/TS-1 in the preparation comparative example is as follows:
the pentahydrate stannic chloride (SnCl) 4 .5H 2 O) and TS-1 molecular sieve (prepared by the method of comparative preparation example 7) are directly and mechanically mixed and then are roasted for 5 hours at 550 ℃ to obtain the molecular sieve with the chemical composition of 0.03TiO 2 :SiO 2 :0.03SnO 2 The molecular sieve of (1). Wherein the dosage of TS-1 is 2g 4 .5H 2 The amount of O used was 0.76g.
The examples and comparative examples illustrate the preparation of methylglyoxal by the catalytic oxidation of sugars using different catalysts.
Example 1
0.15g of the tin-titanium-silicon molecular sieve Sn-Ti-MFI-1 provided in preparation example 1 was weighed as a catalyst and charged in a 100mL polytetrafluoroethylene liner, and then 8g of methanol and 0.1g of glucose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled at about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 1
0.15g of the Sn-Si molecular sieve Sn-MFI provided in preparation comparative example 1 was weighed as a catalyst and charged in a 100mL polytetrafluoroethylene liner, and then 8g of methanol and 0.1g of glucose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 2
0.15g of the Sn-Beta molecular sieve prepared in the comparative example 2 is weighed and used as a catalyst to be filled in a 100mL polytetrafluoroethylene lining, and then 8g of methanol and 0.1g of glucose are sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 3
0.15g of the Sn-USY molecular sieve provided in preparation comparative example 3 was weighed as a catalyst and charged into 100mL of a polytetrafluoroethylene liner, and then 8g of methanol and 0.1g of glucose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled at about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 4
0.15g of the titanium silicalite TS-2 provided in preparation comparative example 5 was weighed out as a catalyst and filled in a 100mL polytetrafluoroethylene liner, and then 8g of methanol and 0.1g of glucose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 5
0.15g of the Ti-Si molecular sieve Ti-Beta provided in preparation comparative example 6 was weighed as a catalyst and charged in a 100mL polytetrafluoroethylene inner liner, and then 8g of methanol and 0.1g of glucose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 6
0.15g of the titanium silicalite TS-1 provided in preparation comparative example 4 was weighed as a catalyst and charged into 100mL of a polytetrafluoroethylene liner, and then 8g of methanol and 0.1g of glucose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 7
0.10g of Sn-MFI provided by preparation comparative example 1 and 0.05g of TS-1 provided by preparation comparative example 4 are weighed as catalysts and filled in a 100mL polytetrafluoroethylene lining, and then 8g of methanol and 0.1g of glucose are added in sequence. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 8
0.05g of the Sn-MFI molecular sieve prepared in the preparation comparative example 1 and 0.10g of the TS-1 molecular sieve prepared in the preparation comparative example 4 are weighed as catalysts and filled in a 100mL polytetrafluoroethylene lining, and then 8g of methanol and 0.1g of glucose are sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 9
0.03g of the Sn-MFI molecular sieve prepared in the comparative example 1 and 0.12g of the TS-1 molecular sieve prepared in the comparative example 4 were weighed as catalysts and filled in a 100mL polytetrafluoroethylene liner, and then 8g of methanol and 0.1g of glucose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 10
0.15g of the hollow titanium silicalite HTS catalyst provided in preparation comparative example 7 was weighed and loaded into 100mL of polytetrafluoroethylene liner, and then 8g of methanol and 0.1g of glucose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 11
0.15g of the Sn/TS-1 catalyst of the Sn-loaded titanium silicalite molecular sieve prepared in the preparation comparative example 8 is weighed and filled in a 100mL polytetrafluoroethylene lining, and then 8g of methanol and 0.1g of glucose are sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled at about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Comparative example 12
Substantially the same as in example 1, except that: the reaction temperature was 160 ℃ and the reaction time was 55 hours. The specific reaction results are shown in Table 1.
Comparative example 13
Substantially the same as in example 1, except that: the reaction temperature was 90 ℃ and the reaction time was 6 hours. The specific reaction results are shown in Table 1.
Example 2
0.15g of the Sn-Ti-MFI-2 molecular sieve provided in preparation example 2 was weighed out and loaded as a catalyst in a 100mL polytetrafluoroethylene liner, and then 8g of pentanol and 0.1g of xylose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Example 3
0.15g of the tin-titanium-silicon molecular sieve Sn-Ti-MFI-3 provided in preparation example 3 was weighed as a catalyst and charged in a 100mL polytetrafluoroethylene liner, and then 8g of ethanol and 0.1g of fructose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Example 4
0.15g of the tin-titanium-silicon molecular sieve Sn-Ti-MFI-4 provided in preparation example 4 was weighed as a catalyst and charged in a 100mL polytetrafluoroethylene liner, and 8g of butanediol and 0.1g of sucrose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Example 5
0.15g of the tin-titanium-silicon molecular sieve Sn-Ti-MFI-5 provided in preparation example 5 was weighed out as a catalyst and charged in a 100mL polytetrafluoroethylene liner, and 8g of butanediol and 0.1g of xylose were sequentially added. The polytetrafluoroethylene lining is placed in a stainless steel reaction kettle for sealing and placed in a homogeneous reactor for starting reaction. The reaction temperature is controlled to be about 120 ℃ and the reaction is carried out for 17 hours. The specific reaction results are shown in Table 1.
Example 6
The same as example 1 except that the tin-titanium-silicon molecular sieve provided in preparation example 6 was used as a catalyst. The specific reaction results are shown in Table 1.
Example 7
The same as example 1 except that the tin-titanium-silicon molecular sieve provided in preparation example 7 was used as a catalyst. The specific reaction results are shown in Table 1.
Example 8
The same as example 1 except that: the molar ratio of sugar to alcohol is 1:50, the reaction temperature is 100 ℃, the reaction time is 10 hours, and the weight ratio of the sugar to the tin-titanium-silicon molecular sieve is 1. The specific reaction results are shown in Table 1.
Example 9
The same as example 1 except that: the molar ratio of sugar to alcohol is 1:600, the reaction temperature is 145 ℃, the reaction time is 50 hours, and the weight ratio of the sugar to the tin-titanium-silicon molecular sieve is 1. The specific reaction results are shown in Table 1.
As can be seen from the results of the above examples and comparative examples, the method of the present invention for preparing methylglyoxal has the advantages of simple operation process, mild reaction conditions, high raw material conversion rate and methylglyoxal selectivity; especially when the catalyst is a binary tin-titanium-silicon molecular sieve, the molar ratio of sugar to alcohol is 1: (50-600), the reaction temperature is more than 100 ℃ and less than 150 ℃, the reaction time is 10-50h, and when the reaction pressure is 0.1-6.0MPa, the weight ratio of the sugar to the tin-titanium-silicon molecular sieve based on the dry weight is 1: (1-6), it is further preferable that the molar ratio of the sugar to the alcohol is 1: (100-500), the weight ratio of sugar to tin-titanium-silicon molecular sieve based on dry weight is 1: (1.2-3), the reaction temperature is 110-140 ℃, the reaction time is 12-40h, and the reaction pressure is 0.1-4MPa, which is more favorable for improving the conversion rate of sugar and the yield of methylglyoxal.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the content of the present invention as long as the idea of the present invention is not violated.
TABLE 1
Numbering Sugar conversion/% Methylglyoxal selectivity/%)
Example 1 90 82
Example 2 88 87
Example 3 86 85
Example 4 90 84
Example 5 90 89
Example 6 87 86
Example 7 88 88
Example 8 95 80
Example 9 90 80
Comparative example 1 55 44
Comparative example 2 56 42
Comparative example 3 53 45
Comparative example 4 41 36
Comparative example 5 40 37
Comparative example 6 40 34
Comparative example 7 75 79
Comparative example 8 78 78
Comparative example 9 75 77
Comparative example 10 43 29
Comparative example 11 29 10
Comparative example 12 90 42
Comparative example 13 25 18

Claims (11)

1. A method of catalyzing a sugar to produce methylglyoxal, the method comprising:
contacting sugar with a catalyst in a reactor in the presence of alcohol and carrying out reaction to obtain a product containing methylglyoxal; wherein the molar ratio of sugar to alcohol is 1: (50-600), the reaction temperature is more than 100 ℃ and less than 150 ℃, the reaction time is 10-50h, the catalyst contains a tin-titanium-silicon molecular sieve, and the weight ratio of sugar to the tin-titanium-silicon molecular sieve based on the dry weight is 1: (1-6); the tin-titanium-silicon molecular sieve is selected from an MFI type tin-titanium-silicon molecular sieve, the molar ratio of a tin element to a silicon element in the tin-titanium-silicon molecular sieve is 0.05-10;
the proportion of the external specific surface area of the tin-titanium-silicon molecular sieve in the total specific surface area is more than 10 percent, and the total specific surface area is 300m 2 More than g, and the external specific surface area is 20m 2 More than g;
the tin-titanium-silicon molecular sieve is at 25 ℃ and P/P 0 An adsorbed amount of benzene of at least 35mg/g as measured under conditions of 0.10 and an adsorption time of 1 hour; at a relative pressure P/P 0 If the molar ratio is about 0.60, the difference between the nitrogen adsorption amount during desorption and the nitrogen adsorption amount during adsorption of the tin-titanium-silicon molecular sieve is greater than 2% of the nitrogen adsorption amount during adsorption of the tin-titanium-silicon molecular sieve;
and a hysteresis loop is arranged between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption of the tin-titanium-silicon molecular sieve.
2. The method of claim 1, wherein the tin-titanium-silicon molecular sieve is selected from Sn-Ti-MFI molecular sieves.
3. The method of claim 1, wherein the tin-titanium-silicon molecular sieve contains elemental silicon, elemental titanium, elemental tin, and elemental oxygen;
at least part of crystal grains of the tin-titanium-silicon molecular sieve have a cavity structure;
the tin-titanium-silicon molecular sieve has a diffraction peak at 0.5-9 degrees of 2 theta in an XRD pattern;
460cm of the tin-titanium-silicon molecular sieve in an FT-IR spectrum -1 、975cm -1 、800cm -1 And 1080cm -1 Nearby absorption;
the tin-titanium-silicon molecular sieve has absorption at 200-300nm in a UV-Vis spectrum;
the radial length of the cavity part of the cavity structure in the crystal grain of the tin-titanium-silicon molecular sieve is 0.5-300nm.
4. The method of claim 1, wherein the ratio of the external specific surface area of the tin-titanium-silicon molecular sieve to the total specific surface area is 10-25%, and the total specific surface area is 310-600m 2 Per g, external specific surface area of 31-150m 2 /g。
5. The method of claim 1, wherein the method of making the tin-titanium-silicon molecular sieve comprises:
(1) Contacting a tin source, a titanium source and a template agent in the presence of an aqueous solvent to obtain a first mixture;
(2) Mixing the first mixture with a silicon molecular sieve to obtain a second mixture;
(3) Crystallizing the second mixture under hydrothermal crystallization conditions;
in the step (1), the contact conditions include: the contact temperature is 20-80 ℃, and the contact time is 1-240min;
the dosage of the silicon molecular sieve and the tin source ensures that the molar ratio of tin element to silicon element in the prepared tin-titanium-silicon molecular sieve is 0.05-10; the dosage of the silicon molecular sieve and the titanium source ensures that the molar ratio of the titanium element to the silicon element in the prepared tin-titanium-silicon molecular sieve is 0.05-10;
the dosage mole ratio of the silicon molecular sieve, the template agent, the titanium source, the tin source and the water is (100) 2 The tin source is calculated by tin element, and the titanium source is calculated by TiO 2 Counting;
the hydrothermal crystallization conditions include: the crystallization temperature is 80-200 ℃ under the closed condition, and the crystallization time is 6-150h;
the tin source is an inorganic tin compound and/or an organic tin compound; the titanium source is an inorganic titanium compound and/or an organic titanium compound; the template agent is one or more of aliphatic amine compound, aliphatic alcohol amine compound and quaternary ammonium base compound; the silicon molecular sieve is S-1;
at least part of crystal grains of the tin-titanium-silicon molecular sieve have a cavity structure, and a diffraction peak is arranged at the position of 0.5-9 degrees of 2 theta in an XRD pattern; 460cm in the FT-IR spectrum -1 、975cm -1 、800cm -1 、1080cm -1 There is absorption nearby; the absorption is carried out at 200-300nm in a UV-Vis spectrum, and the total specific surface area of the tin-titanium-silicon molecular sieve is 300m 2 More than g, and the external specific surface area is 30m 2 More than g, and the proportion of the external specific surface area to the total specific surface area is more than 10 percent.
6. The method of claim 1, wherein the tin-titanium-silicon molecular sieve is obtained by performing a second hydrothermal synthesis on a titanium-silicon molecular sieve with a compound containing a tin source, a template agent, alkali and water at 100-160 ℃, and performing filtering separation, drying and roasting, wherein the tin content of the molecular sieve is 1-5 wt% calculated by oxide;
the tin-titanium-silicon molecular sieve is Sn-TS-1.
7. The method of claim 6, wherein the Sn-TS-1 is a titanium silicalite molecule having an MFI crystal structureA sieve, wherein the crystal grain is of a hollow structure, and the radial length of a cavity part of the hollow crystal grain is 5-300 nanometers; the molecular sieve sample is at 25 ℃, P/P 0 =0.10, the benzene adsorption amount measured under the condition of adsorption time of 1 hour is at least 70 mg/g, and a hysteresis loop exists between the adsorption isotherm and the desorption isotherm of low-temperature nitrogen adsorption of the molecular sieve.
8. The method according to claim 1, wherein the sugar is one or more selected from the group consisting of a pentose, a hexose, and a disaccharide, the pentose is xylose, the hexose is one or more selected from the group consisting of glucose, fructose, and mannose, and the disaccharide is sucrose;
the alcohol is one or more selected from monohydric alcohol, dihydric alcohol and polyhydric alcohol containing more than three hydroxyl groups; the monohydric alcohol is selected from one or more of methanol, ethanol, propanol, n-butanol, isobutanol and pentanol, the dihydric alcohol is selected from one or more of ethylene glycol, propylene glycol, butanediol and hexanediol, and the polyhydric alcohol is selected from one or more of glycerol, trimethylolethane, pentaerythritol, xylitol and sorbitol.
9. The method of claim 1, wherein the molar ratio of sugar to alcohol is 1: (100-500), the weight ratio of sugar to tin-titanium-silicon molecular sieve based on dry weight is 1: (1.2-3), the reaction temperature is 110-140 ℃, the reaction time is 12-40h, and the reaction pressure is 0.1-6MPa.
10. The process according to claim 9, wherein the reaction pressure is 0.1-4MPa.
11. The process of claim 1, wherein the reactor is a tank reactor, a fixed bed reactor, a moving bed, a suspended bed, or a slurry bed reactor.
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