CN112844364A - Multi-metal catalyst and application thereof in preparation of lactide compound - Google Patents

Multi-metal catalyst and application thereof in preparation of lactide compound Download PDF

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CN112844364A
CN112844364A CN202110174369.4A CN202110174369A CN112844364A CN 112844364 A CN112844364 A CN 112844364A CN 202110174369 A CN202110174369 A CN 202110174369A CN 112844364 A CN112844364 A CN 112844364A
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temperature
solution
salt
deionized water
catalyst
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CN112844364B (en
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李奇
张晓龙
张其荣
卞秀英
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Inner Mongolia Jiutai New Material Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

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Abstract

The invention belongs to the technical field of catalyst preparation, and particularly relates to a multi-metal catalyst and application thereof in lactide preparation. Book (I)The multi-metal catalyst provided by the invention is characterized in that the multi-metal catalyst takes silica sol as a carrier, one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate as a precursor, and adopts (NH)2）2CO、Na2CO3、NaOH、K2CO3KOH is a precipitator, and the catalyst is prepared by precipitation. The catalyst provided by the invention has a nano-scale ultrafine particle effect, has a higher specific surface area and higher catalytic activity in a certain temperature and pressure range, is used for producing gas-solid phase lactide, can be used for continuous reaction, and can greatly improve the reaction rate and yield.

Description

Multi-metal catalyst and application thereof in preparation of lactide compound
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a multi-metal catalyst and application thereof in preparation of lactide compounds.
Background
Regarding the multi-metal catalyst, the following patent documents are disclosed: CN111530469A discloses a solid multi-metal catalyst, which comprises a catalyst active component, an auxiliary component, a pore-forming agent, an extrusion aid, and a binder; the active components of the catalyst are single metal elements, metal oxides or hydroxides of two or more than two nano-state and micro-state particles such as Ni, Fe, Co, Cu, Zn, Bi, Mn, La, Ce, Mo and the like, the weight of the active components of the catalyst accounts for 5-60% (w/w%) of the total weight of the catalyst, and the particle size is 5-5000 nm; the auxiliary component is Al2O3、SiO2、TiO2、MgO、CeO2、ZrO2Oxides with the particle size of 0.1-100 microns and auxiliary components accounting for 10-85% (w/w%) of the total weight of the catalyst; the pore-forming agent is one or more of methyl cellulose, polyethylene glycol and water-soluble starch, and the weight of the pore-forming agent accounts for 0.5-10% (w/w%) of the total weight of the catalyst; the extrusion aid is sesbania powder or citric acid, and the weight of the extrusion aid accounts for 0.1-5% (w/w%) of the total weight of the catalyst; the binder is silica sol, aluminum sol or nitric acid water solution, and the weight of the binder accounts for 5-15% (w/w%) of the total weight of the catalyst.
The multi-metal catalyst disclosed in the above documents is mainly used in the preparation of formic acid or acetic acid, although it is also a multi-metal catalyst, and cannot be used in the technical field of lactide preparation.
In the technical field of lactide preparation, the traditional production method is a solution method or a melting method, and most of the adopted catalysts are powder or liquid; however, with the updating and upgrading of the preparation process of lactide, a new production process, namely a gas-solid phase reaction method, appears. In the above new process, there is a need for a catalyst which is in the form of a tablet or granulate, has a certain mechanical strength and can be used in a fixed bed or in a fluidized bed. However, catalysts having the above characteristics and properties are rarely disclosed in the literature.
Disclosure of Invention
In order to solve the technical problems, the invention provides a multi-metal catalyst and an application thereof in lactide preparation, which are used for solving the technical problems of low reaction rate, low yield and continuous generation in the existing lactide preparation process.
In the preparation process of lactide, the gas-solid phase reaction method, the novel synthesis method, has the advantage of continuous operation, and solves the problem of non-uniformity of the quality of products prepared by the traditional method (adopting a kettle reactor).
However, the liquid or powdery catalysts used in the conventional methods mentioned in the background art cannot be used in a fixed bed or a fluidized bed. In order to make the catalyst suitable for a new lactide preparation method, i.e. a gas-solid phase reaction method, the invention provides a catalyst which can be used on a fixed bed or a fluidized bed, and the invention provides a catalyst which is in a sheet shape or a granular shape and has certain mechanical strength.
In addition, in the preparation process of the lactide catalyst, the multi-component catalyst used in the traditional preparation method is usually simply mixed and compounded, but the invention correspondingly combines different metal ions to prepare the catalyst containing multiple metals. Compared with the documents mentioned in the background technology, the preparation of the catalyst of the invention does not need the components of auxiliary agent, pore-forming agent, extrusion aid and the like, is simpler, adopts common metal compounds, does not contain rare earth metals and has lower cost.
The multi-metal catalyst provided by the invention takes silica sol as a carrier, one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate as a precursor, and adopts (NH)2)2CO、Na2CO3、NaOH、K2CO3KOH is a precipitator, and the catalyst is prepared by precipitation.
Preferably, the silica sol has a particle size of 10 to 20 nm.
Preferably, the solution is treated by 1-30 kHz ultrasonic wave in the precipitation process.
The preparation method of the multi-metal catalyst provided by the invention comprises the following steps:
s1: fully dissolving one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate in deionized water to prepare a metal salt solution;
then deionized water is used for dissolving (NH)2)2CO、Na2CO3、NaOH、K2CO3One of KOH and KOH is fully dissolved and prepared into alkaline solution;
weighing SiO2.H2Adjusting the pH value to 2-5 to obtain a silica sol solution;
s2: uniformly mixing the metal salt solution, the alkali solution and the silica sol solution in the step S1 to obtain a mixed solution;
then respectively cleaning containers containing the metal salt solution, the alkali solution and the silica sol solution by using deionized water, pouring the containers into the mixed solution, adjusting the pH value to 1-3, and then diluting by using the deionized water; obtaining a diluted solution;
s3: carrying out ultrasonic treatment on the diluted solution, and stirring simultaneously to uniformly mix the diluted solution; then heating and reacting, and simultaneously continuing ultrasonic treatment and stirring;
s4: detecting the pH value of the solution in the S3 to 6.5 +/-0.3, finishing the reaction, and stopping heating, stirring and ultrasonic treatment;
s5: washing the precipitate after the reaction in S4 with deionized water, and then washing with absolute ethyl alcohol;
s6: drying and washing the precipitate, crushing and sieving the dried precipitate, adding stearic acid or PEG2000 and graphite powder into the sieved powder, uniformly mixing, and tabletting for forming;
s7: roasting the product formed by the pressing sheet in the S6, discharging and transferring into a reducing furnace;
s8: and introducing hydrogen into the reduction furnace, and performing temperature programming reduction in pure hydrogen atmosphere to obtain the multi-metal catalyst.
Preferably, in the above step, S1: SiO 22.H225 percent of O, and the dosage of the O is 57 to 70 percent by weight;
preferably, the weight ratio of one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate to water is as follows: 9 wt% -20 wt%;
preferably, (NH)2)2CO、Na2CO3、NaOH、K2CO3And the weight ratio of one of KOH and water is as follows: 9 wt% -17 wt%;
preferably, in S2, the volume ratio of the metal salt solution, the alkali solution and the silica sol solution is: 2: 1: 2;
preferably, HNO is used3Adjusting the pH value;
preferably, after the pH value of the mixed solution is adjusted, diluting by 1-1.5 times;
preferably, when the container for containing the metal salt solution, the alkali solution and the silica sol solution is cleaned by deionized water, the amount of the deionized water is 5 wt% -15 wt% of the original solution.
Preferably, in S3, the frequency during ultrasonic treatment is 1-30 kHz;
preferably, stirring for the first time for 50-70 min; preferably 60 min;
preferably, stirring for 22-26 h for the second time; preferably 24 h;
preferably, heating to 85-100 ℃;
washing the precipitate after the reaction in the S4 with deionized water at 50-60 ℃ in S5;
preferably, washing for 2-3 times;
preferably, after the precipitate is washed by deionized water, the precipitate is washed by absolute ethyl alcohol for 1-2 times.
Preferably, in S6, the drying temperature is 100-120 ℃;
preferably, the drying time is 12-24 h;
preferably, the dosage of the stearic acid or PEG2000 is 1-10 per mill of the mass of the sieve powder;
preferably, the using amount of the graphite powder is 1-5 per mill of the mass of the sieve powder;
preferably, in S7, the firing is carried out by using a temperature programming: the initial temperature is 55-65 ℃, the temperature is raised to 115-125 ℃ after 25-35 min, the temperature is kept for 70-90 min at 115-125 ℃, the temperature is raised to 190-210 ℃ after 50-70 min, the temperature is kept for 110-130 min at 190-210 ℃, the temperature is raised to 315-325 ℃ after 290-310 min, the temperature is kept for 115-125 min at 315-325 ℃, the temperature is raised to 450-470 ℃ after 290-310 min, the temperature is kept for 290-310 min at 450-470 ℃, and the steel plate is taken out and transferred to a reduction furnace;
preferably, in S7, the firing is carried out by using a temperature programming: the initial temperature is 60 ℃, the temperature is increased to 120 ℃ after 30min, the temperature is preserved for 80min at 120 ℃, the temperature is increased to 200 ℃ after 60min, the temperature is preserved for 120min at 200 ℃, the temperature is increased to 320 ℃ after 300min, the temperature is preserved for 120min at 320 ℃, the temperature is increased to 460 ℃ after 300min, the temperature is preserved for 300min at 460 ℃, and the steel plate is taken out and transferred into a reduction furnace;
preferably, in S8, hydrogen is introduced into the reduction furnace at a flow rate of 100ml/min, and the reduction is carried out at a programmed temperature in the atmosphere of pure hydrogen;
preferably, the temperature is programmed to reduce for 12 hours in the pure hydrogen atmosphere;
preferably, the temperature-programmed reduction process comprises: the initial temperature is 150 ℃, the temperature is raised to 225-235 ℃ after 2 hours, and the temperature is kept at 230 ℃ for 10 hours to obtain the multi-metal catalyst.
More preferably, the preparation method of the multi-metal catalyst comprises the following steps:
s1: fully dissolving one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate by using deionized water to prepare a metal salt solution;
then deionized water is used for dissolving (NH)2)2CO、Na2CO3、NaOH、K2CO3One of KOH and KOH is fully dissolved and prepared into alkaline solution;
weighing SiO2.H2Adjusting the pH value to 2-5 to obtain a silica sol solution;
s2: uniformly mixing the metal salt solution, the alkali solution and the silica sol solution in the step S1 to obtain a mixed solution;
then respectively cleaning containers containing the metal salt solution, the alkali solution and the silica sol solution by using deionized water, pouring the containers into the mixed solution, adjusting the pH value to 1-3, and then diluting by using deionized water to obtain a diluted solution;
s3: carrying out ultrasonic treatment on the diluted solution while stirring to uniformly mix the diluted solution, then heating and reacting, and simultaneously continuing ultrasonic treatment and stirring;
s4: detecting the pH value of the solution in the S3 to 6.5 +/-0.3, finishing the reaction, and stopping heating, stirring and ultrasonic treatment;
s5: washing the precipitate after the reaction in S4 with deionized water, and then washing with absolute ethyl alcohol;
s6: drying and washing the precipitate, crushing and sieving the dried precipitate, adding stearic acid or PEG2000 and graphite powder into the sieved powder, uniformly mixing, and tabletting for forming;
s7: roasting the product formed by the pressing sheet in the S6, discharging and transferring into a reducing furnace; the roasting adopts temperature programming: the initial temperature is 55-65 ℃, the temperature is raised to 115-125 ℃ after 25-35 min, the temperature is kept for 70-90 min at 115-125 ℃, the temperature is raised to 190-210 ℃ after 50-70 min, the temperature is kept for 110-130 min at 190-210 ℃, the temperature is raised to 315-325 ℃ after 290-310 min, the temperature is kept for 115-125 min at 315-325 ℃, the temperature is raised to 450-470 ℃ after 290-310 min, the temperature is kept for 290-310 min at 450-470 ℃, and the steel plate is taken out and transferred to a reduction furnace;
s8: introducing hydrogen into the reduction furnace at the flow rate of 100ml/min, and carrying out temperature programming reduction for 12h in the pure hydrogen atmosphere, wherein the temperature programming reduction process comprises the following steps: the initial temperature is 150 ℃, the temperature is raised to 225-235 ℃ after 2 hours, and the temperature is kept at 230 ℃ for 10 hours to obtain the multi-metal catalyst.
The use of a multimetallic catalyst in the preparation of lactide is also within the scope of the invention.
The invention has the beneficial effects that:
(1) the catalyst has a nano-scale ultrafine particle effect and a high specific surface area; after different samples are detected, the result shows that the specific surface area of the catalyst reaches 355.4-380.3 m2Between/g;
(2) the multi-metal catalyst provided by the invention has higher catalytic activity within a certain temperature and pressure range, is used for producing GAs-solid phase lactide, can be used for continuous reaction, and can greatly improve the reaction rate and yield, the GA conversion rate can reach 49% at most, and the glycolide selectivity can reach 81% at most.
Detailed Description
The present invention will now be further described with reference to specific embodiments in order to enable those skilled in the art to better understand the present invention.
In the process of preparing the multi-metal catalyst, the raw materials used in the invention are as follows:
1. chemical pure reagent for antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate
2、(NH2)2CO、Na2CO3、NaOH、K2CO3KOH chemical pure reagent
3. Basic 25% catalyst was silica sol.
Example 1
A method for preparing a multi-metal catalyst comprising the steps of:
1. 52.10g SnCl was mixed with deionized water4、59.50gZn(NO3)2·6H2Fully dissolving O in a 1000ml beaker to prepare 500ml of mixed solution;
2. 109.1g (NH) was diluted with deionized water2)2CO was sufficiently dissolved in a 1000ml beaker to prepare 500ml of (NH)2)2A CO solution;
3. 418.80g of 25% SiO were weighed precisely2.H2O, in a 1000ml beaker, and adding a proper amount of HNO3Adjusting the pH value of the solution to 2;
4. mixing the salt solution, (NH2)2CO solution and SiO2.H2Pouring the O solution into a 2000ml beaker, mixing uniformly, and then respectively cleaning the beaker with 50ml of deionized water to contain SnCl4、Zn(NO3)2Solution, (NH)2)2CO solution and SiO2.H2O solution beaker, pour 2000ml mixed solution beaker, apply HNO3Adjusting the pH value of the mixed solution to 2, and then diluting the mixed solution to 1500ml by using deionized water;
5. pouring the mixed solution into a flask with a 15kHz ultrasonic generator and a stirrer, starting the stirrer, stirring for 60min to uniformly mix the solution, heating by electric heating, starting the ultrasonic generator to treat the solution, and simultaneously keeping stirring until the reaction is finished, wherein the reaction temperature is controlled at 98 ℃;
6. stirring and reacting for 24 hours, detecting the pH value of the solution by using a pH meter, stopping heating, stirring and ultrasonic treatment when the reaction is finished when the pH value reaches 6.5 +/-0.3;
7. washing the precipitate with 50 deg.C hot deionized water for 3 times, and washing with anhydrous ethanol for 2 times;
8. transferring the washed precipitate into a drying oven, drying at 120 ℃ for 12h, crushing and sieving the dried precipitate, adding 10 per mill of stearic acid or PEG2000 and 1-5 per mill of graphite powder by mass ratio, uniformly mixing, and tabletting for molding;
9. transferring the catalyst after tabletting and forming into a roasting furnace for roasting. The roasting adopts temperature programming:
Figure BDA0002940131550000091
10. pure hydrogen atmosphere (100ml H)2Min) temperature programmed reduction for 12 hours to obtain the multi-metal catalyst of the invention, wherein the temperature programmed reduction process comprises the following steps:
Figure BDA0002940131550000101
example 2
A method for preparing a multi-metal catalyst comprising the steps of:
1. mixing 59.50gZn (NO) with deionized water3)2·6H2Fully dissolving O in a 1000ml beaker to prepare 500ml of mixed solution;
2. adding 36.04g (NH) into deionized water2)2CO was sufficiently dissolved in a 1000ml beaker to prepare 500ml of (NH)2)2CO solution；
3. 209.10g of 25% SiO were weighed out precisely2.H2O, in a 1000ml beaker, and adding a proper amount of HNO3Adjusting the pH value of the solution to 2;
4. zinc nitrate solution, (NH)2)2CO solution and SiO2.H2The O solution was poured into a 2000ml beaker and mixed well, then washed with 50ml of deionized water containing Zn (NO)3)2·6H2O solution, (NH)2)2CO solution and SiO2.H2O solution beaker, pour 2000ml mixed solution beaker, apply HNO3Adjusting the pH value of the mixed solution to 2, and then diluting the mixed solution to 1500ml by using deionized water;
5. pouring the mixed solution into a flask with a 15kHz ultrasonic generator and a stirrer, starting the stirrer, stirring for 60min to uniformly mix the solution, heating by electric heating, starting the ultrasonic generator to treat the solution, and simultaneously keeping stirring until the reaction is finished, wherein the reaction temperature is controlled at 98 ℃;
6. stirring and reacting for 24 hours, detecting the pH value of the solution by using a pH meter, stopping heating, stirring and ultrasonic treatment when the reaction is finished when the pH value reaches 6.5 +/-0.3;
7. washing the precipitate with 50 deg.C hot deionized water for 3 times, and washing with anhydrous ethanol for 2 times;
8. transferring the washed precipitate into a drying oven, drying at 120 ℃ for 12h, crushing and sieving the dried precipitate, adding 10 per mill of stearic acid or PEG2000 and 1-5 per mill of graphite powder by mass ratio, uniformly mixing, and tabletting for molding;
9. transferring the catalyst after tabletting and forming into a roasting furnace for roasting. The roasting adopts temperature programming:
Figure BDA0002940131550000111
10. pure hydrogen atmosphere (100ml H)2Min) temperature programmed reduction for 12 hours to obtain the polymetallic catalystThe agent and the temperature programming reduction process are as follows:
Figure BDA0002940131550000112
example 3
A method for preparing a multi-metal catalyst comprising the steps of:
1. weighing 200g of the catalyst precursor obtained in the steps 1-9 in the embodiment 2;
2. weighing 1g of ZSM-5 molecular sieve;
3. putting the catalyst precursor weighed in the steps 1 and 2 into an agate mortar, and fully grinding and mixing for not less than 1 hour;
4. adding 10 per mill of stearic acid or PEG2000 and 1-5 per mill of graphite powder in the catalyst precursor obtained in the step 3, uniformly mixing, and then pressing and forming;
5. transferring the catalyst after tabletting and forming into a roasting furnace for roasting. The roasting adopts temperature programming:
Figure BDA0002940131550000121
6. the catalyst precursor obtained in the step 5 is in pure hydrogen atmosphere (100ml of H)2Min) temperature programmed reduction for 12 hours to obtain the multi-metal catalyst of the invention, wherein the temperature programmed reduction process comprises the following steps:
Figure BDA0002940131550000122
example 4
A method for preparing a multi-metal catalyst comprising the steps of:
1. mixing 59.50gZn (NO) with deionized water3)2·6H2Fully dissolving O in a 1000ml beaker to prepare 500ml of mixed solution;
2. adding 31.80g of Na into deionized water2CO3Fully dissolved in 1000ml beaker, and prepared into 500ml of Na2CO3Putting the solution into a constant-pressure funnel;
3. 209.10g of 25% SiO were weighed out precisely2.H2O, in a 1000ml beaker;
4. mixing zinc nitrate solution and SiO2.H2The O solution was poured into a 2000ml beaker and mixed well, then washed with 50ml of deionized water containing Zn (NO)3)2·6H2O solution, SiO2.H2Pouring the O solution beaker into a 2000ml mixed solution beaker, and then diluting the mixed solution to 1000ml by using deionized water;
5. mixing zinc nitrate and SiO2.H2Pouring the O mixed solution into a flask which is internally provided with a 15kHz ultrasonic generator and a stirrer, starting the stirrer, and stirring for 60min to uniformly mix the solution. Then Na is filled in2CO3A constant pressure funnel of the solution is arranged on the flask;
6. opening the constant-voltage funnel switch to enable Na2CO3The solution is slowly dropped into zinc nitrate and SiO2.H2In O mixed solution, Na2CO3The dripping time of the solution is not less than 3 hours, and the stirring is started in the dripping process;
7. washing the precipitate with 50 deg.C hot deionized water for 3 times, and washing with anhydrous ethanol for 2 times;
8. transferring the washed precipitate into a drying oven, drying at 120 ℃ for 12h, crushing and sieving the dried precipitate, adding 10 per mill of stearic acid or PEG2000 and 1-5 per mill of graphite powder by mass ratio, uniformly mixing, and tabletting for molding;
9. transferring the catalyst after tabletting and forming into a roasting furnace for roasting. The roasting adopts temperature programming:
Figure BDA0002940131550000131
10. and (3) carrying out temperature programmed reduction for 12 hours in pure hydrogen atmosphere (100ml H2/min) to obtain the multi-metal catalyst of the invention, wherein the temperature programmed reduction process comprises the following steps:
Figure BDA0002940131550000141
example 5
A method for preparing a multi-metal catalyst comprising the steps of:
1. mixing 59.50gZn (NO) with deionized water3)2·6H2Fully dissolving O in a 1000ml beaker to prepare 500ml of mixed solution;
2. accurately weighing 68.06g of tetrabutyl titanate solution, and putting the tetrabutyl titanate solution into a constant-pressure funnel;
3. 209.10g of 25% SiO were weighed out precisely2.H2O, in a 1000ml beaker;
4. mixing zinc nitrate solution and SiO2.H2The O solution was poured into a 2000ml beaker and mixed well, then washed with 50ml of deionized water containing Zn (NO)3)2·6H2O solution, SiO2.H2O solution beaker, pour 2000ml mixed solution beaker, apply HNO3Adjusting the pH value of the mixed solution to 2, and then diluting the mixed solution to 1000ml by using deionized water;
5. mixing zinc nitrate and SiO2.H2Pouring the O mixed solution into a flask which is internally provided with a 15kHz ultrasonic generator and a stirrer, starting the stirrer, and stirring for 60min to uniformly mix the solution. A constant-pressure funnel containing tetrabutyl titanate solution is arranged on a flask, then electric heating is carried out, an ultrasonic generator is started to process the solution, stirring is kept until the reaction is finished, and the reaction temperature is controlled at 98 ℃;
6. and 5, simultaneously opening a constant-pressure funnel switch to slowly drop the tetrabutyl titanate solution into the zinc nitrate and SiO2.H2In the O mixed solution, the dripping time of the tetrabutyl titanate solution is not less than 8 hours, stirring is started in the dripping process, a pH meter is used for detecting the pH value of the solution, the reaction is finished when the pH value reaches 6.5 +/-0.3, and heating, stirring and ultrasonic treatment are stopped;
7. washing the precipitate with 50 deg.C hot deionized water for 3 times, and washing with anhydrous ethanol for 2 times;
8. transferring the washed precipitate into a drying oven, drying at 120 ℃ for 12h, crushing and sieving the dried precipitate, adding 10 per mill of stearic acid or PEG2000 and 1-5 per mill of graphite powder by mass ratio, uniformly mixing, and tabletting for molding;
9. transferring the catalyst after tabletting and forming into a roasting furnace for roasting. The roasting adopts temperature programming:
Figure BDA0002940131550000151
10. pure hydrogen atmosphere (100ml H)2Min) temperature programmed reduction for 12 hours to obtain the multi-metal catalyst of the invention, wherein the temperature programmed reduction process comprises the following steps:
Figure BDA0002940131550000152
example 6
With respect to the use of a multimetallic catalyst in solid phase lactide production, the inventors conducted the following experiments:
experiment of catalytic reaction
The catalyst is respectively subjected to relevant catalytic experiments, and the steps are as follows:
firstly, respectively filling 10g of the catalyst, then purging the reactor for 30min by adopting nitrogen, and heating to 240 ℃; finally, introducing a mixed gas flow (the mass ratio is 98:2) of nitrogen and glycollic acid (or glycollic acid ester) into the reaction system, wherein the weight hourly space velocity is 2h-1The reaction pressure is 0.3MPa, and the glycolide is prepared under the action of the catalyst.
To further illustrate the specific surface properties and applications of the present invention, see tables 1 and 2 below:
TABLE 1 measurement results of catalyst specific surface
Sample numbering Measurement result (m)2/g)
1 367.2
2 355.4
3 380.3
4 359.2
5 372.5
TABLE 2 case of multimetallic catalysts for glycolide production
Figure BDA0002940131550000161
As is clear from tables 1 and 2, the catalysts obtained in examples 1 to 5 exhibited good conversion rates, all of which were 30% or more, in catalyzing the synthesis of glycolide, and good selectivity for glycolide, all of which were 40% or more. Especially, the catalyst prepared in example 3 has a glycolide conversion rate of 49% and a glycolide selectivity of 81%, and achieves excellent technical effects.
The above examples illustrate that the process of the present invention utilizes glycolic acid or glycolate as a starting material directly, and produces glycolide in one step by a gas phase reaction under the action of an inert gas and a catalyst, thus opening up a new approach for the synthesis and preparation of glycolide.

Claims (10)

1. The multi-metal catalyst is characterized in that the multi-metal catalyst takes silica sol as a carrier, one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate as a precursor, and adopts (NH)2）2CO、Na2CO3、NaOH、K2CO3KOH is a precipitator, and the catalyst is prepared by precipitation.
2. The multimetallic catalyst of claim 1, wherein the silica sol has a particle size of from 10 nm to 20 nm.
3. The multi-metal catalyst of claim 1, wherein the solution is treated with 1 to 30kHz ultrasonic waves during the precipitation process.
4. A method for preparing a multi-metal catalyst comprising the steps of:
s1: fully dissolving one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate by using deionized water to prepare a metal salt solution;
then deionized water is used for dissolving (NH)2）2CO、Na2CO3、NaOH、K2CO3One of KOH and KOH is fully dissolved to prepare urea solution;
weighing SiO2.H2Adjusting the pH value to 2-5 to obtain a silica sol solution;
s2: uniformly mixing the metal salt solution, the urea solution and the silica sol solution in the step S1 to obtain a mixed solution;
then respectively cleaning containers containing a metal salt solution, a urea solution and a silica sol solution by using deionized water, pouring the containers into the mixed solution, adjusting the pH value to 1-3, and then diluting by using the deionized water; obtaining a diluted solution;
s3: carrying out ultrasonic treatment on the diluted solution, and stirring simultaneously to uniformly mix the diluted solution; then heating and reacting, and simultaneously continuing ultrasonic treatment and stirring;
s4: detecting the pH value of the solution in the S3 to 6.5 +/-0.3, finishing the reaction, and stopping heating, stirring and ultrasonic treatment;
s5: washing the precipitate after the reaction in S4 with deionized water, and then washing with absolute ethyl alcohol;
s6: drying and washing the precipitate, crushing and sieving the dried precipitate, adding stearic acid or PEG2000 and graphite powder into the sieved powder, uniformly mixing, and tabletting for forming;
s7: roasting the product formed by the pressing sheet in the S6, discharging and transferring into a reducing furnace;
s8: and introducing hydrogen into the reduction furnace, and performing temperature programming reduction in pure hydrogen atmosphere to obtain the multi-metal catalyst.
5. The method for preparing the multimetallic catalyst of claim 4, wherein the ratio of S1:
SiO2.H225 percent of O, and the dosage of the O is 57 to 70 percent by weight;
preferably, the weight ratio of one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate to water is as follows: 9 wt% -20 wt%;
preferably, (NH)2）2CO、Na2CO3、NaOH、K2CO3And the weight ratio of one of KOH and water is as follows: 9 to 17 weight percent.
6. The method for preparing the multi-metal catalyst according to claim 4, wherein in S2, the volume ratio of the metal salt solution, the urea solution and the silica sol solution is as follows:
preferably, HNO is used3Adjusting the pH value;
preferably, after the pH value of the mixed solution is adjusted, diluting by 1-1.5 times;
preferably, when the container for containing the metal salt solution, the urea solution and the silica sol solution is cleaned by deionized water, the amount of the deionized water is 5 wt% -15 wt% of the original solution.
7. The method for preparing the multimetallic catalyst according to claim 4, wherein in S3, the frequency during the ultrasonic treatment is 1 to 30 kHz;
preferably, stirring for the first time for 50-70 min; preferably 60 min;
preferably, stirring for 22-26 h for the second time; preferably 24 h;
preferably, heating to 85-100 ℃;
washing the precipitate after the reaction in the S4 with deionized water at 50-60 ℃ in S5;
preferably, washing for 2-3 times;
preferably, after the precipitate is washed by deionized water, the precipitate is washed by absolute ethyl alcohol for 1-2 times.
8. The method for preparing the multi-metal catalyst according to claim 4, wherein in S6, the drying temperature is 100-120 ℃;
preferably, the drying time is 12-24 h;
preferably, the dosage of the stearic acid or PEG2000 is 1-10 per mill of the mass of the sieve powder;
preferably, the using amount of the graphite powder is 1-5 per mill of the mass of the sieve powder;
preferably, in S7, the firing is carried out by using a temperature programming: the initial temperature is 55-65 ℃, the temperature is raised to 115-125 ℃ after 25-35 min, the temperature is kept for 70-90 min at 115-125 ℃, the temperature is raised to 190-210 ℃ after 50-70 min, the temperature is kept for 110-130 min at 190-210 ℃, the temperature is raised to 315-325 ℃ after 290-310 min, the temperature is kept for 115-125 min at 315-325 ℃, the temperature is raised to 450-470 ℃ after 290-310 min, the temperature is kept for 290-310 min at 450-470 ℃, and the steel plate is taken out and transferred to a reduction furnace;
preferably, in S7, the firing is carried out by using a temperature programming: the initial temperature is 60 ℃, the temperature is increased to 120 ℃ after 30min, the temperature is preserved for 80min at 120 ℃, the temperature is increased to 200 ℃ after 60min, the temperature is preserved for 120min at 200 ℃, the temperature is increased to 320 ℃ after 300min, the temperature is preserved for 120min at 320 ℃, the temperature is increased to 460 ℃ after 300min, the temperature is preserved for 300min at 460 ℃, and the steel plate is taken out and transferred into a reduction furnace;
preferably, in S8, hydrogen is introduced into the reduction furnace at a flow rate of 100ml/min, and the reduction is carried out at a programmed temperature in the atmosphere of pure hydrogen;
preferably, the temperature is programmed to reduce for 12 hours in the pure hydrogen atmosphere;
preferably, the temperature-programmed reduction process comprises: the initial temperature is 150 ℃, the temperature is raised to 225-235 ℃ after 2 hours, and the temperature is kept at 230 ℃ for 10 hours to obtain the multi-metal catalyst.
9. The method for preparing the multi-metal catalyst according to claim 4, comprising the steps of:
s1: fully dissolving one or more of antimony salt, tin salt, zinc salt, nickel salt and tetrabutyl titanate by using deionized water to prepare a metal salt solution;
then deionized water is used for dissolving (NH)2）2CO、Na2CO3、NaOH、K2CO3One of KOH and KOH is fully dissolved to prepare urea solution;
weighing SiO2.H2Adjusting the pH value to 2-5 to obtain a silica sol solution;
s2: uniformly mixing the metal salt solution, the urea solution and the silica sol solution in the step S1 to obtain a mixed solution;
then respectively cleaning containers containing a metal salt solution, a urea solution and a silica sol solution by using deionized water, pouring the containers into the mixed solution, adjusting the pH value to 1-3, and then diluting by using the deionized water; obtaining a diluted solution;
s3: carrying out ultrasonic treatment on the diluted solution, and stirring simultaneously to uniformly mix the diluted solution; then heating and reacting, and simultaneously continuing ultrasonic treatment and stirring;
s4: detecting the pH value of the solution in the S3 to 6.5 +/-0.3, finishing the reaction, and stopping heating, stirring and ultrasonic treatment;
s5: washing the precipitate after the reaction in S4 with deionized water, and then washing with absolute ethyl alcohol;
s6: drying and washing the precipitate, crushing and sieving the dried precipitate, adding stearic acid or PEG2000 and graphite powder into the sieved powder, uniformly mixing, and tabletting for forming;
s7: roasting the product formed by the pressing sheet in the S6, discharging and transferring into a reducing furnace; the roasting adopts temperature programming: the initial temperature is 55-65 ℃, the temperature is raised to 115-125 ℃ after 25-35 min, the temperature is kept for 70-90 min at 115-125 ℃, the temperature is raised to 190-210 ℃ after 50-70 min, the temperature is kept for 110-130 min at 190-210 ℃, the temperature is raised to 315-325 ℃ after 290-310 min, the temperature is kept for 115-125 min at 315-325 ℃, the temperature is raised to 450-470 ℃ after 290-310 min, the temperature is kept for 290-310 min at 450-470 ℃, and the steel plate is taken out and transferred to a reduction furnace;
s8: introducing hydrogen into the reduction furnace at the flow rate of 100ml/min, and carrying out temperature programming reduction for 12h in the pure hydrogen atmosphere, wherein the temperature programming reduction process comprises the following steps: the initial temperature is 150 ℃, the temperature is raised to 225-235 ℃ after 2 hours, and the temperature is kept at 230 ℃ for 10 hours to obtain the multi-metal catalyst.
10. Use of a multimetallic catalyst in the preparation of lactide.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006104138A (en) * 2004-10-06 2006-04-20 Nippon Shokubai Co Ltd Method of manufacturing glycolide
CN102380381A (en) * 2011-09-09 2012-03-21 久泰能源科技有限公司 Nanometer ultrafine glycol copper silicon catalyst and its preparation method
CN108855119A (en) * 2017-05-11 2018-11-23 中国石油化工股份有限公司 A kind of production gamma-butyrolacton catalyst and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006104138A (en) * 2004-10-06 2006-04-20 Nippon Shokubai Co Ltd Method of manufacturing glycolide
CN102380381A (en) * 2011-09-09 2012-03-21 久泰能源科技有限公司 Nanometer ultrafine glycol copper silicon catalyst and its preparation method
CN108855119A (en) * 2017-05-11 2018-11-23 中国石油化工股份有限公司 A kind of production gamma-butyrolacton catalyst and preparation method

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