CN111097523A - Solid base catalyst and preparation method thereof - Google Patents

Solid base catalyst and preparation method thereof Download PDF

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Publication number
CN111097523A
CN111097523A CN201811264037.XA CN201811264037A CN111097523A CN 111097523 A CN111097523 A CN 111097523A CN 201811264037 A CN201811264037 A CN 201811264037A CN 111097523 A CN111097523 A CN 111097523A
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base catalyst
solid base
solution
temperature
carrier
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张信伟
马传军
李�杰
王海洋
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • 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
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • 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 discloses a solid base catalyst and a preparation method thereof. The solid base catalyst contains a nitrided magnesium-zirconium bimetal doped MCM-41 molecular sieve, alkali metal hydroxide and a fluorosilane compound; the content of the alkali metal hydroxide is 0.5-10 wt% based on the weight of the final solid alkali catalyst; the content of the fluorosilane compound is 0.001-0.01 wt%. The solid alkali prepared by the method is used for regenerating anthraquinone degradation products, and has the advantages of difficult loss of an alkali center, high mechanical strength, good regeneration effect and the like.

Description

Solid base catalyst and preparation method thereof
Technical Field
The invention relates to a solid base catalyst and a preparation method thereof, in particular to a solid base catalyst for regenerating anthraquinone degradation products in working solution and a preparation method thereof.
Background
Hydrogen peroxide is an important inorganic chemical raw material and a fine chemical product, is widely applied to many fields of chemical industry, textile, papermaking, food, medicine, chemical synthesis, environmental protection and the like, and is also closely related to the improvement of national quality and level of life. At present, the main technology for producing hydrogen peroxide at home and abroad is the anthraquinone method. The method comprises dissolving alkyl anthraquinone (such as 2-ethyl anthraquinone) in appropriate mixed solvent to obtain working solution; then carrying out hydrogenation reaction under the action of a catalyst to reduce the alkyl anthraquinone into alkyl hydrogen anthraquinone; finally, oxidizing the alkyl anthraquinone hydride into alkyl anthraquinone by air, and simultaneously generating hydrogen peroxide.
Due to the complexity of organic reactions and the selectivity of catalysts, side reactions inevitably occur during the hydrogenation and oxidation processes, and complex kinds of degradation products are generated, such as: 2-alkylhydroxyanthrone, 2-alkylanthrone, 5,6,7, 8-tetrahydro-2-alkylanthraquinone epoxide, and the like. In the actual production process, the accumulation of the degradation products to a certain degree can cause the reduction of the content of the effective anthraquinone in the working solution and simultaneously cause the change of the physical properties of the working solution, such as: the method has the advantages that the density is increased, the viscosity is increased, the interfacial tension is reduced, the intersolubility with water is increased, the system resistance is increased, and operations such as hydrogenation, oxidation and extraction are affected to different degrees, so that the yield of hydrogen peroxide is reduced, the quality is reduced, and the production cost is increased. Therefore, the problem of degradation and regeneration of effective anthraquinones in the working solution is a subject to be intensively studied.
Anthraquinone degradation products in active alumina regeneration working solution are generally adopted in industry, but the currently adopted alumina has the problems of low regeneration capability and the like. Therefore, a plurality of scholars explore to prepare a novel catalyst for regenerating anthraquinone degradation products in the working solution.
Chinese patent CN200810246589.8 provides an anthraquinone degradation product regenerated catalyst and a manufacturing method thereof, wherein the mass content of alumina in the regenerant is about 93-97%, the content of macropores with the diameter of more than 75nm is more than 5%, the pore volume is more than 0.42 ml/g, and the diameter of the micropores is mainly concentrated in 50-100 Å.
The Chinese patent CN20141009092.5 provides a preparation method of a regenerant. Adding a dilute nitric acid solution into aluminum oxide powder, uniformly mixing to prepare strips, roasting at 400-700 ℃ for 3-5 hours, then soaking the strip carriers in a sodium hydroxide solution, and finally taking out and drying the strip carriers. When the regenerant is used, the increment of effective anthraquinone in the working solution is 5.73 g/L.
Although the regenerated catalyst studied at present has a certain effect on the regeneration of the anthraquinone degradation product, the preparation method still does not fundamentally solve the common problems of the regenerated catalyst of the anthraquinone degradation product, such as: loss of basic center, low mechanical strength, large loss of working fluid, and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a solid base catalyst and a preparation method thereof. The solid alkali used for regenerating anthraquinone degradation products has the advantages of difficult loss of an alkaline center, high mechanical strength, good regeneration effect and the like.
A solid base catalyst comprises a nitrided magnesium-zirconium bi-metal doped MCM-41 molecular sieve, an alkali metal hydroxide and a fluorosilane compound; the content of the alkali metal hydroxide is 0.5-10 wt%, preferably 0.5-5 wt% based on the weight of the final solid alkali catalyst; the content of the fluorosilane compound is 0.001-0.01 wt%, preferably 0.005-0.01 wt%; according to the weight of the nitrided magnesium-zirconium bimetal doped MCM-41 molecular sieve carrier, the content of Mg element in the carrier is 0.1-10 wt%, preferably 0.1-1.5 wt%; the content of Zr element in the carrier is 0.01-10 wt%, preferably 0.05-2 wt%.
The contact angle of the solid base catalyst to hexadecane is more than 130 degrees, preferably 145 degrees to 165 degrees; the alkali metal hydroxide is one or more of NaOH and KOH; the specific surface area of the solid base catalyst is 650-850 m2Preferably 700 to 800 m/g2(iv)/g, the crush strength is 80 to 200N, preferably 120 to 180N.
In the solid base catalyst, the fluorosilane compound is one or more of trifluoropropyltrimethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane, preferably one or more of tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane, and most preferably heptadecafluorodecyltrimethoxysilane.
A preparation method of a solid base catalyst comprises the following steps:
(1) preparing a nitrided magnesium-zirconium bimetal doped MCM-41 molecular sieve carrier by adopting a template-free seed crystal induction method;
(2) introducing an alkali metal hydroxide onto the carrier prepared in the step (1) by adopting an impregnation-crystallization-double decomposition method;
(3) and (3) loading a fluorosilane compound on the material obtained in the step (2) to prepare the solid base catalyst.
A preparation method of a solid base catalyst specifically comprises the following steps:
(1) preparing a polyol-water mixed solution (solution A) containing a silicon source, a magnesium source and seed crystals; preparing an alkaline solution (solution B) containing a zirconium source;
(2) mixing the A, B two solutions at a certain temperature, uniformly stirring, and adjusting the pH value of the system to 10.5-11; crystallizing after the colloid is formed;
(3) after crystallization is finished, filtering, washing and drying a crystallized product, and roasting at a certain temperature to obtain the magnesium-zirconium bimetal doped MCM-41 molecular sieve, which is recorded as: Mg-Zr-MCM-41.
(4) And (4) introducing mixed gas of ammonia gas and inert gas into the material prepared in the step (3) at a certain airspeed, performing high-temperature nitridation treatment on the material at a certain temperature, and then cooling to room temperature to obtain the nitrided Mg-Zr-MCM-41 molecular sieve carrier.
(5) And (3) dissolving alkali metal alkoxide in alcohol, adding the carrier prepared in the step (4), and performing crystallization treatment.
(6) And (5) carrying out steam treatment on the crystallized product obtained in the step (5), and then drying and roasting.
(7) And (3) mixing a fluorosilane compound and isopropanol, soaking the material obtained in the step (6), and then filtering and drying to obtain the solid base catalyst.
In the step (1), the silicon source is one or more of water glass and silica sol, preferably water glass; the magnesium source is one or more of magnesium nitrate, magnesium sulfate and magnesium chloride, and preferably magnesium nitrate.
In the step (1), the preparation method of the seed crystal comprises: grinding an MCM-41 molecular sieve to be below 300 meshes, dispersing solid powder into (10-20 vol%) ethylene glycol- (1-5 vol%) glycerol-water ternary solvent according to a liquid-solid ratio of 80-200, performing ultrasonic treatment for 2-6 h at 60-80 ℃, standing at room temperature, and separating to obtain supernatant serving as seed crystals.
In the step (1), Na is contained in the solution A2The mass fraction of O is 0.01-1 wt%, preferably 0.01-0.1 wt%; SiO in the solution A2The mass fraction of (A) is 0.1-10 wt%, preferably 1-5 wt%; the mass fraction of magnesium nitrate in the solution A is 0.01-1 wt%, preferably 0.01-0.1 wt%; the mass fraction of the seed crystal in the solution A is 0.1-10 wt%, preferably 0.1-1 wt%; the polyhydric alcohol is one or more of ethylene glycol and glycerol, and the volume fraction of the polyhydric alcohol in a polyhydric alcohol-water solution is 1-50 vol%, preferably 5-25 vol%.
In the step (1), the zirconium source is ammonium zirconium carbonate; the alkaline solution is one or more of ammonium carbonate solution, ammonium bicarbonate solution and sodium hydroxide solution, and ammonium carbonate solution is preferred.
In the step (1), the mass fraction of ammonium zirconium carbonate in the solution B is 0.001-1 wt%, preferably 0.001-0.1 wt%; the mass fraction of ammonium carbonate in the ammonium carbonate solution is 0.1-10 wt%, preferably 0.1-5 wt%.
In the step (2), the mixing temperature of the A, B solution is 0-40 ℃, preferably 30-40 ℃; the volume ratio of the A, B liquid is 1: 0.1-10, preferably 1: 0.5-2.
In the step (2), the crystallization temperature is 80-200 ℃, preferably 110-140 ℃; the crystallization time is 12-72 h, preferably 24-48 h.
In the step (3), the drying temperature is 80-200 ℃, preferably 100-150 ℃; the drying time is 6-48 h, preferably 8-24 h. The roasting temperature is 400-800 ℃, and preferably 500-650 ℃; the roasting time is 4-48 h, preferably 6-12 h.
In the step (4), the volume percentage of the ammonia gas in the ammonia gas-nitrogen gas mixed atmosphere is 10 to 100vol%, preferably 50 to 100 vol%; the airspeed of the mixed atmosphere is 60-200 h-1Preferably 80 to 110 hours-1. The nitriding temperature is 500-950 ℃, and preferably 600-800 ℃; the nitriding time is 6 to 36 hours, preferably 8 to 12 hours.
In the step (5), the alkoxide is one or more of sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide and sodium tert-pentoxide, and sodium ethoxide is preferred.
In the step (5), the crystallization temperature is 80-220 ℃, preferably 80-100 ℃. The crystallization time is 8-48 h, preferably 8-24 h.
In the above method step (5), the vector: alkoxide: the mass ratio of alcohol is 1: 0.01-0.5: 0.1-1.0, preferably 1: 0.01-0.1: 0.3-0.6.
In the step (6), the material is subjected to double decomposition reaction with water vapor, and the general formula is as follows: ROM + H2O = MOH + ROH, R denotes the corresponding organic functional group,m denotes the corresponding alkali metal.
In the step (6), the steam is preferably a mixed gas of steam and nitrogen, and the volume fraction of the steam in the mixed gas is: 0.1 to 10 vol%, preferably 0.1 to 2 vol%; the water vapor treatment temperature is 80-220 ℃, and preferably 80-120 ℃; the treatment time is 0.5 to 20 hours, preferably 0.5 to 8 hours.
In the step (6), the drying manner is vacuum drying or drying under the protection of inert gas, or drying under an air atmosphere. The drying temperature is 80-220 ℃, and preferably 120-200 ℃. The drying time is 10-48 h, and preferably 12-24 h. The roasting temperature is 300-900 ℃, and preferably 500-700 ℃. The roasting time is 6-48 h, and preferably 8-24 h.
In the step (7), the fluorosilane compound is one or more selected from trifluoropropyltrimethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane, preferably one or more selected from tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane, and more preferably heptadecafluorodecyltrimethoxysilane.
In the step (7), the concentration of the fluorosilane compound after mixing the fluorosilane compound with the isopropanol is 0.001-0.1 mol/L, preferably 0.001-0.02 mol/L.
The solid base catalyst is used for regenerating anthraquinone degradation products in working solution, and the regeneration conditions are as follows: mixing a solid base catalyst and a working solution containing anthraquinone degradation products according to a solid-liquid mass ratio of 1: 5-1: 15, and reacting at normal pressure and 40-60 ℃.
The solid base catalyst and the preparation method thereof provided by the invention have the beneficial effects that:
(1) in order to ensure that the catalyst can continuously keep certain alkalinity, the invention provides the method for making up for the defect of falling off of the active component by adopting the alkaline carrier. According to the design of the solid base catalyst, when the outer NaOH layer falls off, the exposed alkaline carrier is used as a substitute component to continuously provide the required activity for the reaction. Therefore, the service life of the solid base catalyst can be greatly prolonged, the replacement frequency of the solid base catalyst is reduced, the emission of solid wastes is reduced, and the method has obvious economic benefits and environmental protection advantages.
(2) The invention adopts the fluorosilane compound as an oleophobic center, reduces the surface free energy of the solid base catalyst through surface modification, obviously enhances the surface oleophobic property of the solid base catalyst, has a hexadecane contact angle of more than 150 degrees, can greatly weaken the adsorption effect of the solid base catalyst on the working solution, and the experimental result of comparative example 4 shows that the adsorption capacity of the solid base catalyst on the working solution is only 0.02g of working solution/g of catalyst, and can effectively reduce the loss of the working solution.
(3) Through the hydrogen bond effect of alkoxy and hydroxyl on the surface of the carrier, alkoxide is adsorbed on the bimetal-doped nitrided molecular sieve carrier, a basic center is obtained through double decomposition reaction, a covalent bond structure is formed under the action of high temperature, the basic center can be stabilized on the carrier, and the falling and loss of the basic center are greatly reduced, the experimental result of comparative example 6 shows that after the solid base catalyst is reacted for 100 hours, the loss rate of the basic center is only 5.5 percent and is far lower than that of a reference agent; meanwhile, the organic functional group of the alkoxide also plays a role in isolating the basic center, and the dispersibility and the activity of the basic center are greatly improved.
(4) Experimental results show that the solid base catalyst prepared by the invention has high activity and stability, the regeneration amount of the effective anthraquinone reaches more than 19 g/L, and the catalyst can continuously work for more than 18 months without inactivation.
Detailed Description
The technical contents and effects of the present invention will be further described with reference to examples, but the present invention is not limited thereto. The method for evaluating the performance of the solid base catalyst comprises the following steps: 10 g of solid base catalyst and 100 ml of working solution (the concentration of anthraquinone degradation products is 23 g/L) are weighed and added into a conical flask, the conical flask is vibrated in a water bath at the constant temperature of 50 ℃, and the working solution is taken out after the reaction is carried out for 100 hours to analyze the composition. The chromatographic analysis conditions were: agilent 1260 high performance liquid chromatograph, C18 chromatographic column, ultraviolet detector wavelength 245 nm, internal standard substance p-nitrophenol, mobile phase methanol-water volume ratio 70: 30, flow rate 1 ml/min, and internal standard method for quantitative analysis.
The method for measuring the hexadecane contact angle of the solid base catalyst described in the following examples and comparative examples is as follows: the contact angle of solid alkali and hexadecane was measured by the pendant drop method using a contact angle measuring instrument model JC2000D5, the drop size was about 5uL, at least 5 different points were selected for each sample and measured, and the average value was taken as the contact angle.
Example 1
(one) preparation of seed crystals
Grinding an MCM-41 molecular sieve to be below 300 meshes, dispersing solid powder into a ternary solvent consisting of 18 vol% of ethylene glycol, 4.2 vol% of glycerol and 77.8vol% of water according to a liquid-solid ratio of 100, carrying out high-speed stirring at 65 ℃, carrying out ultrasonic treatment for 4 hours, standing at room temperature, carrying out centrifugal separation, and taking supernatant as seed crystals for later use.
(II) preparation of the support
Solution A: weighing water glass, magnesium nitrate and seed crystal, and adding into a ternary solvent with the composition of 18 vol% of ethylene glycol, 4.2 vol% of glycerol and 77.8vol% of water. Wherein, Na in the solution A2O、SiO2The mass fractions of the magnesium nitrate and the seed crystal were 0.039 wt%, 1.3 wt%, 0.049 wt%, and 0.49 wt%, respectively.
Solution B: ammonium zirconium carbonate was weighed and added to water having a composition of 1.5 wt% ammonium carbonate-98.5 wt%. Wherein the mass fraction of ammonium zirconium carbonate in the solution B is 0.01 wt%.
Rapidly mixing A, B solutions at 35 deg.C at volume ratio of 1: 1, stirring at high speed to make them uniform, and adjusting pH to 10.8; after the solution is gelatinized, the solution is transferred into a high-pressure kettle to be crystallized for 36 hours at the temperature of 135 ℃; and after crystallization is finished, filtering and washing the product, drying at 120 ℃ for 12 h, and roasting at 550 ℃ for 8h to obtain the magnesium-zirconium bimetal doped MCM-41 molecular sieve marked as Mg-Zr-MCM-41.
Placing Mg-Zr-MCM-41 in a tube furnace for 100 h-1Introducing mixed gas of 75 vol% ammonia gas and 25 vol% nitrogen gas at the space velocity of (1) and feeding at the temperature of 750 DEG CAnd (3) performing high-temperature nitridation treatment for 8 hours, and then cooling the product to room temperature to obtain the nitrided magnesium-zirconium bimetal doped MCM-41 molecular sieve.
(III) preparation of solid base catalyst
Weighing 1.2 g of sodium ethoxide, dissolving in 28 ml of ethanol, adding the obtained carrier into the solution, standing at room temperature for 1 h, and then transferring into a stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene for crystallization at 90 ℃ for 18 h. After crystallization is finished, the product is put into a quartz tube fixed bed reactor, the temperature is raised to a set temperature under the protection of nitrogen, according to the condition that water vapor accounts for 0.5vol% of the volume fraction of the total gas, the water vapor is added into a system and is subjected to water vapor treatment with sodium ethoxide, double decomposition reaction is carried out on the water vapor to generate sodium hydroxide and ethanol, the water vapor treatment temperature is 120 ℃, the water vapor treatment time is 4 hours, the material is taken out, dried for 12 hours at 120 ℃, and roasted at high temperature of 700 ℃ for 8 hours.
Preparing an isopropanol solution with the concentration of heptadecafluorodecyltrimethoxysilane being 0.015 mol/L, adding the materials obtained in the steps into the solution, soaking for 1 h, filtering, and drying at 120 ℃ for 12 h to obtain the superoleophobic solid base catalyst.
The composition of the solid base catalyst is as follows: 3.45 percent of NaOH, 0.008 percent of heptadecafluorodecyltrimethoxysilane and the balance of carrier. Wherein the mass fraction of Mg element in the carrier is 0.62 wt%, and the mass fraction of Zr element is 0.15 wt%. The specific surface area of the solid base catalyst is 758 m2The crushing strength is 155N, the hexadecane contact angle is 160 degrees, and the regeneration amount of the effective anthraquinone is 21.6 g/L.
Example 2
The preparation method is the same as example 1, except that: na in solution A2O、SiO2The mass fractions of the magnesium nitrate and the seed crystal were 0.01 wt%, 1.0 wt%, 0.015 wt%, and 0.25 wt%, respectively. The mass fraction of ammonium zirconium carbonate in the solution B is 0.005 wt%, and the solvent composition is 0.2 wt% of ammonium carbonate-99.8 wt% of water.
The composition of the solid base catalyst is as follows: 3.45 percent of NaOH, 0.008 percent of heptadecafluorodecyltrimethoxysilane and the balance of carrier. Wherein the mass fraction of Mg element in the carrier is 0.15 wt%, and the mass fraction of Zr element is 0.08 wt%. Fixing deviceThe specific surface area of the bulk base catalyst is 823 m2The crushing strength is 135N, the hexadecane contact angle is 158 degrees, and the regeneration amount of the effective anthraquinone is 19.5 g/L.
Example 3
The preparation method is the same as example 1, except that: na in solution A2O、SiO2The mass fractions of the magnesium nitrate and the seed crystal were 0.07 wt%, 3.0 wt%, 0.062 wt%, and 0.75 wt%, respectively. The mass fraction of ammonium zirconium carbonate in the solution B is 0.05 wt%, and the solvent composition is 3 wt% of ammonium carbonate-97 wt% of water.
The composition of the solid base catalyst is as follows: 3.45 percent of NaOH, 0.008 percent of heptadecafluorodecyltrimethoxysilane and the balance of carrier. Wherein the mass fraction of Mg element in the carrier is 0.98 wt%, and the mass fraction of Zr element is 0.75 wt%. The specific surface area of the solid base catalyst was 735 m2The specific surface area of the resin composition is 163N in crush strength, 157 in hexadecane contact angle and 20.3 g/L in effective regeneration amount of anthraquinone.
Example 4
The preparation method is the same as example 1, except that: na in solution A2O、SiO2The mass fractions of magnesium nitrate and seed crystal were 0.1 wt%, 4.5 wt%, 0.0952 wt%, and 1.0 wt%, respectively. The mass fraction of ammonium zirconium carbonate in the solution B is 0.1 wt%, and the solvent composition is 4.5 wt% of ammonium carbonate-95.5 wt% of water.
The composition of the solid base catalyst is as follows: 3.45 percent of NaOH, 0.008 percent of heptadecafluorodecyltrimethoxysilane and the balance of carrier. Wherein the mass fraction of Mg element in the carrier is 1.27 wt%, and the mass fraction of Zr element is 1.48 wt%. The specific surface area of the solid base catalyst is 682 m2The crushing strength is 178N, the hexadecane contact angle is 159 degrees, and the effective anthraquinone regeneration amount is 21.4 g/L.
Example 5
The preparation method is the same as example 1, except that: and (2) crystallizing the carrier in the step (II) at 115 ℃ for 48 hours, roasting at 500 ℃ for 12 hours.
The composition of the solid base catalyst is as follows: 3.45 percent of NaOH, 0.008 percent of heptadecafluorodecyltrimethoxysilane and the balance of carrier. Wherein the Mg element in the carrierThe amount fraction was 0.58 wt%, and the mass fraction of Zr element was 0.13 wt%. The specific surface area of the solid base catalyst is 722 m2The crushing strength is 148N, the hexadecane contact angle is 160 degrees, and the regeneration amount of the effective anthraquinone is 20.5 g/L.
Example 6
The preparation method is the same as example 1, except that: and (2) crystallizing the carrier in the step (II) at 125 ℃ for 42 h, roasting at 600 ℃ for 8 h.
The composition of the solid base catalyst is as follows: 3.45 percent of NaOH, 0.008 percent of heptadecafluorodecyltrimethoxysilane and the balance of carrier. Wherein the mass fraction of Mg element in the carrier is 0.59 wt%, and the mass fraction of Zr element is 0.16 wt%. The specific surface area of the solid base catalyst is 731 m2The specific surface area of the resin is 165N in crushing strength, 159 in hexadecane contact angle and 21 g/L in effective anthraquinone regeneration amount.
Example 7
The preparation method is the same as example 1, except that: and (2) crystallizing the carrier in the step (II) at 130 ℃ for 24 hours, roasting at 650 ℃ for 6 hours.
The composition of the solid base catalyst is as follows: 3.45 percent of NaOH, 0.008 percent of heptadecafluorodecyltrimethoxysilane and the balance of carrier. Wherein the mass fraction of Mg element in the carrier is 0.65 wt%, and the mass fraction of Zr element is 0.18 wt%. The specific surface area of the solid base catalyst was 746 m2(ii)/g, crushing strength of 171N, hexadecane contact angle of 160 DEG, and effective regeneration amount of anthraquinone of 21.3 g/L.
Example 8
The preparation method is the same as example 1, except that: the space velocity of carrier nitridation in the step (II) is 90 h-1The composition of ammonia in the mixed gas is 85 vol%, the nitriding temperature is 700 ℃, and the nitriding time is 12 h; the fluorosilane in the step (III) is tridecafluorooctyltrimethoxysilane.
The composition of the solid base catalyst is as follows: 3.45 percent of NaOH by weight, 0.005 percent of tridecafluorooctyltrimethoxysilane by weight and the balance of carrier. Wherein the mass fraction of Mg element in the carrier is 0.62 wt%, and the mass of Zr elementThe fraction was 0.15 wt%. The specific surface area of the solid base catalyst is 783 m2(ii)/g, crushing strength of 152N, hexadecane contact angle of 152 DEG, and effective regeneration amount of anthraquinone of 21.5 g/L.
Example 9
The preparation method is the same as example 1, except that: the space velocity of carrier nitridation in the step (II) is 90 h-1The composition of ammonia in the mixed gas is 95 vol%, the nitriding temperature is 800 ℃, and the nitriding time is 8 hours; the fluorosilane in the step (III) is heptadecafluorodecyltriethoxysilane.
The composition of the solid base catalyst is as follows: 3.45wt% NaOH, 0.007 wt% heptadecafluorodecyltriethoxysilane, the balance being carrier. Wherein the mass fraction of Mg element in the carrier is 0.62 wt%, and the mass fraction of Zr element is 0.15 wt%. The specific surface area of the solid base catalyst is 739 m2The specific surface area of the resin is 150N in crushing strength, 156 in hexadecane contact angle and 21.2 g/L in effective anthraquinone regeneration amount.
Example 10
The preparation method is the same as example 1, except that: in the step (III), the alkoxide is sodium methoxide, the alcohol solvent is methanol, the crystallization temperature is 80 ℃, the crystallization time is 24 hours, the composition of water vapor in the mixed gas is 1 vol%, the treatment temperature is 110 ℃, and the treatment time is 6 hours.
The composition of the solid base catalyst is as follows: 3.41 wt% NaOH, 0.008 wt% heptadecafluorodecyltrimethoxysilane, the balance being vehicle. Wherein the mass fraction of Mg element in the carrier is 0.62 wt%, and the mass fraction of Zr element is 0.15 wt%. The specific surface area of the solid base catalyst is 742 m2The crushing strength is 154N, the hexadecane contact angle is 160 degrees, and the regeneration amount of the effective anthraquinone is 20.1 g/L.
Example 11
The preparation method is the same as example 1, except that: in the step (III), the alkoxide is sodium isopropoxide, the alcohol solvent is isopropanol, the crystallization temperature is 100 ℃, the crystallization time is 12 hours, the composition of water vapor in the mixed gas is 1.5 vol%, the treatment temperature is 100 ℃, and the treatment time is 7 hours.
The composition of the solid base catalyst is as follows: 3.26 wt% NaOH, 0.008 wt%Heptadecafluorodecyltrimethoxysilane, and the balance carrier. Wherein the mass fraction of Mg element in the carrier is 0.62 wt%, and the mass fraction of Zr element is 0.15 wt%. The specific surface area of the solid base catalyst is 751 m2The specific surface area of the resin is 153N in crushing strength, 158 degrees in hexadecane contact angle and 19.5 g/L in effective anthraquinone regeneration amount.
Example 12
The preparation method is the same as example 1, except that: in the step (III), the alkoxide is sodium tert-butoxide, the alcohol solvent is tert-butanol, the crystallization temperature is 95 ℃, the crystallization time is 16 h, the composition of water vapor in the mixed gas is 2.0 vol%, the treatment temperature is 90 ℃, and the treatment time is 8 h.
The composition of the solid base catalyst is as follows: 3.04 wt% NaOH, 0.008 wt% heptadecafluorodecyltrimethoxysilane, and the balance carrier. Wherein the mass fraction of Mg element in the carrier is 0.62 wt%, and the mass fraction of Zr element is 0.15 wt%. The specific surface area of the solid base catalyst is 734 m2(ii)/g, the crushing strength is 151N, the hexadecane contact angle is 159 degrees, and the effective regeneration amount of anthraquinone is 19 g/L.
Comparative example 1
The preparation method is the same as example 1, except that: the obtained carrier is not loaded with NaOH and is directly used as a catalyst, and is marked as a reference agent B1.
Under the same conditions as in example 1, the reference agent B1 was used for working fluid regeneration, and the effective anthraquinone regeneration amount was 8.1 g/L, which is much lower than the regeneration performance of example 1.
Comparative example 2
The preparation method is the same as example 1, except that: MCM-41 was doped with magnesium alone without zirconium to make reference B2.
The carrier composition in reference agent B2 is: 0.62 wt% Mg, the balance MCM-41. Reference B2 has a strength of 79N, much lower than the catalyst strength of example 1.
Comparative example 3
The preparation method is the same as example 1, except that: reference B3 was prepared without nitriding.
Under the same conditions as in example 1, after reference agent B3 was used for regeneration of the working solution for 20 months, the regeneration amount of the effective anthraquinone was reduced to 12.8 g/L; and after the catalyst of the example 1 is used for regenerating the working solution for 20 months, the effective regeneration amount of the anthraquinone can still reach 20.1 g/L.
Comparative example 4
The preparation method is the same as example 1, except that: the reference agent B4 was prepared without surface modification with fluorosilane.
Reference B4 has a contact angle of 62 ° to hexadecane. When the reference agent B4 is used for regenerating the working solution, the adsorption capacity of the reference agent B4 on the working solution is 0.39 g of working solution/g of catalyst after the reaction is carried out for 100 hours; under the same conditions, the adsorption amount of the catalyst of example 1 to the working fluid was 0.02g of the working fluid/g of the catalyst.
Comparative example 5
The preparation method is the same as example 1, except that: no steam treatment was performed. Reference B5 was made.
Reference agent B5 has a specific surface area of 582 m2The evaluation of the properties was the same as in example 1 except that the crushing strength was 142N, the hexadecane contact angle was 155 ℃ and the effective regeneration amount of anthraquinone was 9.3 g/L.
Comparative example 6
The support was prepared as in example 1.
The solid base catalyst is prepared by adopting an impregnation method, and the specific operation is as follows: 3.45 g of NaOH was weighed, dissolved in water, and 100 g of the carrier was added to conduct isovolumetric impregnation. Standing at room temperature for 8 hours, placing the mixture into an oven to be treated at 120 ℃ for 12 hours, and then roasting the mixture at 700 ℃ for 8 hours to obtain a reference agent B6.
After the reference agent B6 is reacted for 100 hours under the same conditions, XRF analysis results show that the content of NaOH is reduced from 3.45wt% to 0.23 wt%, the loss of alkaline centers is very serious, and the loss rate is as high as 93.3%; in contrast, the catalyst of example 1 had a NaOH content of 3.26 wt% and a loss of the basic sites of only 5.51% after 100 hours of reaction.
Comparative example 7
Preparation of load type NaOH/Al by dipping method2O3The catalyst is specifically operated as follows: 3.45 g of NaOH was weighed, dissolved in water, and 100 g of alumina carrier was added to perform the same volume impregnation. Standing at room temperatureAfter standing for 8 hours, the mixture is placed into an oven to be treated at 120 ℃ for 12 hours and then roasted at 700 ℃ for 8 hours to prepare a reference agent B7.
Reference B7 had the composition: 96.55 wt% Al2O33.45wt% NaOH, specific surface area 172 m2(ii)/g, crushing strength 72N, and a contact angle of hexadecane 75 deg. The catalyst performance was evaluated in the same manner as in example 1, and the effective regeneration amount of anthraquinone was 6.2 g/L.

Claims (23)

1. A solid base catalyst characterized by: the solid base catalyst contains a nitrided magnesium-zirconium bimetal doped MCM-41 molecular sieve, alkali metal hydroxide and a fluorosilane compound; the content of the alkali metal hydroxide is 0.5-10 wt% based on the weight of the final solid alkali catalyst; the content of the fluorosilane compound is 0.001-0.01 wt%; according to the weight of the nitrided magnesium-zirconium bimetal doped MCM-41 molecular sieve carrier, the content of Mg element in the carrier is 0.1-10 wt%; the content of Zr element in the carrier is 0.01-10 wt%.
2. The catalyst of claim 1, wherein: the contact angle of the solid base catalyst to hexadecane is more than 130 degrees; the alkali metal hydroxide is one or more of NaOH and KOH; the specific surface area of the solid base catalyst is 650-850 m2(iv)/g, the crushing strength is 80 to 200N.
3. The catalyst of claim 2, wherein: the contact angle of the solid base catalyst to hexadecane is 145-165 degrees; the specific surface area of the solid base catalyst is 700-800 m2(iv)/g, the crushing strength is 120 to 180N.
4. The catalyst of claim 1, wherein: the fluorosilane compound is one or more of trifluoropropyltrimethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
5. A process for preparing a solid base catalyst as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps:
(1) preparing a nitrided magnesium-zirconium bimetal doped MCM-41 molecular sieve carrier by adopting a template-free seed crystal induction method;
(2) introducing an alkali metal hydroxide onto the carrier prepared in the step (1) by adopting an impregnation-crystallization-double decomposition method;
(3) and (3) loading a fluorosilane compound on the material obtained in the step (2) to prepare the solid base catalyst.
6. The method of claim 5, wherein: the preparation method of the solid base catalyst specifically comprises the following steps:
(1) preparing a polyol-water mixed solution containing a silicon source, a magnesium source and seed crystals, and marking as solution A; preparing an alkaline solution containing a zirconium source and marking as a solution B;
(2) mixing the A, B two solutions at a certain temperature, uniformly stirring, and adjusting the pH value of the system to 10.5-11; crystallizing after the colloid is formed;
(3) after crystallization is finished, filtering, washing and drying a crystallized product, and roasting at a certain temperature to obtain the magnesium-zirconium bimetal doped MCM-41 molecular sieve, which is recorded as: Mg-Zr-MCM-41;
(4) introducing mixed gas of ammonia gas and inert gas into the material prepared in the step (3) at a certain airspeed, performing high-temperature nitridation treatment on the material at a certain temperature, and then cooling to room temperature to obtain a nitrided Mg-Zr-MCM-41 molecular sieve carrier;
(5) dissolving alkali metal alkoxide in alcohol, adding the carrier prepared in the step (4), and performing crystallization treatment;
(6) carrying out steam treatment on the crystallized product obtained in the step (5), and then drying and roasting;
(7) and (3) mixing a fluorosilane compound and isopropanol, soaking the material obtained in the step (6), and then filtering and drying to obtain the solid base catalyst.
7. The method of claim 6, wherein: in the step (1), the silicon source is one or more of water glass and silica sol; the magnesium source is one or more of magnesium nitrate, magnesium sulfate and magnesium chloride.
8. The method of claim 6, wherein: in the step (1), the preparation method of the seed crystal comprises the following steps: grinding an MCM-41 molecular sieve to be below 300 meshes, dispersing solid powder in a glycol-glycerol-water ternary solvent, performing ultrasonic treatment for 2-6 hours at the temperature of 60-80 ℃, standing at room temperature, and separating to obtain supernatant serving as seed crystals.
9. The method of claim 6, wherein: in the step (1), Na in the solution A2The mass fraction of O is 0.01-1 wt%; SiO in the solution A2The mass fraction of (A) is 0.1-10 wt%; the mass fraction of magnesium nitrate in the solution A is 0.01-1 wt%; the mass fraction of the seed crystal in the solution A is 0.1-10 wt%; the polyhydric alcohol is one or more of ethylene glycol and glycerol, and the volume fraction of the polyhydric alcohol in a polyhydric alcohol-water solution is 1-50 vol%.
10. The method of claim 6, wherein: in the step (1), the zirconium source is ammonium zirconium carbonate; the alkaline solution is one or more of ammonium carbonate solution, ammonium bicarbonate solution and sodium hydroxide solution.
11. The method of claim 6, wherein: in the step (1), the mass fraction of ammonium zirconium carbonate in the solution B is 0.001-1 wt%; the mass fraction of ammonium carbonate in the ammonium carbonate solution is 0.1-10 wt%.
12. The method of claim 6, wherein: in the step (2), the mixing temperature of the A, B liquid is 0-40 ℃; the A, B liquid volume ratio is 1: 0.1-10.
13. The method of claim 6, wherein: in the step (2), the crystallization temperature is 80-200 ℃; the crystallization time is 12-72 h.
14. The method of claim 6, wherein: in the step (3), the drying temperature is 80-200 ℃; the drying time is 6-48 h; the roasting temperature is 400-800 ℃; the roasting time is 4-48 h.
15. The method of claim 6, wherein: in the step (4), the volume percentage of ammonia in the ammonia-nitrogen mixed atmosphere is 10-100 vol%; the airspeed of the mixed atmosphere is 60-200 h-1(ii) a The nitriding temperature is 500-950 ℃; the nitriding time is 6-36 h.
16. The method of claim 6, wherein: in the step (5), the alkoxide is one or more of sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide and sodium tert-amylate.
17. The method of claim 6, wherein: in the step (5), the crystallization temperature is 80-220 ℃; the crystallization time is 8-48 h.
18. The method of claim 6, wherein: in the step (5), the carrier: alkoxide: the mass ratio of alcohol is 1: 0.01-0.5: 0.1-1.0.
19. The method of claim 6, wherein: in the step (6), the water vapor is a mixed gas of water vapor and nitrogen, and the volume fraction of the water vapor in the mixed gas is as follows: 0.1-10 vol%; the water vapor treatment temperature is 80-220 ℃; the treatment time is 0.5-20 h.
20. The method of claim 6, wherein: in the step (6), the drying temperature is 80-220 ℃, the drying time is 10-48 h, the roasting temperature is 300-900 ℃, and the roasting time is 6-48 h.
21. The method of claim 6, wherein: in the step (7), the fluorosilane compound is one or more of trifluoropropyltrimethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
22. The method of claim 6, wherein: in the step (7), the concentration of the fluorosilane compound after mixing the fluorosilane compound and the isopropanol is 0.001-0.1 mol/L.
23. The solid base catalyst of any one of claims 1 to 4 is used for regenerating anthraquinone degradation products in working solution under the following regeneration conditions: mixing a solid base catalyst and a working solution containing anthraquinone degradation products according to a solid-liquid mass ratio of 1: 5-1: 15, and reacting at normal pressure and 40-60 ℃.
CN201811264037.XA 2018-10-29 2018-10-29 Solid base catalyst and preparation method thereof Pending CN111097523A (en)

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