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CN111097518A - Supported solid alkali and preparation method thereof - Google Patents

Supported solid alkali and preparation method thereof Download PDF

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Publication number
CN111097518A
CN111097518A CN201811264038.4A CN201811264038A CN111097518A CN 111097518 A CN111097518 A CN 111097518A CN 201811264038 A CN201811264038 A CN 201811264038A CN 111097518 A CN111097518 A CN 111097518A
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solution
alkali
carrier
supported solid
content
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张信伟
马传军
王海洋
李�杰
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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a supported solid alkali and a preparation method thereof. The supported solid alkali contains an alkaline earth metal modified zirconia carrier, an alkali metal hydroxide and a fluorosilane compound; the total content of the alkali metal hydroxide is 0.5-10 wt% based on the weight of the final supported solid alkali; the content of the fluorosilane compound is 0.001-0.1 wt%; the content of the Mg element in the carrier is 1-30 wt% calculated by MgO according to the weight of the carrier; the content of Sr element in the carrier is 1-30 wt% calculated by SrO. The supported solid base prepared by the method is used for regenerating anthraquinone degradation products, and has the advantages of difficult loss of an alkaline center, high mechanical strength, good regeneration effect and the like.

Description

Supported solid alkali and preparation method thereof
Technical Field
The invention relates to supported solid alkali and a preparation method thereof, in particular to supported solid alkali 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 supported solid base and a preparation method thereof. The supported solid base used for regeneration of anthraquinone degradation products has the advantages of difficult loss of an alkaline center, high mechanical strength, good regeneration effect and the like.
A supported solid base comprising an alkaline earth metal-modified zirconia support, an alkali metal hydroxide and a fluorosilane compound; the total content of the alkali metal hydroxide is 0.5-10 wt%, preferably 0.5-5 wt% based on the weight of the final supported solid alkali; the content of the fluorosilane compound is 0.001-0.1 wt%, preferably 0.005-0.01 wt%; the content of the Mg element in the carrier is 1-30 wt%, preferably 1-10 wt% calculated by MgO; the content of Sr element in the carrier is 1-30 wt%, preferably 1-10 wt%, calculated as SrO, and the balance is ZrO2。
In the above method, the alkali metal hydroxide is a mixture of NaOH and KOH; the molar ratio of NaOH to KOH is 0.01-50, preferably 0.2-5. The alkaline earth metal is one or more of Be, Mg, Ca, Sr and Ba, and Mg and Sr are preferred.
The contact angle of the supported solid alkali to hexadecane is more than 130 degrees, preferably 145 degrees to 165 degrees; the specific surface area of the supported solid alkali is 120-300 m2Preferably 200 to 280 m/g2(iv)/g, the crush strength is 80 to 220N, preferably 180 to 220N.
In the supported solid base, 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 supported solid base comprises the following steps:
(1) preparing an alkaline earth metal modified zirconia carrier by adopting a solvothermal method;
(2) introducing an alkali metal hydroxide onto the support prepared in step (1) by an alkali metal alkoxide metathesis process;
(3) and (3) carrying out gas-phase fluorosilane treatment on the material obtained in the step (2) to prepare the supported solid alkali.
A preparation method of a supported solid base specifically comprises the following steps:
(1) adding the alkaline earth metal precursor and the zirconium-containing precursor into a low-carbon alcohol-amide binary solvent, fully stirring to dissolve the precursors, and adjusting the pH value of the solution to 2-3.5.
(2) Adding an organic ligand and a template agent into the solution obtained in the step (1), uniformly mixing, and then transferring into a high-pressure kettle for crystallization at a certain temperature; after crystallization is finished, washing, drying and roasting the product to obtain the carrier.
(3) Dissolving alkali metal alkoxide in corresponding alcohol solvent, adding the carrier prepared in the step (2), and performing crystallization treatment; and after crystallization is finished, carrying out steam treatment on the product, and then drying and roasting the product.
(4) Placing the material obtained in the step (3) in a tubular furnace under the protection of nitrogen, preheating an alcohol solution containing fluorosilane at a certain temperature, and introducing the alcohol solution into the tubular furnace for gas-phase fluorosilane treatment; and after the treatment is finished, cooling the product to room temperature to obtain the supported solid base.
In the step (1), the alkaline earth metal is one or more of Be, Mg, Ca, Sr and Ba, preferably Mg and Sr.
In the step (1), the alkaline earth metal precursor and the zirconium-containing precursor are both one or more of corresponding nitrate, sulfate, acetate and chloride, preferably chloride.
In the step (1) of the above method, Mg is contained in the solution2+︰Sr2+︰Zr4+The molar ratio of the three metal ions is (0.005-0.7): 0.01-1): 1, preferably (0.005-0.15): 0.01-0.2): 1.
In the step (1), the total content of the alkaline earth metal precursor and the zirconium-containing precursor in the solution is 5 to 60 wt%, preferably 5 to 30 wt%.
In the step (1), the lower alcohol is one or more of methanol, ethanol, isopropanol, n-propanol, tert-butanol and isobutanol, preferably isobutanol.
In the step (1), the amide solvent is one or more of formamide, acetamide, N-dimethylformamide and N, N-dimethylacetamide, and preferably N, N-dimethylformamide.
In the step (1), the content of the lower alcohol in the binary solvent is 0.5 to 20 vol%, preferably 1 to 10 vol%.
In step (2) of the above method, the organic ligand is a mixture of terephthalic acid and 2, 5-dihydroxyterephthalic acid; the molar ratio of the terephthalic acid to the 2, 5-dihydroxy terephthalic acid is 2-60, preferably 5-20; the content of the organic ligand in the solution is 1-50 wt%, preferably 10-30 wt%.
In the step (2), the template is one or more of CTAB, PEG400, PEG600, P123 and F127, preferably PEG 600; the content of the template agent in the solution is 0.1-10 wt%, preferably 0.1-5 wt%.
In the step (2), the crystallization temperature is 100-260 ℃, and preferably 100-140 ℃; the crystallization time is 6-72 h, preferably 12-36 h.
In the step (2), the drying temperature is 80-200 ℃, preferably 100-150 ℃; the drying time is 6-48 h, preferably 8-24 h.
In the step (2), the roasting temperature is 500-900 ℃, preferably 500-700 ℃; the roasting time is 6-24 h, preferably 6-12 h.
In the step (3), the alkali metal alkoxide is one or more of sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide and potassium tert-butoxide, and preferably a mixture of sodium alkoxide and potassium alkoxide; the mass ratio of the sodium alkoxide to the potassium alkoxide is 0.001-30, preferably 0.1-5.
In the step (3), the alcohol solvent is one or more of methanol, ethanol, isopropanol and tert-butanol.
In the above method step (3), 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 (3), the crystallization temperature is 80-220 ℃, preferably 80-100 ℃. The crystallization time is 8-48 h, preferably 8-24 h.
In the step (3), 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 and M denotes the corresponding alkali metal.
In the step (3), 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 80-140 ℃; the treatment time is 0.5 to 20 hours, preferably 0.5 to 8 hours.
In the step (3), the drying is performed in a vacuum drying mode or under an inert gas protection condition, or in 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 (4), 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 step (4), the alcohol is methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, preferably isopropanol.
In the step (4), the concentration of the fluorosilane compound in the solution is 0.001-0.1 mol/L, preferably 0.005-0.01 mol/L.
In the step (4), the temperature of the gas phase fluorosilane treatment is 100-300 ℃, and preferably 200-250 ℃; the treatment time is 2-24 hours, and preferably 6-12 hours.
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 invention provides a load type solid alkali and a preparation method thereof, which has the beneficial effects that:
(1) the invention adopts the fluorosilane compound as an oleophobic center, reduces the surface free energy of the supported solid alkali by surface modification of the carrier, obviously enhances the surface oleophobic property of the supported solid alkali, has a hexadecane contact angle of more than 130 degrees, can greatly weaken the adsorption effect of the supported solid alkali on the working solution, and the experimental result of comparative example 3 shows that the adsorption capacity of the supported solid alkali on the working solution is less than 0.02g of working solution/g of catalyst, and can effectively reduce the loss of the working solution.
(2) Through the hydrogen bond effect of alkoxy and hydroxyl on the surface of the carrier, alkoxide is adsorbed on the magnesium-strontium modified zirconia 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 experiment result of comparative example 1 shows that after the supported solid alkali reacts for 100 hours, the loss rate of the basic center is only 4.7 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.
(3) Experimental results show that the supported solid alkali prepared by the invention has high activity and stability, the regeneration amount of the effective anthraquinone reaches more than 19 g/L, and the supported solid alkali 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: weighing 10 g of supported solid base and 100 ml of working solution (the concentration of anthraquinone degradation products is 23 g/L), adding into a conical flask, oscillating in a water bath at a constant temperature of 50 ℃, taking out the working solution after reacting for 100 hours, and analyzing 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
Step (1):
according to Mg2+︰Sr2+︰Zr4+The molar ratio of the three metal ions is 0.076: 0.039: 1, and weighing the corresponding metal ionsMagnesium chloride, strontium chloride and zirconium chloride were added to a binary solvent (6.3 vol% isopropyl alcohol-93.7 vol% N, N-dimethylformamide), and sufficiently stirred at 40 ℃ to adjust the pH of the solution to 2.8. Wherein the total content of metal chlorides in the solution is 26.8 wt%.
Step (2):
adding the composite organic ligand into the solution in the step (1) according to the molar ratio of terephthalic acid/2, 5-dihydroxy terephthalic acid of 13.5. Wherein, the content of the composite organic ligand in the solution is 22.8 wt%. Adding PEG600 into the solution according to the content of the template agent in the solution of 2.4 wt%, stirring thoroughly, transferring the solution into a high-pressure autoclave, and crystallizing at 135 deg.C for 18.5 h. After centrifugal separation, the crystallized product is washed for 3 times by absolute ethyl alcohol, dried for 12 h at 120 ℃, and roasted for 8 h at 550 ℃ to prepare the carrier.
And (3):
weighing sodium ethoxide and potassium tert-butoxide according to the weight ratio of the sodium ethoxide to the potassium tert-butoxide of 0.9, and adding the sodium ethoxide and the potassium tert-butoxide into 25ml of ethanol to completely dissolve the sodium ethoxide and the potassium tert-butoxide, wherein the concentration of the total alkali metal alkoxide in the solution is 51.2 g/L. Then adding the carrier obtained in the step (2) into the solution, standing for 1 h at room temperature, and then transferring into an autoclave for crystallization at 90 ℃ for 18 h. After crystallization is finished, putting the product into a quartz tube fixed bed reactor, heating to 120 ℃ under the protection of nitrogen, introducing steam into a system to perform double decomposition reaction with alkali metal alkoxide to generate corresponding alkali metal hydroxide according to the condition that the steam accounts for 0.5vol% of the volume fraction of the total gas, and treating the steam for 4.5 h; then the material is taken out after being cooled, dried for 12 hours at 120 ℃ and roasted for 8 hours at 700 ℃.
And (4):
and (3) placing the material obtained in the step (3) in a tube furnace under the protection of nitrogen, heating to 250 ℃, then preheating an isopropanol solution with the concentration of heptadecafluorodecyltrimethoxysilane of 0.009 mol/L at 150 ℃, introducing the preheated isopropanol solution into the tube furnace by using a micro pump at the speed of 0.22 ml/h, carrying out gas-phase fluorosilane treatment for 6h, and cooling the material to room temperature after the treatment is finished, thus obtaining the load type solid alkali.
Supported solid baseThe composition of (A) is as follows: 3.2wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 5.2 wt% MgO, 2.9 wt% SrO, and the balance ZrO2. Specific surface area of 265 m2The crushing strength is 192N, the hexadecane contact angle is 151 degrees, and the regeneration amount of the effective anthraquinone is 22.3 g/L.
Example 2
The preparation method is the same as example 1, except that: mg in step (1)2+︰Sr2+︰Zr4+The molar ratio of the three metal ions is 0.045: 0.018: 1, and the binary solvent is 4.6 vol% ethanol-95.4 vol% N, N-dimethylformamide. The total content of metal chlorides in the solution was 7.5 wt%.
The composition of the supported solid base is as follows: 3.2wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 2.4 wt% MgO, 0.8 wt% SrO, and the balance ZrO2. The specific surface area is 273 m2(ii)/g, crushing strength of 195N, hexadecane contact angle of 150 DEG, and effective regeneration amount of anthraquinone of 21.6 g/L.
Example 3
The preparation method is the same as example 1, except that: mg in step (1)2+︰Sr2+︰Zr4+The molar ratio of the three metal ions is 0.102: 0.092: 1, and the binary solvent is: 1.5 vol% methanol-98.5 vol% N, N-dimethylacetamide. The total content of metal chlorides in the solution was 15.1 wt%.
The composition of the supported solid base is as follows: 3.2wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 7.5 wt% MgO, 4.2 wt% SrO, and the balance ZrO2. The specific surface area is 239 m2The crushing strength is 185N, the hexadecane contact angle is 151 degrees, and the regeneration amount of the effective anthraquinone is 20.9 g/L.
Example 4
The preparation method is the same as example 1, except that: mg in step (1)2+︰Sr2+︰Zr4+The molar ratio of the three metal ions is 0.139: 0.145: 1, and the binary solvent is: 8.9 vol% isopropanol-91.1 vol% N, N-dimethylacetamide. The total content of metal chlorides in the solution was 20.7 wt.%.
The composition of the supported solid base is as follows: 3.2wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 9.6 wt% MgO, 7.3 wt% SrO, and the balance ZrO2. The specific surface area is 206 m2(ii)/g, the crushing strength is 180N, the hexadecane contact angle is 150 degrees, and the regeneration amount of the effective anthraquinone is 19.8 g/L.
Example 5
The preparation method is the same as example 1, except that: in the step (2), the molar ratio of the terephthalic acid to the 2, 5-dihydroxy terephthalic acid is 10.1, and the content of the composite organic ligand in the solution is 26.5 wt%. The content of the template PEG400 in the solution is 1.5 wt%. The crystallization temperature is 125 ℃, and the crystallization time is 24 hours; the roasting temperature is 600 ℃, and the roasting time is 12 h.
The composition of the supported solid base is as follows: 3.2wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 5.3 wt% MgO, 3.0 wt% SrO, and the balance ZrO2. Specific surface area 268 m2The specific surface area of the resin is 189N in terms of crush strength, 151 in terms of hexadecane contact angle and 22.1 g/L in terms of effective regeneration amount of anthraquinone.
Example 6
The preparation method is the same as example 1, except that: in the step (2), the molar ratio of the terephthalic acid to the 2, 5-dihydroxy terephthalic acid is 5.8, and the content of the composite organic ligand in the solution is 16.4 wt%. The content of the template P123 in the solution was 3.1% by weight. The crystallization temperature is 115 ℃, and the crystallization time is 30 h; the roasting temperature is 650 ℃, and the roasting time is 10 hours.
The composition of the supported solid base is as follows: 3.2wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 4.9 wt% MgO, 2.8 wt% SrO,the balance being ZrO2. Specific surface area is 257 m2(ii)/g, crushing strength of 193N, hexadecane contact angle of 151 DEG, and effective regeneration amount of anthraquinone of 21.8 g/L.
Example 7
The preparation method is the same as example 1, except that: in the step (2), the molar ratio of the terephthalic acid to the 2, 5-dihydroxy terephthalic acid is 18.7, and the content of the composite organic ligand in the solution is 10.6 wt%. The content of the template CTAB in the solution is 4.6 wt%. The crystallization temperature is 105 ℃, and the crystallization time is 36 hours; the roasting temperature is 700 ℃, and the roasting time is 6 h.
The composition of the supported solid base is as follows: 3.2wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 4.7 wt% MgO, 2.4 wt% SrO, and the balance ZrO2. Specific surface area of 245 m2(ii)/g, crushing strength of 191N, hexadecane contact angle of 150 degrees, effective regeneration of anthraquinone of 21.2 g/L.
Example 8
The preparation method is the same as example 1, except that: in the step (3), the weight ratio of sodium methoxide/potassium tert-butoxide is 1.4, the solvent is methanol, the crystallization temperature is 85 ℃, and the crystallization time is 24 hours; the steam treatment temperature is 100 ℃, and the treatment time is 8 h; the roasting temperature is 500 ℃, and the roasting time is 16 h.
The composition of the supported solid base is as follows: 2.8 wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 2.3. Specific surface area of 241 m2The specific surface area of the resin is 188N in crushing strength, 151 in hexadecane contact angle and 20.5 g/L in effective anthraquinone regeneration amount.
Example 9
The preparation method is the same as example 1, except that: in the step (3), the weight ratio of sodium isopropoxide to potassium tert-butoxide is 2.2, the solvent is isopropanol, the crystallization temperature is 95 ℃, and the crystallization time is 12 hours; the steam treatment temperature is 110 ℃, and the treatment time is 6 h; the roasting temperature is 550 ℃, and the roasting time is 12 h.
Of supported solid basesComprises the following components: 2.3 wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH was 3.6. Specific surface area of 253 m2The crushing strength is 183N, the hexadecane contact angle is 151 degrees, and the regeneration amount of the effective anthraquinone is 19.3 g/L.
Example 10
The preparation method is the same as example 1, except that: in the step (3), the weight ratio of sodium tert-butoxide to potassium tert-butoxide is 3.1, the solvent is tert-butanol, the crystallization temperature is 100 ℃, and the crystallization time is 8 hours; the steam treatment temperature is 130 ℃, and the treatment time is 3 h; the roasting temperature is 600 ℃, and the roasting time is 10 hours.
The composition of the supported solid base is as follows: 2.5 wt% (NaOH + KOH), 0.007 wt% heptadecafluorodecyltrimethoxysilane, balance carrier. Wherein the molar ratio of NaOH/KOH is 0.8. The specific surface area is 236 m2(ii)/g, the crushing strength is 180N, the hexadecane contact angle is 151 degrees, and the effective regeneration amount of anthraquinone is 18.4 g/L.
Example 11
The preparation method is the same as example 1, except that: the fluorosilane solution in the step (4) is as follows: 0.009 mol/L of an n-propanol solution of heptadecafluorodecyltriethoxysilane, the solution feed rate was 0.36 ml/h, the gas phase fluorosilane treatment temperature was 230 ℃ and the treatment time was 8 h.
The composition of the supported solid base is as follows: 3.2wt% (NaOH + KOH), 0.009 wt% heptadecafluorodecyltriethoxysilane, and the balance carrier. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 5.2 wt% MgO, 2.9 wt% SrO, and the balance ZrO2. The specific surface area is 262 m2The crushing strength is 191N, the hexadecane contact angle is 143 degrees, and the effective regeneration amount of anthraquinone is 22.2 g/L.
Example 12
The preparation method is the same as example 1, except that: the fluorosilane solution in the step (4) is as follows: 0.005 mol/L of ethanol solution of tridecafluorooctyltrimethoxysilane, the solution feeding rate is 0.48 ml/h, the vapor phase fluorosilane treatment temperature is 200 ℃, and the treatment time is 12 h.
Of supported solid basesComprises the following components: 3.2wt% (NaOH + KOH), 0.005 wt% tridecafluorooctyltrimethoxysilane, balance support. Wherein the molar ratio of NaOH/KOH is 1.5. The composition of the carrier is as follows: 5.2 wt% MgO, 2.9 wt% SrO, and the balance ZrO2. Specific surface area of 259 m2The crushing strength is 190N, the hexadecane contact angle is 138 degrees, and the effective regeneration amount of anthraquinone is 21.9 g/L.
Comparative example 1
The support was prepared as in example 1, except that: loading NaOH and KOH by adopting an impregnation method, and specifically operating as follows:
weighing NaOH and KOH according to the loading capacity of the NaOH and the KOH on the solid alkali of 3.2wt%, dissolving the NaOH and the KOH in deionized water, and preparing an impregnating solution, wherein the weight ratio of the NaOH to the KOH is 1.5. Adding the carrier into the impregnation solution for equal-volume impregnation, drying at 120 ℃ for 12 h, and roasting at 700 ℃ for 8 h. Reference B1 was made.
After the reference agent B1 is reacted for 100 hours under the same conditions, XRF analysis results show that the content of alkali metal hydroxide is reduced from 3.2wt% to 0.2 wt%, the loss of alkali centers is very serious, and the loss rate is as high as 93.75%; in contrast, in example 1, after 100 hours of reaction, the alkali metal hydroxide content was 3.05% by weight, and the alkali center loss rate was only 4.69%.
Comparative example 2
The support was prepared as in example 1, except that: reference reagent B2 was obtained without steam treatment in step (3).
Performance evaluation As in example 1, the effective anthraquinone-regenerating amount of reference B2 was only 3.4 g/L. The experimental result shows that no double decomposition reaction is generated to generate alkali metal hydroxide without water vapor treatment, and the regeneration effect of the working solution is far lower than that of the working solution in the example 1.
Comparative example 3
The support was prepared as in example 1, except that: the reference agent B3 was prepared without vapor phase fluorosilane treatment in step (4).
Reference B3 has a contact angle of 53 ° to hexadecane. When the reference agent B3 is used for regenerating the working solution, the adsorption capacity of the reference agent B3 on the working solution is 0.18 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 working solution in example 1 is less than 0.02g of the working solution/g of the catalyst.

Claims (27)

1. A supported solid base, characterized by: the supported solid alkali contains an alkaline earth metal modified zirconia carrier, an alkali metal hydroxide and a fluorosilane compound; the total content of the alkali metal hydroxide is 0.5-10 wt% based on the weight of the final supported solid alkali; the content of the fluorosilane compound is 0.001-0.1 wt%; the content of the Mg element in the carrier is 1-30 wt% calculated by MgO according to the weight of the carrier; the content of Sr element in the carrier is 1-30 wt% calculated by SrO.
2. The solid base of claim 1, wherein: the alkali metal hydroxide is a mixture of NaOH and KOH; the molar ratio of NaOH to KOH is 0.01-50, and the alkaline earth metal is one or more of Be, Mg, Ca, Sr and Ba.
3. The solid base of claim 1, wherein: the contact angle of the solid alkali to hexadecane is more than 130 degrees; the specific surface area of the supported solid alkali is 120-300 m2(iv)/g, the crushing strength is 80 to 220N.
4. The solid base of claim 1, wherein: the contact angle of the solid base to hexadecane is 145-165 degrees; the specific surface area of the supported solid alkali is 200-280 m2(iv)/g, the crushing strength is 180 to 220N.
5. The solid base of claim 1, wherein: the fluorosilane compound is one or more of trifluoropropyltrimethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
6. A preparation method of a supported solid base is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing an alkaline earth metal modified zirconia carrier by adopting a solvothermal method;
(2) introducing an alkali metal hydroxide onto the support prepared in step (1) by an alkali metal alkoxide metathesis process;
(3) and (3) carrying out gas-phase fluorosilane treatment on the material obtained in the step (2) to prepare the supported solid alkali.
7. The method of claim 6, wherein: the method specifically comprises the following steps:
(1) adding the alkaline earth metal precursor and the zirconium-containing precursor into a low-carbon alcohol-amide binary solvent, and adjusting the pH value of the solution to 2-3.5.
Adding an organic ligand and a template agent into the solution obtained in the step (1), and crystallizing at a certain temperature; after crystallization is finished, washing, drying and roasting the product to prepare the alkaline earth metal modified zirconia carrier;
(3) dissolving alkali metal alkoxide in corresponding alcohol solvent, adding the alkaline earth metal modified zirconia carrier prepared in the step (2), and performing crystallization treatment; after crystallization, carrying out water vapor treatment on the product, and then drying and roasting the product;
(4) carrying out gas-phase fluorosilane treatment on the material obtained in the step (3) by adopting an alcoholic solution containing fluorosilane at a certain temperature under the protection of inert atmosphere; and preparing the supported solid alkali after the treatment is finished.
9. The method of claim 7, wherein: in the step (1), the alkaline earth metal is one or more r of Be, Mg, Ca, Sr and Ba.
10. The method of claim 7, wherein: the alkaline earth metal precursor and the zirconium-containing precursor are one or more of corresponding nitrate, sulfate, acetate and chloride.
11. The method of claim 7, wherein: in the step (1), Mg is contained in the solution2+︰Sr2+︰Zr4+The molar ratio of the three metal ions is (0.005-0.7): 0.01-1): 1.
12. The method of claim 7, wherein: in the step (1), the total content of the alkaline earth metal precursor and the zirconium-containing precursor in the solution is 5-60 wt%.
13. The method of claim 7, wherein: in the step (1), the lower alcohol is one or more of methanol, ethanol, isopropanol, n-propanol, tert-butanol and isobutanol.
14. The method of claim 7, wherein: in the step (1), the amide solvent is one or more of formamide, acetamide, N-dimethylformamide and N, N-dimethylacetamide.
15. The method of claim 7, wherein: in the step (1), the content of the lower alcohol in the binary solvent is 0.5-20 vol%.
16. The method of claim 7, wherein: in the step (2), the organic ligand is a mixture of terephthalic acid and 2, 5-dihydroxy terephthalic acid; the molar ratio of the terephthalic acid to the 2, 5-dihydroxy terephthalic acid is 2-60; the content of the organic ligand in the solution is 1-50 wt%.
17. The method of claim 7, wherein: in the step (2), the template agent is one or more of CTAB, PEG400, PEG600, P123 and F127; the content of the template agent in the solution is 0.1-10 wt%.
18. The method of claim 7, wherein: in the step (2), the crystallization temperature is 100-260 ℃; the crystallization time is 6-72 h.
19. The method of claim 7, wherein: in the step (2), the drying temperature is 80-200 ℃; the drying time is 6-48 h; the roasting temperature is 500-900 ℃; the roasting time is 6-24 h.
20. The method of claim 7, wherein: in the step (3), the alkali metal alkoxide is one or more of sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide and potassium tert-butoxide.
21. The method of claim 19, wherein: in the step (3), the alkali metal alkoxide is a mixture of sodium alkoxide and potassium alkoxide; the mass ratio of the sodium alkoxide to the potassium alkoxide is 0.001-30.
22. The method of claim 7, wherein: in the step (3), the alcohol solvent is one or more of methanol, ethanol, isopropanol and tert-butanol; carrier: alkoxide: the mass ratio of alcohol is 1: 0.01-0.5: 0.1-1.0.
23. The method of claim 7, wherein: in the step (3), the crystallization temperature is 80-220 ℃, and the crystallization time is 8-48 h;
the method of claim 7, wherein: in the step (3), 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.
24. The method of claim 7, wherein: in the step (3), the drying temperature is 80-220 ℃, and the drying time is 10-48 h; the roasting temperature is 300-900 ℃, and the roasting time is 6-48 h.
25. The method of claim 7, wherein: in the step (4), the fluorosilane compound is one or more of trifluoropropyltrimethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane; the alcohol is methanol, ethanol, n-propanol, isopropanol, tert-butanol or isobutanol; the concentration of the fluorosilane compound in the solution is 0.001-0.1 mol/L.
26. The method of claim 7, wherein: in the step (4), the temperature of the gas phase fluorosilane treatment is 100-300 ℃; the treatment time is 2-24 h.
27. The solid base catalyst of claim 1 is used for regenerating anthraquinone degradation products in working fluid, 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 ℃.
CN201811264038.4A 2018-10-29 2018-10-29 Supported solid alkali and preparation method thereof Pending CN111097518A (en)

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