CN112158866B - Preparation method of hydroxy alumina and catalyst thereof - Google Patents
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Abstract
The invention provides a preparation method of hydroxy aluminum oxide, which comprises the steps of dispersing aluminum oxide in a solvent, adding organic mercaptan or sulfide salt, introducing hydrogen-containing gas and keeping the gas atmosphere, heating, stirring, filtering, and drying to obtain target AlOOH. The invention also provides a catalyst which comprises a first component of aluminum oxyhydroxide and a second component of active component, wherein the first component of aluminum oxyhydroxide is obtained by the preparation method of the invention, and the second component is noble metal. The method utilizes the relatively low-cost and small amount of sulfide to modify the aluminum oxide to obtain the high-yield hydroxy aluminum oxide, can reduce the cost, and has simple and convenient preparation process and universality. In addition, the catalyst of the invention has good synergistic effect between the nano-hydroxy aluminum oxide and the metal nano-particles, good reaction activity and higher industrial value.
Description
Technical Field
The invention relates to the technical field of hydroxy alumina, in particular to a preparation method of hydroxy alumina and a catalyst prepared by using the hydroxy alumina obtained by the invention as a carrier.
Background
The catalyst is used in large amount in industrial production, the performance of the catalyst directly influences the economic benefit of the industrial production, numerous researches show that the physical performance of a catalyst carrier greatly influences the reaction performance of the catalyst carrier, and in the catalyst, the carrier material not only plays a role of loading an active component, but also provides a proper structure for the catalyst, so that the function of the catalyst is exerted more effectively. The activity and selectivity of the catalyst is related to the pore structure when the diffusion of reactant molecules from the outside of the particle to the inside surface or when the diffusion of reaction products from the inside surface to the outside surface of the particle is hindered. Therefore, it is necessary to intensively study the physical indexes of the carrier, such as specific surface area and pore structure.
As an important catalyst support material, Al2O3Plays an important role throughout the oil processing industry. The traditional hydrogenation catalyst carrier mainly comprises gamma-Al2O3Predominantly, but with the complication of processing feedstocks and the increasing demand of the market for light fuel oils, in certain fields of application, a single conventional gamma-Al2O3The support hardly satisfies the requirements of catalytic reactions. The pore structure of alumina has a great influence on the performance of industrial catalysts. Much research has been conducted on modifying alumina. The most important modification method comprises hole expanding modification and additive modification. Wherein the pore-expanding modification can reduce diffusion resistance, improve mass transfer, improve the effective utilization rate of active sites, enhance the anti-coking performance and further improve the yield of hydrogenation catalysis.
The modification by adding the auxiliary agent can effectively inhibit the high-temperature sintering and phase change of the alumina carrier, prevent the pore structure from being damaged and prolong the service life of the catalyst. Patent CN101590433A uses fluorocarbon surfactant to directly modify alumina or the precursor of alumina, and obtains modified alumina carrier after calcination, but these modifications do not change the crystal form of alumina. Gamma-Al modified by modifying element in patent CN 108339541A2O3Pre-treating to obtain spinel during roasting to obtain spinel modified gamma-Al2O3. Patent CN106964348B discloses a method for preparing a catalyst capable of efficiently catalytically oxidizing formaldehyde in polluted air into harmless carbon dioxide and water, wherein aluminum hydroxide is roasted to prepare alumina monohydrate (AlOOH) serving as a carrier, and noble metals Pt and Pd are loaded on the AlOOH carrier, and the catalyst can be applied to formaldehyde catalytic oxidation reaction.
However, the method of the patent requires roasting treatment for preparing the modified alumina and has large energy consumption. Therefore, the preparation method for modifying the alumina, which has simple and convenient process and reduced energy consumption, has important value and significance for industrial application.
Disclosure of Invention
The invention aims to provide a preparation method of aluminum oxyhydroxide to solve the technical problems in the background technology.
The solution of the invention for solving the technical problem is as follows:
the first aspect of the invention provides a preparation method of aluminum oxyhydroxide, which comprises the following steps:
dispersing aluminum oxide in a solvent, adding a sulfide, introducing a hydrogen-containing gas, keeping the atmosphere, heating, stirring, filtering, and drying to obtain AlOOH; the sulfide is at least one of organic mercaptan and sulfide salt.
Preferably, the alumina is selected from alpha-Al2O3And gamma-Al2O3At least one of (1).
Preferably, the solvent is selected from at least one of water, an alcohol solvent, DMF, and an ester solvent.
In the preparation method of the hydroxy aluminum oxide, the solvent is used corresponding to the sulfide, wherein the organic mercaptan is used in at least one solvent selected from the group consisting of an alcohol solvent, a DMF solvent and an ester solvent; the solvent used for the sulfide salt is water.
Preferably, the organic thiol is at least one selected from the group consisting of n-butylthiol, thioglycolic acid, n-hexylthiol, 1-octylthiol, dodecylthiol, thiophenol, 3, 4-difluorothiophenol, 1-chlorothiophenol and 4-tert-butylthiophenol.
Preferably, the sulfide salt is at least one selected from sodium sulfide and potassium sulfide.
The sodium sulfide and the potassium sulfide used in the invention can be nano-scale and micron-scale materials, and the solubility of the sulfide in water is improved under the action of heating.
Preferably, the heating temperature is (80-200) DEG C.
Preferably, the mass ratio of the alumina to the sulfide is (50-1000) to 1.
Preferably, the gas atmosphere consists of hydrogen and protective gas in a volume ratio of 1: 0-4; the pressure of the gas atmosphere is (0.1-2) MPa.
The aluminum oxyhydroxide is an important inorganic material and has wide application in the fields of polymer composite materials, fireproof materials, adsorbing materials, biological materials and the like. The hydroxy alumina prepared by the invention can be used as a filling material, a ceramic material, a composite material, a semiconductor material, a catalyst, a carrier thereof and the like, particularly, the hydroxy alumina nano material has large specific surface area and high activity, and can improve the performance of the hydroxy alumina nano material in related application fields when being used as a catalyst carrier.
The invention also provides a catalyst which comprises a first component of aluminum hydroxide oxide and a second component of active component, wherein the first component of aluminum hydroxide oxide is prepared by any preparation method provided by the first aspect.
Preferably, the second component is a noble metal.
Further preferably, the noble metal is at least one selected from the group consisting of platinum, palladium, nickel, ruthenium, rhenium, rhodium, osmium, iridium, cobalt, molybdenum, copper, and tin.
Advantageous effects
1. The invention utilizes relatively cheap and a small amount of sulfide to modify alumina, thereby greatly reducing the cost.
2. The hydroxy alumina prepared by the preparation method has high yield which exceeds 85 percent and can reach 99 percent.
3. The preparation method of the hydroxy aluminum oxide is simple and convenient in process, universal and convenient for industrial application.
4. The nano-grade aluminum oxyhydroxide prepared by the method has good synergistic effect with metal nanoparticles, good reaction activity and higher industrial value.
Drawings
FIG. 1 shows γ -Al in example 12O3In Na2XRD patterns before and after S treatment.
FIG. 2 shows Pd/. gamma. -Al in example 12O3Electron micrograph of catalyst.
FIG. 3 is an electron micrograph of the Pd/AlOOH catalyst of example 1.
FIG. 4 shows Pd/. gamma. -Al in example 12O3The activity of the catalyst and the Pd/AlOOH catalyst are compared respectively.
FIG. 5 shows the results of comparative example 1 at H2Or N2gamma-Al in atmosphere2O3In Na2XRD patterns before and after S treatment.
Fig. 6 is a graph showing a comparison of the reaction activities of the catalyst C and the catalyst D in comparative example 2, in which phenylacetylene was hydrogenated separately.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of aluminum oxyhydroxide, which comprises the following steps: dispersing aluminum oxide in a solvent, adding a sulfide, introducing a hydrogen-containing gas, keeping the atmosphere, heating, stirring, filtering, and drying to obtain AlOOH; the sulfide is at least one selected from organic mercaptan and sulfide salt.
According to an embodiment of the invention, the alumina is selected from alpha-Al2O3And gamma-Al2O3At least one of (1).
According to an embodiment of the present invention, the solvent is selected from at least one of water, an alcohol solvent, a DMF solvent, and an ester solvent. The alcoholic solvent may be, for example, but not limited to, ethanol, methanol, propylene glycol, ethylene glycol, n-butanol, isobutanol, and the like; the ester-based solvent may be, for example, but not limited to, methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, butyl glycol ether, dimethyl glutarate, dimethyl adipate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, and the like. Preferably, the solvent is water; or the solvent is ethanol; alternatively, the solvent is DMF.
According to an embodiment of the invention, the sulphide is selected from at least one of an organic thiol, a sulphide salt.
According to an embodiment of the invention, the sulphide salt may be selected from alkali or alkaline earth metal sulphides; in specific embodiments, the sulfide salt is selected from sodium sulfide and potassium sulfide.
According to an embodiment of the present invention, the organothiol is selected from at least one of n-butylthiol, thioglycolic acid, n-hexylthiol, 1-octylthiol, dodecylthiol, thiophenol, 3, 4-difluorothiophenol, 1-chlorothiophenol and 4-tert-butylthiophenol. Preferably, the organic thiol is selected from 3, 4-difluorothiophenol.
According to the embodiment of the invention, the solvent is used corresponding to the sulfide, wherein the organic mercaptan is used in the solvent selected from at least one of alcohol solvent, DMF solvent and ester solvent; the solvent used for the sulphide salt is water.
According to the embodiment of the invention, the heating temperature is (80-200) DEG C.
According to the embodiment of the invention, the mass ratio of the alumina to the sulfide is (50-1000) to 1.
According to the embodiment of the invention, the gas atmosphere consists of hydrogen and protective gas in a volume ratio of 1: 0-4; the pressure of the gas atmosphere is (0.1-2) MPa; more preferably, the gas atmosphere consists of hydrogen and protective gas in a volume ratio of 1: 0-1, the pressure of the gas atmosphere is 0.5-1.5 MPa, and the protective gas is selected from Ar, He and N2At least one of (1).
According to a second aspect of the present invention, there is provided a catalyst comprising a first component of aluminum oxyhydroxide and a second component of active component, wherein the first component of aluminum oxyhydroxide is prepared by any one of the preparation methods provided in the first aspect.
According to an embodiment of the invention, the second component is a noble metal.
According to an embodiment of the invention, the noble metal is selected from at least one of platinum, palladium, nickel, ruthenium, rhenium, rhodium, osmium, iridium, cobalt, molybdenum, copper and tin.
The invention also provides an application of the catalyst, which is applied to hydrogenation reaction.
The hydrogenation reaction refers to the hydrogenation of substances such as alkyne, nitrobenzene and 6-aminocapronitrile; wherein, alkyne hydrogenation refers to the process of alkyne generating alkene, and alkane is not generated by further alkene deep hydrogenation reaction.
According to an embodiment of the present invention, a method for applying a catalyst to a hydrogenation reaction includes the steps of:
transferring an alcohol solvent into a reaction container, selecting a reaction substrate to disperse in the alcohol solvent, adding the catalyst, replacing hydrogen, keeping the hydrogen pressure (0.1-2) MPa, heating to 20-80 ℃ and stirring, wherein the molar ratio of the substrate to the noble metal is (500-2000) to 1.
According to an embodiment of the present invention, the alcoholic solvent is selected from at least one of ethanol, methanol, propylene glycol, ethylene glycol, n-butanol and isobutanol. Preferably, the solvent is ethanol; alternatively, the solvent is methanol.
According to an embodiment of the invention, the reaction substrate is selected from at least one of a terminal alkyne, a middle alkyne, a nitrobenzene and 6-aminocapronitrile.
According to an embodiment of the invention, the terminal alkyne is selected from at least one of acetylene, propyne, 3-aminophenylacetylene, 3-methylphenylacetylene, 4-tert-butylacetylene, 1-octyne, 2-ethynylpyridine, 4-ethynylpyridine, phenylacetylene and phenylpropyne. In a specific embodiment of the invention, the reaction substrate is phenylacetylene.
According to an embodiment of the invention, the intermediate alkyne is selected from at least one of 1-phenyl-1-propyne, 1-phenyl-1-pentyne, tolane, 4-phenyl-3-butyn-2-one, 4-octyne, 3-phenyl-2-propyn-1-ol and methyl phenylpropargyrate. In a specific embodiment of the invention, the substrate is 1-phenyl-1-propyne.
Example 1
S1: mixing gamma-Al2O3Dispersing in water, adding Na2S, is such that gamma-Al2O3With Na2The mass ratio of S is 100: 1, introducing hydrogen and keeping the gas atmosphere, the gas pressure is 1Mpa, heating to 150 ℃, stirring for 3h, and cooling the reaction liquidAnd carrying out suction filtration and drying for 12h to obtain AlOOH. Mixing gamma-Al2O3XRD test is carried out on the prepared AlOOH, and figure 1 shows gamma-Al2O3In Na2XRD patterns before and after S treatment show that the crystal form is gamma-Al by the preparation method of the invention2O3Is converted into AlOOH.
S2: mixing gamma-Al2O3And respectively dispersing the prepared AlOOH in water, dropwise adding a chloropalladate solution, stirring for 12h, performing suction filtration, drying for 12h, drying, placing in a tubular furnace, heating to 80 ℃, and reducing for 3h in a hydrogen atmosphere to obtain Pd/gamma-Al2O3Catalyst and Pd/AlOOH catalyst. For Pd/gamma-Al respectively2O3The catalyst and the Pd/AlOOH catalyst are subjected to electron microscope characterization. FIG. 2 shows Pd/gamma-Al2O3The electron micrograph of the catalyst is shown in FIG. 3, which is an electron micrograph of the Pd/AlOOH catalyst and shows that the catalyst passes through Na2AlOOH obtained by S treatment still maintains Al2O3However, many flaky AlOOH are separated, the specific surface area is increased, and when the catalyst is used, the contact area of the reaction is increased, and the reactivity of the catalyst is further improved.
S3: transferring an ethanol solvent into a reaction vessel, selecting 1-phenyl-1 propyne as a reaction substrate, dispersing the reaction substrate in the solvent, and respectively adding the prepared Pd/gamma-Al2O3Catalyst and Pd/AlOOH catalyst, the molar ratio of the reaction substrate to the noble metal Pd is 2000: 1, displacing hydrogen, keeping the hydrogen pressure at 0.1MPa, heating to 60 ℃, and stirring. FIG. 4 shows Pd/γ -Al2O3The activity of the catalyst and the Pd/AlOOH catalyst which are respectively subjected to hydrogenation reaction are compared, and the comparison result shows that the catalyst passes through Na2The Pd/AlOOH catalyst formed by the noble metal Pd supported by the AlOOH obtained by the S treatment has higher reaction activity when used for hydrogenation reaction.
Example 2
Mixing gamma-Al2O3Dispersing in water, and respectively taking different sulfide salts with the same mass to form test groups 1 and 2, so that the gamma-Al is obtained2O3The mass ratio of the sulfur dioxide to the sulfide salt is 100: 1, introducing hydrogen and maintaining the gas atmosphere, wherein the gas pressure is (1-2) Mpa,heating to 120-200 ℃, stirring for 3h, cooling the reaction solution, performing suction filtration, and drying for 12h to obtain AlOOH. Table 1 shows the experimental results of preparing aluminum oxyhydroxide from different sulfide salts, and it can be seen that both sodium sulfide and potassium sulfide can be used as the materials for preparing AlOOH of the present invention, and the yield of the target AlOOH can reach more than 96%.
TABLE 1 Experimental results of preparation of aluminum oxyhydroxide from different sulfide salts
| Test group | Sulfide compound | Product of | AlOOH yield |
| 1 | Sodium sulfide | AlOOH | 96.6％ |
| 2 | Potassium sulfide | AlOOH | 96.3％ |
Example 3
Mixing gamma-Al2O3Dispersing in DMF solvent, adding 5 groups of different organic thiols to form test groups 3-7, so that gamma-Al2O3The mass ratio of the organic mercaptan to the organic mercaptan is 200: 1, hydrogen is introduced and the gas atmosphere is maintained, the gas pressure is (0.1-1) Mpa, the heating temperature is (80-150) DEG C, the mixture is stirred for 3 hours, and after the reaction liquid is cooled, the reaction liquid is cooledAnd carrying out suction filtration and drying for 12h to obtain AlOOH. Table 2 shows the experimental results of different organothiols for preparing aluminum oxyhydroxide, and it can be seen that various organothiols such as 3, 4-difluorothiophenol, 1-chlorobenzenethiol, n-butylmercaptan, etc. can be used as the material for preparing A1OOH of the present invention, and the yield of the target AlOOH exceeds 88% and can reach as high as 92.5%.
TABLE 2 Experimental results of preparation of aluminum oxyhydroxide from different organic thiols
| Test group | Organic thiols | Product of | AlOOH yield |
| 3 | 3, 4-difluorothiophenol | AlOOH | 92.5％ |
| 4 | 1-Chlorobenzene thiol | AlOOH | 91.6％ |
| 5 | 4-tert-butyl thiophenol | AlOOH | 91.9％ |
| 6 | N-butylmercaptan | AlOOH | 89.6％ |
| 7 | N-hexyl mercaptan | AlOOH | 88.9％ |
In this embodiment, the organic thiol may be thioglycolic acid, 1-octanethiol, dodecanethiol, or thiophenol.
Example 4
alpha-Al is added2O3Dispersing in solvent, adding sodium sulfide to make alpha-Al2O3And (2) introducing hydrogen and keeping the gas atmosphere at the gas pressure of 1Mpa, heating to 150 ℃, stirring for 3h, cooling the reaction liquid, performing suction filtration and drying for 12h to obtain AlOOH, wherein the mass ratio of the AlOOH to sodium sulfide is (10-1200) to 1. TABLE 3 is alpha-Al2O3The data of the experimental results of the preparation of the hydroxy alumina with different mass ratios with the sodium sulfide show that when the alpha-Al is in the alpha-Al state2O3When the mass ratio of the alpha-Al to the sodium sulfide is (10-1200) to 1, the yield of the prepared aluminum hydroxide exceeds 85%, but when the alpha-Al is in the range of alpha-Al2O3When the mass ratio of the AlOOH to the sodium sulfide is within the range of (100-1000) to 1, the AlOOH yield is obviously improved and exceeds 95 percent, and can reach 99 percent, and the optimal mass ratio range is required.
TABLE 3. alpha. -Al2O3Experimental result data of preparing hydroxy alumina by different mass ratios of sodium sulfide
Example 5
alpha-Al is added2O3Dispersing in solvent, adding 3, 4-difluorothiophenol to make alpha-Al2O3The mass ratio of the compound to 3, 4-difluorothiophenol is (10-50)0) Introducing hydrogen gas and keeping the gas atmosphere at the gas pressure of 1Mpa, heating to 150 ℃, stirring for 3h, cooling the reaction liquid, filtering, and drying for 12h to obtain AlOOH. TABLE 4 is alpha-Al2O3The data of the experimental results for the preparation of aluminum oxyhydroxide with different mass ratios to 3, 4-difluorothiophenol show that alpha-Al2O3When the mass ratio of the compound to 3, 4-difluorothiophenol is (50-500) to 1, the AlOOH yield is higher and can reach more than 92%.
TABLE 4. alpha. -Al2O3Data of experimental results for the preparation of aluminum oxyhydroxide with different mass ratios to 3, 4-difluorothiophenol
Comparative example 1
Mixing gamma-Al2O3Dispersing in water, adding Na2S, two sets of test sets A, B were formed such that gamma-Al2O3With Na2The mass ratio of S is 100: 1, and H is respectively introduced2、N2And keeping the gas atmosphere at the gas pressure of 1Mpa, heating to 150 ℃, stirring for 3h, cooling the reaction liquid, performing suction filtration, and drying for 12h to obtain reaction substances A and B. XRD test was carried out on the prepared substance A and substance B, and FIG. 5 shows the results at H2Or N2gamma-Al in atmosphere2O3In Na2XRD patterns before and after S treatment, and Table 5 shows experimental result data of the preparation of the aluminum oxyhydroxide in different gas atmospheres. It can be seen that N is introduced during the preparation2Namely, the crystal form can not be successfully changed from gamma-Al in the inert gas atmosphere2O3Conversion to AlOOH was only 10% yield, while in H2Can be used for preparing gamma-Al under the gas atmosphere2O3The product is converted into AlOOH with the yield up to 96.3 percent, and then the target AlOOH is prepared, namely, the preparation method of the invention provides that H is introduced2And maintaining a gas atmosphere is a critical step.
TABLE 5 data of experimental results for preparing aluminum oxyhydroxide in different gas atmospheres
| Experimental group | Alumina oxide | Sulfide compound | Introducing gas | Crystal form | AlOOH yield |
| A | γ-Al2O3 | Na2S | H2 | AlOOH | 96.3％ |
| B | γ-Al2O3 | Na2S | N2 | γ-Al2O3 | 10.1％ |
Comparative example 2
S1: and respectively dispersing commercial AlOOH with the same mass and AlOOH prepared in the embodiment 1 in water, dropwise adding a chloropalladate solution, stirring for 12 hours, carrying out suction filtration, drying for 12 hours, drying, placing in a tubular furnace, heating to 80 ℃, reducing for 3 hours in a hydrogen atmosphere, loading Pd on the commercial AlOOH to prepare a catalyst C, and loading Pd on the AlOOH prepared in the embodiment 1 to prepare a catalyst D.
S2: transferring an ethanol solvent into a reaction vessel, selecting phenylacetylene as a reaction substrate to disperse in the solvent, adding the prepared catalyst C and the prepared catalyst D, wherein the molar ratio of the reaction substrate to the noble metal Pt is 2000: 1, displacing hydrogen, keeping the hydrogen pressure at 0.1MPa, heating to 30 ℃, and stirring. Sampling is carried out at regular intervals, and product detection is carried out through gas chromatography.
Fig. 6 is a graph showing the comparison of the reaction activities of catalyst C and catalyst D in the phenylacetylene hydrogenation reaction. Compared with the catalyst which is prepared by taking common AlOOH sold in the market as a carrier to load noble metal Pd and is applied to the reaction of converting phenylacetylene into styrene through hydrogenation, the AlOOH prepared by the preparation method has higher reaction activity effect.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (8)
1. A preparation method of aluminum oxyhydroxide is characterized by comprising the following steps:
dispersing aluminum oxide in a solvent, adding a sulfide, introducing a hydrogen-containing gas, keeping the atmosphere, heating, stirring, filtering, and drying to obtain AlOOH; the sulfide is selected from at least one of organic mercaptan or sulfide salt; the heating temperature is (80-200) DEG C;
the organic mercaptan is prepared by using at least one solvent selected from the group consisting of an alcohol solvent, a DMF solvent and an ester solvent; the solvent used for the sulfide salt is water.
2. The method of claim 1, wherein the alumina is selected from the group consisting of alpha-Al2O3And gamma-Al2O3At least one of (1).
3. The method according to claim 1, wherein the organic thiol is at least one member selected from the group consisting of n-butylthiol, thioglycolic acid, n-hexylthiol, 1-octylthiol, dodecylthiol, thiophenol, 3, 4-difluorothiophenol, 1-chlorothiophenol and 4-tert-butylthiophenol.
4. The method according to claim 1, wherein the sulfide salt is at least one selected from sodium sulfide and potassium sulfide.
5. The production method according to claim 1, wherein the mass ratio of the alumina to the sulfide is (50-1000): 1.
6. The preparation method according to claim 1, wherein the gas atmosphere consists of hydrogen and a protective gas in a volume ratio of 1 (0-4); the pressure of the gas atmosphere is (0.1-2) MPa.
7. A catalyst comprising a first component of aluminum oxyhydroxide prepared by the method according to any one of claims 1 to 6 and a second component of active component.
8. The catalyst of claim 7 wherein the second component is a noble metal.
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