CN114471737A - Gallium oxide modified alumina catalyst carrier and preparation method thereof - Google Patents
Gallium oxide modified alumina catalyst carrier and preparation method thereof Download PDFInfo
- Publication number
- CN114471737A CN114471737A CN202111565130.6A CN202111565130A CN114471737A CN 114471737 A CN114471737 A CN 114471737A CN 202111565130 A CN202111565130 A CN 202111565130A CN 114471737 A CN114471737 A CN 114471737A
- Authority
- CN
- China
- Prior art keywords
- gallium
- modified alumina
- gallium oxide
- alumina catalyst
- oxide modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 150000007530 organic bases Chemical class 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- -1 nitrogen-containing organic bases Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 22
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- 239000011148 porous material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000001354 calcination Methods 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- 229940044658 gallium nitrate Drugs 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- B01J35/40—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
Abstract
The invention provides a gallium oxide modified alumina catalyst carrier and a preparation method thereof. The invention takes elemental gallium, elemental aluminum and organic alkali solution as raw materials, directly prepares a gallium oxide modified alumina carrier catalyst precursor by a one-step method, and obtains the gallium oxide modified alumina catalyst carrier by drying and roasting. The invention adopts a one-step method for synthesis and loading, and has simple steps and more uniform dispersion of gallium oxide compared with the conventional impregnation method.
Description
Technical Field
The invention relates to a gallium oxide modified alumina catalyst carrier and a preparation method thereof.
Background
Because of its excellent physical and chemical properties of heat, electricity, light, etc., it can be widely used as catalytic material besides refractory material, wear-resistant material, ceramic material, lamp tube material and integrated circuit substrate, among which, the application of alumina carrier is quite common. As catalyst support, the following properties should generally be present: high porosity, high water absorption, high crushing strength, high wear resistance, high heat resistance, high repeated oxidation-reduction resistance and high catalytic conversion rate. However, there is a problem in that the ceramic support is generally reinforced in one property, meaning that another property is lowered, such as an increase in crushing strength and a decrease in porosity, and therefore it is not easy to obtain a catalyst ceramic support having various good properties and meeting the use requirements.
The preparation method of the present alumina carrier comprises the following steps: 1. alumina powder is prepared by an improved Bayer process and then is extruded into strips for forming. 2. Alumina powder is prepared by an ammonium aluminum carbonate method and then is extruded into strips for forming. The method adopts a thermal cracking process, can obtain the microporous alumina powder with large specific surface area, but has poor dispersibility and low product purity. 3. Alumina powder is prepared by a uniform precipitation method and then is extruded and formed. The method adopts aluminum compound to control certain precipitation conditions (temperature, concentration, feeding speed, stirring speed, PH value, surface active agent and other auxiliary agents) in organic or aqueous solution, so that reactants reach product nucleation conditions in a short time, and a large amount of crystal nuclei are generated and the crystal nucleus growth speed is controlled when the whole system is in a stable state. This process also places high demands on the purity of the starting material. 4. The alumina powder is prepared by a carbonization method and then is extruded into strips for forming. The alumina carrier prepared by the method has low purity, and the total impurity content is about 0.8 percent. 5. Preparing kappa, rho type alumina powder by a high-temperature quick-release method and then rolling ball molding. The alumina carrier prepared by the method has low purity, the total impurity content is about 0.8 percent, and the impurity crystal is more.
Gallium metal, as a metal with catalytic activity, is widely applied to the field of catalysis, and particularly has wide application in the control of lean-burn nitrogen oxides and the convenience of petroleum catalysis. The control of nitrogen oxides in lean-burn gasoline vehicles and diesel vehicles to meet emission standards is becoming a hot point of research at home and abroad. Gallium zeolite catalysts (GA-ZSM-5 and the like) and alumina carrier catalysts (Ga2O3-Al2O3, SnO2-Ga2O3-Al2O3 and the like) prepared by taking gallium nitrate as a raw material have good activity on NOx generated under the condition of selective catalytic reduction and lean combustion of hydrocarbon. The Ga2O3-Al2O3-SiO2 catalyst prepared by gallium nitrate has high efficiency when used for cracking hydrocarbon oil: the polymerization can be catalyzed by the presence of 0.001% gallium in the diester: the catalyst containing gallium, iridium and platinum can effectively catalyze the conversion of heptane into aromatic substances. The alumina carrier is modified by gallium oxide, so that a large number of redox sites and acid sites can be provided for the catalyst carrier, the adsorption and desorption capacity of the surface of the catalyst for reaction gas is increased, and the conversion rate and selectivity of catalytic reaction can be greatly increased under the condition of lower gallium content. Among them, gallium oxide-modified supports have been used in various industrial devices, including the cyclic ar process developed by UOP and BP companies, the aro & orming process developed by IFP and Salutec, and the like.
At present, the method for loading gallium on ZSM or pure alumina carrier is mainly an impregnation method and a small amount of atomic deposition method. In the prior patent, gallium nitrate is prepared by taking gallium as a raw material, and then the gallium nitrate is soaked in self-made pseudo-boehmite, subjected to reduced pressure distillation and drying, and finally roasted at high temperature to form gallium metal loaded alumina; in addition, the method comprises the steps of immersing gallium nitrate serving as a raw material in a self-made ZSM-5 carrier, and then drying and roasting the carrier to form the metal gallium-loaded ZSM-5; in other patent applications, the gallium source is mostly gallium nitrate, gallium chloride, gallium sulfate or organic gallium source, and the loading is basically completed by the processes of dipping, drying and roasting, wherein the loading is also completed by an atomic deposition method. Trimethyl gallium, triethyl gallium and gallium chloride are used as raw materials to generate gallium nitride loaded on an alumina carrier through an atomic deposition method. The existing method has a series of problems of nitrogen oxide emission, complex operation steps and the like.
So far, no one-step method is available at home and abroad for directly preparing the gallium oxide modified alumina catalyst.
Disclosure of Invention
Aiming at the technical defects at present, the invention provides a preparation method of a supported metal gallium aluminum oxide catalyst carrier with simple preparation process and low cost, wherein the preparation method adopts a one-step method, and metal gallium is used as a gallium source, and aluminum powder is used as an aluminum source. The gallium oxide supported alumina catalyst is prepared, and the gallium oxide supported alumina catalyst is prepared by an immersion method instead of the original gallium salt (gallium nitrate, gallium chloride, gallium sulfate or organic gallium). Compared with the existing gallium nitrate impregnation method, the method has the advantage of lower cost by directly using gallium metal and aluminum powder compared with gallium nitrate and aluminum oxide; and compared with the method that the roasting after the gallium nitrate is impregnated can generate a large amount of nitrogen oxides, the method has large pollution to the atmosphere, and because the metal gallium is only used as a gallium source, no nitrogen oxide pollutant is discharged.
The invention provides a preparation method of a gallium oxide modified alumina catalyst carrier, which comprises the following steps:
1) firstly, melting elemental gallium, adding the elemental gallium into aqueous dispersion of aluminum powder, stirring to ensure that the gallium is dispersed at the bottom of the liquid in a droplet shape to obtain mixed dispersion, adding organic alkali into the mixed dispersion under the stirring condition, heating to 50-100 ℃ for reaction, and obtaining aluminum-containing compound solid loaded with the gallium and filtrate through solid-liquid separation after the reaction is finished; wherein the mass ratio of the gallium metal to the aluminum powder to the organic base is 1.8-2.2: 0.5: 1-3;
2) drying and roasting the aluminum-containing compound solid loaded with the metal gallium obtained in the step 1) to obtain the gallium oxide modified alumina catalyst carrier.
In the above preparation method of the present invention, the organic base is preferably one or more selected from triethylamine, 4-dimethylaminopyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and other nitrogen-containing organic bases.
The organic base is added directly or in the form of a solution containing an equal amount of organic base.
In the aqueous dispersion of the aluminum powder, the mass percent of the aluminum powder is 1.8-2.2%.
In the preparation method of the invention, the roasting condition is 500-600 ℃.
In the preparation method, the filtrate obtained in the step 1) is subjected to phase separation, and the gallium metal is separated and recycled.
The invention also provides a gallium oxide modified alumina catalyst carrier prepared by the method, wherein the loading rate of gallium is 4-12 per mill.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation of the alumina precursor and the loading of the gallium oxide on the alumina are completed by a one-step method;
(2) the reaction condition is mild;
(3) the metal gallium can be separated for recycling;
(4) the whole process has no emission of pollutants such as nitrogen oxides, chlorides, sulfur-containing gas and the like;
(5) gallium oxide is distributed on the carrier more uniformly;
(6) compared with an atomic deposition method, the method has the advantages of simple operation steps, easy amplification and realization of large-scale industrial production.
Description of the drawings:
FIG. 1 XRD pattern of gallium oxide modified alumina catalyst powder obtained in example 1;
FIG. 2 TEM image of gallium oxide-modified alumina catalyst obtained in example 1;
FIG. 3 EDS energy spectrum of gallium oxide modified alumina catalyst obtained in example 1.
Detailed Description
The present invention is described in further detail below by way of specific examples. The raw material information used is as follows: aluminum powder (Annealed Steel industries), gallium metal (Zhuhai Fangyuan Co., Ltd.), tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonia, 4-Dimethylaminopyridine (DMAP) were purchased from Chemicals.
Example 1:
(1) 0.4958g of aluminum powder is taken and dispersed in 25mL of water, and the mixture is stirred for about 10min to completely disperse the aluminum powder to obtain a dispersion liquid (1);
(2) melting gallium at 40 ℃, adding 1.9969g of gallium into the dispersion liquid (1), stirring for 10min under the magnetic stirring of 700rpm, and dispersing the gallium at the bottom of the liquid in the form of small droplets to obtain a dispersion liquid (2);
(3) adding 5g of 30% tetramethylammonium hydroxide solution into the dispersion liquid (2), and carrying out magnetic stirring at 700rpm, wherein the reaction temperature is 50 ℃ and the reaction time is 2 hours to obtain a reacted liquid (3);
(4) filtering and separating the reacted liquid (3) to obtain gallium oxide modified alumina precursor solid;
(5) drying the solid obtained in the step (4) at the drying temperature of 100 ℃;
(6) finally, calcining the solid obtained in the step (5), wherein the calcining temperature is 550 ℃; to obtain the final product, namely the gallium oxide modified alumina catalyst.
The obtained product gallium oxide modified alumina catalyst has the following characteristics: the specific surface area is 222.2m2Per g, pore volume 0.2758cm3The pore diameter is 4.96nm, wherein the loading rate of metal gallium is 8 per mill, and the aluminum oxide is gamma-alumina.
Wherein FIG. 1 is a powder XRD pattern of the product, which compares with JCPDS No.29-63 gamma alumina card, and proves that the product is gamma alumina, FIG. 2 is a TEM image of the product, and the morphology of the product is a stacking form of rod-shaped particles, the length of the rod-shaped particles is about 5 μm, and the diameter is 1 micron. FIG. 3 is an EDS energy spectrum in which characteristic peaks of elemental aluminum, elemental oxygen, and elemental gallium appear, demonstrating the completion of gallium oxide loading.
Example 2:
(1) 0.5058g of aluminum powder is taken and dispersed in 25mL of water, and the mixture is stirred for about 10min to completely disperse the aluminum powder to obtain a dispersion liquid (1);
(2) melting gallium at 40 ℃, adding 1.9816g of gallium into the dispersion liquid (1), stirring for 10min under the magnetic stirring of 700rpm, so that the gallium is dispersed at the bottom of the liquid in the form of small drops to obtain a dispersion liquid (2);
(3) adding 1.5g of tetraethyl ammonium hydroxide into the dispersion liquid (2), and reacting for 2 hours at the reaction temperature of 70 ℃ under the magnetic stirring of 700rpm to obtain a reacted liquid (3);
(4) filtering and separating the reacted liquid (3) to obtain gallium oxide modified alumina precursor solid;
(5) drying the solid obtained in the step (4) at the drying temperature of 100 ℃;
(6) finally, calcining the solid obtained in the step (5), wherein the calcining temperature is 550 ℃; to obtain the final product, namely the gallium oxide modified alumina catalyst.
The obtained product gallium oxide modified alumina catalyst has the following characteristics: specific surface area 242.2m2Per g, pore volume 0.3213cm3The pore diameter is 4.84nm, wherein the loading rate of the metal gallium is 5 per mill, and the aluminum oxide is gamma-alumina.
Example 3:
(1) 0.5049g of aluminum powder is taken and dispersed in 25mL of water, and the mixture is stirred for about 10min to completely disperse the aluminum powder to obtain a dispersion liquid (1);
(2) melting gallium at 40 ℃, taking 1.9818g of gallium, adding the gallium into the dispersion liquid (1), stirring for 10min under the magnetic stirring of 700rpm, and dispersing the gallium at the bottom of the liquid in a droplet shape to obtain a dispersion liquid (2);
(3) adding 1.5g of triethylamine into the dispersion liquid (2), and reacting for 2 hours at the reaction temperature of 90 ℃ under the magnetic stirring of 700rpm to obtain reacted liquid (3);
(4) filtering and separating the reacted liquid (3) to obtain gallium oxide modified alumina precursor solid;
(5) drying the solid obtained in the step (4) at the drying temperature of 100 ℃;
(6) finally, calcining the solid obtained in the step (5), wherein the calcining temperature is 550 ℃; to obtain the final product, namely the gallium oxide modified alumina catalyst.
The obtained product gallium oxide modified alumina catalyst has the following characteristics: specific surface area 227.2m2Per g, pore volume 0.3019cm3The pore diameter is 4.75nm, wherein the loading rate of metal gallium is 4 per mill, and the aluminum oxide is gamma-alumina.
Example 4:
(1) 0.5167g of aluminum powder is taken and dispersed in 25mL of water, and the mixture is stirred for about 10min to completely disperse the aluminum powder to obtain a dispersion liquid (1);
(2) melting gallium at 40 ℃, adding 2.0018g of gallium into the dispersion liquid (1), stirring for 10min under the magnetic stirring of 700rpm, so that the gallium is dispersed at the bottom of the liquid in the form of small drops to obtain a dispersion liquid (2);
(3) adding 5g of DMAP into the dispersion liquid (2), and reacting for 2 hours at the reaction temperature of 50 ℃ under the magnetic stirring of 700rpm to obtain reacted liquid (3);
(4) filtering and separating the reacted liquid (3) to obtain gallium oxide modified alumina precursor solid;
(5) drying the solid obtained in the step (4) at the drying temperature of 100 ℃;
(6) finally, calcining the solid obtained in the step (5), wherein the calcining temperature is 550 ℃; to obtain the final product, namely the gallium oxide modified alumina catalyst.
The obtained product gallium oxide modified alumina catalyst has the following characteristics: specific surface area 225.2m2Per g, pore volume 0.2942cm3The pore diameter is 4.81nm, wherein the loading rate of metal gallium is 2 per mill, and the aluminum oxide is gamma-alumina.
Example 5:
(1) 0.5158g of aluminum powder is taken and dispersed in 25mL of water, and the mixture is stirred for about 10min to completely disperse the aluminum powder to obtain a dispersion liquid (1);
(2) melting gallium at 40 ℃, adding 1.9969g of gallium into the dispersion liquid (1), stirring for 10min under the magnetic stirring of 700rpm, so that the gallium is dispersed at the bottom of the liquid in the form of small drops to obtain a dispersion liquid (2);
(3) adding 10g of 30% tetramethylammonium hydroxide solution into the dispersion liquid (2), and reacting at 90 ℃ for 2 hours under the magnetic stirring of 700rpm to obtain a reacted liquid (3);
(4) filtering and separating the reacted liquid (3) to obtain gallium oxide modified alumina precursor solid;
(5) drying the solid obtained in the step (4) at the drying temperature of 100 ℃;
(6) finally, calcining the solid obtained in the step (5), wherein the calcining temperature is 550 ℃; to obtain the final product, namely the gallium oxide modified alumina catalyst.
The obtained product gallium oxide modified alumina catalyst has the following characteristics: the specific surface area is 212.2m2/g, the pore volume is 0.2558cm3/g, the pore diameter is 4.56nm, the loading rate of metal gallium is 6 per mill, and the aluminum oxide is gamma-alumina.
Example 6:
(1) 0.5125g of aluminum powder is taken and dispersed in 25mL of water, and the mixture is stirred for about 10min to completely disperse the aluminum powder to obtain a dispersion liquid (1);
(2) the sample after the reaction in example 1 is subjected to liquid separation treatment, the reacted metal gallium which is settled in the sample is added into the dispersion liquid (1) again, and the mixture is stirred for 10min under the magnetic stirring of 700rpm, so that the metal gallium is dispersed on the bottom of the liquid in a small droplet shape, and a dispersion liquid (2) is obtained;
(3) adding 5g of 30% tetramethylammonium hydroxide solution into the dispersion liquid (2), and carrying out magnetic stirring at 700rpm, wherein the reaction temperature is 50 ℃ and the reaction time is 2 hours to obtain a reacted liquid (3);
(4) filtering and separating the reacted liquid (3) to obtain gallium oxide modified alumina precursor solid;
(5) drying the solid obtained in the step (4) at the drying temperature of 100 ℃;
(6) finally, calcining the solid obtained in the step (5), wherein the calcining temperature is 550 ℃; to obtain the final product, namely the gallium oxide modified alumina catalyst.
The obtained product gallium oxide modified alumina catalyst has the following characteristics: the specific surface area is 252.2m2/g, the pore volume is 0.2849cm3/g, the pore diameter is 5.04nm, the loading rate of metal gallium is 12 per mill, and the aluminum oxide is gamma-alumina.
Comparative example
The procedure was carried out as described in example 6 of CN105813731, in which a gallium oxide-modified alumina catalyst was prepared by an impregnation method, 20g of a high-purity alumina catalyst carrier (Sasol) was taken, the carrier was impregnated with distilled water for 2 hours, 25mL of an aqueous solution containing 1.76g of gallium nitrate nonahydrate (mcolin reagent corporation) was impregnated, aged at room temperature for 2 hours, then dried at 175 ℃ for 1 hour, and finally calcined at 750 ℃ to obtain a gallium oxide-modified alumina catalyst.
The obtained product gallium oxide modified alumina catalyst has the following characteristics: specific surface area 143m2Per g, pore volume 0.2049cm3The pore diameter is 4.04nm, wherein the loading rate of the metal gallium is 9 per mill. Example 1 gives 55% and 35% improvement in the specific surface area and pore volume values over the comparative product.
Claims (6)
1. A preparation method of a gallium oxide modified alumina catalyst carrier is characterized by comprising the following steps:
1) firstly, melting elemental gallium, adding the elemental gallium into aqueous dispersion of aluminum powder, stirring to enable the gallium to be dispersed at the bottom of the liquid in a droplet shape to obtain mixed dispersion, then adding organic alkali into the mixed dispersion, heating to 50-100 ℃ for reaction, and obtaining aluminum-containing compound solid loaded with the gallium and filtrate through solid-liquid separation after the reaction is finished; wherein the mass ratio of the gallium metal to the aluminum powder to the organic base is 1.8-2.2: 0.5: 1-3;
2) drying and roasting the aluminum-containing compound solid loaded with the metal gallium obtained in the step 1) to obtain the gallium oxide modified alumina catalyst carrier.
2. The method according to claim 1, wherein the organic base is one or more selected from triethylamine, 4-dimethylaminopyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and other nitrogen-containing organic bases.
3. The method according to claim 1, wherein the organic base is added directly or in the form of a solution containing an equivalent amount of the organic base.
4. The method of claim 1, wherein the firing conditions are 500 ℃ to 600 ℃.
5. The preparation method of claim 1, further comprising performing phase separation on the filtrate obtained in the step 1) to separate out the metal gallium for recycling.
6. The gallium oxide-modified alumina catalyst support obtained by the preparation method according to any one of claims 1 to 5, wherein the gallium loading rate is 4 to 12% o.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111565130.6A CN114471737B (en) | 2021-12-20 | 2021-12-20 | Gallium oxide modified alumina catalyst carrier and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111565130.6A CN114471737B (en) | 2021-12-20 | 2021-12-20 | Gallium oxide modified alumina catalyst carrier and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114471737A true CN114471737A (en) | 2022-05-13 |
| CN114471737B CN114471737B (en) | 2023-11-07 |
Family
ID=81494606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111565130.6A Active CN114471737B (en) | 2021-12-20 | 2021-12-20 | Gallium oxide modified alumina catalyst carrier and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114471737B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336393A (en) * | 1991-06-12 | 1994-08-09 | Idemitsu Kosan Co., Ltd. | Process for catalytically converting organic compounds |
| US20090253572A1 (en) * | 2008-04-08 | 2009-10-08 | Saleh Elomari | Regeneration of ionic liquid catalyst using a regeneration metal in the presence of added hydrogen |
| KR101473716B1 (en) * | 2013-08-23 | 2014-12-26 | (주)티에스엠 | Manufacturing method of gallium oxide of high purity spherical for minimalize of loss of gallium and high purity spherical gallium oxide therefrom |
| CN109939688A (en) * | 2019-04-03 | 2019-06-28 | 华东理工大学 | Iron gallium base propane dehydrogenation catalyst and preparation method thereof |
| CN111807397A (en) * | 2019-04-10 | 2020-10-23 | 吉林省氢汇新能源有限公司 | Production method of high-purity alumina and high-purity alumina produced by same |
-
2021
- 2021-12-20 CN CN202111565130.6A patent/CN114471737B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336393A (en) * | 1991-06-12 | 1994-08-09 | Idemitsu Kosan Co., Ltd. | Process for catalytically converting organic compounds |
| US20090253572A1 (en) * | 2008-04-08 | 2009-10-08 | Saleh Elomari | Regeneration of ionic liquid catalyst using a regeneration metal in the presence of added hydrogen |
| KR101473716B1 (en) * | 2013-08-23 | 2014-12-26 | (주)티에스엠 | Manufacturing method of gallium oxide of high purity spherical for minimalize of loss of gallium and high purity spherical gallium oxide therefrom |
| CN109939688A (en) * | 2019-04-03 | 2019-06-28 | 华东理工大学 | Iron gallium base propane dehydrogenation catalyst and preparation method thereof |
| CN111807397A (en) * | 2019-04-10 | 2020-10-23 | 吉林省氢汇新能源有限公司 | Production method of high-purity alumina and high-purity alumina produced by same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114471737B (en) | 2023-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101687661B (en) | High specific surface area mixed oxide of cerium and of another rare earth, preparation method and use in catalysis | |
| US5242881A (en) | Perovskite-type rare earth complex oxide combustion catalysts | |
| US5877106A (en) | Stabilized crystalline alumina compositions | |
| CN101884935B (en) | Catalyst material and preparation method thereof | |
| CN104841465A (en) | Load type nickel phosphide catalyst and pre-phosphating preparation method thereof | |
| US8476187B2 (en) | Process for preparing catalyst powder | |
| JP2006516524A (en) | Compositions based on cerium oxide and zirconium oxide and having a specific surface area that is stable at 900 ° C. to 1000 ° C., their production method and their use as catalysts | |
| EP3363540B1 (en) | Copper containing moz zeolite for selective nox reduction catalysis | |
| CN101885663B (en) | Method for converting heavy aromatics to light aromatics and transferring alkyl radical | |
| KR102129749B1 (en) | Ternary catalyst and a method for producing the same | |
| WO2024011711A1 (en) | Coating-free monolithic catalyst for waste gas purification and preparation method therefor | |
| CN101786011B (en) | Preparation method of Ru/Silicalite-1 catalyst for efficiently promoting decomposition of N2O | |
| CN113856749B (en) | Samarium-based CHA molecular sieve catalyst and application thereof | |
| CN114471737A (en) | Gallium oxide modified alumina catalyst carrier and preparation method thereof | |
| CN1191331C (en) | Dual-function reforming catalyst containing Pt and Sn and its preparing process | |
| CN1247773A (en) | Preparation of pseudo-thin diasphore and gamma-alumina | |
| CN108033462B (en) | Hierarchical porous LTL molecular sieve and synthesis method and application thereof | |
| CN101885664B (en) | Trimethylbenzene catalytic conversion method | |
| US20150352525A1 (en) | Co oxidation promoter and a process for the preparation thereof | |
| KR20210109358A (en) | Elimination Method of Chlorine in Inorganics Using Bases and Selective Catalytic Reduction(SCR) Catalysts Manufactured Thereby | |
| CN111659409A (en) | Hydrodesulfurization catalyst and preparation method and application thereof | |
| JP3855045B2 (en) | Method for producing ruthenium perovskite | |
| US20190270082A1 (en) | Nanoporous cerium oxide with interconnected pores for catalysis and a cost- effective method of preparing thereof | |
| CN115532270B (en) | Dynamic copper-zinc catalyst and preparation method and application thereof | |
| CN111744543B (en) | Aviation kerosene catalyst prepared by olefin polymerization, preparation process thereof and olefin polymerization process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |