CN107413388B - α -alumina carrier and preparation method and application thereof - Google Patents
α -alumina carrier and preparation method and application thereof Download PDFInfo
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- CN107413388B CN107413388B CN201610344875.2A CN201610344875A CN107413388B CN 107413388 B CN107413388 B CN 107413388B CN 201610344875 A CN201610344875 A CN 201610344875A CN 107413388 B CN107413388 B CN 107413388B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008247 solid mixture Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 150000004682 monohydrates Chemical class 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000004684 trihydrates Chemical class 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910001648 diaspore Inorganic materials 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 229910000154 gallium phosphate Inorganic materials 0.000 claims description 4
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- 229910005540 GaP Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 238000006735 epoxidation reaction Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229940044658 gallium nitrate Drugs 0.000 claims description 3
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 3
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000006057 reforming reaction Methods 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 10
- 239000000969 carrier Substances 0.000 description 8
- JJBNCYLBHKHXAH-UHFFFAOYSA-N O.O.O.[Ga] Chemical compound O.O.O.[Ga] JJBNCYLBHKHXAH-UHFFFAOYSA-N 0.000 description 5
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000036314 physical performance Effects 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- B01J35/612—
Abstract
The invention relates to an α -alumina carrier and a preparation method and application thereof.A certain amount of gallium-containing compound additive is added in the preparation process of the carrier, wherein the mass content of gallium in the carrier is 0.02-15.00%.
Description
Technical Field
The invention belongs to the technical field of catalyst carriers, and relates to an α -alumina carrier and a preparation method and application thereof.
Background
Alumina materials have been one of the major and hot research targets in the fields of material science and catalysis, etc., and have made great progress in the fields of fine ceramics, composite materials, adsorption separation, catalysis, etc. Especially in the field of petrochemical catalysis, alumina carriers with different shapes have wide application in the aspects of catalytic oxidation and catalytic hydrogenation. The alumina carrier plays a very important role in catalysts, such as: improving the dispersibility of the active components, reducing the dosage of the active components, increasing the effective specific surface, improving the thermal stability of the catalyst and the like, wherein the performance of the alumina carrier is one of the key factors of the performance of the catalyst.
The present invention relates to a method for preparing silver oxide catalyst, and is characterized by that in the course of calcining precursor of aluminium hydroxide the formed amorphous alumina can be converted into metastable phase alumina, and said metastable phase alumina can be converted into α -alumina, and in the course of calcining precursor of aluminium hydroxide said metastable phase alumina can be converted into metastable phase alumina, and said metastable phase alumina can be calcined into metastable phase alumina, and said metastable phase alumina can be converted into α -alumina.
Disclosure of Invention
One of the purposes of the invention is to provide an α -alumina carrier which is prepared by a carrier modification method different from the prior art, has suitable crushing strength and water absorption, and has higher specific surface area compared with the carrier prepared by the prior art, thereby improving the dispersibility of the active components of the catalyst on the carrier and further improving the catalytic performance of the catalyst.
The invention also aims to provide a preparation method of the α -alumina carrier.
The invention also aims to provide the application of the α -alumina carrier.
To this end, the present invention provides, in a first aspect, an α -alumina support containing elemental gallium.
According to the invention, the mass content of the gallium element in the carrier is 0.02-15.00%; preferably 0.02% -5.00%; further preferably 0.05% to 5.00%.
In some embodiments of the invention, the specific surface of the support is 1.0 to 50.0m2A/g, preferably 1.5 to 10.0m2(ii)/g; the water absorption of the carrier is more than or equal to 30 percent, and preferably 40 to 70 percent; the crushing strength of the carrier is 30-300N/grain.
In other embodiments of the present invention, the α -alumina is present in the support in an amount greater than or equal to 85% by mass.
In a second aspect, the present invention provides a method for preparing the carrier of the first aspect, comprising:
step A, mixing alumina trihydrate, alumina monohydrate, a gallium-containing compound and an optional alkaline earth metal compound and/or fluoride to obtain a solid mixture;
step B, adding a binder and water into the solid mixture to obtain α -alumina precursor mixture;
and step C, kneading, molding, drying and roasting the α -alumina precursor mixture to obtain the α -alumina carrier.
According to the method of the invention, the mass content of the alumina trihydrate in the solid mixture is 20-90%.
In the present invention, it is preferable that the aluminum trihydrate comprises gibbsite and/or surge.
According to the method of the invention, the mass content of the monohydrate alumina in the solid mixture is 5-50%.
In the present invention, it is preferable that the aluminum oxide monohydrate includes boehmite and/or diaspore.
According to the method of the invention, the mass content of the gallium-containing compound in the solid mixture is 0.02% -40.00%.
In the present invention, it is preferable that the gallium-containing compound includes one or more of a gallium-containing oxide, a gallium-containing hydroxide, and a gallium-containing salt.
In some embodiments of the invention, the gallium-containing salt comprises one or more of gallium chloride, gallium sulfate, gallium nitrate, gallium phosphide, and gallium phosphate.
In the present invention, the gallium-containing oxide includes, but is not limited to, gallium oxide.
In the present invention, the gallium-containing hydroxide includes, but is not limited to, gallium hydroxide.
According to the method of the invention, the mass content of the alkaline earth metal compound in the solid mixture is 0-3.50%.
In some embodiments of the invention, it is preferred that the alkaline earth metal compound comprises one or more of an oxide, nitrate, sulphate, carbonate, oxalate and chloride of an alkaline earth metal. In the present invention, it is preferred that the alkaline earth metal includes magnesium and/or barium.
According to the method of the invention, the mass content of fluoride in the solid mixture is 0-6.0%.
In some embodiments of the invention, the fluoride comprises one or more of hydrogen fluoride, ammonium fluoride, magnesium fluoride, and lithium fluoride.
According to the method, the weight ratio of the binder to the water is 1 (1-10).
In some embodiments of the invention, the binder comprises one or more of citric acid, nitric acid, formic acid, acetic acid, propionic acid, and hydrochloric acid.
In some embodiments of the invention, in step C, the temperature of the drying is 20 to 120 ℃.
In other embodiments of the present invention, in step C, the drying time is 24-48 h.
According to some embodiments of the invention, in step C, the firing comprises a programmed temperature and constant temperature firing process. In some embodiments of the present invention, the temperature of the constant-temperature roasting is 1000-1600 ℃, preferably 1100-1500 ℃; preferably, the constant-temperature roasting time is 10-30 h.
In a third aspect, the invention provides a use of the carrier of the first aspect of the invention or the carrier prepared by the process of the second aspect of the invention in olefin epoxidation reactions, selective hydrogenation of acetylenes and dienes, and methane reforming reactions.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention is provided below.
In order to improve the performance of α -alumina carrier, the inventor has made extensive research on α -alumina carrier, and the inventor finds that α -alumina carrier prepared by adding a certain amount of gallium-containing compound in the preparation process of α -alumina carrier not only has proper crushing strength and water absorption rate, but also can significantly improve the specific surface area of the carrier.
Therefore, the α -alumina carrier according to the first aspect of the invention is prepared by adding a certain amount of gallium-containing compound in the preparation process of α -alumina carrier, and the supported carrier is characterized in that the mass content of gallium element in the carrier is 0.02-15.00%, preferably 0.02-5.00%, further preferably 0.05-5.00%, even more preferably 0.21-5.00%, the mass content of α -alumina in the carrier is more than or equal to 85%, and the specific surface area is 1.0-50.0m2A/g, preferably 1.5 to 10.0m2Per g, more preferably 2.43 to 10.0m2(ii)/g; the water absorption rate is more than or equal to 30 percent, preferably 40 to 70 percent, and more preferably 51.6 to 70 percent; the crushing strength is 30-300N/grain, preferably 178-300N/grain.
The preparation method of the α -alumina carrier in the second aspect of the invention comprises the following steps:
step A, mixing alumina trihydrate, alumina monohydrate, a gallium-containing compound and an optional alkaline earth metal compound and/or fluoride to obtain a solid mixture;
step B, adding a binder and water into the solid mixture to obtain α -alumina precursor mixture;
and step C, kneading, molding, drying and roasting the α -alumina precursor mixture to obtain the α -alumina carrier.
In the α -alumina carrier preparation method, the alumina trihydrate and the alumina monohydrate are used as an aluminum source and are converted into α -alumina after being roasted, the alumina trihydrate comprises gibbsite and/or surge diaspore, and the mass of the alumina trihydrate comprises 20% -90% of the total mass of the solid mixture, and the alumina monohydrate comprises boehmite and/or diaspore, and the mass of the alumina monohydrate comprises 5% -50% of the total mass of the solid mixture.
In order to improve the specific surface area of the α -alumina carrier, the invention adds a gallium-containing compound in the preparation method of the α -alumina carrier, and the mass of the gallium-containing compound accounts for 0.02-40.00% of the total mass of the solid mixture.
In the present invention, the gallium-containing compound includes one or more of a gallium-containing oxide, a gallium-containing hydroxide, and a gallium-containing salt. In some embodiments of the invention, for example, the gallium-containing salt comprises one or more of gallium chloride, gallium sulfate, gallium nitrate, gallium phosphide, and gallium phosphate. In other embodiments of the present invention, the gallium-containing oxide includes, but is not limited to, gallium oxide. In still other embodiments of the present invention, the gallium-containing hydroxide includes, but is not limited to, gallium hydroxide.
In the α -alumina carrier preparation method, the alkaline earth metal compound is added to improve the mechanical strength of the alumina carrier, wherein the alkaline earth metal compound comprises one or more of alkaline earth metal oxide, nitrate, sulfate, carbonate, oxalate and chloride, and the mass of the alkaline earth metal compound accounts for 0-3.50% of the total mass of the solid mixture.
In the present invention, fluoride including one or more of hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride in an amount of 0 to 6.0% by mass based on the total mass of the solid mixture can promote the transition phase of alumina to α -alumina during calcination, eliminate unnecessary micropores, and reduce pores of 0.1 μm or less.
According to some embodiments of the present invention, in the preparation method of the α -alumina carrier, the solid mixture may further include a thermally decomposable burnout material in addition to the above-mentioned components, and the thermally decomposable burnout material includes one or more of polyethylene, polypropylene, petroleum coke, carbon powder and graphite, and its mass is 0-20.0% of the total mass of the solid mixture.
In the α -alumina carrier preparation method, a binder is used for generating alumina sol with alumina monohydrate in solid powder, and binding the components together to form paste which can be extruded, wherein the mass ratio of the binder to water is 1 (1-10), and the binder comprises one or more of citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid.
The amount of binder used in the present invention is not particularly limited, and is that amount which will form an alumina sol with the alumina monohydrate in the solid mixture and will bond with the components to form an extrudable paste.
In the present invention, sequential addition of the solid mixture and the binder solution is not required between the solid mixture and the binder solution, for example, the fluoride in the solid mixture may be added to the solid mixture together with the binder solution at the end.
In order to mix the precursor mixture uniformly, the precursor mixture is kneaded in a kneader for 5-90 min. After the precursor mixture is sufficiently kneaded, the carrier can be formed into a shape including a sphere, a block, a cylinder, a porous cylinder, a raschig ring, a clover, a honeycomb, etc., and the forming is performed in a forming machine.
Drying the formed product after the precursor mixture is formed, wherein the drying is carried out at the temperature of 20-120 ℃, and the water content in the formed product is controlled to be less than 10%; in some embodiments of the invention, the drying time may be, for example, 24-48 hours.
According to some embodiments of the present invention, in order to facilitate extrusion of the molded object, a molding aid may be added to the solid mixture, the molding aid including one or more of vaseline, graphite, paraffin, and vegetable oil.
In order to obtain the α -alumina carrier with proper characteristics, the dried formed product is roasted, wherein the roasting comprises the processes of temperature programming and constant-temperature roasting, the constant-temperature roasting temperature is 1000-1600 ℃, the constant-temperature roasting temperature is 1100-1500 ℃, the constant-temperature roasting time is 10-30h, and the constant-temperature roasting time is 10-25 h.
The term "optional" as used herein means either with or without, and with or without the addition of.
The term "water" as used herein refers to one or more of deionized water, distilled water and ultrapure water, unless otherwise specified or indicated.
The term "gallium-containing compound" as used herein refers to a compound containing gallium.
The term "fluorine-containing compound" as used herein means a compound containing fluorine.
The α -alumina carrier prepared by adding a certain amount of gallium-containing compound in the preparation process not only has proper crushing strength and water absorption rate, but also has the specific surface area which is obviously higher than that of a α -alumina carrier prepared by the prior art, so that the dispersity of active components of the catalyst on the carrier can be improved, and the catalytic performance of the catalyst is further improved.
Examples
In order that the present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention.
The method for detecting the physical property of the α -alumina carrier comprises the following steps:
the specific surface area of the support is determined according to the international test standard ISO-9277 using the nitrogen physisorption BET method. For example, the specific surface area of the carrier can be measured using a nitrogen physisorption apparatus of model NOVA2000e, conta, usa.
The lateral pressure strength of the carrier can be obtained by, for example, randomly selecting 30 carrier samples by using a DL II type intelligent particle strength tester produced by the institute of chemical engineering and design, measuring the radial crushing strength, and averaging.
The term "water absorption" as used in the present invention refers to the volume of saturated adsorbed water per unit mass of the carrier, in mL/g. The determination method comprises the following steps: first, a certain amount of carrier (assuming its mass m) is weighed1) Boiling in boiling water for 1 hr, taking out the carrier, standing on wet gauze with moderate water content to remove excessive water on the surface of the carrier, and weighing the mass of the carrier after water adsorption (assuming that m is m)2) The water absorption of the carrier was calculated by the following formula.
Where ρ isWater (W)The density of water at temperature and atmospheric pressure was measured.
Example 1:
480.0g of surge aluminum oxide, 120.0g of boehmite, 11.0g of ammonium fluoride, 3.0g of barium sulfate and 1.5g of gallium hydroxide are weighed and put into a mixer to be uniformly mixed, the mixture is transferred into a kneader, dilute nitric acid (nitric acid: water: 1: 3, volume ratio) is added until the mixture is kneaded into paste which can be extruded and molded, the paste is put into a strip extruder to be extruded into a seven-hole column, the seven-hole column is dried for more than 24 hours at the temperature of 60-120 ℃ to reduce the free water content to below 10 percent, then the dried seven-hole column is put into a natural gas kiln to be calcined, the calcination temperature is 1350 ℃, the constant temperature calcination is carried out for 25 hours, and finally the mixture is cooled to the room temperature, so that α -alumina carriers are obtained, and the relevant physical performance data of the α -alumina carriers prepared in the embodiment are shown in table 1.
Example 2:
480.0g of surge aluminum oxide, 120.0g of boehmite, 11.0g of ammonium fluoride, 3.0g of barium sulfate and 15.0g of gallium hydroxide are weighed and put into a mixer to be uniformly mixed, the mixture is transferred into a kneader, dilute nitric acid (nitric acid: water: 1: 3, volume ratio) is added until the mixture is kneaded into paste which can be extruded and molded, the paste is put into a strip extruder to be extruded into a seven-hole column, the seven-hole column is dried for more than 24 hours at the temperature of between 60 and 120 ℃ to reduce the free water content to below 10 percent, then the dried seven-hole column is put into a natural gas kiln to be calcined, the calcination temperature is 1300 ℃, the constant temperature calcination is carried out for 25 hours, and finally the temperature is cooled to room temperature, so that α -alumina carriers are obtained, and the relevant physical property data of the α -alumina carriers prepared in the embodiment are shown in table 1.
Example 3:
480.0g of surge aluminum oxide, 120.0g of boehmite, 11.0g of ammonium fluoride, 3.0g of barium sulfate and 25.0g of gallium phosphate are weighed and put into a mixer to be uniformly mixed, the mixture is transferred into a kneader, dilute nitric acid (nitric acid: water: 1: 3, volume ratio) is added until the mixture is kneaded into paste which can be extruded and molded, the paste is put into a strip extruder to be extruded into a seven-hole column, the seven-hole column is dried for more than 24 hours at the temperature of between 60 and 120 ℃ to reduce the free water content to below 10 percent, then the dried seven-hole column is put into a natural gas kiln to be calcined, the calcination temperature is 1100 ℃, the constant temperature calcination is carried out for 10 hours, and finally the mixture is cooled to the room temperature to obtain α -alumina carrier, wherein the relevant physical performance data of the α -alumina carrier prepared in the embodiment are shown in table 1.
Example 4:
480.0g of surge aluminum oxide, 120.0g of boehmite, 11.0g of ammonium fluoride, 3.0g of barium sulfate and 6.5g of gallium hydroxide are weighed and put into a mixer to be uniformly mixed, the mixture is transferred into a kneader, dilute nitric acid (nitric acid: water: 1: 3, volume ratio) is added until the mixture is kneaded into paste which can be extruded and molded, the paste is put into a strip extruder to be extruded into a seven-hole column, the seven-hole column is dried for more than 24 hours at the temperature of between 60 and 120 ℃ to reduce the free water content to below 10 percent, then the dried seven-hole column is put into a natural gas kiln to be calcined, the calcination temperature is 1200 ℃, the constant temperature calcination is carried out for 20 hours, and finally the temperature is cooled to room temperature, so that α -alumina carriers are obtained, and the relevant physical performance data of the α -alumina carriers prepared in the embodiment are shown in table 1.
Comparative example 1:
480.0g surge alundum, 120.0g boehmite, 11.0g ammonium fluoride and 3.0g barium sulfate are weighed and put into a mixer to be mixed uniformly, the mixture is transferred into a kneader, dilute nitric acid (nitric acid: water 1: 3, volume ratio) is added until the mixture is kneaded into paste which can be extruded and formed, the paste is put into a strip extruder to be extruded into a seven-hole column, the seven-hole column is dried for more than 24h at the temperature of 60-120 ℃ to reduce the free water content to below 10 percent, then the dried seven-hole column is put into a natural gas kiln to be calcined, the calcination temperature is 1350 ℃, the constant temperature calcination is carried out for 25h, and finally the mixture is cooled to room temperature, so that α -alumina carrier prepared by the comparative example is obtained, and the relevant physical property data of the α -alumina carrier prepared by the comparative example are shown in table 1.
TABLE 1 α gallium content in alumina support and associated physical properties
| Sample source | Ga content (%) | Specific surface area (m)2/g) | Crush strength (N/grain) | Water absorption (%) |
| Example 1 | 0.21 | 1.41 | 194 | 52.0 |
| Example 2 | 1.02 | 1.53 | 212 | 51.6 |
| Example 3 | 2.63 | 4.80 | 178 | 52.1 |
| Example 4 | 0.93 | 2.43 | 223 | 51.7 |
| Comparative example 1 | 0 | 0.94 | 101 | 52.3 |
As can be seen by comparing the data in table 1, the addition of a certain amount of gallium-containing compound in the preparation of the support can significantly improve the specific surface area of the α -alumina support.
The results of catalyst activity and selectivity tests on the silver catalyst prepared by the carrier prepared in the above embodiment show that the silver catalyst prepared by the carrier shows good selectivity and reaction activity in olefin epoxidation reaction, selective hydrogenation of alkyne and diene, methane reforming and other reactions.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (28)
1. An α -alumina carrier containing gallium, the preparation method of the carrier comprises:
step A, mixing alumina trihydrate, alumina monohydrate, a gallium-containing compound and an optional alkaline earth metal compound and/or fluoride to obtain a solid mixture;
step B, adding a binder and water into the solid mixture to obtain α -alumina precursor mixture;
step C, kneading, molding, drying and roasting the α -alumina precursor mixture to prepare a α -alumina carrier,
wherein, in the carrier, the mass content of the gallium element is 0.02-5.00%.
2. The carrier according to claim 1, wherein the carrier contains gallium in an amount of 0.05 to 5.00% by mass.
3. The carrier according to claim 1 or 2, wherein the carrier has a specific surface of 1.0-50.0m2/g。
4. The carrier according to claim 3, wherein the carrier has a specific surface of 1.5-10.0m2/g。
5. The carrier according to claim 3, wherein the water absorption of the carrier is equal to or greater than 30%.
6. The carrier of claim 5, wherein the water absorption of the carrier is 40% -70%.
7. The carrier according to claim 3, wherein the crush strength of the carrier is 30-300N/pellet.
8. The carrier as claimed in claim 3, wherein the mass content of α -alumina in the carrier is not less than 85%.
9. The carrier according to claim 1, wherein the alumina trihydrate content in the solid mixture is between 20% and 90% by mass.
10. The support of claim 9, wherein the alumina trihydrate comprises gibbsite and/or trim flash.
11. The carrier according to claim 9, wherein the mass content of the alumina monohydrate in the solid mixture is 5% to 50%.
12. The carrier of claim 11 wherein the alumina monohydrate comprises boehmite and/or diaspore.
13. The carrier according to claim 1, wherein the gallium-containing compound is present in the solid mixture in an amount of 0.02-40.00% by mass.
14. The carrier according to claim 13, wherein the gallium-containing compound comprises one or more of a gallium-containing oxide, a gallium-containing hydroxide, and a gallium-containing salt.
15. The carrier according to claim 14, wherein the gallium-containing salt comprises one or more of gallium chloride, gallium sulfate, gallium nitrate, gallium phosphide and gallium phosphate.
16. The carrier according to claim 1, wherein the solid mixture contains 0 to 3.50% by mass of the alkaline earth metal compound.
17. The carrier according to claim 16, wherein the alkaline earth metal compound comprises one or more of an oxide, nitrate, sulphate, carbonate, oxalate and chloride of an alkaline earth metal.
18. The carrier of claim 17 wherein the alkaline earth metal comprises magnesium and/or barium.
19. The carrier according to claim 16, wherein the fluoride content of the solid mixture is 0-6.0% by mass.
20. The support of claim 19, wherein the fluoride comprises one or more of hydrogen fluoride, ammonium fluoride, magnesium fluoride, and lithium fluoride.
21. The carrier of claim 1 wherein the weight ratio of binder to water is 1 (1-10); the binder comprises one or more of citric acid, nitric acid, formic acid, acetic acid, propionic acid, and hydrochloric acid.
22. The carrier according to claim 1, wherein in step C, the temperature of drying is 20-120 ℃.
23. The carrier of claim 22 wherein in step C, the drying time is 24-48 hours.
24. The carrier of claim 1, wherein in step C, the firing comprises programmed temperature and constant temperature firing processes.
25. The carrier as claimed in claim 24, wherein the temperature of the constant temperature calcination in step C is 1000-1600 ℃.
26. The carrier as claimed in claim 25, wherein in step C, the temperature of the constant temperature calcination is 1100-1500 ℃.
27. The carrier of claim 24, wherein in the step C, the constant temperature roasting time is 10-30 h.
28. Use of a carrier according to any one of claims 1 to 27 in olefin epoxidation reactions, selective hydrogenation of acetylenes and dienes, and methane reforming reactions.
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|---|---|---|---|---|
| CN1915485A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Alumina of containing additive |
| CN104525196A (en) * | 2014-12-11 | 2015-04-22 | 天津大学 | Platinum-gallium catalyst loaded on double-oxide composite carrier as well as preparation method and application of platinum-gallium catalyst |
| CN105435792A (en) * | 2014-08-12 | 2016-03-30 | 中国石油化工股份有限公司 | Alumina carrier, preparation method and silver catalyst |
| CN106622195A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alpha- alumina supporter and preparation method thereof and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915485A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Alumina of containing additive |
| CN105435792A (en) * | 2014-08-12 | 2016-03-30 | 中国石油化工股份有限公司 | Alumina carrier, preparation method and silver catalyst |
| CN104525196A (en) * | 2014-12-11 | 2015-04-22 | 天津大学 | Platinum-gallium catalyst loaded on double-oxide composite carrier as well as preparation method and application of platinum-gallium catalyst |
| CN106622195A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alpha- alumina supporter and preparation method thereof and application |
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