CN107413388A - A kind of alpha-aluminium oxide carrier and preparation method and application - Google Patents
A kind of alpha-aluminium oxide carrier and preparation method and application Download PDFInfo
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- CN107413388A CN107413388A CN201610344875.2A CN201610344875A CN107413388A CN 107413388 A CN107413388 A CN 107413388A CN 201610344875 A CN201610344875 A CN 201610344875A CN 107413388 A CN107413388 A CN 107413388A
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- carrier
- alpha
- gallium
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- 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 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000008247 solid mixture Substances 0.000 claims abstract description 28
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002259 gallium compounds Chemical class 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 229910001679 gibbsite Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 9
- 230000001404 mediated effect Effects 0.000 claims abstract description 7
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 6
- 150000001993 dienes Chemical class 0.000 claims abstract description 6
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 6
- 238000006057 reforming reaction Methods 0.000 claims abstract description 5
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004575 stone Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 7
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- 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 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 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
- 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000007493 shaping process Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 230000036314 physical performance Effects 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241001269238 Data Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 2
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 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
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of alpha-aluminium oxide carrier and preparation method and application.The present invention adds a certain amount of auxiliary agent containing gallium compound in carrier preparation process, and gallium element mass content is 0.02% 15.00% in carrier.Specifically preparation process is：Mixed by gibbsite, boehmite, containing gallium compound and optional alkaline earth metal compound and/or fluoride, obtain solid mixture, binding agent and water are added into solid mixture, obtain alpha-aluminium oxide precursor mixture, the precursor mixture is mediated, is molded, is dried, roasting, finally obtained alpha-aluminium oxide carrier.Catalyst carrier obtained by the present invention can be applied in the selective hydrogenation and methane reforming reaction of epoxidation reaction of olefines, alkynes and alkadienes.
Description
Technical field
The invention belongs to catalyst carrier technical field, is related to a kind of alpha-alumina supports and preparation method and application.
Background technology
Alumina material is always one of emphasis and hot research object in the field such as material science and catalysis, and it is in essence
The fields such as fine ceramic, composite, adsorbing separation, catalysis obtain very big progress.Particularly in petrochemical industry catalytic field, no
The alumina support of similar shape has a wide range of applications in terms of catalysis oxidation, catalytic hydrogenation.Alumina support has to catalyst
Very important effect, such as：Improve active component dispersiveness, reduce active component dosage, increase effectively than surface, improvement
Heat endurance of catalyst etc., the performance of alumina support is one of key factor of performance of catalyst.
There are a variety of crystalline phases in aluminum oxide, wherein common are γ, δ, κ, η, θ, α etc..α phases are stable phases in these phases,
Remaining is metastable phase.In current commercial Application, the technology hand of alpha-alumina supports is prepared by being calcined aluminium hydroxide presoma
Section is more universal.In presoma roasting process, the amorphous alumina of generation changes to metastable phase alumina, and this process belongs to
Non-lattice reforming process, then be calcined by sufficiently high temperature, these metastable phase aluminas can be transformed into Alpha-alumina.This
In high-temperature calcination process, agglomeration phenomenon occurs in alumina particle, causes the specific surface area of alpha-alumina supports prepared
Drastically reduce.Result of study shows that the addition of some auxiliary agents or carrier post-process the specific surface area that can improve alpha-alumina supports.
Patent CN103566980A is disclosed and a certain amount of silicon or silicon-containing compound is introduced in carrier preparation process, the ratio of resulting vehicle
Surface area and intensity are improved, and preparing oxirane for ethylene are energy by silver catalyst prepared by the modified support
Significantly improve the activity of silver catalyst.Patent CN104707665A discloses a kind of alumina support, and it is included siliceous α-oxygen
Change alumina supporter to be handled using acid compound, acid compound processing can improve the specific surface area of carrier, by the modification
Silver catalyst made of obtained alumina support, good activity is shown during ethylene produces oxirane
And selectivity.
The content of the invention
An object of the present invention is to provide a kind of alpha-alumina supports, and it uses support modification unlike the prior art
Method is made, and it not only has suitable crushing strength, water absorption rate, and with higher compared with carrier made from prior art
Specific surface area, it is possible thereby to improve dispersiveness of the catalyst activity component on carrier, and then improve the catalytic performance of catalyst.
The second object of the present invention is to provide a kind of preparation method of above-mentioned alpha-alumina supports.
The third object of the present invention is to provide a kind of purposes of above-mentioned alpha-alumina supports.
Therefore, first aspect present invention provides a kind of alpha-alumina supports, it contains gallium element.
According to the present invention, in the carrier, the mass content of gallium element is 0.02%-15.00%；Preferably
0.02%-5.00%；More preferably 0.05%-5.00%.
In some embodiments of the invention, the ratio surface of the carrier is 1.0-50.0m2/ g, preferably 1.5-
10.0m2/g；Water absorption rate >=30% of the carrier, preferably 40%-70%；The crushing strength of the carrier is 30-300N/
Grain.
In other embodiments of the present invention, mass content >=85% of Alpha-alumina in the carrier.
Second aspect of the present invention provides a kind of preparation method of carrier described in first aspect present invention, including：
Step A, by gibbsite, a water aluminum oxide, containing gallium compound and optional alkaline earth metal compound and/or
Fluoride mixes, and obtains solid mixture；
Step B, binding agent and water are added into solid mixture, obtains Alpha-alumina precursor mixture；
Step C, Alpha-alumina precursor mixture is mediated, is molded, is dried, roasting, alpha-alumina supports are made.
According to the inventive method, the mass content of gibbsite is 20%-90% in the solid mixture.
In the present invention, preferably described gibbsite includes gibbsite and/or surge aluminium stone.
According to the inventive method, the mass content of a water aluminum oxide is 5%-50% in the solid mixture.
In the present invention, preferably described water aluminum oxide includes boehmite and/or diaspore.
According to the inventive method, the mass content containing gallium compound is 0.02%-40.00% in the solid mixture.
It is preferably described to include containing gallium compound containing one kind in gallium oxide, hydroxide containing gallium, salt containing gallium in the present invention
It is or a variety of.
In some embodiments of the invention, the salt containing gallium includes gallium chloride, gallium sulfate, gallium nitrate, gallium phosphide and phosphorus
One or more in sour gallium.
It is described to include but is not limited to gallium oxide containing gallium oxide in the present invention.
In the present invention, the hydroxide containing gallium includes but is not limited to gallium hydroxide.
According to the inventive method, the mass content of alkaline earth metal compound is 0-3.50% in the solid mixture.
In some embodiments of the invention, preferably described alkaline earth metal compound includes oxide, the nitre of alkaline-earth metal
One or more in hydrochlorate, sulfate, carbonate, oxalates and chloride.In the present invention, preferably alkaline-earth metal includes magnesium
And/or barium.
According to the inventive method, the mass content of fluoride is 0-6.0% in the solid mixture.
In some embodiments of the invention, the fluoride is included in hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride
It is one or more.
According to the inventive method, the weight ratio of the binding agent and water is 1:(1-10).
In some embodiments of the invention, the binding agent includes citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid
In one or more.
In some embodiments of the invention, in step C, the temperature of the drying is 20-120 DEG C.
In other embodiments of the present invention, in step C, the time of the drying is 24-48h.
According to certain embodiments of the present invention, in step C, the roasting includes temperature programming and constant temperature calcining mistake
Journey.In some embodiments of the invention, the temperature of the constant temperature calcining is 1000-1600 DEG C, preferably described constant temperature calcining
Temperature is 1100-1500 DEG C；It is preferred that the time of the constant temperature calcining is 10-30h.
Third aspect present invention is provided described in carrier or second aspect of the present invention described in a kind of first aspect present invention
The carrier that is prepared of method in the selective hydrogenation and methane reforming reaction of epoxidation reaction of olefines, alkynes and alkadienes
Application.
Embodiment
To be readily appreciated that the present invention, the present invention is described more detail below.
In order to improve the performance of alpha-alumina supports, the present inventor has done substantial amounts of research for alpha-alumina supports, this
Inventor has found a certain amount of to contain gallium compound, the alpha-oxidation being prepared by adding in alpha-alumina supports preparation process
Alumina supporter not only has suitable crushing strength, water absorption rate, and the specific surface area of carrier can be significantly improved.Catalyst carries
The raising of surface area per unit volume product is expected to improve dispersiveness of the catalyst activity component on carrier, and then improves the catalytic of catalyst
Energy.The present invention is based on what above-mentioned discovery was made.
Therefore, the alpha-alumina supports involved by first aspect present invention are by alpha-alumina supports preparation process
Add it is a certain amount of be made containing gallium compound, it has following feature as the carrier of support type：The quality of gallium element in carrier
Content is 0.02%-15.00%, preferably 0.02%-5.00%, more preferably 0.05%-5.00%, or even more excellent
Select 0.21%-5.00%；Mass content >=85% of Alpha-alumina in carrier；It is 1.0-50.0m than surface2/ g, it is preferably
1.5-10.0m2/ g, more preferably 2.43-10.0m2/g；Water absorption rate is >=30%, preferably 40%-70%, further excellent
Elect 51.6%-70% as；Crushing strength is 30-300N/ grains, preferably 178-300N/ grains.
The preparation method of alpha-alumina supports involved by second aspect of the present invention comprises the following steps：
Step A, by gibbsite, a water aluminum oxide, containing gallium compound and optional alkaline earth metal compound and/or
Fluoride mixes, and obtains solid mixture；
Step B, binding agent and water are added into solid mixture, obtains Alpha-alumina precursor mixture；
Step C, Alpha-alumina precursor mixture is mediated, is molded, is dried, roasting, alpha-alumina supports are made.
In the preparation method of alpha-alumina supports of the present invention, described gibbsite and a water aluminum oxide are as silicon source
It is transformed into Alpha-alumina after roasting.The gibbsite includes gibbsite and/or surge aluminium stone, its quality account for the solid and mixed
The 20%-90% of compound gross mass.The one water aluminum oxide includes boehmite and/or diaspore, and its quality accounts for institute
State the 5%-50% of solid mixture gross mass.
In order to improve the specific surface area of alpha-alumina supports, the present invention with the addition of in the preparation method of alpha-alumina supports
Containing gallium compound, its quality accounts for the 0.02%-40.00% of the solid mixture gross mass.
It is described to include containing gallium compound containing one kind in gallium oxide, hydroxide containing gallium, salt containing gallium or more in the present invention
Kind.In some embodiments of the invention, for example, the salt containing gallium includes gallium chloride, gallium sulfate, gallium nitrate, gallium phosphide and phosphorus
One or more in sour gallium.It is described to include but is not limited to gallium oxide containing gallium oxide in other embodiments of the present invention.
In the other embodiment of the present invention, the hydroxide containing gallium includes but is not limited to gallium hydroxide.
In the preparation method of alpha-alumina supports of the present invention, the addition of alkaline earth metal compound can improve carrying alumina
The mechanical strength of body.The alkaline earth metal compound includes oxide, nitrate, sulfate, carbonate, the oxalic acid of alkaline-earth metal
One or more in salt and chloride, its quality account for the 0-3.50% of the solid mixture gross mass.In the present invention, preferably
Alkaline-earth metal includes magnesium and/or barium.
In the present invention, fluoride can promote transformation of the transition aluminas to Alpha-alumina in roasting process, eliminate
Unnecessary micropore, reduce by less than 0.1 μm of pore.The fluoride is included in hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride
One or more, its quality accounts for the 0-6.0% of the solid mixture gross mass.
According to certain embodiments of the present invention, in the preparation method of above-mentioned alpha-alumina supports, the solid mixture
In, in addition to above-mentioned various ingredients, thermal decomposition burnout materials can also be included.The thermal decomposition burnout materials include poly- second
One or more in alkene, polypropylene, petroleum coke, carbon dust and graphite, its quality account for the 0- of the solid mixture gross mass
20.0%.
In the preparation method of alpha-alumina supports of the present invention, the effect of binding agent in the water in solid, powdery thing
Aluminum oxide generates Alumina gel, and each component is bonded together, turns into the paste of extrudable shaping.The binding agent and water
Mass ratio be 1:(1-10)；The binding agent includes one kind or more in citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid
Kind.
The dosage of binding agent is had no particular limits in the present invention, its dosage is with can be with the water in solid mixture
Aluminum oxide generation Alumina gel to form the paste of extrudable shaping and be defined so as to be glued together with each component.
It need not be added in order between solid mixture and the addition of binder solution in the present invention, such as solid mixing
Fluoride in thing can be just added in solid mixture together with binder solution finally.
In order to which precursor mixture is well mixed, the present invention is mediated precursor mixture, is mediated in kneader
Carry out, kneading time 5-90min.After precursor mixture is mediated fully, carrier can be made to definite shape, including ball
Shape, block shape, cylinder, Round Porous cylindricality, Rasching ring, cloverleaf pattern, honeycombed etc., described is molded in forming machine
OK.
After precursor mixture shaping, article shaped is dried, the drying is carried out at 20-120 DEG C, will be contained in article shaped
Water rate control is below 10%；In some embodiments of the invention, for example, the time of the drying can be 24-48h.
According to certain embodiments of the present invention, for the ease of extrusion molding thing, can be added in solid mixture into
Type auxiliary agent, shaping assistant include the one or more in vaseline, graphite, paraffin and vegetable oil.
In order to obtain the alpha-alumina supports with proper characteristics, dried article shaped is calcined by the present invention.The roasting
Have a swollen head and include temperature programming and constant temperature calcining process, the temperature of the constant temperature calcining is 1000-1600 DEG C, preferably described constant temperature calcining
Temperature be 1100-1500 DEG C；The time of constant temperature calcining is 10-30h, and the time of preferably described constant temperature calcining is 10-25h.
Term of the present invention " optionally " refers to contain or not contain, and also refers to add or is added without.
" water " one word of the present invention, in the case of no particularly specified or explanation, refer to deionized water, distilled water
With the one or more in ultra-pure water.
Heretofore described term " containing gallium compound " refers to the compound containing gallium element.
Heretofore described term " fluorochemical " refers to the compound containing fluorine element.
The present invention a certain amount of not only has by being added in preparation process containing alpha-alumina supports made from gallium compound
There are suitable crushing strength, water absorption rate, and specific surface area is also significantly greater than alpha-alumina supports made from prior art, thus may be used
To improve dispersiveness of the catalyst activity component on carrier, and then improve the catalytic performance of catalyst.The inventive method has
It is simple to operate, pollution it is small the advantages that.Alpha-alumina supports obtained by the present invention can apply to epoxidation reaction of olefines, alkynes
And in the selective hydrogenation of alkadienes, methane reforming reaction.
Embodiment
To make the present invention easier to understand, the present invention is further described below in conjunction with embodiment, these realities
Apply example only serve it is illustrative, it is not limited to application of the invention.
The detection method of the physical property of alpha-alumina supports is as follows in the present invention：
The specific surface area of carrier is determined according to international test standards ISO-9277 using nitrogen physisorption BET methods.Example
Such as, the specific surface area of U.S. Kang Ta companies NOVA2000e type nitrogen physisorptions instrument measure carrier can be used.
The side pressure strength of carrier, it is for instance possible to use Dalian Chemical Research ＆. Design Inst.'s production DL II type intelligence granule strengths are surveyed
Determine instrument, randomly select 30 support samples, average to obtain after determining radial direction crushing strength.
Term " water absorption rate " used refers to the volume of the carrier saturation absorption water of unit mass in the present invention, and unit is mL/
g.Its assay method is as follows：A certain amount of carrier is weighed first (it is assumed that its quality is m1), carrier is taken out after 1h is boiled in boiling water
It is erected on the moderate wet gauze of water content and removes the unnecessary moisture of carrier surface, finally weighs the quality of the carrier after absorption water
(it is assumed that m2), as follows calculate carrier water absorption rate.
Wherein ρWaterIt is the density of water under measurement temperature, atmospheric pressure.
Embodiment 1：
Weigh the surge aluminium stones of 480.0g, 120.0g boehmites, 11.0g ammonium fluorides, 3.0g barium sulfate, 1.5g hydroxides
Gallium, it is put into blender and is well mixed, be transferred in kneader, adds dust technology (nitric acid：Water=1：3, volume ratio) until pinching
The paste of extrudable shaping is synthesized, is pasted placed into banded extruder, is extruded into seven apertures in the human head column, is dried at 60-120 DEG C
More than 24h, free water content is reduced to less than 10%, then dried seven apertures in the human head column is put into natural gas kiln and roasted
Burn, sintering temperature is 1350 DEG C, constant temperature calcining 25h, is finally cooled to room temperature, obtains alpha-alumina supports.It is prepared by the embodiment
The related physical performance datas of alpha-alumina supports be shown in Table 1.
Embodiment 2：
Weigh the surge aluminium stones of 480.0g, 120.0g boehmites, 11.0g ammonium fluorides, 3.0g barium sulfate, 15.0g hydroxides
Gallium, it is put into blender and is well mixed, be transferred in kneader, adds dust technology (nitric acid：Water=1：3, volume ratio) until pinching
The paste of extrudable shaping is synthesized, is pasted placed into banded extruder, is extruded into seven apertures in the human head column, is dried at 60-120 DEG C
More than 24h, free water content is reduced to less than 10%, then dried seven apertures in the human head column is put into natural gas kiln and roasted
Burn, sintering temperature is 1300 DEG C, constant temperature calcining 25h, is finally cooled to room temperature, obtains alpha-alumina supports.It is prepared by the embodiment
The related physical performance datas of alpha-alumina supports be shown in Table 1.
Embodiment 3：
The surge aluminium stones of 480.0g, 120.0g boehmites, 11.0g ammonium fluorides, 3.0g barium sulfate, 25.0g phosphoric acid galliums are weighed,
It is put into blender and is well mixed, be transferred in kneader, adds dust technology (nitric acid：Water=1：3, volume ratio) until being kneaded into
The paste of extrudable shaping, is pasted placed into banded extruder, is extruded into seven apertures in the human head column, at 60-120 DEG C dry 24h with
On, free water content is reduced to less than 10%, dried seven apertures in the human head column is then put into natural gas kiln kiln roasting, roast
It is 1100 DEG C to burn temperature, constant temperature calcining 10h, is finally cooled to room temperature, obtains alpha-alumina supports.α-oxygen prepared by the embodiment
The related physical performance data for changing alumina supporter is shown in Table 1.
Embodiment 4：
Weigh the surge aluminium stones of 480.0g, 120.0g boehmites, 11.0g ammonium fluorides, 3.0g barium sulfate, 6.5g hydroxides
Gallium, it is put into blender and is well mixed, be transferred in kneader, adds dust technology (nitric acid：Water=1：3, volume ratio) until pinching
The paste of extrudable shaping is synthesized, is pasted placed into banded extruder, is extruded into seven apertures in the human head column, is dried at 60-120 DEG C
More than 24h, free water content is reduced to less than 10%, then dried seven apertures in the human head column is put into natural gas kiln and roasted
Burn, sintering temperature is 1200 DEG C, constant temperature calcining 20h, is finally cooled to room temperature, obtains alpha-alumina supports.It is prepared by the embodiment
The related physical performance datas of alpha-alumina supports be shown in Table 1.
Comparative example 1：
The surge aluminium stone aluminium stones of 480.0g, 120.0g boehmites, 11.0g ammonium fluorides, 3.0g barium sulfate are weighed, is put into batch mixing
It is well mixed, is transferred in kneader in device, adds dust technology (nitric acid：Water=1：3, volume ratio) until be kneaded into it is extrudable into
The paste of type, is pasted placed into banded extruder, is extruded into seven apertures in the human head column, and more than 24h is dried at 60-120 DEG C, makes to dissociate
Water content is reduced to less than 10%, and dried seven apertures in the human head column then is put into natural gas kiln kiln roasting, and sintering temperature is
1350 DEG C, constant temperature calcining 25h, room temperature is finally cooled to, obtains alpha-alumina supports.Alpha-alumina supports prepared by the comparative example
Related physical performance data be shown in Table 1.
Gallium content and related physical performance in the alpha-alumina supports of table 1
| Sample source | Ga contents (%) | Specific surface area (m2/g) | Crushing strength (N/ grains) | Water absorption rate (%) |
| Embodiment 1 | 0.21 | 1.41 | 194 | 52.0 |
| Embodiment 2 | 1.02 | 1.53 | 212 | 51.6 |
| Embodiment 3 | 2.63 | 4.80 | 178 | 52.1 |
| Embodiment 4 | 0.93 | 2.43 | 223 | 51.7 |
| Comparative example 1 | 0 | 0.94 | 101 | 52.3 |
By the data in contrast table 1 can be seen that carrier preparation in a certain amount of addition containing gallium compound can
Significantly improve the specific surface area of alpha-alumina supports.
To carrying out catalyst activity and selectivity experiment, knot by the silver catalyst that in above-described embodiment prepared by prepared carrier
Fruit shows by the selective hydrogenation of silver catalyst prepared by above-mentioned carrier in epoxidation reaction of olefines, alkynes and alkadienes, methane
Good selectivity, reactivity are shown in the reaction such as reformation.It can be seen that the alpha-alumina supports obtained by the present invention can be with
In selective hydrogenation, methane reforming reaction applied to epoxidation reaction of olefines, alkynes and alkadienes.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (11)
1. a kind of alpha-alumina supports, it contains gallium element.
2. carrier according to claim 1, it is characterised in that in the carrier, the mass content of gallium element is
0.02%-15.00%；Preferably 0.02%-5.00%；More preferably 0.05%-5.00%.
3. carrier according to claim 1 or 2, it is characterised in that the ratio surface of the carrier is 1.0-50.0m2/ g, it is excellent
Elect 1.5-10.0m as2/g；It is preferred that water absorption rate >=30% of the carrier, the water absorption rate of the further preferred carrier is 40%-
70%；It is preferred that the crushing strength of the carrier is 30-300N/ grains；It is preferred that in the carrier Alpha-alumina mass content >=
85%.
4. the preparation method of carrier described in any one in a kind of claim 1-3, including：
Step A, by gibbsite, a water aluminum oxide, containing gallium compound and optional alkaline earth metal compound and/or fluorination
Thing mixes, and obtains solid mixture；
Step B, binding agent and water are added into solid mixture, obtains Alpha-alumina precursor mixture；
Step C, Alpha-alumina precursor mixture is mediated, is molded, is dried, roasting, alpha-alumina supports are made.
5. preparation method according to claim 4, it is characterised in that the quality of gibbsite in the solid mixture
Content is 20%-90%；It is preferred that the gibbsite includes gibbsite and/or surge aluminium stone；It is preferred that the solid mixture
In the mass content of a water aluminum oxide be 5%-50%；It is preferred that the water aluminum oxide includes boehmite and/or a hydraulic
Aluminium stone.
6. the preparation method according to claim 4 or 5, it is characterised in that containing gallium compound in the solid mixture
Mass content is 0.02%-40.00%；It is preferred that described include containing gallium oxide, hydroxide containing gallium and containing gallium containing gallium compound
One or more in salt；Further preferably described salt containing gallium includes gallium chloride, gallium sulfate, gallium nitrate, gallium phosphide and phosphoric acid gallium
In one or more.
7. according to the preparation method described in any one in claim 4-6, it is characterised in that alkaline earth in the solid mixture
The mass content of metallic compound is 0-3.50%；It is preferred that the alkaline earth metal compound includes oxide, the nitre of alkaline-earth metal
One or more in hydrochlorate, sulfate, carbonate, oxalates and chloride；It is preferred that alkaline-earth metal includes magnesium and/or barium；It is excellent
The mass content for selecting fluoride in the solid mixture is 0-6.0%；It is preferred that the fluoride include hydrogen fluoride, ammonium fluoride,
One or more in magnesium fluoride and lithium fluoride.
8. according to the preparation method described in any one in claim 4-7, it is characterised in that the weight of the binding agent and water
Than for 1:(1-10)；The binding agent includes the one or more in citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid.
9. according to the preparation method described in any one in claim 4-8, it is characterised in that in step C, the drying
Temperature is 20-120 DEG C；It is preferred that the time of the drying is 24-48h.
10. according to the preparation method described in any one in claim 4-9, it is characterised in that in step C, the roasting
Including temperature programming and constant temperature calcining process；It is preferred that the temperature of the constant temperature calcining is 1000-1600 DEG C, preferably described constant temperature roasting
The temperature of burning is 1100-1500 DEG C；It is preferred that the time of the constant temperature calcining is 10-30h.
11. the carrier according to any one in claim 1-3 or the method system according to any one of right 4-10
Application of the standby obtained carrier in the selective hydrogenation and methane reforming reaction of epoxidation reaction of olefines, alkynes and alkadienes.
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| 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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| 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 |
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| CN114433044A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof |
| CN114433044B (en) * | 2020-11-05 | 2023-07-21 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof |
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