CN113649079B - Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof - Google Patents
Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof Download PDFInfo
- Publication number
- CN113649079B CN113649079B CN202010398288.8A CN202010398288A CN113649079B CN 113649079 B CN113649079 B CN 113649079B CN 202010398288 A CN202010398288 A CN 202010398288A CN 113649079 B CN113649079 B CN 113649079B
- Authority
- CN
- China
- Prior art keywords
- acid
- hydrogenation
- ball milling
- drying
- aluminum oxide
- 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.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 98
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000000197 pyrolysis Methods 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical group 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 2
- 239000011707 mineral Substances 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 24
- 238000009826 distribution Methods 0.000 abstract description 13
- 239000010936 titanium Substances 0.000 abstract description 11
- 229910052719 titanium Inorganic materials 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 description 53
- 239000000243 solution Substances 0.000 description 21
- 238000012512 characterization method Methods 0.000 description 20
- 239000003223 protective agent Substances 0.000 description 18
- 238000013507 mapping Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000009827 uniform distribution Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/638—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof
Abstract
The invention discloses a titanium oxide-aluminum oxide composite carrier, a preparation method and application thereof. The preparation method of the titanium oxide-aluminum oxide composite carrier comprises the following steps: (1) Mixing aluminum oxide, meta-titanic acid and a solvent to obtain a mixture I; (2) Performing high-energy ball milling on the mixture I to obtain a mixture II with the median particle diameter smaller than 0.1 mu m; (3) And (3) drying the mixture II, mixing the obtained dried product with acid liquor, and sequentially forming, drying and roasting. The titanium source used by the preparation method has low cost, less pollution in the preparation process, and the TiO in the obtained titanium oxide-aluminum oxide composite carrier 2 And the distribution is uniform.
Description
Technical Field
The invention belongs to the field of composite oxides, and particularly relates to a titanium oxide-aluminum oxide composite carrier, and a preparation method and application thereof.
Background
TiO 2 The hydrogenation catalyst developed as carrier has the characteristics of high activity, good low-temperature activity, strong anti-middle toxicity and the like, but the TiO 2 As a catalyst support, there are also disadvantages such as relatively small specific surface area, easy conversion of active anatase into inert rutile structure at high temperature, poor mechanical strength and weak acidity, generally by formation of TiO 2 -Al 2 O 3 The composite oxide is used as a carrier to overcome the defects and reach the standard of industrial application. Conventional industrial production of TiO-containing materials 2 The method for preparing the composite carrier comprises an impregnation method, a coprecipitation method and a kneading method, wherein the impregnation method adopts titanium organic matters such as tetraethyl titanate, tetrabutyl titanate and the like as active components to impregnate formed aluminum oxide, and the organic matters coprecipitation method can adopt titanium chloride or meta-titanic acid dissolved by concentrated sulfuric acid as a titanium source, and the methods need expensive organic titanium sources or pre-treatment of the meta-titanic acid with concentrated acid and/or concentrated alkali, so that the problems of pipeline and container corrosion can occur, and anions which have influence on subsequent production can be generated, so that the production cost is high and pollution is discharged. Method for preparing TiO-containing material by kneading 2 The TiO in the composite carrier can appear with the increase of the content of the meta-titanic acid 2 The problem of uneven distribution is that the surface activity of the carrier is inferior to that of the catalyst prepared by an impregnation method or a coprecipitation method, so that the hydrogenation activity and stability of the catalyst under the high space velocity condition are affected.
Thus, the titanium source is expensive, the pipelines and the containers are corroded, pollutants are generated and TiO in the titanium oxide-aluminum oxide composite carrier exists in the prior art 2 Uneven distribution and thus affects hydrogenation activity and stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a titanium oxide-aluminum oxide composite carrier, a preparation method and application thereof, and the titanium source used in the preparation method has low cost, thereby reducing the preparation costThe cost, the pollution in the preparation process and the equipment requirement are low, and the TiO in the obtained titanium oxide-aluminum oxide composite carrier 2 The titanium oxide-aluminum oxide composite carrier has the advantages of uniform distribution, high hydrogenation activity and good stability.
To this end, a first aspect of the present invention provides a method for preparing a titania-alumina composite support, comprising:
(1) Mixing aluminum oxide, meta-titanic acid and a solvent to obtain a mixture I;
(2) Performing high-energy ball milling on the mixture I to obtain a mixture II with the median particle diameter smaller than 0.1 mu m;
(3) And (3) drying the mixture II, mixing the obtained dried product with acid liquor, and sequentially forming, drying and roasting.
According to some embodiments of the preparation method of the present invention, the mixing sequence of the alumina, the meta-titanic acid and the solvent is preferably added to the solvent and mixed after the alumina and the meta-titanic acid are mixed for the purpose of being able to be sufficiently mixed.
According to some embodiments of the preparation method of the present invention, the specific surface area of the alumina is 150-300m 2 And/g. For example 150m 2 /g、160m 2 /g、170m 2 /g、180m 2 /g、190m 2 /g、200m 2 /g、210m 2 /g、220m 2 /g、230m 2 /g、240m 2 /g、250m 2 /g、260m 2 /g、270m 2 /g、280m 2 /g、290m 2 /g、300m 2 And/g, and any value between any two of the above values.
According to some embodiments of the preparation method of the present invention, the alumina has a pore volume of 0.6-1.2mL/g, preferably 0.8-1mL/g. Such as 0.8mL/g, 0.9mL/g, 1mL/g, and any value between any two of the foregoing.
According to some embodiments of the preparation method of the present invention, the alumina is a powder, i.e., an alumina powder.
According to some embodiments of the preparation method of the present invention, the weight ratio of alumina to meta-titanic acid is (5-10): 1, preferably (5-7): 1.
according to some embodiments of the preparation method of the present invention, the weight ratio of the total weight of alumina and meta-titanic acid to the solvent is 5: (1-5).
According to some embodiments of the preparation method of the present invention, the solvent may be any solvent capable of sufficiently dissolving alumina and meta-titanic acid, and preferably, the solvent is one or more of deionized water, ethanol, and methanol.
According to some embodiments of the preparation method of the present invention, the conditions of the high energy ball milling include: the time is 6-10h, the revolution speed of the ball mill is 30-350r/min, and the rotation speed of the ball mill is 70-670r/min. The time, revolution speed and rotation speed of the ball mill are aimed at enabling to obtain a mixture II with a median particle diameter smaller than 0.1 μm.
According to some embodiments of the preparation method of the present invention, the high-energy ball milling is stirring ball milling, vibration ball milling or planetary ball milling, more preferably planetary ball milling. The above-mentioned high-energy ball milling apparatus may be a high-energy ball mill such as a stirred ball mill, a vibratory ball mill or a planetary ball mill, and more preferably a planetary ball mill.
According to some embodiments of the methods of preparation of the present invention, the drying conditions include: the temperature is 110-150deg.C, preferably 110-130deg.C, and the time is 2-16 hr, preferably 3-12 hr. The drying conditions are aimed at being able to evaporate the water in the mixture II. In the present invention, the drying apparatus may be an oven conventional in the art.
According to some embodiments of the method of preparation of the invention, the acid solution comprises a solute and a solvent. Further preferably, the solute in the acid solution is an organic acid and/or an inorganic acid; and/or the solvent in the acid liquor is deionized water. Preferably, the concentration of solute in the acid solution is 0.5-4 wt%. For example 0.5 wt%, 1 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, and any value between any two of the above.
According to some embodiments of the preparation method of the present invention, the weight ratio of the acid solution to the dry product in terms of solvent is (1-4): 5, preferably (2-4): 5. "acid solution in solvent" refers to the solvent in acid solution.
According to some embodiments of the preparation method of the present invention, the organic acid is one or more of acetic acid, oxalic acid, citric acid, and tartaric acid; more preferably, the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, and more preferably nitric acid. For example, the acid solution is an aqueous nitric acid solution or an aqueous hydrochloric acid solution, and more preferably an aqueous nitric acid solution.
According to some embodiments of the method of preparation of the invention, the method of shaping is extrusion. The extrusion molding apparatus may be a screw extruder as is conventional in the art.
According to some embodiments of the method of the invention, the conditions of the drying include: the temperature is 110-150deg.C, preferably 110-130deg.C, and the time is 2-16 hr, preferably 3-12 hr. In the present invention, the drying apparatus may be an oven conventional in the art.
According to some embodiments of the method of preparation of the invention, the conditions of calcination include: the temperature is 500-900 ℃, preferably 550-800 ℃, and the time is 3-16h, preferably 4-12h. In the present invention, the roasting apparatus may be a muffle furnace conventional in the art.
The second aspect of the invention provides the titanium oxide-aluminum oxide composite carrier prepared by the method.
The titanium oxide-aluminum oxide composite carrier prepared by the method of the invention, and TiO in the carrier 2 And Al 2 O 3 The distribution is uniform, and the carrier can be characterized by SEM-Mapping by using a scanning electron microscope. The specific characterization method can be as follows: and (3) coating the ground sample on conductive adhesive, spraying metal on the surface of the sample by using an ion sputtering instrument, drying, spraying carbon on the sample before characterization, and characterizing the sample by using a QUANTA 200 scanning electron microscope of FEI company. The results of the characterization can be seen in FIGS. 1a and 1b, from FIGS. 1a and 1bThe titanium oxide-aluminum oxide composite carrier prepared by the invention has uniform distribution of aluminum atoms and titanium atoms (because the original image is a color image, the uniform distribution can be clearly seen, and the display effect is affected after the original image is set to be a black-white image).
The third aspect of the invention provides the application of the titanium oxide-aluminum oxide composite carrier and/or the titanium oxide-aluminum oxide composite carrier prepared according to the method in pyrolysis gasoline hydrogenation and DCC pyrolysis naphtha hydrogenation. The application in pyrolysis gasoline hydrogenation and DCC pyrolysis naphtha hydrogenation.
The term "DCC" as used herein refers to catalytic cracking. DCC cracked naphtha according to the present invention refers to cracked naphtha produced by catalytic cracking.
In one embodiment of the invention, the titanium oxide-aluminum oxide composite carrier is loaded with a first active component and a second active component to prepare the hydrogenation catalyst, wherein the first active component is molybdenum oxide, and the second active component is cobalt oxide and nickel oxide. Preferably, the first active component is present in an amount of from 12 to 20 wt% and the second active component is present in an amount of from 1 to 15 wt%, based on the total weight of the hydrogenation catalyst. Preferably, the content of cobalt oxide in the second active component is 0.5 to 14.5 wt.%, and the content of nickel oxide in the second active component is 0.5 to 14.5 wt.%. Application of the hydrogenation catalyst to C of pyrolysis gasoline 6 ～C 8 、C 9 ～C 10 The fraction hydrogenation process has the characteristics of good low-temperature activity, high hydrogenation activity at high airspeed and good stability.
According to one embodiment of the present invention, the preparation method of the hydrogenation catalyst includes: and impregnating the titanium oxide-aluminum oxide composite carrier with a compound containing a first active component and a compound containing a second active component, and drying and roasting to obtain the hydrogenation catalyst, wherein the first active component is molybdenum element, and the second active component is cobalt element and nickel element. Preferably, the compound containing the first active component is ammonium molybdate. Preferably, the compound containing the second active component is nickel nitrate and cobalt nitrate. Preferably, the drying conditions include: the temperature is 110-150deg.C, preferably 110-130deg.C, and the time is 2-16 hr, preferably 3-12 hr. Preferably, the roasting conditions include: the temperature is 500-900 ℃, preferably 550-800 ℃, and the time is 3-16h, preferably 4-12h.
And carrying out SEM-Mapping on the prepared hydrogenation catalyst for characterization. The results of the characterization can be shown in fig. 2a, 2b, 2c, 2d and 2e, from which it can be seen that the aluminum atoms, titanium atoms, molybdenum atoms, cobalt atoms and nickel atoms of the hydrogenation catalyst prepared by the present invention are uniformly distributed (because the original figure is a color chart, the uniform distribution can be clearly seen, and the display effect is affected after the original figure is set to a black-and-white chart).
According to a preferred embodiment of the present invention, the above hydrogenation catalyst is applied to C of pyrolysis gasoline 6 ～C 8 、C 9 ～C 10 In the distillate hydrogenation process. Before the hydrogenation reaction, the hydrogenation catalyst needs to be vulcanized, and the vulcanization method can be a method conventional in the art, for example, at the temperature of a reactor of 280-350 ℃, the volume ratio of hydrogen to oil is 100-200:1, a cyclohexane solution with the DMDS (dimethyl disulfide) content of 1-5 weight percent is used, and the volume space velocity is 1-2h -1 Vulcanizing for 10-24h, and reducing the temperature to room temperature after vulcanizing.
Preferably, the hydrogenation catalyst is applied to C of pyrolysis gasoline 6 -C 8 When the fraction is hydrogenated, the inlet temperature of the reactor is 220-280 ℃, and the volume space velocity is 2-4h -1 The volume ratio of hydrogen to oil is 300-500:1, and the pressure is 2.5-3.5Mp.
Preferably, the hydrogenation catalyst is applied to C of pyrolysis gasoline 9 ～C 10 When the fraction is hydrogenated, the inlet temperature of the reactor is 220-300 ℃ and the volume space velocity is 1-2h -1 The volume ratio of hydrogen to oil is 400-800:1, and the pressure is 2.5-3.5Mpa.
In another embodiment of the present invention, the above-mentioned titanium oxide-aluminum oxide composite carrier is loaded with molybdenum oxide and nickel oxide to obtain the hydrogenation protecting agent. Preferably, the content of molybdenum oxide is 5 to 20 wt% and the content of nickel oxide is 4 to 15 wt% based on the total weight of the hydrogenation protecting agent. The hydrogenation protective agent is applied to the hydrogenation process of DCC pyrolysis naphtha, and has the characteristics of good low-temperature activity, capability of reducing the inlet temperature of a reactor and improving the operation stability of the device.
According to one embodiment of the present invention, the preparation method of the hydrogenation protecting agent includes: and (3) impregnating the titanium oxide-aluminum oxide composite carrier with a molybdenum element-containing compound and a nickel element-containing compound, and drying and roasting to obtain the hydrogenation protective agent. Preferably, the molybdenum element-containing compound is ammonium molybdate. Preferably, the nickel element-containing compound is nickel nitrate. Preferably, the drying conditions include: the temperature is 110-150deg.C, preferably 110-130deg.C, and the time is 2-16 hr, preferably 3-12 hr. Preferably, the roasting conditions include: the temperature is 500-900 ℃, preferably 550-800 ℃, and the time is 3-16h, preferably 4-12h.
And carrying out SEM-Mapping on the prepared hydrogenation protective agent for characterization. The characterization result shows that the aluminum atoms, titanium atoms, molybdenum atoms and nickel atoms of the hydrogenation protective agent prepared by the invention are uniformly distributed.
According to a preferred embodiment of the present invention, the above hydrogenation catalyst is applied to a hydrogenation process for DCC pyrolysis naphtha. Before the reaction, the hydrogenation protective agent needs to be vulcanized, and the vulcanization method can be a method conventional in the art, for example, at the temperature of a reactor of 280-350 ℃, the volume ratio of hydrogen to oil is 100-200:1, a cyclohexane solution with the DMDS (dimethyl disulfide) content of 1-5 weight percent is used, and the volume space velocity is 1-2h -1 Vulcanizing for 10-24h, and reducing the temperature to room temperature after vulcanizing.
Preferably, the conditions of the hydrogenation process for DCC pyrolysis naphtha include: the inlet temperature of the reactor is 120-180 ℃, and the volume space velocity is 2-4h -1 The volume ratio of hydrogen to oil is 300-500:1, and the pressure is 3.5-8Mpa.
Compared with the existing hydrogenation catalyst and hydrogenation protective agent, the hydrogenation catalyst and hydrogenation protective agent prepared by the titanium oxide-aluminum oxide composite carrier provided by the invention have the advantages of good low-temperature activity, high hydrogenation activity and good stability under high airspeed in the pyrolysis gasoline hydrogenation field and the DCC naphtha hydrogenation field, and the titanium source is the metatitanic acid with relatively low price, so that the problem of relatively high titanium source in the prior art is solved, and the preparation method is simple and easy, so that the method is suitable for large-scale industrial production.
Drawings
FIG. 1a is an SEM-Mapping graph of aluminum atom distribution in a titania-alumina composite carrier according to example 1 of the present invention;
FIG. 1b is an SEM-Mapping graph of the distribution of titanium atoms in a titania-alumina composite support according to example 1 of the present invention;
FIG. 2a is a SEM-Mapping graph of the distribution of aluminum atoms in a hydrogenation catalyst according to example 4 of the present invention;
FIG. 2b is a SEM-Mapping graph of the distribution of titanium atoms in the hydrogenation catalyst according to example 4 of the present invention;
FIG. 2c is an SEM-Mapping graph of cobalt atom distribution in the hydrogenation catalyst according to example 4 of the present invention;
FIG. 2d is a SEM-Mapping graph of molybdenum atom distribution in the hydrogenation catalyst according to example 4 of the invention;
fig. 2e is an SEM-Mapping diagram of the distribution of nickel atoms in the hydrogenation catalyst provided in example 4 of the present invention.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The test method of the invention is as follows:
(1) Measurement of median particle size reference standard NB/SH/T0951-2017, determination of particle size distribution of catalytic cracking catalyst laser scattering method.
(2) SEM-Mapping characterization method: and (3) coating the ground sample on conductive adhesive, spraying metal on the surface of the sample by using an ion sputtering instrument, drying, spraying carbon on the sample before characterization, and characterizing the sample by using a QUANTA 200 scanning electron microscope of FEI company.
[ example 1 ]
This example is intended to illustrate the preparation of a titania-alumina composite support.
Alumina (specific surface area 200m 2 Per gram, pore volume of 1 mL/g) and meta-titanic acid are added into deionized water for uniform mixing, wherein the weight ratio of the alumina to the meta-titanic acid is 5:1, and the weight ratio of the total weight of the alumina and the meta-titanic acid to the solvent is 5:4. After mixing uniformly, a mixture I is obtained. Placing the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball milling is 200r/min, the rotation speed of the ball milling is 500r/min, the high-energy ball milling is carried out for 8 hours, the mixture II with the median particle diameter of 0.087 mu m is obtained after the ball milling, drying the mixture II in an oven at 120 ℃ overnight, placing the obtained dried product into a screw extruder, adding aqueous solution of nitric acid (the solute is nitric acid, the solvent is deionized water, and the concentration of the solute is 2 wt%), wherein the weight ratio of deionized water in the acid solution to the dried product is 3:5, extruding the mixture into strips, drying the strips at 110 ℃ for 5 hours, and then placing the dried product into a muffle furnace for roasting at 550 ℃ for 6 hours, thus obtaining the titanium oxide-aluminum oxide composite carrier A.
SEM-Mapping characterization is carried out on the titanium oxide-aluminum oxide composite carrier A, and the characterization results are shown in FIG. 1a and FIG. 1b. It can be seen from fig. 1a and 1b that the titanium oxide-aluminum oxide composite carrier a prepared by the present invention has a uniform distribution of aluminum atoms and titanium atoms.
[ example 2 ]
This example is intended to illustrate the preparation of a titania-alumina composite support.
Alumina (specific surface area 150m 2 Per gram, pore volume of 0.8 mL/g) and meta-titanic acid are added into deionized water for uniform mixing, wherein the weight ratio of the alumina to the meta-titanic acid is 6:1, and the weight ratio of the total weight of the alumina and the meta-titanic acid to the solvent is 1:1. After mixing uniformly, a mixture I is obtained. Placing the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball milling is 300r/min, the rotation speed of the ball milling is 600r/min, the high-energy ball milling is carried out for 8 hours, the mixture II with the median particle diameter of 0.093 mu m is obtained after the ball milling, the mixture II is placed into an oven for drying at 120 ℃ overnight, the obtained dried product is placed into a screw extruder, nitric acid aqueous solution (the solute is nitric acid, the solvent is deionized water, the concentration of the solute is 1.8 wt%) is added, wherein the weight ratio of the deionized water in the acid solution to the dried product is 4:5, the extrusion molding is carried out, and the temperature is 130 DEG CDrying for 3 hours, and then placing the mixture into a muffle furnace for roasting for 4 hours at 800 ℃ to obtain the titanium oxide-aluminum oxide composite carrier B.
SEM-Mapping characterization was performed on the titania-alumina composite support B, and the characterization results were similar to those of FIGS. 1a and 1B. The titanium oxide-aluminum oxide composite carrier B prepared by the invention has uniform distribution of aluminum atoms and titanium atoms.
[ example 3 ]
This example is intended to illustrate the preparation of a titania-alumina composite support.
Alumina (specific surface area 300m 2 Per gram, pore volume of 1.2 mL/g) and meta-titanic acid are added into deionized water for uniform mixing, wherein the weight ratio of the alumina to the meta-titanic acid is 7:1, and the weight ratio of the total weight of the alumina and the meta-titanic acid to the solvent is 5:3. After mixing uniformly, a mixture I is obtained. Placing the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball milling is 300r/min, the rotation speed of the ball milling is 300r/min, the high-energy ball milling is carried out for 10 hours, the mixture II with the median particle diameter of 0.082 mu m is obtained after the ball milling, the mixture II is placed into an oven for drying at 120 ℃ overnight, the obtained dried product is placed into a screw extruder, aqueous hydrochloric acid solution (the solute is hydrochloric acid, the solvent is deionized water, and the concentration of the solute is 2.5 wt%) is added, wherein the weight ratio of the deionized water in the acid solution to the dried product is 2:5, the extrusion molding is carried out, the drying is carried out at 150 ℃ for 3 hours, and then the mixture II is placed into a muffle furnace for roasting at 550 ℃ for 12 hours, thus obtaining the titanium oxide-aluminum oxide composite carrier C.
SEM-Mapping characterization was performed on the titania-alumina composite support C, and the characterization results were similar to those of FIGS. 1a and 1b. The titanium oxide-aluminum oxide composite carrier C prepared by the invention has uniform distribution of aluminum atoms and titanium atoms.
[ example 4 ]
This example illustrates the preparation of a hydrogenation catalyst.
Preparing 26.68g/100mL of ammonium molybdate tetrahydrate aqueous solution (26.68 g of ammonium molybdate tetrahydrate is contained in every 100mL of deionized water), then adding 5mL of ammonia water with the concentration of 14 wt% to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of titanium oxide-aluminum oxide composite carrier A prepared in example 1, and soaking at normal temperatureSoaking for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain a precursor. Then the precursor is immersed in an aqueous solution of nickel nitrate hexahydrate with the concentration of 23.48g/100mL and cobalt nitrate hexahydrate with the concentration of 11.62g/100mL (each 100mL of deionized water contains 23.48g of nickel nitrate hexahydrate and 11.62g of cobalt nitrate hexahydrate), immersed for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃ and baked for 4 hours at 550 ℃ to obtain MoO 3 Hydrogenation catalyst A (MoO) having a content of 15% by weight, a CoO content of 2.0% by weight and a NiO content of 4.0% by weight 3 -CoO-NiO/Al 2 O 3 -TiO 2 )。
SEM-Mapping characterization of hydrogenation catalyst A was performed, and the characterization results are shown in FIG. 2a, FIG. 2b, FIG. 2c, FIG. 2d and FIG. 2e. From the figure, it can be seen that the aluminum atoms, titanium atoms, molybdenum atoms, cobalt atoms and nickel atoms of the hydrogenation catalyst A prepared by the present invention are uniformly distributed.
[ example 5 ]
This example illustrates the preparation of a hydrogenation catalyst.
Preparing 26.68g/100mL of ammonium molybdate tetrahydrate aqueous solution, adding 5mL of ammonia water with the concentration of 14 wt% to fully dissolve the ammonium molybdate tetrahydrate, soaking 100g of the titanium oxide-aluminum oxide composite carrier B prepared in the example 2 for 2h at normal temperature, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain a precursor. Then the precursor is impregnated with 17.61g/100mL of nickel nitrate hexahydrate and 20.34g/100mL of cobalt nitrate hexahydrate aqueous solution, impregnated for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃ and baked for 4 hours at 550 ℃ to obtain MoO 3 Hydrogenation catalyst B (MoO) having a content of 15 wt.%, a CoO content of 3.5 wt.%, and a NiO content of 3.0 wt.% 3 -CoO-NiO/Al 2 O 3 -TiO 2 )。
SEM-Mapping characterization of hydrogenation catalyst B was performed with similar results as in FIGS. 2a, 2B, 2c, 2d and 2e. From the figure, it can be seen that the aluminum atoms, titanium atoms, molybdenum atoms, cobalt atoms and nickel atoms of the hydrogenation catalyst B prepared by the invention are uniformly distributed.
[ example 6 ]
This example illustrates the preparation of a hydrogenation protecting agent.
Preparing 15.62g/100mL of ammonium molybdate tetrahydrate aqueous solution, adding 5mL of ammonia water with the concentration of 14 wt% to enable the ammonium molybdate tetrahydrate to be fully dissolved, taking 100g of the titanium oxide-aluminum oxide composite carrier C prepared in the example 3, soaking for 2 hours at normal temperature, filtering, drying for 4 hours at 110 ℃, and roasting for 4 hours at 550 ℃ to obtain a precursor. Then the precursor is impregnated with a water solution of nickel nitrate hexahydrate with the concentration of 55.272g/100mL, the impregnation is carried out for 2 hours at normal temperature, the filtration is carried out, the drying is carried out for 4 hours at 110 ℃, the roasting is carried out for 4 hours at 550 ℃, and the MoO is obtained 3 Hydrogenation protecting agent C (MoO) with a content of 8.5 wt% and a NiO content of 10.5 wt% 3 -NiO/Al 2 O 3 -TiO 2 )。
The hydrogenation protecting agent C was subjected to SEM-Mapping characterization, and the characterization results are similar to those of FIG. 2a, FIG. 2b, FIG. 2d and FIG. 2e. From the figure, it can be seen that the aluminum atoms, titanium atoms, molybdenum atoms and nickel atoms of the hydrogenation catalyst C prepared by the present invention are uniformly distributed.
[ example 7 ]
A titanium oxide-alumina composite carrier was prepared in the same manner as in example 1 except that a specific surface area of 200m was used 2 Per gram, the alumina with pore volume of 1mL/g is replaced by the alumina with specific surface area of 370m 2 And/g, alumina with pore volume of 0.53 mL/g. And a hydrogenation catalyst was prepared as in example 4, designated hydrogenation catalyst D.
[ example 8 ]
A titanium oxide-alumina composite carrier was prepared in the same manner as in example 1 except that a specific surface area of 200m was used 2 Per gram, the alumina with pore volume of 1mL/g is replaced by alumina with specific surface area of 350m 2 And/g, alumina with pore volume of 1.5 mL/g. And a hydrogenation catalyst was prepared as in example 4, designated hydrogenation catalyst E.
[ example 9 ]
A titania-alumina composite support was prepared as in example 1, except that the weight ratio of alumina to meta-titanic acid was 15:1. and a hydrogenation catalyst was prepared as in example 4, designated hydrogenation catalyst F.
[ example 10 ]
A titania-alumina composite support was prepared as in example 1, except that the weight ratio of alumina to metatitanic acid was 3:1. and a hydrogenation catalyst was prepared as in example 4, designated hydrogenation catalyst G.
Comparative example 1
Alumina (specific surface area 200m 2 Per gram, pore volume of 1 mL/g) and meta-titanic acid are added into deionized water for uniform mixing, wherein the weight ratio of the alumina to the meta-titanic acid is 5:1, and the weight ratio of the total weight of the alumina and the meta-titanic acid to the solvent is 5:4. After mixing uniformly, a mixture was obtained. And then placing the mixture into a drying oven at 120 ℃ for drying overnight, placing the obtained dried product into a screw extruder, adding aqueous nitric acid solution (nitric acid is used as a solute, deionized water is used as a solvent, and the concentration of the solute is 2 wt%), wherein the weight ratio of the deionized water in the acid solution to the dried product is 3:5, extruding the mixture into strips, drying the strips at 110 ℃ for 5 hours, and then placing the strips into a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the composite carrier D-1.
Preparing 26.68g/100mL of ammonium molybdate tetrahydrate aqueous solution, adding 5mL of ammonia water with the concentration of 14 wt% to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of composite carrier D-1, soaking for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃ to obtain a precursor. Then the precursor is impregnated with aqueous solution of nickel nitrate hexahydrate with the concentration of 23.48g/100mL and cobalt nitrate hexahydrate with the concentration of 11.62g/100mL, the mixture is impregnated for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃ and baked for 4 hours at 550 ℃ to obtain MoO 3 Hydrogenation catalyst DC-1 (MoO) having a content of 15 wt%, a CoO content of 2.0 wt%, and a NiO content of 4.0 wt% 3 -CoO-NiO/Al 2 O 3 -TiO 2 )。
Comparative example 2
A titania-alumina composite support D-2 was prepared according to the method of example 1 of CN 1184289C. The specific operation is as follows:
taking a specific surface area of 160 meters 2 Per gram, pore volume of 0.58 ml/g, most probable pore diameter of 130 angstrom clover shaped alumina 90 g, 53ml titanium sulfate 0.557 g/ml dilute sulfuric acid solution, stirring 15 minutes, drying at 120 ℃ for 8 hours, roasting at 900 ℃ for 4 hours, and obtaining compound D-2. Oxygen of the resulting compositeTitanium oxide content of 10% by weight and specific surface area of 144 m 2 Per gram, pore volume is 0.56 ml/gram, and the most probable pore diameter is 125 angstroms.
Preparing 26.68g/100mL of ammonium molybdate tetrahydrate aqueous solution, adding 5mL of ammonia water with the concentration of 14 wt% to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of composite carrier D-2, soaking for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃ to obtain a precursor. Then the precursor is impregnated with 17.61g/100mL of nickel nitrate hexahydrate and 20.34g/100mL of cobalt nitrate hexahydrate aqueous solution, impregnated for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃ and baked for 4 hours at 550 ℃ to obtain MoO 3 Hydrogenation catalyst DC-2 (MoO) having a content of 15 wt%, a CoO content of 3.5 wt%, and a NiO content of 3.0 wt% 3 -CoO-NiO/Al 2 O 3 -TiO 2 )。
[ comparative example 3 ]
Alumina (specific surface area 200m 2 Per gram, pore volume of 1 mL/g) and meta-titanic acid are added into deionized water for uniform mixing, wherein the weight ratio of the alumina to the meta-titanic acid is 5:1, and the weight ratio of the total weight of the alumina and the meta-titanic acid to the solvent is 5:4. After mixing uniformly, a mixture was obtained. And then the mixture is put into a drying oven for drying overnight at 120 ℃, the dried product is put into a screw extruder, aqueous solution of nitric acid (nitric acid is used as solute, deionized water is used as solvent, and the concentration of the solute is 2 wt%) is added, wherein the weight ratio of the deionized water to the dried product is 3:5, the mixture is extruded and molded, the mixture is dried at 110 ℃ for 5 hours, and then the mixture is put into a muffle furnace for roasting at 550 ℃ for 6 hours, so that the composite carrier D-3 is obtained.
Preparing 26.68g/100mL of ammonium molybdate tetrahydrate aqueous solution, adding 5mL of ammonia water with the concentration of 14 wt% to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of composite carrier D-3, soaking for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃ to obtain a precursor. Then the precursor is impregnated with a water solution of nickel nitrate hexahydrate with the concentration of 55.272g/100mL, the impregnation is carried out for 2 hours at normal temperature, the filtration is carried out, the drying is carried out for 4 hours at 110 ℃, the roasting is carried out for 4 hours at 550 ℃, and the MoO is obtained 3 The content of NiO was 8.5 wt% and the content of NiO was 10.5 wt% of the hydrogenation protecting agent DC-3.
[ comparative example 4 ]
The procedure of example 1 was followed, except that mixture II having a median particle diameter of 0.15 μm was obtained after ball milling. A hydrogenation catalyst was prepared as described in example 4, designated hydrogenation catalyst DC-4.
Test example 1
Benzene making device C using China petrochemical, yanshan petrochemical and olefin part 6 ～C 8 The first-stage hydrogenation product of the fraction is used as a hydrofining raw material, the total sulfur content of the raw material is 98ppm, and the bromine number is 19.09 (gBr) 2 100g of oil). Hydrogenation catalyst A, B, D, E, F, G and hydrogenation catalysts DC-1, DC-2, and DC-4 (loading was 100 mL) were evaluated for comparison. The evaluation conditions and product analysis are shown in Table 1.
TABLE 1
Test example 2
Benzene making device C using China petrochemical, yanshan petrochemical and olefin part 6 ～C 8 The first-stage hydrogenation product of the fraction is used as a hydrofining raw material, the total sulfur content of the raw material is 98ppm, and the bromine number is 19.09 (gBr) 2 100g of oil). The hydrogenation catalyst B and the hydrogenation catalyst DC-2 (loading was 100 mL) were evaluated for comparison. The evaluation conditions and product analysis are shown in Table 2.
TABLE 2
Test example 3
Chemical industry factory C of Dushantian Li Gao New company from Xinjiang 9 ～C 10 Fraction two-stage hydrogenation raw material, total sulfur content of raw material is 400ppm, bromine number is 29 (gBr) 2 100g of oil). Respectively for hydrogenation catalyst AComparative evaluations were performed on B, D, E, F, G and hydrogenation catalysts DC-1, DC-2, and DC-4 (loading was 100 mL). The results of the product analysis are shown in Table 3.
TABLE 3 Table 3
Test example 4
DCC naphtha hydrogenation raw material of certain chemical plant of Shaanxi is used as raw material, and the diene content of the raw material is 10.5 (gI 2 Per 100g of oil) with a bromine number of 31 (gBr) 2 100g of oil). The hydrogenation protecting agent C and the hydrogenation protecting agent DC-3 (the filling amount is 100 mL) are respectively compared and evaluated. The evaluation conditions and product analysis are shown in Table 4.
TABLE 4 Table 4
/>
Test example 5
DCC naphtha hydrogenation raw material of certain chemical plant of Shaanxi is used as raw material, and the diene content of the raw material is 10.5 (gI 2 Per 100g of oil) with a bromine number of 31 (gBr) 2 100g of oil). The 100mL fixed bed reactors are connected in series, the first-stage reactor is filled with 100mL hydrogenation catalyst B, the first-stage hydrogenation product is used as the inlet raw material of the second-stage reactor, and the second-stage reactor is filled with 100mL hydrogenation protecting agent C. The evaluation results of the hydrogenated products are shown in Table 5.
TABLE 5
As can be seen from FIGS. 1a and 1b, the titanium oxide-aluminum oxide composite carrier prepared by the method of the present invention has uniform distribution of aluminum atoms and titanium atoms, namely TiO 2 And the distribution is uniform. And as can be seen from fig. 2a, 2b, 2c, 2d and 2e, the aluminum atoms, titanium atoms, molybdenum atoms, cobalt atoms and nickel atoms of the hydrogenation catalyst prepared by using the titania-alumina composite support of the present invention are uniformly distributed.
In addition, as can be seen from test examples 1-5 and tables 1-5, the hydrogenation catalyst and the hydrogenation protecting agent prepared by adopting the titanium oxide-aluminum oxide composite carrier provided by the invention have higher low-temperature activity and hydrogenation activity and stability under high airspeed in the fields of pyrolysis gasoline hydrogenation and DCC naphtha hydrogenation, and have low preparation cost due to the use of the metatitanic acid as a titanium source, thus being suitable for large-scale industrial production.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (24)
1. The preparation method of the titanium oxide-aluminum oxide composite carrier for pyrolysis gasoline hydrogenation and DCC pyrolysis naphtha hydrogenation is characterized by comprising the following steps:
(1) Mixing aluminum oxide, meta-titanic acid and a solvent to obtain a mixture I;
(2) Performing high-energy ball milling on the mixture I to obtain a mixture II with the median particle diameter smaller than 0.1 mu m;
(3) Drying the mixture II, mixing the obtained dried product with acid liquor, and sequentially forming, drying and roasting;
the weight ratio of the aluminum oxide to the meta-titanic acid is (5-10): 1, the weight ratio of the total weight of the aluminum oxide and the meta-titanic acid to the solvent is 5: (1-5).
2. The method according to claim 1, wherein the specific surface area of the alumina is 150-300m 2 Per g, pore volume is 0.6-1.2mL/g.
3. The method of claim 1, wherein the alumina has a pore volume of 0.8-1mL/g.
4. The method according to claim 1, wherein the weight ratio of alumina to meta-titanic acid is (5-7): 1.
5. the method of claim 1, wherein the solvent is one or more of deionized water, ethanol, and methanol.
6. The method of claim 1, wherein the high energy ball milling conditions comprise: the time is 6-10h, the revolution speed of the ball mill is 30-350r/min, and the rotation speed of the ball mill is 70-670r/min.
7. The method of claim 1, wherein the high energy ball milling is stirred ball milling, vibratory ball milling or planetary ball milling.
8. The method of claim 1, wherein the high energy ball milling is planetary ball milling.
9. The method of claim 1, wherein the drying conditions comprise: the temperature is 110-150 ℃ and the time is 2-16h.
10. The method of claim 1, wherein the drying conditions comprise: the temperature is 110-130 ℃ and the time is 3-12h.
11. The method according to claim 1, wherein the solute in the acid liquor is an organic acid and/or an inorganic acid; and/or the solvent in the acid liquor is deionized water.
12. The method of claim 11, wherein the concentration of solute in the acid solution is 0.5-4 wt%.
13. The method according to claim 1, wherein the weight ratio of acid solution to dry product in terms of solvent is (1-4): 5.
14. the method according to claim 1, wherein the weight ratio of acid liquor to dry product in terms of solvent is (2-4): 5.
15. the method of claim 11, wherein the organic acid is one or more of acetic acid, oxalic acid, citric acid, and tartaric acid.
16. The method of claim 11, wherein the mineral acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid.
17. The method of claim 11, wherein the mineral acid is nitric acid.
18. The method of claim 1, wherein the forming is extrusion.
19. The method of claim 1, wherein the conditions of drying comprise: the temperature is 110-150 ℃ and the time is 2-16h.
20. The method of claim 1, wherein the conditions of drying comprise: the temperature is 110-130 ℃ and the time is 3-12h.
21. The method of claim 1, wherein the firing conditions include: the temperature is 500-900 ℃ and the time is 3-16h.
22. The method according to claim 1, characterized in that the firing conditions comprise: the temperature is 550-800 ℃ and the time is 4-12h.
23. A titania-alumina composite support prepared by the method of any one of claims 1 to 21.
24. The use of the titania-alumina composite support of claim 23 in the hydrogenation of pyrolysis gasoline and the hydrogenation of DCC pyrolysis naphtha.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010398288.8A CN113649079B (en) | 2020-05-12 | 2020-05-12 | Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010398288.8A CN113649079B (en) | 2020-05-12 | 2020-05-12 | Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113649079A CN113649079A (en) | 2021-11-16 |
| CN113649079B true CN113649079B (en) | 2023-10-10 |
Family
ID=78476943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010398288.8A Active CN113649079B (en) | 2020-05-12 | 2020-05-12 | Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113649079B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436594A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Prepn process of waste gas purifying catalyst containing noble metal |
| WO2007114570A1 (en) * | 2006-04-03 | 2007-10-11 | Korea Power Engineering Company, Inc. | Preparation method of vanadium/titania-based catalyst showing excellent nitrogen oxide-removal performance at wide temperature window through introduction of ball milling, and use thereof |
| CN102861593A (en) * | 2011-07-06 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN104043442A (en) * | 2014-05-23 | 2014-09-17 | 天津大学 | Titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation |
| CN106745223A (en) * | 2017-03-16 | 2017-05-31 | 东北大学 | Modifying titanium dioxide raw powder's production technology and modifying titanium dioxide powder |
| CN108246302A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst and its preparation method and application |
-
2020
- 2020-05-12 CN CN202010398288.8A patent/CN113649079B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436594A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Prepn process of waste gas purifying catalyst containing noble metal |
| WO2007114570A1 (en) * | 2006-04-03 | 2007-10-11 | Korea Power Engineering Company, Inc. | Preparation method of vanadium/titania-based catalyst showing excellent nitrogen oxide-removal performance at wide temperature window through introduction of ball milling, and use thereof |
| CN102861593A (en) * | 2011-07-06 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN104043442A (en) * | 2014-05-23 | 2014-09-17 | 天津大学 | Titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation |
| CN108246302A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst and its preparation method and application |
| CN106745223A (en) * | 2017-03-16 | 2017-05-31 | 东北大学 | Modifying titanium dioxide raw powder's production technology and modifying titanium dioxide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113649079A (en) | 2021-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2011502050A (en) | Selective nickel-based hydrogenation catalyst and its production | |
| CN1680025A (en) | Low-temperature hydrolyst for high concentrated organosulfur and preparation thereof | |
| CN104540585A (en) | Improved resid hydrotreating catalyst containing titania | |
| CN105618121A (en) | Preparation method of nitrogen-resisting hydrocracking catalyst | |
| CN102139211A (en) | Method for preparing noble metal/TiO2-C catalyst for hydrofining of crude terephthalic acid | |
| CN102247865A (en) | Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof | |
| CN109225203A (en) | A kind of vanadium base oxide SCR catalyst preparation method and its catalyst of preparation | |
| US11358135B2 (en) | Method for preparing hydrocracking catalyst | |
| CN110773209A (en) | Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof | |
| CN108421557A (en) | Hydrocracking catalyst and preparation method thereof | |
| CN113649079B (en) | Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof | |
| CN105618116A (en) | Preparation method of hydro-cracking catalyst | |
| CN113649016B (en) | Hydrogenation catalyst and preparation method and application thereof | |
| CN113649080B (en) | Hydrogenation protective agent and preparation method and application thereof | |
| CN1769384A (en) | Heavy distillate oil hydrogenation catalyst and its preparation method | |
| CN109304213B (en) | Hydrocracking catalyst, and preparation method and application thereof | |
| JP2017196579A (en) | Production method of catalyst precursor for production of carbon nanotube | |
| CN108404897B (en) | Heavy oil hydrogenation catalyst carrier, preparation method thereof, catalyst using heavy oil hydrogenation catalyst carrier and preparation method of catalyst | |
| CN105621432A (en) | Modified beta molecular sieve and preparation method thereof | |
| CN112452340B (en) | Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof | |
| CN105582943B (en) | A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil | |
| CN116037178A (en) | Hydrodenitrogenation catalyst, preparation method and application thereof | |
| CN112675828A (en) | Hydrodesulfurization catalyst and preparation method thereof | |
| CN105289681B (en) | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil | |
| CN109745985B (en) | Catalyst for preparing cyclopentene from cyclopentadiene and preparation method and application thereof |
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 |