CN107335471A - A kind of preparation method of the multi-stage porous titanium terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity - Google Patents
A kind of preparation method of the multi-stage porous titanium terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity Download PDFInfo
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- CN107335471A CN107335471A CN201710686820.4A CN201710686820A CN107335471A CN 107335471 A CN107335471 A CN 107335471A CN 201710686820 A CN201710686820 A CN 201710686820A CN 107335471 A CN107335471 A CN 107335471A
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- terephthalic acid
- stage porous
- acid metal
- porous titanium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 89
- 239000002184 metal Substances 0.000 title claims abstract description 89
- MTSNJRRMXLTMIX-UHFFFAOYSA-N terephthalic acid;titanium Chemical compound [Ti].OC(=O)C1=CC=C(C(O)=O)C=C1 MTSNJRRMXLTMIX-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 102
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 30
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 18
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 24
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 239000000843 powder Substances 0.000 description 58
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 22
- 230000003647 oxidation Effects 0.000 description 22
- 238000007254 oxidation reaction Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000003321 amplification Effects 0.000 description 7
- 238000003199 nucleic acid amplification method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CTMHWPIWNRWQEG-UHFFFAOYSA-N trans cyclohexenyl ester Natural products CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229910003089 Ti–OH Inorganic materials 0.000 description 3
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical group OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- PQANGXXSEABURG-UHFFFAOYSA-N cyclohex-2-en-1-ol Chemical class OC1CCCC=C1 PQANGXXSEABURG-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- -1 t-butyl peroxy Chemical group 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of the multi-stage porous titanium terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity, is related to a kind of preparation method of multi-stage porous titanium terephthalic acid metal organic catalyst.It is all very good to solve existing most of titaniferous (Ti) MOF crystallinity, there is no utilizable Ti avtive spots, active relatively low in catalytic reaction the problem of.Method：Terephthalic acid (TPA) is added to N, is dissolved in N dimethylformamides, obtains mixed solution；Titanium tetrachloride is added into mixed solution, is placed in stirring on magnetic stirring apparatus, then by the mixed solution crystallization after stirring, is cooled down, is centrifuged, obtain reacted solid；Reacted solid is washed using organic solvent, is separated by filtration, is dried under last vacuum, obtains multi-stage porous titanium terephthalic acid metal organic catalyst.The present invention is used for the preparation method of the multi-stage porous titanium terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity.
Description
Technical field
The present invention relates to a kind of preparation method of multi-stage porous titanium-terephthalic acid metal organic catalyst.
Background technology
Metal-organic framework materials (MOFs) as a kind of new porous material, due to skeleton structure diversity,
Big specific surface area, aperture easily reconcile easy functionalization the features such as, in fields such as sensing, the absorption of gas, separation, accumulating and catalysis
Have a wide range of applications.Wherein, titaniferous (Ti) MOF has Ti active species and received much concern.However, most of titaniferous
(Ti) MOF crystallinity is all very good, there is no utilizable Ti avtive spots, active relatively low in catalytic reaction.
Mesoporous or multi-stage porous material containing Ti, there is big aperture, can ensure that reactant passes in and out duct, promote catalysis anti-
Should carry out.In addition, the mesoporous or multi-stage porous having more can also expose more avtive spots, it is more conducive to catalytic reaction and enters
OK.But even if titanium (Ti) MOF is prepared mesoporous or multi-stage porous, because its crystallinity is still higher, almost all of Ti
Site is all occupied by organic ligand, is exposed without enough avtive spots, and catalytic reaction is not helped much still, existing
There is the sulfur-containing compound that oxidation desulfurization performance is only capable of removing 70%.Therefore, metallo organic material is prepared into undefined structure, just
More avtive spots can be exposed, greatly improve catalytic oxidation performance.
The content of the invention
All very good the invention aims to solve existing most of titaniferous (Ti) MOF crystallinity, there is no can
With the Ti avtive spots utilized, active relatively low in catalytic reaction the problem of, and providing a kind of there is efficiently catalyzing and oxidizing to live
The preparation method of multi-stage porous titanium-terephthalic acid metal organic catalyst of property.
A kind of preparation method of multi-stage porous titanium-terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity
It is specifically realized by the following steps：
First, under magnetic stirring, terephthalic acid (TPA) is added to N, is dissolved in N- dimethylformamides, obtain mixed solution；
Described terephthalic acid (TPA) and the mol ratio of N, N- dimethylformamide are 1:(65~720)；
2nd, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in described mixed solution
Mol ratio is 1:(0.5~2), stirring 2min~10min on magnetic stirring apparatus is subsequently placed in, and the mixed solution after stirring is put
In the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of temperature is 100 DEG C~220 DEG C, crystallization 3h~
30h, question response kettle cooling, centrifuges, obtains reacted solid；
3rd, under conditions of temperature is 20 DEG C~80 DEG C, reacted solid is washed into 3h~12h using organic solvent,
It is separated by filtration, obtains the solid after once washing；
4th, the solid after once washing is repeated 2 times~4 times by step 3, is finally 50 DEG C~160 DEG C true in temperature
Sky is lower to dry, and obtains multi-stage porous titanium-terephthalic acid metal organic catalyst.
The present invention reports the method by Hydrothermal Synthesiss first, is prepared for containing Ti active specy multi-stage porous Ti- to benzene two
Organic (Ti-BDC) catalyst of metal.This catalyst is on oxidation sweetening to removing benzothiophene (BT), dibenzothiophenes
(DBT) and 4,6- dimethyl Dibenzothiophene (4,6-DMDBT) have excellent performance, and in Oxybenzene methyl alcohol and cyclohexene
Also there is excellent performance.
Advantages of the present invention：
1st, method of the invention can obtain organic (Ti-BDC) catalyst of multi-stage porous Ti- terephthalic acid metals；Prepare
Multi-stage porous titanium-terephthalic acid metal organic catalyst powder specific surface area in 600m2/ g or so, there is the spy of multi-stage porous
Property；
2nd, catalyst prepared by method of the invention has more Ti-OH active species in itself, without post processing mode
Obtain；The material of preparation has multistage pore property, is not complete metal organic backbone, and this amorphous material exposes more
Avtive spot, substantially increase its catalytic oxidation performance；
3rd, catalyst prepared by method of the invention has very high catalysis oxygen in oxidation sweetening, Oxybenzene methyl alcohol and cyclohexene
Change performance, relative to other titaniferous MOF materials, its catalytic performance increases into multiple.Oxidation sweetening performance：Can in 30min
To remove DBT completely, 45min can remove the BT that 4,6-DMDBT, 60min just can be removed more than 92% completely；Oxybenzene first
Alcohol：During using TBHP as oxidant, conversion ratio is up to 92.4%, cyclohexene：Using TBHP as oxidation
During agent, conversion ratio is up to 95.1%.
The present invention is used for a kind of multi-stage porous titanium-terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity
Preparation method.
Brief description of the drawings
Fig. 1 is XRD spectrum, and 1 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment one, 2
Multi-stage porous titanium-terephthalic acid metal organic catalyst the powder prepared for embodiment two, 3 be multi-stage porous prepared by embodiment three
Titanium-terephthalic acid metal organic catalyst powder；
Fig. 2 is nitrogen adsorption isotherm, and 1 is multi-stage porous titanium-terephthalic acid metal organic catalysis prepared by embodiment one
Agent powder, 2 be multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two, and 3 be prepared by embodiment three
Multi-stage porous titanium-terephthalic acid metal organic catalyst powder；
Fig. 3 is the scanning electron microscope (SEM) photograph of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment one,
2000 times of amplification；
Fig. 4 is the scanning electron microscope (SEM) photograph of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment one,
10000 times of amplification；
Fig. 5 is the scanning electron microscope (SEM) photograph of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two,
2000 times of amplification；
Fig. 6 is the scanning electron microscope (SEM) photograph of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two,
10000 times of amplification；
Fig. 7 is the scanning electron microscope (SEM) photograph of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment three,
2000 times of amplification；
Fig. 8 is the scanning electron microscope (SEM) photograph of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment three,
10000 times of amplification；
Fig. 9 is the infared spectrum of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two；
Figure 10 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder all elements prepared by embodiment two
XPS collection of illustrative plates；
The XPS figures that Figure 11 is Ti in multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Spectrum；
The XPS figures that Figure 12 is O in multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Spectrum；
The XPS figures that Figure 13 is C in multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Spectrum；
The XPS figures that Figure 14 is N in multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Spectrum；
Figure 15 is that multi-stage porous titanium-terephthalic acid metal organic catalyst Powder Oxidation desulfurization prepared by embodiment two removes
Sulfur-containing compound BT, DBT and 4,6-DMDBT comparison diagram, 1 is DBT, 2 be 4,6-DMDBT, 3 be BT.
Embodiment
Embodiment one：Present embodiment is a kind of multi-stage porous titanium-to benzene two with efficiently catalyzing and oxidizing activity
What the preparation method of metal organic catalyst was specifically realized by the following steps：
First, under magnetic stirring, terephthalic acid (TPA) is added to N, is dissolved in N- dimethylformamides, obtain mixed solution；
Described terephthalic acid (TPA) and the mol ratio of N, N- dimethylformamide are 1:(65~720)；
2nd, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in described mixed solution
Mol ratio is 1:(0.5~2), stirring 2min~10min on magnetic stirring apparatus is subsequently placed in, and the mixed solution after stirring is put
In the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of temperature is 100 DEG C~220 DEG C, crystallization 3h~
30h, question response kettle cooling, centrifuges, obtains reacted solid；
3rd, under conditions of temperature is 20 DEG C~80 DEG C, reacted solid is washed into 3h~12h using organic solvent,
It is separated by filtration, obtains the solid after once washing；
4th, the solid after once washing is repeated 2 times~4 times by step 3, is finally 50 DEG C~160 DEG C true in temperature
Sky is lower to dry, and obtains multi-stage porous titanium-terephthalic acid metal organic catalyst.
Terephthalic acid (TPA) can be abbreviated as BDC, N in present embodiment step 1, and N- dimethylformamides can be abbreviated as DMF；
Titanium tetrachloride (TiCl is added in present embodiment step 24), now mixed solution is saturating from colourless well-illuminated change yellow
Bright solution.
Present embodiment BDC is soluble in DMF, is dissolved in preparation clarification mixed solution；
Present embodiment titanium tetrachloride is easy to DMF reactions, forms compound, prevents titanium tetrachloride from hydrolyzing before the reaction.
The advantages of present embodiment：
1st, the method for present embodiment can obtain multi-stage porous Ti- terephthalic acid metals organic (Ti-BDC) catalysis
Agent；The specific surface area of the multi-stage porous titanium of preparation-terephthalic acid metal organic catalyst powder is in 600m2/ g or so, have more
The characteristic in level hole；
2nd, catalyst prepared by the method for present embodiment has more Ti-OH active species in itself, without after
Processing mode obtains；The material of preparation has multistage pore property, is not complete metal organic backbone, and this amorphous material is sudden and violent
Expose more avtive spots, substantially increase its catalytic oxidation performance；
3rd, catalyst prepared by the method for present embodiment has very high in oxidation sweetening, Oxybenzene methyl alcohol and cyclohexene
Catalytic oxidation performance, relative to other titaniferous MOF materials, its catalytic performance is into multiple increase.Oxidation sweetening performance：
Can removes DBT completely in 30min, and 45min can remove 4,6-DMDBT, 60min completely and just can be removed more than 92%
BT；Oxybenzene methyl alcohol：During using TBHP as oxidant, conversion ratio is up to 92.4%, cyclohexene：With t-butyl peroxy
When change hydrogen is oxidant, conversion ratio is up to 95.1%.
Embodiment two：Present embodiment is with the difference of embodiment one：It is organic described in step 3
Solvent is absolute ethyl alcohol or N, N- dimethylformamide.Other steps are identical with embodiment one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：Institute in step 1
The terephthalic acid (TPA) and the mol ratio of N, N- dimethylformamide stated are 1:260.Other steps and embodiment one or two-phase
Together.
Embodiment four：Present embodiment is with one of embodiment one to three difference：Institute in step 2
The mol ratio of terephthalic acid (TPA) and titanium tetrachloride is 1 in the mixed solution stated:1.Other steps and embodiment one to three
It is identical.
Embodiment five：Present embodiment is with one of embodiment one to four difference：In step 2
Under conditions of temperature is 220 DEG C, crystallization 24h.Other steps are identical with embodiment one to four.
Embodiment six：Present embodiment is with one of embodiment one to five difference：In step 2
Under conditions of temperature is 180 DEG C, crystallization 24h.Other steps are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：In step 2
Under conditions of temperature is 150 DEG C, crystallization 24h.Other steps are identical with embodiment one to six.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：In step 3
Under conditions of temperature is 60 DEG C, reacted solid is washed into 8h using organic solvent.Other steps and embodiment one
It is identical to seven.
Embodiment nine：Present embodiment is with one of embodiment one to eight difference：In step 3
Under conditions of temperature is 60 DEG C~80 DEG C, reacted solid is washed into 8h~12h using organic solvent.Other steps with it is specific
Embodiment one to eight is identical.
Embodiment ten：Present embodiment is with one of embodiment one to nine difference：In step 4 most
Dried afterwards in the case where temperature is 150 DEG C of vacuum.Other steps are identical with embodiment one to nine.
The beneficial effect of this hair name is verified using following examples：
Embodiment one：A kind of multi-stage porous titanium-terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity
Preparation method be specifically realized by the following steps：
First, under magnetic stirring, terephthalic acid (TPA) is added to N, is dissolved in N- dimethylformamides, obtain mixed solution；
Described terephthalic acid (TPA) and the mol ratio of N, N- dimethylformamide are 1:260；
2nd, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in described mixed solution
Mol ratio is 1:1, it is subsequently placed on magnetic stirring apparatus and stirs 10min, and the mixed solution after stirring is placed in polytetrafluoro
In the stainless steel cauldron of ethene liner, under conditions of temperature is 150 DEG C, crystallization 24h, the cooling of question response kettle, centrifuge,
Obtain reacted solid；
3rd, under conditions of temperature is 60 DEG C, reacted solid is washed into 8h using organic solvent, is separated by filtration, obtains
Solid after to once washing；
4th, the solid after once washing is repeated 2 times by step 3, finally dries, obtain in the case where temperature is 150 DEG C of vacuum
To multi-stage porous titanium-terephthalic acid metal organic catalyst powder；
Organic solvent described in step 3 is absolute ethyl alcohol.
Embodiment two：A kind of multi-stage porous titanium-terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity
Preparation method be specifically realized by the following steps：
First, under magnetic stirring, terephthalic acid (TPA) is added to N, is dissolved in N- dimethylformamides, obtain mixed solution；
Described terephthalic acid (TPA) and the mol ratio of N, N- dimethylformamide are 1:260；
2nd, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in described mixed solution
Mol ratio is 1:1, it is subsequently placed on magnetic stirring apparatus and stirs 10min, and the mixed solution after stirring is placed in polytetrafluoro
In the stainless steel cauldron of ethene liner, under conditions of temperature is 180 DEG C, crystallization 24h, the cooling of question response kettle, centrifuge,
Obtain reacted solid；
3rd, under conditions of temperature is 60 DEG C, reacted solid is washed into 8h using organic solvent, is separated by filtration, obtains
Solid after to once washing；
4th, the solid after once washing is repeated 2 times by step 3, finally dries, obtain in the case where temperature is 150 DEG C of vacuum
To multi-stage porous titanium-terephthalic acid metal organic catalyst powder；
Organic solvent described in step 3 is absolute ethyl alcohol.
Embodiment three：A kind of multi-stage porous titanium-terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity
Preparation method be specifically realized by the following steps：
First, under magnetic stirring, terephthalic acid (TPA) is added to N, is dissolved in N- dimethylformamides, obtain mixed solution；
Described terephthalic acid (TPA) and the mol ratio of N, N- dimethylformamide are 1:260；
2nd, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in described mixed solution
Mol ratio is 1:1, it is subsequently placed on magnetic stirring apparatus and stirs 10min, and the mixed solution after stirring is placed in polytetrafluoro
In the stainless steel cauldron of ethene liner, under conditions of temperature is 220 DEG C, crystallization 24h, the cooling of question response kettle, centrifuge,
Obtain reacted solid；
3rd, under conditions of temperature is 60 DEG C, reacted solid is washed into 8h using organic solvent, is separated by filtration, obtains
Solid after to once washing；
4th, the solid after once washing is repeated 2 times by step 3, finally dries, obtain in the case where temperature is 150 DEG C of vacuum
To multi-stage porous titanium-terephthalic acid metal organic catalyst powder；
Organic solvent described in step 3 is absolute ethyl alcohol.
Fig. 1 is XRD spectrum, and 1 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment one, 2
Multi-stage porous titanium-terephthalic acid metal organic catalyst the powder prepared for embodiment two, 3 be multi-stage porous prepared by embodiment three
Titanium-terephthalic acid metal organic catalyst powder；From multi-stage porous titanium-terephthalic acid metal prepared by embodiment one
Organic catalyst powder has characteristic diffraction peak at 2 θ=3 ° and 7.8 °, and multi-stage porous prepared by embodiment two and embodiment three
Titanium-terephthalic acid metal organic catalyst powder is undefined structure.
Fig. 2 is nitrogen adsorption isotherm, and 1 is multi-stage porous titanium-terephthalic acid metal organic catalysis prepared by embodiment one
Agent powder, 2 be multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two, and 3 be prepared by embodiment three
Multi-stage porous titanium-terephthalic acid metal organic catalyst powder；As seen from the figure, the multi-stage porous titanium that prepared by embodiment one to three-
The specific surface area of terephthalic acid metal organic catalyst powder is in 600m2/ g or so, and all there is the characteristic of multi-stage porous.
The nitrogen of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by the embodiment one to three of table 1 is inhaled
Attached-desorption data
As shown in Table 1, the product that prepared by embodiment one is based on microporous properties, and product prepared by embodiment two and three is to be situated between
Based on pore property.
Fig. 3 is the scanning electron microscope (SEM) photograph of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment one,
2000 times of amplification；Fig. 4 is the ESEM of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment one
Figure, amplify 10000 times；Fig. 5 is the scanning of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Electron microscope, amplify 2000 times；Fig. 6 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Scanning electron microscope (SEM) photograph, amplify 10000 times；Fig. 7 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment three
The scanning electron microscope (SEM) photograph at end, amplify 2000 times；Fig. 8 is multi-stage porous titanium-terephthalic acid metal organic catalysis prepared by embodiment three
The scanning electron microscope (SEM) photograph of agent powder, amplify 10000 times；As seen from the figure, multi-stage porous titanium-terephthalic acid metal that prepared by embodiment one
Organic catalyst powder is the prismatic particle that size is 500nm~1000nm；Multi-stage porous titanium prepared by embodiment two-to benzene two
Metal organic catalyst powder is the chrysanthemum shape particle that size is 200nm~800nm；Multi-stage porous prepared by embodiment three
Titanium-terephthalic acid metal organic catalyst powder is the petal shape particle that size is 100nm~700nm.
Fig. 9 is the infared spectrum of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two；By
Map analysis, TiCl4Interacted really between BDC, generate metallo organic material.
Figure 10 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder all elements prepared by embodiment two
XPS collection of illustrative plates, table 4 are the XPS elements point of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Analysis, as can be seen that containing tetra- kinds of elements of Ti, C, O and N from Figure 10 and table 4.
The XPS elementary analyses of multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by the embodiment two of table 4
| Title | Peak position | Half-peak breadth | Peak area | Element mass percent % |
| Ti 2p | 459.00 | 1.13 | 10775.60 | 15.37 |
| O 1s | 530.50 | 1.69 | 8171.67 | 29.89 |
| N 1s | 402.20 | 3.40 | 346.90 | 2.08 |
| C 1s | 285.00 | 1.30 | 5130.44 | 52.66 |
The XPS figures that Figure 11 is Ti in multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Spectrum, from map analysis, contains four-coordination and hexa-coordinate titanium in sample；The multi-stage porous titanium that Figure 12 is prepared for embodiment two-to benzene
O XPS collection of illustrative plates in dioctyl phthalate orgnometallic catalyst powder, atlas analysis is understood, Ti-O-Ti keys and active matter are contained in sample
Kind Ti-OH；The XPS figures that Figure 13 is C in multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Spectrum, analysis profiling results show, C-C keys and Ti-O-C keys are contained in sample；The multi-stage porous titanium that Figure 14 is prepared for embodiment two-right
N XPS collection of illustrative plates in phthalic acid orgnometallic catalyst powder, it was demonstrated that contain C-N keys.Result above shows, the material of preparation
Really there is certain metal organic framework, and these skeletons have crossed multistage pore canal together.
Oxidation sweetening is the sulfur method of industrial acquisition low sulfur content fuel most prospect at present.The institute of embodiment one to three
The multi-stage porous titanium of preparation-terephthalic acid metal organic catalyst powder all has very superior performance on oxidation sweetening,
And result is basically identical.Oxidation sweetening specific implementation process is as follows：Oxidation sweetening experiment is stirred at one equipped with condenser pipe and magnetic force
Carried out in the three-necked flask mixed, BT, DBT or 4,6-DMDBT are sulfur-containing compound, and sulfur-containing compound is added into normal octane, is obtained
To simulation oil, when described sulfur-containing compound is BT or DBT, sulfur content is 1000ppmw in simulation oil, described Containing Sulfur
When compound is 4,6-DMDBT, sulfur content is 500ppmw in simulation oil, and the 10g simulation oils prepared are put into three-necked flask,
Multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by 50mg embodiments two is added afterwards, stirs 10min, then
Continue to be heated with stirring to temperature as 60 DEG C, under conditions of temperature is 60 DEG C, heats 10min, oxidant, oxygen sulphur are added in last
Be 6 than (O/S), obtain mixture, be designated as reacting initial time this moment, after sampling at regular intervals carry out gas-chromatography point
Analysis；
The TBHP that described oxidant is cumyl hydroperoxide (CHP), mass percent is 70%
(TBHP) or mass percent be 30% hydrogen peroxide (H2O2)；
Figure 15 is that multi-stage porous titanium-terephthalic acid metal organic catalyst Powder Oxidation desulfurization prepared by embodiment two removes
Sulfur-containing compound BT, DBT and 4,6-DMDBT comparison diagram, 1 is DBT, 2 be 4,6-DMDBT, 3 be BT；As seen from the figure, embodiment
Two in 30min can remove 4,6-DMDBT, 45min completely and can remove 4,6-DMDBT, 60min completely and just can be removed
More than 92% BT.
Catalytic oxidation of benzyl alcohol reaction is carried out in a three-necked flask for being equipped with condenser pipe, and equipped with band oil bath
Magnetic stirring apparatus, 1mmol phenmethylol is dissolved in 10mL acetonitrile, then adds multistage prepared by 50mg embodiments two
Hole titanium-terephthalic acid metal organic catalyst powder, obtains mixture, mixture is heated to 80 DEG C under magnetic stirring,
Under conditions of temperature is 80 DEG C, 10min is heated, then adds the TBHP that 3mmol mass percents are 70%
(TBHP) or mass percent be 30% hydrogen peroxide (H2O2), after reacting certain time, sampling carries out gas-chromatography point
Analysis.Experimental result is as shown in table 2, and the primary product of the reaction is benzaldehyde, and also accessory substance benzoic acid generates in addition.
Cyclohexene catalytic oxidation is carried out in a three-necked flask for being equipped with condenser pipe, and equipped with band oil bath
Magnetic stirring apparatus, 2mmol cyclohexene is dissolved in 10mL acetonitrile, then adds multistage prepared by 50mg embodiments two
Hole titanium-terephthalic acid metal organic catalyst powder, obtains mixture, mixture is heated to 80 DEG C under magnetic stirring,
10min is heated, then add 3mmol mass percents is for 70% TBHP (TBHP) or mass percent
30% hydrogen peroxide (H2O2), react sampling progress gas chromatographic analysis after certain time.The reaction experiment result such as institute of table 3
Show, primary product is β-cyclonene, in addition also accessory substance β-cyclohexenol, 7-oxa-bicyclo[4.1.0 and 1,2- cyclohexane diol
Generation.
Table 2 is multi-stage porous titanium-terephthalic acid metal organic catalyst Powder Oxidation benzyl carbinol prepared by embodiment two
Performance data
A is benzaldehyde in table 2；B is benzoic acid.
Table 3 is multi-stage porous titanium-terephthalic acid metal organic catalyst Powder Oxidation cyclohexene prepared by embodiment two
Performance data
A is 2- cyclohexenols in table 3；B is 2- cyclonenes；C is 7-oxa-bicyclo[4.1.0；D is 1,2- cyclohexane diols.
Table 2 and table 3 are the design parameters of Oxybenzene methyl alcohol and cyclohexene.Contrast understands that product prepared by embodiment two exists
During using TBHP as oxidant, equally there is excellent oxidation susceptibility in Oxybenzene methyl alcohol and cyclohexene.
Claims (10)
1. a kind of preparation method of multi-stage porous titanium-terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity,
A kind of it is characterized in that preparation side of multi-stage porous titanium-terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity
What method was specifically realized by the following steps：
First, under magnetic stirring, terephthalic acid (TPA) is added to N, is dissolved in N- dimethylformamides, obtain mixed solution；
Described terephthalic acid (TPA) and the mol ratio of N, N- dimethylformamide are 1:(65~720)；
2nd, titanium tetrachloride, and mole of terephthalic acid (TPA) and titanium tetrachloride in described mixed solution are added into mixed solution
Than for 1:(0.5~2), stirring 2min~10min on magnetic stirring apparatus is subsequently placed in, and the mixed solution after stirring is placed in tool
Have in the stainless steel cauldron of polytetrafluoroethyllining lining, under conditions of temperature is 100 DEG C~220 DEG C, crystallization 3h~30h, treat
Reactor cools down, and centrifuges, obtains reacted solid；
3rd, under conditions of temperature is 20 DEG C~80 DEG C, reacted solid is washed into 3h~12h, filtering using organic solvent
Separation, obtains the solid after once washing；
4th, the solid after once washing is repeated 2 times~4 times by step 3, finally in the case where temperature is 50 DEG C~160 DEG C of vacuum
Drying, obtains multi-stage porous titanium-terephthalic acid metal organic catalyst.
2. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that the organic solvent described in step 3 is absolute ethyl alcohol or N, N- dimethyl acyl
Amine.
3. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that the mol ratio of terephthalic acid (TPA) and N, N- dimethylformamide described in step 1
For 1:260.
4. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that terephthalic acid (TPA) and titanium tetrachloride rubs in the mixed solution described in step 2
You are than being 1:1.
5. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that in step 2 under conditions of temperature is 220 DEG C, crystallization 24h.
6. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that in step 2 under conditions of temperature is 180 DEG C, crystallization 24h.
7. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that in step 2 under conditions of temperature is 150 DEG C, crystallization 24h.
8. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that in step 3 under conditions of temperature is 60 DEG C, will be reacted using organic solvent
Solid washing 8h afterwards.
9. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that in step 3 under conditions of temperature is 60 DEG C~80 DEG C, utilize organic solvent
Reacted solid is washed into 8h~12h.
10. a kind of multi-stage porous titanium-terephthalic acid metal with efficiently catalyzing and oxidizing activity according to claim 1 has
The preparation method of machine catalyst, it is characterised in that finally dried in step 4 in the case where temperature is 150 DEG C of vacuum.
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| CN114160102A (en) * | 2020-09-11 | 2022-03-11 | 中国科学院大连化学物理研究所 | Adsorbent and application thereof |
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