CN107335471B - A kind of preparation method with the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing - Google Patents
A kind of preparation method with the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing Download PDFInfo
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- CN107335471B CN107335471B CN201710686820.4A CN201710686820A CN107335471B CN 107335471 B CN107335471 B CN 107335471B CN 201710686820 A CN201710686820 A CN 201710686820A CN 107335471 B CN107335471 B CN 107335471B
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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 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 230000001590 oxidative effect Effects 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 103
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 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 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims description 12
- 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
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 22
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 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
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 17
- 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
- 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
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000003321 amplification Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000003199 nucleic acid amplification method Methods 0.000 description 7
- 229910052719 titanium Inorganic materials 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
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product 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
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 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
- 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
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000006227 byproduct Substances 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
- PQANGXXSEABURG-UHFFFAOYSA-N cyclohex-2-en-1-ol Chemical compound OC1CCCC=C1 PQANGXXSEABURG-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying 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
- 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
- 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
- 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
- 238000000921 elemental analysis Methods 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
- -1 t-butyl peroxy Chemical group 0.000 description 1
Classifications
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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
- 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]
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/638—
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method with the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing, 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 major part titaniferous (Ti) MOF crystallinity, there is no utilizable Ti active site, the lower problem of the activity in catalysis reaction.Method: terephthalic acid (TPA) is added to N, is dissolved in N- dimethylformamide, obtains mixed solution；Titanium tetrachloride is added into mixed solution, is placed on magnetic stirring apparatus and stirs, cooling then by the mixed solution crystallization after stirring, centrifuge separation, the solid after being reacted；The solid after reaction is washed using organic solvent, is separated by filtration, is dried under last vacuum, obtain multi-stage porous titanium-terephthalic acid metal organic catalyst.The present invention is used for the preparation method with the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing.
Description
Technical field
The present invention relates to a kind of preparation methods of multi-stage porous titanium-terephthalic acid metal organic catalyst.
Background technique
Metal-organic framework materials (MOFs) as a kind of novel 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, storage and transportation and catalysis
It has a wide range of applications.Wherein, titaniferous (Ti) MOF has Ti active specy and is concerned.However, most of titaniferous
(Ti) MOF crystallinity is all very good, there is no utilizable Ti active site, and the activity in catalysis reaction is lower.
Mesoporous or multi-stage porous material containing Ti has big aperture, can guarantee that reactant passes in and out duct, promotes catalysis anti-
Should carry out.In addition, the mesoporous or multi-stage porous having more can also expose more active sites, be more conducive to catalysis react into
Row.However even if titanium (Ti) MOF is prepared mesoporous or multi-stage porous, since its crystallinity is still higher, almost all of Ti
Site is all occupied by organic ligand, is exposed without enough active sites, is not helped much still to catalysis reaction, existing
There is oxidation desulfurization performance to be only capable of removing 70% sulfur-containing compound.Therefore, metallo organic material is prepared into undefined structure, just
More active sites can be exposed, catalytic oxidation performance is greatly improved.
Summary of the invention
All very good the invention aims to solve existing major part titaniferous (Ti) MOF crystallinity, there is no can
With the Ti active site utilized, in the lower problem of the activity being catalyzed in reaction, and providing one kind, there is efficiently catalyzing and oxidizing to live
Multi-stage porous titanium-terephthalic acid metal organic catalyst preparation method of property.
A kind of preparation method with the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing
It is specifically realized by the following steps:
One, terephthalic acid (TPA) under magnetic stirring, is added to N, is dissolved in N- dimethylformamide, obtains mixed solution；
The terephthalic acid (TPA) and N, the molar ratio of N- dimethylformamide are 1:(65~720)；
Two, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in the mixed solution
Molar ratio is 1:(0.5~2), it is subsequently placed in stirring 2min~10min on magnetic stirring apparatus, and the mixed solution after stirring is set
In the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of temperature is 100 DEG C~220 DEG C, crystallization 3h~
30h, centrifuge separation cooling to reaction kettle, the solid after being reacted；
Three, under conditions of temperature is 20 DEG C~80 DEG C, the solid after reaction is washed into 3h~12h using organic solvent,
It is separated by filtration, the solid after obtaining once washing；
Four, 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
The lower drying of sky, obtains multi-stage porous titanium-terephthalic acid metal organic catalyst.
The present invention reports the method by hydrothermal synthesis for the first time, 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 removal benzothiophene (BT), dibenzothiophenes
(DBT) and 4,6- dimethyl Dibenzothiophene (4,6-DMDBT) has excellent performance, and in Oxybenzene methyl alcohol and cyclohexene
Also there is excellent performance.
Advantages of the present invention:
1, organic (Ti-BDC) catalyst of the available multi-stage porous Ti- terephthalic acid metal of method of the invention；Preparation
Multi-stage porous titanium-terephthalic acid metal organic catalyst powder specific surface area in 600m2/ g or so, the spy with multi-stage porous
Property；
2, the catalyst of method of the invention preparation itself has more Ti-OH active specy, is not necessarily to post processing mode
It obtains；The material of preparation has multistage pore property, is not complete metal organic backbone, this amorphous material exposes more
Active site, substantially increase its catalytic oxidation performance；
3, the catalyst of method of the invention preparation has very high catalysis oxygen in oxidation sweetening, Oxybenzene methyl alcohol and cyclohexene
Change performance, relative to other titaniferous MOF material, catalytic performance increases at multiple.Oxidation sweetening performance: can in 30min
To remove completely DBT, 45min can remove completely 4,6-DMDBT, 60min just and can be removed 92% or more BT；Oxybenzene first
Alcohol: when using tert-butyl hydroperoxide as oxidant, for conversion ratio up to 92.4%, cyclohexene: being oxidation with tert-butyl hydroperoxide
When agent, conversion ratio is up to 95.1%.
The present invention has the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing for a kind of
Preparation method.
Detailed description of the invention
Fig. 1 is XRD spectrum, the 1 multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared for embodiment one, 2
For multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two, 3 multi-stage porous prepared for embodiment three
Titanium-terephthalic acid metal organic catalyst powder；
Fig. 2 is nitrogen adsorption isotherm, the 1 multi-stage porous titanium-terephthalic acid metal organic catalysis prepared for embodiment one
Agent powder, the 2 multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared for embodiment two, 3 prepare for embodiment three
Multi-stage porous titanium-terephthalic acid metal organic catalyst powder；
Fig. 3 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning electron microscope (SEM) photograph prepared by embodiment one,
2000 times of amplification；
Fig. 4 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning electron microscope (SEM) photograph prepared by embodiment one,
10000 times of amplification；
Fig. 5 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning electron microscope (SEM) photograph prepared by embodiment two,
2000 times of amplification；
Fig. 6 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning electron microscope (SEM) photograph prepared by embodiment two,
10000 times of amplification；
Fig. 7 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning electron microscope (SEM) photograph prepared by embodiment three,
2000 times of amplification；
Fig. 8 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning electron microscope (SEM) photograph prepared by embodiment three,
10000 times of amplification；
Fig. 9 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder infared spectrum prepared by embodiment two；
Figure 10 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder all elements prepared by embodiment two
XPS map；
The XPS figure that Figure 11 is Ti in multi-stage porous titanium-terephthalic acid metal organic catalyst powder of the preparation of embodiment two
Spectrum；
The XPS figure that Figure 12 is O in multi-stage porous titanium-terephthalic acid metal organic catalyst powder of the preparation of embodiment two
Spectrum；
The XPS figure that Figure 13 is C in multi-stage porous titanium-terephthalic acid metal organic catalyst powder of the preparation of embodiment two
Spectrum；
The XPS figure that Figure 14 is N in multi-stage porous titanium-terephthalic acid metal organic catalyst powder of the preparation of 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, the comparison diagram of 6-DMDBT, 1 is DBT, and 2 be 4,6-DMDBT, 3 be BT.
Specific embodiment
Specific embodiment 1: present embodiment is that one kind has the active multi-stage porous titanium-of efficiently catalyzing and oxidizing to benzene two
What the preparation method of metal organic catalyst was specifically realized by the following steps:
One, terephthalic acid (TPA) under magnetic stirring, is added to N, is dissolved in N- dimethylformamide, obtains mixed solution；
The terephthalic acid (TPA) and N, the molar ratio of N- dimethylformamide are 1:(65~720)；
Two, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in the mixed solution
Molar ratio is 1:(0.5~2), it is subsequently placed in stirring 2min~10min on magnetic stirring apparatus, and the mixed solution after stirring is set
In the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of temperature is 100 DEG C~220 DEG C, crystallization 3h~
30h, centrifuge separation cooling to reaction kettle, the solid after being reacted；
Three, under conditions of temperature is 20 DEG C~80 DEG C, the solid after reaction is washed into 3h~12h using organic solvent,
It is separated by filtration, the solid after obtaining once washing；
Four, 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
The lower drying of sky, 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- dimethylformamide can be abbreviated as DMF；
Titanium tetrachloride (TiCl is added in present embodiment step 24), mixed solution is saturating from colourless well-illuminated flavescence color at this time
Bright solution.
Present embodiment BDC is soluble in DMF, is dissolved in preparation clarification mixed solution；
Present embodiment titanium tetrachloride is easy to DMF reaction, forms compound, prevents titanium tetrachloride from hydrolyzing before the reaction.
The advantages of present embodiment:
1, the available multi-stage porous Ti- terephthalic acid metal of the method for present embodiment organic (Ti-BDC) is catalyzed
Agent；The multi-stage porous titanium of preparation-terephthalic acid metal organic catalyst powder specific surface area is in 600m2/ g or so has more
The characteristic in grade hole；
2, the catalyst of the method preparation of present embodiment itself has more Ti-OH active specy, after being not necessarily to
Processing mode obtains；The material of preparation has multistage pore property, is not complete metal organic backbone, this amorphous material is sudden and violent
Expose more active sites, substantially increases its catalytic oxidation performance；
3, the catalyst of the method preparation of present embodiment has very high in oxidation sweetening, Oxybenzene methyl alcohol and cyclohexene
Catalytic oxidation performance, relative to other titaniferous MOF material, catalytic performance increases at multiple.Oxidation sweetening performance:
DBT can be removed completely in 30min, 45min, which can remove completely 4,6-DMDBT, 60min, just can be removed 92% or more
BT；Oxybenzene methyl alcohol: when using tert-butyl hydroperoxide 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%.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: it is organic described in step 3
Solvent is dehydrated alcohol or N, N- dimethylformamide.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 1
The terephthalic acid (TPA) and N stated, the molar ratio of N- dimethylformamide are 1:260.Other steps and specific embodiment one or two-phase
Together.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: institute in step 2
The molar ratio of terephthalic acid (TPA) and titanium tetrachloride is 1:1 in the mixed solution stated.Other steps and specific embodiment one to three
It is identical.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: in step 2
Under conditions of temperature is 220 DEG C, crystallization is for 24 hours.Other steps are identical as specific embodiment one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: in step 2
Under conditions of temperature is 180 DEG C, crystallization is for 24 hours.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: in step 2
Under conditions of temperature is 150 DEG C, crystallization is for 24 hours.Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: in step 3
Under conditions of temperature is 60 DEG C, the solid after reaction is washed into 8h using organic solvent.Other steps and specific embodiment one
It is identical to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: in step 3
Under conditions of temperature is 60 DEG C~80 DEG C, the solid after reaction is washed into 8h~12h using organic solvent.Other steps and specific
Embodiment one to eight is identical.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: in step 4 most
It is dried afterwards in the case where temperature is 150 DEG C of vacuum.Other steps are identical as specific embodiment one to nine.
Using following embodiment verify this hair name the utility model has the advantages that
Embodiment one: one kind having the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing
Preparation method be specifically realized by the following steps:
One, terephthalic acid (TPA) under magnetic stirring, is added to N, is dissolved in N- dimethylformamide, obtains mixed solution；
The terephthalic acid (TPA) and N, the molar ratio of N- dimethylformamide are 1:260；
Two, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in the mixed solution
Molar ratio is 1:1, 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 ethylene liner, under conditions of temperature is 150 DEG C, crystallization is for 24 hours, cooling to reaction kettle, centrifuge separation,
Solid after being reacted；
Three, under conditions of temperature is 60 DEG C, the solid after reaction is washed into 8h using organic solvent, is separated by filtration, obtains
Solid after to once washing；
Four, the solid after once washing is repeated 2 times by step 3, finally dries, obtains 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 dehydrated alcohol.
Embodiment two: one kind having the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing
Preparation method be specifically realized by the following steps:
One, terephthalic acid (TPA) under magnetic stirring, is added to N, is dissolved in N- dimethylformamide, obtains mixed solution；
The terephthalic acid (TPA) and N, the molar ratio of N- dimethylformamide are 1:260；
Two, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in the mixed solution
Molar ratio is 1:1, 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 ethylene liner, under conditions of temperature is 180 DEG C, crystallization is for 24 hours, cooling to reaction kettle, centrifuge separation,
Solid after being reacted；
Three, under conditions of temperature is 60 DEG C, the solid after reaction is washed into 8h using organic solvent, is separated by filtration, obtains
Solid after to once washing；
Four, the solid after once washing is repeated 2 times by step 3, finally dries, obtains 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 dehydrated alcohol.
Embodiment three: one kind having the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing
Preparation method be specifically realized by the following steps:
One, terephthalic acid (TPA) under magnetic stirring, is added to N, is dissolved in N- dimethylformamide, obtains mixed solution；
The terephthalic acid (TPA) and N, the molar ratio of N- dimethylformamide are 1:260；
Two, titanium tetrachloride is added into mixed solution, and terephthalic acid (TPA) and titanium tetrachloride in the mixed solution
Molar ratio is 1:1, 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 ethylene liner, under conditions of temperature is 220 DEG C, crystallization is for 24 hours, cooling to reaction kettle, centrifuge separation,
Solid after being reacted；
Three, under conditions of temperature is 60 DEG C, the solid after reaction is washed into 8h using organic solvent, is separated by filtration, obtains
Solid after to once washing；
Four, the solid after once washing is repeated 2 times by step 3, finally dries, obtains 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 dehydrated alcohol.
Fig. 1 is XRD spectrum, the 1 multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared for embodiment one, 2
For multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two, 3 multi-stage porous prepared for embodiment three
Titanium-terephthalic acid metal organic catalyst powder；By it is found that 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, the 1 multi-stage porous titanium-terephthalic acid metal organic catalysis prepared for embodiment one
Agent powder, the 2 multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared for embodiment two, 3 prepare for embodiment three
Multi-stage porous titanium-terephthalic acid metal organic catalyst powder；As seen from the figure, multi-stage porous titanium-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 with the characteristic of multi-stage porous.
Multi-stage porous titanium prepared by 1 embodiment one to three of table-terephthalic acid metal organic catalyst powder nitrogen 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 multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning electron microscope (SEM) photograph prepared by embodiment one,
2000 times of amplification；Fig. 4 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning electron microscope prepared by embodiment one
Figure amplifies 10000 times；Fig. 5 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder scanning prepared by embodiment two
Electron microscope amplifies 2000 times；Fig. 6 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by embodiment two
Scanning electron microscope (SEM) photograph amplifies 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 amplifies 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 amplifies 10000 times；As seen from the figure, multi-stage porous titanium-terephthalic acid metal prepared by embodiment one
Organic catalyst powder is the prismatic particle having a size of 500nm~1000nm；Multi-stage porous titanium-prepared by embodiment two is to benzene two
Metal organic catalyst powder is the chrysanthemum shape particle having a size of 200nm~800nm；Multi-stage porous prepared by embodiment three
Titanium-terephthalic acid metal organic catalyst powder is the petal shape particle having a size of 100nm~700nm.
Fig. 9 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder infared spectrum prepared by embodiment two；By
Map analysis, TiCl4It is interacted really between BDC, generates metallo organic material.
Figure 10 is multi-stage porous titanium-terephthalic acid metal organic catalyst powder all elements prepared by embodiment two
XPS map, table 4 are multi-stage porous titanium-terephthalic acid metal organic catalyst powder XPS element prepared by embodiment two point
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 elemental analysis of multi-stage porous titanium prepared by 4 embodiment two of table-terephthalic acid metal organic catalyst powder
| 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 figure that Figure 11 is Ti in multi-stage porous titanium-terephthalic acid metal organic catalyst powder of the preparation of embodiment two
Spectrum, by map analysis it is found that containing four-coordination and hexa-coordinate titanium in sample；Figure 12 is the multi-stage porous titanium-of the preparation of embodiment two to benzene
The XPS map of O in dioctyl phthalate orgnometallic catalyst powder, atlas analysis is it is found that contain Ti-O-Ti key and active matter in sample
Kind Ti-OH；The XPS figure that Figure 13 is C in multi-stage porous titanium-terephthalic acid metal organic catalyst powder of the preparation of embodiment two
Spectrum, analysis map the result shows that, in sample contain C-C key and Ti-O-C key；Figure 14 is that multi-stage porous titanium-prepared by embodiment two is right
The XPS map of N in phthalic acid orgnometallic catalyst powder, it was demonstrated that contain C-N key.The above result shows that 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.One to three institute of embodiment
The multi-stage porous titanium of preparation-terephthalic acid metal organic catalyst powder all has very superior performance on oxidation sweetening,
And result is almost the same.Oxidation sweetening specific implementation process is as follows: oxidation sweetening experiment is stirred at one equipped with condenser pipe and magnetic force
It is 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, are obtained
To simulation oil, when the sulfur-containing compound is BT or DBT, sulfur content is 1000ppmw in simulation oil, the Containing Sulfur
When conjunction object is 4,6-DMDBT, sulfur content is 500ppmw in simulation oil, and the 10g simulation oil prepared is put into three-necked flask,
Multi-stage porous titanium-terephthalic acid metal organic catalyst powder prepared by 50mg embodiment two is added afterwards, stirs 10min, then
Continue to be heated with stirring to temperature to be 60 DEG C, under conditions of temperature is 60 DEG C, heats 10min, it is finally middle that oxidant, oxygen sulphur is added
Be 6 than (O/S), obtain mixture, be denoted as reaction initial time this moment, after sampling at regular intervals carry out gas-chromatography point
Analysis；
The oxidant is cumyl hydroperoxide (CHP), the tert-butyl hydroperoxide that 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, the comparison diagram of 6-DMDBT, 1 is DBT, and 2 be 4,6-DMDBT, 3 be BT；As seen from the figure, embodiment
Two can remove completely 4,6-DMDBT, 45min in 30min, which can remove completely 4,6-DMDBT, 60min, just can be removed
92% or more BT.
Catalytic oxidation of benzyl alcohol reaction be carried out in a three-necked flask for being equipped with condenser pipe, and equipped with band oil bath
Magnetic stirring apparatus, the benzyl alcohol of 1mmol is dissolved in the acetonitrile of 10mL, then be added 50mg embodiment two prepare multistage
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, the tert-butyl hydroperoxide that 3mmol mass percent is 70% is then added
(TBHP) or mass percent be 30% hydrogen peroxide (H2O2), after a certain period of time, sampling carries out gas-chromatography point for reaction
Analysis.Experimental result is as shown in table 2, and the primary product of the reaction is benzaldehyde, and in addition there are also by-product benzoic acid to generate.
Cyclohexene catalytic oxidation be carried out in a three-necked flask for being equipped with condenser pipe, and equipped with band oil bath
Magnetic stirring apparatus, the cyclohexene of 2mmol is dissolved in the acetonitrile of 10mL, then be added 50mg embodiment two prepare multistage
Hole titanium-terephthalic acid metal organic catalyst powder, obtains mixture, mixture is heated to 80 DEG C under magnetic stirring,
10min is heated, 3mmol mass percent is added then as 70% tert-butyl hydroperoxide (TBHP) or mass percent is
30% hydrogen peroxide (H2O2), sampling carries out gas chromatographic analysis after a certain period of time for reaction.The reaction experiment result such as 3 institute of table
Showing, primary product is β-cyclonene, in addition there are also by-product β-cyclohexenol, 7-oxa-bicyclo[4.1.0 and 1,2- cyclohexane diol
It generates.
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- cyclohexenol in table 3；B is 2- cyclonene；C is 7-oxa-bicyclo[4.1.0；D is 1,2- cyclohexane diol.
Table 2 and table 3 are the design parameters of Oxybenzene methyl alcohol and cyclohexene.Comparison is it is found that product prepared by embodiment two exists
When using tert-butyl hydroperoxide as oxidant, equally there is excellent oxidation susceptibility in Oxybenzene methyl alcohol and cyclohexene.
Claims (10)
1. a kind of preparation method with the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing,
It is characterized in that a kind of preparation side with the active multi-stage porous titanium-terephthalic acid metal organic catalyst of efficiently catalyzing and oxidizing
What method was specifically realized by the following steps:
One, under magnetic stirring, terephthalic acid (TPA) is added in n,N-Dimethylformamide and is dissolved, mixed solution is obtained；
The molar ratio of the terephthalic acid (TPA) and N,N-dimethylformamide is 1:(65~720)；
Two, titanium tetrachloride is added into mixed solution, and in the mixed solution terephthalic acid (TPA) and titanium tetrachloride mole
Than for 1:(1~2), it is subsequently placed in stirring 2min~10min on magnetic stirring apparatus, and the mixed solution after stirring is placed in has
In the stainless steel cauldron of polytetrafluoroethyllining lining, under conditions of temperature is 100 DEG C~220 DEG C, crystallization 3h~30h, to anti-
Answer kettle cooling, centrifuge separation, the solid after being reacted；
Three, under conditions of temperature is 20 DEG C~80 DEG C, the solid after reaction is washed into 3h~12h, filtering using organic solvent
Separation, the solid after obtaining once washing；
Four, 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. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
The preparation method of machine catalyst, it is characterised in that organic solvent described in step 3 is dehydrated alcohol or N, N- dimethyl formyl
Amine.
3. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
The preparation method of machine catalyst, it is characterised in that mole of terephthalic acid (TPA) described in step 1 and n,N-Dimethylformamide
Than for 1:260.
4. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
The preparation method of machine catalyst, it is characterised in that terephthalic acid (TPA) and titanium tetrachloride rubs in mixed solution described in step 2
You are than being 1:1.
5. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
The preparation method of machine catalyst, it is characterised in that in step 2 under conditions of temperature is 220 DEG C, crystallization is for 24 hours.
6. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
The preparation method of machine catalyst, it is characterised in that in step 2 under conditions of temperature is 180 DEG C, crystallization is for 24 hours.
7. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
The preparation method of machine catalyst, it is characterised in that in step 2 under conditions of temperature is 150 DEG C, crystallization is for 24 hours.
8. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
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 afterwards washs 8h.
9. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
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
Solid after reaction is washed into 8h~12h.
10. there is one kind according to claim 1 the active multi-stage porous titanium-terephthalic acid metal of efficiently catalyzing and oxidizing to have
The preparation method of machine catalyst, it is characterised in that finally dried in the case where temperature is 150 DEG C of vacuum in step 4.
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