CN108906134A - A kind of titanic oxide material, preparation method and load type palladium catalyst - Google Patents
A kind of titanic oxide material, preparation method and load type palladium catalyst Download PDFInfo
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- CN108906134A CN108906134A CN201810738500.3A CN201810738500A CN108906134A CN 108906134 A CN108906134 A CN 108906134A CN 201810738500 A CN201810738500 A CN 201810738500A CN 108906134 A CN108906134 A CN 108906134A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009835 boiling Methods 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000012876 carrier material Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- -1 cyclic hexanols Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000010148 water-pollination Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of titanic oxide material, preparation method and load type palladium catalysts, the preparation method of titanic oxide material is by weight, 5 ~ 6 parts of boric acid is dissolved in 10 ~ 11 parts of dehydrated alcohol, 10 ~ 11 parts of butyl titanate is added thereto again, is placed in autoclave 23 ~ 25h of reaction at 175 ~ 185 DEG C；Separation of solid and liquid obtains white preformed objects, it is boiled to 1 ~ 2h in 100 ~ 300 parts of boiling water, is separated by solid-liquid separation, obtains titanic oxide material after drying；The titanium dioxide carrier material that mass ratio is 35: 1 ~ 350: 1 is mixed with palladium acetylacetonate, is first heated in a hydrogen atmosphere again in nitrogen, up to load type palladium catalyst after cooling.Preparation method operating process of the present invention succinctly facilitates, and dispersion degree of the palladium on carrier is high, and partial size is small, which can be used for catalysis of phenol and hydrogen is added to prepare cyclohexanone, and catalytic activity and target product selectivity with higher are suitable for industrialized production and popularization and application.
Description
Technical field
The present invention relates to a kind of titanic oxide material and load type palladium catalysts, concretely relate to a kind of titanium dioxide
Material, preparation method and load type palladium catalyst.
Background technique
As the important source material of production caprolactam and adipic acid, cyclohexanone is industry important in polymer industry field
Chemicals, production technology have following three kinds：1）Asahi process, the process are related to three-step reaction, i.e. the part of benzene hydrogenates
To cyclohexene, cyclohexene hydration to cyclohexanol, cyclohexanol dehydrogenation to cyclohexanone；2）Cyclohexane oxidation process, the product of the process
Other than having cyclohexanone, there are also by-product cyclic hexanols；3）Phenol hydrogenation prepares cyclohexanone, can be divided into the preparation of direct hydrogenation one-step method
Cyclohexanone and plus hydrogen, dehydration two-step method prepare cyclohexanone.The core principles of green sustainable chemistry be " Atom economy " and
" zero-emission " be raw material one-step synthesis method cyclohexanone by phenol is therefore ideal synthesizing mean, and this method both can be
It carries out, can also be carried out in liquid phase reactor under gas phase condition, wherein the reaction under liquid-phase condition is grasped due to its low energy consumption and easily
The property made is the process flow for more meeting green sustainable chemistry.However, existing in the catalyst with preferable hydrogenation activity
Under, target product cyclohexanone is easy to be generated cyclohexanol into excessive hydrogenation, especially when phenol has higher conversion, very
It is difficult to guarantee catalyst and higher selectivity is still kept to cyclohexanone, therefore, there is high activity and higher target product to select for development
The catalyst of property is an extremely important and extremely challenging project.
The Han Buxing academician seminar of Institute of Chemistry, Academia Sinica（Science, 2009,326,1250）Report
Pd/C+AlCl3Catalyst system, should since the Lewis of AlCl3 is acid under lower reaction temperature and lower Hydrogen Vapor Pressure
Catalyst system can still keep 99.9% cyclohexanone selectivity when the conversion ratio of phenol reaches 99.9%.Zhejiang University Wang Yong
Teach seminar（J.Am.Chem.Soc,2011,133(8):2362-2365.）It reports carbon-supported using graphitization nitridation
The phenol selectivity hydrogenation of Pd nano-particle catalyst catalysis, equally under conditions of more mild, in the conversion of phenol
When rate reaches 99%, still maintain>99% cyclohexanone selectivity, author think that the N in carrier can be with the hydroxyl in phenol
H-shaped has stronger interaction at hydrogen bond, can be by new phenol after the phenol of absorption is hydrogenated into as cyclohexanone
Replaced molecule, therefore the catalyst can keep higher cyclohexanone selectivity during phenol hydrogenation.Titirici etc.
（Chem Commun,2008,999-1001.）It is prepared for hydrophilic Pd/C catalyst using the method for hydrothermal synthesis, due to urging
Agent has hydrophily, and in aqueous solution, the hydrophobic cyclohexanone of generation can be dislodged catalyst surface, avoid cyclohexanone
It is further hydrogenated into as cyclohexanol, therefore also cyclohexanone selectivity with higher.
Although these catalyst are to cyclohexanone selectivity with higher and yield, it is complicated that there are support preparation methods,
The problems such as specific surface area is small, and the active metal of load is more, and the production cycle is long, at high cost, it is difficult to carry out large-scale industry metaplasia
It produces.Therefore, need to develop that a kind of support preparation method is simple, in the case where can satisfy the demand of selectivity and yield, supported active
The less high efficiency load type palladium catalyst of metal.
Summary of the invention
An object of the present invention is to provide a kind of preparation method of titanic oxide material, to solve existing titanium dioxide titanium
The preparation method of material is complicated, and supported active metals are more, problem at high cost.
The second object of the present invention is to provide a kind of titanic oxide material, it is suitable as carrier material.
The third object of the present invention is to provide a kind of application of titanic oxide material in terms of as catalyst carrier.
The fourth object of the present invention is to provide a kind of preparation method of load type palladium catalyst, to solve existing load type palladium
The problem of catalyst preparation process is complicated, and time-consuming.
The fifth object of the present invention is to provide a kind of load type palladium catalyst, to obtain in the less activity gold of supported on carriers
The catalyst of category, phenol hydrogenation prepare catalytic activity and selectivity with higher in hexamethylene reactive ketone.
The sixth object of the present invention is to provide a kind of load type palladium catalyst and prepares in hexamethylene reactive ketone in phenol hydrogenation
Using.
What an object of the present invention was realized in：
5 ~ 6 parts of boric acid is dissolved in 10 ~ 11 parts of dehydrated alcohol by weight by a kind of preparation method of titanic oxide material
In, then the butyl titanate of 10 ~ 11 parts of addition thereto, and stir evenly, obtain mixed solution；Gained mixed solution is placed in
It in autoclave and seals, in 175 ~ 185 23 ~ 25h of lower reaction；After cooling, white preformed objects are obtained through being separated by solid-liquid separation；Later
Gained preformed objects are boiled into 1 ~ 2h in 100 ~ 300 parts of boiling water, is separated by solid-liquid separation, obtains titanic oxide material after drying.
Preferably, it disperses the boric acid of 5 parts by weight in 10 parts by weight dehydrated alcohols, the metatitanic acid of 10 parts by weight is then added
Four butyl esters, obtain mixed solution.
Preferably, it after white preformed objects being boiled 1 ~ 2h in 100 ~ 300 parts of boiling water, is separated by solid-liquid separation using filtering, institute
It states to be filtered into and filter while hot, the drying is to be dried in vacuo at room temperature.
The second object of the present invention is to what is be achieved：
The titanic oxide material being prepared using aforementioned preparation process, doped with a small amount of boron element.
What the third object of the present invention was realized in：
Support applications can be used as in catalyst field using the titanic oxide material that aforementioned preparation process is prepared；It is excellent
Selection of land, the titanic oxide material can be used as the carrier of load type palladium catalyst.
What the fourth object of the present invention was realized in：
A kind of preparation method of load type palladium catalyst, includes the following steps：
（a）Prepare titanium dioxide carrier material：By weight, 5 ~ 6 parts of boric acid is dissolved in 10 ~ 11 parts of dehydrated alcohol,
10 ~ 11 parts of butyl titanate is added thereto again, and stirs evenly, obtains mixed solution；Gained mixed solution is placed in height
It in pressure reaction kettle and seals, in 175 ~ 185 23 ~ 25h of lower reaction；After cooling, white preformed objects are obtained through being separated by solid-liquid separation；Later will
Gained preformed objects boil 1 ~ 2h in 100 ~ 300 parts of boiling water, are separated by solid-liquid separation, obtain titanium dioxide carrier material after drying；
（b）The titanium dioxide carrier material that mass ratio is 35: 1 ~ 350: 1 is mixed with palladium acetylacetonate, it, will after grinding uniformly
The mixture heats 4 ~ 5h at 118 DEG C ~ 122 DEG C in a nitrogen atmosphere, and atmosphere is switched to hydrogen later, keep 30min ~
Load type palladium catalyst can be obtained after cooling in 45min.
Preferably, step（a）In, it disperses the boric acid of 5 parts by weight in 10 parts by weight dehydrated alcohols, 10 weights is then added
The butyl titanate for measuring part, obtains mixed solution.
After white preformed objects are boiled 1 ~ 2h in 100 ~ 300 parts of boiling water, it is separated by solid-liquid separation using filtering, it is described to be filtered into
It filters while hot, the drying is to be dried in vacuo at room temperature.
Step（b）In, titanium dioxide and palladium acetylacetonate mixture are slowly heated to 120 DEG C of holding 4h in nitrogen
Afterwards, atmosphere is switched into hydrogen, continues to keep 30min, cooling obtains product.
What the fifth object of the present invention was realized in：
A kind of load type palladium catalyst, uses preceding method to be prepared, the work loaded in gained load type palladium catalyst
Property Metal Palladium particle diameter be not more than 2nm.
What the sixth object of the present invention was realized in：
Load type palladium catalyst prepares the application in hexamethylene reactive ketone in phenol hydrogenation, and reactivity is high, and selectivity is high.
The present invention is by using the titanium dioxide that boric acid, butyl titanate are that a small amount of boron element of doping has been prepared in raw material
Carrier, resulting vehicle partial size are about 10nm or so；By the way that load type palladium catalysis is prepared in supported on carriers active component palladium
Agent, dispersion degree of the palladium on carrier is high, and partial size is small, and active component content is lower than existing commercialized catalyst, which can
Cyclohexanone, catalytic activity and target product selectivity with higher are prepared for catalysis of phenol plus hydrogen.
Preparation method operating process of the invention succinctly facilitates, and reacting remaining boric acid can recycle, and is conducive to save
About cost is suitable for industrialized production and popularization and application.
Detailed description of the invention
Fig. 1 is the TEM figure of load type palladium catalyst prepared by embodiment 5.
Fig. 2 ~ 6 are the element M apping figures of load type palladium catalyst prepared by embodiment 5, wherein Fig. 2 is each element
Combination chart, Fig. 3 ~ 6 be respectively B element, Ti element, Pd element and O element distribution map.
Fig. 7 ~ 10 are the SEM figures of load type palladium catalyst prepared by embodiment 5.
Specific embodiment
Below with reference to embodiment, the present invention is further elaborated, and following embodiments are only as explanation, not with any
Mode limits the scope of the invention.
Agents useful for same is to analyze pure or chemical pure and commercially available or pass through those of ordinary skill in the art in embodiment
Well known method preparation.Following embodiments realize the purpose of the present invention.
1 B-TiO of embodiment2Preparation
5 g boric acid are dissolved in 10 ml dehydrated alcohols, ultrasonic disperse, 10 ml butyl titanates are then added, and stir evenly,
Obtain mixture；The mixture is enclosed in autoclave, is kept for 24 hours in 180 DEG C of baking ovens；Cooled to room temperature filters
To white preformed objects；Gained white preformed objects are boiled into 2h in 300ml boiling water, are filtered while hot, are washed, it is dry, it obtains for bearing
Carry the titania support of Pd nano particle.
Embodiment 2
5g boric acid is dissolved in 10 ml dehydrated alcohols, ultrasonic disperse, 10 ml butyl titanates is then added, and stir evenly,
Obtain mixture；The mixture is enclosed in autoclave, is kept for 24 hours in 180 DEG C of baking ovens；Cooled to room temperature filters
To white preformed objects；Gained white preformed objects are boiled into 1h in 300ml boiling water, are filtered while hot, are washed, it is dry, obtain titanium dioxide
Titanium carrier.
Embodiment 3
5g boric acid is dissolved in 11 ml dehydrated alcohols, ultrasonic disperse, 11 ml butyl titanates is then added, and stir evenly,
Obtain mixture；The mixture is enclosed in autoclave, keeps 23h in 185 DEG C of baking ovens；Cooled to room temperature filters
To white preformed objects；Gained white preformed objects are boiled into 1h in 300ml boiling water, are filtered while hot, are washed, it is dry, obtain titanium dioxide
Titanium carrier.
Embodiment 4
6g boric acid is dissolved in 10 ml dehydrated alcohols, ultrasonic disperse, 10 ml butyl titanates is then added, and stir evenly,
Obtain mixture；The mixture is enclosed in autoclave, keeps 25h in 175 DEG C of baking ovens；Cooled to room temperature filters
To white preformed objects；Gained white preformed objects are boiled into 1h in 100ml boiling water, are filtered while hot, are washed, it is dry, obtain titanium dioxide
Titanium carrier.
51 wt% Pd-B-TiO of embodiment2Preparation
The titania support that weighing 0.0143g palladium acetylacetonate and 0.5 g embodiment 1 are prepared, places it in agate and grinds
It grinds uniformly in alms bowl, is then slowly heated the mixture in nitrogen atmosphere（Heating rate is 10 DEG C/min）To 120 DEG C, protect
4h is held, atmosphere is then switched into hydrogen, continues to keep 30min, obtains load type palladium catalyst after cooling.According to what is loaded
The mass fraction of palladium is denoted as 1 wt% Pd-B-TiO2。
Transmission electron microscope analysis is carried out to gained load type palladium catalyst, acquired results are as shown in Figure 1.It can from figure
Out, use the Pd in catalyst made from this method for the nanoparticle less than 2nm.
TEM-mapping analysis is carried out to gained load type palladium catalyst, acquired results, can from figure as shown in Fig. 2 ~ 6
To find out, a small amount of Pd element is distributed evenly on titanium dioxide, and Pd nanoparticle is smaller and discovery is not obvious reunites
Phenomenon；It has also been found that a small amount of B element is distributed on titanium dioxide.
Electron microscope analysis is scanned to gained load type palladium catalyst, acquired results, can be with from figure as shown in Fig. 7 ~ 10
Find out, titania support is Nano grade in catalyst, is in amorphous state.
Embodiment 6
It is the catalysis of 0.1wt%, 0.5 wt% and 2wt% according to the mass fraction that the method for embodiment 5 prepares loaded palladium respectively
Agent, and successively it is denoted as 0.1 wt% Pd-B-TiO2、0.5 wt% Pd-B-TiO2With 2 wt% Pd-B-TiO2。
Embodiment 7
The titania support that weighing 0.0143g palladium acetylacetonate and 0.5 g embodiment 1 are prepared, places it in agate and grinds
It grinds uniformly in alms bowl, is then slowly heated the mixture in nitrogen atmosphere（Heating rate is 10 DEG C/min）To 118 DEG C, protect
5h is held, atmosphere is then switched into hydrogen, continues to keep 30min, obtains load type palladium catalyst after cooling.
Embodiment 8
The titania support that weighing 0.0143g palladium acetylacetonate and 0.5 g embodiment 1 are prepared, places it in agate and grinds
It grinds uniformly in alms bowl, is then slowly heated the mixture in nitrogen atmosphere（Heating rate is 10 DEG C/min）To 122 DEG C, protect
4h is held, atmosphere is then switched into hydrogen, continues to keep 45min, obtains load type palladium catalyst after cooling.
Comparative example 1
From the Pd/C catalyst of Aladdin Reagent Company purchase business（Pd content is 5%）, weigh 10mgPd/C catalyst, palladium with
Mole metering of substrate places it in 20mL autoclave, then sequentially add 1mmol phenol thereto than being 0.5%mol
With 3mL water, then after capping kettle, it is filled with hydrogen, Hydrogen Vapor Pressure keeps 0.4 MPa；Reaction kettle is put into 80 DEG C of oil
2h is kept, the conversion ratio and yield reacted using gas chromatographic detection.
Embodiment 9
1 wt%Pd-B-TiO of the preparation of 50mg embodiment 5,6 is weighed respectively2、500 mg 0.1 wt% Pd-B-TiO2、100
mg 0.5 wt% Pd-B-TiO2With 2 wt% Pd-B-TiO of 25mg2, placed it in 20mL autoclave respectively, then to each
1mmol phenol and 3mL water are sequentially added in reaction kettle, keep palladium and substrate（Phenol）Mole metering than be 0.5% mol, so
After rear enclosed reaction kettle, it is filled with hydrogen, Hydrogen Vapor Pressure keeps 0.4 MPa；Reaction kettle is put into 80 DEG C of oil and keeps 2h, utilized
The conversion ratio and yield of gas chromatographic detection reaction.
The reaction result of comparative example 1 and embodiment 9 is as shown in table 1.
Response data of the 1 difference Pd content catalyst of table when the reaction time is 30min
Embodiment 10
4 parts of 1 wt%Pd-B-TiO of 50mg are weighed respectively2, place it in 20mL autoclave, then into each reaction kettle according to
Secondary addition 1mmol phenol and 3mL water then after capping kettle, are filled with hydrogen, and Hydrogen Vapor Pressure keeps 0.4 MPa；By each reaction
Kettle, which is respectively put into 80 DEG C of oil, to be kept 2h, 6h is kept in 80 DEG C of oil, keeps keeping in 25 DEG C of oil for 24 hours in 50 DEG C of oil
9h, the conversion ratio and yield reacted using gas chromatographic detection, acquired results are as shown in table 2.
21 % Pd-B-TiO of difference of table2Response data at different conditions
Claims (10)
1. a kind of preparation method of titanic oxide material, which is characterized in that by weight, 5 ~ 6 parts of boric acid is dissolved in 10 ~ 11
In the dehydrated alcohol of part, then the butyl titanate of 10 ~ 11 parts of addition thereto, and stir evenly, obtain mixed solution；By gained
Mixed solution is placed in autoclave and seals, and 23 ~ 25h is reacted at 175 ~ 185 DEG C；After cooling, obtained through being separated by solid-liquid separation
White preformed objects；Later gained preformed objects are boiled into 1 ~ 2h in 100 ~ 300 parts of boiling water, is separated by solid-liquid separation, obtains titanium dioxide after drying
Titanium material.
2. the preparation method of titanic oxide material according to claim 1, which is characterized in that by the boric acid of 5 parts by weight point
It dissipates in 10 parts by weight dehydrated alcohols, the butyl titanate of 10 parts by weight is then added, obtains mixed solution.
3. the preparation method of titanic oxide material according to claim 1, which is characterized in that by white preformed objects 100 ~
It after boiling 1 ~ 2h in 300 parts of boiling water, is separated by solid-liquid separation using filtering, described be filtered into filters while hot, and the drying is at room temperature
Vacuum drying.
4. a kind of titanium dioxide titanium that the preparation method using titanic oxide material claimed in any one of claims 1 to 3 obtains
Material.
5. a kind of application of titanic oxide material as claimed in claim 4 in terms of catalyst carrier.
6. a kind of preparation method of load type palladium catalyst, which is characterized in that include the following steps：
（a）Prepare titanium dioxide carrier material：By weight, 5 ~ 6 parts of boric acid is dissolved in 10 ~ 11 parts of dehydrated alcohol,
10 ~ 11 parts of butyl titanate is added thereto again, and stirs evenly, obtains mixed solution；Gained mixed solution is placed in height
It in pressure reaction kettle and seals, 23 ~ 25h is reacted at 175 ~ 185 DEG C；After cooling, white preformed objects are obtained through being separated by solid-liquid separation；Later
Gained preformed objects are boiled into 1 ~ 2h in 100 ~ 300 parts of boiling water, is separated by solid-liquid separation, obtains titanium dioxide carrier material after drying；
（b）The titanium dioxide carrier material that mass ratio is 35: 1 ~ 350: 1 is mixed with palladium acetylacetonate, it, will after grinding uniformly
The mixture heats 4 ~ 5h at 118 DEG C ~ 122 DEG C in a nitrogen atmosphere, and atmosphere is switched to hydrogen later, keep 30min ~
Load type palladium catalyst can be obtained after cooling in 45min.
7. the preparation method of load type palladium catalyst according to claim 6, which is characterized in that step（a）In, it will be white
It after preformed objects boil 1 ~ 2h in 100 ~ 300 parts of boiling water, is separated by solid-liquid separation using filtering, described be filtered into filters while hot, described
Dry is to be dried in vacuo at room temperature.
8. the preparation method of load type palladium catalyst according to claim 6, which is characterized in that step（b）In, by dioxy
The mixture for changing titanium carrier material and palladium acetylacetonate is heated to 120 DEG C of holding 4h in nitrogen with the heating rate of 10 DEG C/min
Afterwards, atmosphere is switched into hydrogen, continues to keep 30min, load type palladium catalyst can be obtained after cooling.
9. a kind of load type palladium that the preparation method using load type palladium catalyst described in claim 6,7 or 8 obtains is urged
Agent.
10. a kind of load type palladium catalyst as claimed in claim 9 prepares the application in hexamethylene reactive ketone in phenol hydrogenation.
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| CN115999611A (en) * | 2023-01-19 | 2023-04-25 | 浙江工业大学 | Magnesium-nitrogen co-doped titanium dioxide supported palladium-indium bimetallic catalyst and preparation method and application thereof |
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| CN114315885A (en) * | 2021-12-28 | 2022-04-12 | 山东金城柯瑞化学有限公司 | Method for catalytically synthesizing methyl 3-hydroxy-4- ((trimethylsilyl) ethynyl) benzoate |
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| CN115999611A (en) * | 2023-01-19 | 2023-04-25 | 浙江工业大学 | Magnesium-nitrogen co-doped titanium dioxide supported palladium-indium bimetallic catalyst and preparation method and application thereof |
| CN115999611B (en) * | 2023-01-19 | 2024-07-19 | 浙江工业大学 | Magnesium-nitrogen co-doped titanium dioxide supported palladium-indium bimetallic catalyst and preparation method and application thereof |
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