CN105833902B - The preparation method and reclaiming method of a kind of mesoporous solid sulfonic acid catalyst - Google Patents
The preparation method and reclaiming method of a kind of mesoporous solid sulfonic acid catalyst Download PDFInfo
- Publication number
- CN105833902B CN105833902B CN201610196206.5A CN201610196206A CN105833902B CN 105833902 B CN105833902 B CN 105833902B CN 201610196206 A CN201610196206 A CN 201610196206A CN 105833902 B CN105833902 B CN 105833902B
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- sulfonic acid
- acid catalyst
- silicon oxide
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000007787 solid Substances 0.000 title claims abstract description 103
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 79
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 27
- 239000008103 glucose Substances 0.000 claims abstract description 26
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical class Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- -1 polyoxyethylene Polymers 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 238000006277 sulfonation reaction Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 5
- 229910003978 SiClx Inorganic materials 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 claims 1
- 229940125904 compound 1 Drugs 0.000 claims 1
- 229940126214 compound 3 Drugs 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 78
- 239000003054 catalyst Substances 0.000 abstract description 31
- 239000000377 silicon dioxide Substances 0.000 abstract description 23
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000002023 wood Substances 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical class CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 6
- 206010001497 Agitation Diseases 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 3
- 241000165940 Houjia Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B01J35/60—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
Abstract
The invention discloses the preparation method and reclaiming method of a kind of mesoporous solid sulfonic acid catalyst, by varying eight water basic zirconium chlorides in mesoporous silicon oxide preparation process, the mass ratio of trimethylbenzene and tetraethyl orthosilicate, the pore structure of regulation and control gained Metaporous silicon dioxide material, in the preparation process of mesoporous silicon oxide/carbon composite, change the quality for adding glucose, the pore structure of gained mesoporous silicon oxide/carbon composite can further be regulated and controled, realize gained mesoporous solid sulfonic acid catalyst specific surface area, the regulation and control of pore volume and pore size, obtain the mesoporous solid sulfonic acid catalyst of high specific surface area, its preparation process is simple, it is easy to implement;By calcining during catalyst reclaiming, the carbon in mesoporous solid sulfonic acid catalyst can be removed, retrieves the mesoporous silicon oxide with diverse microcosmic pore structure, then regains the mesoporous solid sulfonic acid catalyst of diverse microcosmic pore structure.
Description
Technical field
The present invention relates to solid sulfoacid catalyst, more particularly, to a kind of preparation method of mesoporous solid sulfonic acid catalyst.
Background technology
Conventional homogeneous acid catalyst sulfuric acid, has difficult recycling, equipment corrosion is strong, environmental pollution is tight in its application process
The problems such as weight.It is immobilized to after on solid material by chemical means by homogeneous acid catalyst sulfuric acid, can be by homogeneous acid catalysis
Agent is changed into out-phase solid sulfoacid catalyst, more with good stability than solid sulfoacid catalyst with sulfuric acid phase, and is easy to
Recycle and activating and regenerating, the carrier material of common solid sulfoacid catalyst have resin, silica etc..But sulfonic acid
Resin does not have regulatable pore structure, its specific surface area is relatively low, therefore contact of the reactant with activated centre is limited, and reduces
The performance of catalyst.With sucrose etc. for raw material, the carbon material that is obtained by low-temperature carbonization (400-700 degrees Celsius), passes through
Also it can obtain solid sulfoacid catalyst after sulfonation, such catalyst achieves ideal achievement in many catalytic fields.But
It is the solid sulfoacid catalyst being prepared in this way, equally without loose structure, therefore specific surface area is low, reaction
Contact of the thing with activated centre is equally limited, limits the raising of its catalytic performance.Solid using porous silica as carrier
Sulfonic acid catalyst, the introducing of its sulfonic acid functional group is typically using 3- mercaptopropyltriethoxysilanes as persursor material, through peroxide
Change obtains solid sulfoacid catalyst.The addition of increase 3- mercaptopropyltriethoxysilanes can increase the activity of such catalyst
Position, improves catalytic performance, but can also reduce specific surface area at the same time, reduces contact of the reactant with activated centre, reduces catalytic
Energy.Therefore, solid sulfoacid of the exploitation with regulatable micropore structure (such as specific surface area, pore volume and pore size) is catalyzed
Agent, increases specific surface area, more places is provided for contact of the reactant with activated centre, so as to expand solid sulfoacid catalyst
Application be still need to solve research hotspot.
Carbon material is introduced into the duct of mesoporous silicon oxide, obtains mesoporous using mesoporous silicon oxide as carrier by the present invention
Silicon/carbon dioxide composite material, by the pore structure for regulating and controlling meso-porous titanium dioxide silicon carrier and silicon/carbon dioxide composite material
(such as specific surface area, pore volume and pore size), realizes the adjustment of gained mesoporous solid sulfonic acid catalyst pore structure, is had
The mesoporous solid sulfonic acid catalyst of high-specific surface area.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of mesoporous solid sulfonic acid catalyst, pass through tune
The pore structure (such as specific surface area, pore volume and pore size) of meso-porous titanium dioxide silicon carrier and silicon/carbon dioxide composite material is controlled,
Realize the adjustment of gained mesoporous solid sulfonic acid catalyst pore structure, make gained mesoporous solid sulfonic acid catalyst that there is higher ratio
Surface area.
Technical solution is used by the present invention solves above-mentioned technical problem:A kind of preparation of mesoporous solid sulfonic acid catalyst
Method, it is characterised in that specifically include following steps:
(1) preparation of mesoporous silicon oxide
By the hydrochloric acid solution of 2mol/L and polyoxyethylene-poly-oxypropylene polyoxyethylene in mass ratio 3:1~5:1 mixing, obtains
To mixture 1, mixture 1 is stirred to polyoxyethylene-poly-oxypropylene polyoxyethylene under 35~45 degrees Celsius and is all dissolved,
Eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicate are added dropwise in mixture 1 in order afterwards, obtain mixture 2, will
Mixture 2 stirred under 35~45 degrees Celsius 20~24 it is small when, mixture 2 is transferred in hydrothermal reaction kettle afterwards, in 80~
When standing 24~72 is small under conditions of 120 degrees Celsius, mixture 3 is obtained, filtering and washing is carried out to mixture 3 with deionized water,
It is placed in 100~120 degrees Celsius of baking ovens and is dried afterwards, obtain white powder material, by the white powder thing of drying
Matter is placed in Muffle furnace, and when 550~580 degrees Celsius of calcinings 6~8 are small under air conditions, heating rate is 1~5 DEG C/min, it
After obtain mesoporous silicon oxide;
(2) preparation of mesoporous silicon oxide/carbon composite
By gained mesoporous silicon oxide and deionized water according to mass ratio 1:3~1:5 mixing, are stirred, Zhi Houjia at room temperature
Enter glucose, add the concentrated sulfuric acid, the mass ratio of the added concentrated sulfuric acid and glucose is 0.4:1~0.6:1, at room temperature stir 8~
12 it is small when;Obtain mixture 4;By gained mixture 4 be put into 100~120 degrees Celsius of low-temperature carbonizations 20~24 of baking oven it is small when, then
Be warming up to 160~180 degree continue carbonization 6~8 it is small when, afterwards under vacuum calcining 3~5 it is small when, heating rate be 3~5
DEG C/min, obtain mesoporous silicon oxide/carbon composite;
(3) preparation of mesoporous solid sulfonic acid catalyst
By the concentrated sulfuric acid and mesoporous silicon oxide/carbon composite according to mass ratio 40:1~60:1 mixing, 120~150 take the photograph
When magnetic agitation sulfonation 10~12 is small under family name's degree, mixture 5 is obtained, mixture 5 is cooled to room temperature afterwards, mixture 5 is slow
Slowly pour into deionized water, then with a large amount of deionized water filtering and washings, when 60~80 degree of drying 12~15 are small, obtain mesoporous solid
Body sulfonic acid catalyst.
The further preferred solution of the present invention:In the preparation process of mesoporous silicon oxide, eight water basic zirconium chlorides, trimethylbenzene and
The mass ratio of tetraethyl orthosilicate is (0~0.15):(0~0.7):1.
The further preferred solution of the present invention:In the preparation process of mesoporous silicon oxide/carbon composite, glucose is added
Quality=glucose Mi Du ╳ (the 20%~80% of mesoporous silicon oxide total pore volume).
The further preferred solution of the present invention:In the preparation process of mesoporous silicon oxide/carbon composite, under vacuum condition
The temperature of calcining is 500~600 degrees Celsius.
A kind of reclaiming method of mesoporous solid sulfonic acid catalyst, it is characterised in that there are following specific steps:
(1) by used mesoporous solid sulfonic acid catalyst, 550~600 degrees Celsius of calcinings 6~8 are small under air conditions
When, heating rate is 1~5 DEG C/min, can retrieve mesoporous silicon oxide;
(2) preparation of mesoporous silicon oxide/carbon composite
By gained mesoporous silicon oxide and deionized water according to mass ratio 1:3~1:5 mixing, are stirred, Zhi Houjia at room temperature
Enter glucose, add the concentrated sulfuric acid, the mass ratio of the added concentrated sulfuric acid and glucose is 0.4:1~0.6:1, at room temperature stir 8~
12 it is small when;Obtain mixture 4;By gained mixture 4 be put into 100~120 degrees Celsius of low-temperature carbonizations 20~24 of baking oven it is small when, then
Be warming up to 160~180 degree continue carbonization 6~8 it is small when, afterwards under vacuum calcining 3~5 it is small when, heating rate be 3~5
DEG C/min, obtain mesoporous silicon oxide/carbon composite;
(3) preparation of mesoporous solid sulfonic acid catalyst
By the concentrated sulfuric acid and mesoporous silicon oxide/carbon composite according to mass ratio 40:1~60:1 mixing, 120~150 take the photograph
When magnetic agitation sulfonation 10~12 is small under family name's degree, mixture 5 is obtained, mixture 5 is cooled to room temperature afterwards, mixture 5 is slow
Slowly pour into deionized water, then with a large amount of deionized water filtering and washings, when 60~80 degree of drying 12~15 are small, retrieve Jie
Hole solid sulfoacid catalyst.
Compared with prior art, advantages of the present invention is by varying eight water oxychlorides in mesoporous silicon oxide preparation process
The mass ratio of zirconium, trimethylbenzene and tetraethyl orthosilicate, can regulate and control the pore structure of gained Metaporous silicon dioxide material, afterwards
In the preparation process of mesoporous silicon oxide/carbon composite, by varying the quality of glucose is added, can further it regulate and control
The pore structure of gained mesoporous silicon oxide/carbon composite, final realization gained mesoporous solid sulfonic acid catalyst specific surface area,
The regulation and control of pore volume and pore size, obtain the mesoporous solid sulfonic acid catalyst with high specific surface area, its preparation process is simple,
It is easy to implement;By calcining during catalyst reclaiming, the carbon in mesoporous solid sulfonic acid catalyst can be removed, is retrieved
Mesoporous silicon oxide with diverse microcosmic pore structure, the afterwards repeatedly preparation of mesoporous silicon oxide/carbon composite and Jie
The preparation process of hole solid sulfoacid catalyst, can regain the mesoporous solid sulfonic acid catalyst of diverse microcosmic pore structure.
Embodiment
The present invention is described in further detail with reference to embodiments.
Embodiment 1
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the tune of pore size
Control,
Specifically include following steps:
(1) 2 grams of polyoxyethylene-poly-oxypropylene polyoxyethylenes are added to the hydrochloric acid solution of 2mol/L, hydrochloric acid solution is with gathering
Ethylene oxide-polyoxypropylene polyoxyethylene is 3 in mass ratio:1, obtain mixture 1, mixture 1 is stirred under 35 degrees Celsius to
Polyoxyethylene-poly-oxypropylene polyoxyethylene all dissolves, afterwards by eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicate
In mass ratio 0.08:0:1, it is added dropwise in order in mixture 1, obtains mixture 2, mixture 2 is stirred under 35 degrees Celsius
20 it is small when, mixture 2 is transferred in hydrothermal reaction kettle afterwards, under conditions of 80 degrees Celsius stand 24 it is small when, mixed
Thing 3, carries out filtering and washing to mixture 3 with deionized water, is placed in 100 degrees Celsius of baking ovens and is dried afterwards, obtain white
Powdered substance, the white powder material of drying is placed in Muffle furnace, when 550 degrees Celsius of calcinings 6 are small under air conditions,
Heating rate is 1 DEG C/min, obtains silica sample 1 afterwards.The specific surface area of meso-porous titanium dioxide silicon sample 1, aperture and total
Pore volume is listed in table 1.
(2) the meso-porous titanium dioxide silicon sample 1 that gained is prepared in 1 gram of step (1) is taken, with deionized water according to mass ratio 1:4
Mixing, is stirred at room temperature, is added 0.422 gram of glucose afterwards, is added the concentrated sulfuric acid, and the mass ratio of the concentrated sulfuric acid and glucose is
0.4:1, when stirring 12 is small at room temperature.By gained mixture be put into 120 degrees Celsius of low-temperature carbonizations 24 of baking oven it is small when, then heat to
160 degree continue carbonization 6 it is small when, afterwards under vacuum 550 degree calcine 3 it is small when, heating rate is 5 DEG C/min, is obtained mesoporous
Silicon/carbon dioxide composite material 1.
(3) by the mesoporous silicon oxide/carbon composite 1 obtained in 2 grams of steps (2) and the concentrated sulfuric acid according to mass ratio 1:60
Mixture when sulfonation 10 is small, is cooled to room temperature afterwards, mixture is slowly poured into by mixing, 120 degrees Celsius of lower magnetic agitations
In ionized water, then with a large amount of deionized water filtering and washings, when 60 degree of drying 12 are small, mesoporous solid sulfonic acid catalyst 1 is obtained.It is situated between
Specific surface area, aperture and the total pore volume of hole solid sulfoacid catalyst 1 are listed in table 2.
(4) by mesoporous solid sulfonic acid catalyst 1 obtained by step (3), when 550 degrees Celsius of calcinings 6 are small under air conditions, rise
Warm speed is 5 DEG C/min, can retrieve meso-porous titanium dioxide silicon sample 1, and repeat step (2) and step (3), can obtain again afterwards
To mesoporous solid sulfonic acid catalyst 1.
Embodiment 2
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with the step (1) in embodiment 1, by hydrochloric acid solution and PULLRONIC F68-polyoxy
Ethene is adjusted to 5 in mass ratio:1, the mass ratio of eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicate is adjusted to
0.08:0.24:1, obtain meso-porous titanium dioxide silicon sample 2, specific surface area, aperture and the total pore volume row of meso-porous titanium dioxide silicon sample 2
In table 1.
(2) 1 gram of meso-porous titanium dioxide silicon sample 2 is taken, with deionized water according to mass ratio 1:5 mixing, are stirred, afterwards at room temperature
0.686 gram of glucose is added, adds the concentrated sulfuric acid, the mass ratio of the concentrated sulfuric acid and glucose is 0.5:1, it is small that 10 are stirred at room temperature
When.By gained mixture be put into 100 degrees Celsius of low-temperature carbonizations 24 of baking oven it is small when, then heat to 160 degree continue carbonization 6 it is small when,
When 580 degree of calcinings 3 are small under vacuum afterwards, heating rate is 5 DEG C/min, obtains mesoporous silicon oxide/carbon composite
2。
(3) by the mesoporous silicon oxide/carbon composite 2 obtained in 2 grams of steps (2) and the concentrated sulfuric acid according to mass ratio 1:50
Mixture when sulfonation 12 is small, is cooled to room temperature afterwards, mixture is slowly poured into by mixing, 140 degrees Celsius of lower magnetic agitations
In ionized water, then with a large amount of deionized water filtering and washings, when 80 degree of drying 12 are small, mesoporous solid sulfonic acid catalyst 2 is obtained.It is situated between
Specific surface area, aperture and the total pore volume of hole solid sulfoacid catalyst 2 are listed in table 2.
(4) step is identical with the step (4) in embodiment 1, and the temperature calcined under air conditions is adjusted to 600, it
Repeat step (2) and step (3) afterwards, can retrieve mesoporous solid sulfonic acid catalyst 2.
Embodiment 3
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with the step (1) in embodiment 2, by eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicic acid
The mass ratio of salt is adjusted to 0.08:0.48:1, obtain meso-porous titanium dioxide silicon sample 3, the ratio surface of meso-porous titanium dioxide silicon sample 3
Product, aperture and total pore volume are listed in table 1.
(2) step is identical with step (2) in embodiment 2, and the quality for adding glucose is 0.818, obtains mesoporous dioxy
SiClx/carbon composite 3.
(3) step is identical with step (3) in embodiment 2, obtains mesoporous solid sulfonic acid catalyst 3, mesoporous solid sulfonic acid
Specific surface area, aperture and the total pore volume of catalyst 3 are listed in table 2.
(4) step is identical with the step (4) in embodiment 2, can retrieve porosu solid sulfonic acid catalyst 3.
Embodiment 4
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with the step (1) in embodiment 2, by eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicic acid
The mass ratio of salt is adjusted to 0.08:0.7:1, obtain meso-porous titanium dioxide silicon sample 4, the specific surface area of meso-porous titanium dioxide silicon sample 4,
Aperture and total pore volume are listed in table 1.
(2) step is identical with step (2) in embodiment 2, and the quality for adding glucose is 0.845, obtains mesoporous dioxy
SiClx/carbon composite 4.
(3) step is identical with step (3) in embodiment 2, obtains mesoporous solid sulfonic acid catalyst 4, mesoporous solid sulfonic acid
Specific surface area, aperture and the total pore volume of catalyst 4 are listed in table 2.
Embodiment 5
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with the step (1) in embodiment 2, by eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicic acid
The mass ratio of salt is adjusted to 0.05:0.48:1, obtain meso-porous titanium dioxide silicon sample 5, the ratio surface of meso-porous titanium dioxide silicon sample 5
Product, aperture and total pore volume are listed in table 1.
(2) 1 gram of meso-porous titanium dioxide silicon sample 5 is taken, with deionized water according to mass ratio 1:3 mixing, are stirred, afterwards at room temperature
0.84 gram of glucose is added, adds the concentrated sulfuric acid, the mass ratio of the concentrated sulfuric acid and glucose is 0.6:1, when stirring 10 is small at room temperature.
By gained mixture be put into 100 degrees Celsius of low-temperature carbonizations 24 of baking oven it is small when, then heat to 180 degree continue carbonization 6 it is small when, afterwards
When 600 degree of calcinings 3 are small under vacuum, heating rate is 1 DEG C/min, obtains mesoporous silicon oxide/carbon composite 5.
(3) by the mesoporous silicon oxide/carbon composite 5 obtained in 2 grams of steps (2) and the concentrated sulfuric acid according to mass ratio 1:50
Mixture when sulfonation 12 is small, is cooled to room temperature afterwards, mixture is slowly poured into by mixing, 150 degrees Celsius of lower magnetic agitations
In ionized water, then with a large amount of deionized water filtering and washings, when 80 degree of drying 12 are small, mesoporous solid sulfonic acid catalyst 5 is obtained.It is situated between
Specific surface area, aperture and the total pore volume of hole solid sulfoacid catalyst 5 are listed in table 2.
Embodiment 6
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with the step (1) in embodiment 2, by eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicic acid
The mass ratio of salt is adjusted to 0.15:0.48:1, it is silica sample 6 to obtain mesoporous silicon oxide, meso-porous titanium dioxide silicon sample 6
Specific surface area, aperture and total pore volume be listed in table 1.
(2) step is identical with step (2) in embodiment 5, and the quality for adding glucose is 0.939, obtains mesoporous dioxy
SiClx/carbon composite 6.
(3) step is identical with step (3) in embodiment 5.Obtain mesoporous solid sulfonic acid catalyst 6.Mesoporous solid sulfonic acid
Specific surface area, aperture and the total pore volume of catalyst 6 are listed in table 2.
Embodiment 7
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with step (2) in embodiment 1, and the Mass adjust- ment for adding glucose is 1.482 grams, be can obtain
Mesoporous silicon oxide/carbon composite 7.
(2) step is identical with step (3) in embodiment 1, can obtain mesoporous solid sulfonic acid catalyst 7.
Embodiment 8
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with step (2) in embodiment 2, and the Mass adjust- ment for adding glucose is 2.406 grams, be can obtain
Silicon/carbon dioxide composite material 8.
(2) step is identical with step (3) in embodiment 2, can obtain porosu solid sulfonic acid catalyst 8.
Embodiment 9
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with step (2) in embodiment 3, and the Mass adjust- ment for adding glucose is 2.878 grams, be can obtain
Silicon/carbon dioxide composite material 9.
(2) step is identical with step (3) in embodiment 3, can obtain porosu solid sulfonic acid catalyst 9.
Embodiment 10
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with step (2) in embodiment 4, and the Mass adjust- ment for adding glucose is 2.965 grams, be can obtain
Silicon/carbon dioxide composite material 10.
(2) step is identical with step (3) in embodiment 4, can obtain porosu solid sulfonic acid catalyst 10.
Embodiment 11
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with step (2) in embodiment 5, and the Mass adjust- ment for adding glucose is 2.94 grams, can obtain two
Silica/carbon composite 11.
(2) step is identical with step (3) in embodiment 5, can obtain porosu solid sulfonic acid catalyst 11.
Embodiment 12
A kind of preparation method of mesoporous solid sulfonic acid catalyst of the present invention, by varying mesoporous silicon oxide/carbon composite wood
The pore structure of material realizes gained mesoporous solid sulfonic acid catalyst specific surface area, pore volume and the regulation and control of pore size, specific bag
Include following steps:
(1) step is identical with step (2) in embodiment 6, and the Mass adjust- ment for adding glucose is 3.299 grams, be can obtain
To silicon/carbon dioxide composite material 12.
(2) step is identical with step (3) in embodiment 6, can obtain porosu solid sulfonic acid catalyst 12.
Comparative example 1:
A kind of customary preparation methods of mesoporous organosilicon solid sulfoacid catalyst, specifically include following steps:
2 grams of polyoxyethylene-poly-oxypropylene polyoxyethylenes are added to the hydrochloric acid solution of 2mol/L, hydrochloric acid solution and polyoxy
Ethene-polyoxypropylene polyoxyethylene is 3 in mass ratio:1, mixture 1 is obtained, mixture 1 is stirred to poly- under 35 degrees Celsius
Ethylene oxide-polyoxypropylene polyoxyethylene all dissolves, and afterwards presses eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicate
Mass ratio 0.08:0.24:1, it is added dropwise in order in mixture 1, obtains mixture 2, mixture 2 is stirred under 35 degrees Celsius
10 it is small when, then by 3- mercaptopropyltriethoxysilanes according to tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes mole
Than being added for 0.05 in mixture 2, when stirring 15 is small under 35 degrees Celsius, mixture 3 is obtained, then by 0.9 milliliter 35%
Hydrogen peroxide is added in mixture 3, and mixture 3 is transferred in hydrothermal reaction kettle afterwards, 24 are stood under conditions of 80 degrees Celsius
Hour, mixture 4 is obtained, filtering and washing is carried out to mixture 4 with deionized water, is placed in 100 degrees Celsius of baking ovens and carries out afterwards
Drying, obtains the mesoporous organic silica solid sulfoacid catalyst 1 of white powder material.Mesoporous organic silica solid sulphur
Specific surface area, aperture and the total pore volume of acid catalyst 1 are listed in table 3.As a comparison case, compared with Example 3, gained is mesoporous for this example
The specific surface area of organic silica solid sulfoacid catalyst 1 is lower than mesoporous solid sulfonic acid catalyst 3.
Comparative example 2:
A kind of customary preparation methods of mesoporous organosilicon solid sulfoacid catalyst, specifically include following steps:
The step is identical with comparative example 1, and tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes molar ratio are adjusted
For 0.15.Obtain the mesoporous organic silica solid sulfoacid catalyst 2 of white powder material.Mesoporous organic silica solid
Specific surface area, aperture and the total pore volume of sulfonic acid catalyst 2 are listed in table 3.As a comparison case, compared with Example 3, gained is situated between this example
The specific surface area of hole organic silica solid sulfoacid catalyst 2 is lower than mesoporous solid sulfonic acid catalyst 3.
Comparative example 3:
A kind of customary preparation methods of mesoporous organosilicon solid sulfoacid catalyst, specifically include following steps:
The step is identical with comparative example 1, and tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes molar ratio are adjusted
For 0.3.Obtain the mesoporous organic silica solid sulfoacid catalyst 3 of white powder material.Mesoporous organic silica solid
Specific surface area, aperture and the total pore volume of sulfonic acid catalyst 3 are listed in table 3.As a comparison case, compared with Example 3, gained is situated between this example
The specific surface area of hole organic silica solid sulfoacid catalyst 3 is lower than mesoporous solid sulfonic acid catalyst 3.
Table 1:Meso-porous titanium dioxide silicon sample specific surface area, aperture and total pore volume in 1-6 of the embodiment of the present invention
Table 2:Mesoporous solid sulfonic acid catalyst specific surface area, aperture and total pore volume in 1-12 of the embodiment of the present invention
Table 3 is mesoporous organosilicon solid sulfoacid catalyst (1-3) specific surface area, aperture and total pore volume
Claims (3)
1. a kind of preparation method of mesoporous solid sulfonic acid catalyst, it is characterised in that specifically include following steps:
(1) preparation of mesoporous silicon oxide
By the hydrochloric acid solution of 2mol/L and polyoxyethylene-poly-oxypropylene polyoxyethylene in mass ratio 3:1~5:1 mixing, is mixed
Compound 1, mixture 1 is stirred to polyoxyethylene-poly-oxypropylene polyoxyethylene under 35~45 degrees Celsius and is all dissolved, afterwards
By eight water basic zirconium chlorides, trimethylbenzene and tetraethyl orthosilicate using mass ratio as 0.08:0.24:1 and mixing is added dropwise in order
In thing 1, obtain mixture 2, mixture 2 is stirred under 35~45 degrees Celsius 20~24 it is small when, mixture 2 is transferred to afterwards
In hydrothermal reaction kettle, when standing 24~72 is small under conditions of 80~120 degrees Celsius, mixture 3 is obtained, with deionized water to mixed
Compound 3 carries out filtering and washing, is placed in 100~120 degrees Celsius of baking ovens and is dried afterwards, obtains white powder material, will
The white powder material of drying is placed in Muffle furnace, when 550~580 degrees Celsius of calcinings 6~8 are small under air conditions, heating
Speed is 1~5 DEG C/min, obtains mesoporous silicon oxide afterwards;
(2) preparation of mesoporous silicon oxide/carbon composite
By gained mesoporous silicon oxide and deionized water according to mass ratio 1:3~1:5 mixing, stir, add Portugal afterwards at room temperature
Grape sugar, adds the concentrated sulfuric acid, the mass ratio of the added concentrated sulfuric acid and glucose is 0.4:1~0.6:1, it is small that 8~12 are stirred at room temperature
When;Obtain mixture 4;By gained mixture 4 be put into 100~120 degrees Celsius of low-temperature carbonizations 20~24 of baking oven it is small when, then heat up
To 160~180 degrees Celsius continue carbonization 6~8 it is small when, afterwards under vacuum calcining 3~5 it is small when, heating rate be 3~5
DEG C/min, obtain mesoporous silicon oxide/carbon composite;
(3) preparation of mesoporous solid sulfonic acid catalyst
By the concentrated sulfuric acid and mesoporous silicon oxide/carbon composite according to mass ratio 40:1~60:1 mixing, 120~150 degrees Celsius
When lower magnetic agitation sulfonation 10~12 is small, mixture 5 is obtained, mixture 5 is cooled to room temperature afterwards, mixture 5 is slowly fallen
Enter in deionized water, then with a large amount of deionized water filtering and washings, when 60~80 degrees Celsius of drying 12~15 are small, obtain mesoporous solid
Body sulfonic acid catalyst.
A kind of 2. preparation method of mesoporous solid sulfonic acid catalyst according to claim 1, it is characterised in that:Mesoporous dioxy
In the preparation process of SiClx/carbon composite, Mi Du ╳ (the total holes of mesoporous silicon oxide of quality=glucose of glucose are added
20%~80% held).
A kind of 3. preparation method of mesoporous solid sulfonic acid catalyst according to claim 1, it is characterised in that:Mesoporous dioxy
In the preparation process of SiClx/carbon composite, the temperature calcined under vacuum condition is 500~600 degrees Celsius.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610196206.5A CN105833902B (en) | 2016-03-31 | 2016-03-31 | The preparation method and reclaiming method of a kind of mesoporous solid sulfonic acid catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610196206.5A CN105833902B (en) | 2016-03-31 | 2016-03-31 | The preparation method and reclaiming method of a kind of mesoporous solid sulfonic acid catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105833902A CN105833902A (en) | 2016-08-10 |
CN105833902B true CN105833902B (en) | 2018-05-15 |
Family
ID=56596263
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610196206.5A Expired - Fee Related CN105833902B (en) | 2016-03-31 | 2016-03-31 | The preparation method and reclaiming method of a kind of mesoporous solid sulfonic acid catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105833902B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107624759A (en) * | 2017-10-13 | 2018-01-26 | 新沂肽科生物科技有限公司 | A kind of method for preparing peroxyacetic acid disinfectant |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101638238A (en) * | 2008-07-30 | 2010-02-03 | 中国科学院理化技术研究所 | Method for preparing silica nano material with controllable shape and structure and containing ordered mesoporous pore canals |
CN101708470A (en) * | 2009-11-18 | 2010-05-19 | 广西科学院 | Method for preparing magnetic solid acid catalyst for production of biodiesel |
CN102600893A (en) * | 2012-03-02 | 2012-07-25 | 宁夏大学 | Carbon-based solid acid catalyst and preparation method thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7868190B2 (en) * | 2008-09-29 | 2011-01-11 | Sabic Innovative Plastics Ip B.V. | Method for producing phenolphthalein using a heteropolyacid catalyst |
-
2016
- 2016-03-31 CN CN201610196206.5A patent/CN105833902B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101638238A (en) * | 2008-07-30 | 2010-02-03 | 中国科学院理化技术研究所 | Method for preparing silica nano material with controllable shape and structure and containing ordered mesoporous pore canals |
CN101708470A (en) * | 2009-11-18 | 2010-05-19 | 广西科学院 | Method for preparing magnetic solid acid catalyst for production of biodiesel |
CN102600893A (en) * | 2012-03-02 | 2012-07-25 | 宁夏大学 | Carbon-based solid acid catalyst and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
SOLID SULFONIC ACID CATALYSTS BASED ON POROUS CARBONS AND CARBON-SILICA COMPOSITES;XIAO NING TIAN et al;《Surface Review and Letters》;20111231;第18卷(第6期);第229-239页 * |
Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores;Dongyuan Zhao et al;《SCIENCE》;19980123;第279卷;第548-552页 * |
Also Published As
Publication number | Publication date |
---|---|
CN105833902A (en) | 2016-08-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11618011B2 (en) | V-Ni2P/g-C3N4 photocatalyst and its preparation method and application thereof | |
US9458330B2 (en) | Method of preparing carbon-coated manganous oxide and carbon-coated manganous oxide prepared using the method | |
CN110422857B (en) | Preparation method of Sn-beta molecular sieve nanocrystal | |
CN115043412B (en) | Porous carbon material and preparation method and application thereof | |
CN105271299A (en) | Mesoporous ZSM-5 zeolite preparing method | |
CN107089669B (en) | A kind of synthetic method of c- axis orientating type Zn-ZSM-5 molecular sieve under externally-applied magnetic field effect | |
CN105833902B (en) | The preparation method and reclaiming method of a kind of mesoporous solid sulfonic acid catalyst | |
CN103922362A (en) | MTW zeolite and preparation method thereof | |
CN110510633A (en) | A kind of preparation method of multi-stage porous ZSM-5 molecular sieve | |
CN104340997B (en) | A kind of preparation method of large-pore alumina | |
CN103922421B (en) | Method for preparing alpha-Fe2O3 | |
CN114931969B (en) | Ferroferric oxide-ZSM-5 composite material and preparation method and application thereof | |
CN109835914B (en) | Method for preparing hierarchical pore molecular sieve by combining thermal dispersion and alkali treatment | |
CN107055563B (en) | A kind of nano whiskers SAPO-34 molecular sieve and its preparation and application | |
CN116003262B (en) | Synthesis method of N, N-dimethylaniline | |
CN107311203A (en) | A kind of multi-stage pore canal molecular sieve and preparation method thereof | |
CN104475149B (en) | A kind of preparation method of tungsten oxide modified micropore molecular sieve shape-selective catalyst | |
CN108609632A (en) | A kind of stanniferous Beta molecular sieves and preparation method thereof | |
CN107285333A (en) | A kind of method that Fast back-projection algorithm AEI molecular sieves are heated with microwave | |
CN106745039A (en) | A kind of size adjustable simultaneously has nanometer Ti-Si zeolite molecular sieve of ultra-high yield and preparation method thereof | |
CN110170332A (en) | A kind of carbonitride and preparation method thereof can be used for photocatalysis seawater liberation of hydrogen | |
CN109368654A (en) | A kind of preparation method of nano Si licalite-1 molecular sieve | |
CN107161977B (en) | Carbon nano-structured modification flaky sequential meso-porous carbon material of one kind and preparation method thereof | |
CN111620366A (en) | High specific surface area ordered large mesoporous spinel zinc gallate and preparation method thereof | |
CN110451519A (en) | A kind of eutectic material and preparation method thereof containing MTW structure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Address after: 315016 Zhejiang Province, Ningbo city Haishu District cypress Road No. 89 Applicant after: Ningbo University of Technology Address before: 315016 Zhejiang Province, Ningbo city Haishu District Stadium Road Cuibai Road No. 89 Applicant before: Ningbo University of Technology |
|
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180515 |